JP2010502797A - Low temperature curable uretdione group-containing polyurethane composition having quaternary ammonium halide - Google Patents

Abstract

  It is a polyurethane composition containing a uretdione group that can be cured at a low temperature. The present invention relates to uretdione group-containing polyurethane compositions that cure at low baking temperatures, methods for making such compositions, and uses for making plastics, especially paint coatings and adhesives.

Description

  The present invention relates to uretdione group-containing polyurethane compositions that cure at low baking temperatures, methods for making such compositions, and uses for making plastics, especially paint coatings and adhesives.

  External or internal block polyisocyanates are useful crosslinkers for thermally crosslinkable polyurethane (PUR) coating compositions and adhesive compositions.

  Thus, for example, DE Publication 2535497 describes a PUR paint having excellent weather resistance and thermal stability. The cross-linking agent whose preparation is described in DE publication 2712931 consists of an isophorone diisocyanate containing isocyanurate groups blocked by ε-caprolactam. Polyisocyanates containing urethane groups, biuret groups, or urea groups are known and these isocyanate groups are similarly blocked.

  The disadvantage of these externally blocked systems is that the blocking agent decomposes during the thermal crosslinking reaction. Therefore, since this blocking agent can be released into the environment, special precautions must be taken to clean the exhaust and / or to recover the blocking agent for environmental and occupational health reasons. In addition to this, the cross-linking agent has little reactivity. A curing temperature of 170 ° C. or higher is required.

  DE publication 3030539 and DE publication 3030572 describe a process for the preparation of polyaddition compounds containing uretdione groups in which the terminal isocyanate groups are irreversibly blocked by monoalcohols or monoamines. In particular, the component of the cross-linking agent that terminates the chain is a drawback, which leads to a low cross-linking density of the PUR paint coating and thus to a mediocre solvent resistance.

  The hydroxy group-terminated uretdione group-containing polyaddition compound is the subject of EP669353. These compounds have improved resistance to solvents due to a functionality of 2. Common to these uretdione group-containing polyisocyanate-based compositions is that they do not release volatile compounds during the curing reaction. However, there is a high level of baking temperature of at least 180 ° C.

  The use of amidine as a catalyst in a PUR coating composition is described in EP 803524. These catalysts do indeed lead to a lower cure temperature, but exhibit considerable yellowing, which is generally undesirable in the coated area. The cause of this yellowing appears to be a reactive nitrogen atom in amidine. These nitrogen atoms react with oxygen atoms in the air and become N oxides that cause discoloration.

  EP 803524 also mentions other catalysts conventionally used for this purpose, but these catalysts have no particular effect on the curing temperature. This applies to organometallic catalysts known from polyurethane chemistry, such as dibutyltin dilaurate (DBTL), or tertiary amines, such as 1,4-diazabicyclo [2.2.2] octane (DABCO).

  WO 00/34355 claims a catalyst based on a metal acetylacetonate, for example zinc acetylacetonate. Such a catalyst can actually lower the curing temperature of a powder coating composition of uretdione group-containing polyurethane, but exhibits mainly allophanate as a reaction product (M. Gedan-Smolka, F. Lehmann, D. Lehmann " New catalysts for the low temperature curing of uretered powder coatings "International Waterbone, High solids and Powder Coatings Symposium, NewOl. Allophanate is a reaction product consisting of 1 mol of alcohol and 2 mol of isocyanate, whereas in conventional urethane chemistry, 1 mol of alcohol and 1 mol of isocyanate are reacted. Undesirable allophanate formation destroys industrially, for example, economically valuable isocyanate groups.

  The object of the present invention is therefore a highly reactive paint which can already be cured at very low temperatures, and in particular for producing plastics, as well as high gloss or matt, light and weather resistant. It was to discover highly reactive uretdione group-containing polyurethane compositions that are suitable for making compositions and adhesive compositions.

  Surprisingly, it has been found that certain catalysts can accelerate the uretdione group rupture so that the curing temperature of the polyurethane composition can be significantly reduced when using uretdione-containing curing agents.

  Conventional uretdione-containing polyurethane compositions can only be cured from 180 ° C. under normal conditions (DBTL catalyst). Using the polyurethane composition curable at low temperature according to the present invention not only can save energy and (curing) time at a curing temperature of 100-160 ° C., but also an undesirable yellowing phenomenon, decomposition phenomenon at 180 ° C. Many temperature sensitive supports that may and / or exhibit embrittlement phenomena can be coated or bonded. In addition to metal, glass, wood, leather, plastic, and MDF plates, certain aluminum substrates are also suitable. In the case of an aluminum substrate, it leads to a temperature load that is too high and sometimes to an undesirable change in the crystal structure.

The subject of the present invention is essentially free ACO containing free NCO based on A) aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanates and hydroxy group-containing compounds. At least one uretdione-containing curing agent B) having a content of less than 5% by weight and a uretdione content of 1-35% by weight, optionally a hydroxy group-containing polymer C) having an OH number of 20 to 500 mg KOH / gram ^{NR 1 R 2 R 3 R 4} ] + [R 5] - [ wherein, R ¹ to R ⁴ simultaneously or independently of one another, an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group A heteroaryl group, an alkoxyalkyl group (which may be linear or branched each time and is not bridged or bridged with other groups R ^{1 to} R ⁴ to form a monocyclic, bicyclic or tricyclic ring It may form a ring And the bridging atom may also be a heteroatom in addition to carbon), and in each case, the radicals R ^{1 to} R ⁴ additionally comprise one or more alcohol groups, amino groups, ester groups, keto Group, thio group, urethane group, urea group, allophanate group, double bond, triple bond, or halogen atom, and R ⁵ represents Cl, Br, or I]. And, in some cases, D) at least one compound reactive to acid groups, having a mass proportion of 0.1 to 10% relative to the total preparation,
E) in some cases at least one acid F in monomer form or in polymer form in a mass proportion of 0.1 to 10% relative to the total preparation F)
G) In some cases, auxiliaries and additives are added so that the proportion of catalyst belonging to C) is 0.001 to 5% by weight of the total amount of components A) and B) (in this case catalyst C) It is a highly reactive uretdione group-containing polyurethane composition, which may be surrounded by an active shell (and thus encapsulated).

  A further subject of the present invention is also a process for the production of polyurethane compositions.

  The subject of the invention is also liquid and powdery on metal supports, plastic supports, glass supports, wood supports, or leather supports, or other heat-resistant substrates. The use of the polyurethane composition according to the invention for the production of a paint coating.

  The subject of the present invention is also an adhesive composition for bonding metal supports, plastic supports, glass supports, wood supports, or leather supports, or other heat resistant substrates. Of the polyurethane composition according to the invention.

  The subject of the invention is likewise a metal coating composition, in particular a metal coating composition, wood coating composition, glass coating composition, leather coating composition for automobile bodies, motorcycles and bicycles, building components and household goods. And plastic coating compositions.

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 417603. A comprehensive overview of industry related methods for dimerizing isocyanate to uretdione can be found in J. Am. Prakt. Chem. 336 (1994), 185-200. The reaction to convert isocyanate to uretdione is generally carried out in the presence of a soluble dimerization catalyst such as dialkylaminopyridine, trialkylphosphine, phosphorous acid-triamide, or imidazole. This reaction (optionally carried out in a solvent, but preferably in the absence of a solvent) is stopped by the addition of a catalyst poison when the desired reaction is achieved. The excess monomeric isocyanate is subsequently separated off by distillation. If the catalyst is sufficiently vaporized, the reaction mixture can be taken out in the process of monomer separation from the catalyst. In this case, the addition of catalyst poison can be eliminated. In general, a wide palette of isocyanates is suitable for producing polyisocyanates containing uretdione groups. According to the present invention, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-dicyclohexylmethylene diisocyanate (hydrogenated MDI) H ₁₂ MDI, 2-methylpentane diisocyanate Nart (MPDI), 2,2,4-trimethyl-hexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI) ), Toluidine diisocyanate (TDI), and tetramethylxylylene diisocyanate (TMXDI) are preferably used. Very particular preference is given to IPDI and HDI.

The reaction of converting these polyisocyanates having uretdione groups into curing agents A) having uretdione groups comprises free NCO groups and hydroxy group-containing monomers or polymers such as polyesters, polythioethers, polyethers, polycaprolactams, polyepoxides, A polyester amide, polyurethane, or reaction with low molecular dialcohols, trialcohols, and / or tetraalcohols as chain extenders and optionally monoamines and / or monoalcohols as chain terminators and It is frequently described (EP669353, EP669354, DE3030572, EP633598, or EP803524). Preferred curing agents A) having uretdione groups have a free NCO content of less than 5% by weight and a uretdione group content of 1 to 35% by weight (calculated as C ₂ N ₂ O ₂ with a molecular weight of 84). Preferably, polyesters having an OH number of 30-150 mg KOH / g and an average molecular weight of 500-6000 g / mol, and monomeric dialcohols such as ethylene glycol, propanediol (1,2), and propanediol (1, 3), 2,2-dimethylpropane- (1,3), butanediol- (1,4), hexanediol- (1,6), 2-methylpentanediol- (1,5), 2,2, 4-trimethylhexanediol- (1,6), 2,4,4-trimethylhexanediol- (1,6), heptanediol- (1,7), dodecanediol- (1,12), octadecene-9, 10-diol- (1,12), thiodiglycol, octadecandiol- (1,18), 2,4-dimethyl-2-propi Luheptanediol- (1,3), diethylene glycol, triethylene glycol, tetraethylene glycol, trans-1,4-cyclohexanedimethanol, and cis-1,4-cyclohexanedimethanol are used.

  In addition to the uretdione group, the curing agent can also have an isocyanurate structure, a biuret structure, an allophanate structure, a urethane structure, and / or a urea structure.

  As hydroxy group-containing polymer B), polyesters, polyethers, polyacrylates, polyurethanes, polyethers and / or polycarbonates having an OH number of 20 to 500 (in mg KOH / gram) are preferably used. Particularly preferably, a polyester having an OH number of 30 to 150 and an average molecular weight of 500 to 6000 g / mol is used. Such binders are described, for example, in EP669354 and EP254152. Of course, mixtures of the above polymers can also be used.

The present invention also relates to the use of a polyurethane composition, wherein ^{[NR 1 R 2 R 3 R} 4] + [R 5] - [ wherein, R ¹ to R ⁴ simultaneously or independently of one another, Alkyl groups having 1 to 18 carbon atoms, aryl groups, aralkyl groups, heteroaryl groups, alkoxyalkyl groups (in each case may be linear or branched, not bridged or other groups R ^{1 to} R ⁴ may be bridged to form a monocyclic, bicyclic or tricyclic ring, and the bridging atom may be a heteroatom in addition to carbon) and in each case the group R ^{1 to} R ⁴ additionally have one or more alcohol groups, amino groups, ester groups, keto groups, thio groups, urethane groups, urea groups, allophanate groups, double bonds, triple bonds, or halogen atoms even well, and R ⁵ is Cl, Br or I, Meaning that, at least one catalyst C) (this time, these catalysts may also be surrounded by an inert shell, the use of thus may be encapsulated), as well as the catalyst itself.

The catalyst C) essential for the present invention has the formula [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ⁻ , wherein R ^{1 to} R ⁴ are simultaneously or independently of one another from 1 to 18 Alkyl groups, aryl groups, aralkyl groups, heteroaryl groups, alkoxyalkyl groups having a carbon atom (in each case may be linear or branched, not bridged or other groups R ^{1 to} R ⁴ Each of which may form a monocyclic, bicyclic or tricyclic ring, and the bridging atom may be a heteroatom in addition to carbon) and in each case the radicals R ^{1 to} R ⁴ May additionally have one or more alcohol groups, amino groups, ester groups, keto groups, thio groups, urethane groups, urea groups, allophanate groups, double bonds, triple bonds, or halogen atoms. and R ⁵ denotes a Cl, Br or I,] (this These catalysts may also be surrounded by an inert shell, satisfy even may) it has been thus encapsulated.

  Examples of catalysts belonging to C) are tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide. , Tetramethylammonium iodide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, methyltributylammonium chloride, methyltripropylammonium chloride, methyltriethylammonium chloride, methyltriphenylammonium chloride, Phenyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzene bromide Rutriethylammonium bromide, benzyltripropylammonium bromide, benzyltributylammonium bromide, methyltributylammonium bromide, methyltripropylammonium bromide, methyltriethylammonium bromide, methyltriphenylammonium bromide, phenyltrimethylammonium bromide, iodine Benzyltrimethylammonium iodide, benzyltriethylammonium iodide, benzyltripropylammonium iodide, benzyltributylammonium iodide, methyltributylammonium iodide, methyltripropylammonium iodide, methyltriethylammonium iodide, methyltriphenylammonium iodide, And phenyltrimethylammonium iodide.

  Of course, mixtures of such catalysts can also be used. Particular preference is given to using tetrabutylammonium chloride. These are in an amount of 0.001 to 5% by weight, preferably 0.01 to 3% by weight, particularly preferably 0.5 to 1.5% by weight, based on the components A) and B). It is contained in the coating composition or the adhesive composition. The catalyst can also contain water of crystallization, in which case water of crystallization is not taken into account in the amount of catalyst used, ie the amount of water is excluded. A variant according to the invention comprises polymer coupling of such a catalyst C) to the curing agent A) or to the hydroxy group-containing polymer B). Thus, for example, by reacting the free alcohol group, thio group, or amino group of an ammonium salt with the acid group, isocyanate group, glycidyl group, or hydroxy group-containing polymer B) of the curing agent A), the catalyst C) Can be integrated in the polymer bond.

  It should be noted in this connection that the activity of these catalysts is clearly reduced in the presence of acids. The conventional reaction partner of the uretdione-containing curing agent is a hydroxyl group-containing polyester. Due to the process for producing the polyester, the polyester sometimes still has acid groups in small quantities. In the presence of such an acid group-containing polyester, it is conceivable to use the aforementioned catalyst in excess relative to the acid group, or to add a reactive compound capable of capturing the acid group. Monofunctional and polyfunctional compounds can also be used for this purpose.

  Reactive compounds D) that scavenge acids are generally known in paint chemistry. Thus, for example, epoxy compounds, carbodiimides, hydroxyalkylamides, or 2-oxazolines and inorganic salts such as hydroxides, hydrogen carbonates or carbonates with acid groups react at elevated temperatures. Considered in this case are, for example, triglycidyl ether isocyanurate (TGIC), Araldit PT 910, Araldit PT 912 (mixture of diglycidyl ester and triglycidyl ester, Hunstman), EPIKOTE 828 (bisphenol A based diester). Glycidyl ether Schell), glycidyl ester of versatic acid, ethylhexyl glycidyl ether, butyl glycidyl ether, POLYPOX R 16 (pentaerythritol tetraglycidyl ether, UPPC AG), and other polyepoxy types with free epoxy groups, VESTAGON EP HA 320, (Hydroxyalkylamide, Degussa AG), 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 materials are also contemplated. These reactive compounds can be used in a mass proportion of 0.1 to 10%, preferably 0.5 to 3%, based on the total preparation.

  The acids mentioned under E) are all substances, solid or liquid, organic or inorganic, monomers or polymers having the properties of Bronsted or Lewis acids. Examples include: sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, phthalic acid, succinic acid, and also copolyesters or copolyamides having an acid value of at least 20.

  Considered as solvents belonging to F) are all liquid substances which do not react with other contained substances such as acetone, ethyl acetate, butyl acetate, xylene, Solvesso 100, Solvesso 150, methoxypropyl acetate, and Basic ester.

  For polyurethane compositions, additives G) customary in the paint industry or in the adhesive industry, such as leveling agents such as polysilicones, or acrylates, light stabilizers such as sterically hindered amines, or other auxiliaries, For example, an auxiliary agent as described in EP669353 can be added in a total amount of 0.05 to 5% by mass. Fillers and pigments, such as titanium dioxide, can be added in amounts up to 50% by weight of the total composition.

  Optionally, additional catalysts already known in polyurethane chemistry may be included. This is in this case mainly an organometallic catalyst, for example dibutyltin dilaurate, or a tertiary amine, for example 1,4-diazabicyclo [2,2,2] octane, in an amount of 0.001 to 1% by weight.

  Homogenization of all the components for producing the polyurethane composition according to the invention can be carried out in a suitable aggregate, for example in a heatable stirrer, kneader or extruder, with the upper temperature limit being It is desirable not to exceed 120-130 ° C. A homogeneous mixture of all components may be solid or liquid according to the respective starting material or according to the use of a solvent. A well mixed material is applied to the support by a suitable application (eg roller, spray). In the case of solid preparations, the sprayed powder can be applied on a suitable support by known methods such as electrostatic powder spraying, fluidized bed coating, or electrostatic fluidized bed coating. After application, the coated workpiece is heated for curing at a temperature of 60-220 ° C., preferably 6-30 minutes, at a temperature of 80-160 ° C. for curing.

  Hereinafter, the object of the present invention will be described in more detail with reference to examples.

Example:

General Preparation of Polyurethane Composition The finely ground use material was thoroughly mixed in a pan mill and subsequently homogenized at a maximum of 130 ° C. in an extruder. After cooling, the extrudate was crushed and pulverized with a pin mill to a particle size of less than 100 microns.

  Examples 2 and 3 each contained 1.6% Araldit PT 912, 0.5% benzoin, 1.0% Resiflow PV 88, and 30.0% Kronos 2160.

  Example 1 and V1 were sprayed on a steel plate and cured at 160 ° C. for 30 minutes.

  Examples 2 and 3 were sprayed onto a steel plate and cured at 150 ° C. for 15 minutes.

result

  The MEK test (twice applied) reflected the solvent resistance of the coating (methyl ethyl ketone), while the pendulum hardness proved the hardness of the coating. Two characteristics depend on the degree of crosslinking of the coating. In Example 1 according to the invention, there is clearly sufficient crosslinking, whereas in Comparative Example 1 it is not.

  Examples 2 and 3 were both fully cured and had good paint industrial mechanical properties.

Claims (30)

A highly reactive uretdione group-containing polyurethane composition,
Basically A) Free NCO content of less than 5% by weight, based on aromatic, aliphatic, (cyclo) aliphatic or alicyclic polyisocyanates and hydroxy group-containing compounds And at least one uretdione-containing curing agent B) having a uretdione content of 1 to 35% by weight, optionally a hydroxy group-containing polymer C) having the OH number of 20 to 500 mg KOH / gram C [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ⁻ [wherein R ^{1 to} R ⁴ are alkyl groups, aryl groups, aralkyl groups, heteroaryl groups, alkoxy groups having 1 to 18 carbon atoms simultaneously or independently of each other. alkyl group (which may be the case-by-case linear or branched, or non-crosslinked, or other groups R ¹ to R ⁴ and bridged monocyclic, form a bicyclic or tricyclic, Well and the bridging atoms are In addition to carbon, which may also be heteroatoms, and in each case the radicals R ^{1 to} R ⁴ additionally contain one or more alcohol groups, amino groups, ester groups, keto groups, thio groups, A urethane group, a urea group, an allophanate group, a double bond, a triple bond, or a halogen atom, and R ⁵ represents Cl, Br, or I]. A highly reactive uretdione group-containing polyurethane composition which is contained so that the ratio of the catalyst belonging to) is 0.001 to 5% by mass of the total amount of components A) and B). D) contains at least one compound reactive to acid groups with a mass proportion of 0.1 to 10% by weight relative to the total preparation and / or E) relative to the total preparation 2. Polyurethane composition according to claim 1, characterized in that it contains at least one acid in monomer form or polymer form in a mass proportion of 0.1 to 10%.   3. A polyurethane composition according to claim 1 or 2, characterized in that it contains a solvent F) and / or auxiliaries and additives. Isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethylene diisocyanate (H ₁₂ MDI), 2-methylpentadiisocyanate (MPDI), 2,2,4-trimethyl-hexamethylene di Isocyanates / 2,4,4-trimethyl-hexamethylene diisocyanate (TMDI), norbornane-diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI), and tetramethylxylyl 4. A uretdione-containing curing agent A) based on lendiisocyanate (TMXDI), alone or in a mixture, is included. Polyurethane composition.   5. A polyurethane composition according to claim 4, characterized in that it contains an IPDI and / or HDI-based uretdione-containing curing agent.   Hydroxy-containing polyesters, polythioethers, polyethers, polycaprolactams, polyepoxides, polyester amides, polyurethanes, low molecular dialcohols, trialcohols and / or tetraalcohols, monoamines and / or monoalcohols, alone or in mixtures 6. Polyurethane composition according to any one of claims 1 to 5, characterized in that it contains a base uretdione-containing curing agent A).   7. Polyurethane composition according to claim 6, characterized in that it contains polyester and / or monomeric dialcohol.   8. Hydroxy-containing polymer B) comprising polyesters, polyethers, polyacrylates, polyurethanes and polycarbonates, alone or in a mixture, according to any one of claims 1 to 7 The polyurethane composition described.   The polyurethane composition according to claim 8, characterized in that it comprises a polyester having an OH number of 30 to 150 mg KOH / g and an average molecular weight of 500 to 6000 g / mol.   The catalyst C) is converted into tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide, iodide. Tetramethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, methyltributylammonium chloride, methyltripropylammonium chloride, methyltriethylammonium chloride, methyltriphenylammonium chloride, phenyltrimethylchloride Ammonium, benzyltrimethylammonium bromide, benzyltrimethyl bromide Tillammonium, benzyltripropylammonium bromide, benzyltributylammonium bromide, methyltributylammonium bromide, methyltripropylammonium bromide, methyltriethylammonium bromide, methyltriphenylammonium bromide, phenyltrimethylammonium bromide, iodide Benzyltrimethylammonium iodide, benzyltriethylammonium iodide, benzyltripropylammonium iodide, benzyltributylammonium iodide, methyltributylammonium iodide, methyltripropylammonium iodide, methyltriethylammonium iodide, methyltriphenylammonium iodide, and 10. The method according to claim 1, characterized in that it is selected from phenyltrimethylammonium iodide. Polyurethane composition according to Re preceding paragraph.   11. Polyurethane composition according to any one of claims 1 to 10, characterized in that tetrabutylammonium chloride is included as catalyst C).   12. The polyurethane according to claim 1, wherein the component D) comprises an epoxy compound, a carbodiimide, a hydroxyalkylamide, a basic salt, and / or 2-oxazoline. Composition.   Triglycidyl ether isocyanurate, Araldit PT910, Araldit PT912, EPIKOTE® 828, Versatic acid glycidyl ester, Vestagon EP HA 320, phenylenebisoxazoline, 2-methyl-2-oxazoline, 2-hydroxyethyl-2-oxazoline , 2-hydroxypropyl-2-oxazoline and / or 5-hydroxypentyl-2-oxazoline, sodium carbonate, potassium carbonate or calcium carbonate alone or in a mixture, The polyurethane composition according to 12.   Acid E) includes sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, phthalic acid, succinic acid, and also a copolyester or copolyamide having an acid value of at least 20, The polyurethane composition according to any one of claims 1 to 13. A method for producing a highly reactive uretdione group-containing polyurethane composition by homogenization,
Basically A) Free NCO content of less than 5% by weight, based on aromatic, aliphatic, (cyclo) aliphatic or alicyclic polyisocyanates and hydroxy group-containing compounds And at least one uretdione-containing curing agent B) having a uretdione content of 1 to 35% by weight, optionally a hydroxy group-containing polymer C) having the OH number of 20 to 500 mg KOH / gram C [NR ¹ R ² R ^{3 R 4] + [R 5]} - [ wherein, R ¹ to R ⁴ simultaneously or independently of one another, an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a heteroaryl group, an alkoxy An alkyl group (which may be linear or branched in each case and is not bridged or bridged with other groups R ^{1 to} R ⁴ to form a monocyclic, bicyclic or tricyclic ring Well and the bridging atoms are In addition to carbon, which may also be heteroatoms, and in each case the radicals R ^{1 to} R ⁴ additionally contain one or more alcohol groups, amino groups, ester groups, keto groups, thio groups, A urethane group, a urea group, an allophanate group, a double bond, a triple bond, or a halogen atom, and R ⁵ represents Cl, Br, or I]. And a ratio of the catalyst belonging to (1) is 0.001 to 5% by mass of the total amount of the components A) and B), and a method for producing a uretdione group-containing polyurethane composition having high reactivity by homogenization. In the polyurethane composition, the formula [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ⁻ , wherein R ^{1 to} R ⁴ are alkyls having 1 to 18 carbon atoms simultaneously or independently of each other. A group, an aryl group, an aralkyl group, a heteroaryl group, an alkoxyalkyl group (which may be linear or branched each time and is not bridged or is bridged with other groups R ^{1 to} R ⁴ to form a single group). Each of which may form a ring, a bicycle or a tricycle and the bridging atom may be a heteroatom in addition to carbon, and in each case the radicals R ^{1 to} R ⁴ additionally One or more alcohol groups, amino groups, ester groups, keto groups, thio groups, urethane groups, urea groups, allophanate groups, double bonds, triple bonds, or halogen atoms, and R ⁵ is Meaning Cl, Br, or I] Of the use of a catalyst Kutomo 1.   Tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, benzyl chloride Trimethyl ammonium, benzyl triethyl ammonium chloride, benzyl tripropyl ammonium chloride, benzyl tributyl ammonium chloride, methyl tributyl ammonium chloride, methyl tripropyl ammonium chloride, methyl triethyl ammonium chloride, methyl triphenyl ammonium chloride, phenyl trimethyl ammonium chloride, benzyl trimethyl bromide Ammonium, benzyltriethylammonium bromide , Benzyltripropylammonium bromide, benzyltributylammonium bromide, methyltributylammonium bromide, methyltripropylammonium bromide, methyltriethylammonium bromide, methyltriphenylammonium bromide, phenyltrimethylammonium bromide, benzyltrimethyl iodide Ammonium, benzyltriethylammonium iodide, benzyltripropylammonium iodide, benzyltributylammonium iodide, methyltributylammonium iodide, methyltripropylammonium iodide, methyltriethylammonium iodide, methyltriphenylammonium iodide, and iodide Use according to claim 16, characterized in that a compound selected from phenyltrimethylammonium is used. . The formula [NR ¹ for accelerating the curing of a uretdione-containing polyurethane composition according to any one of claims 1 to 14, which essentially comprises a uretdione-containing curing agent and optionally a hydroxy group-containing polymer. R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ⁻ [wherein R ^{1 to} R ⁴ are simultaneously or independently of each other, an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, hetero aryl group, an alkoxyalkyl group (may be the case-by-case linear or branched, or non-crosslinked, or other groups R ¹ to R ⁴ and bridged monocyclic, bicyclic, or tricyclic And the bridging atom may also be a heteroatom in addition to carbon), and in each case the radicals R ^{1 to} R ⁴ additionally comprise one or more alcohol groups, amino groups , Ester group, , Thio, urethane groups, urea groups, allophanate groups, double bonds, triple bonds, or a halogen atom may have, and R ⁵ denotes a Cl, Br or I,] catalyst.   Tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, benzyl chloride Trimethyl ammonium, benzyl triethyl ammonium chloride, benzyl tripropyl ammonium chloride, benzyl tributyl ammonium chloride, methyl tributyl ammonium chloride, methyl tripropyl ammonium chloride, methyl triethyl ammonium chloride, methyl triphenyl ammonium chloride, phenyl trimethyl ammonium chloride, benzyl trimethyl bromide Ammonium, benzyltriethylammonium bromide , Benzyltripropylammonium bromide, benzyltributylammonium bromide, methyltributylammonium bromide, methyltripropylammonium bromide, methyltriethylammonium bromide, methyltriphenylammonium bromide, phenyltrimethylammonium bromide, benzyltrimethyl iodide Ammonium, benzyltriethylammonium iodide, benzyltripropylammonium iodide, benzyltributylammonium iodide, methyltributylammonium iodide, methyltripropylammonium iodide, methyltriethylammonium iodide, methyltriphenylammonium iodide, and iodide 19. A catalyst according to claim 18 selected from phenyltrimethylammonium.   20. A catalyst according to claim 19 consisting of tetrabutylammonium chloride. Use of a polyurethane composition for producing a liquid and powder coating composition and an adhesive composition comprising:
The polyurethane composition essentially comprises a free NCO content based on A) an aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanate and a hydroxy group-containing compound. less than 5 wt%, and uretdione content by at least one uretdione-containing curing agent B) if they have 1 to 35% by weight, hydroxyl-containing polymers C) type having an OH number of 20~500mgKOH [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ⁻ [wherein R ^{1 to} R ⁴ are simultaneously or independently of each other, an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a heteroaryl group, An alkoxyalkyl group which may be linear or branched each time and is not bridged or bridged with other groups R ^{1 to} R ⁴ to form a monocyclic, bicyclic or tricyclic ring OK One bridging atom may also be a heteroatom in addition to carbon), and in each case the radicals R ^{1 to} R ⁴ additionally comprise one or more alcohol groups, amino groups, ester groups, keto groups , A thio group, a urethane group, a urea group, an allophanate group, a double bond, a triple bond, or a halogen atom, and R ⁵ represents Cl, Br, or I]. Use of a polyurethane composition comprising a catalyst, wherein the proportion of said catalyst belonging to C) is 0.001 to 5% by weight of the total amount of components A) and B).   Use according to claim 21, characterized in that it contains the starting compound according to any one of claims 2 to 14.   23. For producing liquid or powder coating compositions and adhesive compositions for metals, plastics, wood, glass, leather or other heat resistant substrates. Use as described in. A metal coating composition comprising a polyurethane composition comprising:
The polyurethane composition essentially comprises a free NCO content based on A) an aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanate and a hydroxy group-containing compound. less than 5 wt%, and uretdione content by at least one uretdione-containing curing agent B) if they have 1 to 35% by weight, hydroxyl-containing polymers C) type having an OH number of 20~500mgKOH [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ⁻ [wherein R ^{1 to} R ⁴ are simultaneously or independently of each other, an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a heteroaryl group, An alkoxyalkyl group which may be linear or branched each time and is not bridged or bridged with other groups R ^{1 to} R ⁴ to form a monocyclic, bicyclic or tricyclic ring OK One bridging atom may also be a heteroatom in addition to carbon), and in each case the radicals R ^{1 to} R ⁴ additionally comprise one or more alcohol groups, amino groups, ester groups, keto groups , A thio group, a urethane group, a urea group, an allophanate group, a double bond, a triple bond, or a halogen atom, and R ⁵ represents Cl, Br, or I]. A metal coating composition comprising a catalyst, wherein the proportion of the catalyst belonging to C) is 0.001 to 5% by mass of the total amount of components A) and B). A wood coating composition comprising a polyurethane paint composition comprising:
The polyurethane coating composition basically comprises a free NCO based on A) an aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanate and a hydroxy group-containing compound. min less than 5 wt%, and at least one uretdione-containing curing agent B) If uretdione content 1 to 35 wt%, hydroxyl-containing polymers C) type having an OH number of 20~500mgKOH [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ⁻ [wherein R ^{1 to} R ⁴ are alkyl groups, aryl groups, aralkyl groups, heteroaryl groups having 1 to 18 carbon atoms simultaneously or independently of each other. An alkoxyalkyl group (which may be linear or branched each time, and is not bridged or bridged with other groups R ^{1 to} R ⁴ to form a monocyclic, bicyclic or tricyclic ring. Well And the bridging atom may also be a heteroatom in addition to carbon), and in each case, the radicals R ^{1 to} R ⁴ additionally comprise one or more alcohol groups, amino groups, ester groups, keto Group, thio group, urethane group, urea group, allophanate group, double bond, triple bond, or halogen atom, and R ⁵ represents Cl, Br, or I]. A wood coating composition comprising: a catalyst in which the proportion of the catalyst belonging to C) is 0.001 to 5% by mass of the total amount of components A) and B). A leather coating composition comprising a polyurethane coating composition,
The polyurethane coating composition basically comprises a free NCO based on A) an aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanate and a hydroxy group-containing compound. min less than 5 wt%, and at least one uretdione-containing curing agent B) If uretdione content 1 to 35 wt%, hydroxyl-containing polymers C) type having an OH number of 20~500mgKOH [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ⁻ [wherein R ^{1 to} R ⁴ are alkyl groups, aryl groups, aralkyl groups, heteroaryl groups having 1 to 18 carbon atoms simultaneously or independently of each other. An alkoxyalkyl group (which may be linear or branched each time, and is not bridged or bridged with other groups R ^{1 to} R ⁴ to form a monocyclic, bicyclic or tricyclic ring. Well And the bridging atom may also be a heteroatom in addition to carbon), and in each case, the radicals R ^{1 to} R ⁴ additionally comprise one or more alcohol groups, amino groups, ester groups, keto , thio, urethane groups, urea groups, allophanate groups, double bonds, may have a triple bond, or a halogen atom, and R ⁵ denotes a Cl, Br or I,], at least 1 A leather coating composition in which the proportion of the catalyst belonging to C) is 0.001 to 5 mass% of the total amount of components A) and B). A plastic coating composition comprising a polyurethane composition,
The polyurethane composition essentially comprises a free NCO content based on A) an aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic polyisocyanate and a hydroxy group-containing compound. less than 5 wt%, and uretdione content by at least one uretdione-containing curing agent B) if they have 1 to 35% by weight, hydroxyl-containing polymers C) type having an OH number of 20~500mgKOH [NR ¹ R ² R ³ R ⁴ ] ⁺ [R ⁵ ] ⁻ [wherein R ^{1 to} R ⁴ are simultaneously or independently of each other, an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, a heteroaryl group, An alkoxyalkyl group which may be linear or branched each time and is not bridged or bridged with other groups R ^{1 to} R ⁴ to form a monocyclic, bicyclic or tricyclic ring OK One bridging atom may also be a heteroatom in addition to carbon), and in each case the radicals R ^{1 to} R ⁴ additionally comprise one or more alcohol groups, amino groups, ester groups, keto groups , thio, urethane groups, urea groups, allophanate groups, double bonds, triple bonds, or a halogen atom may have, and R ⁵ is Cl, Br or means I] of at least one A plastic coating composition comprising a catalyst, wherein the proportion of the catalyst belonging to C) is 0.001 to 5% by mass of the total amount of components A) and B).   25. A metallization according to claim 24 for automobile bodies, motorcycles and bicycles, building components, and household items.   Coating composition according to any one of claims 24 to 28, characterized in that it contains at least one of components D) to G).   30. A coating composition according to any one of claims 24 to 29, characterized in that the coating composition comprises a compound according to any one of claims 2 to 14.