EP1218421A1 - Resines contenant des groupes carbamate, leur procede de production et leur utilisation - Google Patents

Resines contenant des groupes carbamate, leur procede de production et leur utilisation

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Publication number
EP1218421A1
EP1218421A1 EP00958513A EP00958513A EP1218421A1 EP 1218421 A1 EP1218421 A1 EP 1218421A1 EP 00958513 A EP00958513 A EP 00958513A EP 00958513 A EP00958513 A EP 00958513A EP 1218421 A1 EP1218421 A1 EP 1218421A1
Authority
EP
European Patent Office
Prior art keywords
resins
resin
groups
carbamate
substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00958513A
Other languages
German (de)
English (en)
Inventor
Sabine Wiguny
Ulrike RÖCKRATH
Hubert Baumgart
Jochem Henkelmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1218421A1 publication Critical patent/EP1218421A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

Definitions

  • the present invention relates to new oligomers and polymers which contain pendant and / or terminal carbamate groups.
  • the present invention relates to the use of the new oligomers and polymers for the production of molding compositions, adhesives and coating materials, in particular paints, and their derivatives, i.e. the molded parts, foils, fibers, adhesive layers and coatings, in particular paintwork.
  • coating materials which contain at least one oligomer and / or polymer (hereinafter collectively referred to as "resin") with at least one pendant and / or terminal carbamate group of the formula:
  • crosslinking agent containing at least 2 functional groups which undergo crosslinking reactions with the carbamate group.
  • These known coating compositions provide clear lacquers which have an extremely high scratch resistance and etch resistance.
  • Highly etherified melamine formaldehyde resins are primarily used as crosslinking agents.
  • the crosslinking itself is acid-catalyzed, preference being given to strong protonic acids, in particular sulfonic acids, which i. d. R. blocked with amines can be used.
  • the introduction of the pendant and / or terminal carbamate groups can be achieved by incorporating monomers containing these groups, respectively.
  • suitable monomers of this type are ethylenically unsaturated monomers which contain a carbamate group.
  • the introduction of the carbamate group can also be introduced into resins by polymer-analogous reactions.
  • suitable methods of this kind are known from the patents US-A-4,758,632, US-A-4,301,257 or US-A-2,979,514.
  • Examples of such polymer-analogous reactions are the reaction of hydroxyl-containing resins with urea or with aryl or alkyl urethanes such as phenyl urethane, methyl urethane or butyl urethane or the reaction of resins containing cyclic carbonate groups with ammonia and amines.
  • the new pendant and / or terminal carbamate-containing resin has been found, which can be prepared by reacting a resin containing at least one hydroxyl group with phosgene to a resin containing at least one chloroformate group, after which this resin is reacted with ammonia, primary amines or secondary amines ,
  • molding compositions, adhesives and coating materials were found, which is hereinafter referred to as “inventive method”.
  • the new molding compositions, adhesives and coating materials were found which contain at least one oligomer and / or polymer according to the invention.
  • These new molding compositions, adhesives and coating materials are referred to below as “molding compositions, adhesives and coating materials according to the invention”.
  • adhesive layers have been found which can be produced from the adhesives according to the invention and are referred to below as “adhesive layers according to the invention”.
  • coatings according to the invention Last but not least, new coatings were found which can be produced from the coating materials according to the invention and are referred to below as "coatings according to the invention".
  • substrates which have at least one adhesive layer according to the invention and / or at least one coating according to the invention and are referred to below as “substrates according to the invention”.
  • hydroxyl group-containing resins are used for the production of the resins according to the invention.
  • Suitable hydroxyl group-containing resins are random, alternating and / or block-like linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated
  • Examples of highly suitable (co) polymers are poly (meth) acrylates and partially saponified polyvinyl esters.
  • Examples of highly suitable polyaddition resins and / or polycondensation resins are polyesters, alkyds, polyurethanes, polylactones. Polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides or polyimides.
  • the resins containing hydroxyl groups to be used according to the invention are oligomers and polymers.
  • oligomers are understood to mean resins which contain at least 2 to 15 recurring monomer units in their molecule.
  • polymers are understood to be resins which contain at least 10 recurring monomer units in their molecule.
  • the hydroxyl group-containing resins to be used according to the invention contain primary and / or secondary hydroxyl groups. It is a very essential advantage of the process and the resins according to the invention that both types of hydroxyl groups can be used. This makes it possible to specifically control the reactivity of the resins according to the invention via steric effects.
  • the OH number of the resins containing hydroxyl groups to be used according to the invention can vary very widely and is primarily based on the intended use of the resins according to the invention. If these are used, for example, as binders in the coating materials and adhesives according to the invention, it is advisable to use resins with a high OH number in the coatings and adhesive layers according to the invention for reasons of high crosslinking density. The person skilled in the art can thus determine the OH number suitable for the intended use in each case on the basis of his specialist knowledge, if necessary with the aid of orienting tests.
  • the OH number is preferably 10 to 500, preferably 20 to 400 and in particular 30 to 350 mg KOH / g.
  • the poly (meth) acrylates are preferably used. Particular advantages result from the use of the poly (meth) acrylates (hereinafter referred to collectively as "polyacrylate resins"), which is why they are used with particular preference for the production of the resins according to the invention.
  • Very particularly suitable polyacrylate resins are obtained by copolymerizing the olefinically unsaturated monomers (a) described below, at least one of which contains at least one hydroxyl group and is essentially free of acid groups.
  • Suitable monomers (a1) containing hydroxyl groups are hydroxyalkyl esters of acrylic acid, methacrylic acid of another alpha, beta-ethylenically unsaturated carboxylic acid which are derived from an alkylene glycol which is esterified with the acid or can be obtained by reacting the acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid or ethacrylic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate or crotonate ; 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7- methano-lH-indene-dimethanol or methyl propanediol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate;
  • Reaction products from cyclic esters e.g. epsilon-caprolactone and these hydroxyalkyl esters; or olefinically unsaturated alcohols such as allyl alcohol or polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether.
  • cyclic esters e.g. epsilon-caprolactone and these hydroxyalkyl esters
  • olefinically unsaturated alcohols such as allyl alcohol or polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether.
  • Monomers (al) are generally used only in minor amounts.
  • minor amounts of higher-functional monomers are understood to mean those amounts which do not lead to crosslinking or gelling of the polyacrylate resins.
  • the proportion of trimethylolpropane monoallyl ether can thus be 2 to 10% by weight, based on the total weight of the monomers (al) to (a6) used to prepare the polyacrylate resin.
  • the olefinically unsaturated polyols (al) can be used as the sole monomers (al), it is advantageous according to the invention to use them in combination with other monomers (al).
  • the monomers (a1) can be used as the sole monomers (a). According to the invention, however, it is advantageous to use them in combination with other monomers (a).
  • Suitable further monomers (a) are:
  • These can be used in minor amounts of higher functional (meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-diol, hexane, 1,6-diol, octahydro-4, 7-methano-1H-indene-dimethanol or cyclohexane-1,2-, 1,3- or -1,4-diol-di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol di, tri or tetra (meth) acrylate; contain.
  • At least one acid group preferably a carboxyl group, per molecule carrying ethylenically unsaturated monomer or a mixture of such monomers.
  • Acrylic acid and or methacrylic acid are particularly preferably used as component (a3).
  • other ethylenically unsaturated carboxylic acids with up to 6 carbon atoms in the molecule can also be used. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
  • ethylenically unsaturated sulfonic or phosphonic acids or their partial esters can be used as component (a3).
  • Suitable monomers (a3) are maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester.
  • Monomers (a4) vinyl esters of monocarboxylic acids branched in the alpha position with 5 to 18 C atoms in the molecule.
  • the branched monocarboxylic acids can be obtained are by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and or cycloaliphatic olefins.
  • olefins When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom.
  • Other olefinic starting materials are, for example, propylene trimer, propylene tetramer and diisobutylene.
  • the vinyl esters can also be prepared from the acids in a manner known per se, for example by letting the acid react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used.
  • Reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 carbon atoms per molecule The reaction of acrylic or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha carbon atom can be carried out before, during or after the polymerization reaction.
  • the reaction product of acrylic and / or methacrylic acid with the glycidyl ester of Versatic® acid is preferably used as component (a5). This glycidyl ester is commercially available under the name Cardura® E10.
  • ethylenically unsaturated monomers such as Olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene;
  • (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl -, N, N-
  • Acrylic acid methacrylic acid, ethacrylic acid, crotonic acid.
  • Maleic acid fumaric acid and or itaconic acid;
  • vinyl aromatic hydrocarbons such as styrene, alpha-alkylstyrenes, especially alpha-methylstyrene, arylstyrenes, in particular
  • Nitriles such as acrylonitrile and or methacrylonitrile
  • Vinyl compounds such as vinyl chloride, vinyl fluoride, vinylidene dichloride,
  • vinylidene N-vinylpyrrolidone
  • Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,
  • Vinyl esters such as vinyl acetate, vinyl propionate, vinylbutyrai, vinyl pivalate, vinyl esters of Versatic® acids, sold under the brand name VeoVa® by the company
  • hydroxyl-containing polyacrylate resins which preferably have an OH number of 100 to 250, preferably 130 to 210, preferably acid numbers of 0 to 80, preferably 0 to 50, entirely particularly preferably 0 to 15, preferably glass transition temperatures Tg from -25 to +80 ° C, preferably -20 to +40 ° C, and preferably number average molecular weights from 1,500 to 30,000, preferably 1,500 to 15,000, very particularly preferably 1,500 to 5,000 (determined by Gel permeation chromatography with polystyrene as the internal standard).
  • the glass transition temperature Tg of the polyacrylate resins is determined by the type and amount of the monomers used (a1) and optionally (a2), (a3), (a4), (a5) and / or (a6).
  • Tg glass transition temperature of the polyacrylate resin
  • W n weight fraction of the nth monomer
  • Tg " glass transition temperature of the homopolymer from the nth
  • the preparation of the polyacrylate resins containing hydroxyl groups to be used according to the invention has no special features, but takes place according to the customary and known methods of radical polymerization in the presence of at least one polymerization initiator.
  • Suitable polymerization initiators are free radical initiators, e.g. tert-butyl peroxyethyl hexanoate, benzoyl peroxide, di-tert-amyl peroxide, azobisisobutyronitrile and tert-butyl perbenzoate.
  • the initiators are preferably used in an amount of 1 to 25% by weight, particularly preferably 2 to 10% by weight, based on the total weight of the monomers.
  • the polymerization is advantageously carried out at a temperature of 80 to 200 ° C., preferably 110 to 180 ° C.
  • Organic solvents which are inert to phosgene, in particular mixtures of aromatic hydrocarbons, are preferably used as solvents.
  • the polyacrylate resin can be produced by a two-step process or a one-step process.
  • a mixture of the monomers (a1) and optionally (a2), (a4), (a5) and / or (a6) or a mixture of parts of the monomers (a1) and optionally (a2), (a4), ( a5) and / or (a6) is polymerized in an organic solvent and
  • the monomers (a4) and / or (a5) can also be added only partially together with at least part of the solvent and the rest of these monomers can be added as described above.
  • at least 20% by weight of the solvent and about 10% by weight of the monomers (a4) and (a5) and, if appropriate, parts of the monomers (al) and (a6) are preferably introduced.
  • the initiator feed be started some time, generally about 1 to 15 minutes, before the monomers feed.
  • a method is further preferred in which the initiator addition begins at the same time as the addition of the monomers and is terminated about half an hour after the addition of the monomers has ended.
  • the initiator is preferably added in a constant amount per unit of time. After completion After the initiator has been added, the reaction mixture is kept at the polymerization temperature (as a rule 1.5 hours) until all of the monomers used have essentially been reacted completely.
  • Substantially completely converted is intended to mean that preferably 100% by weight of the monomers used have been reacted, but it is also possible that a low residual monomer content of at most up to about 0.5% by weight, based on the Weight of the reaction mixture can remain unreacted.
  • the monomers for the preparation of the polyacrylate resins are preferably polymerized in a polymerization solid which is not too high, preferably in a polymerization solid of 80 to 50% by weight, based on the monomers, and then for the reaction with phosgene with organic solvents which are inert to phosgene , diluted to make it easy to stir.
  • the production of the polyacrylate resins to be used according to the invention has no special features in terms of method, but instead takes place with the aid of the methods known and known in the plastics field of continuous or discontinuous copolymerization under atmospheric pressure or overpressure in stirred tanks, autoclaves, tubular reactors or Taylor reactors.
  • the reaction with phosgene is advantageously carried out at temperatures from -10 to 100, preferably 0 to 50 and in particular 10 to 40.degree.
  • the resins containing chloroformate groups can be isolated as such, which can be of advantage in special cases, but in general it is advisable to use the resins in the solution in which they are obtained with ammonia and / or primary and / or secondary amines implement.
  • Suitable primary and secondary amines are those of the general formula I.
  • variable R represents a hydrogen atom or a monovalent organic radical which is derived from the following compounds:
  • (ü) substituted and unsubstituted aromatics or heteroamates such as (üi) alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcyloalkyl,
  • variable R 1 has the meaning given above, except for a hydrogen atom
  • heteroatoms examples include oxygen, nitrogen, boron, silicon, sulfur or phosphorus atoms.
  • Suitable substitutes for the abovementioned radicals R 1 are halogen atoms, in particular ruine and chlorine atoms, nitro groups or nitrile groups.
  • Suitable aromatics are benzene and naphthalene.
  • heteroaromatics examples include thiophene, pyridine or triazine.
  • alkanes are those with 1 to 20 C atoms in the molecule, such as methane, ethane, propane, butane, isobutane, pentane, neopentane, hexane, heptane, octane, isooctane, nonane, dodecane, hexadecane or eicosane.
  • alkenes examples are ethylene and propylene.
  • Suitable cycloalkanes are cyclopentane and cyclohexane.
  • suitable cycloalkenes are cyclopentene and cyclohexene.
  • alkylcycloalkanes examples include methylcyclopentane and methylcyclohexane.
  • alkylcycloalkenes examples include methylcyclopentene and methylcyclohexene.
  • alkenylcycloalkanes examples include allyl and vinylcyclopentane and allyl and vinylcyclohexane.
  • alkenylcycloalkenes examples include vinylcyclopentene and vinylcyclohexene.
  • alkyl alkenyl, cycloalkyl, cycloalkenyl, alkylcyloalkyl, alkylcycloalkenyl, alkenylcycloalkyl or
  • Alkenylcycloalkenyl substituents are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, vinyl, allyl, cyclohexyl, cyclohexenyl, 4-methylcyclohexyl. 4-methylcyclohexenyl, 3-allylcyclohexenyl or 4-vinylcyclohexenyl.
  • the R 1 radicals are preferably derived from organic compounds which are unsubstituted as such or whose substituents are unsubstituted.
  • these compounds also do not contain heteroatoms in their chains and / or in their rings and or in the chains and / or rings of their substitutes.
  • radicals R and R 1 are derived from linear alkanes which have the advantageous conditions mentioned above fulfill. Additional benefits result when they differ from methane. Derive ethane, propane, butane, pentane or hexane.
  • Examples of highly suitable primary amines I are methylamine, ethylamine, propylamine, isobutylamine, hexylamine, cyclohexylamine, allylamine, cyclohexenylamine, aniline, cyclohexylmethylamine. (2-cyclohexyl) ethylamine or benzylamine.
  • Examples of highly suitable secondary amines I are dimethylamine, diethylamine, methylethylamine, dicyclohexylamine, methylcyclohexylamine, dibenzylamine, methylbenzylamine or diphenylamine.
  • Examples of highly suitable cyclic amines I are imidazole, thiazine, morpholine or piperidine.
  • ammonia is very particularly preferably used according to the invention.
  • ammonium chlorides obtained in the reaction of the chloroformate groups with ammonia or the amines I are separated in a customary and known manner from the reaction mixture containing the resins according to the invention. Examples of suitable methods are filtration or extraction, and these methods can be combined with one another in a suitable manner.
  • the resins according to the invention can be isolated before they are used, or the solutions in which they are obtained can be used directly. Which variant is preferred depends primarily on the intended use.
  • the resins according to the invention will preferably be isolated in substance, whereas they will preferably be used in solution for use in coating materials.
  • the resins according to the invention described above are outstandingly suitable for the production of the molding compositions, adhesives and coating materials according to the invention, in particular paints.
  • liquid and / or solid resins according to the invention can be used, which can be processed in a customary and known manner in the presence of suitable crosslinking agents, for example the crosslinking agents described below, by heating to give thermosetting molded parts, films and fibers according to the invention .
  • suitable crosslinking agents for example the crosslinking agents described below
  • solid resins according to the invention which have thermoplastic properties are advantageously used, so that they are used, for example, in a customary and known manner can be processed by extrusion, followed by injection molding, film blowing or the drawing of fibers to give thermoplastic molded parts, films and fibers.
  • thermoplastic and thermosetting molding compositions according to the invention can furthermore contain customary and known plastic additives in effective amounts.
  • the moldings, films and fibers according to the invention can be bonded in an outstanding manner with the adhesives according to the invention and / or coated or painted with the coating materials according to the invention.
  • resins according to the invention which serve as contact adhesives, resins according to the invention are preferably used which do not contain any of the crosslinking agents described below and which advantageously have thermoplastic properties.
  • the liquid or solid resins according to the invention are preferably mixed with suitable crosslinking agents, for example the crosslinking agents described below, so that they can be thermally cured.
  • suitable crosslinking agents for example the crosslinking agents described below
  • the adhesives according to the invention can contain the additives described below for the coating materials, provided that these are suitable for use in adhesives.
  • the substrates described below in particular the moldings, films and fibers according to the invention, can be bonded in an outstanding manner.
  • the resins according to the invention are very particularly preferably used for the production of coating materials, in particular paints.
  • the resins according to the invention also contain functional groups, in particular hydroxyl groups, which react with the carbamate groups at higher temperatures, in particular 50 to 250 ° C.
  • the resins according to the invention as such or the coating materials according to the invention produced therewith are self-crosslinking. If the resins according to the invention contain no such functional groups, they are usually crosslinked with the aid of crosslinking agents.
  • Both the self-crosslinking and the externally crosslinking coating materials according to the invention can be present as liquid lacquers (100% systems), powder lacquers, aqueous powder slurry lacquers or as a solution or dispersion in organic solvents and / or in water.
  • Suitable crosslinking agents for use in the externally crosslinking coating materials of the invention are in principle all crosslinking agents which contain at least two complementary functional groups which react with carbamate groups.
  • suitable complementary functional groups are thio, amino, hydroxyl and / or methylol and / or methylol ether groups.
  • the methylol and methylol ether groups are particularly advantageous and are therefore used with particular preference in accordance with the invention.
  • aminoplast resins for example melamine resins, guanamine resins or urea resins, can be used as crosslinking agents. Any aminoplast resin suitable for transparent topcoats or clearcoats or a mixture of such aminoplast resins can be used.
  • Crosslinking agents of this type are described in the patents US-A-4 710 542 and EP-B-0 245 700 and in the article by B. Singh and co-workers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry” in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207.
  • the content of resin and crosslinking agent according to the invention can vary widely in the coating materials of the invention.
  • the coating materials of the invention advantageously contain, based on their respective solids content, 10 to 99, preferably 15 to 98, particularly preferably 20 to 97, very particularly preferably 25 to 96 and in particular 30 to 95% by weight of at least one resin according to the invention and 1 to 90, preferably 2 to 85, particularly preferably 3 to 80, very particularly preferably 4 to 75 and in particular 5 to 70% by weight of at least one crosslinking agent.
  • the coating material of the invention can be used to produce decorative and / or protective coatings, in particular paints such as transparent clear coats, primers, in particular
  • Stone chip protection primers and fillers, or color and / or effect coatings, in particular top coats and basecoats, can be used.
  • the paintwork can be one or more layers.
  • coating materials of the invention are generally added in effective amounts to customary coating materials.
  • the type and amount of the additives depend primarily on the intended use of the coating material of the invention. These additives are preferably not volatile under the processing and application conditions of the coating material of the invention.
  • the coating material of the invention is used as a filler, topcoat or basecoat, it contains coloring and / or effect pigments in customary and known amounts.
  • the pigments can consist of inorganic or organic compounds and can give effects and / or color. Because of this large number of suitable pigments, the coating material according to the invention therefore ensures a universal range of use for the coating materials and enables the realization of a large number of color tones and optical effects.
  • Metal pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE-A-36 36 183, and commercially available stainless steel bronzes as well as non-metallic effect pigments such as pearlescent or interference pigments can be used as effect pigments.
  • Non-metallic effect pigments such as pearlescent or interference pigments.
  • Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998 pages 176, "Effect Pigments” and pages 380 and 381 "Metal Oxide Mica Pigments" to "Metal Pigments”.
  • suitable inorganic color pigments are titanium dioxide, iron oxides, Sicotrans yellow and carbon black.
  • suitable organic coloring pigments are thioindigo pigments indanthrene blue, cromophthal red, irgazin orange and heliogen green.
  • the coating material of the invention in particular as a filler, can contain organic and inorganic fillers in customary and known, effective amounts.
  • suitable fillers are chalk, calcium sulfate, barium sulfate, silicates such as talc or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour.
  • suitable fillers are chalk, calcium sulfate, barium sulfate, silicates such as talc or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour.
  • additives can also be incorporated into the coating materials using pigment pastes.
  • the resins according to the invention described above come into consideration.
  • oligomeric and polymeric binders such as thermally curable linear and / or branched and / or block-like, comb-like and / or randomly structured poly (meth) acrylates or acrylate copolymers, polyesters, alkyds, polyurethanes, acrylated hydroxyl groups Polyurethanes, acrylated polyesters, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters or polyureas;
  • thermally curable reactive diluents such as positionally isomeric diethyloctanediols or hydroxyl group-containing hyperbranched compounds or dendrimers;
  • crosslinking agents such as compounds or resins containing anhydride groups, compounds containing epoxy groups or
  • Resins tris (alkoxycarbonylamino) triazines, compounds or resins containing carbonate groups, blocked and / or unblocked polyisocyanates, beta-hydroxyalkylamides and compounds with on average at least two groups capable of transesterification, for example reaction products of malonic acid diesters and
  • UV absorbers
  • Azo compounds or CC-cleaving initiators such as dialkyl peroxides, Peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers;
  • Crosslinking catalysts such as dibutyltin dilaurate, lithium decanoate or zinc octoate;
  • Venting agents such as diazadicycloundecane
  • Emulsifiers especially non-ionic emulsifiers such as alkoxylated
  • Alkanols and polyols, phenols and alkylphenols or anionic emulsifiers such as alkali salts or ammonium salts of alkane carboxylic acids, alkanesulfonic acids, and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols;
  • wetting agents such as siloxanes, fluorine-containing compounds,
  • film-forming aids such as cellulose derivatives; transparent fillers based on silicon dioxide, aluminum oxide or zirconium oxide;
  • Sag control agents such as ureas, modified ureas and / or silicas, as described, for example, in references EP-A-192 304, DE-A-23 59 923, DE-A-18 05 693, WO 94/22968, DE-C -27 51 761, WO 97/12945 or "färbe + lack", 11/1992, pages 829 ff.
  • rheology-controlling additives such as those known from the patent specifications WO 94/22968, EP-A-0 276 501, EP-A-0 249 201 or WO 97/12945; crosslinked polymeric microparticles, such as are disclosed, for example, in EP-A-0 008 127; inorganic layered silicates such as aluminum-magnesium silicates, sodium-magnesium and
  • Montmorillonite type Silicas such as aerosils; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, styrene-maleic anhydride or
  • Matting agents such as magnesium stearate.
  • paint additives are described in the textbook “Paint Additives” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998. These additives are added to the coating materials of the invention in customary and known, effective amounts which, depending on the additive, range from 0.001 to 500 parts by weight per 100 parts by weight of the resin and crosslinking agent according to the invention.
  • the coating material of the invention has no special features, but is carried out in a customary and known manner by mixing the constituents described above in suitable mixing units, such as stirred kettles, dissolvers or extruders, using the processes suitable for the production of the respective coating materials.
  • the coating material of the invention is used to produce the coatings of the invention, in particular multilayer coatings ML, on primed or unprimed substrates.
  • Suitable substrates are all surfaces to be painted, which are not damaged by curing the paintwork thereon using heat; these are e.g. B. the moldings, foils and fibers of the invention, metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers. Glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, as well as composites of these materials. Accordingly, the painting according to the invention is also for applications outside of automotive painting, in particular
  • Suitable for automotive painting It is particularly suitable for the varnishing of furniture and industrial varnishing, including coil coating, container coating and the impregnation or coating of electrical components.
  • industrial painting it is suitable for painting practically all parts for private or industrial use such as radiators, household appliances, small parts made of metal such as screws and nuts, hubcaps, rims, packaging or electrical components such as motor windings or transformer windings.
  • primers can be used which are produced in a customary and known manner from electrocoat materials (ETL). Both anodic (ATL) and cathodic (KTL) electrodeposition coatings, but especially KTL, come into consideration for this.
  • primed or non-primed plastics such as. B. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DIN 7728T1) can be painted.
  • the plastics to be painted can of course also be polymer blends, modified plastics or fiber-reinforced plastics.
  • the plastics typically used in vehicle construction, in particular motor vehicle construction, can also be used.
  • non-functionalized and / or non-polar substrate surfaces these can be subjected to a pretreatment, such as with a plasma or with flame treatment, or provided with a hydro primer in a known manner before the coating.
  • the multilayer coatings ML according to the invention can be produced in different ways.
  • the process according to the invention comprises the following process steps:
  • Another preferred variant of the method according to the invention comprises the method steps:
  • a third preferred variant of the method according to the invention comprises the method steps:
  • the clearcoats can also be covered with a clearcoat according to the invention.
  • customary and known clearcoats are generally used in the wet-on-wet process.
  • the scratch resistance of the multilayer coating ML according to the invention is significantly improved by overlaying the resulting conventional and known clearcoats with the clearcoat of the invention.
  • the third variant is particularly preferred for automotive series painting.
  • the multilayer coatings ML according to the invention can have a different structure.
  • the third preferred variant is used in particular in the case of plastic painting.
  • the clearcoats of the multilayer coatings ML described above can additionally be coated with a clearcoat according to the invention.
  • the coating material of the invention can be applied by all customary application methods, such as, for example, spraying, knife coating, brushing, pouring, dipping, soaking, trickling or rolling.
  • the substrate to be coated can rest as such, with the application device or system being moved.
  • the substrate to be coated, in particular a coil can also be moved, the application system being stationary relative to the substrate or being moved in a suitable manner.
  • Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as, for example, hot air - hot spraying.
  • the applications can be used at temperatures of max. 70 to 80.degree. C. are carried out so that suitable application viscosities are achieved without the change in or damage to the coating material and its overspray, which may have to be reprocessed, occurring under the briefly acting thermal load.
  • hot spraying can be designed in such a way that the coating material is heated only very briefly in or shortly before the spray nozzle.
  • the spray booth used for the application can be operated, for example, with a circulation that can be tempered, if necessary, which is equipped with a suitable absorption medium for the overspray, e.g. B. the coating material itself is operated.
  • the filler coat, top coat, basecoat and clear coat are applied in a wet coat thickness so that after curing, layers with the necessary and advantageous layer thicknesses for their functions result.
  • this layer thickness is 10 to 150, preferably 15 to 120, particularly preferably 20 to 100 and in particular 25 to 90 ⁇ m
  • in the case of the topcoat it is 5 to 90, preferably 10 to 80, particularly preferably 15 to 60 and especially 20 to 50 ⁇ m
  • the clearcoats it is 10 to 100, preferably 15 to 80, particularly preferably 20 to 70 and in particular 25 to 60 ⁇ m.
  • the filler coat, top coat, basecoat and or clear coat is or are thermally cured when they are made from the coating materials of the invention. According to the invention, it is advantageous not to harden the basecoat film, or only partially, before applying the clearcoat film, in order to subsequently harden it together with the clearcoat film (wet-on-wet process).
  • the hardening can take place after a certain rest period. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 30 min.
  • the rest period is used, for example, for the course and degassing of the paint layers or for the evaporation of volatile components such as solvents.
  • the rest period can be supported and / or shortened by using elevated temperatures of up to 80 ° C, provided that there is no damage or changes to the lacquer layers, such as premature complete crosslinking.
  • the thermal hardening has no special features in terms of method, but takes place according to the customary and known methods such as heating in a forced air oven or irradiation with IR lamps.
  • the thermal hardening can also be carried out in stages.
  • the thermal curing is advantageously carried out at a temperature of 50 to 100 ° C., particularly preferably 80 to 100 ° C. and in particular 90 to 100 ° C. for a time of 1 minute to 2 hours, particularly preferably 2 minutes to 1 hour and in particular 3 min to 30 min.
  • thermal crosslinking can also be carried out at temperatures above 100 ° C become. In general, it is advisable not to exceed temperatures of 180 ° C., preferably 160 ° C. and in particular 140 ° C.
  • the clearcoats of the invention have an excellent profile of properties, in particular a high gloss, a high acid resistance, a high chemical resistance, a high scratch resistance and a very good flow. When used as additional clearcoats, they adhere well to the clearcoats underneath, so that in many cases they do not have to be sanded before the coating materials of the invention are applied. Another particular advantage is that it shows excellent reflow behavior even at comparatively low temperatures.
  • the multilayer coatings ML according to the invention also have an excellent property profile which is very well balanced with regard to the mechanics, optics, corrosion resistance and adhesion.
  • the multilayer coatings ML according to the invention have the high optical quality and interlayer adhesion required by the market and pose no problems such as insufficient condensation resistance of the filler layers, cracking (mud cracking) in the basecoat rails or flow defects or surface structures in the clearcoats.
  • the multilayer coating ML according to the invention has an excellent metallic effect, an excellent D.O.I. (distinctiveness of the reflected image) and excellent surface smoothness. It is weather-resistant, resistant to chemicals and bird droppings and scratch-resistant and shows very good reflow behavior.
  • Another significant advantage is the very good paintability of the multilayer paint coating ML according to the invention, even without sanding. Thereby it can easily be coated with customary and known highly scratch-resistant coating materials based on organically modified ceramic materials.
  • the substrates according to the invention also have particular advantages, such as a longer service life, a better aesthetic impression on the viewer and better technological usability, which makes them particularly attractive economically.
  • the resulting resin solution was successively mixed with 500 parts by weight of water, 400 parts by weight of ethanol and 500 parts by weight of pentyl acetate, to dissolve the precipitated ammonium chloride and cause phase separation.
  • the resulting mixture was stirred at room temperature for one hour and then left to phase separate. After phase separation, the aqueous phase was separated and the organic phase was dried with sodium chloride.
  • the NMR analysis showed that more than 80% of the chloroformate groups had been converted to carbamate groups.
  • the resulting solution of the polyacrylate resin according to the invention had a solids content of 68.6% by weight (forced air oven; one hour; 130 ° C.), a viscosity of 8.4 dPas (original) and a viscosity of 5.6 dPas in 65% Resolving in solvent naphtha.
  • the clear lacquer according to the invention was prepared by mixing 222 parts by weight of the solution of the polyacrylate resin according to the invention from preparation example 3,
  • Resimene®747 commercially available methyl etherified
  • Tinuvin® 123 commercially available HALS product from Ciba Specialty Chemicals
  • Nacure® 5225 more commercially available
  • butyl diglycol Parts by weight of butyl diglycol are produced. It showed a viscosity of 24 Seconds in the discharge cup according to DIN4 to a solids content of 74% (convection oven; one hour; 130 ° C).
  • test panels were produced as follows:
  • a commercially available filler from BASF Coatings AG was first applied and baked onto a steel pistol coated with a commercially available electrocoat (electrocoat with a layer thickness of 18-22 ⁇ m). The result was a filler layer with a layer thickness of 35 to 40 ⁇ m.
  • a commercial black uni base coat from BASF Coatings AG was then applied in the same way to the filler and predried at 80 ° C. for 10 minutes. After the panels had been cooled, a layer of the clearcoat material of the invention was applied with a pneumatic spray gun and predried for 10 minutes at 50 ° C. and then crosslinked together with the basecoat material at 130 ° C. for 25 minutes. The result was a basecoat layer with a thickness of 15 ⁇ m and a clear lacquer layer with a thickness of 40 ⁇ m.
  • the black uni base coat was chosen because the best way to observe the formation of scratches on the corresponding test panels.
  • the multilayer painting line ML according to the invention had an excellent overall optical impression.
  • the gloss measured according to DIN 67530 with a reflectometer from BYK reflectometrically at an angle of 20 ° was 93.3.
  • the scratch resistance of the multilayer paint coating ML according to the invention was determined with the aid of the brush test.
  • test panels were stored at room temperature for 2 weeks after application of the paints before the test was carried out.
  • the scratch resistance of the sol-gel coating on the test panels was determined using the BASF described in FIG. 2 on page 28 of the article by P. Betz and A. Bartelt, Progress in Organic Coatings, 22 (1993), pages 27-37 -Brush tests, which were modified with regard to the weight used (2000 g instead of the 280 g mentioned there), were assessed as follows:
  • the paint surface was damaged with a sieve fabric that was loaded with a mass.
  • the screen fabric and the varnish surface were wetted liberally with a detergent solution.
  • the test panel was moved back and forth under the screen fabric in a lifting motion by means of a motor drive.
  • test specimen was eraser covered with nylon sieve mesh (No. 11, 31 ⁇ m mesh size, Tg 50 ° C.) (4.5 ⁇ 2.0 cm, wide side perpendicular to the direction of scratching).
  • the weight is 2000 g.
  • the gloss decreased to 87.2 in accordance with DIN 67530. After two hours of regeneration at 60 ° C, it had risen to 89 again. This demonstrated, on the one hand, the very good scratch resistance of the clearcoat according to the invention and, on the other hand, its good reflow behavior. In addition, the scratch resistance of the multilayer paint coating ML according to the invention was determined using the sand test.
  • the lacquer surfaces were loaded with sand (20g quartz-silver sand 1.5-2.0 mm).
  • the sand was placed in a beaker (floor cut off flat), which was firmly attached to the test panel.
  • the same test panels as described above in the brush test were used.
  • the table with the cup and the sand was shaken by means of a motor drive.
  • the movement of the loose sand caused damage to the paint surface (100 double strokes in 20 s).
  • the test area was cleaned of abrasion, carefully wiped under a cold water jet and then dried with compressed air.
  • the gloss was measured according to DIN 67530 before and after damage.
  • the chemical resistance was determined according to BART.
  • the BART (BASF ACID RESISTANCE TEST) was used to determine the resistance of paint surfaces to acids, alkalis and water drops.
  • the coating was exposed to a further temperature load on a gradient oven after baking (30 min 40 ° C, 50 ° C, 60 ° C and 70 ° C).
  • VE fully desalinated
  • Each individual marking range (spot) was evaluated and the result for each coating was recorded in a suitable form (e.g. sums of notes for a temperature).
  • Test substance 40 ° C 50 ° C 60 ° C 70 ° C
  • the BART underpins the extraordinary acid resistance of the multilayer paint coat ML according to the invention or the clear lacquer according to the invention.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne des résines contenant des groupes carbamate en position latérale et/ou terminale, pouvant être produites selon un procédé consistant à faire réagir une résine contenant au moins un groupe hydroxyle avec du phosgène pour former une résine contenant au moins un groupe chloroformiate, puis à faire réagir la résine ainsi obtenue avec de l'ammoniac, des amines primaires ou des amines secondaires. L'invention concerne également l'utilisation de ces résines pour la production de matières moulables, adhésifs et agents de revêtement, notamment peintures et vernis.
EP00958513A 1999-09-25 2000-08-30 Resines contenant des groupes carbamate, leur procede de production et leur utilisation Withdrawn EP1218421A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1999146048 DE19946048A1 (de) 1999-09-25 1999-09-25 Carbamatgruppen enthaltende Harze, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19946048 1999-09-25
PCT/EP2000/008428 WO2001023439A1 (fr) 1999-09-25 2000-08-30 Resines contenant des groupes carbamate, leur procede de production et leur utilisation

Publications (1)

Publication Number Publication Date
EP1218421A1 true EP1218421A1 (fr) 2002-07-03

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EP00958513A Withdrawn EP1218421A1 (fr) 1999-09-25 2000-08-30 Resines contenant des groupes carbamate, leur procede de production et leur utilisation

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Country Link
EP (1) EP1218421A1 (fr)
JP (1) JP2003510423A (fr)
BR (1) BR0014517A (fr)
DE (1) DE19946048A1 (fr)
WO (1) WO2001023439A1 (fr)

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Publication number Priority date Publication date Assignee Title
US6504028B2 (en) * 2000-07-11 2003-01-07 The Procter & Gamble Co. Process for preparing benzoxazin-4-one polymer conjugates
DE10118532B4 (de) * 2001-04-14 2006-10-26 Basf Coatings Ag Carbamat- und/oder Allophanatgruppen enthaltende, thermisch härtbare, thixotrope Gemische sowie das Verfahren zur Herstellung und die Verwendung derselben
US7807743B2 (en) * 2006-09-22 2010-10-05 Basf Corporation Coating composition and film system therefrom
CN110684176B (zh) * 2019-10-17 2023-01-03 嘉宝莉化工集团股份有限公司 聚酯改性环氧丙烯酸酯树脂及其制备方法和应用
CN111659848A (zh) * 2020-06-17 2020-09-15 丹阳市丹水铸造新材有限公司 一种环保覆膜砂的制备方法

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Publication number Priority date Publication date Assignee Title
DE1595645A1 (de) * 1966-06-18 1970-08-20 Hoechst Ag Verfahren zur Carboxychlorierung von Polyolefinen
GB1131010A (en) * 1966-06-23 1968-10-16 Raychem Corp Crosslinked polymers
US5192335A (en) * 1992-03-20 1993-03-09 Chevron Research And Technology Company Fuel additive compositions containing poly(oxyalkylene) amines and polyalkyl hydroxyaromatics
US5356669A (en) * 1992-10-23 1994-10-18 Basf Corporation Composite color-plus-clear coating utilizing carbamate-functional polymer composition in the clearcoat
BR9307434A (pt) * 1992-10-30 1999-06-01 Ppg Industries Inc Composição formadora de película carável

Non-Patent Citations (1)

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Title
See references of WO0123439A1 *

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DE19946048A1 (de) 2004-03-18
JP2003510423A (ja) 2003-03-18
BR0014517A (pt) 2002-06-25
WO2001023439A1 (fr) 2001-04-05

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