WO2009068377A1 - Polyurethane compounds containing uretdione groups and hardenable at low temperature and also containing adhesion-improving resins - Google Patents

Abstract

The invention relates to polyurethane compounds, which contain uretdione groups and are hardenable at low temperature and also contain adhesion-improving resins, in particular for polyurethane powder coating and adhesive compounds, which can be hardened at low temperature, to a method for the production thereof, and to the use thereof.

Description

 Uretdione group-containing polyurethane compositions which are curable at low temperature and contain adhesion-improving resins

The invention relates to uretdione group-containing polyurethane compositions which are curable at low temperature and contain adhesion-improving resins, in particular for polyurethane powder coating and adhesive compositions which are curable at low temperature, a process for their preparation and their use.

Solid at room temperature, externally or internally blocked polyisocyanates are valuable crosslinkers for thermally crosslinkable polyurethane (PUR) -Pulverlack- and adhesive compositions.

DE-OS 30 30 539 and DE-OS 30 30 572 describe processes for the preparation of uretdione-containing polyaddition compounds whose terminal

Isocyanate groups with monoalcohols or monoamines are irreversibly blocked. Disadvantages are, in particular, the chain-breaking constituents of the crosslinkers which lead to low network densities of the PU powder coating and thus to moderate solvent resistances.

Hydroxyl-terminated, polyaddition compounds containing uretdione groups are the subject of EP 669 353. Due to their functionality of two, they have improved resistance to solvents. The powder coating compositions based on these polyisocyanates containing uretdione groups have in common that they do not emit volatile compounds during the curing reaction. However, the baking temperatures are at least 180 ⁰ C at a high level.

Certain catalysts greatly reduce the activation energy for the cleavage of uretdione groups, so that when uretdione group-containing curing agents are used, the curing temperature of powder coating or adhesive compositions can be considerably lowered. This is beneficial since This way energy can be saved and it is possible to coat thermosensitive substrates by means of powder coatings. Due to the low curing temperature, there is a high melt viscosity of the applied paint formulation. This leads to development problems and surface defects of the powder coating films. In addition, owing to the high melt viscosity, a significantly lower wetting of the substrate surface is frequently observed, which manifests itself in the reduction of the values for mechanical characteristics and in particular in the deterioration of the substrate adhesion. Course problems and surface defects can, as described in DE 10 2004 020 451, be remedied by addition of hydroxyl-containing (partially) khallins polymers, improved substrate wetting is not achieved, so that the substrate adhesion is still problematic.

The object of the present invention was therefore to find highly reactive uretdione-containing polyurethane compositions which can be cured even at very low temperatures and are particularly suitable for the production of light- and weather-stable powder coatings and which have comparable good substrate adhesion values, as correspondingly at higher temperatures hardened Puvehackformulierungen.

Surprisingly, it has been found that in low-temperature curing uretdione-containing systems, the use of special adhesion resins based on unsaturated polyester substrate wetting and thus the adhesion of such powder coating formulations, with and without the addition of hydroxyl-containing (partially) crystalline polymers, significantly improved without negatively affecting resistance properties ,

Conventional uretdione-containing paint or adhesive compositions can be cured under normal conditions (DBTL catalysis) only from 180 ⁰ C, thereby resulting in coatings, which are usually to the substrate, eg. B. not pretreated steel, have excellent adhesion. With the aid of the inventive low-temperature curing compositions can at 100 to 160 ⁰ C curing not only energy and curing time can be saved, but it can also coat many temperature-sensitive substrates or stick, which would show at 180 ⁰ C undesirable yellowing, decomposition and / or embrittlement phenomena. In addition to metal, glass, wood, leather, plastics and MDF boards, certain aluminum substrates are also predestined. In the latter case, an excessively high temperature load sometimes leads to an undesired change in the crystal structure and thus to the loss of the desired mechanical properties.

The present invention relates to solid, highly reactive uretdione-containing polyurethane compositions having a melting point above 40 ⁰ C, a very good substrate wetting and a very good adhesion, essentially containing

A) at least one hardener containing uretdione groups, based on aromatic, aliphatic, (cyclo) aliphatic and / or cycloaliphatic polyisocyanates and hydroxyl-containing compounds having a free NCO content of less than 5% by weight and a uretdione group content of 1 to 18% by weight. %, in amounts between 15 and 45 wt .-% based on the total formulation; and

B) at least one catalyst

1. of the formula [XR ¹ R ² R ³ R ⁴ I ⁺ [R ⁵ COO] ^" , where X is N or P, where R ¹ to R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl Alkoxyalkyl radicals, in each case linear or branched, unbridged or bridged with other radicals R ¹ to R ⁴ , with the formation of cycles, bicycles or

Tricyclene and the bridging atoms in addition to carbon may also be heteroatoms having 1 to 18 carbon atoms and each radical R ¹ to R ⁴ additionally one or more alcohol, amino, ester, keto, thio, urethane, urea , Allophanate groups, double bonds, triple bonds or halogen atoms, and R ^{5 is} an alkyl,

Aryl, aralkyl, heteroaryl, alkoxyalkyl, linear or branched, having 1 to 18 carbon atoms and additionally one or more alcohol, May have amino, ester, keto, thio, acid, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms,

2. of the formula [XR ¹ R ² R ³ R ⁴ I ⁺ [R ⁵ ] ^" , where X is N or P, where R ¹ to R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, Alkoxyalkyl radicals, in each case linear or branched, unbridged or with others

R ¹ to R ⁴ bridged to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms, having 1 to 18 carbon atoms and each radical R ¹ to R ⁴ additionally one or more alcohol, amino , Ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds,

May have triple bonds or halogen atoms, and R ^{5 is} either OH or F,

3. of the formula M (OR ¹ ) _n (OR ² ) _m (OR ³ ) _O (OR ⁴ ) _P (OR ⁵ ) _q (OR ⁶ ) _r , where M is a metal in any positive oxidation state and identical to the sum n + m + o + p + q + r, m, o, p, q, r represent integers from 0 to 6 and for the

Total n + m + o + p + q + r = 1 to 6 applies, the radicals R ¹ to R ⁶ mean independently or independently of one another hydrogen or alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals having 1 to 8 carbon atoms and the radicals are in each case linear or branched, unbridged or bridged with other radicals, with the formation of cycles, bicyclic or tricyclic compounds and

Bridging atoms in addition to carbon may also be heteroatoms and may additionally have one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms, said catalysts from groups 1 to 3 are contained individually or in mixtures and C) at least one hydroxyl- and carboxyl-containing unsaturated, amorphous polyester, substantially containing at least one α, ßunsaturated dicarboxylic acid component and an alcohol component, wherein the alcohol component of a Dicidolgemisch the isomeric Compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ² ' ⁶ ] decane, 4.8- Bis (hydroxymethyl) tricyclo [5.2.1.0 ² ' ⁶ ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] decane, each isomer in an amount of 20 to 40% by weight in the mixture may be contained and the sum of the three isomers 90 to 100 wt .-%, and the mixture at least 5 wt .-% in the alcohol component of

Polyester is present, with an OH number between 1 and 100 mg KOH / gram and a COOH number between 1 and 75 mg KOH / gram, wherein the ratio of OH and acid number is always> 1, with a weight fraction based on the total formulation, from 1 to 12%; D) optionally at least one acid group-reactive compound;

E) optionally at least one acid in monomeric or polymeric form;

F) optionally at least one amorphous hydroxyl-containing or amine-containing polymer having an OH number between 20 and

500 mg KOH / gram or a comparable amine content; G) at least one (partially) khstallines hydroxyl-containing polymer having an OH number between 10 and 500 mg KOH / gram with a weight fraction, based on the total formulation, of 1 to 35%; H) optionally auxiliaries and additives and / or further catalysts;

wherein the proportion of the catalyst under B) 0.001 to 5 wt .-% of the

Total formulation is and the sum of the starting materials A) to H) 100 wt .-% results.

Another object of the invention is also a process for the preparation of the polyurethane composition.

The invention also provides powder coating compositions and pulverulent adhesive compositions and the use of the polyurethane compositions according to the invention for the production of powder coating coatings on metal, plastic, glass, wood or leather substrates or other heat-sensitive substrates or for the production of powdered adhesive coatings on metallic coatings. , Plastic, glass, wood or leather substrates or other heat-sensitive substrates.

The invention likewise relates to powder coating compositions for metal, in particular for automobile bodies, motorcycles and bicycles, building parts and household appliances, powder coating compositions for wood, glass, leather and plastics.

In addition, the articles coated in this way are part of the invention.

Polyisocyanates containing uretdione groups are well known and are described, for example, in US 4,476,054, US 4,912,210, US 4,929,724 and EP 0 417 603. For a comprehensive overview of industrially relevant processes for the dimerization of isocyanates to uretdiones J. Prakt. Chem. 336 (1994) 185-200. In general, the reaction of isocyanates to uretdiones in the presence of soluble Dimehsierungskatalysatoren, such as. As dialkylaminopyridines, Thalkylphosphinen, phosphorous acid triamides or imidazoles. The reaction - optionally carried out in solvents, but preferably in the absence of solvents - is stopped when a desired conversion is achieved by addition of catalyst poisons. Excess monomeric isocyanate is subsequently separated by short path evaporation. If the catalyst is volatile enough, the reaction mixture can be freed from the catalyst in the course of the monomer separation. The addition of catalyst poisons can be dispensed with in this case. In principle, a wide range of isocyanates is suitable for the preparation of polyisocyanates containing uretdione groups. According to the invention, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI),

Diisocyanatodicyclohexylmethane (Hi ₂ MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-thmethylhexamethylene diisocyanate ^^^ thymethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI) and tetramethylxylylene diisocyanate (TMXDI) used. Very particular preference is given to IPDI and HDI.

The implementation of these uretdione group-bearing polyisocyanates Uretdione group-containing hardeners A) includes the reaction of the free NCO groups with hydroxyl-containing monomers or polymers, such as. As polyesters, polythioethers, polyethers, polycaprolactams, polyepoxides, polyester amides, polyurethanes or low molecular weight di-, tri- and / or tetra alcohols as chain extenders and optionally monoamines and / or monoalcohols as chain terminators and has been described frequently (EP 669 353, EP 669 354, DE 30 30 572, EP 639 598 or EP 803 524). Preference is given to polyesters having an OH number of 30 to 150 mg KOH / g and an average molecular weight of 500 to 6000 g / mol and low molecular weight dialcohols. Preferred uretdione hardeners A) have a free NCO content of less than 5% by weight and a uretdione group content of 1 to 18% by weight (calculated as C ₂ N ₂ O ₂ , molecular weight 84). In addition to the uretdione groups, the hardeners A) may also have isocyanurate, biuret, allophanate, urethane and / or urea structures.

The catalysts B) essential to the invention satisfy 1. the formula [XR ¹ R ² R ³ R ⁴ I ⁺ [R ⁵ COO] ^" , where X is N or P, where R ¹ to R ^{4 are} simultaneously or independently alkyl-, aryl- , Aralkyl, heteroaryl, alkoxyalkyl radicals, in each case linear or branched, unbridged or bridged with other radicals R ¹ to R ⁴ , forming cyclics, bicyclic or tricyclic radicals and the bridging atoms besides carbon may also be heteroatoms having 1 to 18 carbon atoms and each radical R ¹ to R ^{4 may} additionally have one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R ^{5 is} an alkyl, , Aryl, aralkyl, heteroaryl, alkoxyalkyl, linear or branched, having 1 to 18 carbon atoms and additionally one or more alcohol, amino, ester, keto, thio, acid, urethane, urea -, allophanate groups, double bonds, triple or of the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ] ^" , where X is N or P, where R ¹ to R ^{4 are} simultaneously or independently alkyl-, aryl- , Aralkyl, heteroaryl, alkoxyalkyl radicals, in each case linear or branched, unbridged or with other radicals R ¹ to R ⁴ bridged to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon may also be heteroatoms, having 1 to 18 carbon atoms and each radical R ¹ to R ⁴ additionally one or more alcohol, amino, ester, keto , Thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R ^{5 is} either OH or F, or 3. of the formula M (OR ¹ ) _n (OR ² ) _m (OR ³ ) _O (OR ⁴ ) _P (OR ⁵ ) _q (OR ⁶ ) _r , where M is a metal in any positive oxidation state and is identical to the sum n + m + o + p + q + r, m, o, p , q, r represent integers from 0 to 6, and for the sum n + m + o + p + q + r = 1 to 6, the radicals R ¹ to R ⁶ simultaneously or independently of one another denote hydrogen or alkyl, aryl , Aralkyl, heteroaryl, alkoxyalkyl, having 1 to 8 carbon atoms and the radicals in each case linear or branched, unbridged or bridged with other radicals, inter alia Formation of cyclen, bicyclic or tricyclic compounds and the bridging atoms besides carbon may also be heteroatoms and additionally one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, May have triple bonds or halogen atoms.

Examples of such catalysts under 1. are tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate,

Tetramethylammonium butyrate, tetramethylammonium benzoate,

Tetraethylammonium formate, tetraethylammonium acetate,

Tetraethylammonium propionate, tetraethylammonium butyrate,

Tetraethylammonium benzoate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate,

Tetrapropylammonium butyrate, tetrapropylammonium benzoate

Tetrabutylammonium formate, tetrabutylammonium acetate,

Tetrabutylammonium propionate, tetrabutylammonium butyrate,

Tetrabutylammonium benzoate, tetrabutylphosphonium acetate, tetrabutylphosphonium formate, ethyltriphenylphosphonium acetate,

Tetrabutylphosphoniumbenzothazolate, Tetraphenylphosphoniumphenolat and

Trihexyltetradecylphosphoniumdecanoat. Examples of such catalysts under 2. are methyltributylammonium, methyltriethylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, Tetradecylammoniumhydroxid, Tetradecyltrihexylammoniumhydroxid, Tetraoctadecylammoniumhydroxid, benzyltrimethylammonium, benzyltriethylammonium, trimethylphenylammonium, Thethylmethylamnnoniunnhydroxid, Trimethylvinylammoniumhydroxid, tetramethylammonium fluoride, tetraethylammonium, tetrabutylammonium tetraoctylammonium, Benzyltrimethylammonium fluoride, tetrabutylphosphonium hydroxide and tetrabutylphosphonium fluoride.

Examples of such catalysts under 3. are lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, zinc hydroxide, lithium methoxide, sodium methoxide, potassium methoxide, magnesium methoxide, calcium methoxide, barium methoxide, lithium ethoxide, sodium ethanolate, potassium ethanolate, Magnesium ethanolate, calcium ethanolate, barium ethanolate, lithium propyl alcoholate, sodium propyl alcoholate, potassium propyl alcoholate, magnesium propyl alcoholate, calcium propyl alcoholate, barium propyl alcoholate, lithium isopropyl alcoholate, sodium isopropyl alcoholate, potassium isopropyl alcoholate, magnesium isopropyl alcoholate, calcium isopropyl alcoholate, barium isopropyl alcoholate, lithium 1-butyl alcoholate, sodium 1-butyl alcoholate, potassium 1-butyl alcoholate, magnesium 1-butyl alcoholate, calcium 1-butyl alcoholate, barium 1-butyl alcoholate, lithium 2-butyl alcoholate, sodium 2-butyl alcoholate , Potassium 2-butyl alcoholate, magnesium 2-butyl alcoholate, calcium 2-butyl alcoholate, barium 2-butyl alcoholate, lithium isobutyl alcoholate, sodium isobutyl alcoholate,

Potassium isobutyl alcoholate, magnesium isobutyl alcoholate, calcium isobutyl alcoholate, barium isobutyl alcoholate, lithium tert. butyl alcoholate, sodium tert. -butylalkoholat, Potassium tert-butyl alcoholate, magnesium tert-butyl alcoholate, calcium tert-butyl alcoholate, barium tert-butyl alcoholate, lithium phenolate, sodium phenolate, potassium phenolate, magnesium phenolate, calcium phenolate and barium phenolate.

Of course, mixtures of such catalysts can be used. The catalysts are contained in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 3 wt .-%, based on the total formulation, in the polyurethane composition. The catalysts may contain water of crystallization, which is not taken into account in the calculation of the amount of catalyst used, d. H. the amount of water is deducted. Particular preference is given to using tetraethylammonium benzoate and tetrabutylammonium hydroxide.

A variant according to the invention includes the polymeric attachment of such catalysts B) to the curing agents A) or hydroxyl-containing polymers C) or F). So z. B. free alcohol, thio or amino groups of the ammonium salts with acid, isocyanate, or glycidyl groups of the powder coating hardener A) or hydroxyl-containing polymers C) or F) are reacted to integrate the catalysts B) in the polymeric composite. These catalysts may also be encased in a shell and encapsulated therewith.

As component C) is at least one hydroxyl and carboxyl-containing unsaturated, amorphous polyester having an OH number between 1 and 100 mg KOH / gram and a COOH number between 1 and 75 mg KOH / gram, wherein the ratio of OH and Acid number is always> 1, with a

Weight fraction, based on the total formulation, from 1 to 12% used.

Component C) comprises unsaturated polyesters containing amorphous hydroxyl and carboxyl groups, essentially containing at least one α, β-unsaturated dicarboxylic acid component and an alcohol component, the alcohol component of a mixture of dicidol of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ² ' ⁶ ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] decane, each isomer may be present in a proportion of 20 to 40 wt .-% in the mixture and the sum of the three isomers 90 to 100 wt .-% results, and the mixture at least 5 wt .-% in the alcohol component of the polyester is present.

The unsaturated amorphous polyester resins C) are obtained by reacting the alcohol component and the acid component.

The alcohol component according to the invention is a Dicidolgemisch the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ² ' ⁶ ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] decane and 5.8-bis (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] decane used, wherein each isomer may be present in a proportion of 20 to 40 wt .-% in the mixture and the sum of the three isomers 90 to 100 wt .-%, preferably 95 to 100% by weight, and the mixture is at least 5% by weight in the alcohol component of the polyester. The isomer content of the Dicidolgemisches can qualitatively and quantitatively z. B. by GC analysis or quantitatively determined by separation by preparative GC or HPLC and subsequent NMR spectroscopy. All corresponding isomers of dicidol in the 9-position are just as suitable, but due to the mirror symmetry of the above isomers, as well as the cis and trans isomers, indistinguishable under normal, practical circumstances.

In addition, the Dicidolgemisch may contain up to 10 wt .-% further isomers of diclidol and / or trimeric and / or higher isomeric diols of the Diels-Alder reaction product of cyclopentadiene. Preferably, the alcohol component consists of 20 wt .-%, from 50 wt .-%, preferably from 90 wt .-%, particularly preferably from 100 wt .-% Dicidolgemisch, this more preferably 95 to 100 wt .-% of the above contains three isomeric compounds. In addition to the dicidol mixture, the alcohol component may contain further linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols. Preferred additional alcohols are ethylene glycol, 1, 2 and / or 1, 3-propanediol, diethylene, dipropylene, ethylene, tetraethylene glycol, 1, 2 and / or 1, 4-butanediol, 1, 3-butylethylpropanediol, 1, 3-methylpropanediol, 1, 5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and bisphenol A, B, C, F, norbornylene glycol, 1, 4-benzyldimethanol and ethanol, 2, 4-dimethyl-2-ethylhexane-1, 3-diol used.

The unsaturated, amorphous polyester resins C) contain as starting acid component at least one α, ß-unsaturated dicarboxylic acid. The unsaturated polyester resins preferably contain citraconic, fumaric, itaconic, maleic and / or mesaconic acid.

It may also contain additional aromatic and / or aliphatic and / or cycloaliphatic monocarboxylic acids and / or dicarboxylic acids and / or polycarboxylic acids, such as. Phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid,

Tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and / or trimellitic acid. Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, adipic acid and / or azelaic acid.

The acid component can consist partly or completely of anhydrides and / or alkyl esters, preferably methyl esters.

In general, the alcohol component is contained in the molar ratio of 0.5 to 2.0 to 1 to the acid component, preferably 0.8 to 1, 5 to 1. Particularly preferred is the implementation of the alcohol component in the molar ratio of 1, 0 to 1, 1 to 1 to the acid component instead. The unsaturated, amorphous polyesters C) may have an acid number between 1 and 75 mg KOH / g, preferably between 1 and 50, more preferably between 1 and 35 mg KOH / g and an OH number between 1 and 100 mg KOH / g between 1 and 75, more preferably between 1 and 50 mg KOH / g, wherein the ratio of OH and acid number is always> 1.

The Tg of the unsaturated amorphous polyester C) varies from -30 to +80 ⁰ C, preferably from -20 to +50 ⁰ C, more preferably - 10 to + 40 ⁰ C.

In a preferred embodiment I, the unsaturated polyester resins C) (UP resins) consist of an alcohol component having at least 90% by weight, preferably 95% by weight, particularly preferably 100% by weight, of the dicidol mixture of the isomeric compounds 3,8 Bis (hydroxymethyl) tricyclo [5.2.1.0 ² ' ⁶ ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 ²⁶ ] decane and from fumaric acid and / or maleic acid (anhydride). In a further preferred embodiment II, the polyesters C) contain the abovementioned starting components as under I, but additionally an additional acid selected from adipic acid or phthalic acid (anhydride), the ratio of the α, β-unsaturated to the additional acid being from 2: 1 to 1: 1 can vary to 4. Ratios of about 1 to 1 to 1 to 2 are preferred. These polyesters generally have acid numbers of 1 to 75 mg KOH / g, preferably 1 to 50 mg KOH / g, particularly preferably 1 to 35 mg KOH / g, OH numbers from 1 to 100 mg KOH / g, preferably 1 to 75 mg KOH / g, particularly preferably 1 to 50 mg KOH / g, the ratio of OH and acid number always being> 1, and a Tg of -30 to +80 ⁰ C, preferably -20 to +50 ⁰ C, more preferably -10 to +40 ⁰ C on.

The polyesters C) may also contain auxiliaries and additives selected from inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or free-radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, anti-skinning agents, defoamers, antistatic agents, thickeners . thermoplastic additives, dyes, pigments, fire retardants, internal release agents, fillers and / or blowing agents.

The polyesters C) are prepared by (semi) continuous or discontinuous esterification and condensation of the starting acids and alcohols in a one-stage or two-stage procedure.

Polyester resins based on dicidol as diol component are also known from DE 924 889, DE 953 117, DE 22 45 110, DE 27 21 989, EP 114 208, EP 934 988, EP 1 492 834.

EP 1 398 337 describes adhesion-improving additives of an unsaturated, amorphous polyester. The adhesion-improving additives are polymer-containing in aqueous, solvent-containing (normal, medium, high, very high solids) and / or solvent-free (powder and / or liquid), thermosetting, radiation-curable, air-drying (oxidative and physical) coating materials, fillers and / or sealants and adhesives and are suitable as a modification resin for primers, fillers, basecoats, single-coat finishes, clearcoats, adhesives, sealants, road marking paints, anti-corrosive paints.

The use in uretdione-containing powder coatings that can crosslink at low temperature is not described. Polymers according to EP 1 398 337 can carry OH and carboxylic acid groups, wherein both the OH number and the acid number can assume values between 1 and 200 mg KOH / g. Thus, the polymers described in EP 1 398 337 can have a high carboxylic acid and low OH functionality. In the case of the present invention, their use would be in highly reactive uretdione-containing polyurethane compositions

1. reduce the reactivity of the formulation due to the presence of high concentrations of acid groups and

2. lead to uncrosslinked portions due to the low OH functionality, which would negatively impact resistance properties.

For this reason, it is essential in the present invention that the ratio of OH and acid number is always> 1. Polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates having an OH number of 10 to 500 (in mg KOH / gram) are preferably used in the hydroxyl-containing (partially) khallene polymers G). Particularly preferred are hydroxyl-containing polyesters having an OH number of 15 to 150 and an average molecular weight of 500 to 6,000 g / mol. Of course, mixtures of such polymers can be used. The proportion by weight of this (partially) crystalline component G) in the overall formulation A-H can be between 1 and 95% by weight, preferably from 2 to 50% by weight.

Preferred (partial) crystalline hydroxyl-containing polyesters G) are prepared by polycondensation. For this purpose, an acid component consisting of 80 to 100 mole percent of a saturated, linear aliphatic or cycloaliphatic dicarboxylic acid having 4 to 14 carbon atoms and 0 to 20 mole percent of another aliphatic or cycloaliphatic or aromatic di- or polycarboxylic acid, having an alcohol component consisting of 80 to 100 Mole percent of a linear aliphatic diol of 2 to 15 carbon atoms and 0 to 20 mole percent of another aliphatic or cycloaliphatic di or polyol of 2 to 15 carbon atoms. The (partially) crystalline hydroxyl-containing polyesters thus produced have an OH number of 15 to 150 mg KOH / g, an acid number <5 mg KOH / g and a melting point of 40 to 130 ^° C.

Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid, are preferred carboxylic acids for the preparation of (partly) khallins polyesters G),

Hexahydroterephthalsäure, endomethylene tetrahydrophthalic acid, glutaric acid or - as far as accessible - their anhydrides. Particularly suitable and preferred is dodecanedioic acid.

As polyols, the following diols are ethylene glycol, propanediol (1, 2) and - (1, 3), 2,2-dimethylpropanediol (1, 3), butanediol (1, 4), pentanediol (1, 5) , Hexanediol (1, 6), 2-methylpentanediol (1, 5), 2,2,4-trimethylhexanediol (1,6), 2,4,4-thymethylhexanediol (1,6), Heptanediol (1, 7), decanediol (1, 10), dodecanediol (1, 12), octadecene-9, 10-diol (1, 12), octadecanediol (1, 18), 2,4- Dimethyl-2-propylheptandiol- (1, 3), butenediol (1, 4), butynediol (1, 4), diethylene glycol, triethylene glycol, tetraethylene glycol, trans and cis 1, 4-cyclohexanedimethanol, the triols glycerol, hexanetriol - (1, 2.6), 1, 1, 1 - trimethylolpropane and 1, 1, 1 -Thmethylolethan and the tetraol pentaerythritol, suitable. Preference is given to ethylene glycol, propanediol (1, 2) and - (1, 3), 2,2-dimethylpropanediol (1,3), butanediol (1,4), pentanediol (1,5), hexanediol ( 1, 6), 2-methylpentanediol (1, 5), heptanediol (1, 7), decanediol (1, 10), dodecanediol (1, 12), octadecene-9, 10-diol (1, 12), octadecanediol (1,18), butenediol (1,4), butynediol (1,4), diethylene glycol, triethylene glycol, tetraethylene glycol, trans and cis 1,4-cyclohexanedimethanol.

It should be noted in this context that the activity of the catalysts under B) in the presence of acids decreases significantly. The conventional reactants of the uretdione-containing paint or adhesive hardener include hydroxyl-containing polyester. Due to the method of preparation of polyesters, they sometimes carry acid groups to a small extent. In the presence of such acid groups-bearing polyesters, it is advisable to use the catalysts mentioned either in excess, based on the acid groups, or to add reactive compounds which are capable of intercepting acid groups. Both monofunctional and polyfunctional compounds can be used for this purpose.

Reactive acid scavenging compounds D) are well known in paint chemistry. Thus, for example, epoxy compounds, carbodiimides, hydroxyalkylamides or 2-oxazolines, but also inorganic salts, such as hydroxides, bicarbonates or carbonates, react with acid groups at elevated temperatures. In question come here z. B. triglycidyl ether isocyanurate (TGIC), EPIKOTE ^® 828 (diglycidyl ether based on bisphenol A, Schell), versatic, ethylhexyl glycidyl ether, butyl glycidyl ether, Polypox R 16 (pentaerythritol tetraglycidyl ether, UPPC AG) as well as other Polypoxtypen having free epoxy groups, .beta.-hydroxyalkylamides (z. B. Vestagon EP HA 320, Evonik Degussa GmbH), but also phenylenebisoxazoline, 2-methyl-2-oxazoline, 2-hydroxyethyl-2- oxazoline, 2-hydroxypropyl-2-oxazoline, 5-hydroxypentyl-2-oxazoline, barium hydroxide, sodium carbonate and calcium carbonate. Of course, mixtures of such substances come into question. If present, these reactive compounds can be used in proportions by weight of from 0.1 to 10% by weight, preferably from 0.5 to 3% by weight, based on the total formulation A) to H).

Acids which are mentioned under E) are all substances, solid or liquid, organic or inorganic, monomeric or polymeric, which have the properties of a Bronsted or a Lewis acid. Examples include: sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, but also copolyester or

Copolyamides having an acid number of at least 20 mg KOH / g. They are contained, if present, in a proportion by weight, based on the total formulation, of 0.1 to 10%.

In the case of the hydroxyl-containing amorphous polymers F), preference is given to using polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates having an OH number of 20 to 500 mg KOH / gram. Particularly preferred are hydroxyl-containing polyesters having an OH number of 20 to 150 mg / KOH / g, an average molecular weight of 500 to 6000 g / mol. Of course, mixtures of such polymers can be used. Such amorphous polymers can, if present, be used in a proportion by weight of 1 to 95%, preferably 1 to 90%, based on the total formulation. As the alcohol component for the production of the polyesters linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols can be contained. Are preferred as dicidol, ethylene glycol, 1, 2 and / or 1, 3-propanediol, diethylene, dipropylene, ethylene, tetraethylene glycol, 1, 2 and / or 1, 4-butanediol, 1, 3-Butylethylpropandiol, 1, 3-methylpropanediol, 1, 5-pentanediol, cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and bisphenol A, B, C, F, norbornylene glycol, 1, 4-benzyldimethanol and ethanol, 2, 4-dimethyl-2-ethylhexane-1, 3-diol used.

As the acid component for the preparation of the polyester can linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic monocarboxylic acids and / or dicarboxylic acids and / or polycarboxylic acids may be contained, such as. Phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid, pyromellitic acid and / or trimellitic acid. Preference is given to phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, adipic acid and / or azelaic acid.

The acid component can consist partly or completely of anhydrides and / or alkyl esters, preferably methyl esters.

For the polyurethane composition customary in the paint or adhesive technology auxiliaries and additives H) as leveling agents, for. As polysilicones or polyacrylates, light stabilizers z. As sterically hindered amines, or other auxiliaries, such as. As described in EP 669 353, be added in a total amount of 0.05 to 5 wt .-%. Fillers and pigments, such as. Titanium dioxide, if present, can be added in an amount up to 50% by weight of the total composition.

Optionally, additional catalysts, such as are already known in polyurethane chemistry may be included. These are mainly organometallic catalysts, such as. As dibutyltin dilaurate, or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2,] octane, in amounts of 0.001 to 1 wt .-%.

The total amount of H) may be from 0.001 to 55% by weight, based on the total formulation.

The homogenization of all constituents for the preparation of the polyurethane composition according to the invention can be carried out in suitable aggregates, such. B. heated kneaders, but especially in extruders at temperatures of 40 to 130 ⁰ C, carried out, with upper temperature limits of 120 to 130 ⁰ C not exceeded should be. The well-mixed mass is removed by suitable application, eg. As rollers, spraying, applied to the substrate. The application of ready-to-spray powders on suitable substrates can according to the known methods, such. B. by electrostatic powder spraying, vortex sintering, or electrostatic vortex sintering done. After application, the coated workpieces are cured for 4 to 60 minutes at a temperature of 60 to 220 ⁰ C, preferably 6 to 30 minutes at 80 to 150 ⁰ C heated.

The subject matter of the invention will be explained in more detail below with reference to examples.

Example 1 for the preparation of component C)

Starting component Dicidol mixture in the isomer ratio of approximately 1: 1: 1. Adipic acid and maleic acid (molar ratio 1: 1) are reacted with dicidol in MoI ratio 1: 1, 05 at 180 ⁰ C in a nitrogen atmosphere until an acid number of 27 mg KOH / g and an OH number of 36 mg KOH / g is reached. For this purpose, the maleic acid is first esterified with diclidol for one hour and then added to the adipic acid. M _n = 1800 g / mol, M _w = 4400 g / mol, glass transition temperature 14 ⁰ C.

Examples for the preparation of polyurethane powder coatings

Table 1: Feedstocks

T _G : glass transition point; Table 2-1: Polyurethane Powder Coating Formulations:

Information in mass fractions; ^* V not comparative examples according to the invention

Table 2-2: Polyurethane Powder Coating Formulations:

Allgemeine Herstellungsvorschrift für die Pulverlacke 1 bis 3 sowie V1 bis V3:

General manufacturing instructions for the powder coatings 1 to 3 and V1 to V3:

The comminuted feedstocks according to Table 2 are intimately mixed in a pug mill and then homogenized in the extruder at temperatures up to 130 ⁰ C maximum. After cooling, the extrudate is crushed and ground with a pin mill to a particle size <100 microns and sieved by means of a screening machine to <63 microns. The powder thus produced is applied with an electrostatic powder spray system at 60 KV on degreased iron sheets and baked in a convection oven for 30 minutes at 150 ⁰ C and 30 minutes at 130 ⁰ C. (Layer thickness 70 to 80 microns). The results of the test data are shown in Tables 3 to 4.

Erichsentiefung nach DIN 53 156

Erichsentiefung according to DIN 53 156

Ball impact according to ASTM D 2794-93

Cross cut according to DIN EN ISO 2409, cutting distance 2 mm

Claims

Patent claims: 1. Solid, highly reactive polyurethane compositions containing uretdione groups with a melting point above 40 ⁰ C, essentially containing A) at least one hardener containing uretdione groups, based on aromatic, aliphatic, (cyclo)aliphatic and/or cycloaliphatic polyisocyanates and compounds containing hydroxyl groups with a free NCO content of less than 5% by weight and a uretdione group content of 1 to 18% by weight. %, in amounts between 15 and 45% by weight based on the total formulation; and B) at least one catalyst 1. of the formula [XR ¹ R ² R ³ R ⁴ I ⁺ [R ⁵ COO] ^" , with X equal to N or P, where R ¹ to R ⁴ are simultaneously or independently alkyl, aryl, aralkyl, heteroaryl , alkoxyalkyl radicals, each linear or branched, unbridged or bridged with other radicals R ¹ to R ⁴ , forming cycles, bicycles or tricycles and the bridging atoms can also be heteroatoms in addition to carbon, with 1 to 18 carbon atoms and each radical R ¹ to R ⁴ may additionally have one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R ⁵ is an alkyl, aryl, aralkyl , heteroaryl, alkoxyalkyl radical, linear or branched, with 1 to 18 carbon atoms and additionally one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, may have triple bonds or halogen atoms, 2. the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ] ^" , where X is N or P, where R ¹ to R ⁴ simultaneously or independently of one another are alkyl, aryl, aralkyl, heteroaryl, Alkoxyalkyl radicals, each linear or branched, unbridged or bridged with other radicals R ¹ to R ⁴ , forming cycles, bicycles or tricycles and the bridging atoms can also be heteroatoms in addition to carbon, with 1 to 18 carbon atoms and each radical R ¹ to R ⁴ may additionally have one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R ⁵ means either OH or F, 3. the formula M (OR ¹ ) _n (OR ² ) _m (OR ³ ) _o (OR ⁴ )p (OR ⁵ ) _q (OR ⁶ ) _r , where M is a metal in any positive oxidation state and identical to the sum n +m+o+p+q+r is, m, o, p, q, r represent integers from 0 to 6 and for the sum n+m+o+p+q+r = 1 to 6, the Radicals R ¹ to R ⁶ simultaneously or independently of one another represent hydrogen or Al kyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals with 1 to 8 carbon atoms and the radicals are each linear or branched, unbridged or bridged with other radicals, forming Cycles, bicycles or tricycles and the bridging atoms can also be heteroatoms in addition to carbon and additionally one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or May have halogen atoms, these catalysts from groups 1 to 3 being contained individually or in mixtures and C) at least one unsaturated, amorphous polyester containing hydroxyl and carboxyl groups, essentially containing at least one α, ß-unsaturated dicarboxylic acid component and an alcohol component, the alcohol component consisting of a dicidol mixture of the isomers Compounds 3,8-Bis(hydroxymethyl)tricyclo [5.2.1.0 ² ' ⁶ ]decane, 4,8- Bis(hydroxymethyl)tricyclo [5.2.1.0 ²⁶ ]decane and 5,8-bis(hydroxymethyl)tricyclo [5.2.1.0 ²⁶ ]decane, whereby each isomer can be contained in the mixture in a proportion of 20 to 40% by weight and the sum of the three isomers results in 90 to 100% by weight, and the mixture is at least 5 % by weight in the alcohol component of the Polyester is present, with an OH number between 1 and 100 mg KOH/gram and a COOH number between 1 and 75 mg KOH/gram, where the ratio of OH number and acid number is always >1, with a proportion by weight, based on the total formulation, of 1 to 12%; D) optionally at least one compound reactive towards acid groups; E) optionally at least one acid in monomeric or polymeric form; F) optionally at least one amorphous polymer containing hydroxyl groups or containing amine groups with an OH number between 20 and 500 mg KOH/gram or a comparable amine content; G) at least one polymer containing (partially) stableline hydroxyl groups with an OH number between 10 and 500 mg KOH/gram with a weight proportion, based on the total formulation, of 1 to 35%; H) optionally auxiliaries and additives and/or further catalysts; where the proportion of the catalyst under B) is 0.001 to 5% by weight of the total formulation and the sum of the starting materials A) to H) is 100% by weight. 2. Polyurethane composition according to claim 1, characterized in D) that at least one compound reactive towards acid groups with a weight proportion, based on the total formulation, of 0.1 to 10%; and or E) that at least one acid in monomeric or polymeric form in a proportion by weight, based on the total formulation, of 0.1 to 10%; and or F) that at least one amorphous polymer containing hydroxyl groups or containing amine groups with an OH number between 20 and 500 mg KOH/gram or a comparable amine content with a weight proportion, based on the total formulation, of 1 to 95%; is included. 3. Polyurethane composition according to claim 1 or 2, characterized in that auxiliaries and additives and/or further catalysts H) are contained in a proportion by weight, based on the total formulation, of 0.001 to 55%. 4. Polyurethane compositions according to at least one of claims 1 to 3, characterized in that hardeners A) containing uretdione groups are based on isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (Hi ₂ MDI), 2-methylpentadiisocyanate (MPDI), 2, 2.4- Thmethylhexamethylene diisocyanate^^^-Thmethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI) and tetramethylxylylene diisocyanate (TMXDI), alone or in mixtures, are included. 5. Polyurethane compositions according to claim 4, characterized in that hardeners containing uretdione groups based on IPDI, Hi ₂ MDI and / or HDI are included. 6. Polyurethane compositions according to at least one of claims 1 to 5, characterized in that hardeners A) containing uretdione groups are based on polyesters containing hydroxyl groups, polythioethers, polyethers, polycaprolactams, polyepoxides, polyesteramides, polyurethanes, low molecular weight di-, tri- and / or tetra-alcohols, Monoamines and/or monoalcohols, alone or in mixtures, are contained. 7. Polyurethane compositions according to claim 6, characterized in that polyester and/or monomeric dialcohols are contained. 8. Polyurethane compositions according to claim 7, characterized in that polyester with an OH number of 30 to 150 mg KOH/g and a medium Molecular weight of 500 to 6000 g / mol are included. 9. Polyurethane compositions according to at least one of claims 1 to 8, characterized in that hardener A) also has isocyanurate, biuret, allophanate, urethane and / or urea structures. 10. Polyurethane compositions according to at least one of claims 1 to 9, characterized in that catalysts 1. selected from tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium ben zoat, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate , tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, tetrabutylammonium benzoate, tetrabutylphosphonium acetate, tetrabutylphosphonium formate, ethyltriphenylphosphonium acetate, tetrabutylphosphonium benzothazolate, tetraphenylphosphonium phenolate and trihexyltetradecylphosphonium decanoate . 11. Polyurethane compositions according to at least one of claims 1 to 9, characterized in that catalysts 2. selected from methyltributylammonium hydroxide, methyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, Tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetradecyl ammonium hydroxide, tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylannnnoniunnhydroxide, trimethylvinylannnnnoniunnhydroxide, tetramethylammonium fluoride , tetraethylammonium fluoride, tetrabutyl ammonium fluoride, tetraoctylammonium fluoride, benzyltrimethylammonium fluoride, tetrabutylphosphonium hydroxide and tetrabutylphosphonium fluoride are included. 12. Polyurethane compositions according to at least one of claims 1 to 10, characterized in that catalysts 3. selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, berillium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, zinc hydroxide, lithium methoxide, sodium methoxide, potassium methoxide , magnesium methoxide, calcium methoxide, barium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, magnesium ethoxide, calcium ethoxide, barium ethoxide, lithium propyl alcoholate, sodium propyl alcoholate, potassium propyl alcoholate, magnesium propyl alcoholate, calcium propyl alcoholate, barium propyl alcoholate, lithium isopropyl alcoholate, sodium isopropyl alcoholate, potassium isopropyl alcoholate, magnesium isopropyl alcoholate, calcium isopropyl alcoholate, barium isopropyl alcoholate , lithium-1-butyl alcoholate, sodium -1 -butyl alcoholate, potassium 1 -butyl alcoholate, magnesium 1 -butyl alcoholate, calcium 1 -butyl alcoholate, barium 1 -butyl alcoholate, lithium 2-butyl alcoholate, sodium 2-butyl alcoholate, potassium 2-butyl alcoholate, magnesium-2 -butyl alcoholate, calcium 2-butyl alcoholate, barium 2-butyl alcoholate, lithium isobutyl alcoholate, sodium isobutyl alcoholate, potassium isobutyl alcoholate, magnesium isobutyl alcoholate, calcium isobutyl alcoholate, barium isobutyl alcoholate, lithium tert. -butyl alcoholate, sodium tert. -butyl alcoholate, potassium tert. -butyl alcoholate, magnesium tert. -butyl alcoholate, calcium tert-butyl alcoholate, barium tert. -butyl alcoholate, lithium phenolate, sodium phenolate, Potassium phenolate, magnesium phenolate, calcium phenolate and barium phenolate are included. 13. Polyurethane compositions according to at least one of the preceding claims 1 to 12, characterized in that the catalysts are surrounded and encapsulated with an inert shell. 14. Polyurethane compositions according to at least one of the preceding claims 1 to 13, characterized in that the catalysts are polymer-bound. 15. Polyurethane compositions according to at least one of the preceding claims 1 to 14, characterized in that (partially) khstalline polymers G) containing hydroxyl groups are polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates with an OH number of 10 to 500 mg KOH /gram are included. 16. Polyurethane compositions according to claim 15, characterized in that hydroxyl-containing polyesters G) with an OH number of 15 to 150 and an average molecular weight of 500 to 6000 g / mol are included. 17. Polyurethane compositions according to claim 16, characterized in that polyester G) based on succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, Endemethylenetetrahydrophthalic acid, glutaric acid or - if accessible - their anhydrides are included. 18. Polyurethane compositions according to at least one of claims 16 to 17, characterized in that polyester G) based on ethylene glycol, propanediol-(1,2) and -(1,3), 2,2-dimethylpropanediol-(1,3) , butanediol-(1,4), pentanediol-(1,5), hexanediol-(1,6), 2-methylpentanediol-(1,5), 2,2,4-thmethylhexanediol-(1,6), 2 ,4,4-trimethylhexanediol-(1,6), heptanediol-(1,7), decanediol-(1,10), dodecanediol-(1,12), octadecene-9,10-diol-(1,12) , octadecanediol-(1,18), 2,4-dimethyl-2-propylheptanediol-(1,3), butenediol-(1,4), butenediol-(1,4), diethylene glycol, thylene glycol, tetraethylene glycol, trans- and cis-i ^-cyclohexanedimethanol, the triols glycerol, hexanetriol-(1,2,6), 1,1,1-thmethylolpropane and 1,1,1-thmethylolethane and the tetraol pentaerythritol. 19. Polyurethane compositions according to at least one of claims 1 to 18, characterized in that component D) contains epoxy compounds, carbodiimides, hydroxyalkylamides, basic salts and / or 2-oxazolines. 20. Polyurethane compositions according to at least one of claims 1 to 19, characterized in that the acid E) contains sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, but also copolyesters or copolyamides with an acid number of at least 20 mg KOH / g. 21. Polyurethane compositions according to at least one of claims 1 to 20, characterized in that amorphous polymers F) containing hydroxyl groups contain polyester, polyethers, polyacrylates, polyurethanes, polyethers and / or polycarbonates with an OH number of 20 to 500 mg KOH / gram are. 22. Polyurethane compositions according to at least one of the preceding claims, characterized in that component C) contains up to 10% further isomers of dicidol and/or trimeric and/or higher isomeric diols of the Diels-Alder reaction product from cyclopentadiene. 23. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the acid component additionally contains aromatic and/or aliphatic and/or cycloaliphatic monocarboxylic acids and/or dicarboxylic acids and/or polycarboxylic acids. 24. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the acid component is partially or completely made up Anhydrides and/or alkyl esters exist. 25. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the alcohol component contains further linear and/or branched, aliphatic and/or cycloaliphatic and/or aromatic diols and/or polyols. 26. Polyurethane compositions according to at least one of the preceding claims, characterized in that component C) contains citraconic, fumaric, itaconic, maleic and/or mesaconic acid as α,ß-unsaturated dicarboxylic acid. 27. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) as additional acids are phthalic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid , azelaic acid, pyromellitic acid and/or trimellitic acid, whose acid anhydrides and/or methyl esters, and/or isononanoic acid and/or 2-ethylhexanoic acid are contained. 28. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) as additional alcohols are ethylene glycol, 1,2- and / or 1,3-propanediol, diethylene, dipropylene, thethylene, tetraethylene glycol, 1, 2- and/or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, cyclohexanedimethanol, glycerin, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane and/or pentaerythritol, bisphenol A, B, C, F, norbornylene glycol, 1,4-benzyldimethanol and -ethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol are included. 29. Polyurethane compositions according to at least one of the preceding claims, characterized in that component C) contains fumaric acid and/or maleic acid (anhydride) as the α,β-unsaturated acid component. 30. Polyurethane compositions according to at least one of the preceding claims, characterized in that component C) contains adipic acid and/or phthalic acid (anhydride) as a further dicarboxylic acid component. 31. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the alcohol component in a molar ratio of 0.5 to 2.0 to 1 to the acid component is included. 32. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the alcohol component in a molar ratio of 0.8 to It contains 1.5 to 1 to the acid component. 33. Polyurethane compositions according to at least one of the preceding claims, characterized in that in component C) the alcohol component in a molar ratio of 1.0 to 1.1 to 1 to the acid component is included. 34. Polyurethane compositions according to at least one of the preceding claims, characterized in that the polyester C) has an acid number between 1 and 50 mg KOH/g, preferably between 1 and 35 mg KOH/g. 35. Polyurethane compositions according to at least one of the preceding claims, characterized in that the polyester C) has an OH number between 1 and 75, preferably between 1 and 50 mg KOH/g. 36. A process for producing polyurethane compositions according to at least one of claims 1 to 35 by homogenization at temperatures of 40 to 130 ⁰ C. 37. Powder coating composition containing compounds according to at least one of the preceding claims 1 to 35. 38. Powdered adhesive composition containing compounds according to at least one of the preceding claims 1 to 35. 39. Use of the polyurethane compositions according to at least one of claims 1 to 36 for the production of powdery paint and adhesive coatings for metal, plastic, wood, glass, leather or other heat-sensitive substrates. 40. Powdered metal coating compositions, essentially containing a polyurethane composition according to at least one of claims 1 to 35. 41. Powdered wood coating composition, essentially containing a polyurethane composition according to at least one of claims 1 to 35. 42. Powdered leather coating compositions, essentially containing a polyurethane composition according to at least one of claims 1 to 35. 43. Powdered plastic coating compositions, essentially containing a polyurethane composition according to at least one of claims 1 to 35. 44. Metal coating compositions according to claim 40 for Automobile bodies, motorbikes and bicycles, building parts and household appliances. 45. Coated objects with the polyurethane compositions according to at least one of claims 1 to 35.