DE19946048A1 - Resins containing carbamate groups, process for their preparation and their use - Google Patents

Abstract

Resins containing pendant and / or terminal carbamate groups can be prepared by reacting a resin containing at least one hydroxyl group with phosgene to give a resin containing at least one chloroformate group, after which this resin is reacted with ammonia, primary amines or secondary amines; as well as their use for the production of molding compositions, adhesives and coating materials, in particular paints.

Description

The present invention relates to new oligomers and polymers, the pendant and / or terminal carbamate groups contain. Moreover The present invention relates to the use of the new oligomers and polymers for the production of molding compounds, adhesives and coating materials, in particular paints, as well as their secondary products, i.e. the molded parts, Films, fibers, adhesive layers and coatings, in particular paintwork.

From the patents US-A-5,474,811, US-A-5,356,669, US-A-5,605,965, WO 94/10211, WO 94/10212, WO 94/10213, EP-A-0 594 068, EP-A-0 594 071 or EP-A-0 594 142, coating materials are known 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: -O- (CO) -NH ₂ and at least one 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 using strong protic acids, in particular sulfonic acids, which are generally blocked with amines, as catalysts.

The introduction of the lateral and / or terminal Carbamate groups can be created by the incorporation of monomers Groups included. Examples of suitable monomers of these Kinds are ethylenically unsaturated Monomers containing a carbamate group.

Examples of suitable ethylenic unsaturated Monomers containing carbamate groups are described in the patents US-A-3,479,328, US-A-3,674,838, US-A-4,126,747, US-A-4,279,833 or US-A-4,340,497 described.

The introduction of the carbamate group can but can also be introduced into resins by polymer-analogous reactions. Examples of suitable methods of this type are from the patents US-A-4,758,632, US-A-4,301,257 or US-A-2,979,514. Examples for such polymer-analogous reactions are the conversion of hydroxyl groups 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.

These known manufacturing processes have disadvantages such as the comparatively complex Synthesis of starting compounds such as those containing carbamate groups Monomers or aryl or alkyl urethanes, or the required ones Reaction temperatures are u. U. too high as in the implementation Resins containing hydroxyl groups with urea so that discoloration or even damage the products enter. Frequently have to for the polymer-analogous reactions, catalysts are also used, that remain in the product and impair its application properties. So there is a risk that coating materials, the resins based on catalyst residues have been providing coatings that have reduced weathering resistance and condensation resistance exhibit.

Precisely because of the excellent application technology Characteristics of the lateral and / or terminal Resins containing carbamate groups and those produced therewith However, coating materials, molding compounds and adhesives exist urgent need for a new manufacturing process that is simple Way new side-by-side and / or terminal Resins containing carbamate groups provides the disadvantages of State of the art no longer exhibit. The process is said to be comparatively low Temperatures feasible be and get along without catalysts, so that in the new pendant and / or terminal Resins containing carbamate groups have no catalyst residues negatively influence the application properties of the resins could there are more.

Accordingly, the new side-by-side and / or terminal Resin containing carbamate groups, which can be prepared, by using a resin containing at least one hydroxyl group with phosgene converted to a resin containing at least one chloroformate group, after which this resin with ammonia, primary amines or secondary amines implements.

In the following the new side-by-side and / or terminal Resin containing carbamate group for the sake of being shorter than “resin according to the invention” designated.

• (I) polymeranaloge Umsetzung Hydroxylgruppen enthaltender Harze mit Phosgen, wodurch Chlorformiatgruppen enthaltende Harze resultieren, und
• (II) polymeranaloge Umsetzung der Chlorformiatgruppen enthaltenden Harze mit Ammoniak und/oder primären und/oder sekundären Aminen

gefunden, das im folgenden als „erfindungsgemäßes Verfahren" bezeichnet wird.In addition, the new process for the production of the resin according to the invention was carried out

• (I) polymer-analogous reaction of hydroxyl-containing resins with phosgene, resulting in resins containing chloroformate groups, and
• (II) polymer-analogous reaction of the chloroformate-containing resins with ammonia and / or pri mares and / or secondary amines

found, which is referred to below as the "inventive method".

In addition, the new molding compounds, Adhesives and coatings found at least one Oligomer according to the invention and / or contain polymer. In the following, these new molding compounds, Adhesives and coating materials as “molding compositions according to the invention, Adhesives and coating materials ".

Furthermore, new molded parts, Films and fibers found from the molding compositions of the invention are producible. In the following, they are called “molded parts according to the invention, Films and fibers ".

New adhesive layers were also found, from the adhesives of the invention can be produced and are hereinafter referred to as “adhesive layers according to the invention” be designated.

Last but not least, new coatings found that can be produced from the coating materials of the invention and in the following as "coatings according to the invention" be designated.

In addition, new substrates found the at least one adhesive layer according to the invention and / or at least a coating according to the invention have and in the following as "substrates according to the invention" be designated.

According to the invention for the production of the resins according to the invention Resins containing hydroxyl groups are used.

Examples of suitable hydroxyl groups Resins containing are statistical, alternating and / or block-like constructed linear and / or branched and / or comb-like (Co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or polycondensation resins. These terms are supplemented by Rompp Lexicon Varnishes and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, Page 457, »Polyaddition« and »Polyaddition Resins (Polyadducts) " and pages 463 and 464, "Polycondensates", "Polycondensation" and "Polycondensation Resins".

Examples of very suitable (co) polymers are poly (meth) acrylates and partially saponified polyvinyl esters.

Examples of suitable polyaddition resins and / or polycondensation resins are polyesters, alkyds, polyurethanes, Polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, Polyamides or polyimides.

The hydroxyl groups to be used according to the invention Resins containing are oligomers and polymers. As part of the present Invention are understood as oligomeric resins that at least Contain 2 to 15 recurring monomer units in their molecule. In the context of the present invention, polymers are resins understood the at least 10 recurring monomer units in their molecule contain. additional becomes these terms on Römpp Lexicon of lacquers and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Oligomers", page 425.

The hydroxyl groups to be used according to the invention Resins containing contain primary and / or secondary hydroxyl groups. It is a very significant advantage of the method and the resins according to the invention, that both Types of hydroxyl groups can be used. This enables the reactivity the resins of the invention via steric Control effects in a targeted manner.

The OH number of those to be used according to the invention Resins containing hydroxyl groups can vary widely depends primarily on the intended use of the resins according to the invention. Become these, for example, as binders in the coating materials of the invention and adhesives, it is recommended for reasons of one high crosslinking density in the coatings and adhesive layers according to the invention Use resins with a high OH number. Thus, the expert can for the appropriate OH number based on its intended use Expertise if necessary with the help of location tests to investigate. The OH number is preferably from 10 to 500, preferably 20 to 400 and especially 30 to 350 mg KOH / g.

Of those described above Resins containing hydroxyl groups are the poly (meth) acrylates, the polyesters and the polyurethanes are preferably used. Special Advantages result from the use of the poly (meth) acrylates (below in summary as "polyacrylate resins" designated), which is why they are particularly preferred for the production of the resins according to the invention be used.

Particularly suitable polyacrylate resins are obtained by the copolymerization of those described below olefinically unsaturated Monomers (a), at least one of which has at least one hydroxyl group contains and essentially free of acid groups is.

Examples of suitable hydroxyl group-containing monomers (a1) 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 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-hydro xypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate or crotonate; 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indene-dimethanol or methyl propanediol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate; or reaction products from cyclic esters, such as, for example, epsilon-caprolactone and these hydroxyalkyl esters; or olefinically unsaturated alcohols such as allyl alcohol or polyols such as trmethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or trallyl ether. These higher-functional monomers (a1) are generally used only in minor amounts. In the context of the present invention, minor amounts of higher-functional monomers are understood to mean those amounts which do not lead to crosslinking or gelling of the polyacrylate resins. For example, the proportion of trimethylolpropane monoallyl ether can be 2 to 10% by weight, based on the total weight of the monomers (a1) to (a6) used to prepare the polyacrylate resin. In addition, however, it is also possible to add 2 to 10% by weight, based on the total weight of the monomers (a) used to prepare the polyacrylate resin, to methylmethylpropane monoallyl ether to the finished polyacrylate resin. Although the olefinically unsaturated polyols (a1) can be used as the sole monomers (a1), it is advantageous according to the invention to use them in combination with other monomers (a1). Furthermore, 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).

Examples of suitable other monomers (a) are:

Monomers (a2)

(Meth) acrylic acid alkyl or cycloalkyl esters with up to 20 carbon atoms in the alkyl radical, especially methyl, Ethyl, propyl, n-butyl, sec.-butyl, tert.-butyl, hexyl, ethylhexyl, Stearyl and lauryl acrylate or methacrylate; cycloaliphatic (Meth) acrylate, especially cyclohexyl-, isobornyl-, dicyclopentadienyl-, octahydro-4,7-methano-1H-inden-methanol- or tert-butylcyclohexyl (meth) acrylate; (Meth) Acrylsäureoxaalkylester or oxacycloalkyl esters such as ethyl triglycol (meth) acrylate and methoxy oligoglycol (meth) acrylate with a molecular weight Mn of preferably 550; or others ethoxylated and / or propoxylated hydroxyl-free (meth) acrylic acid derivatives. these can in minor quantities more functional (Meth) acrylic 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. In the context of the present invention are here under minor amounts of higher functional Monomers (a2) understand such amounts that are not used for crosslinking or gelation of the polyacrylate resins.

Monomers (a3)

At least one acid group, preferably one Carboxyl group, per molecule bearing ethylenically unsaturated Monomer or a mixture of such monomers. As component (a3) acrylic acid and / or methacrylic acid are particularly preferably used. It can but also other ethylenically unsaturated carboxylic acids up to 6 carbon atoms in the molecule be used. examples for such acids are ethacrylic acid, crotonic, maleic acid, fumaric acid and itaconic acid. Can continue ethylenically unsaturated Sulfonic or phosphonic acids, or their partial esters can be used as component (a3). As Monomers (a3) are furthermore maleic acid mono (meth) acryloyloxyethyl ester, Succinic acid mono (meth) acryloyloxyethyl and phthalic acid mono (meth) acryloyloxyethyl ester into consideration.

Monomers (a4)

Vinyl ester from in alpha position branched monocarboxylic acids with 5 to 18 carbon atoms in the molecule. The branched monocarboxylic acids can are obtained by reacting formic acid or carbon monoxide and Water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can Cracked products of paraffinic hydrocarbons, such as mineral oil fractions, be and can both branched and straight-chain acyclic and / or cycloaliphatic Contain olefins. When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is created which the carboxyl groups predominantly on a quaternary carbon atom sit. Other olefinic starting materials are e.g. propylene trimer, Propylene tetramer and diisobutylene. The vinyl esters can can also be prepared from the acids in a manner known per se, e.g. by looking at the acid can react with acetylene. Especially be preferred - because of of good availability - vinyl ester of saturated aliphatic monocarboxylic acids with 9 to 11 carbon atoms which are branched on the alpha carbon atom.

Monomers (a5)

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 take place 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. In addition, reference is made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 605 and 606.

Monomers (a6)

s essentially free of acid groups ethylenically unsaturated Monomers like

• - olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, Cyclopentene, norbounen, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene;
• - (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N-butyl, N, N-dibutyl, N-cyclohexyl and / or N, N-cyclohexyl-methyl- (meth) acrylic acid amide;
• - epoxy groups containing monomers such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid;
• - vinyl aromatic Hydrocarbons, such as styrene, alpha-alkyl styrenes, in particular alpha-methylstyrene, arylstyrenes, especially diphenylethylene, and / or vinyltoluene;
• - Nitrtle such as acrylonitrile and / or methacrylonitrile;
• - Vinyl compounds such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride; N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinyl cyclohexyl ether; Vinyl esters such as vinyl acetate, vinyl propioriate, vinyl butyrate, vinyl pivalate, vinyl esters of Versatic ^® acids, which are sold by Deutsche Shell Chemie under the brand name VeoVa ^® (in addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598 and pages 605 and 606, referenced) and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid; and or
• - polysiloxane macromonomers, which have a number average molecular weight Mn of 1,000 to 40,000, preferably from 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferred 0.5 to 1.5, ethylenically unsaturated Double bonds per molecule have, as in DE-A-38 07 571 on pages 5 to 7, DE-A 37 06 095 in columns 3 to 7, EP-B-0 358 153 pages 3 to 6, in US Pat. No. 4,754,014 in columns 5 to 9, in DE-A 44 21 823 or in the international patent application WO 92/22615 on page 12, line 18, to page 18, line 10 are, or acryloxysilane-containing vinyl monomers by reaction of hydroxy-functional silanes with epichlorohydrin and followed by Implementation of the reaction product with methacrylic acid and / or hydroxyalkyl esters the (meth) acrylic acid.

According to the invention, it is very special Advantage of selecting the monomers (a) in such a way that hydroxyl-containing polyacrylate resins result, which preferably has an OH number of 100 to 250, preferably 130 to 210, preferably acid numbers from 0 to 80, preferably 0 to 50, very particularly preferably 0 to 15, preferably glass transition temperatures Tg of -2u5 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 preferred 1,500 to 5,000 (determined by gel permeation chromatography with Have polystyrene as internal standard).

Tg = Glasübergangstemperatur des Polyacrylatharzes
W_n = Gewichtsanteil des n-ten Monomers
Tg_n = Glasübergangstemperatur des Homopolymers aus dem n-ten Monomer
x = Anzahl der verschiedenen MonomerenThe glass transition temperature Tg of the polyacrylate resins is determined by the type and amount of the monomers (a1) and, if appropriate, (a2), (a3), (a4), (a5) and / or (a6). The selection of the monomers can be carried out by a person skilled in the art with the aid of the following Fox formula, with which the glass transition temperatures Tg of (co) polymers, in particular polyacrylate resins, can be approximately calculated:

Tg = glass transition temperature of the polyacrylate resin
W _n = weight fraction of the nth monomer
Tg _n = glass transition temperature of the homopolymer from the nth monomer
x = number of different monomers

Methodologically speaking, the manufacturing process those to be used according to the invention Polyacrylate resins containing hydroxyl groups have no special features on, but takes place according to the usual and known methods of radical polymerization in the presence at least one polymerization initiator.

Examples of suitable polymerization initiators are free radical initiators, e.g. tert-butyl peroxyethylhexanoate, Benzoyl peroxide, di-tert-amyl peroxide, azobisisobutyronitrile and called tert-butyl perbenzoate. The initiators are preferred in an amount of 1 to 25 wt .-%, particularly preferably from 2 to 10 wt .-%, based on the total weight of the monomers used.

The polymerization is convenient at a temperature of 80 to 200 ° C, preferably 110 to 180 ° C, carried out.

Preferred solvents organic solvents used that opposite Phasgene are inert, especially mixtures of aromatic hydrocarbons.

The polyacrylate resin can after a Two-step process or a one-step process can be produced.

In the two-step process

1. a mixture of the monomers (a1) and optionally (a2), (a4), (a5) and / or (a6) or a mixture from parts of the monomers (a1) and optionally (a2), (a4), (a5) and / or (a6) is polymerized in an organic solvent and

2. after at least 60 wt .-% of consisting of (a1) and optionally (a2), (a4) (a5) and / or (a6) Mixture have been added, the monomer (a3) and the optionally present remainder of the monomers (a1) and optionally (a2), (a4), (a5) and / or (a6) added and further polymerized.

In addition, it is also possible that Monomers (a4) and / or (a5) together with at least part of the solvent to submit and meter in the remaining monomers. You can also the monomers (a4) and / or (a5) only partially together with at least part of the solvent be given in the template and the rest of these monomers, such as described above can be added. For example, are preferred at least 20% by weight of the solvent and about 10 wt .-% of the monomers (a4) and (a5) and optionally Parts of the monomers (a1) and (a6) submitted.

It is preferred that with the Initiator feed for some time, generally approx. 1 to 15 minutes, before the monomers are fed in. It is also a procedure preferred, in which the initiator addition at the same time as the addition of the monomers started and about half an hour after the addition of the monomers has ended, is ended. The initiator is preferably added in a constant amount per unit of time. After the initiator addition has ended, the reaction mixture is still so long (usually 1.5 hours) at the polymerization temperature held until all of the monomers used are essentially fully implemented have been. "In the essentially complete implemented "is intended to mean that preferably 100 wt .-% of the monomers used have been implemented, but that it also possible is that a low residual monomer content of at most up to about 0.5% by weight, based on the weight of the reaction mixture, remain unreacted can.

The monomers are preferred for Production of the polyacrylate resins in the case of a not too high polymerization solid, preferred in the case of a polymerization solid from 80 to 50% by weight, based on the monomers, polymerized and subsequently for the Reaction with phosgene with organic solvents, which are against phosgene are inert, diluted, to stir them well close.

The production also has apparatus those to be used according to the invention Polyacrylate resins have no special methodological features, but is carried out using the methods which are customary and known in the plastics field continuous or discontinuous copolymerization under Normal pressure or overpressure in stirred tanks, Autoclaves, tubular reactors or Taylor reactors.

Examples of suitable copolymerization processes are described in the patents DE-A-197 09 465, DE-C-197 09 476, DE-A-28 48 906, DE-A-195 24 182, EP-A-O 554 783, WO 95/27742 or WO 82/02387.

The hydroxyl groups described above Resins containing, in particular the polyacrylate resins, according to the invention are in solution with Phosgene to the resins containing at least one chloroformate group implemented.

Methodologically speaking, the manufacturing process the resins containing chloroformate groups have no peculiarities on but takes place according to the usual and known methods of phosgene chemistry, the corresponding suitable equipment and the usual for the handling of phosgene Safety measures to be hit.

Depending on the reactivity of the hydroxyl groups, the reaction with phosgene is advantageously included Resins and / or the stirrability of the relevant solution of the resin at temperatures from -10 to 100, preferably 0 to 50 and in particular 10 to 40 ° C.

Although the chloroformate groups containing resins can be isolated as such, which is quite special cases can be an advantage, but in general it is recommended Resins in the solution, in which they occurred, with ammonia and / or primary and / or secondary Implement amines.

• (i) Substituierte und unsubstiuierte, kein oder mindestens ein Heteroatom in der Kette und/oder im Ring enthaltende, lineare oder verzweigte Alkane, Alkene, Cycloalkane, Cycloalkene, Alukylcycloalkane, Alkylcycloalkene, Alkenylcycloalkane oder Alkenylcycloalkene;
• (ii) substituierte und unsubstituierte Aromaten oder Heteroamaten; sowie
• (iii) Alkyl-, Alkenyl-, Cycloalkyl-, Cycloalkenyl-, Alkylcyloalkyl-, Alkylcycloalkenyl-, Alkenylcycloalkyl- oder Alkenylcycloalkenyl-substitiuierte Aromaten oder Heteroaromaten, deren Substituenten substituiert oder unsubstituiert sind und kein oder mindestens ein Heteroatom in ihrer Kette und/oder ihrem Ring enthalten;

und worin die Variable R¹ die vorstehend angegebene Bedeutung hat, ausgenommen ein Wasserstoffatom;
oder worin die Reste R, ausgenommen ein Wasserstoffatom, und R¹ cyclisch miteinander verknüpft sind.Examples of suitable primary and secondary amines are those of the general formula I. NHRR ¹ (I), where the variable R stands for a hydrogen atom or for a monovalent organic radical which is derived from the following compounds:

• (i) Substituted and unsubstituted linear or branched alkanes, alkenes, cycloalkanes, cycloalkenes, alucylcycloalkanes, alkylcycloalkenes, alkenylcycloalkanes or alkenylcycloalkenes containing no or at least one heteroatom in the chain and / or in the ring;
• (ii) substituted and unsubstituted aromatics or heteroamates; such as
• (iii) alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcyloalkyl, alkylcycloalkenyl, alkenylcycloalkyl or alkenylcycloalkenyl-substituted aromatics or heteroaromatics, their substituents are substituted or unsubstituted and no or at least one heteroatom in their chain and / or their Ring included;

and wherein the variable R ^{1 has} the meaning given above, except for a hydrogen atom;
or in which the radicals R, with the exception of a hydrogen atom, and R ^{1 are} cyclically linked to one another.

Examples of suitable heteroatoms are oxygen, nitrogen, boron, silicon, sulfur or phosphorus atoms.

Examples of suitable substitutes for the abovementioned radicals R ¹ are halogen atoms, in particular fluorine and chlorine atoms, nitro groups or nitrile groups.

Examples of suitable aromatics are Benzene and naphthalene.

Examples of suitable heteroaromatics are thiophene, pyridine or triazine.

Examples of suitable alkanes are those with 1 to 20 carbon atoms in the molecule such as methane, ethane, propane, butane, Isobutane, pentane, neopentane, hexane, heptane, octane, isooctane, nonane, Dodecan, Hexadecan or Eicosan.

Examples of suitable alkenes are Ethylene and propylene.

Examples of suitable cycloalkanes are cyclopentane and cyclohexane.

Examples of suitable cycloalkenes are cyclopentene and cyclohexene.

Examples of suitable alkylcycloalkanes are methylcyclopentane and methylcyclohexane.

Examples of suitable alkylcycloalkenes are methylcyclopentene and methylcyclohexene.

Examples of suitable alkenylcycloalkanes are allyl and vinyl cyclopentane and alkyl and vinyl cyclohexane.

Examples of suitable alkenylcycloalkenes are vinylcyclopentene and vinylcyclohexene.

Examples of suitable alkyl, alkenyl, Cycloalkyl, cycloalkenyl, alkylcyloalkyl, alkylcycloalkenyl, Alkenylcycloalkyl or alkenylcycloalkenyl substituents are methyl, Ethyl, propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, vinyl, Alkyl, cyclohexyl, cyclohexenyl, 4-methylcyclohexyl, 4-methylcyclohexenyl, 3-allylcyclohexenyl or 4-vinylcyclohexenyl.

The radicals R ^{1 are} preferably derived from organic compounds which are unsubstituted as such or whose substituents are unsubstituted.

These advantageously contain Compounds also do not have heteroatoms in their chains and / or in theirs Rings and / or in the chains and / or rings of their substitutes.

Particular advantages result if the radicals R and R ^{1 are derived} from linear alkanes which meet the advantageous conditions mentioned above. Further advantages result if they are derived from methane, ethane, propane, butane, pentane or hexane.

Examples of well suited primary amines I are methylamine, ethylamine, propylamine, isobutylamine, hexylamine, Cyclohexylamine, allylamine, cyclohexenylamine, aniline, cyclohexylmethylamine, (2-cyclohexyl) ethylamine or benzylamine.

By reacting with these primary amines I result in resins according to the invention with sideways and / or terminal secondary Carbamate.

Examples of 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.

By reacting with these secondary amines I result in resins according to the invention with sideways and / or terminal tertiary Carbamate.

Since resins according to the invention, the pendant and / or terminal primary carbamate groups contain, are particularly advantageous, ammonia is used according to the invention very particularly preferably.

From a methodological point of view, the implementation of ammonia and / or of amines I containing the chloroformate groups Resin does not have any peculiarities, but takes place according to the usual and known methods of organic chemistry and polymer chemistry. The one for this The devices and methods used depend primarily on this whether solid, liquid or gaseous Amines I or whether gaseous or solved Ammonia is or will be used. The expert can therefore in due to the appropriate methods and devices select his expertise.

The implementation of the chloroformate groups with ammonia or the amines I resulting ammonium chlorides in more usual and in a known manner from the reaction mixture containing the resins according to the invention separated. Examples of suitable methods are filtration or the extraction, using these methods in an appropriate manner can be combined.

Depending on the intended use, the resins according to the invention be isolated before use, or else the Solutions, in which they occur are used directly. Which variant preference is given primarily to the intended use. This is how you become for the use in molding compositions or adhesives the resins of the invention preferably isolate in substance, whereas they are used for use in coating materials, preferably in solution.

The inventive resins described above are great for the production of the molding compositions, adhesives and coating materials, especially paints.

For the production of the molding compositions according to the invention can be liquid and / or solid resins according to the invention used in the usual and in a known manner in the presence of suitable crosslinking agents, for example the crosslinking agents described below, by heating to thermosetting molded parts, films and Fibers can be processed. Meanwhile, solid resins according to the invention are advantageously used, which have thermoplastic properties so that they are in more common and in a known manner, for example by extrusion, followed by injection molding, film blowing or drawing fibers to the thermoplastic molded parts according to the invention, Films and fibers can be processed.

The thermoplastic and thermosetting according to the invention Molding compounds can further usual and known plastic additives in effective amounts.

The moldings, films and fibers according to the invention can be excellently with the adhesives of the invention glue and / or coat with the coating materials of the invention or paint.

For the production of adhesives according to the invention, which are used as contact adhesives serve, resins according to the invention are preferably used, which none contain the crosslinking agents described below and advantageously have thermoplastic properties.

For the production of adhesives according to the invention, which are used as reactive adhesives serve the liquid or solid resins according to the invention preferably with suitable crosslinking agents, for example the Crosslinking agents described below, mixed so that they are thermal hardened can be. Furthermore can the adhesives according to the invention the additives described below for the coating materials included, provided these are for use in adhesives.

With the help of the adhesives according to the invention the substrates described below, in particular the moldings according to the invention, Foils and fibers, glue in an excellent way.

Those are very particularly preferred resins according to the invention for the manufacture; of coating materials, in particular paints, used.

Contain the resins according to the invention still functional groups, especially hydroxyl groups with the carbamate groups at higher ones Resins, in particular 50 to 250 ° C., are the resins according to the invention as such or the coating materials according to the invention produced therewith self-crosslinking. If the resins according to the invention contain no such functional ones Groups, they usually become networked with the help of crosslinking agents. This is supplemented by the Römpp Lexikon Lacke und Druckfarben, Stuttgart, New York, 1998, "Hardening", pages 274 to 276.

External crosslinking coating materials according to the invention indicate the manageability and the numerous possibilities the variation of their property profile has special advantages on and are therefore very special according to the invention preferably used.

Both the self-networking as the externally crosslinking coating materials according to the invention can also be used as liquid Lacquers (100% systems), powder coatings, aqueous powder slurry coatings 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. Examples of suitable complementary functional groups are thio, amino, hydroxyl and / or methylol and / or methylol ether groups. From to these the methylol and methylol ether groups are particularly advantageous and are therefore used with particular preference in accordance with the invention.

In particular, aminoplast resins, for example melamine resins, guanamine resins or urea resins, usable as a crosslinking agent. Here, each can be used for transparent Topcoats or clearcoats suitable aminoplast resin or a mixture can be used from such amino resins. In addition, on Rompp Lexicon Varnishes and Printing Inks, Georg Thieme Verlag, 1998, page 29, "Aminoharze", and the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff, or on the book “Paints, Coatings and Solvents ", second completely revised edition, edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pp 80 ff., Referenced. The usual and known aminoplast resins also come into consideration, the methylol and / or methoxymethyl groups z. T. are defunctionalized by means of carbamate or allophanate groups. Crosslinking agents of this type are described in US-A-4 710 542 and EP-B-0 245 700 and in the article by B. Singh and Coworker "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry "in Advanced Organic Coatings Science and Technology Series, 1991, volume 13, pages 193 to 207.

In the coating materials of the invention can the content of resin according to the invention and crosslinking agents vary widely. Advantageously included the coating materials of the invention, in each case based on their respective solids content, 10 to 99, preferred 15 to 98, particularly preferably 20 to 97, very particularly preferred 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 at least one crosslinking agent.

The coating material of the invention can for the production of decorative and / or protective coatings, in particular Coatings such as transparent clearcoats, primers, in particular Stone chip protection primers and fillers, or color and / or effect Paints, especially top coats and basecoats, be used. You can the paintwork can be one or more layers.

For these uses the coating material of the invention generally customary paint Additives added in effective amounts. Type and amount of additives depend primarily on the intended use of the coating material of the invention. These additives are preferably under the processing and application conditions of the coating material of the invention nonvolatile.

Will the coating materials of the invention as a fountain pen, Used topcoat or basecoat, it contains color and / or effect Pigments in usual and known amounts. The pigments can be inorganic or organic compounds exist and can give effect and / or color his. The coating material of the invention guaranteed therefore a universal one due to the large number of suitable pigments Range of application of the coating materials and enables the realization of a Variety of shades and optical effects.

Metal flake pigments can be used as effect pigments like commercial ones Aluminum bronze, according to DE-A-36 36 183 chromated aluminum bronzes, and commercially available stainless steel bronzes as well as non-metallic effect pigments, such as pearlescent or interference pigments can be used. In addition, the Römpp Lexicon Varnishes and Printing Inks, Georg Thieme Verlag, 1998, pages 176, »Effect Pigments« and pages 380 and 381 "Metal oxide mica pigments" to "Metal pigments".

Examples of suitable inorganic coloring Pigments are titanium dioxide, iron oxides, Sicotrans yellow and soot. Examples for suitable organic coloring pigments are thioindigo pigments indanthrene blue, Cromophthal red, irgazine orange and heliogen green. In addition, the Römpp Lexicon Varnishes and printing inks, Georg Thieme Verlag, 1998, pages 180 and 181, "Iron Blue Pigments" to "Iron Oxide Black", pages 451 to 453 »Pigments« to »Pigment Volume Concentration«, page 563 »Thioindigo pigments and page 567 »Titanium dioxide pigments directed.

Furthermore, the coating material of the invention, especially as a fountain pen, organic and inorganic fillers in usual and contain known effective amounts. Examples of suitable ones 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. additional is on Römpp Lexicon of lacquers and printing inks, Georg Thieme Verlag, 1998, pages 250 ff., "Fillers".

These additives can also be added to the coating materials via pigment pastes can be incorporated, whereby as rubbing resins u.a. those described above resins according to the invention be considered.

These additives are eliminated if the coating materials according to the invention in their most preferred use as clear coats be used.

Examples of suitable additives which both in the clearcoats of the invention, fillers, Basecoats and topcoats may be present

• - Common and known oligomeric and polymeric binders such as thermally curable hydroxyl-containing linear and / or branched and / or block-like, comb-like and / or randomly constructed poly (meth) acrylates or acrylate copolymers, polyesters, alkyds, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (meth ) Acrylate diols, partially saponified polyvinyl esters or polyureas;
• - usual and known thermally curable reactive diluents such as positionally isomeric diethyloctanediols or hydroxyl groups hyperbranched compounds or dendrimers;
• - other Crosslinking agents such as compounds containing anhydride groups or Resins, compounds or resins containing epoxy groups, tris (alkoxycarbonylamino) trtazine, 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 diesters and polyisocyanates or of esters and partial esters of polyhydric alcohols malonic acid with monoisocyanates, as described in European patent EP-A-0 596 460 will be described;
• - low boiling and / or high-boiling organic solvents ("hinge solvents");
• - UV absorber;
• - light stabilizers such as HALS compounds, benzotrtazoles or oxalanilides;
• - radical scavenger;
• - thermolabile radical initiators such as organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, Peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers;
• - catalysts for the Crosslinking such as dibutyltin dilaurate, lithium decanoate or zinc octoate;
• - venting agents, such as diazadicycloundecane;
• - slip additives;
• - polymerization inhibitors;
• - defoamer;
• - emulsifiers, especially non-ionic emulsifiers such as alkoxylated alcohols and polyols, phenols and alkylphenols or anionic emulsifiers such as alkali salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids, and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols;
• - wetting agent such as siloxanes, fluorine-containing compounds, carboxylic acid half-esters, phosphoric acid esters, polyacrylic and their copolymers or polyurethanes;
• - Adhesion promoter such as tricyclodecane dimethanol;
• - leveling agent;
• - film-forming Auxiliaries such as cellulose derivatives;
• - transparent fillers based on silicon dioxide, aluminum oxide or zirconium oxide; is complementary still on the Römpp Lexicon of varnishes and printing inks, Georg Thieme Verlag, Stuttgart, 1998, Pages 250 to 252, referenced;
• - Say control agents such as ureas, modified ureas and / or silicas, as for example in the 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 "color + lacquer", 11/1992, pages 829 ff.
• - rheology control Additives such as those from the patent specifications WO 94/22968, EP-A-0 276 501, EP-A-0 249 201 or WO 97/12945 known; cross-linked polymeric microparticles, as disclosed, for example, in EP-A-0 008 127; inorganic Layered silicates such as aluminum-magnesium silicates, sodium-magnesium and montmorillonite type sodium magnesium fluorine lithium layered silicates; silicas like aerosils; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, Poly (meth) acrylic acid, Polyvinylpyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates;
• - flame retardant and or
• - matting agents like magnesium stearate.

Further examples of suitable paint additives are described in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998.

These additives are the coating materials of the invention in usual and known effective amounts, which, depending on the additive at 0.001 to 500 parts by weight per 100 parts by weight of resin according to the invention and crosslinking agents.

The production of the coating material of the invention has no peculiarities, but takes place in the usual and known manner by mixing those described above Components in suitable mixing units such as stirred tanks, dissolvers or extruders after the for the production of the respective coating materials suitable processes.

The coating material of the invention serves the production of the coatings according to the invention, in particular Multilayer coatings ML, on primed or unprimed substrates.

All come to be painted as substrates Surfaces, by hardening the paintwork on it using heat not harmed be considered; these are e.g. B. the moldings according to the invention, Foils and fibers, 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 also for Applications outside automotive painting, especially suitable for automotive painting. in this connection it comes especially for the painting of furniture and industrial painting, including coil coating, containers Coating and impregnation or coating of electrical components. As part of of industrial painting, it is practically suitable for painting 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.

In the case of electrically conductive substrates can Primers are used in the usual and known manner be made from electrocoat (ETL). Come for this both anodic (ATL) and cathodic (KTL) electrodeposition paints, but especially KTL.

With the multi-layer coating according to the invention can also primed or non-primed plastics such. 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 after DIN 7728T1) can be painted. The plastics to be painted can of course also be used Polymer blends, modified plastics or fiber-reinforced plastics his. It can also the usual plastics used in vehicle construction, in particular motor vehicle construction Come into play.

In the case of non-functionalized ones and / or non-polar substrate surfaces, these can be applied prior to coating in a known manner a pretreatment, such as with a plasma or with flame, subjected to or provided with a hydro primer become.

The multi-layer coatings according to the invention ML can can be produced in different ways.

In a first preferred variant comprises the inventive method the following process steps:

• (I) Production of a filler lacquer layer by application a fountain pen on the substrate,
• (II) hardening the filler layer, causing the filler layer results,
• (III) Production of a solid-color topcoat by application of a solid-color topcoat on the filler layer and
• (IV) hardening the solid-color topcoat, which results in the solid-color topcoat.

Another preferred variant of the method according to the invention comprises the procedural steps:

• (I) making a basecoat film by Application of a basecoat to the substrate,
• (II) drying the basecoat film,
• (III) Production of a clear lacquer layer by application of a Clear coats on the basecoat and
• (IV) common hardening the basecoat and the clearcoat, creating the basecoat and the clearcoat result (wet-on-wet process).

A third preferred variant of the inventive method comprises the procedural steps:

• (I) Production of a filler lacquer layer by application a fountain pen on the substrate,
• (II) hardening the filler layer, causing the filler layer results,
• (III) Production of a basecoat film by application of a Basecoat on the filler layer,
• (IV) drying the basecoat film,
• (V) production of a clear lacquer layer by application of a Clear coats on the basecoat and
• (VI) common hardening the basecoat and the clearcoat, creating the basecoat and the clearcoat result (wet-on-wet process).

As part of the second and third preferred variant can the clearcoats are still covered with a clearcoat according to the invention become. With this additional advantageous variants are generally customary in the wet-on-wet process known clearcoats used. By overlaying the resulting usual ones and known clearcoats with the clearcoat of the invention the scratch resistance of the multilayer coating ML according to the invention significantly improved.

Which preferred variant is chosen depends on the intended use of the multi-coat coatings according to the invention ML. This is especially the third variant in automotive OEM painting applied particularly preferably.

Accordingly, the multi-layer coatings according to the invention can ML have a different structure.

• (1) eine mechanische Energie absorbierende Füllerschicht und
• (2) eine farb- und/oder effektgebende Decklackierung

in der angegebenen Reihenfolge übereinander.In a first preferred variant of the multilayer coating ML according to the invention

• (1) a mechanical energy absorbing filler layer and
• (2) a color and / or effect top coat

on top of each other in the given order.

• (1) eine mechanische Energie absorbierende Füllerschicht,
• (2) eine farb- und/oder effektgebende Basislackierung und
• (3) eine Klarlackierung

in der angegebenen Reihenfolge übereinander.In a second preferred variant of the multilayer coating ML according to the invention

• (1) a mechanical energy absorbing filler layer,
• (2) a color and / or effect basecoat and
• (3) a clear coat

on top of each other in the given order.

• (1) eine farb- und/oder effektgebende Basislackierung und
• (2) eine Klarlackierung

in der angegebenen Reihenfolge übereinander. Die dritte bevorzugte Variante wird insbesondere bei der Kunststofflackierung angewandt.In a third preferred variant of the multilayer coating ML according to the invention

• (1) a color and / or effect basecoat and
• (2) a clear coat

on top of each other in the given order. The third preferred variant is used in particular in the coating of plastics.

In addition, the Clear coats of the multilayer coats ML described above Additionally with a clearcoat according to the invention be coated.

The application of the coating material of the invention can by all usual Application methods, such as Spraying, knife coating, painting, pouring, diving, Watering, trickling or Rolling done. The substrates to be coated can be used as such rest, with the application device or system moving becomes. However, the substrate to be coated can also, in particular a coil, are moved, the application system relative to the Substrate rests or is moved in a suitable manner.

Spray application methods are preferred applied, such as compressed air spraying, airless spraying, High rotation, electrostatic spray application (ESTA), if necessary combined with hot spray application such as hot air hot spray. The applications can be used at temperatures of max. 70 to 80 ° C are carried out so that appropriate application viscosities can be achieved without a change in the briefly acting thermal load or damage of the coating material and its optionally to be reprocessed Enter overspray. This is how hot spraying can be designed that the Coating material only heated very briefly in or just before the spray nozzle becomes.

The one used for the application Spray booth can, for example, with an optionally temperature-controlled Circulation operated with a suitable absorption medium for the Overspray, e.g. B. the coating material itself is operated.

Generally the filler coat, Top coat, basecoat and clear coat in one wet coat thickness applied that after their curing Layers with the for their functions result in necessary and advantageous layer thicknesses. In the case of the filler layer this layer thickness is 10 to 150, preferably 15 to 120, particularly preferably 20 to 100 and in particular 25 to 90 μm, in the case the top coat is 5 to 90, preferably 10 to 80, particularly preferably 15 to 60 and in particular 20 to 50 μm, in the case the base coat is 5 to 50, preferably 10 to 40, particularly preferably 12 to 30 and in particular 15 to 25 μm, and in In the case of the clearcoats, it is preferably 10 to 100 15 to 80, particularly preferably 20 to 70 and in particular 25 to 60 μm.

The filler coat, top coat, Basecoat and / or clearcoat is or will be thermal hardened, if they are from the coating materials of the invention getting produced. According to the invention, it is advantageous to apply the basecoat before the application of the clear lacquer layer not at all or only partially cure, to them afterwards Cure together with the clear coat (wet-in-wet process).

The hardening can take place after a certain Rest period. It can last from 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, to run and degas the paint layers or to evaporate volatile Ingredients such as solvents. The rest period can be supported and / or by using elevated temperatures up to 80 ° C be shortened provided there is no damage or changes of the lacquer layers occur, 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. If substrates are used that can withstand high thermal loads, thermal crosslinking can also be carried out at temperatures above 100 ° C. 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 property profile, especially a high one Gloss, high acid resistance, high chemical resistance, a high scratch resistance and a very good flow. In your Use as additional Clear coatings adhere well to those underneath Clearcoats so this before application of the coating materials according to the invention in many cases no longer need to be sanded. Another special advantage is, that you an excellent one even at comparatively low temperatures Reflow behavior shows.

The multi-layer coatings according to the invention ML also have an excellent property profile very good in terms of mechanics, optics, corrosion resistance and adhesion is balanced. The multi-layer coatings according to the invention thus have ML the high optical quality and interlayer adhesion required by the market and pose no problems such as lack of condensation resistance the filler layers, cracking (mudcracking) in the basecoats or flow problems or surface structures in the clear coats.

In particular, the multilayer coating according to the invention has ML honor excellent metallic effect, an excellent D.O.I. (distinctiveness of the reflected image) and an excellent one Surface smoothness, on. It is weather-resistant, resistant to chemicals and bird droppings and scratch-resistant and shows very good reflow behavior.

Another major advantage is the very good paintability the multi-layer coating according to the invention ML also without grinding. This makes it easy to use with usual and known highly scratch-resistant coating materials on the basis organically modified ceramic materials are coated.

Last but not least, it turns out as a very special advantage that with With the help of the methods described above, a multi-layer coating ML can be realized, which is based exclusively on the coating materials of the invention based.

Accordingly, the substrates according to the invention also have special advantages like a longer one Service life, better aesthetic Impression by the viewer and better technological usability on what makes them particularly attractive economically.

Examples

Production Example 1

The making of a Polyacrylate resin containing hydroxyl groups

In a 4 liter reactor, equipped with a stirrer, two dropping funnels as inlets for the Monomer mixture and the initiator solution, nitrogen inlet tube, Thermometer and reflux condenser was 731 parts by weight of a fraction of aromatic hydrocarbons Weighed in with a boiling range of 158 to 172 ° C and heated to 140 ° C. Thereafter, a monomer mixture of 183 parts by weight of n-butyl methacrylate, 458 parts by weight of ethylhexyl methacrylate, 214 parts by weight of styrene, 183 parts by weight of hydroxyethyl acrylate, 458 parts by weight of 4-hydroxybutyl acrylate and 31 parts by weight of acrylic acid within four hours and an initiator solution of 153 parts by weight tert-butyl perethyl hexanoate in 92 parts by weight of the above aromatic solvent described evenly metered into the reactor within 4.5 hours. With the metering of the monomer mixture and the initiator solution started at the same time. After the initiator has finished metering the reaction mixture was stirred for a further two hours Heated 140 ° C and then cooled. The resulting resin solution had a solids content of 65% (convection oven; one hour; 130 ° C).

Preparation example 2

The preparation of a chloroformate group containing polyacrylate resin

700 parts by weight of the resin solution according to the preparation example 1 were diluted with 700 parts by weight of xylene to make them more stirrable. The resulting mixture was placed in a suitable reactor. Subsequently were stirring at room temperature during 400 parts by weight of phosgene were metered into the resin solution in one hour. After a reaction time of 30 minutes the degree of implementation was determined by IR spectroscopy. in this connection no more hydroxyl groups were detectable. The excess phosgene was separated under vacuum. Based on the chlorine value determination sales> 90% determined.

Preparation example 3

The preparation of the resin solution according to the invention

1450 parts by weight of the chloroformate groups containing resin solution according to manufacturing example 2 were placed in a suitable reactor. Then were 61 parts by weight of ammonia are introduced into the resin solution at room temperature, whereby ammonium chloride failed.

The resulting resin solution was successively with 500 parts by weight of water, 400 parts by weight of ethanol and 500 parts by weight of pentyl acetate to make up the precipitated Dissolve ammonium chloride and induce phase separation. The resulting mixture was during stirred for one hour at room temperature and then for phase separation ditched. After phase separation, the aqueous phase separated and the organic phase was dried with sodium chloride.

The NMR analysis showed that the chloroformate groups more than 80% were converted to carbamate groups. The resulting one solution of the polyacrylate resin of 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% partial solution in solvent naphtha.

example

The production a clearcoat according to the invention and its application properties

The clearcoat of the invention was prepared by mixing 222 parts by weight of the solution of the polyacrylate resin according to the invention in accordance with Preparation 3, 25.7 parts by weight of Resimene ^® 747 (commercially available methylverethertes melamine resin of the Firm Monsanto), 5.2 parts by weight of Tinuvin® 384 (commercial UV-absorber from Ciba Specialty Chemicals), 2.6 parts by weight of Tinuvin ^® 123 (commercial HALS product from Ciba Specialty Chemicals), 6.8 parts by weight Nacure ^® 5225 (commercial catalyst aminblockiertes Sulfonesäurederivat from King), 6.0 parts by weight of a 5% solution of a commercially available polydimethylsiloxane leveling agent in xylene, 0.8 part by weight of ^Byk® 306 (commercial additive from Byk), 37 parts by weight of ethyl hexanol, 20 parts by weight of n-butanol, 7 parts by weight of pine oil (85% strength) and 30 parts by weight of butyl diglycol. It had a solids content of 74% (circulating air oven; one hour; 130 ° C) at a viscosity of 24 seconds in the outlet spout according to DIN4.

To check the application technology Properties of the clear lacquer according to the invention became test boards manufactured as follows: cathodic with a commercially available electrocoat coated steel panels (electrocoating with a layer thickness of 18 - 22 μm) with a cup gun first a commercial one ink pen applied and baked by BASF Coatings AG. It resulted a filler layer with a layer thickness of 35 to 40 μm. Then the filler was in same a commercial one black base coat from BASF Coatings AG applied and while Predried for 10 min at 80 ° C. After cooling the panels became a layer of the clear lacquer according to the invention with a pneumatic Spray gun applied and during Predried for 10 min at 50 ° C and then for 25 min at 130 ° C Object temperature networked together with the basecoat. It resulted a basecoat of a starch of 15 μm and a clear coat of 40 µm thick. The black uni base coat has been elected, because you can see the formation of scratches on the corresponding test boards could best watch.

The multilayer coating ML according to the invention had an excellent overall optical impression. The after DIN 67530 with a reflectometer from BYK reflectometric measured at an angle of 20 ° Gloss was 93.3.

The scratch resistance of the multi-layer coating according to the invention ML was tested using the brush test certainly.

For this test became the test panels after application of the paints, stored for 2 weeks at room temperature, before the exam carried out has been.

The scratch resistance of the sol-gel coating on the test boards was with the help of the in Fig. 2 on page 28 of the article by P. Betz and A. Bartelt, Progress in Organic Coatings, 22 (1993), pages 27-37 described BASF brush tests, which, however, regarding the weight used (2000 g instead of the 280 g mentioned there) was modified as follows was assessed: In the test, the paint surface was covered with a screen cloth, which was loaded with a mass, damaged. The screen mesh and the paint surface were using a detergent solution abundantly wetted. The test board was made by means of a motor drive in lifting movements under the screen cloth pushed back and forth.

The test specimen was with nylon mesh (No. 11, 31 μm Mesh size, Tg 50 ° C) covered eraser (4.5 × 2.0 cm, wide side perpendicular to the direction of scratching). The bearing weight was 2000 g.

Before each test, the sieve fabric was renewed, the direction of the mesh was parallel to the direction of scratching. About 1 ml of a freshly stirred 0.25% Persil solution was applied in front of the eraser with a pipette. The number of revolutions of the motor was set so that 80 double strokes were carried out in a time of 80 s. After the test, the remaining washing liquid was rinsed off with cold tap water and the test panel was blown dry with compressed air.

Due to the damage, the gloss decreased DIN 67530 to 87.2. After two hours Regeneration at 60 ° C he had risen to 89 again. On the one hand, this was very clear good scratch resistance of the clearcoat according to the invention and others their good reflow behavior.

In addition, the scratch resistance the multi-layer coating according to the invention ML determined using the sand test.

For this, the lacquer surfaces were used Sand loaded (20g quartz-silver sand 1.5–2.0 mm). The sand was in given a mug (cut off flat), which firmly on the test panel was attached. The same test panels were used as in the brush test above described used. The board was powered by a motor shaken with the mug and the sand. The Movement of the loose sand caused damage to the paint surface (100 double strokes in 20 s). After the sand exposure, the test area was cleaned of abrasion, under carefully wiped with a cold water jet and then with Compressed air dried. The gloss was measured according to DIN 67530 and after damage.

Due to the damage, the gloss dropped to 79.5. After two hours Regeneration at 60 ° C it had risen again to 81.6. This again proved on the one hand the very good scratch resistance of the clearcoat according to the invention and others their good reflow behavior.

The chemical resistance was determined according to BART.

The BART (BASF ACID RESISTANCE TEST) served to determine the resistance of paint surfaces against acids, Alkalis and drops of water. The coating was on a Gradient oven after burning in further temperature loads exposed (30 min 40 ° C, 50 ° C, 60 ° C and 70 ° C). before the test substances (sulfuric acid 1%, 10%, 36%; sulphurous acid 5%, hydrochloric acid 10%, Sodium hydroxide solution 5%, VE (= fully desalinated) water - 1, 2, 3 or 4 Drops) applied with a pipette. Following the Exposure to the substances became under running water removed and the damage after 24 h visually assessed on a given scale:

grading

 Appearance

0

 no defect

1

 slight marking

2

 Marking / matting / no softening

3

 Mark / Vermattung7Farbtonveränderung / softening

4

 Cracks / incipient through etch

5

 Clear varnish removed

It was every single mark (Spot) evaluated and the result for each coating in a suitable Form (e.g. sums of notes for a temperature) fixed portion.

The results of the test can be found in the table.

Table The acid resistance of the multilayer coating ML according to the invention according to BART

The BART underpins the extraordinary acid resistance the multi-layer coating according to the invention ML or the clearcoat of the invention.

Claims (16)

Permanent page and / or terminal Resin containing carbamate groups, can be prepared by at least one a hydroxyl group-containing resin with at least one phosgene a resin containing chloroformate group, after which this Resin with ammonia, primary Amines and / or secondary Amines. The carbamate group-containing resin according to claim 1, characterized in that the hydroxyl group-containing resins are random, alternating and / or block-like linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, in particular poly (meth) acrylates and partially saponified polyvinyl esters, or polyaddition resins and / or polycondensation resins, in particular polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts Polyureas, polyamides or polyimides can be used. The carbamate group-containing resin according to claim 1 or 2, characterized in that the hydroxyl groups are primary and / or secondary Are hydroxyl groups. The carbamate group-containing resin according to one of claims 1 to 3, characterized in that those of the general formula I as primary and secondary amines NHRR ¹ (I), are used, in which the variable R stands for a hydrogen atom or for a monovalent organic radical which is derived from the following compounds: (i) Substituted and unsubstituted, containing no or at least one heteroatom in the chain and / or in the ring, linear or branched Alkanes, alkenes, cycloalkanes, cycloalkenes, alkylcycloalkanes, alkylcycloalkenes, alkenylcycloalkanes or alkenylcycloalkenes; (ii) substituted and unsubstituted aromatics or heteroamates; and (iii) alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcyloalkyl, alkylcycloalkenyl, alkenylcycloalkyl or alkenylcycloalkeriyl-substituted aromatics or heteroaromatics, their substituents are substituted or unsubstituted and no or at least one hetero atom in their chain and / and contain; and wherein the variable R ^{1 has} the meaning given above, except for a hydrogen atom; or in which the radicals R, with the exception of a hydrogen atom, and R ^{1 are} cyclically linked to one another. Process for the production of lateral and / or terminated Resins containing carbamate groups (I) polymer analogs Reaction of hydroxyl-containing resins with phosgene, whereby Resins containing chloroformate groups result, and (II) polymer-analogous implementation of the resins containing chloroformate groups with ammonia and / or primary and / or secondary Amines. The method according to claim 5, characterized in that as Resins containing hydroxyl groups statistically, alternately and / or linear and / or branched and / or comb-like structure copolymers of ethylenically unsaturated monomers, in particular Poly (meth) acrylates and partially saponified polyvinyl esters, or polyaddition resins and / or Polycondensation resins, especially polyesters, alkyds, polyurethanes, Polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides or polyimides can be used. The method according to claim 5 or 6, characterized in that that the Hydroxyl groups primary and / or secondary Are hydroxyl groups. The method according to any one of claims 5 to 7, characterized in that those of the general formula I as primary and secondary amines NHRR ¹ (I), are used, in which the variable R stands for a hydrogen atom or for a monovalent organic radical which is derived from the following compounds: (i) Substituted and unsubstituted, containing no or at least one heteroatom in the chain and / or in the ring, linear or branched Alkanes, alkenes, cycloalkanes, cycloalkenes, alkylcycloalkanes, alkylcycloalkenes, alkenylcycloalkanes or alkenylcycloalkenes; (ii) substituted and unsubstituted aromatics or heteroamates; and (iii) alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcyloalkyl, alkylcycloalkenyl, alkenylcycloalkyl or alkenylcycloalkenyl substituted aromatics or heteroaromatics, their substituents are substituted or unsubstituted and no or at least one heteroatom in their chain and / or their chain and / or contain; and wherein the variable R ^{1 has} the meaning previously assumed, except for a hydrogen atom; or in which the radicals R, with the exception of a hydrogen atom, and R ^{1 are} cyclically linked to one another. The use of the resins containing carbamate groups according to one of claims 1 to 4 or the carbamate group-containing resins produced by the process according to one of claims 5 to 8 for the production of molding compositions, adhesives and coating materials, in particular paints. Molding compounds, adhesives and coating materials, characterized in that they at least one resin containing carbamate groups according to a of claims 1 to 4 or at least one according to one of claims 5 to Contain 8 produced resins containing carbamate groups. Use of molding compounds, adhesives and coating materials according to claim 10, for the production of molded parts, foils, fibers, adhesive layers and decorative and / or protective Coatings, in particular paints. Molded parts, foils and fibers, can be produced from molding compounds according to claim 10th Adhesive layers, producible from adhesives according to claim 10th Coatings, especially paints, can be produced from coating materials, in particular paints, according to claim 10th Substrates which have at least one adhesive layer according to claim 13 and / or at least one coating, in particular painting, according to claim 14 have. Substrates according to claim 15, characterized in that it are molded parts, films and fibers according to claim 12, motor vehicle bodies, industrial components, including electrotechnical components, coils and packaging, or furniture is.