WO2008116895A1 - Curing compositions - Google Patents

Abstract

The invention relates to color-stable curing compositions for polyurethane lacquers.

Description

 hardener compositions

description

The present invention relates to color stable hardener compositions for polyurethane coatings.

WO 2005/089085 describes polyisocyanate compositions as curing agents for 2K polyurethane coatings which, in addition to a catalyst for the reaction between isocyanate groups and reactive groups, contain a stabilizer mixture selected from hindered phenols and secondary arylamines and organophosphites, in particular trialkyl phosphites. Explicitly disclosed in the examples is a polyisocyanate composition, the isocyanurate tolonate HDT, with dibutyltin dilaurate as catalyst in butyl acetate / methyl amyl ketone / xylene 1: 1: 0.5.

EP 643 042 B1 describes stabilizer mixtures for the stabilization of monomeric isocyanates which have been obtained by a cleavage of the corresponding carbamic acid esters. The monomeric isocyanates stabilized in this way are advantageously convertible to oligomeric isocyanates. In this case, generally phosphorus-containing compounds fertilize, preferably triesters of phosphorous acid (phosphites) named as a possibility of one of the three stabilizing groups.

A disadvantage of the stabilizer systems disclosed therein is that they can be used only for phosgene-free monomeric isocyanates and that the oligomeric isocyanates obtained are not yet ready for the reaction in polyurethane coatings, since they lack the presence of a polyurethaneization catalyst.

EP 735027 A1 describes a process for the preparation of uretdiones with improved color quality by reacting (cyclo) aliphatic diisocyanates with catalysis of pyridine derivatives, which additionally contain 0.1-4% of trivalent phosphorus compounds of a generic formula. Explicitly disclosed are phosphines, phosphites and phosphonate. Specifically listed are "dibutyl phosphite" and "dibenzyl phosphite". However, these are not trivalent phosphorus compounds but five-membered ones, since the hydrogen atom and one of the oxygen atoms are bound to the phosphorus via a double bond. Correctly, these compounds are therefore phosphonates.

However, EP 735027 A1 relates only to the production of uretdiones. These phosphorus compounds are distilled off after the preparation together with the unreacted isocyanate. Addition of phosphites to stabilize polyisocyanates is not described, especially not in the presence of urethanization catalysts. The object of the present invention was to provide further storage-stable polyisocyanate compositions which already contain a catalyst for the reaction between isocyanate groups and reactive groups and are color-stable and whose stabilizing effect is at least comparable with the prior art. The stabilizing effect should be independent of the origin of the monomeric isocyanate.

The object has been achieved by polyisocyanate compositions containing

(A) at least one polyisocyanate obtainable by reacting at least one monomeric isocyanate,

(B) at least one compound capable of accelerating the reaction of isocyanate groups with isocyanate-reactive groups,

- (C) at least one phosphonate,

- (D) optionally at least one sterically hindered phenol, - (E) optionally at least one solvent

- (F) optionally at least one acidic stabilizer

- (G) optionally other paint-typical additives.

Phosphonates (C) are often referred to in the literature as Phosphorigsäurediester. The central phosphorus atom has an oxidation state of + IV in this structural variant of the phosphorus.

Such polyisocyanate compositions can be reacted directly with components containing isocyanate-reactive groups in polyurethane paints and have good color stability in storage.

In a preferred embodiment, the polyisocyanate compositions according to the invention after storage at 50 ^° C. for seven weeks do not show more than 40% of the increase in the color number (APHA color number according to DIN EN 1557) of a similar prior art polyisocyanate composition in which neither one component ( C) nor a component (D) is present, on.

The monomeric isocyanates used may be aromatic, aliphatic or cycloaliphatic, preferably aliphatic or cycloaliphatic, which is referred to in this document briefly as (cyclo) aliphatic, particularly preferred are aliphatic isocyanates.

Aromatic isocyanates are those which contain at least one aromatic ring system, ie both purely aromatic and also araliphatic compounds.

Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system. Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie acyclic compounds.

The monomeric isocyanates are preferably diisocyanates which carry exactly two isocyanate groups. In principle, however, it may also be monoisocyanates with an isocyanate group.

In principle, higher isocyanates having on average more than 2 isocyanate groups are also considered. For example, triisocyanates such as triisocyanato-nano, 2'-isocyanatoethyl- (2,6-diisocyanatohexanoate), 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanatodiphenyl ether or the mixtures of di-, are suitable for this purpose. Tri- and higher polyisocyanates, which are obtained for example by phosgenation of corresponding aniline / formaldehyde condensates and represent methylene bridged polyphenyl polyisocyanates.

These monomeric isocyanates have no significant reaction products of the isocyanate groups with itself.

The monomeric isocyanates are preferably isocyanates having 4 to 20 C atoms. Examples of customary diisocyanates are aliphatic diisocyanates, such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, (for example methyl or ethyl-2, 6-diisocyanatohexanoate), trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3 , 3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and also 3 ( or 4), 8 (or 9) -bis (isocyanatomethyl) -tricyclo [5.2.1.0 ²⁶ ] decane isomer mixtures, and aromatic diisocyanates such as 2,4- or 2,6-toluene diisocyanate and their isomer mixtures, m- or p Xylylene diisocyanate, 2,4'- or 4,4'-diisocyanate natodiphenylmethane and isomeric mixtures thereof, 1,3-or 1,4-phenylenediisocyanate, 1-chloro-2,4-phenylenediisocyanate, 1,5-naphthylenediisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3, 3'-dimethyldiphenyl, 3-methyldi-phenylmethane-4,4'-diisocyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate.

Particular preference is given to 1,6-hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and 4,4'- or 2,4'-

Di (isocyanatocyclohexyl) methane, most preferably isophorone diisocyanate and 1,6-hexamethylene diisocyanate, particularly preferred is 1,6-hexamethylene diisocyanate.

There may also be mixtures of said isocyanates.

Isophorone diisocyanate is usually present as a mixture, namely the cis and trans isomers, usually in the ratio of about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75:25 and most preferably in the ratio of about 75:25.

Dicyclohexylmethane-4,4'-diisocyanate may also be present as a mixture of the different cis and trans isomers.

For the present invention, it is possible to use both those diisocyanates which are obtained by phosgenation of the corresponding amines and those which can be obtained without the use of phosgene, ie. H. after phosgene-free process, are produced. According to EP-AO 126 299 (US Pat. No. 4,596,678), EP-A-126 300 (US Pat. No. 4,596,679) and EP-A-355 443 (US Pat. No. 5,087,739), for example, (cyclo) aliphatic diisocyanates, eg such as 1,6-hexamethylene diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, 4,4'- or 2,4'-

Di (isocyanatocyclohexyl) methane and 1-isocyanato-S-isocyanato-methyl-S ^^ - trimethylcyclohexane (isophorone diisocyanate or IPDI) are prepared by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols to (cyclo) aliphatic Biscarbaminsäureestern and their thermal cleavage into the corresponding diisocyanates and alcohols. The synthesis is usually carried out continuously in a cyclic process and optionally in the presence of N-unsubstituted carbamic acid esters, dialkyl carbonates and other by-products recycled from the reaction process. Thus obtained diisocyanates generally have a very low or even non-measurable proportion of chlorinated compounds, which is advantageous, for example, in applications in the electronics industry.

In one embodiment of the present invention, the isocyanates used have a total hydrolyzable chlorine content of less than 200 ppm, preferably less than 120 ppm, more preferably less than 80 ppm, even more preferably less than 50 ppm, in particular less than 15 ppm and specifically less than 10 ppm. This can be measured, for example, by ASTM D4663-98. Of course, it is also possible to use monomeric isocyanates having a higher chlorine content, for example up to 500 ppm.

Of course, mixtures of such monomeric isocyanates obtained by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols and cleavage of the resulting (cyclo) aliphatic biscarbamic acid have been obtained with such diisocyanates, which have been obtained by phosgenation of the corresponding amines.

The polyisocyanates (A) to which the monomeric isocyanates can be oligomerized are generally characterized as follows:

The average NCO functionality of such compounds is generally at least 1.8, and may be up to 8, preferably 2 to 5 and more preferably 2.4 to 4.

The content of isocyanate groups after the oligomerization, calculated as NCO = 42 g / mol, is, unless stated otherwise, usually from 5 to 25% by weight.

The polyisocyanates (A) are preferably the following compounds:

1) isocyanurate polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl

Isocyanurates, which are cyclic trimers of diisocyanates, or mixtures with their higher, more than one isocyanurate homologues. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 8.

2) polyisocyanates containing uretdione groups with aromatic, aliphatic and / or cycloaliphatic bonded isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.

The polyisocyanates containing uretdione groups are obtained in the context of this invention in a mixture with other polyisocyanates, in particular those mentioned under 1). For this purpose, the diisocyanates can be reacted under reaction conditions under which both uretdione groups and the other polyisocyanates are formed, or the uretdione groups are first formed and subsequently converted to the other polyisocyanates or the diisocyanates first to the other polyisocyanates and these subsequently to uretdione groups containing products. 3) biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, especially tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues. These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 6.

4) containing urethane and / or allophanate polyisocyanates having aromatically, aliphatically or cycloaliphatically bonded, preferably aliphatically or cycloaliphatically bound isocyanate groups, as for example by

Reacting excess amounts of diisocyanate, for example hexamethylene diisocyanate or isophorone diisocyanate, with monohydric or polyhydric alcohols (A). These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of from 12 to 24% by weight and an average NCO functionality of from 2.5 to 4.5. Such polyisocyanates containing urethane and / or allophanate groups can be used uncatalyzed or, preferably, in the presence of catalysts, such as, for example, ammonium carboxylates or hydroxides, or allophanatization catalysts, e.g. Zn (II) compounds, in each case in the presence of mono-, di- or polyvalent, preferably monohydric alcohols.

5) oxadiazinetrione-containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates are accessible from diisocyanate and carbon dioxide.

6) polyisocyanates containing iminooxadiazinedione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such iminooxadiazine-dione-containing polyisocyanates can be prepared from diisocyanates by means of special catalysts.

7) Uretonimine-modified polyisocyanates.

8) carbodiimide-modified polyisocyanates.

9) Hyperbranched polyisocyanates, as are known, for example, from DE-A1 10013186 or DE-A1 10013187.

10) polyurethane-polyisocyanate prepolymers of di- and / or polyisocyanates with alcohols.

1 1) polyurea-polyisocyanate prepolymers. 12) The polyisocyanates 1) -11), preferably 1), 3), 4) and 6), after preparation thereof, may contain polyisocyanates having aryl-, cycloaliphatic- or aliphatic-bound biuret-group- or urethane- / allophanate-groups, ( cyclo) aliphatically bound isocyanate groups. The formation of biuret groups takes place, for example, by addition of water or reaction with amines. The formation of urethane and / or allophanate groups by reaction with mono-, di- or polyhydric, preferably monohydric alcohols, optionally in the presence of suitable catalysts. These biuret or urethane / allophanate-containing polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 6 on.

13) Hydrophilic modified polyisocyanates, i. Polyisocyanates which, in addition to the groups described under 1-12, contain those which are formally obtained by addition of

Molecules with NCO-reactive groups and hydrophilizing groups are formed on the isocyanate groups of the above molecules. The latter are nonionic groups such as alkyl polyethylene oxide and / or ionic, which are derived from phosphoric acid, phosphonic acid, sulfuric acid or sulfonic acid, or their salts.

14) Modified Polyisocyanates for Dual Cure Applications, i. Polyisocyanates which, in addition to the groups described under 1-12, contain those which formally form by addition of molecules with NCO-reactive groups and groups which can be crosslinked by UV or actinic radiation to the isocyanate groups of the above molecules. These molecules are, for example, hydroxyalkyl (meth) acrylates and other hydroxy-vinyl compounds.

The diisocyanates or polyisocyanates listed above may also be present at least partially in blocked form.

Classes of compounds used for blocking are described in D.A. Wicks, Z. W. Wicks, Progress in Organic Coatings, 36, 148-172 (1999), 41, 1-83 (2001) and 43, 131-140 (2001).

Examples of classes of compounds used for blocking are phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic acid esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic esters or alkyl acetoacetates.

In a preferred embodiment of the present invention, the polyisocyanate (A) is selected from the group consisting of isocyanurates, biurets, urethanes and allophanates, preferably from the group consisting of isocyanurates, urethanes and allophanates, more preferably from the group consisting of isocyanurates and allophanates, in particular is an isocyanurate group-containing polyisocyanate.

In a particularly preferred embodiment, the polyisocyanate (A) is isocyanurate group-containing polyisocyanates of 1,6-hexamethylene diisocyanate.

In a further particularly preferred embodiment, the polyisocyanate (A) is a mixture of polyisocyanates containing isocyanurate groups of 1,6-hexamethylene diisocyanate and of isophorone diisocyanate.

In a particularly preferred embodiment, the polyisocyanate (A) is a mixture comprising low-viscosity polysiocyanates, preferably polyisocyanates containing isocyanurate groups, having a viscosity of 600-1500 mPa ^* s, in particular less than 1200 mPa ^* s, low-viscosity urethanes and / or allophanates having a viscosity of 200-1600 mPa ^* s, in particular 600-1500 mPa ^* s, and / or iminooxadiazine dione group-containing polyisocyanates.

In this document, the viscosity at 23 ⁰ C according to DIN EN ISO 3219 / A.3 in a cone-plate system with a speed gradient of 1000 S " ¹ indicated, unless otherwise noted.

The process for producing the polyisocyanates can be carried out as described in the published European patent application with the file reference 06125323.3 and the date of filing 04.12.2006, there especially from page 20, line 21 to page 27, line 15, which is hereby incorporated by reference the present application.

The reaction can be stopped, for example, as described there from page 31, line 19 to page 31, line 31 and the workup carried out as described there from page 31, line 33 to page 32, line 40, which hereby incorporated by reference in each of the present Registration is.

Alternatively, the reaction can also be stopped, as described in WO 2005/087828 from page 11, line 12 to page 12, line 5, which is hereby incorporated by reference in the present application.

In thermally labile catalysts, it is further also possible to interrupt ERS the reaction by heating the reaction mixture to a temperature above at least 80 ⁰ C, preferably at least 100 ⁰ C, particularly preferably at least 120 ⁰ C. For this purpose usually ranges already the heating of the reaction mixture, as they are to separate the unreacted isocyanate by distillation in the workup is required.

Both thermally labile and non-labile catalysts have the potential to terminate the reaction at lower temperatures by adding deactivators. Suitable deactivators are, for example, hydrogen chloride, phosphoric acid, organic phosphates, such as dibutyl phosphate or diethylhexyl phosphate, bamates such as hydroxyalkyl carbamate or organic carboxylic acids.

These compounds are added neat or diluted at the appropriate concentration necessary for reaction termination.

Compounds (B) which are capable of accelerating the reaction of isocyanate groups with isocyanate-reactive groups are those compounds which, owing to their presence in a starting material mixture, lead to a higher proportion of urethane group-containing reaction products than the same starting material mixture in their absence under the same reaction conditions ,

These compounds (B) are known from the literature, for example from G. Oertel (ed.), Polyurethane, 3rd edition 1993, Carl Hanser Verlag, Munich - Vienna, pages 104 to 1 10, chapter 3.4.1. "Catalysts", preferred are organic amines, in particular tertiary aliphatic, cycloaliphatic or aromatic amines, Brønsted acids and / or Lewis acidic organometallic compounds, particularly preferred are Lewis acidic organometallic compounds.

As the Lewis acidic organic metal compounds, e.g. Tin compounds, such as tin (II) salts of organic carboxylic acids, e.g. Tin (II) diacetate, tin (II) dioctoate, tin (II) bis (ethylhexanoate) and tin (II) dilaurate, and the dialkyltin (IV) salts of organic carboxylic acids, e.g. Dimethyltin diacetate, di-butyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate and dioctyltin diacetate. In addition, zinc (II) salts can be used, such as zinc (II) dioctoate.

Unless otherwise stated, the carboxylic acids, e.g. in octoate, are branched and / or unbranched isomers, preferably unbranched.

Metal complexes such as acetylacetonates of iron, titanium, aluminum, zirconium, manganese, nickel, zinc and cobalt are also possible.

Other metal catalysts are described by Blank et al. in Progress in Organic Coatings, 1999, Vol. 35, pages 19-29. Zirconium, bismuth and aluminum compounds are used as tin and zinc-free alternatives. These are, for example, zirconium tetraacetylacetonate (eg K-KAT® 4205 from King Industries); Zirconium dionates (eg K-KAT® XC-9213; XC-A 209 and XC-6212 from King Industries); Bismuth compounds, in particular tricarboxylates (eg K-KAT® 348, XC-B221, XC-C227, XC 8203 from King Industries); Aluminum dionate (eg K-KAT® 5218 from King Industries). Tin- and zinc-free catalysts are otherwise also available, for example, under the trade name Borchi® Kat from Borchers, TK from Goldschmidt or BICAT® from Shepherd, Lausanne.

These catalysts are suitable for solvent, water-based and / or blocked systems.

Molybdenum, wofram and vanadium catalysts are described in particular for the conversion of blocked polyisocyanates under WO 2004/076519 and WO 2004/076520.

(C_nH_2n-₃O₂)- sowie (Cn+iH_2n-₂O₄)²-, wobei n für die Zahlen 1 bis 20 steht.Cesium salts can also be used as catalysts. Suitable cesium salts are those compounds in which the following anions are used: F, Ch, CIO ^" , CIO ₃ , CIO ₄ , Br, J, JO ₃ , CN, OCN, NO ₂ - , NO ₃ -, HCO ₃ -, CO ₃ 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 "} , H ₂ PO ₂ -, H ₂ PO ₄ -, HPO ₄ ² -, PO ₄ ³ -, P ₂ O ₇ ^{4 "} , (OC _n H _{2n +} i) -,

(C _n H _2n - ₃ O ₂ ) - as well as (Cn + iH _2n - ₂ O ₄ ) ² -, where n is the numbers 1 to 20.

Cesium carboxylates in which the anion is the formula are preferred

(C _n H _2n -i0 ₂ ) - as well as (C _n + iH _2n - ₂ O ₄ ) ² - with n equal to 1 to 20, obeys. Particularly preferred cesium salts have as anions monocarboxylates of the general formula (C _n H _2n -i0 ₂ ) -, where n is the numbers 1 to 20. Particular mention should be made here of formate, acetate, propionate, hexanoate and 2-ethylhexanoate.

Preferred Lewis acidic organic metal compounds are dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin dilaurate, zinc (II) dioctoate, zirconium acetylacetonate and zirconium-2, 2,6,6-tetramethyl-3,5-heptanedionate.

However, particularly preferred is dibutyltin dilaurate.

By phosphonates (C) are meant compounds having the formula

erfüllen,

fulfill,

wherein

R ¹ , R ² and R ³ independently of one another may be C ¹ -C 6 -alkyl, C 6 -C 12 -aryl and C 5 -C 12 -cycloalkyl, where the radicals mentioned are in each case by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or Heterocycles may be substituted, and R ^{3 may} additionally be hydrogen.

These may be mononuclear or polynuclear, aliphatic, cycloaliphatic and / or aromatic substituted phosphonates.

"Polynuclear" phosphonates are understood to mean those which carry a plurality of phosphonate groups within one molecule, that is to say simply organically substituted phosphorus atoms, which in turn carry two organically substituted oxygen atoms and one unsubstituted oxygen atom.

Mean in it

optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - cis-alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl , 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3,3-tetramethylbutyl, benzyl, 1-phenylethyl , 2-phenylethyl, α, α-

Dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p -methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2- Ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolan-2-yl, 1, 3 Dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2- Chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6- Methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl, C 3 -C 12 aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example phenyl, ToIyI, XyIyI, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-

Propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6 - dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, A-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl, and

optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Cs - Ci2-cycloalkyl, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as Norbornyl or norbornenyl.

Preferred radicals R ¹ and R ² are, independently of one another, C 1 -C 18 -alkyl which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, or C 3, which is optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles. Ci2-aryl, particularly preferably optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Cβ - Ci2-aryl and in particular phenyl or sterically hindered aryl.

The term "sterically hindered" means in this document that at least one, preferably both ortho positions based on the functional group carries a tert-butyl group.

Preferably, R ¹ and R ^{2 are} independently selected from the group consisting of n-butyl, phenyl and benzyl.

More preferably, R ¹ and R ^{2 are the} same.

The radical R ³ is preferably hydrogen.

The phosphonate functions primarily as a secondary antioxidant in this invention. These are usually understood by the skilled person as compounds which prevent the formation of radicals, in particular intercept and / or decompose peroxides. Optionally, at least one phenol, preferably at least one sterically hindered phenol (D) may be present, preferably at least one, more preferably exactly one phenol (D) is present. For the purposes of the invention, phenols have the function of a primary antioxidant. This is usually understood by the person skilled in the art as meaning compounds which scavenge radicals.

Examples of phenols are alkylphenols, for example o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethyl-phenol, 2,6- Di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert Butyl-2,6-dimethylphenol, or 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 4,4'-oxydiphenyl, 3,4-methylenedioxydiphenol (sesamol), 3 , 4-dimethylphenol, hydroquinone, catechol (1, 2-dihydroxybenzene), 2- (1'-methylcyclohex-1'-yl) -4,6-dimethylphenol, 2- or 4- (1'-phenyl-eth-1 '-yl) -phenol, 2-tert-butyl-6-methylphenol, 2,4,6-tris-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol , 4-tert-butylphenol, nonylphenol [1 1066-49-2], octylphenol [140-66-9], 2,6-dimethylphenol, bisphenol A, bisphenol F, bisphenol B, bisphenol C, bisphenol S, 3, 3 ', 5,5'-tetrabromobisphenol A, 2,6-di-tert-butyl-p-cresol, Koresin® from BASF AG, 3,5-di-tert-butyl-4-hydroxybenzoic acid methyl ester, 4-tert-butylcatechol, 2-hydroxybenzyl alcohol, 2-methoxy-4-methylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2-isopropylphenol, 4- isopropylphenol, 6-

Isopropyl-m-cresol, n-octadecyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) butylphenyl) butane, 1, 3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1, 3.5, -Tris- (3,5 di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyloxyethyl isocyanurate, 1,3,5-tris- (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate or pentaerythritol tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2.6 -Di-tert-butyl-4-dimethylaminomethyl-phenol, 6-iso-butyl-2,4-dinitrophenol, 6-sec-butyl-2,4-dinitrophenol, Irganox® 565, 1 141, 1 192, 1222 and 1425 from Ciba Spezialitätenchemie, octadecyl 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 3- (3', 5'-di-tert-butyl-4'- hydroxyphenyl) propionic acid hexadecyl ester, octyl 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 3-thia-1, 5-pentanediol bis - [(3', 5'-di-tert .-butyl-4'-hydroxyphenyl) propionate], 4,8-dioxa 1,1,1-undecanediol bis - [(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate], 4,8-dioxa-1,1,1-undecanediol bis - [( 3'-tert-butyl-4'-hydroxy-5'-methylphenyl) propionate], 1, 9-nonanediol bis - [(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate ], 1, 7-heptanediamine bis [3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionic acid amide], 1, 1-methanediamine bis [3- (3', 5 ' di (tert-butyl-4'-hydroxyphenyl) propionic acid amide], 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionic acid hydrazide, 3- (3', 5'-di- Methyl 4'-hydroxyphenyl) propionic acid hydrazide, bis (3-tert-butyl-5-ethyl-2-hydroxy-phen-1-yl) methane, bis (3,5-di-tert-butyl-4-hydroxy -phen-1-yl) methane, bis [3- (1'-methylcyclohex-1'-yl) -5-methyl-2-hydroxy-phen-1-yl] methane, bis (3-tert.-butyl) 2-hydroxy-5-methyl-phen- 1-yl) methane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphen-1-yl) ethane, bis (5-tert-butyl-4-hydroxy-2- methyl-phen-1-yl) sulfide, bis (3-tert-butyl-2-hydroxy-5-methylphen-1-yl) sulfide, 1,1-bis (3,4-dimethyl-2-hydroxy -phen-1-yl) -2-methylpropane, 1,1-bis (5-tert-butyl-3-methyl-2-hydroxy-phen-1-yl) -butane, 1,3,5-tris [1 '- (3 ", 5" -di-tert-butyl-4 "-hydroxy-phen-1" -yl) -meth-1'-yl] -2,4,6-trimethylbenzene, 1,1,4 Tris (5'-tert-butyl-4'-hydroxy-2'-methyl-phen-1'-yl) butane, aminophenols such as para-aminophenol, 3-diethylaminophenol, nitrosophenols such as para-nitrosophenol, p-nitroso-o-cresol, alkoxyphenols, for example 2-methoxyphenol (guaiacol, catechol monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl-4 methoxyphenol, 3,5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-dimethoxy-4-hydroxybenzyl alcohol (syringa alcohol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 4 - hydroxy-3 ethoxybenzaldehyde (ethylvanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1- (4-hydroxy-3-methoxyphenyl) ethanone (acetovanillon), eugenol, dihydroeugenol, isoeugenol, tocopherols, such as α-, β-, v-, δ- and ε-tocopherol, tocol, α-tocopherol hydroquinone, hydroquinone or hydroquinone monomethyl ether, 2,5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethyl- hydroquinone, 4-methylcatechol, tert-butylhydroquinone, 3-methylcatechol, benzoquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 3-methylcatechol, 4-methylcatechol, tert-butylhydroquinone, 4-

Ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2-methylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, and 2,3-dihydro-2,2-dimethyl 7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox®), and derivatives thereof

These are preferably those phenols which have exactly one phenolic hydroxyl group on the aromatic ring and particularly preferably those which are in the ortho position, very particularly preferably in the ortho and para position to the phenolic hydroxy group, an arbitrary substituent, preferably one Have alkyl group.

Such phenols may also be components of a polyphenolic system having a plurality of phenolic groups, such as pentaerythritol tetrakis- [β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate] (eg Irganox® 1010), Irganox® 1330, 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (eg Irganox® 31 14), in each case products of Ciba Specialty Chemicals.

Corresponding products are available, for example, under the trade names Irganox® (Ciba Specialty Chemicals), Sumilizer® from Sumitomo, Lowinox® from Great Lakes, Cyanox® from Cytec. Also conceivable are, for example, thiodiethylene-bis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate] (Irganox® 1035) and 6,6'-di-tert-butyl-2,2 ' -thiodi-p-cresol (eg Irganox® 1081), in each case products of Ciba Specialty Chemicals.

Furthermore, optionally, a solvent or solvent mixture (E) may be present.

Useful solvents are those which have no groups reactive toward isocyanate groups or blocked isocyanate groups and in which the polyisocyanates are at least 10% by weight, preferably at least 25, more preferably at least 50, most preferably at least 75, in particular at least 90 and especially at least 95 wt% are soluble.

Examples of such solvents are aromatic (including alkylated benzene and naphthalenes) and / or (cyclo) aliphatic hydrocarbons and mixtures thereof, chlorinated hydrocarbons, ketones, esters, alkoxylated Alkansäurealkylester, ethers, respectively mixtures of solvents.

As aromatic hydrocarbon mixtures, preferred are those which comprise predominantly aromatic C7- to Cu-hydrocarbons and may comprise a boiling range from 1 10 to 300 ⁰ C, more preferably toluene, o-, m- or p-xylene, trimethylbenzene isomers, tetramethylbenzene, ethylbenzene , Cumene, tetrahydronaphthalene and mixtures containing such.

Examples include the Solvesso® brands of ExxonMobil Chemical, especially Solvesso® 100 (CAS No. 64742-95-6, predominantly Cg and Cio-aromatics, boiling range about 154-178 ⁰ C), 150 (boiling range about 182 207 ⁰ C) and 200 (CAS No. 64742-94-5), as well as the Shellsol® brands from Shell, Caromax® (eg Caromax® 18) from Petrochem Carless and Hydrosol from DHC (eg as Hydrosol® A 170). Hydrocarbon mixtures of paraffins, cycloparaffins and aromatics are also available under the designations crystal oil (for example, crystal oil 30, boiling range about 158-198 ⁰ C or crystal oil. 60: CAS No. 64742-82-1), petroleum spirit (for example likewise CAS No. 64742-. 82-1) or solvent naphtha (light: boiling range about 155-180 ⁰ C, heavy: boiling range about 225-300 ⁰ C) lent commercially. The aromatic content of such hydrocarbon mixtures is generally more than 90% by weight, preferably more than 95, more preferably more than 98, and very preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.

Examples of (cyclo) aliphatic hydrocarbons include decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkanes. The content of aliphatic hydrocarbons is generally less than 5, preferably less than 2.5 and more preferably less than 1% by weight.

Esters include, for example, n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate.

Ethers are, for example, THF, dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.

Examples of ketones are acetone, diethyl ketone, ethyl methyl ketone, isobutyl methyl ketone, methyl amyl ketone and tert-butyl methyl ketone.

Surprisingly, it has been found that the solvents are problematic in terms of the problem. Patentful Polyisocyanatzu- compositions containing ketones or aromatic mixtures (for example, solvent naphtha mixtures) are particularly critical in terms of color formation on storage. In contrast, esters, ethers, and individual aromatics such as XyIoI or its isomer mixtures are less problematic. This is surprising insofar as xylenes also carry benzylic hydrogen atoms analogously to the aromatic mixtures, which could be involved in color formation. In addition, solvent naphtha mixtures, depending on the source of supply and storage times, can have significantly different effects on the color number drift when used in the polyisocyanate compositions.

Optionally, it is also possible to add at least one, preferably exactly one acidic, stabilizer (F) as a further stabilizing compound. These are Bransted acids.

Suitable organic monocarboxylic acids and / or organic polycarboxylic acids, for example linear or branched, aliphatic monocarboxylic acids having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, optionally with halogen atoms, preferably chlorine atoms and / or alkoxy groups with 1 to 12 C atoms, preferably 1 to 6 C atoms, in particular methoxy and / or ethoxy groups may be substituted, such as formic acid, acetic acid, propionic acid, 2,2-dimethylpropionic acid, butyric acid, isobutyric acid, 2-methoxybutyric acid, n-valeric acid, Chloroacetic acid, caproic acid, 2-ethylhexanoic acid, n-heptanoic acid, n-octylic acid, caprylic acid and perboronic acid, aromatic monocarboxylic acids having 6 to 12 C atoms, such as, for example, benzoic acid, toluic acid and naphthenic acid, aliphatic polycarboxylic acid having 2 to 12 C atoms. Atoms, preferably 4 to 6 C-atoms, such as oxalic acid, succinic acid, maleic acid, fumaric acid, 2-ethyl-succinic acid, glutaric acid, 2-methylglutaric acid, A dipin- acid, 2-methyl, 2,2-dimethyl-adipic acid, 1, 8-octanoic acid, 1, 10-decanoic acid and 1, 12-dodecanoic acid, aromatic dicarboxylic acids having 8 to 12 carbon atoms, such as phthalic acid, terephthalic acid and isophthalic acid Carboxylic acid chlorides, for example aliphatic and aromatic monocarboxylic acid chlorides, carboxylic acid mono- and dichlorides of aliphatic and aromatic polycarboxylic acids, preferably dicarboxylic acids, inorganic acids, such as phosphoric acid, phosphorous acid and hydrochloric acid and diesters, for example the alkyl and / or aryl diesters of phosphoric acid and / or phosphorous acid or inorganic acid chlorides such as phosphorus oxychloride or thiophyl chloride. The acidic stabilizers may be used singly or in the form of a mixture of at least two acidic stabilizers.

Preferably used as acidic stabilizers use aliphatic monocarboxylic acids having 1 to 8 carbon atoms, such as. Formic acid, acetic acid, aliphatic dicarboxylic acids having 2 to 6 C atoms, such as e.g. Oxalic acid and in particular 2-ethylhexanoic acid, chloropropionic acid and / or methoxyacetic acid.

As further paint typical additives (G) can be used for example: other antioxidants such as phosphites of the type P (OR ^a ) (OR ^b ) (OR ^C ) with R ^a , R ^b , R ^c as the same or different aliphatic or aromatic radicals (which can also build up cyclic or spiro structures), UV stabilizers such as UV absorbers and suitable radical scavengers (in particular HALS compounds, hindered amine light stabilizers), activators (accelerators), drying agents, fillers, pigments, dyes, antistatic agents, Flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents. Preference is given to UV stabilizers.

Suitable UV absorbers include oxanilides, triazines and benzotriazole (the latter available as, for example, Tinuvin® brands from Ciba Specialty Chemicals) and benzophenones (e.g., Chimassorb® 81 from Ciba Specialty Chemicals). Preferred are e.g. 95% benzene propanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy, C7-9 branched and linear alkyl esters; 5% 1-methoxy-2-propyl acetate (eg Tinuvin® 384) and α- [3- [3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxyphenyl] - 1-oxopropyl] -ω-hydroxypoly (oxo-1,2-ethanediyl) (eg Tinuvin® 1 130), in each case products eg Ciba Specialty Chemicals. DL-alpha-tocopherol, tocopherol, cinnamic acid derivatives and cyanoacrylates can also be used for this purpose.

These may be used alone or together with suitable radical scavengers, for example sterically hindered amines (often also referred to as HALS or HAS compounds; hindered amines (Light) Stabilizers) such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert - butylpiperidine or its derivatives, for. For example, bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate can be used. These are available, for example, as Tinuvin® and Chi- massorb® grades from Ciba Specialty Chemicals. Preferably in common use with Lewis acids, however, preferred are those hindered amines which are N-alkylated, for example, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) - [[3,5-bis (1,1-dimethylethyl ) -4-hydroxyphenyl] methyl] butyl malonate (eg Tinuvin® 144 from Ciba Specialty Chemicals); a mixture of bis (1, 2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1, 2,2,6,6-pentamethyl-4-piperidinyl) sebacate (eg Tinuvin® 292 from Ciba Specialty Chemicals ); or the N- (O-alkylated), such as decanoic acid, bis (2, 2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) esters, reaction products with 1, 1-dimethylethyl hydroperoxide and octane (eg Tinuvin® 123 from Ciba Specialty Chemicals).

UV stabilizers are usually used in amounts of 0.1 to 5.0 wt .-%, based on the solid components contained in the preparation.

Suitable thickeners besides free-radically (co) polymerized (co) polymers, customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite are also suitable.

As chelating agents, e.g. Ethylenediaminetic acid and its salts and ß-di-ketones are used.

Furthermore, fillers, dyes and / or pigments may also be present as component (H).

Pigments in the true sense are according to CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 with reference to Dl N 55943 particulate "practically insoluble in the application medium, inorganic or organic, colored or achromatic colorant".

In this case, virtually insoluble means a solubility at 25 ^° C. below 1 g / 1000 g of application medium, preferably below 0.5, more preferably below 0.25, even more preferably below 0.1 and in particular below 0.05 g / 1000 g application medium.

Examples of pigments in the true sense include any systems of absorption and / or effect pigments, preferably absorption pigments. Number and selection of the pigment components are not subject to any restrictions. They can be adapted to the particular requirements, for example the desired color impression, as desired, for example as described in step a). For example, all the pigment components of a standardized mixed-paint system can be based.

Effect pigments are to be understood as meaning all pigments which have a platelet-shaped structure and a decorative surface coating with special decorative color effects to lend. The effect pigments are, for example, all effect pigments which can usually be used in vehicle and industrial coating. Examples of such effect pigments are pure metal pigments; such as aluminum, iron or copper pigments; Interference pigments such as titanium dioxide coated mica, iron oxide coated mica, mixed oxide coated mica (eg with titanium dioxide and Fe2O3 or titanium dioxide and O2O3), metal oxide coated aluminum, or liquid crystal pigments.

The coloring absorption pigments are, for example, customary organic or inorganic absorption pigments which can be used in the coatings industry. Examples of organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments. Examples of inorganic absorption pigments are iron oxide pigments, titanium dioxide and carbon black.

Dyes are also colorants and differ from the pigments by their solubility in the application medium, ie they have at 25 ⁰ C, a solubility above 1 g / 1000 g in the application medium.

Examples of dyes are azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine, triarylmethane dyes. These dyes may find application as basic or cationic dyes, mordant, direct, disperse, development, vat, metal complex, reactive, acid, sulfur, coupling or substantive dyes.

Coloriferous inert fillers are understood as meaning all substances / compounds which on the one hand are coloristically inactive; ie show a low intrinsic absorption and their refractive index is similar to the refractive index of the coating medium, and on the other hand are able to influence the orientation (parallel orientation) of the effect pigments in the surface coating, ie in the applied paint film, also properties of the coating or the Coating compositions, for example hardness or rheology. In the following, examples of usable inert substances / compounds are mentioned, but without limiting the term coloristically inert topology-influencing fillers to these examples. Suitable inert fillers according to the definition can be, for example, transparent or semitransparent fillers or pigments, for example silica gels, blancfixes, diatomaceous earth, talc, calcium carbonates, kaolin, barium sulfate, magnesium silicate, aluminum silicate, crystalline silica, amorphous silica, aluminum oxide, microspheres or hollow microspheres, for example made of glass, ceramic or polymers with sizes of for example 0.1-50 microns. Furthermore, as inert fillers, any solid inert organic particles, such as, for example, urea-formaldehyde condensation products, micronized polyolefin wax and micronized amide wax, can be used. The inert fillers can also be used in each case in a mixture. Preferably, however, only one filler is used in each case. Preferred fillers include silicates, e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonate, etc.

In a preferred form polyisocyanates (A) in admixture with phosphonate (C), optionally hindered phenol (D), optionally solvent (s) (E), optionally acidic stabilizer (F), optionally additives (G) in a first step for further processing. The content of polyisocyanate is usually more than 50%, in particular 65-99.99% by weight. These mixtures are then converted in a second step by adding optionally further of components (B) to (G), and optionally (H), into the polyisocyanate compositions according to the invention.

Preferred solvents for premixes of this first step are n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2, 2-methoxyethyl acetate, and mixtures thereof, in particular with the abovementioned aromatic hydrocarbon mixtures. Such mixtures can be prepared in a volume ratio of 5: 1 to 1: 5, preferably in a volume ratio of 4: 1 to 1: 4, more preferably in a volume ratio of 3: 1 to 1: 3 and most preferably in a volume ratio of 2: 1 to 1: 2 ,

Preferred examples are butyl acetate / xylene, methoxypropyl acetate / xylene 1: 1, butyl acetate / solvent naphtha 100 1: 1, butyl acetate / Solvesso® 100 1: 2 and crystal oil 30 / Shellsol® A 3: 1.

The polyisocyanate compositions according to the invention are composed, for example, as follows:

(A) 20 to 99.998% by weight, preferably 30 to 90% by weight, particularly preferably 40-80% by weight, (B) 10 to 10000 ppm by weight, preferably 20 to 5000, particularly preferably 30 to 2000 and very particularly preferably 50 to 1000 ppm by weight,

(C) 10 to 5000 ppm by weight, preferably 20 to 2000, particularly preferably 50 to 1000 and very particularly preferably 100 to 1000 ppm by weight,

(D) 0 to 5000 ppm by weight, preferably 10 to 2000, particularly preferably 20 to 600 and very particularly preferably 50 to 200 ppm by weight, and

(E) 0 to 80, preferably 10-70%, particularly preferably 20 to 60% by weight,

(F) 0-5000 ppm by weight, preferably 20 to 500 ppm by weight,

(G) 0-5% additives.

with the proviso that the sum is always 100% by weight. If components (H) are present, they are not included in the composition of components (A) to (G).

The polyisocyanate compositions according to the invention can be used with advantage as hardener components in addition to at least one binder in polyurethane paints.

If appropriate, the reaction with binders can take place after a long period of time which requires appropriate storage of the polyisocyanate composition. Although the storage of polyisocyanate preferably takes place at room temperature, but can also be carried out at higher temperatures. In practice, heating of such Polyisocyanatzusammensetzung at 40 ⁰ C, 60 ⁰ C, even up to 80 ⁰ C quite possible.

The binders may be, for example, polyacrylate polyols, polyester polyols, polyether polyols, polyurethane polyols; polyurea; Polyester polyacrylate latpolyols; polyester polyurethane polyols; Polyurethane polyacrylate polyols, polyurethane modified alkyd resins; Fatty acid-modified polyester polyurethane polyols, copolymers with allyl ethers, graft polymers of the substance groups mentioned with e.g. different glass transition temperatures, as well as mixtures of said binders act. Preference is given to polyacrylate polyols, polyester polyols and polyether polyols.

Preferred OH numbers, measured according to DIN 53240-2, are 40-350 mg KOH / g solid resin for polyester, preferably 80-180 mg KOH / g solid resin, and 15-250 mg KOH / g solid resin for polyacrylatols, preferably 80 -160 mg KOH / g.

In addition, the binders may have an acid number according to DIN EN ISO 3682 up to 200 mg KOH / g, preferably up to 150 and particularly preferably up to 100 mg KOH / g.

Polyacrylate polyols preferably have a molecular weight M _n of at least 1000, particularly preferably at least 2000 and very particularly preferably at least 5000 g / mol. The molecular weight M _n may in principle be unlimited upwards, preferably up to 200,000, particularly preferably up to 100,000, very particularly preferably up to 80,000 and in particular up to 50,000 g / mol.

The latter can be, for example, monoesters of α, β-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (referred to in this document as "(meth) acrylic acid"), with diols or polyols which preferably have 2 to 20 C atoms and at least two hydroxypolyols. such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,4 Butanediol, 1, 5-pentanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, 6 Hexanediol, 2-methyl-1, 5-pentanediol, 2-ethyl-1,4-butanediol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-octane-1,3-diol, 2,2- Bis (4-hydroxycyclohexyl) propane, 1, 1-, 1, 2-, 1, 3- and 1, 4-bis (hydroxymethyl) -cyclohexane, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, Glycerol, trimethylololethane, trimethylolpropane, trimethylolbutane, pentaerythritol, ditrimethylolpropane, denta-pentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol, isomalt, poly -THF having a molecular weight between 162 and 4500, preferably 250 to 2000, poly-1, 3-propanediol or polypropylene glycol having a molecular weight between 134 and 2000 or polyethylene glycol having a molecular weight between 238 and 2000 be.

Preference is given to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate or 3- (acryloyloxy) -2-hydroxypropyl acrylate and particularly preferably 2-hydroxyethyl acrylate and / or 2-hydroxyethyl methacrylate.

The hydroxy-group-containing monomers are used in the copolymerization in admixture with other polymerizable, preferably free-radically polymerizable monomers, preferably those which contain more than 50% by weight of C 1 -C 20, preferably C 1 -C 4 -alkyl (meth) acrylate, (meth) acrylic acid, vinylaromatics having up to 20 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides, non-aromatic hydrocarbons having 4 to 8 carbon atoms and 1 or 2 double bonds, unsaturated nitriles and mixtures thereof. Particularly preferred are the polymers containing more than 60% by weight of C1-C10-

Alkyl (meth) acrylates, styrene and its derivatives, vinylimidazole or mixtures thereof.

In addition, the polymers may contain hydroxy-functional monomers corresponding to the above hydroxy group content and optionally other monomers, e.g. (Meth) acrylic acid glycidyl epoxyesters, ethylenically unsaturated acids, in particular carboxylic acids, acid anhydrides or acid amides.

Other polymers are e.g. Polyesterols, as are obtainable by condensation of polycarboxylic acids, in particular dicarboxylic acids with polyols, in particular diols. In order to ensure a functionality of the polyester polyol which is suitable for the polymerization, triols, tetrols, etc., as well as triacids, etc. are also used in some cases.

Polyesterpolyols are known, for example, from Ullmanns Encyklopadie der technischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. be obtained. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated. Examples include:

Oxalic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, o-phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, azelaic acid, 1-cyclohexanedicarboxylic acid or tetrahydrophthalic acid, suberic acid, azelaic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride , Tetrachlorphthalsäureanhydrid, Endomethylentetra- hydrophthalsäureanhydrid, glutaric anhydride, maleic anhydride, dimer fatty acids, their isomers and hydrogenation products and esterifiable derivatives, such as anhydrides or dialkyl esters, for example Ci-C4-alkyl esters, preferably methyl, ethyl or n-butyl esters, said acids be used. Preference is given to dicarboxylic acids of the general formula HOOC- (CH 2) _y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.

Suitable polyhydric alcohols for the preparation of the polyesterols 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1, 2-ethanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1,3-diol, 2,4-diethyloctane-1,3-diol, 1,6-hexanediol, poly-THF having a molecular weight between 162 and 4500, preferably 250 to 2000, poly-1,3-propanediol having a molecular weight between 134 and 1 178, poly-1,2-propanediol having a molecular weight between 134 and 898, polyethylene glycol having a molecular weight between 106 and 458, Neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3- and 1, 4-cyclohexanedimethanol, 1, 2-, 1, 3- or 1, 4-cyclohexanediol, trimethylolbutane, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, Threit , Erythritol, adonite (ribitol), A rabit (lyxite), xyNt, dulcitol (galactitol), maltitol or isomalt, which may optionally be alkoxylated as described above.

Alcohols of the general formula HO- (CH 2) _X -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20. Preferred are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol. Also suitable are polycarbonate diols, as can be obtained, for example, by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyester polyols.

Also suitable are lactone-based polyesterdiols, which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules. Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2) Σ-COOH, where z is a number from 1 to 20 and an H atom of a methylene unit by a C 1 to C 4 alkyl radical may be substituted. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and / or methyl-ε-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivolactone, and mixtures thereof. Suitable starter components are e.g. the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of lactones, it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.

Also suitable as polymers are polyetherols which are prepared by addition of ethylene oxide, propylene oxide or butylene oxide to H-active components. Likewise, polycondensates of butanediol are suitable.

Furthermore, it is possible to use hydroxy-functional carboxylic acids, for example dimethylolpropionic acid or dimethylolbutanoic acid.

The polymers may of course also be compounds with primary secondary amino groups.

For this purpose, the polyisocyanate composition and binder in a molar ratio of isocyanate groups to isocyanate-reactive groups of 0.1: 1 to 10: 1, preferably 0.2: 1 to 5: 1, particularly preferably 0.3: 1 to 3: 1, completely particularly preferably 0.5: 1 to 2: 1, in particular 0.8: 1 to 1, 2: 1 and especially 0.9: 1 to 1, 1: 1 mixed with each other, it being possible, where appropriate, to admix further typical constituents of the paint, and applied to the substrate.

Subsequently, ambient temperature to 140 ⁰ C, preferably 20 to 80 ⁰ C, more preferably cured to 60 ⁰ C, the paint mixture. Depending on the temperature, this usually requires no more than 12 hours, preferably up to 8 hours, more preferably up to 6, very preferably up to 4 and in particular up to 3 hours.

The substrates are coated by customary methods known to the person skilled in the art, at least one coating composition being applied to the substrate to be coated in the desired thickness and the volatile constituents of the coating composition, if appropriate with heating, being removed. If desired, this process can be repeated one or more times. The application to the substrate can in a known manner, for. B. by spraying,

Filling, doctoring, brushing, rolling, rolling, pouring, lamination, injection molding or coextrusion done.

The thickness of such a layer to be hardened may range from 0.1 μm to several mm, preferably from 1 to 2,000 μm, particularly preferably 5 to 200 μm, very particularly preferably from 5 to 60 μm (based on the lacquer in the state in FIG the solvent is removed from the paint).

Furthermore, substrates coated with a multilayer coating according to the invention are also the subject of the present invention.

Particularly suitable are such polyurethane coatings for applications in which a particularly high application safety, outdoor weather resistance, appearance, solvent, chemical and water resistance are required.

The resulting two-component coating compositions and paint formulations are suitable for coating substrates such as wood, wood veneer, paper, cardboard, textile, film, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials such as cement blocks and fiber cement boards or metals, the each optionally optionally precoated or pretreated.

Such coating compositions are suitable as or in inner or outer coatings, ie applications that are exposed to daylight, preferably of building parts, coatings on (large) vehicles and aircraft and industrial applications, commercial vehicles in the agricultural and construction sector, decoupling - bridges, buildings, electricity pylons, tanks, containers, pipelines, power plants, chemical plants, ships, cranes, piles, sheetpings, fittings, pipes, fittings, flanges, couplings, halls, roofs and structural steel, furniture, windows, doors, Parquet, Can-Coating and Coil-Coating, for floor coverings, as for parking decks or in hospitals in automotive lacquers as OEM and refinish application. Such coating compositions are preferably at temperatures between ambient temperature to 80 ⁰ C, preferably ⁰ to 60 C, particularly preferably ⁰ to 40 C. Preferably, these are those items that can not be cured at high temperatures, such as large machines, airplanes, open space vehicles, and refinish applications.

In particular, the coating compositions of the invention are used as clearcoats, basecoats and topcoats, primers and fillers.

It is an advantage of the polyisocyanate compositions according to the invention that they keep color-stable polyisocyanate mixtures in the presence of urethanization over a long period of time.

Such polyisocyanate compositions can be used as curing agents in paints, adhesives and sealants.

Due to their low color number and high color stability, they are of particular interest for coating compositions for clearcoats. In particular, refinish applications are preferred.

Examples

In the examples and reference examples, the following substances were used:

Polyisocyanates A

Polyisocyanate A-1: Polyisocyanate A-1 was prepared as follows:

1, 6-hexamethylene diisocyanate from a phosgene process was stirred in the presence of 0.7% by weight of 2-ethylhexanol at a temperature of 95 ⁰ C for 90 min. Subsequently, 65 ppm by weight of (2-hydroxypropyl) -N, N, N-trimethylammonium 2-ethylhexanoate was added as a catalyst for the trimerization and allowed to react at 65 ⁰ C.

At an NCO value of 40.5% by weight of the reaction mixture, the reaction was stopped by adding 150 ppm by weight of 2-hydroxyethyl carbamate. The excess monomeric isocyanate was removed by vacuum distillation at 145 ° C. Measured data of the pure connection: color number = 23 Hz; NCO content = 21, 4%; Viscosity = 3250 mPa ^* s.

To carry out the example, formulated as 90% by weight solution in n-butyl acetate / Solvesso® 100 = 1: 1.

Catalysts B

Catalyst B-1: dibutyltin dilaurate (DBTL, DBTDL) Phosphonate C

Phosphonate C-1: diphenyl (C 6 H ₅ O) 2 P (= O) H phosphonate C-2: Di-n-butyl phosphonate (C4H ₉ O) 2 P (= O) H phosphonate C-3: dibenzyl phosphonate (C6H ₅ CH2θ) 2P (= O) ll

Phenols D

Phenol D-1: Benzenepropionic acid, 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy-C7-C9 branched alkyl ester (e.g., Irganox® 1135 from Ciba Specialty Chemicals)

Solvent E

Solvent E-1: solvent naphtha (boiling range about 170-180 ⁰ C)

Polyisocyanates A were in about 50 wt .-% with the specified in the experiments concentrations of catalysts (B), phosphonates (C), phenols (D), in each case 10 wt .-% - ig in butyl acetate, and about 50 wt. -% solvent (E) stored in tightly sealed screw-top containers to exclude air under nitrogen. Traces of air are not excluded.

The percentages by weight are based on 100% total weight. The concentrations of the compounds (B), (C), (D) in ppm in each case undiluted state of the compounds (B) to (D) refer to the total amount of polyisocyanate (A).

The storage is carried out in each case at 50 ⁰ C in a convection oven. The color numbers are measured directly (immediately before the start of storage) and at different time intervals.

The color number measurement is performed in APHA according to DIN EN 1557 on a Lico 300 from Langejn a 5 cm measuring cuvette with a volume of 5 mL. The error tolerances for the setpoint value are 20 Hz (+/- 5, actual value 18 Hz); Setpoint 102 Hz (+/- 10, actual value 99 Hz); Reference value 202 Hz (+/- 20, actual value 197 Hz).

Each measurement was immediately compared to a reference example (Ref) that was free of stabilizer.

Table 1: Experiments with 50% A-1 (as a 90 wt% solution), 1000 ppm of catalyst B-1 (DBTL), about 50% solvent E-1 and other components according to the following table at 50 ⁰ C.

The test results show that antioxidant stabilization by Compound C-1 to C-3 and D-1 is significant.

Claims

claims 1. Polyisocyanate compositions containing (A) at least one polyisocyanate obtainable by reacting at least one monomeric isocyanate, (B) at least one compound capable of accelerating the reaction of isocyanate groups with isocyanate-reactive groups, - (C) at least one phosphonate, - (D) optionally at least one sterically hindered phenol, - (E) optionally at least one solvent - (F) optionally at least one acidic stabilizer - (G) optionally other paint-typical additives. 2. polyisocyanate compositions according to claim 1, characterized in that the monomeric isocyanate is selected from the group consisting of 1, 6-hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 4,4'-di ( isocyanatocyclohexyl) methane and 2,4'-di (isocyanatocyclohexyl) methane. 3. Polyisocyanate compositions according to claim 1 or 2, characterized in that the polyisocyanate (A) has isocyanurate, biuret, urethane and / or allophanate groups and / or Iminooxadiazindiongruppen. Polyisocyanate compositions according to one of claims 1 or 2, characterized in that the polyisocyanate is an isocyanate-containing polyisocyanate having a viscosity of 600-1500 mPa ^* s, a low-viscosity urethane and / or allophanate having a viscosity of 200-1600 mPa ^* s containing polyisocyanate. 5. Polyisocyanate compositions according to one of the preceding claims, characterized in that the compound (B) is a Lewis acidic organic metal compound. 6. Polyisocyanate compositions according to claim 4, characterized in that the Lewis acid organic metal compound contains a metal selected from the group consisting of tin, zinc, iron, titanium, aluminum, zirconium, manganese, nickel, cobalt, bismuth and cesium , preferably selected from the group consisting of tin and zinc. Polyisocyanate compositions according to any one of the preceding claims, characterized in that compound (C) is a phosphonate of the formula

fulfill, wherein R ¹ , R ² and R ³ independently of one another may denote C 1 -C 6 -alkyl, C 6 -C 12 -aryl and C 2 -C 12 -cycloalkyl, where the radicals mentioned are each substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles may be, and R ^{3 may} additionally be hydrogen, which may be mononuclear or polynuclear phosphonates. 8. Polyisocyanate compositions according to one of the preceding claims, characterized in that at least one compound (D) is present which has exactly one phenolic hydroxyl group per aromatic ring and in the at least one, preferably both ortho positions, based on the functional group carries tert-butyl group. 9. Polyisocyanate compositions according to one of the preceding claims, characterized in that the compound (D) is 2,6-bis-tert-butyl-4-methyl-phenol or 3,5-bis (1, 1-dimethyl ethyl) -4-hydroxy-C7-C9 branched alkyl ester of benzenepropionic acid. 10. Polyisocyanate compositions according to one of the preceding claims, characterized in that at least one solvent (E) is present, selected from the group consisting of aromatic hydrocarbons, (cyclo) aliphatic hydrocarbons, ketones, esters, Ethers and carbonates, in particular from distillation cuts of aromatic hydrocarbons with predominantly Cg and Cio-aromatics, and from dialkyl ketones. 1 1. A process for the stabilization of polyisocyanate compositions containing in addition to polyisocyanate (A) at least one compound (B), which is capable of accelerating the reaction of isocyanate groups with isocyanate-reactive groups, characterized in that the Polyisocya- natzusammensetzung additionally at least one phosphonate (C), and if appropriate, at least one phenol (D), optionally solvent (E) and optionally other paint typical additives (F) added. 12. A process for the preparation of polyurethane coatings, characterized in that a polyisocyanate composition according to one of the claims 1 to 12 with at least one binder which contains isocyanate-reactive groups. 13. A process for the preparation of polyurethane coatings, characterized in that a polyisocyanate composition according to any one of claims 1 to 1 1 with at least one binder selected from the group consisting of polyacrylate polyols, polyester polyols, polyether polyols, polyurethane polyols, polyurea polyols, polyetherols, polycarbonates, polyester polyacrylate Polyolen, Polyesterpolyurethanpolyolen, Polyurethanpolyacry- latpolyolen, polyurethane-modified alkyd resins, fatty acid-modified polyester polyurethane polyols, copolymers with allyl ethers and Co- or graft polymers from the substance groups mentioned. 14. Use of polyisocyanate according to one of the claims 1 to 1 1 as a curing agent in polyurethane coatings. 15. Use of polyisocyanate compositions according to any one of claims 1 to 1 1 as a curing agent in applications in which the polyisocyanate is cured with a binder at a temperature up to 80 ⁰ C. 16. Use of Polyisocyanatzusammensetzungen according to any one of claims 1 to 1 1 as a curing agent in refinish, wood or Großfahrzeug- coatings applications. 17. A process for the preparation of polyurethane coatings, characterized in that at least one polyisocyanate with at least one compound (B), which is capable of accelerating the reaction of isocyanate groups with isocyanate-reactive groups, at least one phosphonate (C), optionally at least one phenol (D), optionally at least one solvent (E), optionally at least one acidic stabilizer (F) and optionally at least one paint typical additive mixed, then mixed with at least one binder and then applied to the substrate and cured. 18. Use of polyisocyanate compositions according to any one of claims 1 to 1 1 as a curing agent in paints, adhesives and sealants.