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WO2006066653A1 - Agent de revetement servant a produire des revetements façonnables antirayures et antisalissures, corps moules façonnables antirayures et antisalissures, et procede de production correspondant - Google Patents

Agent de revetement servant a produire des revetements façonnables antirayures et antisalissures, corps moules façonnables antirayures et antisalissures, et procede de production correspondant Download PDF

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Publication number
WO2006066653A1
WO2006066653A1 PCT/EP2005/011675 EP2005011675W WO2006066653A1 WO 2006066653 A1 WO2006066653 A1 WO 2006066653A1 EP 2005011675 W EP2005011675 W EP 2005011675W WO 2006066653 A1 WO2006066653 A1 WO 2006066653A1
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Prior art keywords
meth
scratch
acrylate
weight
acrylates
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PCT/EP2005/011675
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German (de)
English (en)
Inventor
Patrick Becker
Rolf Neeb
Ghirmay Seyoum
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Röhm Gmbh
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Publication of WO2006066653A1 publication Critical patent/WO2006066653A1/fr

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    • 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.
  • DE 195 07 174 describes UV-curable, scratch-resistant coatings for plastics which have a particularly high UV stability. These coatings already show a good property spectrum.
  • plastic moldings even coated scratch-resistant, especially in the form of outdoor construction panels, such as noise barriers or as glazings of facades, bus stops, advertising space, advertising columns, so-called "mobile urban” used where they Both natural pollution as well as by vandalism-related impurities, such as the graffiti smudges are exposed. The cleaning of such Surfaces are very expensive, as the surface is often attacked.
  • Fluorine-containing acrylates are frequently added to the coating compositions to solve these problems.
  • Such coating compositions are described, for example, in DE 43 19 199.
  • a disadvantage of known coating compositions is that the coatings produced therefrom form cracks on plastic bodies during thermal forming, the coating on the formed body becoming milky and unsightly.
  • coated formable structural members can be made for much wider customer circles than custom preformed panels.
  • 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, cloth, surfactant, high-pressure cleaner, mild solvents ("Easy-to-clean”) are sufficient.
  • the invention has for its object to provide scratch-resistant, dirt-repellent moldings available, which can be produced particularly easily.
  • 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.
  • claims 12-21 provide a solution to the underlying problems.
  • A1 1 to 10 parts by weight of at least one sulfur compound containing at least 3 thiol groups and
  • 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.
  • the coating compositions according to the invention for the production of deformable scratch-resistant coatings with dirt-repelling action comprise 1-30% by weight, preferably 2-25% by weight, based on the weight of the coating composition, of a prepolymer obtainable by free-radical polymerization of a mixture
  • A1) 1 to 10 parts by weight, preferably 2 to 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 of alkyl (meth) acrylates.
  • Sulfur compounds with 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 to carry out the invention.
  • the sulfur regulators contain at least 3, preferably at least 6 carbon atoms in the molecule, but not over 40.
  • Advantageous is the presence of one or preferably more ⁇ -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-hexanetriol trithiogiycolate, trimethylol ethane 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 pent
  • 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 C-J to C-8 alkyl esters of acrylic acid and 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 2 471 959). 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 20 0 C.
  • the coating compositions of the present invention contain, as an essential ingredient, from 0.2 to 10% by weight, preferably from 0.3 to 5.0% by weight and most preferably from 0.5 to 2% by weight, based on the total weight of the composition Coating agent, Fluoralkyi (meth) acrylates having 3 to 30, preferably 8 to 25 and particularly preferably 10 to 20 carbon atoms in the alkyl radical which comprises 6 to 61, preferably 7 to 51 and particularly preferably 9 to 41 fluorine atoms.
  • the alkyl radical of the fluoroalkyl (meth) acrylate may include, 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 alkyl radical to be both linear and branched.
  • a fluoroalkyl (meth) acrylate according to the formula II is used
  • radical Ri is a hydrogen atom or a methyl radical and n is an integer in the range of 2 to 10, preferably 3 to 8, particularly preferably 3 to 5.
  • fluoroalkyl (meth) acrylates which are present in component B) in the coating compositions according to the invention include, inter alia
  • the fluoroalkyl (meth) acrylates are known compounds, wherein 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.
  • initiators are used which are added to the coating composition in an amount of 0.01-10% by weight, preferably 1-3% 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-ethylhexanoyl-peroxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5- trimethylhexanoate, dicumyl peroxide, 1,1-bis
  • photoinitiators for example 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, benzoin methyl, ethyl or butyl ether, acetoin, benzil, benzil dimethylketal or benzophenone.
  • UV initiators are commercially available, for example, from Ciba AG under the trade names ⁇ Darocur 1116, ⁇ Irgacure 184, ⁇ Irgacure 907 and from BASF AG under the trade name ®Lucirin TPO.
  • photoinitiators which absorb in the short-wave visible range of light are ⁇ Lucirin TPO and ⁇ Lucirin TPO-L from BASF, Ludwigshafen.
  • the coating compositions contain from 0.2 to 75, preferably 0.5 to 50 wt .-%, based on the total weight of the coating composition, thinners, which can also be used as a mixture.
  • Range of about 10 to about 250 mPa s is set. Coating materials intended for flood or dip coatings are rather low
  • Viscosities of about 1 - 20 mPa-s in use are used in these coatings.
  • organic solvents in concentrations of up to 75% by weight can be used in these coatings. be used.
  • the appropriate viscosities are in the range of 20 to 250 mPas. 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 Veriaufseigenschaften 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-dimethylpropene, 3-methyl-1-diisobutylene, 4-methylpentene-1
  • Vinyl esters such as vinyl acetate
  • Styrene substituted styrenes having an alkyl substituent in the side chain, such as.
  • alkyl substituent in the side chain such as.
  • ⁇ -methylstyrene and ⁇ -ethylstyrene substituted styrenes with a
  • Alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, halogenated
  • Styroids such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and
  • Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl
  • 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;
  • Maleic acid derivatives such as maleic anhydride
  • (meth) acrylates examples include methacrylates and acrylates as well as mixtures of both.
  • 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,
  • Hydroxylalkyl (meth) acrylates such as
  • Glycol di (meth) acrylates such as 1,4-butanediol di (meth) acrylate, (Meth) acrylates of ether alcohols, such as
  • Particularly preferred monofunctional reactive diluents are e.g.
  • EP 0 035 272 describes common organic solvents for coating compositions and for scratch-resistant coatings which can be used as thinners. Suitable examples are 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. Also, ether compounds such as diethyl ether or ester compounds such as ethyl acetate, n-butyl acetate or ethyl propionate can be used. The compounds can be used alone or in combination. Component F
  • Customary additives are understood to mean additives customary for coating compositions for scratch-resistant coatings, which may optionally be present in amounts of from 0 to 40% by weight, in particular from 0 to 20% by weight. The use of these additives is not considered critical to the invention.
  • Silicones such as various types of polymethylsiloxanes are used in concentrations of 0.0001 to 2 wt .-%.
  • UV absorbers which are present in concentrations of e.g. 0.2 to 20 wt .-%, preferably from 2 to 8 wt .-% may be included. UV absorbers may e.g. from the group of hydroxybenzotriazoles, triazines and hydroxybenzophenones (see for example EP 247 480).
  • the coating compositions of the present invention contain, as an essential compatibilizer, 0.01-10% by weight, preferably 0.03-5.0% by weight and most preferably 0.05-3% by weight, based on the total weight the coating agent, fluoroalkyl (meth) acrylates having 1 to 4 and particularly preferably 1 to 3 carbon atoms in the alkyl radical which comprises 1 to 6, and particularly preferably 1 to 4 fluorine atoms.
  • the alkyl radical of the fluoroalkyl (meth) acrylate may include, in addition to the fluorine atoms, further substituents. These include in particular ester groups, amide groups, Amine groups, nitro groups and halogen atoms, wherein this alkyl radical may be both linear and branched. Particularly preferred is 2,2,3,3-tetrafluoropropyl (meth) acrylate.
  • the coating composition according to the invention is intended for the production of scratch-resistant, weather-resistant coatings on plastic substrates.
  • plastic substrates 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 ,
  • 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 accessible by reaction of diglycols or bisphenols with phosgene or carbonic acid diesters in polycondensation or transesterification reactions. Here, 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), 1, 1-bis (4-hydroxyphenyl ) cyclohexane (bisphenol C), 2,2'-methylenediphenol (bisphenol F), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (tetrabromobisphenol A) and 2,2-bis (3,5-bis) dimethyl-4-hydroxyphenyl) propane (tetramethyl bisphenol A).
  • aromatic polycarbonates are prepared by interfacial polycondensation or transesterification, details of which are set forth in Encycl. Polym. Be. Engng. 11, 648-718 are shown.
  • the bisphenols are emulsified as an aqueous, alkaline solution in inert organic solvents, such as methylene chloride, chlorobenzene or tetrahydrofuran, 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 aikylderivate 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 (ethylnorbornene), 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,
  • 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, styrenes 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 i.a. in Japanese Patent Nos. 11818/1972, 43412/1983, 1442/1986 and 19761/1987 and Japanese Patent Laid-Open Nos. 75700/1975, 129434/1980, 127728/1983, 168708/1985, 271308/1986, 221118/1988 and 180976 / 1990 and European Patent Applications EP-A-6 610 851, EP-A-6 485 893, EP-A-0 6 407 870 and EP-A-6 688 801.
  • the cycloolefinic polymers can be polymerized in a solvent using, for example, aluminum compounds, vanadium compounds, tungsten compounds or boron compounds as a catalyst. It is believed that 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.
  • 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 are used in an amount of 0 to 60% by weight, preferably 0 to 40% by weight and more preferably 0 to 20% by weight, * ⁇
  • 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 to 3 wt .-%, preferably from 0.05 to 1 wt .-%, based on the weight of the monomers.
  • 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.
  • generally thermoplastic molding processes are used, such as extrusion or injection molding.
  • the weight average molecular weight M w of the present invention as a molding material for the preparation of the plastic substrates to be used in homo- and / or copolymers can vary within wide ranges, the molecular weight usually being matched to the intended use and the processing of the molding composition.
  • the plastic substrates can be produced by Gußsch.
  • suitable (meth) acrylic mixtures are added in a mold and polymerized.
  • Such (meth) acrylic mixtures generally have the previously set forth (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 M w of the 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.
  • the weight-average molecular weight of polymers prepared by cast-chamber processes is in the range of 500,000 to 10,000,000 g / mol, without limitation.
  • Preferred plastic substrates produced by the casting chamber method can be obtained commercially from Degussa, PLEXIGLAS division, 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, dyes, 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 include, but are not limited to, antistatics, antioxidants, mold release agents, flame retardants, lubricants, dyes, 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
  • molding compositions which comprise poly (meth) acrylates are commercially available under the trade name PLEXIGLAS® from the company Degussa, business unit PLEXIGLAS, Darmstadt or under the trade name ⁇ Acrylite from the company Cyro Inc. USA.
  • Preferred molding compositions comprising cycloolefinic polymers can be obtained under the trade names ⁇ Topas from Ticona and ⁇ Zeonex from Nippon Zeon.
  • Polycarbonate molding compositions 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 32 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 composition is preferably applied to plastic bodies in such a way that the layer thickness of the cured layer is 0.5 to 50 ⁇ m, preferably 1 to 20 ⁇ m, and very particularly preferably 3 to 15 ⁇ m.
  • 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 can advantageously be carried out under an inert atmosphere to exclude the polymerization-inhibiting atmospheric oxygen, for example under nitrogen. However, this is not an essential requirement.
  • the polymerization is carried out at temperatures below the glass transition temperature of the plastic body.
  • 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. 500 -
  • 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.
  • bend forming are particularly preferred bend forming. 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 ⁇ o65 / 10 according to DIN 5033 being at least 70%, preferably at least 75%.
  • the shaped body preferably has an E modulus according to ISO 527-2 of at least 1000 MPa, in particular at least 1500 MPa, without this being intended to limit it.
  • 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 yellow index according to DIN 6167 (D65 / 10) of preferred shaped bodies is smaller or 9
  • the anti-graffiti effect is achieved by hydrophobicizing 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.
  • the contact angle with water at 2O 0 C is 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, the implementation being described in the user manual of the contact angle measuring system G40, 1993.
  • the measurement is carried out at 20 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.
  • a coating composition was prepared comprising
  • PLEX 8770 prepolymer available from Röhm GmbH & Co. KG
  • Tinuvin 1130 available from Ciba AG.
  • the coating composition thus obtained is applied with a wire bar to Plexiglas® plates and hardened after every two minutes running time with a high pressure mercury jet F 450 from Fusion Systems (rated power 120 W / cm) at 1 m / min feed rate and under nitrogen atmosphere.
  • the set-up panels were sprayed with spray paint from the company Beiton (Black, Item No. 324187) from a distance of about 20 cm.
  • the weight of the spray paint is considered as a reference. Is the weight of the spray greater than its adhesion to the substrate, it flows from the established plate from. If it is lower, the paint will adhere.
  • a coating composition was prepared comprising 16.6 parts by weight of pentaerythritol tetraacrylate (a mixture of 70
  • Irgacure 184 composition 2 parts by weight Irgacure 184 composition:
  • the coated surface can be wetted by the spray paint. A drainage of the spray is not initially observed.
  • oligomeric fluoroacrylates Zony-TAN
  • low molecular weight fluoromethacrylates significantly reduces the adhesion of the spray paint to the surface again.
  • Spray paint shows good adhesion to the substrate, so at the same time a spread of the sprayed paint is observed. However, substrates whose surface energy is very low cause contraction of the sprayed paint.
  • Example 1 With the paint Devil red (Montana), the above spraying experiments in Example 1 and Comparative Example No. 7 were repeated. The color shows a higher adhesion than Beiton Color Black.
  • Example 1 The combination of the low molecular weight fluoropropyl methacrylate with oligomeric fluoroacrylates (Example 1) further reduces the surface energy compared to the sample without a low molecular weight transport agent (Comparative Example No. 7). Since identical amounts of oligomeric fluoroacrylates are present in both samples and the low molecular weight fluoropropyl methacrylate in the coating does not significantly contribute to the reduction of surface energy (see Experiment I, Comparative Example No. 9), the additional reduction of surface energy can only be attributed to synergistic effects the combination of the two substances.

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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 servant à produire des revêtements façonnables antirayures et antisalissures. Ces agents de revêtement comprennent : A) entre 1 et 30 % en poids d'un prépolymère productible par polymérisation radicalaire d'un mélange comprenant A1) entre 1 et 10 parties en poids d'au moins un composé de soufre comportant au moins 3 groupes thiol, et A2) entre 90 et 99 parties en poids d'un alkyl(méth)acrylate ; B) entre 0,2 et 10 % en poids d'au moins un fluoroalkyl(méth)acrylate comportant entre 3 et 30 atomes de carbone dans le radical alcool, qui comprend entre 6 et 61 atomes de fluor ; C) entre 20 et 80 % en poids de (méth)acrylates multifonctionnels ; D) entre 0,01 et 10 % en poids d'au moins un initiateur ; E) entre 0,2 et 75 % en poids d'au moins un diluant ; F) entre 0 et 40 % en poids d'additifs courants ; G) entre 0,01 et 10 % en poids de fluoroalkyl(méth)acrylate de formule (I), dans laquelle le groupe R1 représente un atome d'hydrogène ou un groupe méthyle, et le groupe R2 désigne un groupe alcoxy fluoré de formule O - CaHbFc, formule dans laquelle a représente un nombre entier compris entre 1 et 4, en particulier entre 1 et 3, b désigne un nombre entier compris entre 0 et 4, et c représente un nombre entier compris entre 2 et 4, de préférence entre 2 et 4, c étant égal à 2a + 1 b. Cette invention concerne en outre des corps moulés façonnables antirayures et antisalissures qui comportent un substrat en plastique et un revêtement antirayures.
PCT/EP2005/011675 2004-12-21 2005-11-02 Agent de revetement servant a produire des revetements façonnables antirayures et antisalissures, corps moules façonnables antirayures et antisalissures, et procede de production correspondant WO2006066653A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410062773 DE102004062773A1 (de) 2004-12-21 2004-12-21 Beschichtungsmittel zur Herstellung von umformbaren Kratzfestbeschichtungen mit schmutzabweisender Wirkung, kratzfeste umformbare schmutzabweisende Formkörper sowie Verfahren zu deren Herstellung
DE102004062773.8 2004-12-21

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Cited By (1)

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US8207295B2 (en) 2008-06-04 2012-06-26 Synergy Pharmaceuticals, Inc. Agonists of guanylate cyclase useful for the treatment of gastrointestinal disorders, inflammation, cancer and other disorders

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DE102007007999A1 (de) * 2007-02-15 2008-08-21 Evonik Röhm Gmbh Antigraffiti Beschichtung
DE102007028601A1 (de) * 2007-06-19 2008-12-24 Evonik Röhm Gmbh Reaktivgemisch zur Beschichtung von Formkörpern mittels Reaktionsspritzguss sowie beschichteter Formkörper

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US5418304A (en) * 1993-06-09 1995-05-23 Roehm Gmbh Chemische Fabrik Scratch-resistant coating agent based on acrylates
USRE36294E (en) * 1993-06-09 1999-09-07 Rohm Gmbh Chemische Fabrik Scratch-resistant coating agent based on arcylates
DE10260067A1 (de) * 2002-12-19 2004-07-01 Röhm GmbH & Co. KG Beschichtungsmittel zur Herstellung von umformbaren Kratzfestbeschichtungen mit schmutzabweisender Wirkung, kratzfeste umformbare schmutzabweisende Formkörper sowie Verfahrn zu deren Herstellung

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US5418304A (en) * 1993-06-09 1995-05-23 Roehm Gmbh Chemische Fabrik Scratch-resistant coating agent based on acrylates
USRE36294E (en) * 1993-06-09 1999-09-07 Rohm Gmbh Chemische Fabrik Scratch-resistant coating agent based on arcylates
DE10260067A1 (de) * 2002-12-19 2004-07-01 Röhm GmbH & Co. KG Beschichtungsmittel zur Herstellung von umformbaren Kratzfestbeschichtungen mit schmutzabweisender Wirkung, kratzfeste umformbare schmutzabweisende Formkörper sowie Verfahrn zu deren Herstellung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8207295B2 (en) 2008-06-04 2012-06-26 Synergy Pharmaceuticals, Inc. Agonists of guanylate cyclase useful for the treatment of gastrointestinal disorders, inflammation, cancer and other disorders

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