EP1851279A1 - Agents de revetement destines a la fabrication de revetements antirayures deformables, resistants a la salissure, corps moules resistants a la salissure, deformables, antirayures et procede de fabrication de ceux-ci - Google Patents

Agents de revetement destines a la fabrication de revetements antirayures deformables, resistants a la salissure, corps moules resistants a la salissure, deformables, antirayures et procede de fabrication de ceux-ci

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Publication number
EP1851279A1
EP1851279A1 EP05818695A EP05818695A EP1851279A1 EP 1851279 A1 EP1851279 A1 EP 1851279A1 EP 05818695 A EP05818695 A EP 05818695A EP 05818695 A EP05818695 A EP 05818695A EP 1851279 A1 EP1851279 A1 EP 1851279A1
Authority
EP
European Patent Office
Prior art keywords
meth
weight
scratch
resistant
acrylate
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Withdrawn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
EP05818695A
Other languages
German (de)
English (en)
Inventor
Patrick Becker
Rolf Neeb
Ghirmay Seyoum
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.)
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP1851279A1 publication Critical patent/EP1851279A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen

Definitions

  • the present invention relates to coating compositions for the production of deformable scratch-resistant coatings with dirt-repellent effect, molded articles coated with these coating compositions with a scratch-resistant, formable and dirt-repellent coating and to processes for producing the coated molded bodies.
  • thermoplastically deformable plastics do not achieve the scratch resistance of many metals or mineral glasses. Particularly disadvantageous is the susceptibility to scratches in transparent plastics noticeable, since the objects in question are very quickly unsightly.
  • Scratch-resistant coatings for plastics are known per se.
  • the publication DE 19507 174 describes UV-curing, scratch-resistant coatings for plastics which have a particularly high UV stability. These coatings already show a good property spectrum.
  • plastic moldings also coated scratch-resistant, especially in the form of outdoor construction panels, such as noise barriers or as glazings of facades, bus stops, advertising space, Litutz columns, so-called "mobile urban” used where they are both more natural Pollution as well as by vandalism-related impurities, such as the graffiti smearings are exposed.
  • the cleaning of such surfaces is very expensive, since often the surface is attacked by this.
  • fluorine-containing acrylates are frequently added to the coating compositions. Such coating compositions are described for example in DE 43 19 199.
  • Forming form cracks the coating on the formed body is milky cloudy and unsightly.
  • coated formable structural members can be made for much wider customer circles than custom preformed panels.
  • Plastic substrates have. This property should not be affected by thermal forming.
  • plastic body with a scratch-resistant coating according to the invention have a high durability, in particular a high resistance to UV irradiation or weathering.
  • Another object of the present invention was to provide antigraffiti-effect coating agents which do not adversely affect the properties of the substrate.
  • the spray paints used to make graffiti should no longer or only very weakly adhere to the plastic body by an antigraffiti finish according to the invention, wherein sprayed substrates should be easy to clean, so that e.g. Water, cloths, surfactants, high-pressure coater, mild solvents ("Easy-to-clean”) are sufficient.
  • the invention was the object of providing scratch-resistant, dirt-repellent moldings available, especially can be easily made.
  • substrates which can be obtained by extrusion, injection molding and casting methods should be able to be used to produce the moldings.
  • a further object of the present invention was to provide scratch-resistant, formable, dirt-repellent moldings which show excellent mechanical properties. This property is particularly important for applications in which the plastic body should have a high stability against impact.
  • the moldings should have particularly good optical properties.
  • a further object of the present invention was to provide scratch-resistant, formable, dirt-repellent moldings which can be easily adapted to the requirements in a larger form.
  • the coatings should be easy to produce and handle. On an industrial scale, it must be avoided that parts of the coating material precipitate and so the filters are added. It is therefore desirable to formulate the coating composition which allows more parts by weight of the fluorinated oligomer mixture to dissolve. Therefore, the varnish should be modified so that more of the fluorinated oligomer mixtures of zonyl-TAN go into solution.
  • claims 12-21 provide a solution to the underlying problems.
  • Sulfur compound containing at least 3 thiol groups and A2) 90 parts by weight to 99 parts by weight of alkyl (meth) acrylates,
  • Alcohol radical comprising 13 to 121 fluorine atoms
  • the scratch-resistant coatings obtained with the coating compositions of the invention have a particularly high adhesion to the plastic substrates, and this property is not impaired by weathering.
  • the coated moldings show high resistance to UV radiation.
  • coated plastic body show a particularly low surface energy.
  • the present moldings are particularly easy to clean.
  • Scratch-resistant moldings of the present invention can easily be adapted to specific requirements.
  • the size and shape of the plastic body can be varied within wide limits, without this affecting the formability.
  • the present invention also provides moldings having excellent optical properties.
  • the scratch-resistant, formable, dirt-repellent moldings of the present invention have good mechanical properties.
  • Component G) acts as a compatibilizer for the long-chain fluoroalkyl (meth) acrylates, so that the concentration of active substance in the formulation can be increased without the mechanical properties (elongation at break) being too great deteriorate.
  • the coating compositions according to the invention for the production of deformable scratch-resistant coatings with soil-repelling action comprise 1% by weight to 30% by weight, preferably 2% by weight to 25% by weight, based on the weight of the coating composition, of a prepolymer obtainable by free-radical Polymerization of a mixture comprising
  • A1) 1 - 10 parts by weight, preferably 2 - 6 parts by weight of at least one
  • Sulfur compound containing at least three thiol groups and A2) 90-99 parts by weight, preferably 94-98 parts by weight
  • Sulfur compounds having more than two thiol groups in the molecule are known, for example, from US Pat. No. 4,521,567.
  • sulfur compounds having at least three, preferably four, thiol groups in the molecule are used.
  • the sulfur regulators contain at least 3, preferably at least 6 carbon atoms in the molecule, but not over 40.
  • the presence of one or preferably several ⁇ -mercapto carboxylic acid ester groups in the molecule preferably starting from polyols, such as glycerol or pentaerythritol.
  • Suitable sulfur regulators with more than three thiol groups are, for example, 1, 2,6-hexanetrioltrithioglycolate, trimethylolethane trithioglycolate, pentaerythritol tetrakis- (2-mercaptoacetate), trimethylolethane-tri- (3-mercaptopropionate), pentaerythritol tetrakis- (3- mercaptopropionate), trimethylolpropane trithioglycolate, trimethylolpropane tri- (3-mercaptopropionate), tetrakis (3-mercaptopropionate) pentaerythritol, 1,1,1-propanetriyl tris (mercaptoacetate), 1,1,1-propanetriyl tris ( 3-mercaptopropionate), dipentaerythritol hexa- (3-mercatopropionate).
  • pentaerythritol te pen
  • the acryl (meth) acrylates which can be used according to the invention for the preparation of the prepolymer are known per se, the term (meth) acrylate being acrylates, methacrylates and mixtures of both.
  • the alkyl (meth) acrylates preferably have 1 to 20, in particular 1 to 8, carbon atoms.
  • Examples of the C1 to C8 alkyl esters of acrylic acid and of methacrylic acid are methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate and 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate and butyl methacrylate.
  • Preferred monomers are methyl methacrylate and n-butyl acrylate.
  • alkyl (meth) acrylates which comprise at least 10% by weight of methyl (meth) acrylate and / or ethyl acrylate and at least 2% by weight of alkyl (meth) acrylates having 3-8 carbon atoms.
  • the ratios of regulator to monomers can be varied.
  • the polymerization of regulators and monomers can be carried out in a manner known per se as bulk, suspension or bead, solution or emulsion polymerization with the aid of radical initiators.
  • DE 33 29 765 C2 / US Pat. No. 4 521 567 discloses or deduces a suitable process for bead polymerization (polymerization step A).
  • free radical initiators come e.g. peroxidic or azo compounds in question (US-PS 2471 959). Called e.g. organic peroxides such as dibenzoyl peroxide, lauryl peroxide or peresters such as tert-butly-per-2-ethylhexanoate, furthermore azo compounds such as azobisisobutyronitrile.
  • the resulting thickener polymers can have molecular weights of about 2,000 to 50,000.
  • the molecular weight can be determined in particular by viscometry, wherein the prepolymer A) preferably a viscosity number according to DIN ISO 1628-6 in the range of 8 to 15 ml / g, in particular 9 to 13 ml / g and particularly preferably 10 to 12 ml / g measured having in CHCl 3 at 2O 0 C.
  • the coating compositions of the present invention contain as essential constituent 0.2% by weight-10% by weight, preferably 0.3% by weight to 5.0% by weight and very particularly preferably 0.5% by weight.
  • the alcohol radical of the fluoroalkyl (meth) acrylate may comprise, in addition to the fluorine atoms, further substituents. These include, in particular, ester groups, amide groups, amine groups, nitro groups and halogen atoms, it being possible for this alcohol radical to be both linear and branched.
  • a fluoroalkyl (meth) acrylate according to the formula II is used
  • H 2 C CC - R (CF 2 CF 2 ) n F wherein the radical R 1 is a hydrogen atom or a methyl radical and n is an integer in the range from 2 to 10, preferably 3 to 8, particularly preferably 3 to 5. R represents a -O-CH 2 -CH 2 - group.
  • the fluoroalkyl (meth) acrylates which are contained in the coating compositions according to the invention in component B) include, inter alia, 2,2,3,4,4,4-hexafluorobutyl acrylate,
  • the fluoroalkyl (meth) acrylates are known compounds, where the fluoroalkyl (meth) acrylates can be used individually or as a mixture.
  • crosslinking monomers are added to the coating composition according to the invention. These have at least two polymerizable units e.g. Vinyl groups per molecule (see Brandrup-Immergut-Polymerhandbook).
  • meltblowns and higher esters of acrylic or methacrylic acid of polyhydric alcohols such as glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol, dimethylolpropane, ditrimethylolethane, dipentaerythritol, trimethylhexanediol-1, 6, cyclohexanediol-1, 4.
  • crosslinking monomers include i.a. Ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate,
  • the polyfunctional acrylates or methacrylates may also be oligomers or polymers which optionally contain further functional groups. Mentioned in particular urethane di- or triacrylate or corresponding ester acrylates.
  • Coating composition in an amount of 0.01% by weight to 10% by weight, preferably 1% by weight to 3% by weight, based on the total weight of the coating composition.
  • the preferred initiators include the azo initiators well known in the art, such as AIBN and 1, 1-azobiscyclohexanecarbonitrile, and peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide , tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, Dicumyl peroxide, 1, 1-bis
  • photoinitiators such as UV initiators
  • UV initiators are compounds which split off radicals when exposed to visible or UV light and thus initiate the polymerization of the coating agent.
  • Common UV initiators are according to DE-OS 29 28 512, for example benzoin, 2-methylbenzoin, gasoline methyl, ethyl or butyl ether, acetoin, benzil, benzil dimethylketal or benzophenone.
  • UV initiators are, for example commercially available from Ciba AG under the trade designations Darocur ® 1116, Irgacure ® 184, Irgacure ® 907 and available from BASF AG under the trade name Lucirin ® TPO.
  • Lucirin ® TPO and Lucirin ® TPO-L from BASF, Ludwigshafen, Germany.
  • the coating compositions contain 2 wt .-% to 75 wt .-%, preferably 6 wt .-% to 50 wt .-%, based on the total weight of
  • Coating agent thinner, which can also be used as a mixture.
  • a viscosity of the coating agent in the range of about 10 to about 250 mPa.s is adjusted.
  • coating agents which are intended for flood or dip coatings are rather low viscosities of about 1 - 20 mPa.s common.
  • organic solvents in concentrations up to 75 wt .-% can be used.
  • knife coatings or roll coat coatings the appropriate viscosities are in the range of 20 to 250 mPa.s. The values given are to be understood as indicative only and refer to the measurement of the viscosity at 20 ° C. with a rotation viscometer according to DIN 53 019.
  • the monofunctional reactive diluents contribute to good flow properties of the paint and thus to a good processability.
  • the monofunctional reactive diluents have a radically polymerizable group, usually a vinyl function.
  • 1-alkenes such as hexene-1, heptene-1
  • branched alkenes such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methylpentene-1
  • acrylonitrile vinyl esters, such as vinyl acetate
  • Styrene substituted styrenes having an alkyl substituent in the side chain, such as.
  • Alpha-methylstyrene and alpha-ethylstyrene substituted styrenes having an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes;
  • Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, Vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, Vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles;
  • (meth) acrylates Vinyl and isoprenyl ethers; Maleic acid derivatives such as maleic anhydride, methylmaleic anhydride, maleimide and methylmaleimide; and (meth) acrylates, with (meth) acrylates being particularly preferred.
  • the term (meth) acrylates include methacrylates and acrylates as well as mixtures of both.
  • (meth) acrylates derived from saturated alcohols, such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl ( meth) acrylate, pentyl (meth) acrylate and 2-ethylhexyl (meth) acrylate;
  • (Meth) acrylates derived from unsaturated alcohols, such as. Oleyl (meth) acrylate, 2-propynyl (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate; Aryl (meth) acrylates, such as benzyl (meth) acrylate or phenyl (meth) acrylate, wherein the aryl radicals may each be unsubstituted or substituted up to four times; Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate, bomyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; Glycol di (meth) acrylates such as 1,4
  • Particularly preferred monofunctional reactive diluents are e.g. Butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 2-ethoxyethyl methacrylate, methyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate.
  • EP 0 035 272 describes common organic solvents for coating compositions for scratch-resistant coatings which can be used as thinners. Suitable are e.g. Alcohols such as ethanol, isopropanol, n-propanol, isobutyl alcohol and n-butyl alcohol, methoxypropanol, methoxyethanol. Likewise, aromatic solvents such as benzene, toluene or xylene can be used. Ketones such as acetone or methyl ethyl ketone are suitable. Likewise, ether compounds such as diethyl ether or ester compounds such as e.g. Ethyl acetate, n-butyl acetate or ethyl propionate can be used. The compounds can be used alone or in combination.
  • Alcohols such as ethanol, isopropanol, n-propanol, isobutyl alcohol and n-butyl alcohol, methoxypropanol, methoxyethanol.
  • Customary additives are to be understood to mean additives customary for coating compositions for scratch-resistant coatings, which may optionally be present in amounts of from 0% by weight to 40% by weight, in particular from 0% by weight to 20% by weight.
  • the use of these additives is not considered critical to the invention.
  • surfactants to name with the help of the surface tension of the coating formulation regulated and good application properties can be achieved.
  • silicones such as various polymethylsiloxane types, in concentrations of 0.0001% by weight to 2% by weight.
  • UV absorbers which are present in concentrations of e.g. 0.2 wt .-% to 20 wt .-%, preferably from 2 wt .-% to 8 wt .-% may be included.
  • UV absorbers may e.g. are selected from the group of hydroxybenzotriazoles, triazines and hydroxybenzophenones (see for example EP 247480).
  • the coating compositions of the present invention contain, as an essential compatibilizer, 0.01% by weight to 10% by weight, preferably 0.03% by weight to 5.0% by weight and most preferably 0.05% by weight. % - 2 wt .-%, based on the total weight of the coating agent, a fluoroalkyl (meth) acrylate.
  • the coating composition according to the invention is intended for the production of scratch-resistant, weather-resistant coatings on plastic substrates.
  • polycarbonates include in particular polycarbonates, polystyrenes, polyesters, for example polyethylene terephthalate (PET), which may also be modified with glycol, and polybutylene terephthalate (PBT), cycloolefinic copolymers (COC), acrylonitrides / butadiene / styrene copolymers and / or poly (meth) acrylates ,
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • COC cycloolefinic copolymers
  • acrylonitrides / butadiene / styrene copolymers and / or poly (meth) acrylates
  • Polycarbonates, cycloolefinic polymers and poly (meth) acrylates are preferred, with poly (meth) acrylates being particularly preferred.
  • Polycarbonates are known in the art. Polycarbonates can be formally considered as polyesters of carbonic acid and aliphatic or aromatic dihydroxy compounds. They are readily available by reacting diglycols or bisphenols with phosgene or carbonic acid diester in polycondensation or transesterification reactions.
  • polycarbonates are preferred which are derived from bisphenols.
  • bisphenols include, in particular, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) butane (bisphenol B),
  • the bisphenols are used as an aqueous, alkaline solution in inert organic solvents, such as Methylene chloride, chlorobenzene or tetrahydrofuran, emulsified and reacted in a step reaction with phosgene.
  • inert organic solvents such as Methylene chloride, chlorobenzene or tetrahydrofuran
  • Amines are used as catalysts, and in the case of sterically hindered bisphenols also phase transfer catalysts are used. The resulting polymers are soluble in the organic solvents used.
  • Cycloolefinic polymers are polymers obtainable using cyclic olefins, especially polycyclic olefins.
  • Cyclic olefins include, for example, monocyclic olefins, such as cyclopentene, cyclopentadiene, cyclohexene, cycloheptene, cyclooctene and alkyl derivatives of these monocyclic olefins having 1 to 3 carbon atoms, such as methyl, ethyl or propyl, such as methylcyclohexene or dimethylcyclohexene, and acrylate and / or methacrylate derivatives of these monocyclic Links.
  • cycloalkanes having olefinic side chains can also be used as cyclic olefins, such as cyclopentyl methacrylate.
  • bridged, polycyclic olefin compounds Preference is given to bridged, polycyclic olefin compounds. These polycyclic olefin compounds may have the double bond both in the ring, which are bridged polycyclic cycloalkenes, as well as in side chains. These are vinyl derivatives, allyloxycarboxy derivatives and (meth) acryloxy derivatives of polycyclic cycloalkane compounds. These compounds may further include alkyl, aryl or aralkyl substituents.
  • Illustrative polycyclic compounds include, but are not limited to, bicyclo [2.2.1] hept-2-ene (norbornene), bicyclo [2.2.1] hept-2,5-diene (2,5-norbornadiene), ethyl -bicyclo [2.2.1] hept-2-ene (ethylnorbomene), ethylidenebicyclo [2.2.1] hept-2-ene (ethylidene-2-norbornene), phenylbicyclo [2.2.1] hept-2-ene, bicyclo [4.3 .0] nona-3,8-diene, tricyclo [4.3.0.1 2 ' 5 ] - 3-decene, tricyclo [4.3.0.1 2 ' 5 ] -3,8-decene- (3,8-dihydrodicyclopentadiene), tricyclo [4.4.0.1 2> 5 ] -3-undecene, t
  • the cycloolefinic polymers are prepared using at least one of the cycloolefinic compounds described above, in particular the polycyclic hydrocarbon compounds.
  • further olefins can be used which can be copolymerized with the aforementioned cycloolefinic monomers. These include u.a. Ethylene, propylene, isoprene, butadiene, methylpentene, styrene and vinyltoluene.
  • olefins especially the cycloolefins and polycycloolefins, can be obtained commercially.
  • many cyclic and polycyclic olefins are available through Diels-Alder addition reactions.
  • the preparation of the cycloolefinic polymers can be carried out in a known manner, as described, inter alia, in Japanese Patent Nos. 11818/1972, 43412/1983, 1442/1986 and 19761/1987 and Japanese Patent Laid-Open Nos.
  • EP-A-6 610 851 EP-A-6 485 893, EP-A-0 6407 870 and EP-A-6 688 801 is.
  • the cycloolefinic polymers can be prepared, for example, using aluminum compounds, vanadium compounds, tungsten compounds or
  • Boron compounds are polymerized as a catalyst in a solvent.
  • the polymerization may occur under ring opening or under opening of the double bond, depending on the conditions, in particular the catalyst used.
  • cycloolefinic polymers by radical polymerization using light or an initiator as a radical generator.
  • This type of polymerization can be carried out both in solution and in substance.
  • Another preferred plastic substrate comprises poly (meth) acrylates.
  • These polymers are generally obtained by radical polymerization of mixtures containing (meth) acrylates. These have been set forth above, it being possible to use both monofunctional and polyfunctional (meth) acrylates, which are described under components C) and E), depending on the preparation. According to a preferred aspect of the present invention, these mixtures contain at least 40% by weight, preferably at least 60% by weight and more preferably at least 80% by weight, based on the weight of the monomers, of methyl methacrylate.
  • compositions to be polymerized may also contain other unsaturated monomers which are copolymerizable with methyl methacrylate and the abovementioned (meth) acrylates. Examples of this were explained in more detail in particular under component E).
  • these comonomers in an amount of 0 wt .-% to 60 wt -%, preferably 0 wt .-% to 40 wt .-% and particularly preferably 0 wt .-% to 20 wt .-%, based on the weight of the monomers used, wherein the compounds can be used individually or as a mixture.
  • the polymerization is generally started with known free-radical initiators, which are described in particular under component D). These compounds are often used in an amount of 0.01 wt .-% to 3 wt .-%, preferably from 0.05 wt .-% to 1 wt .-%, based on the weight of the monomers used.
  • the aforementioned polymers may be used singly or as a mixture. It is also possible to use various polycarbonates, poly (meth) acrylates or cycloolefinic polymers which differ, for example, in molecular weight or in the monomer composition. •
  • the plastic substrates according to the invention can be produced, for example, from molding compositions of the abovementioned polymers.
  • thermoplastic molding processes are used, such as extrusion or injection molding.
  • the weight-average molecular weight M w of the homo- and / or copolymers to be used according to the invention as a molding composition for the production of the plastic substrates can vary within wide limits, the molecular weight usually being matched to the intended use and the method of processing of the molding composition.
  • the plastic substrates can be produced by Gußsch Kunststoffmaschinen.
  • suitable (meth) acrylic mixtures are added in a mold and polymerized.
  • Such (meth) acrylic mixtures generally have the above-described (meth) acrylates, in particular methyl methacrylate.
  • the (meth) acrylic mixtures can contain the copolymers described above and, in particular for adjusting the viscosity, polymers, in particular poly (meth) acrylates.
  • the weight average molecular weight Mw of polymers prepared by cast-chamber processes is generally higher than the molecular weight of polymers used in molding compositions. This results in a number of known advantages. In general, that is Weight average molecular weight of polymers produced by casting chamber processes in the range of 500,000 to 10,000,000 g / mol, without this being a limitation.
  • Preferred plastic substrates produced by the casting chamber method can be obtained commercially from Degussa, BU PLEXIGLAS, Darmstadt under the trade name PLEXIGLAS® GS or from Cyro Inc. USA under the trade name Acrylite®.
  • the molding compositions to be used for the preparation of the plastic substrates and the acrylic resins may contain conventional additives of all kinds. These include, but are not limited to, antistatics, antioxidants, mold release agents, flame retardants, lubricants, colorants, flow improvers, fillers, light stabilizers and organic phosphorus compounds such as phosphoric acid esters, phosphoric acid diesters and phosphoric acid monoesters, phosphites, phosphorinanes, phospholanes or phosphonates, pigments, weathering agents and plasticizers.
  • additives is limited to the purpose of use.
  • Particularly preferred molding compositions containing poly (meth) acrylates include, under the trade name PLEXIGLAS ® by the company Degussa, BU
  • Plexiglas ® XT Extruded sheets of Plexiglas ® - molding compounds are marketed under the name Plexiglas ® XT.
  • Preferred molding compositions comprising cycloolefinic polymers can be obtained under the trade names Topas® from Ticona and Zeonex® from Nippon Zeon.
  • Polycarbonate molding compounds are available, for example, under the trade name Makrolon® from Bayer or Lexan® from General Electric.
  • the plastic substrate particularly preferably comprises at least 80% by weight, in particular at least 90% by weight, based on the total weight of the substrate, of poly (meth) acrylates, polycarbonates and / or cycloolefinic polymers.
  • the plastic substrates are made of polymethyl methacrylate, wherein the polymethyl methacrylate may contain conventional additives.
  • plastic substrates may have an impact strength according to ISO 179/1 of at least 10 kJ / m 2, preferably at least 15 kJ / m 2.
  • the shape and size of the plastic substrate are not essential to the present invention.
  • plate or tabular substrates are often used which have a thickness in the range of 1 mm to 200 mm, in particular 5 to 30 mm.
  • the moldings may be vacuum-formed parts, blow-molded parts, injection molded parts or extruded plastic parts, the z. B. used as components in the open, as parts of automobiles, housing parts, components of kitchens or sanitary facilities.
  • coating compositions for solid, flat plates and web double or web multiple plates are particularly suitable.
  • Usual dimensions e.g. for solid panels are in the range of 3 x 500 to 2000 x 2000 to 6000 mm (thickness x width x length).
  • Web plates can be approx. 16 to 64 mm thick.
  • the plastic substrates Before the plastic substrates are provided with a coating, they can be activated by suitable methods to improve the adhesion.
  • the plastic substrate can be treated with a chemical and / or physical method, wherein the respective method is dependent on the plastic substrate.
  • the above-described coating mixtures can be applied to the plastic substrates by any known method. These include, but are not limited to, dipping, spraying, knife coating, flood coating and roller or roller application.
  • the coating agent is applied to plastic body so that the layer thickness of the cured layer is 1 to 50 microns, preferably 5 to 30 microns.
  • the layer thicknesses below 1 ⁇ m the weathering protection and the scratch resistance are often inadequate, and layer thicknesses of more than 50 ⁇ m can lead to cracking under bending stress.
  • the polymerization takes place, which can be carried out thermally or by means of UV radiation.
  • the polymerization may advantageously be carried out under an inert atmosphere to exclude the polymerization-inhibiting atmospheric oxygen, e.g. under
  • Nitrogen fumigation be performed. However, this is not essential
  • the applied coating agent is cured by UV irradiation.
  • the UV irradiation time necessary for this depends on the temperature and the chemical composition of the coating composition, on the type and performance of the UV source, on the distance from the coating agent and whether an inert atmosphere is present. As a guideline, a few seconds to a few minutes may apply.
  • the corresponding UV source should emit radiation in the range of about 150 to 400 nm, preferably with a maximum between 250 and 280 nm.
  • the irradiated energy should be approx. 50 - 4000 mJ / cm2.
  • As a guideline for the distance between the UV source and the paint layer approx. 100 to 200 mm can be specified.
  • the moldings of the present invention can be excellently thermoformed without their scratch-resistant, dirt-repellent coating would be damaged.
  • the forming is known in the art.
  • the shaped body is heated and formed over a suitable template.
  • the temperature at which the transformation takes place depends on the softening temperature of the substrate from which the plastic body was produced.
  • the other parameters, such as the forming speed and forming force are also dependent on the plastic, these parameters are known in the art.
  • bending forming methods are particularly preferred. Such methods are used in particular for processing cast glass. Further details can be found in "Acrylic glass and polycarbonate correct processing" by H. Kaufmann et al. issued by the Technology-Transfer-Ring Tire NRW and in VDI-guideline 2008 sheet 1 as well as DIN 8580/9 /.
  • the moldings of the present invention provided with a scratch-resistant, dirt-repellent coating exhibit high scratch resistance.
  • the shaped body is transparent, the transparency ⁇ D65 / 10 according to DIN 5033 being at least 70%, preferably at least 75%.
  • the molding has an E-modu! according to ISO 527-2 of at least 1000 MPa, in particular at least 1500 MPa, without this being a limitation.
  • the moldings according to the invention are generally very resistant to weathering.
  • the weathering resistance according to DIN 53387 (Xenotest) at least 4000 hours.
  • the yellowness index according to DIN 6167 (D65 / 10) of preferred shaped bodies is less than or equal to 8, preferably less than or equal to 5, without this being intended to limit it.
  • the anti-graffiti effect is achieved by hydrophobizing the surface. This is reflected in a large contact angle with alpha-bromonaphthalene, which has a surface tension of 44.4 mN / m.
  • the contact angle is at 20 0 C of alpha-bromonaphthalene with the surface of the plastic body after hardening of the scratch-resistant coating preferably at least 50 °, in particular at least 70 ° and more preferably at least 75 ° without thereby effected that a restriction should.
  • Embodiment preferably at least 80 °, in particular at least 90 ° and particularly preferably at least 100 °
  • the contact angle can be determined with a contact angle measuring system G40 from. Krüss, Hamburg, whereby the implementation in
  • the measurement is carried out at 2O 0 C.
  • the moldings of the present invention can be used, for example, in the construction sector, in particular for the production of greenhouses or conservatories, or as a noise barrier.
  • the 2,2,3,3-tetrafluoropropyl methacrylate used as solubilizer allows a better dissolving behavior of the oligomer mixture contained in the Zonyl- TAN.
  • the combination with 2,2,3,3-tetrafluoropropyl methacrylate dissolves a larger proportion of Zonyl TAN in the paint.
  • a coating composition hereinafter referred to as basecoat, was prepared comprising 16.6 parts by weight of pentaerythritol tetraacrylate,
  • the results of the turbidity measurement thus confirm an improvement in the dissolving behavior of zonyl by adding 2,2,3,3-tetrafluoropropyl methacrylate to the basecoat.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des agents de revêtement destinés à la fabrication de revêtements antirayures déformables, résistants à la salissure, contenant A) 1 à 30 % en poids d'un prépolymérisat pouvant être obtenu par polymérisation radicalaire d'un mélange contenant A1) 1 à 10 parts en poids d'au moins un composé de soufre contenant au moins 3 groupes thiol, et A2) 90 à 90 parts en poids d'alkyl(méth)acrylates ; B) 0,2 à 10 % en poids d'au moins un fluoroalkyl(méth)acrylate portant 6 à 60 atomes de carbone dans le radical alcool contenant 13 à 121 atomes de fluor ; C) 20 à 80 % en poids de (méth)acrylates polyvalents ; D) 0,01 à 10 % en poids d'au moins un initiateur ; E) 2 à 75 % en poids d'au moins un agent diluant ; F) 0 à 40 % en poids d'additifs habituels ; et, G) 0,01 à 10 % en poids de 2,2,3,3-tétrafluoropropylméthacrylate. L'invention concerne également des corps moulés résistants à la salissure, déformables, antirayures, contenant un substrat plastique et un revêtement antirayures.
EP05818695A 2005-02-25 2005-12-10 Agents de revetement destines a la fabrication de revetements antirayures deformables, resistants a la salissure, corps moules resistants a la salissure, deformables, antirayures et procede de fabrication de ceux-ci Withdrawn EP1851279A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005009209A DE102005009209A1 (de) 2005-02-25 2005-02-25 Beschichtungsmittel zur Herstellung von umformbaren Kratzfestbeschichtungen mit schmutzabweisender Wirkung, kratzfeste umformbare schmutzabweisende Formkörper sowie Verfahren zu deren Herstellung
PCT/EP2005/013264 WO2006089580A1 (fr) 2005-02-25 2005-12-10 Agents de revetement destines a la fabrication de revetements antirayures deformables, resistants a la salissure, corps moules resistants a la salissure, deformables, antirayures et procede de fabrication de ceux-ci

Publications (1)

Publication Number Publication Date
EP1851279A1 true EP1851279A1 (fr) 2007-11-07

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EP05818695A Withdrawn EP1851279A1 (fr) 2005-02-25 2005-12-10 Agents de revetement destines a la fabrication de revetements antirayures deformables, resistants a la salissure, corps moules resistants a la salissure, deformables, antirayures et procede de fabrication de ceux-ci

Country Status (7)

Country Link
US (1) US20080139690A1 (fr)
EP (1) EP1851279A1 (fr)
JP (1) JP2008531771A (fr)
CN (1) CN101087858A (fr)
DE (1) DE102005009209A1 (fr)
TW (1) TW200641072A (fr)
WO (1) WO2006089580A1 (fr)

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CN102898940A (zh) * 2012-11-14 2013-01-30 无锡卡秀堡辉涂料有限公司 阻止黑咖啡污染的溶剂型涂料及其生产方法
JP2014151218A (ja) * 2013-02-04 2014-08-25 Mitsubishi Rayon Co Ltd 浄水器
JP6409770B2 (ja) * 2013-04-18 2018-10-24 Jsr株式会社 シリコーン系樹脂用表面改質剤、表面が改質されたシリコーン系樹脂、表面が改質されたコンタクトレンズ、並びに上記樹脂およびレンズの製造方法
KR101761979B1 (ko) * 2014-04-02 2017-07-26 (주)엘지하우시스 복합판넬 및 이의 제조방법
DE102015209381A1 (de) 2015-05-21 2016-11-24 Wacker Chemie Ag Polymerisate für schmutzabweisende Beschichtungen
DE102016004047B4 (de) 2016-04-04 2017-10-19 Niebling Gmbh Verfahren und Formwerkzeug zur Warmumformung eines ebenen thermoplastischen Schichtstoffes
PL3428199T3 (pl) 2017-07-12 2021-01-25 Arkema France Kompozycja powłokowa do utwardzania promieniowaniem do poprawy właściwości powierzchniowych tworzyw sztucznych
CN108775101A (zh) * 2018-08-02 2018-11-09 广州市精合致新材料科技有限公司 一种自带保护膜功能的天花铝扣板
CN111534185B (zh) * 2020-04-28 2021-12-28 广州大学 一种水下防原油黏附涂料及其制备方法和应用
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Also Published As

Publication number Publication date
JP2008531771A (ja) 2008-08-14
US20080139690A1 (en) 2008-06-12
CN101087858A (zh) 2007-12-12
WO2006089580A1 (fr) 2006-08-31
TW200641072A (en) 2006-12-01
DE102005009209A1 (de) 2006-08-31

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