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
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C08F277/00—Macromolecular compounds obtained by polymerising monomers on to polymers of carbocyclic or heterocyclic monomers as defined respectively in group C08F32/00 or in group C08F34/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
  • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
  • C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds

Definitions

• Binding agents based on cycloolefinic if appropriate
• Coating agents and their use relate to polymers based on cycloolefinic homo- and copolymers (COC), which can be peroxygenated, and free-radically polymerizable monomers, which are suitable as binders for the preparation of coating agents.
• COC cycloolefinic homo- and copolymers
• Such coating agents are particularly suitable for the production of scratch-resistant and acid-resistant coatings. They can be used, for example, for the production of automotive paints and for the coating of polyolefin substrates.
• Patent Abstracts of Japan, C-339, April 15, 1986 describes heat-resistant graft polymers of vinyl monomers on unsaturated cyclopentadiene polymers. However, as described in Patents Abstracts of Japan, C-432, June 30, 1987, they are not suitable for the coating of polyolefins.
• the object of the invention is to provide polymers or binders which are suitable for acid-resistant coatings do not cause toxicity problems which have improved scratch resistance and which also enable improved adhesion to plastic substrates, in particular to polyolefins.
• the invention therefore relates to binders which are suitable for coating agents and are obtainable by free-radically initiated polymerization of
• Cycloolefin homopolymer Cycloolefin copolymers, peroxygenated cycloolefin homopolymers and / or peroxygenated cycloolefin copolymers which are free of olefinic double bonds.
• the binders obtained in this way are suitable for preparing solvent-containing and / or water-containing coating compositions which are suitable for producing scratch-resistant and acid-resistant coatings. They adhere well to plastic surfaces, especially non-polar plastic surfaces such as polyolefin surfaces, polyethylene, polypropylene and / or cycloolefin copolymers.
• the coating agents also form an object of the invention.
• the coating compositions of the invention can in addition to the inventive Containers contain one or more crosslinkers, one or more organic solvents and / or water, as well as other additives and auxiliaries customary in paint.
• the binders according to the invention they can also contain one or more further film-forming binders which are not crosslinkers for the binders according to the invention.
• COC cycloolefin homopolymers and cycloolefin copolymers free of olefinic double bonds used according to the invention
• COC cycloolefin homopolymers and cycloolefin copolymers free of olefinic double bonds used according to the invention
• known homopolymers and copolymers are described, for example, in EP-A-0 407 870, EP-A-0 485 893 and EP-A-0 503 422.
• Peroxygenated COC are, for example, known homo- and copolymers which have been peroxygenated by reaction with oxygen.
• Usual COC resins which can serve as the basis for the peroxigenated COC resins, are described, for example, in the aforementioned EP-A. The peroxygenated COC are therefore homo- and oxygen-containing
• the oxygen is preferably in a peroxidic function as a peroxide and / or as a hydroperoxide.
• the oxygen content is, for example, 0.01 to 50% by weight, preferably
• Examples of usable cycloolefin homopolymers and cycloolefin copolymers contain
• They can be prepared, for example, by polymerizing or copolymerizing monounsaturated cycloolefin monomers with the acyclic monounsaturated olefin monomers which may also be used. This can be done using customary methods, such as those described in the above-mentioned EP-A publications. For example, they can be obtained by radical-initiated polymerization or copolymerization.
• oxygen can be introduced into the polymers obtained as described above by reaction with gaseous oxygen, which can optionally be diluted by inert gas, in the presence of radicals.
• gaseous oxygen which can optionally be diluted by inert gas
• the reaction can be carried out in the presence of auxiliaries, such as solvents, dispersants and free radical initiators.
• auxiliaries such as solvents, dispersants and free radical initiators.
• the reaction mixture can be heterogeneous or homogeneous with respect to the polymer used.
• Radical formers can be used as water-soluble or water-insoluble radical formers, such as are used, for example, in the polymerization of olefinically unsaturated monomers. It can
• radical initiators are used, as described below for the preparation of the binders by radical copolymerization.
• Preferred examples of the monoolefinically unsaturated monomers for the preparation of the cycloolefin components are compounds of the general Formulas I, II, III, IV, V, VI and VII
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are the same or different and represent a hydrogen atom or a C 1 -C 8 alkyl radical, the same
• Residues in the different formulas can have a different meaning and n is a number from 2 to 10.
• Preferred acyclic olefins with no more than one olefinic double bond are alpha-olefins with 2 to 20 carbon atoms, for example ethylene or propylene.
• the COC used according to the invention particularly preferably contains a cycloolefin component and an alpha-olefin component.
• Preferred are COC, the norbornene or tetracyclododecene, which may be substituted, for example, by (C 1 -C 6 ) alkyl, with ethylene as a comonomer.
• Copolymers containing ethylene / norbornene are of particular importance.
• the oxygen is preferably in a peroxidic function as a peroxide and / or hydroperoxide.
• the COC used according to the invention has component A (cycloolefin content), for example, in a proportion of from 20 to 100% by weight, preferably 20 to 90% by weight, based on the total mass of the monomers used.
• component A cycloolefin content
• the peroxygenic COC used according to the invention has component A (cycloolefin component), for example, in a proportion of 0.1 to 100% by weight, preferably 1 to 100, particularly preferably 10 to 90% by weight, based on the total mass of the monomers used .
• component A cycloolefin component
• the oxygen content is, for example, 0.01 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 0.1 to 10% by weight, based on the total weight of the polymer.
• the proportion of component B (acyclic olefin component) is, for example, 0 to 80% by weight, preferably 10 to 80% by weight, particularly preferably 2 to 50% by weight, based on the total mass of the monomers used.
• the weight average molecular weight (Mw) is preferably between 5000 and 100000 g / mol.
• the glass transition temperature is preferably -20-200 ° C, particularly preferably 0-200 ° C.
• the polymers (COC-containing binders) obtained by polymerizing the monomers used according to the invention in the presence of the COC preferably have a number average molecular weight (Mn) of 5000 to 100000, particularly preferably 5000 to 20,000.
• all known monofunctional (meth) acrylic monomers can optionally be differentiated together with others.
• racikaliscn copolymerizable monomers are used, which preferably have only a single olefinic double bond.
• the proportion of additional monomers can e.g. 0 to 50 wt .-%, preferably 0 to 40 wt .-%, based on the weight of the (meth) acrylic monomers.
• (meth) acrylic is synonymous with acrylic unc / cer methacrylic, which can be substituted.
• (meth) acrylic monomers are (meth) acrylic esters, such as alkyl (meth) acrylates, which also have other functional grues, such as hydroxyl groups, amino groups, especially tert-amine crucians, glycidyl functions or carboxy-functionalized monomers.
• alkyl (meth) acrylates with C 8 -C 18 chains in the alkyl part for example ethylhexyl (meth) acrylate, octyl (meth) acrylate, 3,5,5-trimethylhexyl (meth ) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylet, hexacecyl (meth) acrylate, octadecyl (meth) acrylate, lauryl acrylate, isobornyl (meth) acrylate, 4-tertiary butylcyclohexyl methacrylate.
• alkyl (meth) acrylates with C 8 -C 18 chains in the alkyl part for example ethylhexyl (meth) acrylate, octyl (meth) acrylate, 3,5,5-trimethylhexyl (meth ) acrylate, decy
• alkyl (meth) acrylates with C 1 -C 7 chains in the alkyl part for example methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate ,, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate.
• alkyl (meth) acrylates with C 1 -C 7 chains in the alkyl part for example methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate , butyl (meth) acrylate, isobutyl (meth) acrylate
• the (meth) acrylic monomers used can carry, for example, primary or secondary hydroxy functions.
• monomers with primary hydroxy functions are hydroxyalkyl esters of acrylic acid and / or methacrylic acid with a primary OH group and a C 2 -C 3 -hydroxyalkyl radical with hydroxyethyl (meth) acrylate, and also hydroxyalkyl esters of acrylic acid and / or methacrylic acid with one primary OH group and a C 4 - C 18 hydroxyalkyl residue such as butanediol monoacrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates and reaction products of hydroxyethyl (meth) acrylate with caprolactone.
• Examples of monomers with secondary OH functions are: hydroxypropyl (meth) acrylate, adducts of glycidyl (meth) acrylate and saturated short-chain fatty acids with C 1 -C 3 -alkyl radicals, for example acetic acid or propionic acid, and adducts of Cardura E (glycidyl ester of versatic acid) ) with unsaturated COOH-functional compounds such as acrylic or.
• unsaturated anhydrides such as maleic anhydride
• reaction products from glycidyl (meth) acrylate with saturated branched or unbranched fatty acids with C 4 -C 20 -alkyl radicals eg butanoic acid, caproic acid, lauric acid, palmitic acid, stearic acid, stearic acid Arachidonic acid.
• carboxy-functionalized monomers examples include acrylic acid, methacrylic acid and crotonic acid.
• glycidyl-functionalized monomers examples include glycidyl (meth) acrylate, 1,2-epoxybutyl acrylate or 2,3-epoxycyclopentyl acrylate.
• copolymerizable glycidyl monomers are e.g. (Meth) allyl glycidyl ether or 3,4-epoxy-1-vinylcyclohexane.
• (meth) acrylic monomers with terminal tert-amino groups.
• examples of such monomers are tert-aminomethyl methacrylate or tert-aminopropyl methacrylate. If such monomers are used, the simultaneous use of glycidyl-functionalized monomers should be avoided, otherwise gelling of the polymer cannot be ruled out.
• Radically polymerizable monomers that can be used with the (meth) acrylic monomers are, for example, vinyl aromatic monomers, such as styrene and styrene derivatives, such as vinyl toluenes, chlorostyrenes, o-, m- or p-methylstyrene, 2,5-dimethylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-dimethylaminostyrene, p-acetamidostyrene and m-vinylphenol.
• Vinyl toluenes and in particular styrene are preferably used.
• Examples of usable carboxyl-functionalized monomers are crotonic acid, unsaturated anhydrides such as maleic anhydride, and also half esters of maleic anhydride by addition of saturated aliphatic alcohols, such as e.g. Ethanol, propanol, butanol and / or isobutanol.
• ethylenically unsaturated monomers examples include the alkyl esters of maleic, fumaric, tetrahydrophthalic, crotonic, isocrotonic, vinyl acetic and itaconic acids, e.g.
• the monomers used have only one olefinically unsaturated double bond.
• the proportion of these monomers is preferably less than 5% by weight, based on the total weight of the monomers.
• Examples of such compounds are hexanediol diacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, hexamethylene bismethacrylamide, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and similar compounds.
• the free-radically polymerizable monomers are reacted in the presence of one or more COC and / or peroxygenated COC.
• the addition of solvents can be used to be dispensed with.
• solvents it is possible to work in the presence of solvents so that a liquid reaction medium is achieved. It is beneficial to keep the amount of solvent as small as possible.
• solvents that can be used are conventional solvents, such as aromatic hydrocarbons or esters, for example xylene or butyl acetate.
• the amount of COC or peroxygenated COC is selected so that it is 0.5 to 95% by weight, based on the total solids content of the finished product
• Binder is.
• the optionally peroxygenated COC can optionally be introduced with a little solvent.
• the total amount of COC and / or peroxygenated COC to be used is presented.
• this optionally peroxygenated COC matrix can be heated, for example to temperatures in the order of 100 to 150 ° C, e.g. up to 140 ° C.
• the monomers can then be introduced into this matrix. This can be done, for example, by dropping, for example over a period of 3 to 5 hours.
• the monomers or the monomer mixture used can contain initiators. This is not necessary, but it is also possible if peroxygenated COC are used.
• the peroxy groups of the peroxygenated COC can then serve as initiators. If work is carried out in the presence of initiators, these can, if they are not already present in the monomer mixture, be added to the monomer mixture with a slight time lag or metered in separately. You can then continue for a longer period, e.g. be polymerized for several hours. It is then possible to adjust to a desired solids content, for example in the order of 30 to 60% by weight, for example 50% by weight, using a conventional paint solvent.
• the binders are produced by radical copolymerization.
• the amount of monomer is adjusted so that the desired Specifications regarding molar mass, OH group ratio, OH number and acid number can be achieved.
• the preparation takes place, for example, as radical solution polymerization in the presence of a radical initiator, as is known to the person skilled in the art.
• radical initiators are dialkyl peroxides, such as di-tert-butyl peroxide, di-cumyl peroxide; Diacyl peroxide such as dibenzoyl peroxide, dilauroyl peroxide; Hydroperoxides, such as cumene hydroperoxide, tert-butyl hydroperoxide; Peresters such as tertiary butyl perbenzoate, tertiary butyl perpivalate, tertiary butyl per 3,5,5-trimethylhexanoate, tertiary butyl per 2-ethylhexanoate; Peroxide dicarbonates such as di-2-ethylhexyl peroxydicarbonate, dicyclohexyl peroxydicarbonate; Perketals such as 1,1-bis (tert-butylperoxy) 3,5,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohex
• the polymerization initiators are generally added, for example, in an amount of 0.1 to 4% by weight, based on the weight of monomers. If an aqueous emulsion is to be created, the solvent used in the production is removed (instead of the solids setting by adding customary paint solvents). This can be done, for example, by distillation, if appropriate under vacuum.
• the resin concentrate obtained which has a high solids content, for example 90% by weight, can then, if acidic groups are contained in the resin, be mixed with a conventional base, e.g. Ammonia or an organic amine, e.g.
• Triethylamine to be neutralized The neutralized resin concentrate obtained can be emulsified in water. This can be done, for example, with vigorous stirring and if necessary with heating, for example at temperatures from 30 to 80 ° C, e.g. 50 ° C.
• the resins with basic monomers Groups for example those containing tertiary amines, are also polymerized.
• the resin containing basic groups and prepared in this way can then be neutralized with acids, for example inorganic or organic acids, such as formic acid, acetic acid and then emulsified in water.
• the resin does not contain acidic, basic or ionic groups, it can be emulsified using a conventional, non-ionic emulsifier. This can be done continuously or discontinuously. This happens e.g. by homogenizing the resin concentrate and the nonionic emulsifier, optionally with heating, for example to temperatures from 30 to 80 ° C, e.g. 60 ° C. Such a mixture can be emulsified in a conventional homogenization device. Examples of this are rotor / stator homogenizers, which operate at speeds of, for example, 8000 to 10,000 revolutions per minute. The emulsifiers are used, for example, in amounts of 3 to 30% by weight, based on the resin concentrate. It is assumed that the procedure according to the invention fixes the COC in the binder matrix formed by polymerizing the monomers. Without being bound to a specific theory here, it is assumed that, on the one hand, the polymerization of
• Part of the monomers is grafted onto the COC matrix. It is believed that this achieves the favorable weather resistance of coatings made on the basis of the binders according to the invention.
• binders according to the invention are particularly suitable for the production of coating compositions.
• Such coating agents can contain, in addition to the binders of the invention, customary lacquer additives, in particular crosslinking agents.
• COC in which, inter alia, hydroxy- and / or carboxy-functionalized (meth) acrylic monomers are polymerized, with crosslinking agents based on la) polyisocyanates, which can be blocked, and / or
• COC in which, inter alia, epoxy and optionally hydroxy-functionalized (meth) acrylic monomers are copolymerized, with crosslinkers based on
• polyisocyanates la are diisocyanates, such as customary aliphatic, cycloaliphatic and aromatic diisocyanates, e.g. 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate; 3,5,5-trimethyl-1-isocyanate-3-isocyanatomethylcyclohexane; m-xylylene diisocyanate, p-xylylene diisocyanate; Tetramethyl diisocyanate, isophorone diisocyanate or cyclohexane-1,4-diisocyanate.
• diisocyanates such as customary aliphatic, cycloaliphatic and aromatic diisocyanates, e.g. 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 4,4-diphenylmethane diiso
• the polyisocyanates can be linked to prepolymers with a higher molecular weight.
• examples include adducts of tolylene diisocyanate and trimethylolpropane, a biuret formed from 3 molecules of hexamethyl diisocyanate, as well as the trimers of hexamethylene diisocyanate and the trimers of isophorone diisocyanate.
• the isocyanate groups of the polyisocyanates used may be completely blocked.
• Common capping agents can be used, e.g. Malonic acid dimethyl ester, malonic acid diethyl ester, acetoacetic ester, caprolactone, 1,2-propanediol and / or butanone oxime and the other capping agents known to the person skilled in the art.
• melamine resins Ib) are conventional crosslinking resins, such as e.g. Methyl etherified melamines, such as the commercial products Cymel 325, Cymel 327, Cymel 350 and Cymel 370, Maprenal MF 927.
• melamine resins 1b) which can be used are butanol- or isobutanol-etherified melamines, such as, for example, the commercial products Setamin US 138 or Maprenal MF 610; mixed etherified melamines which are etherified with both butanol and methanol, such as Cymel 254, and hexamethyloxymethylmelamine (HMM melamines) such as Maprenal 900 or Maprenal 904, the latter of which may require an external acid catalyst such as p-toluenesulfonic acid for crosslinking.
• HMM melamines hexamethyloxymethylmelamine
• the acid catalyst can be blocked ionically with amines such as, for example, triethylamine or non-ionically, such as with Cardura E, the glycidyl ester of versatic acid.
• amines such as, for example, triethylamine or non-ionically, such as with Cardura E, the glycidyl ester of versatic acid.
• the binders according to the invention, as described under 1) can be crosslinked with the uncapped polyisocyanates in a further temperature range, for example between 20 ° C. and 180 ° C., the range between 20 ° C. and 80 ° C. being preferred.
• baking temperatures between 80 ° C and 180 ° C are preferred.
• polyepoxides 1c) which contain acid groups e.g. Can crosslink COOH group-containing binder 1
• di- or polyfunctional epoxy compounds which are produced using, for example, di- or polyfunctional epoxy compounds, such as diglycidyl or polyglycidyl ether of (cyclo) aliphatic or aromatic hydroxy compounds such as ethylene glycol, glycerol, 1,2 - and 1,4-cyclohexanediol, bisphenols such as bisphenol A, polyglycidyl ethers of phenol formaldehyde novolaks, polymers of ethylenically unsaturated groups which contain epoxy groups, such as glycidyl (meth) acrylate, N-glycidyl (meth) acrylamide, and / or allyl glycidyl ether, optionally copolymerized with various other ethylenically unsaturated monomers, glycidyl ethers of fatty acids with 6-24 C
• the crosslinking can be additionally catalyzed using catalysts which are used, for example, in an amount between 0.1% and 10%, based on the total solid resin content.
• Phosphonium salts such as benzyl triphenylphonium acetate, chloride, bromide or iodide, or e.g. Ammonium compounds such as Tetraethylammonium chloride or fluoride.
• carboxy-functionalized compounds 2a) which can crosslink the epoxy-functionalized binders under 2) are carboxy Functionalized poly (meth) acrylic copolymers and / or one or more carboxy-functionalized polyesters.
• the carboxy-functionalized poly (meth) acrylic copolymers have a number average molecular weight (Mn) of 1000 to 10000 g / mol.
• the correspondingly usable carboxy-functionalized polyesters preferably have a calculated molecular weight of 500 to 2000 g / mol.
• the acid number of these starting materials is 15 to 200 mg KOH / g, preferably 30 to 140 mg KOH / g and particularly preferably 60 to 120 mg KOH / g.
• the carboxyl groups can be introduced directly by using building blocks containing carboxyl groups, for example when building up polymers such as (meth) acrylic copolymers.
• suitable carboxyl-containing monomers that can be used for this purpose are unsaturated carboxylic acids, such as e.g. Acrylic, methacrylic, itacon, croton, isoerotonic, aconitic, maleic and fumaric acid, half esters of maleic and fumaric acid as well as ß-carboxyethyl acrylate and adducts of hydroxyalkyl esters
• Acrylic acid and / or methacrylic acid with carboxylic anhydrides e.g. the phthalic acid mono-2-methacryloyloxyethyl ester.
• Carboxylic anhydrides suitable for addition to the hydroxyl-containing polymers are the anhydrides of aliphatic, cycloaliphatic and aromatic saturated and / or unsaturated di- and polycarboxylic acids, such as, for example, the anhydrides of phthalic acid, tetra hydrophthalic acid, hexahydrophthalic acid, succinic acid, maleic acid,
• Itaconic acid glutaric acid, trimellitic acid and pyromellitic acid and their halogenated or alkylated derivatives.
• Anhydrides of phthalic acid, tetrahydro- and hexahydrophthalic acid and 5-methylhexahydrophthalic anhydride are preferably used.
• Carboxylic acids with primary hydroxyl groups for the preparation of hydroxy-functional poly (meth) acrylates are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamylacrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates.
• Examples of usable hydroxyalkyl esters with a secondary hydroxyl group are 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates.
• the hydroxyl-functionalized component can be at least partially a reaction product of one mole of hydroxyethyl acrylate and / or hydroxyethyl methacrylate and an average of two moles of epsilon-caprolactone.
• a reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha carbon atom can also be used at least in part as the hydroxy-functionalized component.
• Glycidyl esters of strongly branched monocarboxylic acids are available under the trade name "Cardura”.
• the reaction of acrylic acid or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha carbon can take place before, during or after the polymerization reaction.
• ethylenically unsaturated monomers can also be used in the preparation of the (meth) acrylic copolymers.
• the selection of the other ethylenically unsaturated monomers is not critical. It is only necessary to ensure that the incorporation of these monomers does not lead to undesirable properties of the copolymer.
• alkyl esters of acrylic and methacrylic acid such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth ) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, decyl (meth ) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth)
• ethylenically unsaturated monomers examples include the alkyl esters of maleic, fumaric, tetrahydrophthalic, croton, isocrotonic, vinyl acetic and itaconic acids, such as e.g.
• Small portions of monomers with at least two polymerizable, olefinically unsaturated double bonds can also be used.
• the proportion of these monomers is preferably less than 5% by weight, based on the total weight of the monomers.
• Examples of such compounds are hexanediol diacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, hexamethylene bismethacrylamide, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and similar compounds.
• Another suitable component is a monovinyl aromatic compound fertilizer It preferably contains 8 to 10 carbon atoms per molecule.
• Suitable compounds are styrene, vinyl toluenes, alpha
• Vinyl toluenes and in particular styrene are preferably used.
• the carboxyl group-containing polyesters can be constructed from aliphatic and / or cycloaliphatic di-, by the usual methods (see, for example, B. Vollmert, floor plan of macromolecular chemistry, E. Voll-mert-Verlag Düsseldorf 1982, Volume II, page 5 ff. Tri- or higher alcohols, optionally together with monohydric alcohols and from aliphatic, aromatic and / or cycloaliphatic carboxylic acids as well as higher polycarboxylic acids.
• suitable alcohols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1 , 5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,4-dimethylclcyclohexane , Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etherification products of diols and polyols, for example Di- and triethylene glycol, polyethylene glycol, neopentyl glycol ester of hydroxypivalic acid.
• carboxylic acids examples include adipic, azelaine, 1,3- and 1,4-cyclohexanedicarboxylic acids, tetrahydrophthalic, hexahydrophthalic, endomethylene tetrahydrophthalic acid, isophthalic acid, o-phthalic acid, terephthalic acid or their anhydrides and their derivatives capable of esterification.
• the calculated molecular weights of the polyesters are, for example, between 500 and 2000 g / mol.
• the carboxy-functional poly (meth) acrylic copolymers and polyester which can be used can be "chain extended” with a lactone.
• the lactones (cyclic esters) attach to carboxyl groups, when the ring is opened and a new terminal carboxyl group is formed.
• lactones of this type can be substituted:
• Examples include 6-methyl-epsilon-caprolactone, 3-methyl-epsilon-caprolactone, 5-methyl-epsilon-caprolactone, 5-phenol-epsilon-caprolactone, 4-methyl-delta-valerolactone, 3,5-dimethyl-epsilon-caprolactone , and mixtures thereof.
• the reaction with the lactone can, for example, take place immediately after the resin synthesis, that is to say after the synthesis of the poly (meth) acrylic polymer and / or of the polyester.
• the reaction takes place, for example, at an elevated temperature, for example at temperatures up to 100.degree.
• the reaction can be carried out, for example, with stirring for up to 10 hours, for example.
• the catalysts which can accelerate crosslinking between the epoxy-functionalized polysiloxanes 2) and component 2a) are those described in the description of component 1c).
• the quantitative ratios of components 2) and 2a) are preferably chosen so that the ratio of the epoxy groups and carboxy groups is between 1: 1.5 and 1.5: 1, preferably 1: 1.2 and 1.2: 1.
• the melamine resins mentioned under 2b) are the same as those described under lb) above.
• Component 2c) is a polyamine component with at least two functional groups of the formula R 4 HN-, where R is a hydrogen atom or a straight or branched alkyl radical with 1 to 10 carbon atoms or cycloalkyl radical with 3 to 8, preferably 5 or 6 carbon atoms.
• Suitable polyamines are diamines and amines with more than two amino groups, where the amino groups can be primary and / or secondary.
• adducts consisting of polyamines having at least two primary amino groups and at least one, preferably one, secondary amino group, with epoxy compounds, polyisocyanates and acryloyl compounds are also suitable as polyamines.
• Aminoamides and adducts of carboxyl-functionalized acrylates with imines which have at least two amino groups are also suitable.
• Examples of suitable di- and polyamines are described, for example, in EP-A-0 240 083 and EP-A-0 346 982. Examples of these are aliphatic and / or cycloaliphatic amines having 2 to 24 carbon atoms, which contain 2 to 10 primary amino groups, preferably 2 to 4 primary amino groups, and 0 to 4 secondary amino groups.
• polyamines based on adducts of polyfunctional amine components with di- or polyfunctional epoxy compounds for example those which are produced using, for example, di- or polyfunctional epoxy compounds, such as di-glycidyl or polyglycidyl ether of (cyclo) aliphatic or aromatic Hydroxy compounds such as ethylene glycol, glycerol, 1,2- and 1,4-cyclohexanediol, bisphenols such as bisphenol A, polyglycidyl ethers of phenol formaldehyde novolaks, polymers of ethylenically unsaturated groups which contain epoxy groups, such as glycidyl (meth) acrylate, N-glycidyl ( meth) acrylamide and / or allyl glycidyl ether, optionally copolymerized with various other ethylenically unsaturated monomers, glycidyl ether of fatty acids with 6 to 24 carbon atoms, epoxidized
• the addition of the polyamines to the epoxy compounds mentioned takes place with the ring opening of the oxirane grouping.
• the reaction can take place, for example, in a temperature range of 20-100 ° C, but preferably between 20-60 ° C.
• a Lewis base such as triethylamine or an ammonium salt such as tetrabutylammonium iodide can be used for catalysis.
• Suitable polyamines are also polyamine-isocyanate adducts.
• Common isocyanates for polyamine-isocyanate adducts are aliphatic, cycloaliphatic and / or aromatic di-, tri- or tetraisocyanates, which can be ethylenically unsaturated.
• Examples include 1,2-propylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 2,3-butylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, w, w'-dipropyl ether diisocyanate, 1,3- Cyclopentane diisocyanate, 1,2- and 1,4-cyclohexane diisocyanate,
• Isophorone diisocyanate 4-methyl-1,3-diisocyanate-cyclohexane, transvinylidene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3,3'-dimethyldicyclohexylmethane-4,4'-diisocyanate, tolylene diisocyanate, 1, 3-bis (1-isocyanato -1-methylethyl) benzene, 1,4-bis (1-isocyanato-1-methylethyl) benzene, 4,4'-diisocyanatodiphenyl, 3,3'-dichloro-4,4'-diisocyanatodiphenyl, adducts of 2 moles of a diisocyanate , e.g.
• a diol e.g. Ethylene glycol
• polyamines to the isocyanate compounds mentioned takes place, for example, in a temperature range of 20-80 ° C., preferably 20-60 ° C.
• a tertiary amine such as triethylamine and / or 0.1-1% by weight of a Lewis acid, such as dibutyltin laurate
• the polyamines can also be adducts with acryloyl compounds. Examples of di- or polyfunctional acryloylungesjut costume compounds for the manufacture of polyamine adducts are described in U.S. Patent No.
• ethylene glycol diacrylate diethylene glycol diacrylate, trimethylene, 1,3-butylene glycol diacrylate, 1,6-hexamethylene, trimethylolpropane, and Pentaerytrituoltetraacrylat Pentaerytrituoltriacrylat.
• polyfunctional acryloyl-unsaturated acrylates that can be used are:
• Urethane acrylates obtained by the reaction of an isocyanate group of a polyisocyanate with a hydroxyacrylate, e.g. Hexamethylene diisocyanate and hydroxyethyl acrylate, the preparation is described in US Pat. No. 3,297,745,
• polyfunctional acrylates obtained by the reaction of a hydroxyl functionalized acrylate, e.g. Hydroxyethyl acrylate with a) dicarboxylic acids with 4 - 15 C atoms,
• Acrylic acid a polyol with at least three hydroxy functions and a dicarboxylic acid, described in US Pat. No. 3,567,494,
• Epoxy functionalized vinyl polymer e.g. Polymers with glycidyl acrylate or vinyl glycidyl ether described in U.S. Patent 3,530,100,9) polyacrylate obtained by the reaction of acrylic anhydride with polyepoxides described in U.S. Patent 3,676,398.
• Urethane polyacrylate obtained by the reaction of a hydroxy-functionalized polyester with acrylic acid and a polyisocyanate, described in US Pat. No. 3,759,809.
• the acryloyl end groups of the di- or polyacrylic monomers or the polyacrylates from Examples 1) to 12) can be functionalized with polyamines.
• the attachment can e.g. in a temperature range of 20-100 ° C, preferably at 40-60 ° C.
• Another method for synthesizing an amine-functionalized hardener is described in EP-A-0 002 801. Here acrylic ester copolymers are amidized with diamines with elimination of alcohol.
• the reactive group obtained has the following structure:
• R 5 H or CH 3 ,
• R 6 alkylene groups with 2 or 3 carbon atoms, which can be the same or different
• n 0, 1, 2 or 3
• the acrylic acid ester copolymer has a number average molecular weight Mn of 1000-20000, preferably 2000-5000.
• examples of possible comonomers are esters of (meth) acrylic acid such as e.g. Methyl, ethyl, eutyl, cyclohexyl (meth) acrylate, hydroxyethyl (meth) arylate, hydroxyprcpyl (meth) acrylate, furthermore (meth) acrylic acid, styrene and vinyl toluene.
• Methyl acrylate is particularly preferred since this monomer is particularly easily accessible to aminolysis.
• the proportion of (meth) acrylate in the copolymer is 2 to 35% by weight.
• the copolymers are prepared by solution polymerization in customary solvents such as toluene, xylenes, acetates, e.g. B. butyl acetate or ethyl glycol acetate, ethers such as tetrahydrofuran or aromatic mixtures such as the commercial product Solvesso 100.
• customary solvents such as toluene, xylenes, acetates, e.g. B. butyl acetate or ethyl glycol acetate, ethers such as tetrahydrofuran or aromatic mixtures such as the commercial product Solvesso 100.
• Copolymers are known to the person skilled in the art and require no further
• polyamines used in aminolysis must contain at least two primary or secondary amine groups and have already been described.
• Reaction products from the reaction of a (meth) acrylic acid copolymer with alkyleneimines as described in cer EP-A-0 179 954 can also be used as hardeners.
• the functional gruccs obtained have the structure:
• R 5 H or CH 3
• R 7 alkylene group with 2 to 4 carbon atoms
• the copolymer can contain esters of (meth) acrylic acid or vinyl compounds such as styrene.
• esters of (meth) acrylic acid or vinyl compounds such as styrene.
• alkyleneimines are e.g. Propylene or butylene imine.
• polyamines which can likewise be used according to the invention as hardeners are also those which are prepared by reacting copolymers of alpha-dimethyl-m-isopropenylbenzyl isocyanate (TMI) which have a number average molecular weight (Mn) of 1000 to 10,000 with mono- or diketimines that contain either an OH or sec.NH grouping.
• TMI alpha-dimethyl-m-isopropenylbenzyl isocyanate
• Mn number average molecular weight
• esters of (meth) acrylic acid such as e.g. Methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl and / or lauryl
• (Meth) acrylate can be selected, styrene, vinyl toluene and / or methyl styrene.
• the copolymers are prepared by conventional free-radical solution polymerization, as is known to the person skilled in the art. Work is carried out, for example, in aprotic organic solvents. e.g. Toluene and xylene, and esters, e.g. Butyl acetate.
• Common radical initiators such as peroxides and azo compounds are generally used for this purpose.
• the reaction takes place e.g. with heating, for example to temperatures of 80 to 140 ° C.
• the monomeric TMI can range from 2 to 40% by weight, based on: the weight of all monomers are copolymerized, but preferably in a range from 2 to 25% by weight.
• the isocyanate-terminated copolymer is then reacted with one or more mono- and / or diketenimines and / or mono- and / or dialdimines functionalized with OH or sec.NH.
• ketimines and / or aldimines are produced e.g. by reacting alkanolamines or
• Di- or triamines which have at least one primary amino group, in the case of
• Di- or triamines additionally carry a secondary amine function with
• alkanolamines examples are:
• Monoethanolamine monopropanolamine, monohexanolamine or 2-amino-2-hydroxypropane.
• di- and triamines which carry at least one primary amino group and one secondary amino group are:
• N-methylpropylamine diethylenetriamine, dipropylenetriamine or bishexamethyltriamine.
• the primary amino groups of the amines mentioned above must be blocked.
• the primary amines are reacted with aldehydes or ketones with elimination of water to give boat bases or aldimines or ketimines. Examples of such aldehydes and ketones are:
• C 3 - C 10 compounds the hexyl aldehyde, octyl aldehyde, diisopropyl ketone and / or methyl isobutyl ketone.
• the last two compounds are particularly preferred because they show little tendency to undergo side reactions.
• the OH- or sec.NH-functionalized mono- or diketimines are preferably used in deficiency in the addition to the isocyanate-terminated copolymers, preferably 90-95% of the isocyanate groups are reacted with OH or NH groups. The remaining excess isocyanate groups are urethanized in a final reaction step with monoalcohols such as ethanol, propanol or butanol.
• a TMI copolymer is first prepared by free-radical solution polymerization.
• An alkanolamine or di- or triketimine, which carries both at least one primary and a secondary amine function, is then introduced with the desired blocking agent, aldehyde or ketone, in an organic solvent which forms an azeotropic mixture with water.
• the water of reaction formed is distilled off azeotropically by heating this mixture.
• the blocking agent can be used in excess, which can be distilled off after the reaction. It is expedient to choose a ketone / aldehyde as the capping agent which itself forms an azeotrope with water, so that an additional organic solvent can be dispensed with.
• the ketimine is used in e.g. 80 ° C under inert gas and the copolymer in e.g. metered in for two hours. With the help of a Lewis acid, e.g. Dibutyltin laurate can optionally catalyze the reaction.
• an alcohol e.g. Added butanol. If necessary, e.g. about 10 to 30 min. touched.
• the above preparation is merely an example of a procedure.
• the copolymer is initially introduced and the ketimine is added.
• the terminated (free) amino groups of the polyamine hardener component can be blocked, for example with ketones or aldehydes with the formation of Schiff bases. All the polyamines described so far have a very high reactivity with the binder components according to the invention, which can manifest itself in a very short pot life. For this reason, it may be expedient to react the terminated amine groups of the polyamines mentioned with aldehydes or ketones with elimination of water to give bases or aldimines or ketimines.
• aldehydes and ketones which can be used for capping are C 3 -C 10 compounds, such as hexylaldehyde, octylaldehyde, diisopropyl ketone and / or methyl isobutyl ketone.
• the last two compounds are particularly preferred because they show little tendency to undergo side reactions.
• the quantitative ratio of epoxy-functionalized COC- (meth) acrylate 2) to 2c) in the curable lacquer is preferably chosen so that the ratio between epoxy groups and amine functions is between 1: 1.5 and 1.5: 1, preferably 1: 1.2 and 1.2: 1.
• the COC can contain, for example, polymerized epoxy-functionalized (meth) acrylic monomers.
• Some of the glycidyl functions present can be esterified with alpha, beta-unsaturated carboxylic acids, as a result of which unsaturated groups are incorporated in the resin; this is described, for example, in DE-A-40 27 259.
• the partial reaction of glycidyl groups with alpha, beta-unsaturated carboxylic acid to form component 3) can e.g. in such a way that one or more alpha, beta-unsaturated carboxylic acids are introduced into a heated (e.g. 50 to 100 ° C, e.g. 80 ° C) polysiloxane / acrylic resin solution until the desired acid number is reached. This can be done, for example, by dropping. The mixture is stirred until the acid number is preferably below 1 mg KOH / g.
• Examples of usable acids are mono- or polyunsaturated monocarboxylic acids with, for example, 2 to 10, preferably 3 to 6, carbon atoms Men, such as cinnamic acid, crotonic acid, citraconic acid, mesaconic acid, dihydrolevulinic acid, sorbic acid and preferably acrylic acid and / or methacrylic acid.
• the amount of acid is preferably such that there is a ratio between acryloyl groups and epoxy groups of 8: 2 to 2: 8, preferably 7: 3 and 3: 7.
• Polyamines can be used as crosslinker component 3a). Such polyamines correspond to the polyamines already described above under 2c).
• the ratio between epoxy and acryloyl groups to amine functions is chosen so that it is between 1: 1.5 and 1.5: 1, preferably between 1: 1.2 and 1.2: 1.
• the CH-acidic component 3b) which can be used as a crosslinking agent for component 3) according to the invention can e.g. are produced by transesterification of an aliphatic beta-ketocarboxylic acid ester with a polyol.
• Suitable beta-ketocarboxylic acid esters are, for example, esters of acetoacetic acid or alkyl-substituted acetoacetic acids, such as alpha- and / or gamma-methylacetoacetic acid.
• Suitable esters of these acids are those with aliphatic alcohols, preferably lower alcohols with 1 to 4 carbon atoms, such as methanol, ethanol or butanol.
• suitable polyols for the reaction with the beta-ketocarboxylic acid esters are monomers and polymers which are selected from: i) polyols from the group of straight or branched alkane diols and polyols having 2 to 12 carbon atoms, ii) Hydroxyl group-containing poly (meth) acrylates or poly (meth) acrylamides based on (meth) acrylic acid hydroxyalkyl esters or (meth) acrylic acid-hydroxyalkylamides each having 2 to 12 carbon atoms in the alkyl part, optionally copolymerized with alpha, beta-unsaturated monomers, with a number average of Molecular weight (Mn) from 1000 to 10000, iii) hydroxyl-containing poly (meth) acrylates based on
• Number average molecular weight (Mn) from 500 to 2000.
• Suitable alkane di- and polyols of group i) are those with straight and branched chains with 2 to 12 carbon atoms. They contain at least two hydroxyl functions, but preferably at least three. Examples include propanediol, butanediol, hexanediol, glycerin, trimethylolpropane and pentaerythritol.
• hydroxyl-containing poly (meth) acrylates ii) based on (meth) acrylic acid hydroxyalkyl esters with 2 to 12 carbon atoms in the alkyl part are hydroxyalkyl esters of acrylic acid or methacrylic acid with alcohols with at least two hydroxyl groups, such as 1,4-butanediol, mono (meth) acrylate , 1,6-hexanediol mono (meth) acrylate or 1,2,3-propanetriol mono (meth) acrylate.
• hydroxyl-containing poly (meth) acrylamides ii) based on (meth) acrylic acid hydroxyalkylamides are amides of acrylic acid or methacrylic acid with hydroxyalkylamines or di
• (hydroxyalkyl) amines each having 2 to 12 carbon atoms in the alkyl part, which may have one or more hydroxyl groups, such as acrylic acid hydroxyethylamide.
• (meth) acrylic used in the present description and the claims is intended to mean and / or methacrylic.
• the hydroxyl-containing poly (meth) acrylates of component ii) can be homopolymers or copolymers. They have a number average molecular weight from 1000 to 10,000, preferably from 3000 to 6000.
• Copolymerizable monomers for the preparation of the copolymers are alpha, beta unsaturated monomers, radically polymerizable monomers from the group of the esters of alpha, beta-unsaturated carboxylic acids, such as acrylic acid or methacrylic acid, examples of the alcohol components of the esters being methyl, ethyl, propyl alcohol and their isomers and higher
• homologues are diesters of maleic or fumaric acid, the alcohol component being the same as mentioned above.
• Other examples are vinyl aromatic compounds such as styrene, alpha methyl styrene and vinyl toluene.
• Other examples are vinyl esters of short-chain carboxylic acids, such as vinyl acetate, vinyl propionate and vinyl butyrate.
• the hydroxyl group-containing poly (meth) acrylates of component iii) defined above can be modified poly (meth) acrylate homo- and copolymers, as are described under ii), the hydroxyl groups of which are wholly or partially with cyclic esters, such as e.g. of hydroxycarboxylic acids with 4 to 6 carbon atoms, such as butyrolactone or caprolactone.
• the modified poly (meth) acrylates of component iii) obtained have a number average molecular weight Mn of 1,000 to 10,000.
• polyester polyols and polyether polyols of component iv) are those with a number average molecular weight Mn of 500 to 2000. Specific examples are reaction products of di- or
• Tricarboxylic acids such as adipic acid or trimellitic acid
• polyols such as adipic acid or trimellitic acid
• reaction products of di- or triols such as propanediol or butanediol or
• Glycerin with ethylene oxide or propylene oxide.
• the C-H-acidic component can be synthesized, for example, over several stages.
• the polyol is first transesterified with the aliphatic beta-ketocarboxylic acid ester after removal of any solvent present.
• the transesterification of the polyol can be carried out, for example, in such a way that the polyol, if appropriate freed from solvent by applying a vacuum, is initially introduced.
• the beta-ketocarboxylic acid ester is then added in excess, for example added dropwise.
• the reaction takes place at elevated temperature; the alcohol released is removed from the system.
• a catalyst can also be added to accelerate the reaction. Examples of such catalysts are acids such as formic acid or p-toluenesulfonic acid. It is favorable to increase the reaction temperature continuously during the transesterification (for example in steps of 10 ° C / 20 min) until a temperature is reached which is just below (about 10 ° C) below the boiling point of the beta-ketocarboxylic acid ester. After quantitative transesterification, the excess beta-ketocarboxylic acid ester is removed, for example by applying a vacuum. The mixture can then be cooled and adjusted to a desired solids content using an inert solvent.
• the hardener component 3b) can also contain 2-acetoacetoxy-ethyl methacrylate as a reactive diluent to adjust the viscosity.
• Acetoacetic ester functionalized components can be increased in their CH acidity by reacting the beta-carbonyl groups with primary and / or secondary monoamines, e.g. DE-A-39 32 517.
• Component 3b) preferably contains one or more mixed in
• Catalysts in the form of Lewis bases or Brönstedt bases the conjugated acids of the latter having a pKA value of at least 10.
• Lewis bases such as e.g. those of the group of cycloaliphatic amines, such as diazabicyclooctane (DABCO), tert.-aliphatic amines, such as triethylamine, tripropylamine, N-methyldiethanolamine, N-methyldiisopropylamine or N-butyl-diethanolamine, and amidines such as diazabicyloundecane (DBU), and guin, and such as N, N, N ', - N'-tetramethylguanidine.
• DBU diazabicyloundecane
• alkyl or aryl substituted phosphanes e.g. Tributylphosphine, triphenylphosphine, tris-p-tolylphosphine, methyldiphenylphosphine, and also hydroxy- and amine-functionalized phosphines, e.g. Trishydroxymethylphosphine and tris-dimethylamino-ethylphosphane.
• Brönstedt bases examples include alcoholates, such as sodium or potassium ethylate, quaternary ammonium compounds, such as alkyl,
• Aryl or benzylammonium hydroxides or halides such as, for example, tetraethyl or tetrabutylammonium hydroxide or fluoride, and trialkyl or Triaryl phosphonium salts or hydroxides.
• the amount of the catalysts is, for example, 0.01 to 5% by weight, preferably 0.02 to 2% by weight, based on the total solids content of components 3) and 3b).
• crosslinkers mentioned under 3c) are those which contain at least two groups capable of transesterification, which come from, for example, one or more of the following groups, which may be the same or different:
• R alkyl and preferably H
• alkyl and alkylene preferably have 1 to 6 carbon atoms, and wherein the carboxyl or carponamide groups defined above for the radicals W 1 , W 2 and W 3 are each bonded to the group CR via the carbon atom and the group CR via at least one of the radicals W 1 , W 2 and / or W 3 is bound to a polymeric or oligomeric unit.
• the functionality of component 3c) averages over 2 per molecule.
• component 3c) is in Medium above 2. This means that monofunctional molecules can also be used in a mixture with higher-functionality molecules.
• the crosslinker components 3c) described above contain with W "at least one ester group which can crosslink with compounds containing hydroxyl groups in the sense of a transesterification action.
• crosslinker compounds are preferably essentially free of primary, secondary or tertiary amino groups, since these can adversely affect the storage stability and the light resistance.
• crossester components 3c capable of transesterification, which fall under the above preferred general formula. These examples are divided into three groups A1, A2 and A3 below.
• Group A1 contains on average at least two groups in the molecule which are derived from methane tricarboxylic acid monoamide units or acetoacetic acid ester-2-carboxylic acid amides.
• Suitable compounds A1 are, for example, reaction products of malonic diesters such as dimethyl malonate, diethyl, dibutyl, dipentyl or acetoacetic esters such as methyl acetoacetate, ethyl or butyl pentyl with polyisocyanates.
• malonic diesters such as dimethyl malonate, diethyl, dibutyl, dipentyl or acetoacetic esters such as methyl acetoacetate, ethyl or butyl pentyl with polyisocyanates.
• the known polyisocyanates which are mainly used in the production of lacquers, e.g. Biuret, isocyanurate or urethane groups containing modification products of the simple polyisocyanates mentioned above, in particular tris (6-isocyanatohexyl) biburet or low molecular weight polyisocyanates containing urethane groups, such as those obtained by reacting excess IPDI with simple polyhydric alcohols
• Suitable polyisocyanates are also the known prepolymers containing terminal isocyanate groups, as are accessible in particular by reacting the simple polyisocyanates mentioned above, especially diisocyanates, with inadequate amounts of organic compounds having at least two groups which are reactive toward isocyanate groups.
• a total of at least two amino group and / or hydroxyl group-containing compounds with a number average molecular weight of 300 to 10,000, preferably 400 to 6000, are preferably used.
• the corresponding polyhydroxyl compounds e.g. the hydroxypolyesters, hydroxypolyethers and / or hydroxyl group-containing acrylate resins known per se in polyurethane chemistry are used.
• the ratio of isocyanate groups to hydrogen atoms reactive towards NCO corresponds to 1.05 to 10: 1, preferably 1.1 to 3: 1, the hydrogen atoms preferably originating from hydroxyl groups.
• the nature and proportions of the starting materials used in the preparation of the NCO prepolymers are preferably chosen so that the NCO prepolymers a) have an average NCO functionality of 2 to 4, preferably 2 to 3 and b) a number average molecular weight from 500 to 10,000, preferably from 800 to 4000.
• reaction products of esters and partial esters of polyhydric alcohols of malonic acid with monoisocyanates are also suitable as compound A1.
• Polyhydric alcohols are e.g. di- to pentavalent alcohols such as
• Ethanediol the various propane, butane, pentane and hexanediols, polyethylene and polypropylene diols, glycerin, trimethylolethane and propane, pentaerythritol, hexanetriol and sorbitol.
• Suitable monoisocyanates are e.g. aliphatic isocyanates such as n-butyl isocyanate, octadecyl isocyanate, cycloaliphatic isocyanates such as cyclohexyl isocyanate, araliphatic isocyanates such as benzyl isocyanate or aromatic isocyanates such as phenyl isocyanate.
• malonic esters of aeryl resins include polyesters, polyurethanes, polyethers, polyester amides and imides containing OH groups and / or reaction products of malonic acid semiesters such as malonic acid monoethyl ester with aliphatic and aromatic epoxy resins, e.g. epoxy group-containing acrylate resins, glycidyl ethers of polyols such as hexanediol, neopentyl glycol, diphenylolpropane and methane and glycidyl group-containing hydantoins, and also mixtures of these compounds.
• malonic acid semiesters such as malonic acid monoethyl ester with aliphatic and aromatic epoxy resins, e.g. epoxy group-containing acrylate resins, glycidyl ethers of polyols such as hexanediol, neopentyl glycol, diphenylolpropane
• hydrocarbon radical preferably an alkyl radical having 1 to 12, preferably 1 to 6, carbon atoms, which can also be interrupted by oxygen or an N-alkyl radical.
• the number of group (II) in the hardener that can be used is preferably 2 to 20 and in particular 2 to 10, the larger numerical values relating to oligomeric or polymeric products and representing mean values here.
• the curing component A2 which can be used according to the invention preferably has the formula (III)
• R 2 is the remainder of a polyol
• n is at least 2, preferably 2 to 20, in particular 2 to 10.
• n is at least 2, preferably 2 to 20, in particular 2 to 10.
• curing components which fall under group A2 and which are obtained by non-quantitative transesterification of compounds of the formula (IV) or of the formula (V)
• the polyols R 2 (OH) mentioned above can be a polyhydric alcohol which preferably contains 2 to 12, in particular 2 to 6, carbon atoms.
• examples include: ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), di-ß-hydroxyethylbutanediol, hexanediol (1,6), 0ctanediol (1.8), neopentyl glycol,
• Polyesters obtained from or with lactones for example epsilon-caprolactone or hydroxycarboxylic acids, such as, for example, hydroxypivalic acid, gamma-hydroxydecanoic acid, gamma-hydroxycaproic acid, thioglycolic acid, can also be used.
• the index n in the above formula (III) preferably stands for 2 to 4.
• the polyol can be an oligomeric or polymeric polyol compound (polyol resin) whose number average molecular weight, Mn,
• oligomers / polymers (determined by means of gel chromatography; polystyrene standard), usually in the range from about 170 to 10,000, preferably about 500 to about 5000. In special cases, however, Mn can be 10,000 g / mol and more.
• Polymers, polycondensates or polyaddition compounds are suitable as oligomers / polymers.
• the hydroxyl number is generally 30 to 250, preferably 45 to 200 and in particular 50 to 180 mg KOH / g.
• These OH group-containing compounds can optionally also contain other functional groups, such as carboxyl groups.
• polyols examples include polyether polyols, polyacetal polyols, polyester amide polyols, polyamide polyols, epoxy resin polyols or other reaction products with CO 2 , phenol resin polyols, polyurea polyols, polyurethane polyols, cellulose esters and ether polyols, partially saponified homo- and copolymersalcohols, polyalkylene polyols, vinyl acetate polyols, vinyl alcohols .
• Polyether polyols, polyester polyols are preferred. Acrylate resins and polyurethane polyols.
• Such polyols which can also be used in a mixture, are described, for example, in DE-OS 31 24 784.
• polyurethane polyols result from the reaction of di- and polyisocyanates with an excess of di- and / or polyols.
• Appropriate Nete isocyanates are, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate and isocyanates, formed from three moles of a diisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate, and biurets which result from the reaction of three moles of a diisocyanate with one mole of water.
• Suitable polyurea polyols can be obtained in a similar manner by reacting di- and polyisocyanates with equimolar amounts of amino alcohols, for example ethanolamine or diethanolamine.
• polyester polyols are the known polycondensates of di- or polycarboxylic acids or their anhydrides, such as phthalic anhydride, adipic acid etc., and polyols such as ethylene glycol, trimethylolpropane, glycerol etc.
• Suitable polyamide polyols can be obtained in a similar manner to the polyesters by at least partially replacing the polyols with polyamines such as isophorone diamine, hexamethylene diamine, diethylene triamine, etc.
• polyacrylate polyols or polyvinyl compounds containing OH groups are the known copolymers of hydroxyl-containing (meth) acrylic acid esters or vinyl alcohol and other vinyl compounds, such as styrene or (meth) acrylic acid esters.
• the above polycarboxylic acids R 2 (CO 2 H) n where n here is preferably 2 to 4, can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or saturated.
• carboxylic acids and their derivatives are: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 1,3- and 1,4-cyclic acid and tetrahydrofluoric acid, endodehydrochloric acid, endogenous tetrachloroacetic acid, and tetranoic acid their hexachloro derivative, glutaric acid, maleic acid, fumaric acid, dimeric and trimeric fatty acids, such as oleic acid, optionally in a mixture with monomeric fatty acids or cyclic monocarboxylic acids, such as benzoic acid, p-tert-butylbenzoic acid re or hexahydrobenzoic acid.
• the reaction products of the above-mentioned polyols R 2 (OH) n with cyclic carboxylic acid anhydrides are more or less viscous liquids or solids which are largely soluble at least in the conventional paint solvents and preferably less than 5% by weight, in particular contain less than 1% by weight of crosslinked fractions.
• the transesterification equivalent weight which is a measure of the amount of groups (II) or structural units (II ') in (A2), is generally between 100 and 5000, preferably 200 and 2000, and the number average molecular weight Mn is generally between 200 and 10,000, preferably between 500 and 5000 (determined by gel chromatography; polystyrene standard). Processes for the preparation of such compounds are described in more detail in EP-A-0 310 011.
• the above groupings of A3 can be attached to at least one polyvalent monomeric or polymeric compound.
• they can be bound to at least one compound from the group of mono- or polyhydric alcohols, polymers containing OH groups, polyamine and polymercaptans.
• the transesterification function they are multi-valued.
• they can be esterified by a polyepoxide with a grouping dicarboxylic acid monoester, e.g. Malonic acid monoesters.
• Component A3 is thus obtained with one transesterifiable group per epoxy group.
• Aromatic or aliphatic polyepoxides can be used here.
• suitable dicarboxylic acid monoesters are malonic acid monoalkyl esters, acetone dicarboxylic acid monoalkyl esters, where the alkyl radical can be straight-chain or branched with 1 to 6 atoms, for example methyl, ethyl, n-butyl or t-butyl.
• the hardener components 3c) can be produced in conventional solvents. It is expedient to use solvents which do not later interfere with the production of the coating agent. It is also favorable to keep the organic solvent content as low as possible. If the hardener component 3c) contains polar groups, for example amide or urethane groups, then easy dispersion in water is possible. This can optionally also be supported by the fact that the crosslinker components contain neutralizable ionic groups, for example carboxyl groups, in the oligomer or polymer structure. Such crosslinkers with ionic
• Groups can be well dispersed in water.
• the content of organic solvents can be reduced to low values without significantly increasing the viscosity of the crosslinking agent solution.
• the ratio between 3) and 3c) is preferably chosen so that the
• Ratio of cer OH functions 3) obtained by the addition reaction of the alpha, beta-unsaturated acids to the glycidyl groups and the groups capable of transesterification between 1: 1.5 and 1.5: 1, preferably between 1: 1.2 and 1 , 2: 1 lies.
• the unsaturated bonds contained in the resin 3) can also be polymerized in the presence of radical initiators, as a result of which a further crosslinking effect is achieved.
• the initiators described above for polymerizing the monomers can be used, for example, as radical initiators.
• the binder compositions according to the invention can be formulated in a customary manner to form coating compositions. This is generally done by adding solvents or water. Suitable organic solvents for the production of coating agents. for example, paints are those that can also be used in the production of the individual components 1), 1a) - 1c), 2), 2a) - 2c, 3), 3a) - 3c). Examples of such solvents are organic solvents, such as aliphatic and aromatic hydrocarbons, for example toluene, xylene, mixtures of aliphatic and / or aromatic hydrocarbons, esters, ethers and alcohols. These are common paint solvents. To produce the coating compositions from the inventive Binders can also be prepared in aqueous solutions. Suitable emulsifiers, such as those on the
• Lacquer sector are common.
• Customary additives such as are customary in the paint sector, for example, can be added to produce the coating compositions.
• additives are pigments, for example transparent or opaque color pigments such as titanium dioxide or carbon black and effect pigments such as metal flake pigments and / or pearlescent pigments.
• binder compositions according to the invention are particularly suitable for coating compositions which are said to have high scratch resistance and acid resistance.
• additives are fillers such as Talc and silicates; Plasticizers, light stabilizers, stabilizers and leveling agents, such as silicone oils.
• the coating agents produced from the binders according to the invention can be adjusted to the desired application viscosity by appropriately regulating the addition of solvents and / or water and / or additives.
• the coatings produced from the coating compositions can be cured in a wide temperature range, for example from -10 ° C. to 200 ° C., and depend on the particular type of crosslinking reaction.
• the coating compositions produced from the binders according to the invention are suitable for coatings which adhere to a large number of substrates, such as, for example, wood, textiles, plastic, glass, ceramic, plaster, cement and in particular metal. It has proven to be particularly advantageous that they give excellent adhesion to non-polar plastic substrates, in particular polyolefin surfaces, for example polyethylene, polypropylene and / or cycloolefin copolymers.
• the coating agents can also be used in the multi-layer process. For example, they can be applied to common primers, basecoats, fillers or already existing top coats are applied.
• a particularly preferred area of application for the binders according to the invention is the provision of coating agents for coatings which are said to have high scratch resistance and acid resistance.
• the present invention thus also relates to processes for the production of coatings on various substrates, in which a coating agent prepared from the binders according to the invention is applied to the substrate, whereupon drying and curing is carried out.
• the invention also relates to the use of the binder compositions according to the invention in paints, in particular automotive top coats or clear coats. In any case, films with good hardness and good water and solvent resistance, chemical resistance, scratch resistance and high dirt-repellent effect are obtained with the coating compositions prepared from the binders according to the invention, the dirt-repellent effect being retained over long periods even under unfavorable weather conditions.
• compositions according to the invention can be applied in the customary manner
• first clear coat which can consist of a commercially available, conventionally organically dissolved or aqueous clear coat, and then as a second coat
• COC-containing clear coat Of course, it is also possible to use the COC lacquer as the first layer.
• the polymer has a solids content of 60.3%, an acid number of 19.5 and a viscosity of 2250 mPas and has a very slightly opaque, colorless appearance.
• a slightly opaque, colorless COC lap polymer with a viscosity of 30300 mPas (Höppler at 25 ° C.) and an acid number of 19 mg KOH / g solid resin body is obtained.
• the polymer has a solids content of 60.1% and a viscosity of 2400 mPas.
• the acid number is 19 mg KOH / gFH.
• the paint films were coated with 38% H 2 SO 4 . dropped at 65 ° C.
• the paint film based on the resin from Example 2 was destroyed after 24 minutes, the film based on the resin from the comparison test after 16 minutes.

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• 1994
  • 1994-12-21 WO PCT/EP1994/004260 patent/WO1995018161A1/de active Application Filing
  • 1994-12-23 JP JP33591794A patent/JPH07252461A/ja not_active Withdrawn

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