EP1922348A1

EP1922348A1 - Curable compositions free from molybdenum and tungsten compounds, comprising caesium compounds and based on blocked polyisocyanates, processes for producing them, and their use

Info

Publication number: EP1922348A1
Application number: EP06791710A
Authority: EP
Inventors: Marco Deyda; Hubert Baumgart; Bianca Giesen; Michael Tecklenborg
Original assignee: BASF Coatings GmbH
Current assignee: BASF Coatings GmbH
Priority date: 2005-08-31
Filing date: 2006-08-29
Publication date: 2008-05-21
Also published as: DE102005041246A8; JP2009506178A; DE102005041246A1; US20080319111A1; WO2007025716A1

Abstract

Curable mixtures free from molybdenum compounds and tungsten compounds and comprising (A) at least one constituent containing blocked isocyanate groups (a1) and isocyanate-reactive functional groups (a2), and (B) at least one caesium compound, processes for producing them, and their use.

Description

Free, molybdenum and tungsten compounds containing cesium compounds, curable mixtures based on blocked polyisocyanates, processes for their preparation and their use

description

Field of the invention

The present invention relates to new, free from molybdenum and tungsten compounds, cesium compounds containing curable mixtures based on blocked

Polyisocyanates. Moreover, the present invention relates to a new method for

Preparation of molybdenum and tungsten compounds of free, cesium-containing, curable mixtures based on blocked polyisocyanates. Of

Furthermore, the present invention relates to the use of the new, free of molybdenum and tungsten compounds, cesium compounds containing curable

Mixtures based on blocked polyisocyanates and the mixtures of the type mentioned produced by the novel process.

State of the art

German patent application DE 103 08 104 A1 discloses one-component baking systems based on blocked polyisocyanates which contain organic and / or inorganic compounds of molybdenum and / or tungsten of an oxidation state of at least +4, in particular +6. It is given a large number of suitable compounds, u. a. also lithium, sodium, potassium, rubidium and cesium molybdate. In the examples, only lithium and sodium and potassium molybdate are used. Thus, the German patent application for the expert no suggestions and hints that cesium compounds as such could have particular advantages in Einkomponenten- burn-in systems based on blocked polyisocyanates. On the contrary, the examples of the German patent application substantiate that it is precisely not the use of cesium that matters but the use of the molybdate anion - and this independently of the counterion.

The compounds of molybdenum and / or tungsten are intended to allow a significant lowering of the baking temperatures. However, molybdenum and tungsten are known to form, under a variety of conditions, intense colored compounds such as molybdenum blue, molybdophosphoric acid (yellow), tungsten blue or tungsten bronzes, some of which are of great importance to analytical chemistry, such as molybdenum blue as a sensitive molybdenum or molybdophosphoric acid sensitive evidence of phosphate. In the known use of compounds of molybdenum and / or tungsten, therefore, there is always the danger that the clearcoats, which have been prepared from the known one-component baking systems based on blocked polyisocyanates, intensively discolour over time, so that they are suitable for a use in automotive OEM finishes, where it just depends on the fact that they provide years of consistently good overall visual appearance (Appearance) are basically not suitable.

From the German patent application DE 101 61 156 A1 a process for the preparation of aqueous polyurethane dispersions is known in which cesium salts as catalysts of

Polyaddition of unblocked polyisocyanates can be used. The resulting aqueous polyurethane dispersions can be used for coating or bonding of

Objects are used in metals, plastics, paper, textile, leather or wood. For this purpose, hydrophobic auxiliary agents, such as polymer-based adhesion promoters, or commercially available auxiliaries and additives, such as propellants, defoamers,

Emulsifiers, thickeners and thixotropic agents and colorants, such as dyes and pigments, are added. It can not be inferred from the patent application, whether the catalyst residues, which may still be in the aqueous

Polyurethane dispersions are present, in addition to their original catalytic effect in addition, the performance properties of the coating materials and adhesives and the coatings produced therefrom influence adhesive layers or not.

German Patent Application DE 103 20 267 A1 discloses low-temperature curable polyurethane powder coating compositions containing uretdione groups. They contain metal hydroxides and alcoholates, u. a. also cesium hydroxide, which greatly accelerate the cleavage of uretdione groups, so that the curing temperatures can be considerably reduced.

European patent EP 0 447 074 B1 discloses that isocyanate trimerization and urethane formation can be accelerated by cesium fluoride as catalyst so that milder reaction conditions are possible. task

The present invention has for its object to find new, free of molybdenum and tungsten compounds, cesium compounds, curable mixtures based on blocked polyisocyanates (hereinafter called "new mixtures" called) to find that should no longer have the disadvantages of the prior art ,

In particular, the new mixtures should contain no other toxicologically and ecologically questionable metal compounds, such as organic tin compounds, in particular dibutyltin dilaurate, instead of molybdenum and tungsten compounds.

The new mixtures should be able to be cured at comparatively low temperatures. They should very well wet the surfaces of different substrates, d. h., they should have a particularly low wetting limit.

The new mixtures are to provide new hardened materials that show no signs of yellowing when overburning and long-term exposure in the atmosphere, even in high layer thicknesses no paint defects, such as cookers, specks, runners, craters or micro-disturbances (starry sky), have and a very good Course, a high gloss and a low haze, high chemical stability, high weathering stability and high hardness, high flexibility and high scratch resistance. Overall, they should easily reach the so-called automobile quality, as defined in European Patent EP 0 352 298 B1, page 15, lines 42, to page 17, line 40.

solution

Accordingly, the novel, molybdenum and tungsten free, curable mixtures containing

(A) a complementary reactive system containing blocked isocyanate groups (a1) and isocyanate-reactive functional groups (a2), and

(B) at least one cesium compound,

found, which are hereinafter referred to as "mixtures according to the invention". In addition, the novel process for the preparation of the mixtures according to the invention was found, in which at least the components (A) and (B) are mixed together and the resulting mixture is homogenized and hereinafter referred to as "inventive method".

Furthermore, the novel use of the mixtures according to the invention and of the mixtures prepared by the process according to the invention was found as coating materials, adhesives, sealants and starting materials for the production of moldings and films, which is referred to below as "use according to the invention".

The advantages of the invention

In view of the prior art, it was surprising and unforeseeable for the skilled worker that the object on which the present invention was based could be achieved with the aid of the mixtures according to the invention, the method according to the invention and the use according to the invention.

In particular, it was surprising that the mixtures according to the invention no longer had the disadvantages of the curable mixtures of the prior art.

In particular, the mixtures of the invention contained no other toxicologically and ecologically questionable metal compounds, such as organic tin compounds, in particular dibutyltin dilaurate, in place of the molybdenum and tungsten compounds of the prior art. Nevertheless, they are infested, if at all, only to a small extent by microorganisms.

The mixtures according to the invention could be cured quickly and easily at comparatively low temperatures. They wet the surfaces of different substrates very well, d. they had a particularly low wetting limit.

The mixtures according to the invention provided new, hardened materials which no longer showed yellowing on overburning and long-term exposure to the atmosphere, even in high layer thicknesses no paint defects, such as stoves, specks, Runners, craters or micro-disturbances (starry sky), had and have a very good flow, a high gloss and a low haze, high chemical stability, high weathering stability and high hardness, high flexibility and high scratch resistance. Overall, they readily achieved the so-called automotive quality, as defined in European Patent EP 0 352 298 B1, page 15, lines 42 to page 17, line 40.

Detailed description of the invention

The mixtures according to the invention are free of molybdenum and tungsten compounds. This means that the mixtures according to the invention at most contain traces of molybdenum and tungsten compounds which are introduced by the constituents of the mixtures according to the invention. Preferably, the content of molybdenum and tungsten compounds is below the detection limits of the conventional and known methods of qualitative and quantitative detection of molybdenum and tungsten.

Preferably, the mixtures of the invention are also free of metal compounds, especially compounds of toxicologically and ecologically questionable metals, especially tin compounds such as dibutyltin dilaurate.

The mixtures according to the invention are thermally curable. That is to say that they crosslink three-dimensionally via thermally initiated reactions of complementary, reactive, functional groups, isocyanate groups (a1) blocked according to the invention and isocyanate-reactive functional groups (a2), and give cured thermoset materials.

The thermal curing by the complementary, reactive, functional groups (a1) and (a2) can be supported by other conventional and known curing mechanisms. Examples of other curing mechanisms are the thermal curing by other complementary, reactive, functional groups than the groups (a1) and (a2), the physical hardening by the filming of film-forming constituents, the air drying by the cross-linking of corresponding constituents with oxygen as well as the hardening with actinic radiation , in particular UV radiation or electron radiation. These hardening mechanisms and methods are additionally used and serve to modify and optimize the thermal curing to be used according to the invention by the complementary, reactive, functional groups (a1) and (a2), which characterizes the performance property profile of the mixtures according to the invention and of the materials according to the invention produced therefrom.

The mixtures according to the invention contain a complementary reactive system (A) ₁ which comprises blocked isocyanate groups (a1) and isocyanate-reactive functional groups (a2).

In this case, the complementary reactive system (A) at least one, in particular a self-crosslinking component (A1 / 2), the statistical average of at least two blocked isocyanate groups (a1) and at least one isocyanate-reactive functional group (a2) or at least one blocked isocyanate group ( a1) and contains at least two isocyanate-reactive functional groups (a2), comprising or consisting thereof.

Preferably, the self-crosslinking component (A1 / 2) contains on statistical average 2 to 10, preferably 2.5 to 6.5 and in particular 3 to 6 blocked isocyanate groups (a1) and 2 to 10, preferably 2.5 to 6.5 and in particular 3 to 6 isocyanate-reactive functional groups (a2).

Preferably, the complementary reactive functional groups (a1) and (a2) are in the self-crosslinking. Ingredients (A1 / 2) linked to oligomeric and polymeric structural units.

Here and below, are oligomers compounds or structural units understood, ^'the monomeric statistical average of 3 to 12 structural units which may be the same or different, are constructed;

Here and in the following, polymers are understood to mean compounds or structural units which are built up on a statistical average from more than 8 monomeric structural units, which may be the same or different from one another.

Whether a self-crosslinking constituent (A1 / 2), which is constructed on a statistical average of 8 to 12 monomeric structural units, is regarded by the skilled person as an oligomer or as a polymer depends in particular on the number-average and mass-average molecular weight of the relevant constituent. If the molecular weights are comparatively high, one will speak of a polymer, they are relatively low from an oligomer. The monomeric structural units of the self-crosslinking constituents (A1 / 2) are structural units which are derived from customary and known, low molecular weight, organic compounds.

The oligomers and polymeric structural units of the self-crosslinking constituents (A1 / 2) are derived from the customary and known, organic and organometallic oligomers and polymers. They are preferably derived from the oligomers and polymers customarily used as binders (see Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders"). The oligomers and polymers can have a wide variety of structures. For example, they may be linear, star-shaped, comb-shaped or irregularly branched, dendrimeric or ring-shaped, with more than one of these structures being present in a self-crosslinking component (A1 / 2). The structures may have a statistical and / or block-shaped distribution of the monomeric structural units.

Preferably, the complementary reactive system (A) is externally crosslinking, d. h., It comprises at least one blocked polyisocyanate (A1) containing at least two blocked isocyanate groups (a1), and at least one component (A2), containing on statistical average at least two isocyanate-reactive functional groups (a2), or it consists thereof. More preferably, the complementary reactive system (A) consists of a blocked polyisocyanate (A1) and a component (A2).

In the preferred complementary reactive system, the equivalent ratio of blocked isocyanate groups (a1) to isocyanate-reactive functional groups (a2) can vary widely. Preferably, the equivalent ratio (a1): (a2) is close to 1, preferably from 1.5: 1 to 1: 1.5, more preferably from 1.3: 1 to 1: 1.3 and especially from 1.2: 1 to 1: 1, 2.

Preferably, the blocked polyisocyanate (A1) contains on average 2 to 10, preferably 2.5 to 6.5 and in particular 3 to 6 blocked isocyanate groups (a1).

Preferably, the blocked polyisocyanate (A1) is low molecular weight or oligomeric in the above sense. Preferably, its blocked isocyanate groups (a1) are prepared by the reaction of isocyanate groups with blocking agents. The isocyanate groups are preferably present in the customary and known polyisocyanates.

Examples of suitable, conventional and known polyisocyanates are

Diisocyanates, such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, omega, omega-dipropyl-ether-diisocyanate, cyclohexyl-1, 4- diisocyanate, cyclohexyl-1, 3-diisocyanate, cyclohexyl-1, 2-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1, 5-dimethyl 1-2,4-di (isocyanato-methyl) -benzene, 1, 5 -Di-methyl-2,4-di (isocyanatoethyl) benzene, 1, 3.5-

Trimethyl-2,4-di (isocyanatomethyl) benzene, 1, 3,5-triethyl-2,4-di (isocyanatomethyl) benzene, Dicyclohexyldimethylmethan- ^{4,4'-diisocyanate} isophorone diisocyanate, 2,4-tolylene diisocyanate, 2 , 6-toluylene diisocyanate,

^{Diphenylmethane-4,4'-diisocyanate;} and

Polyisocyanates such as triisocyanates such as nonane triisocyanate (NTl) and polyisocyanates based on the diisocyanates and triisocyanates described above, in particular oligomers containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, carbodiimide, urea and / or uretdione For example, from the patents and

Patent Applications CA 2,163,591 A 1, US 4,419,513 A, US 4,454,317 A, EP 0 646 608 A1, US 4,801, 675 A, 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 Pat. No. 5,258,482 A, US Pat. No. 5,290,902 A, EP 0 649 806 A1, DE 42 29 183 A1 or EP 0 531 820 A1 are known;

the high-viscosity polyisocyanates, as described in German Patent Application DE 198 28 935 A1; such as

German patent application DE 199 24 170 A1, column 2, lines 6 to

34, column 4, line 16, to column 6, line 62, published in international patent applications WO 00/31194, page 11, line 30, to page 12, line 26, and WO 00/37520, page 5, line 4, to page 6, line 27, and the polyisocyanates known from European patent application EP 0 976 723 A2, page 12, paragraph [0128], to page 22, paragraph [0284].

Examples of suitable, conventional and known blocking agents are Phenols, such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylpheπol, tert-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;

Lactams, such as ε-caprolactam, δ-valerolactam, γ-butyrolactam or β-propiolactam;

active methylenic compounds such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;

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 monobutyl ether, diethylene glycol monomethyl ether,

Diethylene glycol monoethyl ether, propylene glycol monomethyl ether,

Methoxymethanol, glycolic acid, glycolic acid ester, lactic acid, lactic acid ester, methylolurea, methylolmelamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-dichloro-2-propanol, 1,4-cyclohexyldimethanol or acetocyanohydrin;

Mercaptans such as butylmercaptan, hexylmercaptan, t-butylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol;

Acid amides such as acetoanilide, acetoanisidine amide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;

Imides such as succinimide, phthalimide or maleimide;

Amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;

Imidazoles such as imidazole or 2-ethylimidazole;

Ureas such as urea, thiourea, ethyleneurea, ethylene thiourea or 1,3-diphenylurea; Carbamates such as N-phenylcarbamic acid phenyl ester or 2-oxazolidone;

Imines such as ethyleneimine;

Oximes such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oximes;

Salts of sulfurous acid, such as sodium bisulfite or potassium bisulfite;

Hydroxamic acid esters such as benzyimethacrylohydroxamate (BMH) or allyl methacrylohydroxamate;

- pyrazole or substituted pyrazoles, in particular 3,4- or 3,5-dimethylpyrazole, or triazoles; or

Mixtures of these blocking agents, in particular 3,4- or 3, 5-dimethylpyrazole and triazoles, malonates and acetoacetic acid esters or 3,4- or 3,5-dimethylpyrazole and succinimide.

The constituent (A2) preferably contains on statistical average at least 2, preferably at least 3 and in particular at least 4 isocyanate-reactive, functional groups (a2).

Preferably, the isocyanate-reactive functional groups (a2) are selected from the group consisting of hydroxyl groups, thiol groups, primary and secondary amino groups, primary and secondary amide groups, and primary and secondary carbamate groups.

In particular, hydroxyl groups (a2) are used.

The hydroxyl groups (a2) in the constituents (A2) are preferably present in an amount such that hydroxyl numbers of 50 to 500, preferably 80 to 300 and in particular 100 to 250 mg KOH / g result. In addition to the isocyanate-reactive functional groups (a2), constituents (A2) may contain other, non-isocyanate-reactive, reactive, functional groups which may undergo thermal crosslinking reactions with complementary, reactive, functional groups. Examples of suitable pairs of complementary, non-isocyanate-reactive, reactive, functional groups are known from international patent application WO 03/010247, page 18, line 12, to page 21, line 15.

In addition, the constituents (A2) may also contain ion-forming, functional groups which can be converted into salt groups by neutralization and can thus assume ionic stabilization in water. Examples of suitable ion-forming functional groups are also known from international patent application WO 03/010247, page 12, line 9, to page 13, line 11.

In addition, the constituents (A2) may also contain reactive, functional groups which can be activated with actinic radiation, in particular UV radiation and electron radiation. Examples of suitable groups of this kind are also known from international patent application WO 03/010247, page 23, line 29, to page 26, line 4.

The constituents (A2) are preferably oligomers or polymers in the abovementioned sense. They are preferably selected from the group of customary and known binders. Examples of suitable binders (A2) are known from international patent application WO03 / 010247, page 13, line 13, to page 15, line 8. In particular, (meth) acrylate copolymers (A2) are used.

The mixtures according to the invention contain at least one cesium compound, in particular at least one cesium salt (B).

Preferably, the anions of the cesium salts are selected from the group consisting of F ^" , he, CiO-, CiO ₃ ^' , CiO ₄ ^" , Br, r, JO ₃ ^" , CNΓ, OCNΓ, SCN ^" , NO ₂ -, NO ₃ ^" , HCO ₃ -, CO ₃ ² -, SiO ₄ ^{2 "} ,

SiF ₆ ^{2 '} , S ^{2 "} , SH ^" , HSO ₃ ^" , SO ₃ ^2" , HSO ₄ ^" , SO ₄ ^2" , S ₂ O ₂ ^{2 "} , S ₂ O ₄ ^2" , S ₂ O ₅ ^{2 "} , S ₂ O ₆ ^{2 "} , S ₂ O ₇ ^2" , S ₂ O ₈ ^{2 "} , R (SO ₂ H ₂ PO ₂ -, H ₂ PO ₃ -, HPO ₃ ^2" , R (-PHO ₃ ^" ) _n , R (-PO ₃ ^{2 "} ) _n , H ₂ PO ₄ ^" , HPO ₄ ^{2 "} , PO ₄ ^3" , P ₂ O ₇ ^{4 "} , PF ₆ ^3" , R (-O ^" ) _n and R (- COO-) _n , wherein the variable R is n-bonded organic radicals and n is a number from 1 to 100, preferably 1 to 50, particularly preferably 1 to 30 and in particular 1 to 20 selected. Accordingly, the n-bonded organic radicals R in the above-explained sense are low molecular weight, oligomeric or polymeric, in particular low molecular weight.

Preferably, the organic radicals R are selected from the group consisting of:

n-bonded, substituted and unsubstituted alkyl having 1 to 20, preferably 2 to 16 and especially 2 to 10 carbon atoms, cycloalkyl having 3 to 20, preferably 3 to 16 and especially 3 to 10 carbon atoms and aryl having 5 to 20, preferably 6 to 14 and especially 6 to 10 carbon atoms;

n-linked, substituted and unsubstituted alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylaryl,

Alkyicycloalkylaryl, alkylarylcycloalkyl, arylcycloalkylalkyl, arylalkylcycloalkyl, cycloalkylalkylaryl and cycloalkylarylalkyl radicals, wherein the alkyl, cycloalkyl and aryl groups contained herein each have the above-mentioned number of

Contain carbon atoms; and

n-linked, substituted and unsubstituted radical of the type mentioned above, containing at least one, in particular one, heteroatom selected from the group consisting of oxygen atom, sulfur atom,

Nitrogen atom, phosphorus atom and silicon atom, in particular oxygen atom, sulfur atom and nitrogen atom;

selected ^' .

Suitable substituents for the radicals R are all groups and atoms which are inert, d. H. do not affect the effect of the cesium salts (B), do not inhibit the curing reactions in the mixtures of the invention, do not lead to undesirable side reactions and cause no toxic effect. Examples of suitable substituents are halogen atoms, nitrile groups or nitro groups, preferably halogen atoms, in particular fluorine atoms, chlorine atoms and bromine atoms.

In particular, the anions are selected from the group consisting of bicarbonate, carbonate, formate, acetate, propionate, butyrate, pentanoate, hexanoate and 2-ethylhexanoate. The content of the mixtures according to the invention on the cesium compounds (B) can vary widely and depends on the requirements of the individual case. Preferably, the mixtures of the invention contain the cesium compounds (B) in an amount of 0.01 to 10 wt .-%, preferably 0.05 to 5 wt .-% and in particular 0.1 to 3 wt .-%, each based on the Solid body of the relevant mixture according to the invention.

Here and in the following, the term "solid" is understood to mean the sum of all constituents of a mixture according to the invention minus any organic and inorganic solvents (C) which may be present. Accordingly, the term "solids content" of a mixture according to the invention means the percentage fraction of the solid in the total amount of the mixture according to the invention.

Accordingly, the solids content of the mixtures according to the invention can be 100% by weight. If the mixtures according to the invention contain organic and / or inorganic solvents (C), the solids content is preferably from 10 to 90% by weight, preferably from 15 to 80% by weight, particularly preferably from 20 to 70% by weight and in particular from 20 to 60% by weight .-%.

As mentioned above, the mixtures according to the invention may contain at least one additive (C) in effective amounts.

Preferably, the additive (C) is selected from the group consisting of reactive and inert, oligomeric and polymeric, film-forming binders other than the components (A); Crosslinking agents other than components (A); Water; reactive and inert, organic and inorganic solvents; with actinic radiation, in particular UV radiation and electron radiation, activatable compounds; organic and inorganic, colored and achromatic, optically effecting, electrically conductive, magnetically shielding and fluorescent pigments; transparent and opaque, organic and inorganic fillers; nanoparticles; UV absorbers; Light stabilizers; Radical scavengers; Photoinitiators; Initiators of radical polymerization; Driers; Venting means; slip additives;

polymerization inhibitors; defoamers; Emulsifiers and wetting agents; Adhesion promoters; Leveling agents; Coalescing agents; rheology-controlling additives and flame retardants selected. ₁

Examples of suitable additives (C) which can be used in particular in aqueous mixtures according to the invention are disclosed in International Patent Application WO 03/010247, page 9, line 16, to page 10, line 19, and page 26, line 27, to page 35 , Line 2, known.

Further examples of suitable additives (C) are known from German patent application DE 199 48 004 A1, page 14, lines 4 to 31, and page 16, line 24, to page 17, line 5.

The mixtures according to the invention can be present in a wide variety of physical states and three-dimensional forms.

Thus, the mixtures according to the invention can be solid or liquid or flowable at room temperature. However, they may also be solid at room temperature and flowable at higher temperatures, preferably exhibiting thermoplastic behavior. In particular, they may contain conventional mixtures containing organic solvents, aqueous mixtures, substantially or completely solvent- and water-free liquid mixtures (100% systems), substantially or completely solvent- and water-free solid powders or substantially or completely solvent-free, aqueous powder suspensions ( Puiverslurries).

Preferably, they are substantially or completely solvent-free, aqueous powder suspensions (Puiverslurries), in particular powder slurry clearcoats, as they - except for the inventive use of the cesium compounds (B) - from the international patent application WO 03/010247 or the German patent DE 198 41 842 C2 are known.

Methodically, the preparation of the mixtures according to the invention has no special features, but takes place in the context of the process according to the invention by mixing and homogenizing the above-described constituents by means of customary and known mixing methods and devices such as stirred tank, stirred mills, extruders, kneaders, Ultraturrax, In-line Dissolvers, static mixers, micromixers, sprocket dispersers, pressure relief nozzles and / or microfluidizers optionally with the exclusion of actinic radiation. The selection of the optimum method for a given individual case depends above all on the physical state and the three-dimensional shape which the mixture according to the invention is intended to have. For example, if a thermoplastic invention Mixture in the form of a film or a laminate, in particular the extrusion through a slot die for the production of the mixture according to the invention and its shaping into consideration.

In particular, the powder slurries according to the invention can be produced by means of secondary dispersion methods, as described, for example, in International Patent Application WO 03/010247, page 35, line 4, to page 38, line 19, or in German Patent DE 198 41 842 C2, page 5, line 43, to page 6, line 3 described. However, it is also possible to use the melt emulsification methods as described, for example, in German patent application DE 101 26 652 A1, page 4, paragraph [0040], to page 5, paragraph [0058].

In the context of the use according to the invention, the mixtures according to the invention are used for the production of new hardened materials, in particular new thermosetting materials, which serve a very wide variety of purposes and are referred to below as "materials according to the invention".

The mixtures according to the invention are preferably starting materials for molded parts and films or coating materials, adhesives and sealants, in particular coating materials.

The novel materials are preferably new moldings, films, coatings, adhesive layers and seals, in particular new coatings.

The novel coating materials are preferably novel electrocoating lacquers, fillers, antistonechip primers, solid-color topcoats, water-based lacquers and / or clearcoats, more preferably clearcoats, in particular powder clearcoats, for the production of new color and / or effect, electrically conductive, magnetically shielding or fluorescent multi-layer finishes, in particular color and / or effect Multicoat paint systems used. For the production of the multicoat paint systems according to the invention, the customary and known wet-on-wet processes and / or extrusion processes as well as the customary and known paint or film structures can be used.

To prepare the materials according to the invention, the mixtures according to the invention are applied to conventional and known temporary or permanent substrates. For the production of the films and moldings according to the invention, conventional and known temporary substrates are preferably used, such as metal and plastic tapes and films or hollow bodies made of metal, glass, plastic, wood or ceramic, which can be easily removed without leaving the products according to the invention Mixtures produced inventive films and Foπnteile be damaged.

When the mixtures according to the invention are used for the production of the coatings, adhesives and gaskets according to the invention, permanent substrates are used, such as bodies of locomotion, in particular motor vehicle bodies, and parts thereof, interior and exterior structures and parts thereof, doors, windows, furniture, hollow glass body , Coils, containers, packaging, small parts, optical, mechanical and electrotechnical components as well as components for white goods. The films and moldings according to the invention can likewise serve as permanent substrates.

Methodically, the application of the mixtures according to the invention has no special features, but can by all customary and known, suitable for the respective mixture according to the invention application methods, such as. Extrusion, electrocoating, spraying, spraying, including powder spraying, knife coating, brushing, pouring, dipping, trickling or rolling. Preferably, extrusion and spray application methods, in particular spray application methods, are used.

After their application, the mixtures according to the invention are thermally cured in a conventional manner.

The thermal curing generally takes place after a certain rest period or ventilation time. It may have a duration of 30 seconds to 2 hours, preferably 1 minute to 1 hour and especially 1 to 45 minutes. The rest period serves, for example, for the course and degassing of layers of the mixtures according to the invention and for the evaporation of volatile constituents, such as optionally present solvent and / or water. The ventilation can be accelerated by an elevated temperature, which is not sufficient for curing, and / or by a reduced humidity.

This process measure is also used for drying the applied mixtures according to the invention, in particular the layers of the coating materials of the invention, especially the layers of the ^

17

Coating layers according to the invention, applied, which are not or only partially cured.

The thermal curing takes place, for example, with the aid of a gaseous, liquid and / or solid, hot medium, such as hot air, heated oil or heated rollers, or of microwave radiation, infrared light and / or near infrared light (NIR). Preferably, the heating takes place in a convection oven or by irradiation with IR and / or NIR

Lamps. Curing can also be done gradually. Preferably, the thermal curing is carried out at temperatures from room temperature to 200 ⁰ C, preferably from room temperature to 18O ⁰ C and in particular from room temperature to 160 -, ° OQ

The thermal curing can be further supported by the additional curing methods described above, including, if appropriate, the customary and known devices, for example for curing with actinic radiation, in particular UV radiation or Elektronenstrahiung be used.

The resulting materials according to the invention, in particular the resulting films, moldings, coatings, adhesive layers and seals, are outstandingly suitable for coating, bonding, sealing, wrapping and packaging bodies of vehicles, in particular motor vehicle bodies, and parts thereof, buildings in the interior and Exterior and parts thereof, doors, windows, furniture, glass hollow bodies, coils, containers, packaging, small parts, such as nuts, screws, rims or hubcaps, optical components, mechanical components, electrical components, such as windings (coils, stators, rotors), and Components for white goods, such as radiators, appliances, refrigerator covers or washing machine covers.

The mixtures according to the invention offer very particular advantages when they are used as powder slurry clearcoats according to the invention for the production of novel clearcoats.

The clearcoats of the invention are usually the outermost layers of multicoat paint systems or films or laminates which essentially determine the overall visual appearance (appearance) and the substrates and / or the color and / or effect layers of multicoat paint systems or films or laminates protect against mechanical and chemical damage and radiation damage. That's why deficits in hardship, -

Scratch resistance, chemical resistance and stability to yellowing in the clearcoat particularly noticeable. However, the clearcoats of the invention produced have only a slight yellowing. They are highly scratch-resistant and show only very slight gloss loss after scratching. In particular, the loss of gloss in the car wash simulation test according to Amtec / Kistler is very low. At the same time they have a high hardness and a particularly high chemical resistance. Last but not least, they have excellent substrate adhesion and intercoat adhesion. In addition, they have excellent recoatability.

Examples

Production Example 1

The preparation of the methacrylate copolymer (A2)

39.75 parts by weight of methyl ethyl ketone were placed in a reaction vessel equipped with stirrer, reflux condenser, oil heater, nitrogen inlet tube and two feed vessels, and heated to 78 ° C.

Thereafter, an initiator solution of 4 parts by weight of methyl ethyl ketone and 5 parts by weight TBPEH was uniformly metered in from the first feed vessel for 6.75 hours.

15 minutes ^' after the initiation of the initiator feed, a monomer mixture of 27.5 parts by weight of n-butyl methacrylate, 9.15 parts by weight of i-butyl methacrylate, 12.75 parts by weight of hydroxyethyl methacrylate and 0.6 part by weight was obtained from the second feed vessel

Methacrylic acid evenly added during 6 h. Subsequently, the

Monomer line with 0.25 parts by weight of methyl ethyl ketone and the feed vessel with 0.5

Rinsed parts by weight of methyl ethyl ketone. After completion of the Initiatorzulaufs the relevant feed vessel was also rinsed with 0.5 parts by weight of methyl ethyl ketone.

The reaction mixture was allowed to react for 3 h at 78 ° C again. Subsequently, the volatiles were removed by vacuum distillation until a solids content of 70 wt .-% was set. Thereafter, the resin solution was discharged. It had a viscosity of 7.0 to 10.0 dPas (solid resin 60 percent in XyIoI at 23 ° C). The acid number was 9.0 to 11.0 and the hydroxyl number was 110 mg KOH / g of solid resin. Production Example 2

The preparation of the blocked polyisocyanate (A1)

534 parts by weight Desmodur® N 3300 (commercial isocyanurate of hexamethylene diisocyanate from Bayer AG) and 200 parts by weight of methyl ethyl ketone were placed in a reaction vessel and heated to 40 ° C. To the solution was added, with cooling, 100 parts by weight of 3,5-dimethylpyrazole, waiting for the exothermic reaction to disappear. Thereafter, with continued cooling, 100 parts by weight of 3,5-dimethylpyrazole were added again. After renewed decay of the exothermic reaction, an additional 66 parts by weight of 3,5-dimethylpyrazole were added. Thereafter, the cooling was turned off, causing the reaction slowly heated to 80 ⁰ C. It was held at this temperature until its isocyanate content had dropped below 0.1%. Thereafter, the reaction mixture was cooled and discharged.

The resulting solution of the blocked polyisocyanate had a solids content of 81% by weight (1 h at 130 ° C.) and a viscosity of 3.4 dPas (70% in methyl ethyl ketone, plate and cone viscometer at 23 ° C.).

example 1

The preparation of the powder slurry clearcoat according to the invention

961.8 parts by weight of the methacrylate copolymer solution (A2) of Preparation Example 1 and 484.6 parts by weight of the solution of the blocked polyisocyanate (A1) of Preparation Example 2 were mixed together at room temperature in an open stirrer vessel for 15 minutes. To the resulting mixture were added 21.5 parts by weight of Tinuvin® 400 and 10.7 parts by weight of Tinuvin® 123 (commercial light stabilizer from Ciba Specialty Chemicals, Inc.) and 15 parts by weight of Lutensol® AT 50 (ethoxylated alcohol having 16 to 18 carbon atoms in the alkyl radical and on average 50 ethylene oxide groups in the molecule from BASF Aktiengesellschaft) were added, after which the mixture was stirred at room temperature for 30 minutes. Subsequently, 11.3 parts by weight of a 30% aqueous solution of cesium carbonate and 4.68 parts by weight of dimethylethanolamine were added. The resulting mixture was stirred for another two hours at room temperature. Then, it was added with 735 parts by weight of deionized water in which 1.462 parts by weight of ammonium acetate were dissolved in small portions. After a 15-minute break, another 780 parts by weight deionized water was added evenly over 30 minutes.

The resulting aqueous emulsion was diluted with 739 parts by weight of deionized water. Thereafter, it was removed on a rotary evaporator under vacuum, the same amount of a mixture of volatile organic solvents and water until the solids content was 37 wt .-% (1 h at 13O ⁰ C).

To set the desired intrinsic viscosity, 90 parts by weight of Acrysol® RM-8W (commercial nonionic associative thickener from Rohm & Haas) and 1.75 parts by weight of Baysilon® AI 3468 (commercial leveling agent from Bayer AG) were stirred into the slurry.

Example 2

The preparation of the multicoat paint systems 1

For the production of the multi-layer coatings 1 test panels were used, which had been coated with a conventional and known, cathodically deposited and thermally cured electrodeposition coating BASF Coatings AG.

The electrodeposition coatings were each wet-on-wet coated with a commercial water filler from BASF Coatings AG and a commercial black water-based paint from BASF Coatings AG. After each application, the respective wet layers were predried.

To determine the boiling and wetting limits, the predried, black aqueous basecoat films were coated in a wedge shape with the powder slurry clearcoat 1 of Example 1 pneumatically. In each case, the wet film thicknesses of the clearcoat films 1 were selected such that dry film thicknesses of 15 to 70 μm resulted. The clearcoat films 1 were each predried at 80 ° C. for 10 minutes. Subsequently, the surfacer layers, the aqueous basecoat films and the clearcoat films 1 were baked at 150 ° C. for 23 minutes. ₁

In the area Kocher occurred only from a dry film thickness of 51 microns. The wetting limit was at a dry film thickness of 19 microns. This underpinned that the clearcoat 1 wetted the substrates very well and had an excellent cooker boundary in the area.

For the evaluation of the chemical resistance, the gloss and the course, the method described above was repeated, except that the powder slurry clearcoat 1 was applied in a constant wet layer thickness, so that a dry layer thickness of 40 microns resulted.

Chemical resistance was determined in a conventional manner with a DC gradient oven. Visible damage occurred when loaded with 1% - percent sulfuric acid from 46 ⁰ C, with 1% by percent NaOH from 55 ° C, with tree resin from 38 ⁰ C and with deionized water from 41 ⁰ C. This underpinned that the clearcoat 1 also had a high chemical resistance.

The gloss and haze were determined according to DIN 67530. Gloss (20 °, 83 units) and Haze (20 °, 13.6 units) were very good.

The course was very good (meter: Byk / Gardner company - Wave scan plus: Long wave: 2.8, Short wave: 15.5).

The mechanical dynamic properties of the clearcoat 1 were determined using self-supporting films with a layer thickness of 40 μm using Dynamic Mechanical Thermal Analysis (DMTA). The measuring frequency was 1 Hz, the amplitude at 0.2% and the heating rate at 2 ° C / min from - 30 ° C to + 200 ⁰ C (see also the German patent application DE 102 24 381 A1, page 5, paragraph [0047]). The following values were measured:

Loss factor tangent delta = 0.1 at 48 ° C;

Maximum of the loss factor tangent delta at 83 ⁰ C; Loss modulus E "(max) at 63 ° C and storage modulus E '(min) = 1, 4x10 ⁷ .

The measured values underpin the excellent hardness, flexibility, crosslinking density and scratch resistance of the clearcoat 1.

Claims

claims

1. Of molybdenum and tungsten compounds free, curable mixtures containing

(A) a complementary reactive system containing blocked

Isocyanate groups (a1) and isocyanate-reactive functional groups (a2), as well as

(B) at least one Cesiumverbiπdung.

2. Mixtures according to claim 1, characterized in that the cesium compounds are cesium salts.

3. Mixtures according to claim 1 or 2, characterized in that the anions of the cesium salts from the group consisting of F ^" , Cl ^" , CIO, CIO ₃ ^' , CIO ₄ ^' , Br ^" , I ^" ,

JO ₃ ^" , CN ^' , OCN ^" , SCN ^' , NO ₂ ^' , NO ₃ ^" , HCO ₃ ^" , CO ₃ ^{2 "} , SiO ₄ ^2" , SiF ₆ ^{2 "} , S ^2" , SH ^" , HSO ₃ ^' , SO ₃ ^{2 "} , HSO ₄ ^" , SO ₄ ^{2 "} , S ₂ O ₂ ^{2 '} , S ₂ O ₄ ^2" , S ₂ O ₅ ^2' , S ₂ O ₆ ^{2 "} , S ₂ O ₇ ^2" , S ₂ O ₈ ^{2 "} , R (-SO ₃ ^" ) _n , H ₂ PO ₂ -, H ₂ PO ₃ -, HPO ₃ ^{2 "} , R (-PHO ₃ ^" ) _n , R (-PO ₃ ^{2 "} ) _n , H ₂ PO ₄ ^" , HPO ₄ ^2" , PO ₄ ^{3 '} , P ₂ O ₇ ^4' , PF ₆ ^{3 "} , R (-O ^" ) _n and R (-COO ^" ) _n , wherein the variable R stands for n-bonded organic radicals and n is a number from 1 to 10, are selected.

4. Mixtures according to one of claims 1 to 3, characterized in that the complementary reactive system (A) at least one self-crosslinking component (A1 / 2), the statistical average of at least two blocked isocyanate groups (a1) and at least one isocyanate-reactive, functional

Group (a2) or at least one blocked isocyanate group (a1) and contains at least two isocyanate-reactive functional groups (a2), or consists thereof.

5. Mixtures according to one of claims 1 to 4, characterized in that the complementary reactive system (A) at least one blocked Polyisocyaπat (A1) containing at least two blocked isocyanate groups (a1), and at least one component (A2), containing in the statistical Agent comprises at least two isocyanate-reactive functional groups (a2), comprises or consists thereof.

6. Mixtures according to one of claims 1 to 5, characterized in that the blocked isocyanate groups (a1) can be prepared by the reaction of isocyanate groups with blocking agents.

7. Mixtures according to claim 6, characterized in that the blocking agents from the group consisting of phenols, lactams, active methylenic compounds, alcohols, mercaptans, acid amides, imides, amines, imidazoles, ureas, carbamates, imines, oximes, salts of the sulfurous Acid hydroxamic acid esters, pyrazoles and triazoles.

8. Mixtures according to claim 7, characterized in that the blocking agents are substituted pyrazoles.

9. Mixtures according to one of claims 1 to 8, characterized in that isocyanate-reactive functional groups (a2) from the group consisting of hydroxyl groups, thio groups, primary and secondary amino groups, primary and secondary amide groups and primary and secondary carbamate groups are selected.

10. Mixtures according to claim 9, characterized in that the isocyanate-reactive functional groups (a2) are hydroxyl groups.

11. Mixtures according to one of claims 1 to 10, characterized in that the constituents (A2) are oligomers or polymers.

12. Mixtures according to one of claims 1 to 11, characterized in that the constituents (A1) are low molecular weight compounds or oligomers.

13. Mixtures according to one of claims 1 to 12, characterized in that the mixtures still contain at least one additive (C) in effective amounts.

14. Mixtures according to claim 13, characterized in that the additive (C) from the group consisting of reactive and inert, oligomeric and polymeric, film-forming binders which are different from the components (A); Crosslinking agents other than components (A); Water; reactive and inert, organic and inorganic solvents; with actinic radiation, in particular UV radiation and electron radiation, activatable compounds; organic and inorganic, colored and achromatic, optically effecting, electrically conductive, magnetically shielding and fluorescent pigments; transparent and opaque, organic and inorganic fillers; nanoparticles; UV absorbers; Light stabilizers; Radikaifängern; Photoinitiators; Initiators of radical polymerization; Driers; Venting means; slip additives; Poiymerisationsinhibitoren; defoamers; Emulators and wetting agents; adhesion promoters; Leveling agents; Coalescing agents; rheology-controlling additives and flame retardants.

15. A mixture according to any one of claims 1 to 14, characterized in that the mixtures contain the cesium compounds (B) in an amount of 0.01 to 10 wt .-%, based on the solids of a mixture.

16. Mixtures according to one of claims 1 to 15, characterized in that they have a solids content of 10 to 100 wt .-%.

17. Mixtures according to oneπvder claims 1 to 16, characterized in that they contain water.

18. Mixtures according to claim 17, characterized in that the mixtures are in the form of aqueous dispersions of finely divided, dimensionally stable particles.

19. Mixtures according to claim 18, characterized in that the aqueous dispersions are powder slurries.

20. Mixtures according to one of claims 17 to 19, characterized in that the mixtures are pseudoplastic.

21. A process for the preparation of molybdenum and tungsten compounds free, curable mixtures according to any one of claims 1 to 20, characterized in that the components (A) and (B) or (A), (B) and (C) with each other mixed and the resulting mixture homogenized.

22. The method according to claim 21, characterized in that dispersing at least the constituents (A) in the form of finely divided, dimensionally stable particles in water or an aqueous medium and homogenizing the resulting mixture.

23. Use of the molybdenum and tungsten compounds-free, curable mixtures according to any one of claims 1 to 20 and prepared by the method according to claim 21 or 22, free of molybdenum and tungsten compounds, curable mixtures as coating materials, adhesives, sealants and starting materials for Films and molded parts, for the production of coatings, adhesive layers, gaskets, films and molded parts.