WO2001083578A1 - Multicomponent coating, adhesive and sealing materials and the utilization thereof - Google Patents

Abstract

The invention relates to multicomponent coating, adhesive and sealing materials, containing (A) liquid mixtures of (co)polymers and thermally hardenable reactive diluents, which can be produced by (co)polymerizing olefinically unsaturated monomers (a1) with isocyanate reactive groups in thermally hardenable reactive diluents with isocyanate reactive groups and (B) an adduct, that can be produced from (b1) a diisocyanate and (b2) a compound of general formula (I) with an isocyanate reactive group, wherein R?1 and R2¿ represent hydrogen atoms or alkyl radicals, X and Y represent oxygen atoms, sulfur atoms or >N-R6, wherein R6 = alkyl radical or aryl radical; R3 represents an alkyl radical and R?4 and R5¿ represents hydrogen atoms, isocyanate reactive groups or radicals R6; wherein R?4, R5 or R6¿ contain an isocyanate reactive group or R4 or R5 is an isocyanate reactive functional group, wherein R?4, R5 or R6¿ whenever present- do not have any isocyanate reactive groups and the mol ratio of isocyanate groups in (b1) relative to the isocyanate reactive groups in compound (I) is 1.0.

Description

Multi-component coating materials, adhesives and sealants and their use

The present invention relates to new multi-component coating materials, adhesives and sealing compounds. In addition, the present invention relates to the use of the new multi-component coating materials for the production of new clearcoats or color and effect-giving solid-color topcoats, base coats and multi-coat coats in automotive OEM painting and refinishing, painting indoor and outdoor structures, furniture, window and Door painting as well as industrial painting, including coil coating, container coating and the impregnation of electrical components. Furthermore, the present invention relates to the use of the new multi-component adhesives and sealants for the production of new adhesive layers and seals, in particular in the fields of application listed above.

Two-component coating materials which - generally reactive components with isocyanate-reactive functional groups, customary and known polyisocyanates and adducts of diisocyanates and dioxolanes, dioxanes or oxazolidines, which have an isocyanate-reactive functional group, in a molar ratio of 1: 1, are known from German patent application DE 196 09 617 A 1 known.

According to page 3, line 68, to page 4, line 10, the reactive components inter alia are hydroxy-functional polymers with a hydroxyl group content of 0.1 to 20% by weight (corresponding to 33 to 660 mg KOH / g) , The number average molecular weight of the polymers is preferably 1,000 to 100,000. The polymers preferably contain more than 50 wt .-% C ^ Ca _ö -Alky metl jacrylat, vinylaromatics having up to 20 Carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides, non-aromatic hydrocarbons with 4 to 8 carbon atoms and 1 or 2 double bonds, unsaturated nitriles and mixtures thereof. Polymers are preferred which contain up to 60% by weight of C 1 -C 8 alkyl (meth) acrylates, styrene or mixtures thereof.

In addition, the polymers contain hydroxy-functional monomers, corresponding to the above hydroxyl group content, as well as other monomers such as unsaturated acids not specified, in particular carboxylic acids, acid anhydrides or acid amides.

No information is given on the production of the polymers.

According to page 9, lines 30 to 45, "Preparation and testing of the clear lacquers with the compounds A - two-component system", the hydroxy-functional vinyl polymer Lumitol® H 136 from BASF Aktiengesellschaft with an OH number of 136 mg KOH / g is used as the reactive component. These are known Clear lacquers have a high solids content of up to 16% by weight, and the clear lacquers produced from them have good mechanical properties, in particular high hardness and flexibility, and high chemical resistance.

The two-component coating materials known from DE 19609617 A 1 are, however, not as widely applicable as would actually be desirable. In addition, their service life, i.e. the time within which they can be processed without any problems after the two components have been mixed and deliver perfect coatings can be extended even further.

In the unpublished patent application DE 198 50 243 (meth) acrylate copolymers are described which are characterized by free radicals Copolymerization of olefinically unsaturated monomers in liquid, thermally crosslinkable reactive diluents. become. The (meth) acrylate copolymers or their liquid mixtures with the said reactive diluents can be used in multi-component coating materials, adhesives and sealing compounds. The resulting coatings, adhesive layers and seals are thermostable, weather-resistant, scratch-resistant and light-resistant. However, their property profile in terms of hardness, flexibility, chemical resistance, gloss, reflow and polishability needs to be further improved.

The object of the present invention is to further develop the known multicomponent coating materials while fully maintaining the property profile already achieved, so that new advantageous multicomponent coating materials result which have a high solids content with low viscosity and a long service life, and coatings, in particular clearcoats and color and or effect-giving solid-color coatings, Deliver basecoats and multi-coat paints that, in addition to high hardness, flexibility and chemical resistance, also have an excellent flow, very good interlayer adhesion, an excellent overall optical impression, very good weather resistance, very high scratch resistance and very good polishability. In addition, it is the object of the present invention to further develop the previously known two-component adhesives and sealants, so that new multicomponent adhesives and sealants with a high solids content at low viscosity and a long service life result, the adhesive layers of particularly high adhesive strength and seals of particularly high sealability also deliver to chemically aggressive substances. Accordingly, the new multi-component coating materials, adhesives and sealants have been found to contain

(A) at least one liquid mixture of at least one (co) polymer and at least one thermally curable reactive diluent can be prepared by at least one olefinically unsaturated monomer (al) with at least one isocyanate-reactive functional group in at least one thermally curable reactive diluent with at least two isocyanate-reactive functional parts Groups (co) polymerized,

and

(B) at least one adduct, producible from

(bl) at least one diisocyanate and

(b2) at least one compound of the general formula I with an isocyanate-reactive functional group:

RR ¹

'"\ /

R ³ C (I),

R ⁵ ^ VR ²

(I)

where the variables have the following meaning: R ¹ and R ² : independently of one another = hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms;

U and V: independently of one another = oxygen atom, sulfur atom or a radical> NR ⁶ , where R ⁶ = aliphatic radical having 1 to 30 carbon atoms, the carbon chains of which can be interrupted by one or more oxygen atoms, or aromatic group having 6 to 30 carbon atoms;

R ³ : alkylene radical having 1 to 5 carbon atoms;

R ⁴ and R ⁵ : independently of one another hydrogen atoms, isocyanate-reactive functional groups or

Residues R ⁶ ;

with the proviso that a radical R ⁴ , R. ⁵ or R ^{6 contains} an isocyanate-reactive functional group or a radical R ⁴ or R ^{5 is} an isocyanate-reactive functional group, the other radicals R ⁴ , R ⁵ or R ⁶ - if present - have no isocyanate-reactive functional groups;

the molar ratio of isocyanate groups in the diisocyanates (bl) to the isocyanate-reactive functional groups in the compound I

0.8: 1.2 to 1.2: 0.8.

For the sake of brevity, the new multi-component coating materials, adhesives and sealing compounds are referred to below as "coating materials, adhesives and sealing compounds according to the invention". In addition, the new process for producing a clearcoat by applying a clearcoat to a primed or unprimed substrate or a paint thereon was found, in which the coating material according to the invention is used as clearcoat.

Furthermore, the new process for producing a color and / or effect coating by applying a pigmented solid-color topcoat to a primed or unprimed substrate was found, in which the coating material of the invention is used as solid-color topcoat.

Last but not least, the new process for producing a color and / or effect multi-layer coating was carried out on a primed or unprimed substrate

(1) applying a basecoat to the substrate,

(2) drying and / or partial hardening or complete hardening of the basecoat film,

(3) application of a clearcoat to the dried and / or partially hardened basecoat or the hardened basecoat and

(4) curing the clear lacquer layer together with the basecoat layer or separately hardening the clear lacquer layer,

found where one

(a) a basecoat known per se and the coating material of the invention as a clearcoat, (b) a clear lacquer known per se and the coating material according to the invention as a base lacquer or

(c) a pigmented and a non-pigmented coating material according to the invention is used as the basecoat and as the clearcoat.

Last but not least, the new process for the production of new adhesive layers and / or sealants on and in primed and unprimed substrates was found, in which adhesives and or sealants according to the invention are applied to and / or in the substrates and cured.

In the following, the new methods are collectively referred to as “methods according to the invention”.

Further objects according to the invention are evident from the description.

In view of the prior art, it was surprising and unforeseeable for the person skilled in the art that the object on which the present invention is based was achieved by the special combination of a liquid mixture (A) and an adduct (B), which the excellent property profile of the new coating materials according to the invention, Adhesives and sealants and the coatings, adhesive layers and seals produced therefrom, could be solved. In addition, the extraordinarily broad applicability of the special combination was surprising. Furthermore, the good reflow behavior and the polishability of the coatings according to the invention were surprising.

The coating materials, adhesives and sealants according to the invention are multi-component systems. This means that their highly reactive Ingredients divided into several components, which in themselves are stable in storage, are available and are only added comparatively shortly before use. In the context of the present invention, “comparatively short” means a period of 1 minute to 24 hours and “storage-stable” means that the component in question can be stored for at least 24 hours, preferably at least one week, without decomposition and or premature crosslinking. The constituents are preferably present in two components, the binders and, if appropriate, the reactive diluents in one component and the crosslinking agents in the other component.

The first component of the coating materials, adhesives and sealants according to the invention is the liquid, (co) polymer-containing, i.e. binder-containing mixture (A).

The liquid mixture (A) to be used according to the invention can be obtained by at least one olefinically unsaturated monomer (al) which contains at least one, preferably one, isocyanate-reactive functional group in at least one thermally curable reactive diluent, which has at least two, preferably two, isocyanate-reactive contains functional groups, (co) polymerized, preferably radical (co) polymerized.

Examples of suitable isocyanate-reactive functional groups are hydroxyl groups, thiol groups or primary or secondary amino groups, in particular hydroxyl groups.

Examples of suitable olefinically unsaturated monomers (al) with an isocyanate-reactive functional group are hydroxyl group, thiol group and / or amine group-containing, preferably hydroxyl group and / or amine group-containing, especially hydroxyl group-containing monomers (al) such as Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-ethylenically unsaturated carboxylic acid which (i) are derived from an alkylene glycol which is esterified with the acid, or (ii) can be obtained by reacting the acid with an alkylene oxide such as ethylene oxide or propylene oxide , in particular hydroxyalkyl esters

Acrylic acid, methacrylic acid, crotonic acid or ethacrylic acid in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-

Hydroxybutyl acrylate, methacrylate, ethacrylate or crotonate or 2-methyl, 2-ethyl, 2-propyl, 2-isopropyl or 2-n-butyl-propane-l, 3-diol monoacrylate, methacrylate, -ethacrylate or -crotonate; 1,4-bis (hydroxymethyl) cyclohexane or octahydro-4,7-methano-1H-indenedimethanol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate; or 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. 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 (a1) are to be understood as amounts which do not lead to crosslinking or gelling of the copolymers, unless they are intended to be in the form of crosslinked microgel particles;

ethoxylated and / or propoxylated allyl alcohol, which is available from Arco

Chemicals is sold, or 2-hydroxyalkyl allyl ether, especially 2-hydroxyethyl allyl ether; if used, they are preferably not used as sole monomers (al), but in an amount of 0.1 to 10% by weight, based on the (meth) acrylate copolymer (A); Reaction products from acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule branched in the alpha position, in particular one Versatic® acid, or instead of the reaction products, an equivalent amount of acrylic and / or methacrylic acid, which then during or after

Polymerization reaction with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule branched in the alpha position, in particular one Versatic® acid (cf. Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, »Versatic® - Acids «, pages 605 and 606), is implemented; and or

Allylamine, crotylamine, 2-amino, 2-N-methylamino, 2-N-ethylamino, 2-N-propylamino or 2-N-n-butylamino, 2-N-

Cyclohexylaminoethyl acrylate, methacrylate, ethacrylate or crotonate or 3-amino-, 3-N-memylarrιino-, 3-N-ethylamino-, 3-N-propylamino-,

3-N-n-butylamino or 3-N-cyclohexylaminopropyl acrylate, methacrylate, ethacrylate or crotonate.

The monomer (al) or the monomers (al) are preferably chosen such that (meth) acrylate (co) polymers, in particular

(Meth) acrylate copolymers.

According to the invention, it is advantageous to polymerize in at least one further monomer (a2) in addition to the monomer (al) or the monomers (al), because in this way the profile of properties of the (co) polymers and thus also that of the liquid mixtures (A) to be used according to the invention advantageously varied widely and can be optimally adapted to the respective purpose. According to the invention, it is particularly advantageous to select the monomers (al) and / or (a2) so that the profile of properties of the resulting copolymers is essentially determined by the (meth) acrylates. Consequently the (meth) acrylate copolymers are very particularly preferably used in the mixtures (A) to be used according to the invention.

Examples of suitable monomers (a2) are

Monomers (a21:

Essentially acid group-free (meth) acrylic esters such as (meth) acrylic or alkyl cycloalkyl esters with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, Hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; cycloaliphatic (meth) acrylic acid esters, in particular cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene methanol or tert-butylcyclohexyl (meth) acrylate; (Meth) acrylic acid oxaalkyl esters or oxacycloalkyl esters such as ethoxytriglycol (meth) acrylate and methoxyoligoglycol (meth) acrylate with a molecular weight Mn of preferably 550 or other ethoxylated and / or propoxylated hydroxyl group-free (meth) acrylic acid derivatives (further examples of suitable monomers (a21) of this type are from the Offenlegungsschrift DE 196 25 773 A1, column 3, line 65, to column 4, line 20, are known). These can be used in minor amounts of higher functional (meth) acrylic or alkyl 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. With regard to the amounts of higher-functional monomers (a21), what has been said above for the monomers (a2) applies.

Monomers (a22: At least one acid group, preferably a carboxyl group, per molecule carrying ethylenically unsaturated monomers or a mixture of such monomers. Acrylic acid and / or methacrylic acid are particularly preferably used as component (a22). However, 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. Furthermore, ethylenically unsaturated sulfonic or phosphonic acids or their partial esters can be used as component (a22). Monomers (a22) furthermore include maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester as well as vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or

Vinylbenzenesulfonic acid (all isomers). Further examples of monomers containing acid groups (a22) are known from published patent application DE 196 25 773 A1, column 2, line 58 to column 3, line 8, or from international patent application WO 98/49205, page 3, lines 23 to 34

Monomers (a23):

Vinyl esters of monocarboxylic acids with 5 to 18 carbon atoms in the molecule, branched in the alpha position. The branched monocarboxylic acids can be obtained 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. 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. However, the vinyl esters can also be prepared from the acids in a manner known per se, for example, by allowing the acid to 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. Vinyl esters of this type are sold under the VeoVa® brand (see also Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598).

Monomers (a24):

N, N-diethylamino-alpha-methylstyrene (all isomers), N, N-diemylaminostyrene (all isomers), 2-N, N-dimethyl, 2-N-ethyl, 2-N, N-diethyl, 2 -N, N-dipropyl-, 2-N, N-dibutyl-, 2-N-cyclohexyl- or 2-N, N-cyclohexyl-memyl-amino- or 2- N, N, N, N-tetramemylammonium- or 2 -N, N-dimethyl-N, N-diethylammonium, 2-tetramethylphosphonium or 2-triethylsulfonium ethyl acrylate, ethyl methacrylate, propyl acrylate or propyl methacrylate or 3-N, N-dimethyl, 3-N, N-diethyl , 3-N, N-dipropyl-, 3-N, N-dibutyl-, or 3-N, N-cyclohexylmethylamino- or 3-N, N, N, N-tetramethylammonium- or 3-N, N-dimethyl-N, N-diethylammonium, 3-tetramethylphosphonium or 3-triethylsulfonium propyl acrylate or propyl methacrylate.

Monomers (a25):

Diarylethylenes, in particular those of the general formula VII:

wherein the radicals R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 are} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl residues. Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl or 2-ethylhexyl. Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl. Examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane. Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylcyclohex-1-yl. Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl, preferably phenyl and naphthyl and in particular phenyl. Examples of suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diyl-benzene. Examples of suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-l-yl. Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylphen-1-yl. Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-l-yl. The aryl radicals R ¹³ , R ¹⁴ , R ¹⁵ and / or R ¹⁶ are preferably phenyl or naphthyl radicals, in particular phenyl radicals. The substituents optionally present in the radicals R ¹³ , R ¹⁴ , R ¹⁵ and / or R ^{] 6} are electron-withdrawing or electron-donating atoms or organic radicals, in particular halogen atoms, nitrile, nitro, partially or fully halogenated alkyl, cycloalkyl, alkylcycloalkyl -, Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; Aryloxy, alkyloxy and cycloalkyloxy radicals; Arylthio, alkylthio and cycloalkylthio residues and / or primary, secondary and / or tertiary amino groups. Diphenylethylene, dinaphthaleneethylene, ice or trans-stilbene, vinylidene-bis (4-N, N-dimethylaminobenzene), vinylidene-bis (4-aminobenzene) or vinylidene-bis (4-nitrobenzene), in particular diphenylethylene (DPE), are particularly advantageous. which is why they are preferred. In the context of the present invention, the monomers (a25) are used in order to regulate the copolymerization advantageously in such a way that a free-radical copolymerization in batch mode is also possible. If they have isoeyanate-reactive functional groups, they can also act as monomers (al). Monomers (a26):

Cyclic and / or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene.

Monomers (a27):

Monido-containing monomers such as (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-, N, N-cyclohexyl-methyl- and / or N-methylol-, N, N-dimethylol-, N-methoxymethyl-, N, N-di (methoxymethyl) -, N-ethoxymethyl- and / or N, N-di (ethoxyethyl) - (meth) acrylic acid amide; monomers containing carbamate groups such as

(Meth) acryloyloxyethyl carbamate or (meth) acryloyloxypropyl carbamate; or monomers containing urea groups, such as ureidoacrylate or methacrylate;

Monomers (a28):

Monomers containing epoxy groups, such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid.

Monomers (a29):

Vinylaromatic hydrocarbons such as styrene, vinyltoluene, diphenylethylene or alpha-alkylstyrenes, especially alpha-methylstyrene;

Monomers (a210):

Nitriles such as acrylonitrile and / or methacrylonitrile;

Monomers (a211): Vinyl compounds, especially vinyl and / or vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N-vinylamides such as vinyl-N-methylformamide, N-vinylcaprolactam or N-vinylpyrrolidone; 1-vinylimidazole; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinylcyclohexyl ether; and / or vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid.

Monomers (a212):

Allyl compounds, especially allyl ethers and esters such as allyl methyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.

Monomers (a213): polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; in particular

Polysiloxane macromonomers which have a number average molecular weight Mn of 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, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, such as it in DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A1 in columns 3 to 7, EP 0 358 153 B1 on pages 3 to 6, in US 4,754,014 A1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18 to page 18, line 10.

and or

Monomers (a214): Acryloxysilane-containing vinyl monomers, which can be prepared by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with (meth) acrylic acid and / or hydroxyalkyl and / or - cycloalkyl esters of (meth) acrylic acid and / or other hydroxyl-containing ones. Monomers (a2).

According to the invention, it is very particularly advantageous to select the monomers (al) and / or (a2) in such a way that hydroxyl-containing (meth) acrylate (co) polymers result which have an OH number of 40 to 240, preferably 60 to 210, acid numbers of 0 to 80, preferably 0 to 50, very particularly preferably 3.9 to 15.5, glass transition temperatures from -35 to +70

° C, preferably -20 to +60 ° C, and number average molecular weights of 1,500 to 30,000, preferably 1,500 to 15,000, very particularly preferably 1,500 to 5,000.

In addition, the monomers (a2) which contain reactive functional groups which are not isocyanate-reactive are selected by type and amount so that they crosslink the reactions of the isocyanate-reactive functional groups with the adducts (B) and / or crosslinking agents (D) described below in do not inhibit or completely prevent the second component.

The selection of the monomers (al) and / or (a2) to adjust the

Glass transition temperatures can be carried out by the person skilled in the art with the aid of the following formula from Fox, with which the glass transition temperatures of poly (meth) acrylates can be approximately calculated: n = x

1 / Tg = Σ Wn / Tg _n ; Σ "W _n = ln = l Tg = glass transition temperature of the poly (meth) acrylate; W _n = weight fraction of the nth monomer;

Tg _n = glass transition temperature of the homopolymer from the nth monomer and x = number of different monomers.

The production of the (co) polymers to be used according to the invention, in particular the (meth) acrylate (co) polymers, has no special procedural features, but is carried out using the methods of continuous or discontinuous copolymerization which are customary and known in the plastics field, in particular those initiated by free radicals Copolymerization, in solution under normal pressure or overpressure in stirred tanks, autoclaves, tube reactors, loop reactors or Taylor reactors at temperatures from 50 to 200 ° C.

Examples _ of suitable copolymerization processes are described in the patent applications DE 197 09 465 A1, DE 197 09 476 A1, DE 28 48 906 A1, DE 195 24 182 A1, DE 198 28 742 A1, DE 19628 143 A1, DE 196 28 142 A1, EP 0 554783 A1, WO 95/27742, WO 82/02387 or WO 98/02466.

Examples of suitable free-radical initiators are dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; peroxodicarbonates; Potassium, sodium or

ammonium peroxodisulfate; Azo initiators, for example azo dinitriles such as azobisisobutyronitrile; CC-cleaving initiators such as benzpinacol silyl ether; or a combination of a non-oxidizing initiator with hydrogen peroxide. Combinations of the initiators described above can also be used. Further examples of suitable initiators are described in German patent application DE 196 28 142 A1, page 3, line 49, to page 4, line 6.

Comparatively large amounts of free-radical initiator are preferably added, the proportion of the initiator in the reaction mixture, based in each case on the total amount of the monomers (a) and the initiator, particularly preferably 0.2 to 20% by weight, very particularly preferably 0.5 is up to 15 wt .-% and in particular 1.0 to 10 wt .-%.

Preferably, the resulting (co) polymers, especially the (meth) acrylate copolymers, selected by type and quantity that the inventive coating materials adhesives, and sealing compounds after curing has a storage modulus E 'in the rubber-elastic range of at least lθ7 ₅ 6 p _{a and} d have a loss factor tan δ at 20 ° C of a maximum of 0.10, the memory module E 'and the loss factor having been measured using dynamic mechanical thermal analysis on free films with a layer thickness of 40 + 10 μm (cf. the German patent DE 197 09 467 C 2).

It is essential for the present invention that the (co) polymerization, in particular the radical (co) polymerization, is carried out in at least one thermally curable reactive diluent with at least two isocyanate-reactive functional groups. For the property "thermally curable", reference is made to Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Härtung", pages 274 to 276.

The thermally curable reactive diluents to be used according to the invention contain at least two of the isocyanate-reactive agents described above functional groups. Accordingly, in principle all polyols, polythiols, polyamines, polyol polythiols, polythiol polyamines, amino alcohols and / or polyol polyamine polythiols are suitable as reactive diluents, provided that they do not inhibit or suppress the (co) polymerization of the monomers (al) or (al) and (a2) or do not lead to undesirable side reactions such as the precipitation of salts with monomers (a2) or the oligomers or polymers containing them, or the decomposition of the reactive diluents during the (co) polymerization. Of the thermally curable reactive diluents mentioned, the polyols are particularly advantageous and are therefore preferably used according to the invention.

Examples of suitable polyols are hyperbranched compounds with a tetra-functional central group, derived from ditrimethylolpropane, diglycerol and / or ditrimethylolethane, or a tetrafunctional central group of the general formula V,

C [-A _q -X-] _m [-A _r -X-] _n [-A _s -X-] ₀ [-A _t -X-] _p (V),

where the indices and the variables have the following meaning:

m + n + o + p = 4; with m = an integer from 1 to 3 and n, o and p = 0 or an integer from 1 to 3;

q, r, s and t = an integer from 1 to 5, where q> r, s, t, in particular q> r, s, t;

X = -O-, -S- or -NH-;

A = -C (R ⁷ ) ₂ -; With R ⁷ = -H, -F, -Cl, -Br, -CN, -NO ₂ , Cι-C ₃ alkyl- or -

Haloalkyl or CrCs alkoxy radical or - for q, r, s and / or t = at least 2 - R ⁷ = a C ₂ -C -

Alkanediyl and / or -Oxaalkandiylrest, which has 2 to 5 carbon atoms and / or an oxygen atom -O-, which bridges 3 to 5 carbon atoms of the radical -A-.

The term “derived” is to be understood here as the conceptual abstraction of the hydrogen atoms from the hydroxyl groups of the tetrols.

According to the invention, the central groups V are advantageous and are therefore used with particular preference.

In the general formula V, the indices q, r, s and t denote integers from 1 to 5. Here, the index q can be equal to the indices r, s and t. Under this framework, symmetrical central groups V result.

Examples of suitable symmetrical central groups V to be used according to the invention are derived from symmetrical tetrols such as pentaerythritol, tetrakis (2-hydroxyethyl) methane or tetrakis (3-hydroxypropyl) methane.

According to the invention, central groups V in which the index q is greater than the indices r, s and t and therefore have a value of at least 2 are advantageous and are therefore used with very particular preference. Under this framework, asymmetric central groups V result.

In the general formula V, the indices m, n, o and p add up to 4. The index m is always greater than 0 and stands for an integer from 1 to 3, in particular for 1. The indices n, o and p have the value 0 in consideration of the above boundary condition or stand for an integer from 1 to 3. This means that not each of these indices can assume the value 0.

According to the invention, the following value combinations of the indices are advantageous:

m = 1 and n, o, p = 1; m = 1, n = 2, o, p = 1; m = 1, n = 2, o = 1 and p = 0; m = 1, n = 3, o, p = 0;

m = 2, n = 1, o = 1 and p = 0; m = 2, n = 2 and o, p = 0;

m = 3, n = 1 and o, p = 0.

Of these, the number combinations in which m = 1 are particularly advantageous.

The following number combinations of the indices are advantageous according to the invention:

q = 2, r, s and / or t = 1; q = 3, r, s and / or t = 1 and / or 2; q = 4, r, s and / or t = 1, 2 and / or 3; q = 5, r, s and / or t = 1, 2, 3 and / or 4.

The variable -X- in the general formula V denotes double-bonded oxygen atoms -O- or sulfur atoms -S- or a secondary amino group - NH-. According to the invention, it is advantageous if -X- stands for -O-. The variable -A- in the formula V means a double-bond radical -C (R ⁷ ) ₂ -.

The radical R ⁷ here stands for hydrogen atoms -H, fluorine atoms -F, chlorine atoms - Cl, bromine atoms -Br, nitrile groups -CN, nitro groups -NO ₂ , CrCralkyl or - haloalkyl groups or CrC ₃ -alkoxy groups. Examples of suitable groups of this type are methyl, ethyl, propyl, trifluoromethyl, trichloromethyl, perfluoroethyl, perfluoropropyl, methoxy, ethoxy or propoxy groups.

According to the invention, hydrogen atoms or methyl groups are advantageous and are therefore preferably used. In particular, hydrogen atoms are used. The variables -A- which are particularly preferred according to the invention are accordingly methylene groups.

If in the general formula V at least one of the indices q, r, s and / or t is at least the number 2, the radical R ^{7 can} also be a C ₂ -C -alkanediyl and / or oxaalkanediyl radical which has 2 to 5 carbon atoms the rest - A- cyclically bridged. The radical -R ⁷ - can, however, also represent an oxygen atom - O-, which cyclically bridges 3 to 5 carbon atoms of the radical -A-. As a result, cyclopentane-1, 2- or -1, 3-diyl groups, tetrahydrofuran-2,3-, -2,4-, -2,5- or -3,4-diyl groups, cyclohexane-1, 2-, -1,3- or -1,4-diyl groups or tetrahydropyran-2,3-, 2,4-, 2,5- or 2,6-diyl groups, but no epoxy groups.

Examples of central groups V which are particularly advantageous according to the invention are derived from the tetrols of the general formula VA described below:

C [-A _q -XH] _m [-A _r -XH] _n [-A _S -XH] ₀ [-A _r XH] _p (VA), In the general formula Va, the indices and the variables have the same meaning as given above for the general formula V. According to the invention, it is particularly advantageous if the variable X represents an oxygen atom -O-.

Accordingly, the tetrols of the general formula VA are of particular advantage for the preparation of the central group V or of the compounds to be used according to the invention and are therefore used with particular preference. For the sake of brevity, they are referred to below as "Tetrole VA".

Examples of very particularly suitable tetrols VA to be used according to the invention are the symmetrical tetrols pentaerythritol, tetrakis (2-hydroxyethyl) methane or tetrakis (3-hydroxypropyl) methane or the asymmetrical tetrols (VA 1) to (VA 10):

HO - (- CH ₂ -) ₂ -C (-CH ₂ -OH) ₃ , (VA1)

HO - (- CH ₂ -) ₃ -C (-CH ₂ -OH) ₃ , (VA2)

HO - (- CH ₂ -) ₄ -C (-CH ₂ -OH) ₃ , (VA3)

HO - (- CH ₂ -) ₅ -C (-CH ₂ -OH) ₃ ,

(VA4)

[HO - (- CH ₂ -) ₂ -] ₂ C (CH ₂ -OH) ₂ , (VA5) [HO - (- CH ₂ -) ₂ -] ₃ C-CH ₂ -OH, (VA6)

HO - (- CH ₂ -) ₃ -C [- (- CH ₂ -) ₂ -OH] ₃ , (VA7)

HO - (- CH ₂ -) ₃ -C [- (- CH ₂ -) ₂ -OH] ₂ (-CH ₂ -OH), (VA8)

HO - (- CH ₂ -) ₄ -C (-CH ₂ -OH) [- (- CH ₂ -) ₂ -OH] [- (- CH ₂ -) ₃ -OH] or (VA9)

HO - (- CH ₂ -) ₅ -C (-CH ₂ -OH) [- (- CH ₂ -) ₄ -OH] 2 (VA10).

Of these, the tetrol (VA1) (2,2-bis-hydroxymethylbutanediol- (1,4); homopentaerythritol) is particularly noteworthy because it is very particular about the reactive diluents to be used according to the invention and thus the liquid mixtures (A) to be used according to the invention mediates advantageous properties. It is therefore used with very particular preference.

In the reactive diluents which are particularly preferred according to the invention, the variables -X- described above are each connected to a hydroxyl group via spacer groups. This also applies mutatis mutandis to the central groups which are derived from the tetrols ditrimethylolpropane, diglycerol or ditrimethylolethane, the oxygen atoms of which correspond to the variable -X-. The following description of the spacer groups therefore also applies to these central groups, which are different from central groups V. According to the invention, all double-bonded organic residues are suitable as spacer groups.

Examples of highly suitable double-bonded organic radicals are those which are derived from the following compounds:

(i) an alkane, alkene, cycloalkane, cycloalkene, alkylcycloalkane, alkylcycloalkene, alkenylcycloalkane, or alkenylcycloalkene, aromatics and heteroamates as well as an alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcycloalkyl, alkylcycloalkenyl, alkenyl or alkenyl alkenyl or alkenyl alkenyl or alkenyl alkenyl or alkenyl Aromatics or heteroaromatics; or from

(i) an abovementioned radical which contains at least one heteroatom in the chain and / or in the radical; or from

(iii) a radical mentioned under (i) or (ii), the chain and / or ring of which is substituted.

Examples of suitable substituents to be used according to the invention for the divalent organic radicals are all organic radicals which are essentially inert, i.e. That is, they do not undergo any reactions with the compounds which are used for the construction of the reactive diluents which are particularly preferred according to the invention or for their further reaction with isocyanates (B) and (D), in particular halogen atoms, nitro groups, nitrile groups or alkoxy groups.

The spacer groups are connected in particular via carbonyl groups to the central groups V or to the central groups which are derived from the other tetrols mentioned. Examples of organic compounds which are particularly suitable for the preparation of these spacer groups, epsilon-caprolactone, hexahydrophthalic acid, hexahydrophthalic anhydride, phthalic acid, phthalic anhydride, hexahydroterephthalic acid, terephthalic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, oxalic acid, malonic acid, malonic acid, succinic acid , Succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, pimelic acid, suberic acid, azelaic acid, sebacic acid or decanoic, undecanoic or dodecanedicarboxylic acid. Of these, epsilon-caprolactone, maleic acid or maleic anhydride and hexahydrophthalic anhydride are particularly suitable and are therefore used with particular preference.

In the preparation of the particularly preferred reactive diluents to be used according to the invention, the tetrols VA or the other tetrols mentioned are reacted with the above-mentioned difunctional compounds to form an intermediate into which the hydroxyl groups can be introduced.

All organic compounds which can react with the intermediates to form a hydroxyl group or to obtain a hydroxyl group are suitable for this purpose. According to the invention, it is advantageous to use a compound which reacts with the intermediates to form a hydroxyl group.

Examples of highly suitable organic compounds of this type are compounds containing epoxy groups, in particular those containing glycidyl groups.

Examples of highly suitable compounds containing epoxy groups, in particular those containing glycidyl groups, are ethylene oxide, propylene oxide, Epichlorohydrin, glycidol, glycidyl ether, in particular aryl and alkyl glycidyl ether, or glycidyl ester, in particular the glycidyl ester of tertiary, highly branched, saturated monocarboxylic acids, which are sold under the trade name Versatic® acids by Deutsche Shell Chemie. Of these, the Versatic ^® acid glycidyl esters are particularly advantageous and are therefore used with very particular preference.

It is essential for the present invention that the reactive diluents described above are liquid at room temperature. Either single liquid hyperbranched compounds or liquid mixtures of these compounds can thus be used. This is particularly the case when hyperbranched compounds are used which are solid as individual compounds because of their high molecular weight and / or their symmetry. The person skilled in the art can therefore select the corresponding hyperbranched connections in a simple manner.

The reactive diluents which are particularly preferred according to the invention can be prepared by the customary and known methods of producing hyperbranched and dendrimeric compounds. Suitable synthetic methods are described, for example, in patent applications WO 93/17060 or WO 96/12754 or in the book by GR Newkome, CN Moorefield and F. Vögtle, "Dendritic Molecules, Concepts, Syntheses, Perspectives", VCH, Weinheim, New York, 1996 , described.

Further examples of suitable polyols are the cyclic and / or acyclic C ₉ -C ₁₆ alkanes, which are functionalized with at least two hydroxyl groups and, for the sake of brevity, are referred to below as "functionalized alkanes".

Advantageous functionalized alkanes are derived from branched acyclic alkanes with 9 to 16 carbon atoms, which each form the basic structure. Examples of suitable alkanes of this type with 9 carbon atoms are 2-methyloctane, 4-methyloctane, 2,3-dimethyl-heptane, 3,4-dimethyl-heptane, 2,6-dimethyl-heptane, 3,5-dimethyl-heptane, 2 -Methyl-4-ethylhexane or isopropylcyclohexane.

Examples of suitable alkanes of this type with 10 carbon atoms are 4-ethyloctane, 2,3,4,5-tetramethyl-hexane, 2,3-diethyl-hexane or l-methyl-2-n-propyl-cyclohexane.

Examples of suitable alkanes of this type with 11 carbon atoms are 2,4,5,6-tetramethyl-heptane or 3-methyl-6-ethyl-octane.

Examples of suitable alkanes of this type with 12 carbon atoms are 4-methyl-7-ethyl-nonane, 4,5-diethyl-octane, r-ethyl-butyl-cyclohexane, 3,5-diethyl-octane or 2,4-diethyl-octane ,

Examples of suitable alkanes of this type with 13 carbon atoms are 3,4-dimethyl-5-ethyl-nonane or 4,6-dimethyl-5-ethyl-nonane.

An example of a suitable alkane of this type with 14 carbon atoms is 3,4-dimethyl-7-ethyl-decane.

Examples of suitable alkanes of this type with 15 carbon atoms are 3,6-diethyl-undecane or 3,6-dimethyl-9-ethyl-undecane.

Examples of suitable alkanes of this type with 16 carbon atoms are 3,7-diethyl-dodecane or 4-ethyl-6-isopropyl-undecane. . Of these basic structures, the alkanes with 10 to 14 and in particular 12 carbon atoms are particularly advantageous and are therefore used with preference. Of these, the octane derivatives are particularly advantageous.

It is essential for the present invention that the functionalized alkanes, which are derived from these branched, cyclic or acyclic alkanes as basic frameworks, are liquid at room temperature. Either single liquid functionalized alkanes or liquid mixtures of these compounds can thus be used. This is particularly the case when functionalized alkanes are used which are solid as individual compounds due to their high number of carbon atoms in the alkane backbone. The person skilled in the art can therefore select the corresponding functionalized alkanes or the reactive diluents in a simple manner.

It is also essential for the invention that the functionalized alkanes have a boiling point of over 200, preferably 220 and in particular 240 ° C. In addition, they are said to have a low evaporation rate.

According to the invention, it is also advantageous if the functionalized alkanes are acyclic.

The functionalized alkanes have primary and / or secondary hydroxyl groups or primary and / or secondary hydroxyl groups and thiol groups. According to the invention, it is advantageous if primary and secondary groups of this type are present in a functionalized alkane.

The functionalized alkanes can be used individually or together as mixtures. Particular advantages arise when the polyols are diols and / or triols, but especially diols. They are therefore used with particular preference.

The positionally isomeric dialkyloctanediols, in particular diethyloctanediols, are very particularly advantageous diols. Of these, 2,4-diethyl-octanediol-1,5 is particularly noteworthy.

The reactive diluents described above are compounds known per se and can be prepared using customary and known synthetic methods of organic chemistry, such as base-catalyzed aldol condensation, or they are obtained as by-products of large-scale chemical syntheses, such as the preparation of 2-ethylhexanol.

Further examples of particularly preferred reactive diluents according to the invention are obtained by using oligomers of the formula VI,

R ⁹ R ¹⁰ C = [= CH-R ⁸ -CH =] _v = CR ^π R ¹² (VI),

wherein R ⁸ = - (- CH ₂ -) _W -, where the index w is an integer from 1 to 6, or

wherein W - -CH - or an oxygen atom;

R ⁹ , R ¹⁰ , R ^π and R ¹² independently from each other = hydrogen atoms or alkyl; and

Index v = an integer from 1 to 15;

5 hydroformylated and the resultant aldehyde-containing products VI are reduced to the polyols VI, which are optionally partially or completely hydrogenated.

The index v in formula VI stands for the number of divalent radicals R ⁸ ,

10 which in the of cyclic olefins such as cyclopropene,

Cyclopentene, cyclobutene, cyclohexene, cycloheptene, norbornene, 7-oxanorbone or cyclooctene derived oligomers VI by ring-opening

Metathesis reaction were introduced. Preferably, the

Oligomer mixtures VI with the largest possible proportion, such as at least

15 40% by weight (determined by the area integration of the gas chromatograms;

Device: Hewlett Packard; Detector: flame ionization detector; Pillar; DB 5.30 m x 0.32 mm, assignment lμ; Temperature program: 60 ° C 5 min, isothermal,

Heating rate 10 ° C / min max: 300 ° C), a value of v> 1. The value v and thus the degree of the ring-opening metathesis can be determined by the activity of the

20 used metathesis catalyst can be influenced.

The radicals R ⁹ , R ¹⁰ , R ¹¹ and R ¹² independently of one another represent hydrogen or alkyl, the term “alkyl” encompassing straight-chain and branched alkyl groups.

25

It is preferably straight-chain or branched C 1 -C 8 alkyl, preferably C 1 -C 10 alkyl, particularly preferably d- alkyl groups. Examples of alkyl groups are in particular methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl. n-

30 pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-2-dimethylpropyl, 1,1- Dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylpropyl, 1,2,2-trimethylpropyl. 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl, etc.

The degree of branching and the number of carbon atoms of the terminal alkyl radicals R ⁹ , R ¹⁰ , R ¹¹ and R ¹² depend on the structure of the acyclic monoolefins of the hydrocarbon mixture used and the activity of the catalyst, which underlies the degree of cross-metathesis (self-metathesis) of the acyclic olefins Formation of structurally new olefins is influenced, in which cyclopentene is then formally inserted in the sense of a ring-opening metathesis polymerization.

Oligomer mixtures are preferably used which have an increased proportion of oligomers with only one terminal double bond. The oligomer is preferably prepared by using a hydrocarbon mixture containing acyclic monoolefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbones or 7-oxanorbones and also acyclic monoolefins from petroleum processing by cracking (C ₅ cut) in a homogeneous or heterogeneous metathesis reaction implemented.

The metathesis reaction includes formal

a) the disproportionation of the acyclic monoolefins of the hydrocarbon mixture by cross metathesis,

b) the oligomerization of the cyclic monoelefin by ring-opening metathesis, c) chain termination by reacting the oligomers from b) with an acyclic olefin of the hydrocarbon mixture or a product from a),

the steps a) and or b) and / or c) can be carried out several times alone or in combination.

Step a)

The cross-metathesis of acyclic monoolefins will be explained using the example of the metathesis of 1-pentene and 2-pentene:

CH = CH-C ₃ H ₇

+ ^ Propene + 1-butene + 2-hexene + 3-heptene

CH ₃ -CH = CH-C ₂ H ₅

By combining cross metathesis of different and self-methathesis of the same acyclic olefins, e.g. the self-metathesis of 1-pentene to ethene and 4-octene and by going through this reaction several times,

Variety of mono-screens with different structure and

Obtained number of carbon atoms, which form the end groups of the oligomers VI.

The proportion of cross-metathesis products, which increases with increasing activity of the catalyst used, also increases the double bond proportion of the

Oligomers affected. For example, at the previously described

Self-methathesis of 1-pentene ethene is released, which can possibly escape in gaseous form, a double bond equivalent being removed from the reaction. At the same time, the proportion of oligomers without terminal double bonds increases. In the example above, for example, by inserting cyclic monoolefin in 4-octene, an oligomer without terminal double bonds.

Step b)

The average number of insertions of the cyclic monoolefin in the growing chain in the sense of a ring-opening metathesis polymerization determines the average molecular weight of the oligomer mixture VI formed. Oligomer mixtures VI having an average molecular weight of at least 274 g per mole are preferably formed by the process according to the invention, which corresponds to an average number of three units of a cyclic monoolefin per oligomer.

Step c)

The chain termination takes place by reacting oligomers which still have an active chain end in the form of a catalyst complex (alkylidene complex) with an acyclic olefin, ideally recovering an active catalyst complex. In this case, the acyclic olefin can originate unchanged from the hydrocarbon mixture originally used for the reaction or can have been modified beforehand in a cross metathesis according to step a).

The process is generally suitable for the preparation of oligomers VI from hydrocarbon mixtures which contain acyclic and cyclic monoolefins. Mono-olefins such as Cyclobutene, cyclopentene, cyclohexene,

Cyclohepten, norbonen or 7-oxanorbonen, in particular cyclopentene.

Variants of this process are described, for example, in the article by M.

Schuster and S. Bleckert in Angewandte Chemie, 1997, Volume 109, pages 2124 to 2144. A hydrocarbon mixture obtained on a large industrial scale in petroleum processing is preferably used, which, if desired, can be subjected to a catalytic partial hydrogenation beforehand to remove dienes. For example, a mixture enriched in saturated and unsaturated C ₅ hydrocarbons (C _{5 cut} ) is particularly suitable for use in the present process. To obtain the C _{5 cut} , pyrolysis gasoline obtained in the steam cracking of naphtha can first be subjected to a selective hydrogenation in order to selectively convert the dienes and acetylenes contained into the corresponding alkanes and alkenes and then subjected to a fractional distillation, one of which is used for further distillation chemical syntheses important C ₆ -C ₈ cut, which contains the aromatic hydrocarbons, as well as the Cs cut used for the process according to the invention.

The Cs cut generally has a total olefin content of at least 30% by weight, preferably at least 40% by weight, in particular at least 50% by weight.

Cs-hydrocarbon mixtures with a total cyclopentene content of at least 5% by weight, preferably at least 10% by weight, in particular at least 12% by weight, and generally not more than 30% by weight, preferably not more than 20, are suitable wt .-%.

In addition, suitable Cs-hydrocarbon mixtures have a pentene isomer content of the acycyclic monoolefins of at least 70% by weight, preferably at least 80% by weight, in particular at least 90% by weight.

The production process can also be a large-scale Cs cut with a total olefin content of, for example, 50 to 60% by weight Cyclopentene content of, for example, 10 to 20% by weight and a content of pentene isomers of, for example, 33 to 43% by weight are carried out, the weight percentages adding up to 100% by weight.

According to a special embodiment, a hydrocarbon mixture is used in the production process, which comprises the Cs cut and an oil fraction (raffonate-2) containing acyclic C -olefins.

According to another specific embodiment of the production process, a hydrocarbon mixture is used which comprises the Cs cut and ethene. Oligomer mixtures VI with an increased double bond content are obtained. This is achieved, on the one hand, by ethenolysis of the acyclic n- and iso-pentenes contained in the Cs cut to give shorter-chain α-olefins, such as propene and 1-butene, which react with cyclopentene in a ring-opening metathesis reaction to form oligomers VI, each with a terminal one Double bond react. In the presence of ethene, the self-metathesis of the acyclic olefins with formation of further ethene, e.g. suppresses the self-metathesis of 1-pentene to ethene and 4-octene, which as a chain termination reagent leads to products without terminal double bonds. On the other hand, the double bond content is further increased by the ethenolysis of cyclopentene with ethene to 1,6-heptadiene. This results in sequences of oligomers, each of which has two terminal double bonds. When the oligomer mixtures VI thus obtained with an increased double bond content are used for functionalization, oligomer mixtures VI with increased functionality density preferably result.

Suitable catalysts for metathesis are known in the prior art and include homogeneous and heterogeneous catalyst systems. In general, the catalysts suitable for the production process are based on a transition metal of the 6th, 7th or 8th subgroup of the periodic table, preferably catalysts based on Mo, W, Re and Ru are used.

Suitable homogeneous catalyst systems are e.g. by RH Grubbs in Comprehensive Organometallic Chemistry, Pergamon Press, Ltd., New York, Volume 8, page 499 ff. (1982), by RR Schrock in Accounts of Chemical Research, Volume 23, page 158 ff. (1990), in Angewandte Chemie, volume 107, pages 2179 ff. (1995), in Journal of the American Chemical Society, volume 118, pages 100 ff. (1996) and in Journal of the Chemical Society, Chemical Communications, page 1127 ff. (1995) ,

Suitable heterogeneous catalyst systems generally include one

Transition metal compound on an inert support that is capable without

Cocatalyst to form a catalytic active alkylidene complex by reaction with the olefin ducts. Re O and CH ₃ ReO ₃ are preferably used.

Suitable inorganic carriers are the oxides customary for this, in particular silicon and aluminum oxides, aluminosilicates, zeolites, carbides, nitrides, etc. and mixtures thereof. Al O ₃ , SiO and mixtures thereof, optionally in combination with BO ₃ and Fe ₂ O ₃ , are preferably used as carriers.

The reaction temperature of the metathesis is from -20 to 200 ° C, preferably 0 to 100 ° C, in particular 20 to 80 ° C.

The metathesis can be carried out at an increased pressure of up to 20 bar, preferably up to 10 bar, or in particular at ambient pressure.

The process engineering execution of the manufacturing process can take place both continuously and discontinuously. Suitable reaction apparatuses are known to the person skilled in the art and are described, for example, in Ullmanns Encyclopedia of Industrial Chemistry, Volume 1, page 743 ff. (1951). These include, for example, stirred tanks for the batch process and, for example, tubular reactors for the continuous process.

The metathesis mixture is separated using customary methods. This includes e.g. the fractional distillation, if appropriate under reduced pressure, or the separation at elevated temperatures and normal pressure in a falling film evaporator. Low-boiling fractions which contain unreacted olefins can, if desired, be returned to the reaction apparatus. Advantageously, a further conversion of the olefins contained in the Cs cut to oligomers VI is achieved in the production process, so that the separated low boilers comprise a C5 hydrocarbon mixture with predominantly saturated cyclic and acyclic compounds.

Preferably, the iodine number of the oligomer VI is at least 250 g I _2/100 g oligomers VI, preferably at least 300 g I _2/100 g VI oligomers.

The average molecular weight of these oligomers VI derived from cyclic monoolefins, in particular cyclopentene, is at least 274 g / mol, which corresponds to an average conversion of three cyclopentene units per oligomer VI, in which case chain termination by an acyclic pentene (and not by a Cross metathesis product) is assumed.

To prepare the reactive diluents to be used according to the invention (polyols VI), the oligomers VI described in detail above are hydroformylated in a customary and known manner. In general, the oligomers VI in the presence of suitable transition metal-containing catalysts with hydrogen and carbon monoxide under normal pressure or implemented under elevated pressure at temperatures of 50 to 150 ° C to products VI containing aldehyde groups.

An example of a suitable transition metal is rhodium.

The polyaldehydes VI thus obtained are isolated and reduced in a customary and known manner to the reactive diluents to be used according to the invention. All reducing agents with which aldehyde groups can be reduced to hydroxyl groups are suitable for this. Examples of suitable reducing agents are borohydrides such as sodium tetrahydroboranate or hydrogen in the presence of hydrogenation catalysts.

Examples of suitable hydroformylation and reduction processes are described in European patent application EP 0 502 839 A1.

The polyols VI can be partially or completely hydrogenated in a customary and known manner. This includes the above-mentioned reducing agents.

The particularly advantageous polyols VI have a hydroxyl number (OHZ) of 200 to 650, in particular 250 to 450. The number average molecular weight M _n determined with the aid of gel permeation chromatography with polystyrene as the internal standard is in the range from 400 to 1,000, in particular 400 to 600. The mass average molecular weight M _w determined with the aid of gel permeation chromatography and polystyrene as the internal standard is in the range from 600 to 2,000 , in particular 600 to 1,100. The inconsistency M _n / M _w is 1.4 to 3, in particular 1.7 to 1.9. The thermally curable reactive diluents described above can be added to the liquid mixture (A) after their preparation as additives (C).

The content of (co) polymers, in particular (meth) acrylate (co) polymers, on the one hand and reactive diluents on the other hand in the liquid mixtures (A) to be used according to the invention can vary very widely. It depends primarily on the intended use of the liquid mixture (A) and the viscosity required for this and on whether additives (C) are still present. The content of reactive diluent, based in each case on the sum of (co) polymer and reactive diluent, is 1.0 to 50, preferably 2.0 to 45, particularly preferably 3.0 to 40, very particularly preferably 4.0 to 35 and in particular 5.0 to 30% by weight.

The content of the liquid mixtures (A) described above in the coating materials, adhesives and sealants according to the invention can likewise vary very widely. The content depends in particular on the functionality of the binders on the one hand and the functionality of the adducts (B) and the crosslinking agents (D) described below on the other. The content is preferably 5.0 to 80, preferably 6.0 to 75, particularly preferably 7.0 to 70, very particularly preferably 8.0 to 65 and in particular 9.0 to 60% by weight, in each case based on the Solids content of the coating materials, adhesives and sealants according to the invention.

The binder component to be used according to the invention, ie the liquid mixture (A), can contain customary and known additives (C) in effective amounts. It is essential that they do not inhibit or completely prevent the crosslinking reactions. 4698

42

Examples of suitable additives (C) are color and or effect pigments, organic and inorganic, transparent or opaque fillers, nanoparticles, thermally and or with actinic radiation reactive diluents, low-boiling organic solvents and high-boiling organic solvents ("long solvents"), water , UV absorbers, light stabilizers, radical scavengers, thermolabile free radical initiators, photoinitiators and coinitiators, other additional binders, crosslinking agents, such as are used in one-component systems, catalysts for thermal crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents Detergents, adhesion promoters, leveling agents, film-forming aids, sag control agents (SCA), rheology control additives (thickeners), flame retardants, siccatives, drying agents,

Skin prevention agents, corrosion inhibitors, waxes, matting agents, precursors of organically modified ceramic materials or additional binders.

The type and amount of additives (C) depend on the intended use of the coatings produced using the coating materials of the invention.

If, for example, a coating material according to the invention is used to produce solid-color top coats or basecoats, it usually contains color and / or effect pigments (C) and optionally opaque fillers. If a coating material according to the invention is used, for example, to produce clearcoats or sealers - which is the preferred use - these additives (C) are naturally not present in the coating material in question.

Examples of suitable effect pigments (C) are metal plate pigments such as commercially available aluminum bronzes, chromated according to DE 36 36 183 A1 Aluminum bronzes, and commercially available stainless steel bronzes as well as non-metallic effect pigments, such as pearlescent or interference pigments. In addition, reference is made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 176, "Effect Pigments" and pages 380 and 381 "Metal Oxide Mica Pigments" to "Metal Pigments".

Examples of suitable inorganic color pigments (C) are titanium dioxide, iron oxides, Sicotrans yellow and carbon black. Examples of suitable organic color pigments (C) are thioindigo pigments indanthrene blue, cromophthal red, irgazine orange and heliogen green. In addition, Römpp Lexikon Lacke und Druckfarben, 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”.

Examples of suitable organic and inorganic fillers (C) are chalk, calcium sulfates, 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. In addition, reference is made to Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 250 ff., "Füllstoffe".

Examples of suitable thermally curable reactive diluents (C) are those described in detail above.

Examples of suitable reactive thinners (C) curable with actinic radiation are those described in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the keyword “reactive diluents”. Examples of suitable low-boiling organic solvents (C) and high-boiling organic solvents (C) (“long solvents”) are ketones such as methyl ethyl ketone or methyl isobutyl ketone, esters such as ethyl acetate or butyl acetate, ethers such as dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Butylene glycol or

Dibutylene glycol dimethyl, diethyl or dibutyl ether, N-methylpyrrolidone or xylenes or mixtures of aromatic hydrocarbons such as Solventnaphtha® or Solvesso®.

Examples of suitable thermolabile free-radical initiators (C) are 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.

Examples of suitable catalysts (C) for crosslinking are dibutyltin dilaurate, lithium decanoate or zinc octoate.

Examples of suitable photoinitiators and coinitiators (C) are described in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446.

Examples of suitable other additional binders (C) are oligomeric and polymeric, linear and / or branched and / or block-like, comb-like and or randomly structured (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and or or thermally and / or with actinic radiation Polycondensation resins, such as those in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1 98, page 457: "Polyaddition" and "Polyadditionharze (Poly adducts)", pages 463 and 464: "Polycondensates", "Polycondensation" and "Polycondensation Resins", as well as pages 73 and 74: "Binder". Further examples Other suitable additional binders (C) are the poly (meth) acrylates or acrylate copolymers described in the patent DE 197 36 535 A1, polyesters, in particular the alkyds described in the patents DE 40 09 858 A1 or DE 44 37 535 A1 Acrylated polyesters, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters, polyurethanes and acrylated polyurethanes, such as those in the patents EP 0 521 928 A 1, EP 0 522420 A 1, EP 0 522419 A 1, EP

0 730 613 A1 or DE 44 37 535 A1 described, or polyureas.

Examples of suitable additional crosslinking agents (C) are aminoplast resins, as described, for example, in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29, "Aminoharze", the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York , 1998, pages 242 ff., The book "Paints, Coatings and Solvents", second completely revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A1 or EP-B-0 245 700 A1 as well as 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, compounds containing carboxyl groups or resins, such as those described, for example, in the patent specification DE 196 52 813 A1, compounds or resins containing epoxy groups, as described, for example, in the patent specifications EP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, US 4,091,048 A1 or US 3,781,379 A1 are blocked polyisocyanates, as described, for example, in the patents US 4,444,954 A1, DE 196 17 086 A1, DE 196 31 269 A1, EP 0 004 571 A1 or EP 0 582 051 A1

1 and / or tris (alkoxycarbonylamino) triazines as described in the patents US 4,939,213 A1, US 5,084,541 A1, US 5,288,865 A1 or EP 0 604 922 A1. Examples of suitable deaerating agents (C) are diazadicycloundecane or benzoin.

Examples of suitable emulsifiers (C) are nonionic emulsifiers, such as alkoxylated alkanols and polyols, phenols and alkylphenols or anionic emulsifiers such as alkali metal salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids, and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols.

Examples of suitable wetting agents (C) are siloxanes, fluorine-containing compounds, carboxylic acid half-esters, phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes.

An example of a suitable adhesion promoter (C) is tricyclodecanedimethanol.

Examples of suitable film-forming aids (C) are cellulose derivatives such as cellulose acetobutyrate (CAB).

Examples of suitable transparent fillers (C) are those based on silicon dioxide, aluminum oxide or zirconium oxide; In addition, reference is made to the Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252.

Examples of suitable Sag control agents (C) are ureas, modified ureas and / or silicas, as described, for example, in references EP 0 192 304 A1, DE 23 59 923 A1, DE 18 05 693 A1, WO 94/22968, DE 27 51 761 C 1, WO 97/12945 or "färbe + lack", 11/1992, pages 829 ff. Examples of suitable rheology control additives (C) are those known from the patent specifications WO 94/22968, EP 0 276 501 A1, EP 0 249 201 A1 or WO 97/12945; crosslinked polymeric microparticles, as disclosed, for example, in EP 0 008 127 A1; inorganic layered silicates such as aluminum-magnesium silicates, sodium-magnesium and

Montmorillonite type sodium magnesium fluorine lithium layered silicates; 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 ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates;

An example of a suitable matting agent (C) is magnesium stearate.

Examples of suitable precursors (C) for organically modified ceramic materials are hydrolyzable organometallic compounds, in particular of silicon and aluminum.

Further examples of the additives (C) listed above and examples of suitable UV absorbers, free radical scavengers, leveling agents,

Flame retardants, desiccants, drying agents, anti-skinning agents, corrosion inhibitors and waxes (B) are described in detail in the textbook "Varnish Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998.

The preparation of the binder component containing additives (C) to be used according to the invention has no peculiarities, but is carried out in a customary and known manner by mixing the mixtures (A) and additives (C) described above in suitable mixing units such as stirred kettles, dissolvers, stirrer mills or extruders , The second component of the coating materials, adhesives and sealants according to the invention contains at least one adduct (B).

The adduct (B) can be prepared from a diisocyanate (bl) and a compound I (b2).

Examples of suitable diisocyanates are isophorone diisocyanate (= 5-isocyanato-l-isocyanatomethyl-l, 3,3-trimethyl-cyclohexane), 5Tsocyanato-l- (2-isocyanatoeth-l-yl) -l, 3,3-trimethyl-cyclohexane, 5-isocyanato-l- (3-isocyanatoprop-l-yl) -l, 3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-y 1) - 1, 3, 3-trimethyl-cyclohexane , l-isocyanato-2- (3-isocyanatoprop-l-yl) cyclohexane, l-isocyanato-2- (3-isocyanatoeth-l-yl) cyclohexane, l-isocyanato-2- (4-isocyanatobut-l-yl ) - cyclohexane, 1,2-diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2-diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane, 1,2-

Diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-

Diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate, diisocyanate tri-, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), ethylethylene, trimethylhexane dusocyanat, heptamethylene or diisocyanates derived from dimer fatty acids, as sold under the commercial designation DDI 1410 by Henkel and in the patents WO 97/49745 and WO 97/49747, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -l-pentylcyclohexane, or 1,2-, 1,4- or l , 3-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,4- or 1,3-bis (2-isocyanatoeth-l-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-l-yl) cyclohexane , 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-l-yl) cyclohexane or liquid bis (4-isocyanatocyclohexyι) methane with a trans / trans content of up to 30% by weight, preferably 25% by weight and in particular 20% by weight, as described in patent applications DE 44 14 032 A1, GB 1220717 A1, DE 16 18 795 A1 or DE 17 93 785 A1 n is, preferably isophorone diisocyanate, 5- Isocyanato-1 - (2-isocyanatoeth-1-y 1) - 1, 3, 3-trimethyl-cyclohexane, 5-isocyanato-1 - (3-isocyanatoprop-l-yl) -l, 3,3-trimethyl-cyclohexane , 5-isocyanato- (4-isocyanatobut-l-yl) -l, 3,3-trimethyl-cyclohexane, l-isocyanato-2- (3-isocyanatoprop-l-yl) -cyclohexane, l-isocyanato-2- ( 3-isocyanatoeth-l-yl) cyclohexane, l-isocyanato-2- (4-isocyanatobut-l-yl) cyclohexane or HDI, in particular HDI.

The compounds I have an isocyanate-reactive functional group. Examples of suitable isocyanate-reactive functional groups are hydroxyl groups, thiol groups and primary or secondary amino groups.

The compounds I have the general formula I:

In the general formula I, R ¹ and R ² independently of one another represent hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms, preferably methyl, ethyl. Propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, n-pentyl, isoamyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-hex-l-yl, n-nonyl or n-decyl, especially isopropyl;

U and V independently of one another represent oxygen atoms, sulfur atoms or residues> NR ⁶ , in which R ^{6 is} an aliphatic residue with 1 to 30 carbon atoms, the carbon chain of which can be interrupted by one or more oxygen atoms, such as the residues R ¹ and R ² described above , Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosanyl or OHgo (ethylene glycol) -l-yl, oligo (propylene glycol) -l-yl or Oligo (butylene glycol) -l-yl or the corresponding mixed oligomers with a degree of oligomerization of up to 15. In addition, R ⁶ can be an aromatic radical with 6 to 30 carbon atoms, such as phenyl, naphthyl or diphenyl-1-yi

R ³ stands for an alkylene radical with 1 to 5 carbon atoms such as methylene, eth-1,2-ylene, trimethylene, tetramethylene or pentamethylene.

R ⁴ and R ⁵ independently of one another represent hydrogen atoms, isocyanate-reactive functional groups or radicals R ⁶ .

It is essential for the compounds I that a radical R ⁴ , R ⁵ or R ^{6 contains} an isocyanate-reactive functional group or a radical R ⁴ or R ^{5 is} an isocyanate-reactive functional group, the other radicals R ⁴ , R ⁵ or R ⁶ - if present - have no isocyanate-reactive functional groups.

Examples of highly suitable compounds I are

Dioxolanes of the general formula II

Dioxanes of the general formula III:

Oxazolidines of the general formula IV:

wherein the radicals R ¹ , R ² , R ⁴ , R ⁵ and R ^{6 have} the meaning given above, the radicals R ⁴ or R ⁶ containing an isocyanate-reactive functional group.

Examples of suitable dioxolanes (II), dioxanes (III) and dioxazolidines (IV) and their preparation are described in detail in the examples of German patent application DE 196 09 617 A1, page 5, line 54, to page 9, line 27 ,

Of these, the oxazolidines (IV) have particular advantages, which is why they are used with particular preference according to the invention. Examples of particularly suitable oxazolidines (IV) are N- (2-hydroxyethyl) -1, 3-oxazolidine or N- (2-hydroxyethyl) -2-isopropyl-1,3-oxazoHdin, as described on page 6, Table 1, No. 5a and No. 5b, the German patent application DE 196 09 617 A1 are described.

For the preparation of the adduct (B) it is essential that the molar ratio of isocyanate groups in the dusocyanates (b1) to the isocyanate-reactive functional groups in the compound I (b2) is 0.8: 1.2 to 1.2: 0, 8, preferably 0.9: 1.1 to 1.1: 0.9 and in particular 1: 1. The content of the adducts (B) described in the coating materials, adhesives and sealants according to the invention can vary very widely. It depends in particular on the functionality of the crosslinking agent (D) and the liquid mixture (A) and on the viscosity of the coating materials, adhesives and sealants according to the invention. The content is preferably 10 to 90, preferably 15 to 85, particularly preferably 20 to 80, very particularly preferably 22 to 75 and in particular 25 to 70% by weight, in each case based on the solids content of the coating materials, adhesives and sealants according to the invention, where the content of (B) up to twice as high as the content of (A) can be chosen.

The second component to be used according to the invention also contains at least one reactive crosslinking agent (D). However, this crosslinking agent (D) can also be contained in a third component to be used according to the invention.

In the context of the present invention, a reactive crosslinking agent (D) is understood to mean a crosslinking agent which, in contrast to the crosslinking agents (C) described above, for one-component systems is already below 90, preferably below 70, preferably below 60, particularly preferably below 50, particularly preferably below 40, very particularly preferably below 30 ° C. and in particular at room temperature, react with the liquid mixtures (A) described above, the adducts (B) after the ketone is split off and with any additional reactive diluents (C) which are present for the thermal curing.

Examples of suitable reactive crosslinking agents (D) are polyisocyanates which, on a statistical average, have more than two isocyanate groups in the molecule and are, if appropriate, modified hydrophilically or hydrophobically. Preferably, the Polyisocyanates (D) are liquid and preferably of low viscosity, so that they can easily be incorporated into the second component or into the mixture of the first and second components. Polyisocyanates (D) with 2 to 5 isocyanate groups per molecule and with viscosities at 23 ° C. of 100 to 2000 mPa.s are particularly preferably used. If necessary, small amounts of organic solvents (C), preferably 1 to 25% by weight, based on pure polyisocyanate (D), can be added to the polyisocyanates (D) in order to improve the incorporation of the polyisocyanate (D) and, if appropriate, its Reduce viscosity to a value within the above ranges.

Examples of suitable polyisocyanates (D) are polyurethane prepolymers containing isocyanate groups, which can be prepared by reacting polyols with an excess of the above-described diisocyanates (b1) and are preferably low-viscosity. Polyisocyanates (D) containing isocyanurate, biuret, AUophanat, iminooxadiazindone, urethane, urea and / or uretdione groups can also be used. Polyisocyanates containing urethane groups are obtained, for example, by reacting some of the isocyanate groups with polyols, e.g. Trimethylolpropane and glycerin. Aliphatic or cycloaliphatic diisocyanates (b1), in particular hexamethylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, dicyclohexylmethane-2,4'-diisocyanate or

Dicyclohexylmethane-4,4'-diisocyanate or mixtures of these dusocyanates are used.

Mixtures of uretdione and / or isocyanurate groups and / or allophanate groups containing polyisocyanates (D) based on hexamethylene diisocyanate or isophorone diisocyanate, such as those obtained by catalytic oligomerization of hexamethylene diisocyanate or Isophorone diisocyanate are formed using suitable catalysts.

The content of the crosslinking agents (D) described above in the coating materials, adhesives and sealants according to the invention can also vary very widely. In particular, it depends on the functionality of the crosslinking agent (D) and the (meth) acrylate copolymer (A) and the amount of adduct (B). The content is preferably 10 to 70, preferably 15 to 65, particularly preferably 17 to 60, very particularly preferably 20 to 55 and in particular 22 to 50% by weight, in each case based on the solids content of the coating materials, adhesives and sealants according to the invention.

Otherwise, the second component to be used according to the invention or - if used - also or only the third component to be used according to the invention may contain at least one of the additives (C) described above, provided that these are not combined with the adducts (B) and / or the crosslinking agents (D ) enter undesirable reactions such as decomposition reactions or premature crosslinking reactions.

Otherwise, all or some of the additives (C) described above, which are used in the coating materials, adhesives and sealants according to the invention, may also be present as a separate, separate, third or fourth component.

The production of the coating materials, adhesives and sealants according to the invention from the components described above does not offer any special features in terms of method, but rather is carried out with the aid of the customary and known mixing devices and methods described above or by means of conventional two- or multi-component metering and mixing systems. The mixing should ideally be done by hand. The coating materials, adhesives and sealants according to the invention are used to produce coatings, adhesive layers and seals on and / or in primed and unprimed substrates. In particular, the coating materials according to the invention are used to produce solid-color top coats, clear coats and basecoats and clear coats in multi-coat paint and / or effect coatings.

In terms of method, the application of the coating materials according to the invention has no peculiarities, but can be carried out by all the usual application methods, such as Spraying, knife coating, brushing, pouring, dipping, trickling or rolling. Preferably be

Spray application methods are used, such as compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), if appropriate combined with hot spray application such as hot air - hot spraying.

Suitable substrates are surfaces which are not damaged by hardening of the coating materials, adhesives and / or sealing compounds located thereon using heat and, if appropriate, actinic radiation; these are e.g. B. metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as plaster and cement boards or roof tiles, as well as composites of these materials. Accordingly, the coating materials, adhesives and sealants according to the invention are also suitable for applications outside the automotive industry. They are particularly suitable for painting, gluing and / or sealing furniture, windows, doors, structures indoors and outdoors and industrial painting, including coil coating, container coating and the impregnation or coating of electrical components. in the As part of industrial painting, they are suitable for painting, gluing and / or sealing practically all parts for private or industrial use such as radiators, household appliances, small parts made of metal such as screws and nuts, hub caps, rims, packaging or electrical components such as motor windings or transformer windings.

In the case of electrically conductive substrates, 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.

The electrodeposition coating or the electrodeposition coating layer can be covered with a filler which is cured either on its own or together with the electrodeposition coating layer (wet-on-wet method). The overlay with a filler takes place in particular in areas that are exposed to strong mechanical stress, such as stone chips.

Examples of suitable cathodic electrocoating materials and, if appropriate, wet-on-wet processes are described in Japanese Patent Application 1975-142501 (Japanese Patent Application Laid-Open JP 52-065534 A 2, Chemical Abstracts Section No. 87: 137427) or in the patent specifications and applications US 4,375,498 A 1, US 4,537,926 A 1, US 4,761,212 A 1, EP 0 529 335 A 1, DE 41 25 459 A 1, EP 0 595 186 A 1, EP 0 074 634 A 1, EP 0 505 445 A 1, DE 42 35 778 A 1, EP 0 646 420 A 1, EP 0 639 660 A 1, EP 0 817 648 A 1, DE 195 12 017 C 1, EP 0 192 113 A 2, DE 41 26 476 A 1 or WO 98 / 07794.

Likewise, suitable fillers, especially aqueous fillers, are also available as

Stone chip protection primers or functional layers are referred to, from the patents and applications US 4,537,926 A1, EP 0 529 335 A1, EP 0 595 186 A1, EP 0 639 660 A1, DE 44 38 504 A1, DE 43 37 961 A1, WO 89/10387, US 4,450,200 A1, US 4,614,683 A1 or WO 490/26827.

Primed or unprimed plastic parts made of e.g. B. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC / PBT, PC / PA, 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, glued or sealed. In the case of 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.

According to the invention, in order to produce the clearcoats and solid-color coatings according to the invention, the coating materials of the suitable composition according to the invention are applied to the substrates described above, after which the resulting clearcoat and solid-color lacquer layers are cured.

According to the invention, for the production of the adhesive layers and seals according to the invention, the adhesives and sealants according to the invention are applied to and / or in the substrates described above. When bonding substrates, the surfaces to be bonded of two or more substrates are preferably coated with the adhesive according to the invention, after which the surfaces in question may be brought into contact under pressure and the resulting adhesive layers are cured.

According to the invention, the production of a multi-layer paint and / or effect coating according to the invention is carried out on a primed or unprimed substrate (1) applying a basecoat to the substrate,

(2) drying and / or partial hardening or complete hardening of the basecoat layer,

(3) application of a clearcoat to the dried and / or partially hardened basecoat or the hardened basecoat and

10 (4) joint curing of the clear coat with the basecoat or separate curing of the clear coat.

In a first, preferred variant, a basecoat known per se and a clearcoat according to the invention are used as the clearcoat. 15

In a second, preferred variant, a clear lacquer known per se and a basecoat according to the invention are used as the basecoat.

In a third, preferred variant, a basecoat 20 according to the invention and a clearcoat according to the invention are used.

Examples of known basecoats are from the patent applications EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0

25 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A1, EP 0 593 454 A1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1 , EP 0 590 484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95/14721, EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649 865 A1, EP 0 536 712 A1, EP 0 596 460 A1, EP 0 596 461 A1, EP 0 584 818 A1, EP 0 669 356 A1, EP 0 634

30 431 A1, EP 0 678 536 A1, EP 0 354 261 A1, EP 0 424 705 A1, WO 97/49745, WO 97/49747, EP 0 401 565 A1 or EP 0 817 684, column 5, lines 31 to 45, are known.

Clearcoats known per se are one- or multi-component clearcoats, powder clearcoats, powder slurry clearcoats, UV-curable clearcoats or sealers, as described in patent applications, patent specifications and publications DE 4204 518 A1, EP 0 594 068 A1, EP 0 594 071 A1, EP 0 594 142 A1, EP 0 604 992 A1, EP 0 596 460 A1, WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615, US 5,474,811 A1 , US 5,356,669 A 1 or US 5,605,965 A 1, DE 42 22 194 A 1, product information from BASF Lacke + Farben AG, “Powder Coating”, 1990, company lettering from BASF Coatings AG “Powder Coating, Powder Coating for Industrial Applications”, January 2000, US 4,268,542 A1, DE

195 40 977 A1, DE 195 18 392 A1, DE 196 17 086 A1, DE-A-196 13 547, DE

196 52 813 A1, DE-A-198 14 471 A1, EP 0 928 800 A1, EP 0 636 669 A1, EP 0 410 242 A1, EP 0 783 534 A1, EP 0 650 978 A1 , EP 0 650 979 A1, EP 0 650

985 A1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1, EP 0 002 866 A1, DE 197 09 467 A1, DE 42 03 278 A1, DE 33 16 593 A 1, DE 38 36 370 A 1, DE 24 36 186 A 1, DE 20 03 579 B 1, WO 97/46549, WO 99/14254, US 5,824,373 A 1, US 4,675,234 A 1, US 4,634,602 A 1, US 4,424,252 A1, US 4,208,313 A1, US 4,163,810 A1, US 4,129,488 AI, US 4,064,161 A1, US 3,974,303 A1, EP 0 844 286 A1, DE 43 03 570 A1, DE 34 07 087 AI, DE 40 11 045 A1, DE 40 25 215 A1, DE 38 28 098 A1, DE 40 20 316 A1 or DE 41 22 743 A1 are known.

The curing of the applied coating materials, adhesive layers and sealants according to the invention is also not methodologically peculiar, but generally takes place at room temperature in the course of 30 minutes to several days, for example 4 to 10 days. Hardening can be supported by the application of heat and / or actinic radiation. This is particularly the case when the inventive Coating materials, adhesive layers and sealants contain constituents (C) which can be activated with actinic radiation and / or constituents (C) which are thermally curable, such as the crosslinking agents (C) for one-component systems. This is also the case if customary and known thermally and / or actinic radiation-curable clearcoats or basecoats are used in the production of the multi-layer paint and / or effect paint system according to the invention. Curing with heat and actinic radiation is also referred to by experts as "dual cure".

The usual and known devices such as infrared and near infrared emitters, hot air blowers or convection ovens come into consideration for thermal curing.

In the context of the present invention, xinter actinic radiation is understood to mean electromagnetic radiation such as near infrared, visible light, UV light or X-rays, but especially UV light, and corpuscular radiation, in particular electron radiation. The appropriate radiation sources, such as UV lamps, are used for curing.

The coating materials, adhesives and sealants according to the invention have a high solids content with low viscosity and a long service life.

The resulting coatings according to the invention, in particular the solid-color top coats, clear coats and color and / or effect multi-layer lacquers, have high hardness, flexibility and chemical resistance, an excellent flow, a very good interlayer adhesion, an excellent overall optical impression, one very good weather resistance, very high scratch resistance and very good polishability.

The adhesive layers according to the invention are permanently adhesive, even under extreme and / or very strongly and rapidly changing climatic conditions.

In the long term, the seals according to the invention completely seal against chemically aggressive substances.

Thus, the primed and unprimed substrates according to the invention, which are coated with at least one coating according to the invention, bonded with at least one adhesive layer according to the invention and / or sealed with at least one seal according to the invention, have a particularly long service life in addition to the advantages listed above, which makes them particularly economical makes you valuable.

Examples

Production Example 1

The Production of a Liquid Mixture (A) to be Used According to the Invention

150 parts by weight of 2,4-diethyloctanediol-1,5 (DEOD), 75 parts by weight of vinyl versatate (VeoVa® 10) were placed in a laboratory reactor equipped with a stirrer, two dropping funnels for the monomer feed and the initiator feed, nitrogen inlet tube, thermometer and reflux condenser, 172.5 parts by weight of methyl amyl ketone and 132.5 ethoxyethyl propionate are introduced and heated to 145 ° C. with stirring under an inert gas. When the temperature is reached the initiator feed was started (solution of 67.5 parts by weight of di-tert-butyl peroxide in 45 parts by weight of methyl amyl ketone), which was continued uniformly for 5 hours. 15 minutes after the start of the initiator feed, a monomer mixture of 225 parts by weight of styrene, 150 parts by weight of tert-butylcyclohexyl acrylate, 450 parts by weight of n-butyl methacrylate and 600 parts by weight of hydroxypropyl methacrylate was metered in uniformly over a period of 4 hours. The resulting reaction mixture was diluted with 285 parts by weight of a solvent mixture (n-butyl acetate, xylene and methyl amyl ketone in a weight ratio of 8: 1: 1). The resulting liquid mixture (A) had a solids content of 67.8% by weight (lg / 1 h / 130 ° C.) and a viscosity of 18 dPas.

Preparation example 2

The production of an adduct (B)

N- (2-hydroxyethyl) -2-isopropyl-l, 3-oxazolidine was, as on page 9, lines 7 to 17, "V4 - Monourethane from HDI", which is described in DE 196 09 617 A1, with HDI in a molar ratio Converted 1: 1 to the adduct (B).

Preparation example 3

The preparation of a reactive thinner (C)

136 parts by weight of pentaerythritol and 616 parts by weight of phthalic anhydride were placed in a 4 1 steel reactor and heated to 120 ° C. with stirring for 6.5 hours. 904 parts by weight of Versatic acid® glycidyl ester were added to the resulting reaction mixture. The resulting reaction mixture was further heated until an acid number of 0.7 mg KOH / g was reached. After cooling to 90 ° C, the reactive diluent adjusted to a solids content of 83.2% by weight with n-butyl acetate (lg / lh / 130 ° C.). The number average molecular weight, determined with the aid of gel permeation chromatography with polystyrene as standard, was 1,684 daltons, and the mass average was 3,280 daltons.

Examples 1 and 2

The production of clearcoats and clearcoats according to the invention

For example 1, 25.82 parts by weight of the reactive diluent (C) according to preparation example 3, 19.92 of the liquid mixture (A) according to preparation example 1, 6.67 parts by weight of DEOD, 25.04 parts by weight of the commercially available Desmodur® 3600 polyisocyanate from Bayer AG (NCO content: 23% by weight), 3.28 parts by weight of the commercially available Desmodur® N 3390 polyisocyanate from Bayer AG (90%; NCO content: 19.5% by weight), 0.34 Parts by weight of the commercially available additive Antigel from Schwego (solids content: 16% by weight), 0.08 parts by weight of the commercially available defoamer BYK® 331 from Byk Chemie, 0.02 parts by weight of dibutyltin dilaurate (10% in butyl acetate), 0.82 Parts by weight of the commercial additive Baysilon® oil OL 44 from Bayer AG, 0.7 parts by weight of the light stabilizer Tinuvin® 400 and 0.08 part by weight of the light stabilizer Tinuvin® 292, both from the company Ciba Specialty Chemicals, 17.2 parts by weight of butyl acetate and 14 , 02 parts by weight d it mixed adduct (B) of preparation example 2 and homogenized, so that a clear coat with 70 wt .-% solids resulted (lg / lh 130 ° C).

Example 1 was repeated for example 2, except that instead of 14.02 parts by weight, 49.8 parts by weight of the adduct (B) from preparation example 2 was used, so that a clear lacquer with a solids content of 80% by weight resulted (lg / lh / 130 ° C). The clearcoats of Examples 1 and 2 were applied to glass panels with a wet layer thickness of 150 μm. The clear lacquer layers were fully cured after heating for 45 minutes at 90 ° C. The clear coats were hard, clear and transparent and free from stoves. They had a smooth, structure-free and tack-free surface. The clearcoats were outstandingly suitable as automotive refinish paints or for the production of color and / or effect multi-layer coatings by the wet-on-wet process.

Claims

Multi-component coating materials, adhesives and sealants and their use

claims

1. Containing multi-component coating materials, adhesives and sealing compounds

(A) at least one liquid mixture of at least one

(Co) polymer and at least one thermally curable reactive diluent, can be prepared by polymerizing at least one olefinically unsaturated monomer (al) with at least one isocyanate-reactive functional group in at least one thermally curable reactive diluent with at least two isocyanate-reactive functional groups; and

(B) at least one adduct, producible from

(b 1) at least one diisocyanate and

(b2) at least one compound of the general formula I with an isocyanate-reactive functional group:

R ⁴ R ¹

R ³ C (I), where the variables have the following meaning:

1

5 R and R: independently of each other

Hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms;

U and V: independently of one another = oxygen atom, 10 sulfur atom or a radical> NR ⁶ , in which R ⁶

= aliphatic radical with 1 to 30 carbon atoms, the carbon chain of which can be interrupted by one or more oxygen atoms, or aromatic grappa with 6 to 30 carbon atoms;

R ³ : alkylene radical having 1 to 5 carbon atoms;

R and R ⁵ : independently of one another hydrogen atoms, 20 isocyanate-reactive functional groups or

Residues R ⁶ ;

with the proviso that a radical R ⁴ , R ⁵ or R ^{6 contains} an isocyanate-reactive functional group or a radical

25 R ⁴ or R ^{5 is} an isocyanate-reactive functional group, the other radicals R ⁴ , R ⁵ or R ⁶ - if present, have no isocyanate-reactive functional groups; the molar ratio of isocyanate groups in the diisocyanates (b1) to the isocyanate-reactive functional grapples in the compound I being 0.8: 1.2 to 1.2: 0.8.

2. Multi-component coating materials, adhesives and sealing compounds according to spoke 1, characterized in that the (co) polymer is a (meth) acrylate (co) polymer.

3. Multi-component coating materials, adhesives and sealing compounds according to spoke 1 or 2, characterized in that the copolymer

(A) contains at least one further olefinically unsaturated monomer (a2), which contains no isocyanate-reactive functional grappa, in copolymerized form.

4. Multi-component coating materials, adhesives and sealing compounds according to one of claims 1 to 3, characterized in that hydroxyl, thiol or primary and secondary amino groups are used as isocyanate-reactive functional groups.

5. Multi-component coating materials, adhesives and sealing compounds according to one of claims 1 to 4, characterized in that polyols, polythiols, polyamines, polyol polythiols, polythiol polyamines, amino alcohols and / or polyol polyamine polythiols are used as reactive thinners.

Multi-component coating materials, adhesives and sealing compounds according to spoke 5, characterized in that polyols are used as reactive thinners. Multi-component coating materials, adhesives and sealing compounds according to spoke 6, characterized in that as polyols

(i) hyperbranched compounds having a tetrafunctional central group derived from ditrimethylolpropane, diglycerol and / or ditrimethylolethane, or a tetrafunctional central group of the general formula I,

C [-A _q -X-] _m [-A _r -X-] _π [-A _s -X-] ₀ [-A _t -X-] _p (V),

where the indices and the variables have the following meaning:

m + n + o + p = 4; with m = an integer from 1 to 3 and n, o and p = 0 or an integer from 1 to 3;

q, r, s and t = an integer from 1 to 5, where q> r, s, t, in particular q> r, s, t;

X = -O-, -S- or -NH-;

A = -C (R ⁷ ) ₂ -; With

R ⁷ = -H, -F, -Cl, -Br, -CN, -NO ₂ , CC ₃ -alkyl or - haloalkyl or -Cralkoxy, or - for q, r, s and / or t = at least 2 - R ⁷ = C ₂ -C ₄ alkanediyl and / or oxaalkanediyl radical which has 2 to 5 carbon atoms and / or an oxygen atom -O- which bridges 3 to 5 carbon atoms of the radical -A-; (ii) cyclic and / or acyclic C ₉ -C ₆ alkanes which are functionalized with at least two hydroxyl groups;

(iii) polyols obtainable by using oligomers of the formula VI,

R ⁹ R ¹⁰ C = [= CH-R ⁸ -CH =] _v = CR ^π R ¹² (VI),

wherein

R ⁸ = - (- CH ₂ -) _W -, where the index w is an integer from 1 to 6, or

wherein W = -CH ₂ - or an oxygen atom;

R ⁹ , R ¹⁰ , R ¹¹ and R ¹² independently of one another = hydrogen atoms or alkyl; and

Index v = an integer from 1 to 15;

hydroformylated and the resulting products are hydrogenated;

be used. Multi-component coating materials, adhesives and sealing compounds according to claim 7, characterized in that

as polyols (i) a hyperbranched compound, obtainable by reacting 2,2-bis-hydroxymethyl-butanediol-1,4 with

Phthalic anhydride and subsequent reaction of the resulting intermediate with glycidyl esters of tertiary, highly branched, saturated monocarboxylic acids,

- As polyols (ii) dialkyloctanediols, especially diethyloctanediols, and

as polyols (iii) hydroformylated and hydrogenated oligomers, obtainable by metathesis of acyclic monoolefins and cyclic monoolefins, hydroformylation of the resulting

Oligomers and subsequent hydrogenation, using cyclopentene as cyclic monoolefin and hydrocarbon mixtures obtained by cracking in petroleum processing (Cs cut) as cyclic monoolefins, and wherein the polyols (iii) have a hydroxyl number (OHZ) of 200 to 650, in particular 250 to 450, a number-average molecular weight M _n of 400 to 1,000, in particular 400 to 600, a mass-average molecular weight M _w in the range from 600 to 2,000, in particular 600 to 1,100 and a non-uniformity Mn / M _w of 1.4 to 3, in particular 1 , 7 to 1.9;

be used. Multi-component coating materials, adhesives and sealing compounds according to one of Claims 1 to 8, characterized in that the compounds of the general formula I are

Dioxolanes of the general formula II:

Dioxanes of the general formula III:

Oxazolidines of the general formula IV:

where the radicals R ¹ , R ² , R ⁴ , R ⁵ and R ^{6 have} the meaning given above, the radicals R ⁴ or R ⁶ containing an isocyanate-reactive functional group.

Multi-component coating materials, adhesives ^"and sealing compounds according to one of claims 1 to 9, characterized in that they contain at least one polyisocyanate as crosslinking agent. 4698

72

11. Multi-component coating materials, adhesives and sealing compounds according to one of claims 1 to 10, characterized in that they contain at least one coloring and / or effect pigment.

12. A process for the production of a coloring and / or effect coating by applying a solid-color topcoat to a primed or unprimed substrate, characterized in that a multicomponent coating according to Claim 11 is used as solid-color topcoat.

13. A process for producing a clearcoat by applying a clearcoat to a primed or unprimed substrate or a paint thereon, characterized in that a multi-component coating material according to one of claims 1 to 9 is used as the clearcoat.

14. Process for the production of a coloring and / or effect-giving multi-layer lacquer coating on a primed or unprimed substrate

(1) applying a basecoat to the substrate,

(2) drying and / or partial hardening or complete hardening of the basecoat film,

(3) application of a clearcoat to the dried and / or partially hardened basecoat or the hardened basecoat and

(4) curing the clear lacquer layer together with the base lacquer layer or separately hardening the clear lacquer layer, characterized in that one

(a) a basecoat known per se and, as a clearcoat, a multicomponent coating material according to one of claims 1 to 9,

(b) a known clear coat and as a base coat a multi-component coating material according to claim 10 or

(c) as a basecoat a multi-component coating material according to spoke 10 and as a clearcoat a multi-component coating material according to one of claims I to 9

used.

15. A process for the production of adhesive layers and / or seals by applying adhesives and / or sealants on and / or in primed and unprimed substrates, characterized in that multicomponent adhesives and sealants according to one of claims 1 to 10 are used as adhesives and Sealants used.

16. The method according to any one of claims 12 to 15, characterized in that motor vehicle bodies or parts thereof, interior and exterior structures, doors, windows, furniture and industrial components, including coils, containers and electrical components, are used as substrates.