DE10017651A1 - Di- and polyisocyanates blocked with pyrazoles disubstituted in the 3,4-position and their use - Google Patents

Abstract

The invention relates di- and polyisocyanates blocked by 3,4-disubstituted pyrazoles, and to the use thereof for producing coating materials, adhesives and sealing materials that can be cured thermally or by exposure to heat and actinic radiation.

Description

The present invention relates to new pyrazoles disubstituted in the 3,4-position blocked di- and polyisocyanates. The present invention also relates to Use of the new di- and blocked with pyrazoles disubstituted in the 3,4-position Polyisocyanates for the production of thermal or thermal and with actinic Radiation-curable coating materials, adhesives and sealants.

Di- and polyisocyanates blocked with pyrazoles in the 3-position are monosubstituted, disubstituted in the 3,5 position or trisubstituted in the 3,4,5 position, are known from European patent EP 0 159 117 B1. Expressis become verbis 3-methyl, 3,5-dimethyl, 3-methyl-5-phenyl, 4-benzyl-3,5-dimethyl, 4-nitro-3,5- dimethyl- and 4-bromo-3,5-dimethyl-pyrazole and 3,5-dimethylpyrazole-4-carboxylate or - called carboxanilide. The blocked di- and polyisocyanates are used in the manufacture of coating materials, in particular electro-dipping paints, used.

From the German patent application DE 44 41 418 A1 is a process for the production of 3,5-Dimethylpyrazol-blocked Poylisocyanten known in which the Production of 3,5-dimethylpyrazole resulting anhydrous reaction mixture directly for the blocking is used.

The known di- and blocked with the pyrazole derivatives described above Polyisocyanates have the advantage that they operate at comparatively low temperatures deblock and react with isocyanate-reactive functional groups, so that corresponding coating materials, adhesives and sealants at temperatures Cross-link thermally below 160 ° C.

Because of the advantage of pyrazole blocking of di- and polyisocyanates, it is but highly desirable, as many differently substituted ones as possible Pyrazole derivatives available to have the property profile of the blocked Polyisocanate and the coating materials, adhesives and Sealing compounds and ultimately the corresponding coatings, adhesive layers and Varying the seals widely and adapting them to the requirements of the individual case.  

The object of the present invention is to create new, blocked with substituted pyrazoles To provide di- and polyisocyanates that have the advantageous property profile of the previous known blocked di- and polyisocyanates, if not this surpass and which the production of new advantageous coating materials, adhesives and Allow sealing compounds as well as new coatings, adhesive layers and seals.

Accordingly, the new pyrazoles blocked with 3,4-disubstituted were blocked Found di- and polyisocyanates, which are hereinafter referred to as "blocked di- and polyisocyanates ".

In addition, the new coating materials, adhesives and sealants found which contain the blocked di- and polyisocyanates according to the invention and which hereinafter referred to as "coating materials, adhesives and Sealants "are referred to.

Furthermore, the new coatings, adhesive layers and seals were found, with the help of the coating materials, adhesives and Sealants are obtained and the following as "inventive Coatings, adhesive layers and seals "are referred to.

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

The pyrazoles disubstituted in the 3,4-position to be used according to the invention are in the following, for brevity, as "pyrazoles to be used according to the invention" designated.

The pyrazoles to be used according to the invention are disubstituted. Here, a such pyrazole carry two identical or two different substituents. Which variant is chosen in the individual case depends on the one hand on the Accessibility of the starting products, the yield in the production and that for the Application required property profile.  

Basically, all atoms come apart from hydrogen atoms, electron-withdrawing or electron-donating groups and organic residues, inclusive elemental organic residues, if they are not themselves under the conditions of Production of the di- and polyisocyanates according to the invention and / or the thermal ones React curing with isocyanates and thus the desired blocking reaction and / or disrupt or completely prevent thermal networking. Preferably increase the Substituents not the deblocking temperature.

Examples of suitable atoms are halogen atoms, in particular fluorine, chlorine and bromine.

Examples of electron-withdrawing or electron-donating groups are nitro or Nitrile groups; Carboxylic acid, sulfonic acid or phosphonic acid groups; Carboxylate, Sulfonate or phosphonate groups; Carboxylic acid, sulfonic acid or phosphonic acid esters, the substituted and unsubstituted alkyl, cycloalkyl, Alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or Contain arylcycloalkyl radicals; primary, secondary, or tertiary amide groups or quaternary ammonium groups which are substituted and described below unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, Contain cycloalkylaryl, arylalkyl or arylcycloalkyl radicals; as well as urea groups.

Examples of suitable organic radicals are substituted and unsubstituted alkyl, Cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, Arylalkyl or arylcycloalkyl radicals.

Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.

Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.

Examples of suitable alkylcycloalkyl radicals are methylene cyclohexane and ethylene cyclohexane or propane-1,3-diyl-cyclohexane.

Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl, ethyl, propyl or -Butylcyclohex-1-yl.  

Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl, preferably Phenyl and naphthyl and especially phenyl.

Examples of suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diyl benzene.

Examples of suitable cycloalkylaryl radicals are 2-, 3-, or 4-phenylcyclohex-1-yl.

Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, -propyl- or - Butylphen-1-yl.

Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl.

The aforementioned alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, Alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals can be with the above mentioned atoms and electron-donating or electron-withdrawing groups, in particular with chlorine and / or fluorine atoms, and / or with the following described elemental organic radicals can be partially or completely substituted.

Examples of suitable elemental organic radicals are aryloxy, alkyloxy and Cycloalkyloxy radicals, in particular phenoxy, naphthoxy, methoxy, ethoxy, propoxy, Butyloxy or cyclohexyloxy radicals; Polyether residues such as di, TH, tetra or Pentaethylene or propylene glycol residues; Arylthio, alkylthio and cycloalkylthio radicals, especially phenylthio, naphthylthio, methylthio, ethylthio, propylthio, butylthio or cyclohexylthio residues; Silyl radicals that are substituted and described above unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, Cycloalkylaryl, arylalkyl or arylcycloalkyl radicals and / or aryloxy, alkyloxy and Contain cycloalkyloxy radicals; such as trimethyl, tripropyl, triethyl, dimethylethyl, Diethylmethyl, trimethoxy, dimethoxyethyl, triethoxy, tripropoxy or Propoxydimethylsilyl residues; or tertiary sulfonium groups which meet the above Substituted and unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals contain.  

Preferred substituents are unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals

Particularly preferred substituents are unsubstituted alkyl radicals, especially those lower alkyl radicals such as methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl. Of these, the methyl residues in turn offer the most advantages and are therefore used very particularly preferably.

Accordingly, it is particularly preferred according to the invention used pyrazole around 3,4-dimethylpyrazole.

The pyrazoles to be used according to the invention, in particular 3,4-dimethylpyrazole, are known compounds and can by the usual and known methods of Production of substituted pyrazoles, for example from suitable 1,3- Dicarbonyl compounds and hydrazine can be synthesized.

The diisocyanates and polyisocyanates to be blocked are practically all customary and known aromatic, aliphatic and cycloaliphatic di- and polyisocyanates, in Consideration. In particular, the diisocyanates and polyisocyanates come into consideration referred to in the art as paint polyisocyanates.

Examples of suitable aromatic diisocyanates to be blocked are tolylene diisocyanate, Xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyanate or Diphenylmethane diisocyanate.

Examples of suitable acyclic aliphatic diisocyanates to be blocked are tri methylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene diisocyanate, ethylethylene diisocyanate, trimethylhexane diisocyanate, Heptamethylene diisocyanate, 4-isocyanatomethyl-1,8-octamethylene diisocyanate, or Diisocyanates derived from dimer fatty acids, such as those under the trade name DDI 1410 sold by the Henkel company and in the patents WO 97/49745 and WO 97/49747 be described, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -1- pentyl-cyclohexane, or 1,2-, 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,4-  or 1,3-bis (2-isocyanatoeth-1-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-1-yl) cyclohexane or 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-1-yl) cyclohexane.

Examples of suitable cycloaliphatic diisocyanates are isophorone diisocyanate (= 5- Isocyanato-1-isocyanatomethyl-1,3,3-trimethyl-cyclohexane), 5-isocyanato-1- (2- isocyanatoeth-1-yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) - 1,3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) -1,3,3-trimethyl- cyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3- isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) cyclohexane, 1,2- Diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2-diisocyanatocyclopentane, 1,3- Diisocyanatocyclopentane, 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4- Diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate or dicyclohexylmethane 4,4'-diisocyanate, especially isophorone diisocyanate.

Examples of suitable polyisocyanates to be blocked are those containing isocyanate groups Polyurethane prepolymers obtained by reacting polyols with an excess of aromatic, aliphatic and cycloaliphatic, described above, preferably aliphatic and cycloaliphatic, diisocyanates can and are preferably low viscosity. Within the scope of the present invention the term "cycloaliphatic diisocyanate" denotes a diisocyanate in which at least one isocyanate group is attached to a cycloaliphatic radical.

Isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, Polyisocyanates containing urea, carbodiimide and / or uretdione groups are used be, which in a conventional and known manner from those described above Diisocyanates are produced. Examples of suitable manufacturing processes and Polyisocyanates are known, for example, from the patents and patent applications CA 2,163,591 A1, US 4,419,513 A1, US 4,454,317 A1, EP 0 646 608 A1, US 4,801,675 A1, EP 0 183 976 A1, DE 40 15 155 A1, EP 0 303 150 A1, EP 0 496 208 A1, EP 0 524 500 A1, EP 0 566 037 A1, US 5,258,482 A1, US 5,290,902 A1, EP 0 649 806 A1, DE 42 29 183 A1 or EP 0 531 820 A1.

In addition, low molecular weight, oligomeric and polymeric compounds also come in Consider that contain isocyanate groups and groups that are exposed to actinic radiation,  in particular UV light or electron radiation can be activated. Examples of more suitable Compounds of this type are those in European patent application EP 0 928 800 A1 described urethane (meth) acrylates, the (meth) acrylate groups and free Have isocyanate groups.

In the context of the present invention, here and below, among oligomers Resins understood that contain at least 2 to 15 monomer units in their molecule. In the context of the present invention, polymers are understood to be resins which contain at least 10 monomer units in their molecule. Complementary to these Terms in Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Oligomers", page 425.

According to the invention, the di- and polyisocyanates described above are partial or completely blocked with the pyrazoles to be used according to the invention.

The partial blocking with the pyrazoles to be used according to the invention becomes applied if the di- and polyisocyanates with other suitable Blocking agents should be blocked in order to achieve special technical effects Realizing deblocking and networking.

Examples of suitable customary and known blocking agents are those known from US Pat. No. 4,444,954:

• a) phenols such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, t- Butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4- hydroxytoluene;
• b) lactams, such as ε-caprolactam, δ-valerolactam, γ-butyrolactam or β- Propiolactam;
• c) active methylenic compounds, such as diethyl malonate, dimethyl malonate, Ethyl or methyl acetoacetate or acetylacetone;  
• d) alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Propylene glycol monomethyl ether; Methoxymethanol, glycolic acid, Glycolic acid esters, lactic acid, lactic acid esters, methylol urea, Methylolmelamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3- Dichloro-2-propanol, 1,4-cyclohexyldimethanol or acetocyanhydrin;
• e) mercaptans such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t- Dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or Ethylthiophenol;
• f) acid amides such as acetoanilide, acetoanisidinamide, acrylamide, methacrylamide, Acetic acid amide, stearic acid amide or benzamide;
• g) imides such as succinimide, phthalimide or maleimide;
• h) amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, Carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;
• i) imidazoles such as imidazole or 2-ethylimidazole;
• j) ureas such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenylurea;
• k) carbamates such as phenyl N-phenylcarbamate or 2-oxazolidone;
• l) imines such as ethyleneimine;
• m) oximes such as acetone oxime, formal doxime, acetaldoxime, acetoxime, Methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oximes;  
• n) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite;
• o) hydroxamic acid esters such as benzyl methacrylohydroxamate (BMH) or Allyl methacrylohydroxamate; or
• p) substituted pyrazoles such as 3,5-dimethylpyrazole, imidazoles or triazoles.

However, these customary and known blocking agents are only used in subordinate ones Amounts applied. This means that for use in the invention Coating materials, adhesives and sealants essential application properties such as the baking temperature in the main of the pyrazoles to be used according to the invention is determined.

In addition, the partial blocking with those to be used according to the invention Pyrazoles applied when the partially blocked di- and polyisocyanates in question Binder that is curable thermally or thermally and with actinic radiation should be. This is expediently carried out via the reaction of in the binders existing isocyanate-reactive functional groups, such as primary amino groups, Hydroxyl groups and / or thiol groups, especially hydroxyl groups, with the free Isocyananate groups. By installing the binders get self-crosslinking Characteristics.

In the context of the present invention, the term “self-crosslinking” denotes the Property of a binder (for the term see Römpp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders", pages 73 and 74) engage in cross-linking reactions with themselves. The prerequisite for this is that Both types of complementary reactive functional already in the binders Groups, here the isocyanate groups blocked in the manner according to the invention and the Isocyanate-reactive groups are included, which are necessary for crosslinking.

Such coating materials, adhesives and Sealants referred to, wherein the one type of complementary reactive functional groups, here the isocyanate-reactive, in the binder, and the other type  in a hardener or crosslinking agent, here the blocked according to the invention Polyisocyanate. In addition, here on the Römpp Lexicon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 to 276, especially page 275, below.

In addition, the partial blocking with those to be used according to the invention Pyrazoles applied when the partially blocked di- and polyisocyanates in question can be used as crosslinking agents in two- or multi-component systems should. In the case of coating compositions, adhesives and sealants according to the invention this type of crosslinking agents are due to their high reactivity up to Application stored separately from the other ingredients and only shortly before Application mixed with these.

The di- and polyisocyanates are preferably added completely with those according to the invention using pyrazoles blocked.

From a methodological point of view, the blocking according to the invention has no special features, but is done by stoichiometric implementation of the di and to be blocked Polyisocyanates with the pyrazoles to be used according to the invention in the melt or in at least one organic which is essentially inert to isocyanates Solvent preferably under a protective gas atmosphere and in the presence of a suitable catalyst, as described, for example, in European Patent EP 0 159 117 B1 or the German patent application DE 44 41 418 A1 for 3,5-dimethylpyrazole is described.

Due to their special advantageous application properties the blocked di- and polyisocyanates according to the invention for all purposes into consideration, in which blocked di- and polyisocyanates are usually used. They are preferably used as crosslinking agents in the thermal or coating materials, adhesives and curable thermally with actinic radiation Sealants used. They are particularly preferred in the inventive Coating materials used.  

The statements made below for the coating materials of the invention apply to the adhesives and sealants according to the invention analogously.

The content of the coating materials of the invention in the di- and polyisocyanates can vary widely. Since the di- and polyisocyanates function the conventional blocked di- and polyisocyanates the crosslinking agent for thermally and thermally curable with actinic radiation Can completely replace coating materials, they can in the usual, from Known amounts of prior art are used. However, they can their advantageous application properties in many cases in less Amounts are used.

The coating materials of the invention contain customary and known binders such as those in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, under the keyword "binder", pages 73 and 74, to be discribed. Well-suited binders are statistical, alternating and / or linear and / or branched and / or comb-like structures (Co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or polycondensation resins as used in Römpp Lexikon lacquers and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457: "Polyaddition" and "Polyaddition Resins (Polyadducts)", pages 463 and 464: "Polycondensates", "Polycondensation" and "polycondensation resins" are described. The binders contain the isocyanate-reactive functional groups described above. About that In addition, they can contain other reactive functional groups that correspond to the complementary reactive functional groups of the optionally present usual and known crosslinking agents thermally initiated crosslinking reactions can enter into. They can also contain groups that are exposed to actinic radiation can be activated, such as acrylate groups.

Furthermore, you can still use conventional and known crosslinking agents in subordinate Contain amounts, which means that the blocked di- and Polyisocyanates still have the curing properties of the coating materials in the The main thing is to determine.  

Examples of suitable crosslinking agents are aminoplast resins, as described, for example, in Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29, "Aminoharze", the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff., The book "Paints, Coatings and Solvents", second completely revised edition, edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A1 or EP-B-0 245 700 A1 as well as in the article by B. Singh and co-workers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry ", in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207. Compounds or resins containing carboxyl groups, as described, for example, in US Pat Patent specification DE 196 52 813 A1 are described, containing epoxy groups Compounds or resins as described, for example, in the patents EP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, US 4,091,048 A1 or US 3,781,379 A1 Blocked polyisocyanates, such as those described in the Patents US 4,444,954 A1, DE 196 17 086 A1, DE 196 31 269 A1, EP 0 004 571 A1 or EP 0 582 051 A1, and / or tris (alkoxycarbonylamino) - triazines as described in the patents US 4,939,213 A1, US 5,084,541 A1, US 5,288,865 A1 or EP 0 604 922 A1.

Furthermore, the coating compositions of the invention can have at least one Additive included.

Examples of suitable additives are organic and inorganic color and / or effect pigments, organic and inorganic fillers, thermally curable Reactive diluents or reactive diluents curable with actinic radiation (cf.Römpp Lexicon Lacke und Druckfarben, Stuttgart, New York, 1998, pages 491), low boiling organic solvents and / or high boiling organic solvents ("long Solvents "), binders curable with actinic radiation, UV absorbers, Light stabilizers, radical scavengers, thermolabile free radical initiators, photoinitiators, Crosslinking catalysts, deaerating agents, silane additives, Polymerization inhibitors, defoamers, emulsifiers, wetting agents, adhesion promoters, Leveling agents, film-forming aids, rheology-controlling additives or Flame retardant. Further examples of suitable paint additives are given in the textbook  "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, described.

The coating materials of the invention can be one-component systems.

In the context of the present invention is a one-component (1K) system coating material that cures thermally or thermally and with actinic radiation understand, in which the binder and the crosslinking agent side by side, d. H. in a Component. The prerequisite for this is that the two components only at higher temperatures and / or when irradiated with actinic radiation network.

As already explained above, the coating material can also be a Be a two-component (2K) or multi-component system.

Furthermore, the coating materials of the invention can be essentially free of Water and / or organic solvents and powder or liquid (100% - Systems). In the context of the present invention, "essentially free" means that the content of water and / or organic solvents below 5.0, preferably below 3.0, preferably below 2.0, particularly preferably below 1.0, very particularly preferably below 0.5% by weight and in particular lies below the gas chromatographic detection limit. In You can use this form, for example, as a powder filler, powder basecoat, powder clearcoat or liquid clear coats can be used.

However, it can also be a water-based coating material, in particular an electrocoat, a water filler, a waterborne basecoat, a Water clearcoat or an aqueous powder coating dispersion (powder slurry clearcoat or Powder slurry basecoat).

Last but not least, it can also be a conventional, i.e. H. around one on organic Solvent-based coating material, for example a conventional one Filler, basecoat or clearcoat.  

The production of the coating materials according to the invention has no special features on, but is done in a conventional and known manner by mixing the above described components in suitable mixing units such as stirred kettles, dissolvers, Agitator mills, static mixers, gear rim dispersers or extruders according to the processes suitable for the production of the respective coating materials.

The application of the coating materials according to the invention can be carried out by all customary methods Application methods, such as. B. electrocoating, spraying, knife coating, painting, Pouring, dipping, watering, trickling or rolling. This can be too resting substrate as such, the application device or system is moved. However, the substrate to be coated, in particular a coil, are moved, the application system being at rest relative to the substrate or in a more suitable manner Way is moved.

The thermal curing of the applied coating materials according to the invention has likewise no methodological particularities, but takes place in the usual and known manner by heating with infrared or near infrared radiation or with Hot air blowers, if necessary supported by irradiation with actinic Radiation if the coating materials according to the invention have corresponding constituents contain.

This is where the particular advantage of the coating materials according to the invention occurs open to the day, namely that the thermal crosslinking already at temperatures below 160, preferably 150 and in particular 140 ° C completely, what the coating of comparatively heat sensitive substrates.

The basecoats and / or clearcoats of the invention are excellent for Production of color and / or effect multi-layer coatings after wet-in suitable wet method, in which a basecoat is applied, dried and coated with a Clear coat is overlaid, after which basecoat layer after clear coat be hardened together. As is known, this method is used by Automotive paintwork and refinish applied with advantage.  

In addition, however, the coating materials of the invention come because of their particularly advantageous properties also for the coating of buildings in the Indoor and outdoor use, for painting furniture, windows or doors and the industrial painting, including coil coating, container coating and impregnation or coating of electrical components. As part of the industrial Paintings are suitable for painting practically all parts for private or industrial use such as radiators, household appliances, small metal parts such as Screws and nuts, hubcaps, rims, packaging or electrical components such as motor windings or transformer windings.

The adhesives and sealants according to the invention are ideal for Manufacture of adhesive layers and seals, even under climatically extreme and / or rapidly changing climatic conditions in the long term of particularly high Adhesion and sealing ability are.

Accordingly, they point to the technological areas listed above Usually used primed or unprimed substrates with at least a coating according to the invention coated with at least one adhesive layer according to the invention glued and / or with at least one Seal according to the invention are sealed in a particularly advantageous application-technical property profile a particularly long service life on what makes them particularly attractive economically.

Claims (10)

1. Di- and polyisocyanates blocked with pyrazoles disubstituted in the 3,4-position. 2. Blocked di- and polyisocyanates according to claim 1, characterized in that the substituents are the same or different from one another. 3. Blocked di- and polyisocyanates according to claim 1 or 2, characterized characterized in that atoms, electron-withdrawing or electron-donating groups and / or organic residues, inclusive elemental organic residues that under the conditions of manufacture of the di- and Polyisocyante and / or thermal curing itself with isocyanates react, be used. 4. Blocked di- and polyisocyanates according to claim 3, characterized in that halogen atoms as atoms; as electron-withdrawing or electron-withdrawing Groups nitro or nitrile groups, carboxylic acid, sulfonic acid or Phosphonic acid groups, carboxylate, sulfonate or phosphonate groups; Carboxylic acid, sulfonic acid or phosphonic acid esters, the substituted and unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, Contain alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals; primary secondary, or tertiary amide groups or quaternary ammonium groups, the substituted and unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or Contain arylcycloalkyl residues, or urea groups; as organic residues substituted and unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or Arylcycloalkyl residues and as element organic residues aryloxy, alkyloxy or Cycloalkyloxy, arylthio, alkylthio or cycloalkylthio, silyl, the the substituted and unsubstituted alkyl,  Cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, Arylalkyl or arylcycloalkyl radicals and / or aryloxy, alkyloxy and Contain cycloalkyloxy radicals; or tertiary sulfonium groups which meet the above Substituted and unsubstituted alkyl, cycloalkyl, Alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or contain arylcycloalkyl radicals; be used. 5. Blocked di- and polyisocyanates according to claim 4, characterized in that unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, Alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals can be used. 6. Blocked di- and polyisocyanates according to claim 5, characterized in that unsubstituted alkyl groups, especially methyl groups, can be used. 7. Blocked di- and polyisocyanates according to claim 6, characterized in that the blocking agent is 3,4-dimethylpyrazole. 8. Blocked di- and polyisocyanates according to one of claims 1 to 7, characterized characterized in that aliphatic, cycloaliphatic or aromatic diisocyanates and polyisocyanates based on these diisocyanates can be used. 9. Use of the blocked di- and polyisocyanates according to one of claims 1 to 8 for the production of thermal or thermal and with actinic Radiation-curable coating materials, adhesives and sealants. 10. Thermally or thermally curable with actinic radiation Paints, adhesives and sealants containing at least one blocked di- and polyisocyanate according to one of claims 1 to 8.