EP1844084A1

EP1844084A1 - Highly reactive uretdione group-containing polyurethane compositions based on 1,4-diisocyanato-dicyclohexyl methane

Info

Publication number: EP1844084A1
Application number: EP05811082A
Authority: EP
Inventors: Emmanouil Spyrou; Andrea Henschke; Nicole Fresmann
Original assignee: Evonik Degussa GmbH; Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2004-12-24
Filing date: 2005-10-28
Publication date: 2007-10-17
Also published as: CN1878837A; DE102004062588A1; WO2006069839A1; US20080139753A1

Abstract

The invention relates to uretdione group-containing polyurethane compositions based on 1,4-diisocyanato-cyclohexyl methane especially for polyurethane coating powder and adhesive compositions that can be hardened at a low temperature. Also disclosed are a method for the production thereof and the use thereof.

Description

HIGHLY REACTIVE URETDION GROUPS-BASED POLYURETHANE COMPOSITIONS BASED ON 1, 4 -DIISOCYANATODI CYCLOHEXYLMETHANE

The invention relates to uretdione group-containing polyurethane compositions based on 1,4-diisocyanatocyclohexylmethane, 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.

So describes z. For example, DE-OS 27 35 497 PUR powder coatings with excellent weathering and heat stability. The crosslinkers, the preparation of which is described in DE-OS 27 12 931, consist of ε-caprolactam blocked isocyanurate-containing isophorone diisocyanate. There are also known urethane, biuret or urea group-containing polyisocyanates whose isocyanate groups are also blocked.

The disadvantage of these externally blocked systems is the cleavage of the blocking agent during the thermal crosslinking reaction. Since the blocking agent can thus emit into the environment, special measures for cleaning the exhaust air and recovery of the blocking agent must be made for environmental and occupational hygiene reasons. In addition, the crosslinkers have a low reactivity. Curing temperatures above 170 ° C are required.

DE-OS 30 30 539 and DE-OS 30 30 572 describe processes for the preparation of uretdione polyaddition compounds whose terminal isocyanate groups are blocked irreversibly with monoalcohols or monoamines. 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 resistance.

Hydroxyl-terminated, uretdione group-containing polyaddition compounds The subject of EP 669 353. They have due to their functionality of two an 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 ° C at a high level.

The use of amidines as catalysts in PU powder coating compositions is described in EP 803 524. Although these catalysts lead to a lowering of the curing temperature, but show a considerable yellowing, which is generally undesirable in the coating area. The reason for this yellowing is probably the reactive nitrogen atoms in the amidines. These can react with atmospheric oxygen to N-oxides, which are responsible for the discoloration.

EP 803 524 also mentions other catalysts which have hitherto been used for this purpose, but without showing any particular effect on the curing temperature. These include known from polyurethane chemistry organometallic catalysts such. As dibutyltin dilaurate (DBTL), or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2] octane (DABCO).

In WO 00/34355 catalysts based on Metallacetylacetonaten, z. As zinc acetylacetonate claims. Such catalysts are in fact capable of lowering the curing temperature of polyurethane powder coating compositions containing uretdione groups, but mainly show allophanates as reaction products (Gedan-Smolka, F. Lehmann, D. Lehmann, New catalysts for the low-temperature curing of uretdione powder coatings "International Waterborne, High solids and Powder Coatings Symposium, New Orleans, 21-22 / 02/2001). Allophanates are the reaction products of one mole of alcohol and two moles of isocyanate, while in conventional urethane chemistry, one mole of alcohol reacts with one mole of isocyanate. Due to the unwanted allophanate formation so technically and economically valuable isocyanate groups are destroyed. The object of the present invention was, on the one hand, to find particularly flexible but also highly reactive polyurethane compounds containing uretdione groups, which can be cured even at very low temperatures and in particular for the production of plastics and of flexible high-gloss or matt, light and weather-stable powder coatings and adhesives are suitable.

Surprisingly, it has been found that the combination of uretdione group-containing polyurethanes based on diisocyanatodicyclohexylmethane (H ₁₂ MDI) and certain catalysts leads to highly reactive and also to particularly flexible coatings.

Conventional uretdione-containing paint or adhesive compositions can be cured under normal conditions (DBTL catalysis) only from 180 ° C. With the aid of the low-temperature-curing lacquer or adhesive compositions according to the invention, not only energy and curing time can be saved at a curing temperature of from 100 to 160 ° C., but also many temperature-sensitive substrates can be coated or bonded, which at 180 ° C. undesirable yellowing, Show signs of decomposition and / or embrittlement. 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.

The present invention relates to highly reactive uretdione group-containing polyurethane compositions, essentially containing

A) at least one hardener containing uretdione groups, comprising the reaction product of the uretdione of diisocyanatodicyclohexylmethane (H ₁₂ MDI) and hydroxyl-containing compounds having a free NCO content of less than 5% by weight and a uretdione content of from 1 to 18% by weight and B) at least one catalyst from the group of catalysts

1. of the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ COO] -, where X is either N or Pist, R ¹ to R ⁴ simultaneously or independently of one another alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals, in each case linear or branched, bridged or bridged with other radicals R ¹ to R ⁴ , forming cyclics, bicyclic or tricyclic compounds and the bridging atoms besides carbon and heteroatoms may be, with 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, 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 bonds or halogen atoms,

2. of the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ] ^" , where X is either N or P, R ¹ to R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, Alkoxyalkyl radicals, in each case linear or branched, bridged 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 ³ ^{4 may} additionally have one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms, and R ^{5 is} either OH or F,

3. of the formula M (OR ¹ ), (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 which is identical to is 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 are} simultaneously or independently of one another hydrogen or alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals 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, May have double bonds, triple bonds or halogen atoms, these catalysts from groups 1 to 3 are contained individually or in mixtures and may optionally be surrounded with an inert shell and encapsulated with it; C) optionally at least one hydroxyl-containing polymer having an OH number between 20 and 500 mg KOH / gram with a weight fraction, based on the total formulation, of 1 to 95%; D) optionally at least one acid group reactive compound with a

Weight fraction, based on the total formulation, of 0.1 to 10%; E) optionally at least one acid in monomeric or polymeric form in a weight proportion, based on the total formulation, of 0.1 to 10%;

F) optionally auxiliaries and additives and / or further catalysts having a weight fraction, based on the total formulation, of 0.01 to 55%;

G) optionally solvents in amounts of from 1 to 75% by weight, based on the total formulation,

wherein the proportion of the catalyst under B) is 0.001 to 3 wt .-% of the total amount of the formulation.

The invention also provides the use of the polyurethane compositions according to the invention for the production of flexible lacquer coatings on metal, plastic, glass, wood or leather substrates or other heat-resistant substrates.

The invention also provides the use of the polyurethane compositions according to the invention for the production of bonds of metal, plastic, glass, wood or leather substrates or other heat-resistant substrates.

The invention also relates to metal coating compositions, in particular for automobile bodies, motorcycles and bicycles, building parts and

Household appliances, wood-coating compositions, glass-coating compositions Settlements, leather coating compositions and plastic coating compositions.

The hardener A) preferably consists entirely of H ₁₂ MDI as starting material for the isocyanate component. Furthermore, the invention also includes hardener A) whose isocyanate component consists of H ₁₂ MDI and at least one further aliphatic, aromatic, cycloaliphatic and / or (cyclo) aliphatic isocyanate component. Preferred isocyanates are isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethyl-hexamethylene diisocyanate / 2,4,4-trimethyl-hexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI) .

Methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI) and tetramethylxylylene diisocyanate (TMXDI), alone or in mixtures, especially HDI, IPDI, in amounts of 1 to 50 wt .-%, based on the total amount of all isocyanates.

The isocyanate component is dimerized to uretdione polyisocyanates and then reacted with hydroxyl-containing compounds to the curing agent A).

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 417,603. The dimerization of H ₁₂ MDI has been described recently in WO 04 005 363 and WO 04 005 364. 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 dimerization catalysts, such as. As dialkylaminopyridines, trialkylphosphines, 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. Basically, for the production of uretdione-containing Polyisocyanates suitable for a wide range of isocyanates.

The implementation of these uretdione polyisocyanates, according to the invention the uretdione group-containing H ₁₂ MDI, preferably as the sole polyisocyanate, or H ₁₂ MDI in admixture with other uretdiongrupenhaltigen polyisocyanates, preferably HDI, IPDI, uretdione groups having curing agents 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). 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). Preference is given to polyesters and monomeric dialcohols. In addition to the uretdione groups, the paint or adhesive hardeners may also have isocyanurate, biuret, allophanate, urethane and / or urea structures.

The invention also provides the use of at least one catalyst from the group of the catalysts of the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ COO] -, wherein X is N or P, R ¹ to R ^{4 are the} same or independently of one another are 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 and heteroatoms can, with 1 to 18 carbon atoms and each radical R ¹ to R ⁴ additionally one or more alcohol, amino, ester, keto,

May have thio, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R ^{5 represents} 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, double bonds, triple bonds or

May have halogen atoms, 2. the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ] ^" , wherein X is N or P, R ¹ to R ^{4 are the} same or independently alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl , in each case linear or branched, bridged 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 - R ⁴ additionally may have one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate, double bonds, triple bonds or halogen atoms, and R ^{5 is} either OH or F, 3. of the formula M (OR ¹ ), (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 which 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 radicals having 1 to 8 carbon atoms and the radicals in each case linear or branched, unbridged or with others

Bridged bridged to form cyclen, bicyclic or tricyclic and the bridging atoms in addition to carbon heteroatoms can be and additionally one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, Allophanate groups, double bonds, triple bonds or halogen atoms,

in solid polyurethane lacquer or adhesive compositions containing uretdione-group-containing polyurethane compositions based on H ₁₂ MDI.

The catalysts essential to the invention B) suffice

1. of the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ COO] -, where X is N or P, R ¹ to R ^{4 are} simultaneously or independently alkyl, aryl, aralkyl, heteroaryl, Alkoxyalkyl radicals, in each case linear or branched, bridged 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 ³ ⁴ additionally one or more alcohol, amino, ester, keto, May have thio, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R ^{5 represents} 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, double bonds, triple bonds or

May have halogen atoms, or

2. the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ] ^" , wherein X is N or P, R ¹ to R ^{4 are the} same or independently alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl , in each case linear or branched, unbridged or bridged with other radicals R ¹ to R ⁴ , with the formation of cycles, bicyclic or tricyclic radicals and the bridging atoms in addition

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

3. of the formula M (OR ¹ ), (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 which is identical to is 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 R ¹ to R ⁶ simultaneously or independently of one another are hydrogen or alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals having 1 to 8 carbon atoms and the radicals are each linear or branched, unbridged or bridged with other radicals, forming 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 , 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, tetrapropyl ammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate and tetrabutylammonium benzoate. Tetrabutylphosphonium acetate, tetrabutylphosphonium benzotriazolate, ethyltriphenylphosphonium acetate, tetraphenylphosphonium phenolate and trihexyltetradecylphosphonium decanoate.

Examples of such catalysts under 2. are methyltributylammonium hydroxide, methyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrabutyl phosphonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, Tetradecylammoniumhydroxid, Tetradecyltrihexyl- hydroxide, Tetraoctadecylammoniumhydroxid, benzyltrimethylammonium hydroxide, benzyl-triethylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammo ammonium hydroxide, trimethylvinylammonium hydroxide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetrabutylphosphonium fluoride,

Tetraoctylammonium fluoride and benzyltrimethylammonium 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 ethanolate, sodium ethoxide, potassium methoxide, magnesium ethanolate, calcium ethoxide, 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-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.

Of course, mixtures of such catalysts B) 1. - 3. 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. 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 agent A) or hydroxyl-containing polymers C). So z. B. free alcohol, thio or amino groups of the ammonium salts with acid, isocyanate, or glycidyl groups of the curing agent A) or hydroxyl-containing polymers C) are reacted to integrate the catalysts B) in the polymeric composite.

In the case of the hydroxyl-containing polymers C), preference is given to using either polyesters, polyacrylates, polyurethanes, polyethers and / or polycarbonates having an OH number of 20 to 500 (in mg KOH / gram). Particularly preferred are polyesters having an OH number of 30 to 150, an average molecular weight of 500 to 6,000 g / mol. Such binders have been described, for example, in EP 669 354 and EP 254 152. These polymers can be either amorphous or (partially) crystalline. Of course, mixtures of such polymers can be used. The polymers C) can be used in amounts of 1 to 95 wt .-%, based on the total formulation. It should be noted in this context that the activity of these catalysts 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. The content of the polyesters on acid groups should be below 20 mg KOH / g, otherwise the catalysts will be inhibited too much. 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. The possibly cross-linking effect of the polyfunctional compounds is undesirable because of the viscosity-increasing effect, but does not usually interfere because of the low concentration.

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, Vestagon EP HA 320 (hydroxyalkyl amide, Degussa AG), but also phenylenebisoxazoline, 2-methyl-2-oxazoline, 2-hydroxyethyl-2-oxazoline, 2-hydroxypropyl-2-oxazoline, 5-hydroxypentyl-2-oxazoline, sodium carbonate, potassium carbonate and calcium carbonate. Of course, mixtures of such substances come into question. These reactive compounds can be used in proportions by weight of from 0.1 to 10%, preferably from 0.5 to 3%, based on the total formulation.

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 copolyesters or copolyamides having an acid number of at least 20. The acid component E) can be used in amounts of 0.1 to 10 wt .-% based on the total formulation , For the production of lacquers or adhesives, it is possible to use the additives F) customary in lacquer or adhesive technology, such as leveling agents, eg. As polysilicone or acrylates, 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. As titanium dioxide, in an amount up to 50 wt .-% of

Total composition can be added. 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 .-%.

As solvent under G) are all liquid substances in question that do not react with other ingredients, eg. Acetone, ethyl acetate, butyl acetate, xylene, Solvesso 100, Solvesso 150, methoxypropyl acetate and dibasic ester. They can be used in amounts of 1 to 75 wt .-%, 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. As heated stirred tanks, kneaders, flow tubes or extruders, carried out, with upper temperature limits of 120 to 130 ° C should not be exceeded. 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 heated to a temperature of 60 to 220 ° C, preferably 6 to 30 minutes at 80 to 160 ° C for curing for 1 to 60 minutes.

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

Examples:

1) Preparation of uretdione group-containing 1,4-diisocyanatocyclohexylmethane (not according to the invention)

a) Preparation of the dimerization catalyst sodium 1,2,4-triazolate (WO 2004/005364, p. 15)

14.2 g of sodium ethoxide were diluted in 200 ml of methanol and treated portionwise with 17.4 g of 1,2,4-triazole. After four hours of heating to reflux temperature, the solvent was distilled off on a rotary evaporator and the residue was treated with methylene chloride. The precipitated product was freed from residues of solvent at room temperature in a vacuum oven. This gave 26.3 g of sodium 1,2,4-triazolate.

b) Dimerization of 1,4-diisocyanatocyclohexylmethane (WO 2004/005364, S 19)

1000 g of VESTANAT H ₁₂ MDI were treated with a solution of 2 g of sodium triazolate (Ia) in 25 ml of dimethyl sulfoxide and stirred at 30 ° C. for four hours. The NCO content had dropped to 26.4 wt .-%. After addition of 4.6 g of dibutyl phosphate, the precipitate was filtered off and the filtrate using a thin-film evaporator at a temperature of 155 ° C and a pressure of 0.08 mbar freed of excess diisocyanate. A viscous oil containing latent NCO- Groups of 14.5%.

c) Preparation of a uretdione group-containing hardener based on VESTANAT H ₁₂ MDI

In a reactor, 315 g of dodecanediol-1.12 and 0.5 g of dibutyltin dilaurate were dissolved in 1 liter of acetone. The solution was heated to 50 ° C. With vigorous stirring and inert gas atmosphere, 684 g of uretdione from Example Ib) were added. The reaction was monitored by titrimetric NCO determination and was complete after 6 hours. Thereafter, the solvent was removed on a rotary evaporator, the product was cooled and comminuted. The product has a melting range of 112 to 114 ° C and a latent NCO content of 9.8%.

d) Preparation of a comparative hardener based on IPDI uretdione

In a reactor, 316 g of dodecanediol-1.12 and 0.5 g of dibutyltin dilaurate were dissolved in 1 liter of acetone. The solution was heated to 50 ° C. With vigorous stirring and inert gas atmosphere, 683 g of IPDI uretdione were added. The reaction was monitored by titrimetric NCO determination and was complete after 6 hours. Thereafter, the solvent was removed on a rotary evaporator, the product was cooled and comminuted. The product has a melting range of 101 to 103 ° C and a latent NCO content of 13.9%.

2) powder coating compositions (A, B according to the invention, C, D not according to the invention)

(In% by weight):

General manufacturing instructions for the powder coatings:

The comminuted feedstocks - powder coating hardener, catalysts, leveling agents - are used in intimately mixed in a pug mill and then homogenized in the extruder to a maximum of 130 ° C. After cooling, the extrudate is crushed and ground with a pin mill to a particle size <100 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 ° C. (Layer thickness 70 to 80 μm)

3) Results (A, B according to the invention, C, D not according to the invention):

Errichsentiefung according to DIN 53 156 Kugelschlag ASTM D 2794-93

As is clear from these results, composition A according to the invention is both reactive and flexible (direct and indirect ball impact measurable). If, on the other hand, the catalyst is omitted (C), the reactivity also decreases (see MEK test or Errichsentiefung). In D) an alternative uretdione based on IPDI was used. The reactivity is similar to the A of the invention, the flexibility (Kugelschlag), however, much lower.

The composition B according to the invention makes it clear that the flexibility can be significantly increased by adding crystalline resins.

Claims

Patent claims:

1. Highly reactive polyurethane compositions containing uretdione groups with a

Melting point above 40 ° C, essentially containing

A) at least one hardener containing uretdione groups, containing the reaction product from the uretdione of diisocyanatodicyclohexylmethane (H ₁₂ MDI) and compounds containing hydroxyl groups with a free NCO content of less than 5% by weight and a uretdione content of 1 to 18% by weight; and

B) at least one catalyst

1. of the formula [ ^XR ¹ R ² R ³ R ⁴ ^J ⁺ [R ⁵ COO] ^" , with , 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 additionally one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms can have, and R ⁵ means either OH or F,

3. the formula M (OR ¹ ),, (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, which is identical to for 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 applies, the radicals R ¹ to R ⁶ simultaneously or independently of one another represent hydrogen or alkyl, 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 Formation of cycles, bicycles or tricycles and the bridging atoms can also be heteroatoms in addition to carbon and one or more

Alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, these catalysts from groups 1 to 3 being contained individually or in mixtures and optionally surrounded and encapsulated with an inert shell; where the proportion of the catalyst under B) is 0.001 to 5% by weight of the total formulation.

2. Polyurethane composition according to claim 1, characterized in

C) at least one hydroxyl-containing polymer with an OH number between 10 and 500 mg KOH/gram, with a weight proportion, based on the total formulation, of 1 to 95%; and/or D) that at least one compound reactive towards acid groups with one

Weight fraction, based on the total formulation, from 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) Auxiliaries and additives and/or further catalysts are included in a proportion by weight, based on the total formulation, of 0.01 to 55%. 3. Polyurethane composition according to claim 1 or 2, characterized in that solvent G) is contained in amounts of 1 to 75% by weight.

4. Polyurethane compositions according to at least one of claims 1 to 3, characterized in that additional uretdione-containing hardeners A) based on isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethyl-hexamethylene diisocyanate /2,4,4-trimethyl hexamethylene 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 uretdione-containing hardeners based on IPDI and / or HDI are also contained.

6. Polyurethane compositions according to at least one of claims 1 to 5, characterized in that uretdione-containing hardeners A) based on hydroxyl-containing polyesters, 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 at least one of claims 1 to 7, characterized in that the hydroxyl group-containing polymers B) are polyester, polyether, polyacrylates,

Polyurethanes and polycarbonates, alone or in mixtures, are included.

9. Polyurethane compositions according to claim 8, characterized in that polyesters with an OH number of 30 to 150 mg KOH/g and an average molecular weight of 500 to 6000 g/mol are contained.

10. Polyurethane compositions according to at least one of claims 1 to 9, characterized in that catalysts B1) selected from tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium butyrate - ethyl ammonium benzoate, Tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate

Tetrabutylphosphonium acetate, tetrabutylphosphonium formate, ethyltriphenylphosphonium acetate, tetrabutylphosphonium benzotriazolate, tetraphenylphosphonium phenolate and trihexyltetradecylphosphonium decanoate are included.

11. Polyurethane compositions according to at least one of claims 1 to 9, characterized in that catalysts B2) are selected from methyltributylammonium hydroxide, methyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide , tetradecyl ammonium hydroxide, tetradecyl trihexy ammonium hydroxide, tetra - octadecylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, triethylammonium hydroxide, trimethylvinylammonium hydroxide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride,

Benzyltrimethylammonium fluoride, tetrabutylphosphonium hydroxide and tetrabutyl contain phosphonium fluoride.

12. Polyurethane compositions according to at least one of claims 1 to 10, characterized in that catalysts B3) are 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.

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 the hydroxyl-containing polymers C) contain polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates with an OH number of 10 to 500 (in mg KOH / gram). are.

16. Polyurethane compositions according to claim 15, characterized in that hydroxyl-containing polyesters with an OH number of 15 to 150 and an average molecular weight of 500 to 6,000 g / mol are included.

17. Polyurethane compositions according to claim 16, characterized in that polyester based on succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid, hexahydrophthalic acid,

Hexahydroterephthalic acid, endemethylentetrahydrophthalic 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 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-trimethylhexanediol-(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, triethylene glycol, tetraethylene glycol, trans- and ice- 1,4- Cyclohexanedimethanol, the triols glycerol, hexanetriol-(1,2,6), 1,1,1-trimethylolpropane and 1,1,1-trimethylolethane 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, hydroxyalkyalamides, 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.

21. Polyurethane compositions according to at least one of claims 1 to 20, characterized in that the auxiliaries and additives F) are leveling agents, such as. B. polysilicones or acrylates,

Light stabilizers such as B. sterically hindered amines, fillers and pigments are included.

22. Process for the production of highly reactive, uretdione group-containing

Polyurethane compositions, essentially comprising

A) at least one hardener containing uretdione groups, containing the reaction product from the uretdione of diisocyanatodicyclohexylmethane (H ₁₂ MDI) and compounds containing hydroxyl groups with a free NCO content of less

5% by weight and a uretdione content of 1 to 18% by weight; and

B) at least one catalyst

1. the formula [XR ¹ ^R ² ^R ³ R ⁴ J ⁺ [R ⁵ COO] ^" , where

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 additionally contains 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 represents 1 to 18 carbon atoms and may additionally have one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms,

2. of the formula [ ^XR ¹ ^R ² R ³ R ⁴ J ⁺ [R ⁵ ]-, with 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 ),, (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, which is identical to that 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 applies , the radicals R ¹ to R ⁶ simultaneously or independently of one another represent hydrogen or alkyl, 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, under training of 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 can have halogen atoms, whereby these catalysts from groups 1 to 3 are contained individually or in mixtures and can optionally be surrounded and encapsulated with an inert shell; and C) optionally at least one hydroxyl-containing polymer with an OH number between 10 and 500 mg KOH/gram in a proportion by weight, based on

Total formulation from 1 to 95%; D) optionally at least one compound reactive towards acid groups with a weight proportion, based on the total formulation, of 0.1 to 10%; E) optionally at least one acid in monomeric or polymeric form in one

Weight fraction, based on the total formulation, from 0.1 to 10%;

F) optionally auxiliaries and additives and/or further catalysts with a weight proportion, based on the total formulation, of 0.01 to 55%;

G) optionally solvents in amounts of 1 to 75% by weight based on the total formulation;

where the proportion of the catalyst under B) is 0.001 to 5% by weight of the total formulation, by homogenization at temperatures of 60 to 150 ° C.

23. Powder coating composition containing compounds according to at least one of the preceding claims 1 to 21.

24. Adhesive composition containing compounds according to at least one of the preceding claims 1 to 21.

25. Use of at least one catalyst

1. the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ COO]-, where X can be N or P, where R ¹ to

R ⁴ simultaneously or independently of one another alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals, each linear or branched, unbridged or with other radicals

R ¹ to R ⁴ bridged, forming cycles, bicycles or tricycles and the In addition to carbon, bridging atoms can also be heteroatoms, with 1 to 18 carbon atoms and each radical R ¹ to R ⁴ additionally represents one or more alcohol, amino, ester, keto, thio, urethane, urea, allophanate groups, can have double bonds, triple bonds or halogen atoms, and R ⁵ represents an alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radical, linear or branched, with 1 to 18 carbon atoms and additionally represents one or more alcohol, amino, ester , keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, 2. the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ] ^" , with X equal N or P, where R ¹ to R ⁴ simultaneously or independently of one another 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 also has one or more alcohol, amino, ester, keto, thio, acid, urethane, urea,

can have allophanate groups, double bonds, triple bonds or halogen atoms, and R ⁵ means either OH or F,

3. the formula M (OR ¹ ),, (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, which is identical to for 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 applies, the radicals R ¹ to R ⁶ simultaneously or independently of one another represent hydrogen or alkyl, 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 training of cyclers,

Bicycles or tricycles and the bridging atoms can also be heteroatoms in addition to carbon and additionally have one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms can, these catalysts from groups 1 to 3 being contained individually or in mixtures and optionally being surrounded and encapsulated with an inert shell can;

in polyurethane compositions according to at least one of claims 1 to 21.

26. Catalyst for accelerating the curing of highly reactive, uretdione group-containing polyurethane compositions, essentially containing

B) at least one catalyst

1. the formula [XR ¹ ^R ² ^R ³ R ⁴ J ⁺ [R ⁵ COO] ^" , where 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, can have double bonds, 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

1 to 18 carbon atoms and each radical R ¹ to R ⁴ additionally represents one or may have several 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 ),, (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, which is 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 are hydrogen or alkyl, aryl, aralkyl, heteroaryl,

Alkoxyalkyl radicals with 1 to 8 carbon atoms mean and the radicals are each linear or branched, unbridged or bridged with other radicals

Formation of 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,

may have allophanate groups, double bonds, triple bonds or halogen atoms, these catalysts from groups 1 to 3 being contained individually or in mixtures and optionally being surrounded and encapsulated with an inert shell; and C) optionally at least one hydroxyl-containing polymer with an OH number between 10 and 500 mg KOH/gram with a weight proportion, based on the total formulation, of 1 to 95%; D) optionally at least one compound reactive towards acid groups with a weight proportion, based on the total formulation, of 0.1 to 10%; E) optionally at least one acid in monomeric or polymeric form in one

Weight fraction, based on the total formulation, from 0.1 to 10%;

G) optionally solvents in amounts of 1 to 75% by weight based on the total formulation; where the proportion of the catalyst under B) is 0.001 to 5% by weight of the total formulation.

27. Use of highly reactive polyurethane compositions containing uretdione groups, essentially containing

B) at least one catalyst

1. the formula [XR ¹ ^R ² ^R ³ R ⁴ J ⁺ [R ⁵ COO]-, where 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, triple bonds or may have halogen atoms, 2. of the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ]-, 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 Rest 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,

Alkoxyalkyl radicals with 1 to 8 carbon atoms mean 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 in addition one or more alcohol, amino , ester, keto, thio, acid, urethane, urea,

may have allophanate groups, double bonds, triple bonds or halogen atoms, these catalysts from groups 1 to 3 being contained individually or in mixtures and optionally being surrounded and encapsulated with an inert shell; and

C) optionally at least one hydroxyl-containing polymer with an OH number between 10 and 500 mg KOH/gram in a proportion by weight, based on

Total formulation from 1 to 95%;

D) optionally at least one compound reactive towards acid groups with a weight proportion, based on the total formulation, of 0.1 to 10%;

E) optionally at least one acid in monomeric or polymeric form in a proportion by weight, based on the total formulation, of 0.1 to 10%;

where the proportion of the catalyst under B) is 0.001 to 5% by weight of the Overall formulation is.

28. Use according to claim 26 or 27 for the production of liquid and powdery paint and adhesive compositions for metal, plastic, wood, glass, leather or other heat-resistant substrates.

29. Metal coating compositions, essentially containing a polyurethane composition

B) at least one catalyst 1. of the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ COO] ^" , where X can be 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 mean and each radical R ¹ to R ⁴ can 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,

may have acid, urethane, urea, allophanate groups, double bonds, 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 with others

Residues R ¹ to R ⁴ are bridged, 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 also has 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 ),, (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, which is identical to for 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 applies, the radicals R ¹ to R ⁶ simultaneously or independently of one another are hydrogen or alkyl, aryl, aralkyl, heteroaryl,

C) optionally at least one hydroxyl-containing polymer with an OH number between 10 and 500 mg KOH/gram or with a proportion by weight, based on the total formulation, of 1 to 95%; D) optionally at least one compound reactive towards acid groups with a weight proportion, based on the total formulation, of 0.1 to 10%;

G) optionally solvents in amounts of 1 to 75% by weight based on the overall formulation;

where the proportion of the catalyst under B) is 0.001 to 5% by weight of the total formulation,

30. Wood coating composition, essentially containing a polyurethane lacquer composition

5% by weight and a uretdione content of 1 to 18% by weight; and

B) at least one catalyst

1. the formula [XR ¹ ^R ² ^R ³ R ⁴ J ⁺ [R ⁵ COO]-, where

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 additionally one or more alcohol, amino, ester, keto, thio,

Urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, and R ⁵ represents an alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radical, linear or branched, with 1 to 18 carbon atoms and additionally one or more may have alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms,

2. of the formula [ ^XR ¹ ^R ² R ³ R ⁴ J ⁺ [R ⁵ ]-, with 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 1 to 18 carbon atoms and each radical R ¹ to R ⁴ additionally has one or more alcohol, amino, ester, keto, thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms can, and R ⁵ means either OH or F, 3. of the formula M (OR ¹ ),, (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, which 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 mean hydrogen or alkyl, aryl, aralkyl, heteroaryl, alkoxyalkyl radicals with 1 to 8 carbon atoms and the radicals are each linear or branched, unbridged or bridged with other residues, forming cycles, bicycles or tricycles and the bridging atoms can also be heteroatoms in addition to carbon and in addition one or more alcohol, amino, ester, keto, thio, acid , urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, these catalysts from groups 1 to 3 being contained individually or in mixtures and optionally surrounded and encapsulated with an inert shell; and

C) optionally at least one hydroxyl-containing polymer with an OH number between 10 and 500 mg KOH/gram with a weight proportion, based on the total formulation, of 1 to 95%;

F) optionally auxiliaries and additives and/or further catalysts with a weight proportion, based on the total formulation, of 0.01 to 55%; G) optionally solvents in amounts of 1 to 75% by weight based on the

overall formulation; where the proportion of the catalyst under B) is 0.001 to 5% by weight of the total formulation,

31. Leather coating compositions, essentially containing a polyurethane lacquer composition

B) at least one catalyst

Weight fraction, based on the total formulation, from 0.1 to 10%;

G) optionally solvents in amounts of 1 to 75% by weight based on the total formulation; where the proportion of the catalyst under B) is 0.001 to 5% by weight of the total formulation,

32. Plastic coating compositions, essentially containing a polyurethane composition

B) at least one catalyst

1. the formula [XR ¹ ^R ² ^R ³ R ⁴ J ⁺ [R ⁵ COO]-, where 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 additionally represents 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, triple bonds or halogen atoms can have, 2. the formula [XR ¹ R ² R ³ R ⁴ J ⁺ [R ⁵ ]-, with X equal to 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 additionally 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,

Sum n+m+o+p+q+r = 1 to 6 applies, the radicals R ¹ to R ⁶ simultaneously or independently of one another represent hydrogen or alkyl, 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, may have thio, acid, urethane, urea, allophanate groups, double bonds, triple bonds or halogen atoms, these catalysts from groups 1 to 3 being contained individually or in mixtures and optionally surrounded and encapsulated with an inert shell; and

Total formulation from 1 to 95%;

where the proportion of the catalyst under B) is 0.001 to 5% by weight of the Overall formulation is,

33. Metal coating according to claim 29 for automobile bodies, motorbikes and bicycles, building parts and household appliances.

34. Coating compositions according to one of claims 29 to 33, characterized in that at least one of components C) to G) is contained.

35. Coating compositions according to one of claims 29 to 34, characterized in that these contain compounds according to at least one of claims 1 to 21.