DE102009016173A1 - protective lacquer - Google Patents

Abstract

The invention relates to coating compositions with a high solids content based on polyurea polymers and their use as a protective topcoat.

Description

The This invention relates to high solids coating compositions based on polyurea polymers and their use as a protective topcoat.

reaction products aliphatic or cycloaliphatic polyamines with fumaric acid esters and / or maleic esters, so-called polyaspartic esters, are as formulation ingredients for low-solvent or -free two component (2K) polyurethane or polyurea paints known.

As hindered secondary amines have polyaspartic esters, as described for example in the EP-A 0 403 921 as a main binder or as a reactive diluent for hydroxy-functional lacquer binders, a for aliphatic amines relatively moderate reactivity to aliphatic polyisocyanates, but still allows rapid curing of the coatings even at low temperatures. With their help, hard and elastic coatings can be obtained, which are characterized by high abrasion and solvent resistance and good weathering stability. Due to their low intrinsic viscosity, the use of polyaspartic acid esters in coating formulations significantly reduces volatile organic compounds (VOC) levels.

Coating compositions based on polyaspartic acid esters have been described for a large number of different applications, for example for vehicle repair and large vehicle painting (eg. EP-A 0 470 461 . EP-A 0 531 249 . EP-A 1 581 575 ), the leather and textile coating (eg EP-A 1 277 876 ) or as a binder for electrical insulating paints (eg. EP-A 1 199 320 ).

Polyaspartic esters have also been used as part of corrosion protection coatings. For example, this describes EP-A 0 689 881 Binder combinations with high solids contents up to 95 wt .-%, consisting of polyaspartic acid esters, polyketimines or -aldiminen and preferably aliphatic or cycloaliphatic lacquer polyisocyanates as crosslinking component, for coating steel parts.

Across from conventional 2K-PUR systems carry these polyol-free pure polyurea due to the very low solvent content and the faster drying for the user to one noticeable increase in productivity. To increase productivity In addition to the faster drying essentially carries the Possibility to bubble-free thick layers in one operation to apply. Compared to conventional coating systems Therefore, it is possible to achieve the same total layer thicknesses with less coating layers achieve. Thus, in the case of a three-coat paint system, which is usually consists of primer, interlayer and topcoat, for example to dispense with the intermediate layer, without sacrificing the quality the paintwork suffers. Compared to common ones two-layer epoxy-priming and anti-corrosion coatings Polyurethane topcoat can reduce the paint time when using a single-coat topcoat system based on polyaspartic esters and polyisocyanates even be halved without the primer.

In spite of the described ecological as well as economical Advantages could be such single-layer corrosion protection coatings in practice so far not prevail widely. The cause of beer lies in the inadequate adhesion of the polyaspartic ester systems on some special metallic substrates, such as B. on aluminum, galvanized or cold rolled steel containing a primer layer indispensable.

task The present invention was therefore, new solid-rich 2K coating systems based on polyaspartic esters and to provide polyisocyanate crosslinkers which improved adhesion on critical metallic surfaces and thus have a direct application to unprimed Materials allow.

These Task could be closer with the provision of the following be dissolved described coating agent.

• A) mindestens ein Amin der Formel (I)
  
  in welcher X für einen n-wertigen, gegenüber Isocyanatgruppen inerten Rest steht, wie er durch Entfernen der primären Aminogruppen aus einem organischen Amin des Molekulargewichtsbereiches 60 bis 6000 mit n primären aliphatisch und/oder cycloaliphatisch gebundenen Aminogruppen erhalten wird, der gegebenenfalls ein oder mehrere Heteroatome und/oder weitere, gegenüber Isocyanatgruppen reaktive und/oder bei Temperaturen bis 100°C inerte funktionelle Gruppen enthält, R¹ und R² für gleiche oder verschiedene organische Reste mit 1 bis 18 Kohlenstoffatomen stehen und n für eine ganze Zahl ≥ 1 steht,
• B) gegebenenfalls weitere gegenüber Isocyanatgruppen reaktive Komponenten,
• C) eine Silangruppen enthaltende Polyisocyanatkomponente,
• D) gegebenenfalls organische Lösungsmittel und
• E) gegebenenfalls weitere Hilfs- und Zusatzmittel,

mit der Massgabe, dass die Komponenten A), gegebenenfalls B) und C) in solchen Mengenverhältnissen vorliegen, dass auf jede gegenüber Isocyanaten reaktive Gruppe der Komponenten A) und gegebenenfalls B) 0,7 bis 2,0 Isocyanatgruppen der Komponente C) entfallen.The present invention therefore relates to coating compositions containing

• A) at least one amine of the formula (I)
  
  in which X is an n-valent, isocyanate-inert radical, as obtained by removing the primary amino groups from an organic amine in the molecular weight range 60 to 6000 with n primary aliphatic and / or cycloaliphatically bonded amino groups, optionally one or more heteroatoms and / or further isocyanate-reactive and / or inert at temperatures up to 100 ° C containing functional groups, R ¹ and R ^{2 are} identical or different organic radicals having 1 to 18 carbon atoms and n is an integer ≥ 1,
• B) optionally further isocyanate-reactive components,
• C) a silane group-containing polyisocyanate component,
• D) optionally organic solvents and
• E) optionally further auxiliaries and additives,

with the proviso that the components A), optionally B) and C) are present in such proportions that account for each isocyanate-reactive group of components A) and optionally B) 0.7 to 2.0 isocyanate groups of component C).

object The invention also relates to the use of these coating compositions for coating any substrates, in particular as corrosion protection topcoat.

in welcher
X für einen n-wertigen, gegenüber Isocyanatgruppen inerten Rest steht, wie er durch Entfernen der primären Aminogruppen aus einem organischen Amin des Molekulargewichtsbereiches 60 bis 6000 mit n primären aliphatisch und/oder cycloaliphatisch gebundenen Aminogruppen erhalten wird, der gegebenenfalls ein oder mehrere Heteroatome und/oder weitere, gegenüber I socyanatgruppen reaktive und/oder bei Temperaturen bis 100°C inerte funktionelle Gruppen enthält,
R¹ und R² für gleiche oder verschiedene organische Reste mit 1 bis 18 Kohlenstoffatomen stehen und
n für eine ganze Zahl ≥ 1 steht.The component A) present in the coating compositions of the invention are amines of the formula (I)

in which
X is an n-valent isocyanate-inert radical as obtained by removing the primary amino groups from an organic amine of the molecular weight range 60 to 6000 with n primary aliphatically and / or cycloaliphatically bonded amino groups which optionally has one or more heteroatoms and / or further functional groups which are reactive toward isocyanate groups and / or which are inert at temperatures of up to 100 ° C.,
R ¹ and R ^{2 represent the} same or different organic radicals having 1 to 18 carbon atoms and
n stands for an integer ≥ 1.

in welcher X und n die oben angegebene Bedeutung aufweisen, mit Fumarsäureestern und/oder Maleinsäureestern der Formel (III) R¹ OOC–CH=CH-COOR² (III)in welcher R1 und R2 die oben angegebene Bedeutung aufweisen, erfolgen.The preparation of such amines A) - hereinafter also referred to as aspartic acid ester or polyaspartic acid ester - is known in principle and can, for example, as in EP-A 0 403 921 . EP-A 0 689 881 or EP-A 0 816 326 described by reaction of a primary amino-containing component of the formula (II)

in which X and n have the abovementioned meaning, with fumaric acid esters and / or maleic acid esters of the formula (III) R ¹ OOC-CH = CH-COOR ² (III) in which R1 and R2 have the abovementioned meaning, take place.

Suitable amines for the preparation of the polyaspartic esters A) are, for example, difunctional amines, ie those of the formula (II) in which n is 2, such as. As ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diamino-2-methylpentane (Dytek ^® A Fa. DuPont), 1,6-diaminohexane, 2,5-diamino-2,5 dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl- 5-aminomethylcyclohexane (IPDA), 1,3-diamino-2- and / or 4-methylcyclohexane, isopropyl-2,4- and / or 2,6-diaminocyclohexane, 1,3-bis (aminomethyl) -cyclohexane, 2,4'- and / or 4,4'-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (Laromin C 260 ^®, BASF SE, Ludwigshafen, DE), the isomeric, a Methyl group as a core substituent diaminodicyclohexylmethane (C-monomethyl-diaminodicyclohexylmethane), 3 (4) -aminomethyl-1-methylcyclohexylamin and 1,3-bis (aminomethyl) benzene.

suitable tri- or higher-functional amines for the preparation of polyaspartic esters A) are those of the formula (II) in which n is an integer Number ≥ 3 stands, such as. B. 4-aminomethyl-1,8-octanediamine, 2,2 ', 2' '- triaminotriethylamine, 1,3,5-tris (aminomethyl) -2,4,6-triethylbenzene, tris-1,1,1-aminoethylethane, 1,2,3-triamionopropane, Tris (3-aminopropyl) amine and N, N, N ', N'-tetrakis (2-aminoethyl) ethylenediamine.

suitable Amines (II) for the production of aspartic acid esters or Polyaspartic esters A) are in principle also monoamines (n = 1) and diamines (n = 2), the others, in the temperature range of 20 to 200 ° C to isocyanate-reactive groups contain, for example, amino alcohols, such as. B. 2-aminoethanol, the isomeric aminopropanols and -butanols, 3-amino-1,2-propanediol and 1,3-diamino-2-propanol.

Also, low molecular weight polyether polyamines having aliphatically bonded primary amino groups, such as those marketed under the name Jeffamine ^® (Huntsman Performance Products, The Woodlands, Texas, USA), are in principle suitable amino components for the preparation of polyaspartic esters A).

preferred However, amino components are those of the formula (II) in which n is 2, in particular aliphatic and / or cycloaliphatic Diamines of the type mentioned above. Very particularly preferred amino components for the preparation of the polyaspartic esters A) are 1,5-diamino-2-methylpentane, 2,4'- and / or 4,4'-diamino-dicyclohexylmethane and / or 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane.

Fumaric acid diesters or maleic diesters of the formula (III) are used in the preparation of the aspartic acid esters or polyaspartic esters A), in which the radicals R ¹ and R ^{2 represent} identical or different radicals and organic radicals having 1 to 18, preferably 1 to 9 , particularly preferably 1 to 4, mean carbon atoms.

Preference is given to using maleic acid esters of formula (III) in which the radicals R ¹ and R ^{2 represent} identical or different radicals and are a methyl, ethyl, n-butyl or 2-ethylhexyl radical. Very particularly preferred polyaspartic esters A) are those which have been prepared using diethyl maleate.

The Preparation of aspartic acid esters or polyaspartic esters A) can be used both in solution and solvent-free be performed. In both cases occurs preferably an equimolar reaction of the amine (II) with the fumaric acid diester and / or maleic diester (III). For targeted variation of application properties can the equivalence ratio of maleic acid ester and / or fumaric acid esters (III) to amino groups of the component (II) from 1.2: 1 to 1: 2. In the case, that in the coating composition according to the invention Mixtures of aspartic acid esters or polyaspartic esters A) can be used, the preparation of polyaspartic esters carried out separately or in a reaction vessel.

Next the amines A), the inventive Coating agent optionally further to isocyanate groups containing reactive group-containing components B).

aufweisen. Diese Verbindungen B), die im Rahmen der vorliegenden Erfindung als Polyaldimine bzw. Polyketimine bezeichnet werden, weisen in der Regel Molekulargewichte von 112 bis 6500, vorzugsweise von 140 bis 2500, besonders bevorzugt von 140 bis 458, auf.These are, for example, compounds which contain at least two structural elements of the formula (IV)

exhibit. These compounds B), which are referred to as polyaldimines or polyketimines in the context of the present invention, generally have molecular weights of from 112 to 6500, preferably from 140 to 2500, particularly preferably from 140 to 458.

in welcher
R³ und R⁴ für gleiche oder verschiedene Reste stehen und Wasserstoff oder inerte organische Reste, wie z. B. Kohlenwasserstoffreste mit bis zu 8 Kohlenstoffatomen, insbesondere Alkylreste mit 1 bis 8 Kohlenstoffatomen bedeuten, und wobei die Reste R³ und R⁴ auch zusammen mit dem Kohlenstoffatom einen 5- oder 6-gliedrigen cycloaliphatischen Ring bilden können, mit der Massgabe, dass die Reste R³ und R⁴ nicht gleichzeitig für Wasserstoff stehen, und
X die oben bei der Beschreibung der Amine A) genannte Bedeutung aufweist und
m für eine ganze Zahl ≥ 2 steht.The preferred polyaldimines or polyketimines optionally used as component B) include compounds of the formula (V)

in which
R ³ and R ^{4 are the} same or different radicals and hydrogen or inert organic radicals, such as. B. hydrocarbon radicals having up to 8 carbon atoms, in particular alkyl radicals having 1 to 8 carbon atoms, and wherein the radicals R ³ and R ⁴ together with the carbon atom can form a 5- or 6-membered cycloaliphatic ring, with the proviso that the Radicals R ³ and R ^{4 are} not simultaneously hydrogen, and
X has the meaning given above in the description of amines A) and
m stands for an integer ≥ 2.

Particular preference is given to compounds of the formula (V) in which all the radicals R ^{3 are} hydrogen, the radicals R ^{4 are} hydrocarbon radicals having up to 8 carbon atoms and m = 2.

und weisen vorzugsweise ein Molekulargewicht von 58 bis 198 (Ketone) bzw. 44 bis 128 (Aldehyde) auf.The aldehydes or ketones which can be used for the preparation of the polyaldimines or polyketimines correspond to the formula (VI)

and preferably have a molecular weight of 58 to 198 (ketones) and 44 to 128 (aldehydes).

suitable Aldehydes for the preparation of the optionally used as component B) Polyaldimines are, for example, acetaldehyde, propionaldehyde, n-butyraldehyde, Isobutyraldehyde, trimethylacetaldehyde, 2,2-dimethylpropanal, 2-ethylhexanal, 3-cyclohexane-1-carboxaldehyde, hexanal, heptanal, octanal, valeraldehyde, Benzaldehyde, tetrahydrobenzaldehyde, hexahydrobenzaldehyde, propargylaldehyde, p-tolualdehyde, phenylethanal, 2-methylpentanal, 3-methylpentanal, 4-methylpentanal, sorbaldehyde.

Especially preferred are n-butyraldehyde, isobutyraldehyde, trimethylacetaldehyde, 2-ethylhexanal and hexahydrobenzaldehyde.

suitable Ketones for the preparation of the optionally used as component B) Polyketimines are, for example, acetone, methyl ethyl ketone, methyl propyl ketone, Methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, Methyl n-amyl ketone, methyl isoamyl ketone, methyl heptyl ketone, methyl undecyl ketone, Diethyl ketone, ethyl butyl ketone, ethyl amyl ketone, diisopropyl ketone, Diisobutyl ketone, cyclohexanone, cyclopentanone, methylcyclohexanone, Isophorone, 5-methyl-3-heptanone, 1-phenyl-2-propanone, acetophenone, Methyl nonyl ketone, dinonyl ketone, 3,3,5-trimethylcyclohexanone.

Especially Cyclopentanone, cyclohexanone, methylcyclopentanone, Methylcyclohexanone, 3,3,5-trimethylcyclopentanone, cyclobutanone, Methylcyclobutanone, acetone, methyl ethyl ketone, methyl isobutyl ketone.

Of course can also be any mixtures of different ketones or Aldehydes and mixtures of ketones with aldehydes used to achieve special properties.

at for the preparation of the optionally in the inventive Coating agents used as component B) polyaldimines Polyketimines used are polyamines to those already mentioned above in connection with the preparation of polyaspartic esters A) explicitly described amines of the general formula (II), in where n is an integer ≥ 2, or any Mixtures of such polyamines. Preferred polyamine for the preparation of component B) is 1-amine 3,3,5-trimethyl-5-aminomethylcyclohexane (IPDA). This is very particularly preferred by reaction of IPDA Polyaldimine obtainable with isobutyraldehyde.

The Production of the polyaldimines or polyketimines B) takes place according to known methods by reaction of the starting components while maintaining a stoichiometric ratio of amino groups to aldehyde or keto groups of 1: 1 to 1: 1.5. Optionally, can be used to accelerate the reaction catalytic Amounts of acidic substances such. For example, p-toluenesulfonic acid, Hydrogen chloride, sulfuric acid or aluminum chloride mitverwendet become.

The Implementation is generally within the temperature range from 20 to 180 ° C, wherein the reaction optionally under Use of an entraining agent (eg toluene, xylene, cyclohexane and octane) to remove the water of reaction carried out so long until the calculated amount of water (1 mole of water per mole of primary Amino group) is split off or split off until no more water becomes. Subsequently, the phases are separated or the entraining agent and optionally present unreacted starting materials by distillation separated. The products thus obtained can be used without further Purification as component B) in the inventive Coating agents are used.

Further, also as isocyanate-reactive groups containing component B) for the inventive Coating compositions suitable compounds are the usual Polyurethane compounds known from polyurethane chemistry, such as z. Example, polyester polyols, polyether polyols and / or polyacrylate polyols.

suitable Polyester polyols B) are, for example, those of a middle, from functionality and hydroxyl number of calculable molecular weight from 200 to 3000, preferably from 250 to 2500, having a hydroxyl group content from 1 to 21 wt .-%, preferably 2 to 18 wt .-%, as they are in a conventional manner by implementation of polyvalent Alcohols with minor amounts of polybasic carboxylic acids, corresponding carboxylic acid anhydrides, corresponding polycarboxylic acid esters of lower alcohols or lactones.

to Preparation of these polyester polyols suitable polyhydric alcohols are especially those of the molecular weight range 62 to 400 such as 1,2-ethanediol, 1,2- and 1,3-propanediol, the isomeric butanediols, Pentanediols, hexanediols, heptanediols and octanediols, 1,2- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4 '- (1-methylethylidene) biscyclohexanol, 1,2,3-propanetriol, 1,1,1-trimethylolethane, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 2,2-bis (hydroxymethyl) -1,3-propanediol or 1,3,5-tris (2-hydroxyethyl) isocyanurate.

The acids used to prepare the polyester polyols B) or acid derivatives may be aliphatic, cycloaliphatic and / or heteroaromatic nature and optionally, for. B. by halogen atoms, substituted and / or unsaturated. Examples of suitable acids are, for example, polybasic carboxylic acids the molecular weight range 118 to 300 or their derivatives such as for example, succinic acid, adipic acid, sebacic acid, Phthalic acid, isophthalic acid, trimellitic acid, Phthalic anhydride, tetrahydrophthalic acid, maleic acid, Maleic anhydride, dimeric and trimeric fatty acids, Terephthalic acid dimethyl ester and terephthalic acid bis-glycol ester.

to Preparation of the polyester polyols B) may also be any Mixtures of these exemplified starting compounds used become.

suitable Polyesterpolyols B) are also those which are known per se Way of lactones and simple polyhydric alcohols, such. As the above exemplified, as starter molecules make ring opening. Suitable lactones for the preparation of these polyester polyols are, for example, β-propiolactone, γ-butyrolactone, γ- and δ-valerolactone, ε-caprolactone, 3,5,5- and 3,3,5-trimethylcaprolactone or any mixtures of such lactones.

The Preparation of these lactone polyesters is generally carried out in the presence of catalysts such as Lewis or Brönstedt acids, organic tin or titanium compounds at temperatures of 20 to 200 ° C, preferably 50 to 160 ° C.

Suitable polyether polyols B) are, for example, those having a mean molecular weight, which can be calculated from functionality and hydroxyl number, of 200 to 6000, preferably 250 to 4000, having a hydroxyl group content of 0.6 to 34% by weight, preferably 1 to 27% by weight. , as they are accessible in a conventional manner by alkoxylation of suitable starter molecules. For the preparation of these polyether polyols, any polyhydric alcohols, for example those of the molecular weight range 62 to 400, as described above in the preparation of polyester polyols, can be used as starter molecules the.

For the alkoxylation reaction suitable alkylene oxides are in particular Ethylene oxide and propylene oxide, in any order or also be used in a mixture in the alkoxylation reaction can.

suitable Polyacrylatpoylole B) are for example those of a middle from functionality and hydroxyl number of calculable molecular weight from 800 to 50,000, preferably from 1,000 to 20,000, with one Hydroxyl group content of 0.1 to 12 wt .-%, preferably 1 to 10, as in a conventional manner by copolymerization Hydroxyl-containing olefinically unsaturated monomers can be prepared with hydroxyl-free olefinic monomers.

Examples for suitable monomers for the preparation of the polyacrylate polyols B) are vinyl or vinylidene monomers such. Styrene, α-methylstyrene, o- or p-chlorostyrene, o-, m- or p-methylstyrene, p-tert-butylstyrene, acrylic acid, Acrylonitrile, methacrylonitrile, acrylic and methacrylic acid esters of alcohols having up to 8 carbon atoms, such as. Ethyl acrylate, Methyl acrylate, n- or isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate or isooctyl methacrylate, diesters of fumaric acid, itaconic acid or maleic acid with alcohols having from 4 to 8 carbon atoms, Acrylic acid amide, methacrylamide, vinyl ester of alkane monocarboxylic acids having 2 to 5 carbon atoms, such as As vinyl acetate or vinyl propionate, hydroxyalkyl esters of Acrylic acid or methacrylic acid having 2 to 4 carbon atoms in the hydroxyalkyl, such as. 2-hydroxyethyl, 2-hydroxypropyl, 4-Hydroxybutyl-, Trimethylolpropanmono- or Pentae rythritmonoacrylat or methacrylate, as well as any mixtures of such by way of example mentioned monomers.

In the coating compositions of the invention can the said isocyanate-reactive components B) optionally also in the form of any mixtures with each other be used.

Case at all the components B) come here in an amount of up to 50 wt .-%, preferably up to 40% by weight, more preferably up to 30% by weight, based on the total amount of components A) and B) are used.

When Crosslinker component C) contain the inventive Coating agents Silane-containing polyisocyanate components.

These are, for example, the known reaction products of low-monomer aliphatic and / or cycloaliphatic lacquer polyisocyanates with molar amounts of isocyanate-reactive silane units relative to the content of isocyanate groups. Suitable silane-containing polyisocyanates C) are, for example, those in WO 2003/054049 . JP-A 2005 015644 and EP-A 1 273 640 described reaction products of aliphatic or cycloaliphatic polyisocyanates, such as. Polyisocyanurates of 1,6-diisocyanatohexane (HDI) or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IP-DI), with secondary, N-alkyl-substituted aminoalkyltrialkoxysilanes or N, N-bis- (3-trialkoxysilylpropyl) -amines or the in EP-B 0 994 139 claimed reaction products of aliphatic or cycloaliphatic polyisocyanates with substoichi quantities of alkoxysilane-functional aspartic acid esters, as described in the EP-A 0 596 360 be described as reactants for isocyanate-functional compounds. Also suitable as crosslinking component C) are reaction products of aliphatic or cycloaliphatic polyisocyanates with substoichiometric amounts of alkoxysilane-functional aspartic acid esters or secondary aminoalkylsilanes WO 02/058569 known.

• c1) mindestens eines aus der Reaktion von Aminosilanen mit cyclischen Carbonaten bzw. Lactonen erhältlichen Silangruppen aufweisenden Hydroxyurethans und/oder Hydroxyamids

mit einer bezogen auf die NCO-reaktiven Gruppen der Komponente c1) molar überschüssigen Menge an

• c2) mindestens einem Diisocyanat mit aliphatisch, cycloaliphatisch, araliphatisch und/oder aromatisch gebundenen Isocyanatgruppen und gegebenenfalls nachfolgender Entfernung des nicht umgesetzten Diisocyanatüberschusses erhalten wurden.

In the coating compositions according to the invention, however, the polyisocyanate component C) used is preferably allophanate polyisocyanates containing silane groups, which are prepared by reacting

• c1) at least one of the reaction of aminosilanes with cyclic carbonates or lactones available silane groups having hydroxyurethane and / or hydroxyamide

with a relation to the NCO-reactive groups of component c1) molar excess amount

• c2) at least one diisocyanate having aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups and optionally subsequent removal of the unreacted diisocyanate excess were obtained.

The preparation of such silane-containing allophanate polyisocyanates is in the context of underlying invention. It is carried out by reacting silane-containing hydroxyurethanes or hydroxyamides which are accessible from aminoalkylsilanes with cyclic carbonates or lactones with ring opening, with excess amounts of monomeric diisocyanates, and is the subject of EP-A 2 014 692 ,

starting compounds c1) for the preparation of the silane-containing polyisocyanate component C) particularly suitable allophanate polyisocyanates are any Reaction products of aminosilanes with cyclic carbonates or Lactones.

in welcher
R⁵, R⁶ und R⁷ für gleiche oder verschiedene Reste stehen und jeweils einen gesättigten oder ungesättigten, linearen oder verzweigten, aliphatischen oder cycloaliphatischen oder einen gegebenenfalls substituierten aromatischen oder araliphatischen Rest mit bis zu 18 Kohlenstoffatomen bedeuten, der gegebenenfalls bis zu 3 Heteroatome aus der Reihe Sauerstoff, Schwefel, Stickstoff enthalten kann,
Y für einen linearen oder verzweigten organischen Rest mit mindestens 2 Kohlenstoffatomen steht, der gegebenenfalls bis zu 2 Iminogruppen (-NH-) enthalten kann,
und
R⁸ für Wasserstoff, einen gesättigten oder ungesättigten, linearen oder verzweigten, aliphatischen oder cycloaliphatischen oder einen gegebenenfalls substituierten aromatischen oder araliphatischen Rest mit bis zu 18 Kohlenstoffatomen oder einen Rest der Formel

steht, in welchem R⁵, R⁶, R⁷ und Y die vorstehend angegebene Bedeutung haben.Suitable aminosilanes for preparing the starting compounds c1) are, for example, those of the general formula (VII)

in which
R ⁵ , R ⁶ and R ^{7 are} identical or different radicals and are each a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted aromatic or araliphatic radical having up to 18 carbon atoms, optionally up to 3 heteroatoms the series may contain oxygen, sulfur, nitrogen,
Y is a linear or branched organic radical having at least 2 carbon atoms, which may optionally contain up to 2 imino groups (-NH-),
and
R ^{8 is} hydrogen, a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted aromatic or araliphatic radical having up to 18 carbon atoms or a radical of the formula

in which R ⁵ , R ⁶ , R ⁷ and Y have the meaning given above.

suitable Aminosilanes are, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyltributoxysilane, 3-aminopropylphenyldiethoxysilane, 3-aminopropylphenyldimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 2-aminoisopropyltrimethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldimethoxysilane, 4-aminobutylmethyldiethoxysilane, 4-aminobutylethyldimethoxysilane, 4-aminobutylethyldiethoxysilane, 4-aminobutyldimethylmethoxysilane, 4-aminobutylphenyldimethoxysilane, 4-aminobutylphenyldiethoxysilane, 4-amino (3-methylbutyl) methyldimethoxysilane, 4-amino (3-methylbutyl) methyldiethoxysilane, 4-amino (3-methylbutyl) trimethoxysilane, 3-aminopropylphenylmethyl-n-propoxysilane, 3-aminopropylmethyldibutoxysilane, 3-aminopropyldiethylmethylsilane, 3-aminopropylmethylbis (trimethylsiloxy) silane, 11-aminoundecyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N- (n-butyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltris (2-ethylhexoxy) silane, N- (6-aminohexyl) -3-aminopropyltrimethoxysilane, N-benzyl-N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, Bis (3-trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) amine, (Aminoethylaminomethyl) phenethyltrimethoxysilane, N-vinylbenzyl-N- (2-aminoethyl) -3-aminopropylpolysiloxane, N-vinylbenzyl-N (2-aminoethyl) -3-aminopro-pylpolysiloxane, 3-ureidopropyltriethoxysilane, 3- (m-aminophenoxy) -propyltrimethoxysilane, m- and / or p-aminophenyltrimethoxysilane, 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, 3-aminopropylmethylbis (trimethylsiloxy) silane, 3-aminopropyltris (trimethylsiloxy) silane, 3-Aminopropylpentamethyldisiloxan or any mixture of such Aminosilanes.

steht, in welchem R⁵, R⁶, R⁷ und Y die vorstehend angegebene Bedeutung haben.Preferred aminosilanes for preparing the starting component c1) are those of the general Formula (VII), in which
R ⁵ , R ⁶ and R ^{7 are the} same or different radicals and are each a saturated, linear or branched, aliphatic or cycloaliphatic radical having up to 6 carbon atoms, which may optionally contain up to 3 oxygen atoms,
Y is a linear or branched alkylene radical having 2 to 10 carbon atoms, which may optionally contain up to 2 imino groups (-NH-),
and
R ^{8 is} hydrogen, a saturated, linear or branched, aliphatic or cycloaliphatic radical having up to 6 carbon atoms or a radical of the formula

in which R ⁵ , R ⁶ , R ⁷ and Y have the meaning given above.

steht, in welchem R⁵, R⁶, R⁷ und Y die vorstehend angegebene Bedeutung haben.Particularly preferred aminosilanes for preparing the starting component c1) are those of the general formula (VII) in which
R ⁵ , R ⁶ and R ⁷ each represent alkyl radicals having up to 6 carbon atoms and / or alkoxy radicals containing up to 3 oxygen atoms, with the proviso that at least one of R ⁵ , R ⁶ and R ⁷ for such Alkoxy radical,
Y is a linear or branched alkylene radical having 3 or 4 carbon atoms, and
R ^{8 is} hydrogen, a methyl radical or a radical of the formula

in which R ⁵ , R ⁶ , R ⁷ and Y have the meaning given above.

steht, in welchem R⁵, R⁶, R⁷ und Y die vorstehend angegebene Bedeutung haben.Particularly preferred aminosilanes for preparing the starting component c1) are those of the general formula (VII) in which
R ⁵ , R ⁶ and R ^{7 are} each methyl, methoxy and / or ethoxy, with the proviso that at least one of R ⁵ , R ⁶ and R ^{7 is} a methoxy or ethoxy radical,
Y is a propylene radical (-CH ₂ -CH ₂ -CH ₂ -), and
R ^{8 is} hydrogen, a methyl radical or a radical of the formula

in which R ⁵ , R ⁶ , R ⁷ and Y have the meaning given above.

All particularly preferred aminosilanes are aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane and / or 3-aminopropylmethyldiethoxysilane.

at the preparation of the starting compounds c1) for the inventive Processes are called aminosilanes with any cyclic Carbonates and / or lactones reacted with ring opening.

Suitable cyclic carbonates are in particular those having 3 or 4 carbon atoms in the ring, which may optionally also be substituted, such as. 1,3-dioxolan-2-one (ethylene carbonate, EC), 4-chloro-1,3-dioxolan-2-one, 4,5-dichloro-1,3-dioxolan-2-one, 4-methyl -1,3-dioxolan-2-one (propylene carbonate, PC), 4-ethyl-1,3-dioxolan-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, 4,4- Dimethyl 1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one (glycerin carbonate), 4-phenoxymethyl-1,3-dioxolan-2-one, 1,3-dioxane-2 -one (trimethylene carbonate), 5,5-dimethyl-1,3-dioxan-2-one, 5-methyl-5-propyl-1,3-dioxan-2-one, 5-ethyl-5- (hydroxymethyl) -1,3 dioxan-2-one (TMP carbonate), 4-isopropyl-5,5-dimethyl-1,3-dioxan-2-one (2,2,4-trimethyl-pentane-1,3-diol carbonate), 4 tert-butyl-5-methyl-1,3-dioxan-2-one (2,4,4-trimethyl-pentane-1,3-diol carbonate), 2,4-dioxaspiro [5.5] -undecan-3-one (Cyclohexane-1,1-dimethanol spiro-carbonate) or any mixtures of such cyclic carbonates. Preferred cyclic carbonates are ethylene carbonate and / or propylene carbonate.

suitable Lactones are, for example, those having 3 to 6 carbon atoms in the ring, which may optionally be substituted, such as Β-propiolactone, (3-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, γ-phenyl-γ-butyrolactone, α, α-diphenyl-γ-butyrolactone, γ-hexalactone (γ-caprolactone), γ-heptalactone, γ-octalactone, γ-nonalactone, γ-decalactone, γ-undecalactone, γ-dodecalactone, γ-methyl-γ-decanolactone, α-acetyl-γ-butyrolactone, δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decalactone, δ-undecalactone, δ-tridecalactone, δ-tetradecalactone, γ-ethyl-γ-butyl-δ-valerolactone, Octahydrocoumarin, ε-caprolactone, γ-phenyl-ε-caprolactone, ε-decalactone or any mixtures of such lactones. Preferred lactones are β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-caprolactone and / or ε-caprolactone.

The preparation of the starting compounds c1) by reacting said aminosilanes with the cyclic carbonates or lactones is known per se and can be carried out, for example, according to the methods described in SU-A 295764 . US Pat. No. 4,104,296 . EP-A 0 833 830 or WO 1998/018844 described method. In general, the reactants are reacted at temperatures of 15 to 100 ° C, preferably 20 to 60 ° C in equimolar amounts with each other. But it is also possible that one of the components, for example the aminosilane or the cyclic carbonate or lactone, is used in a molar excess amount, but preferably in an excess of not more than 10 mol%, particularly preferably not more than 5 mol% , The hydroxy-functional starting compounds c1) thus obtainable, which contain urethane groups when cyclic carbonates are used, amide groups when lactones are used, are generally colorless, low-viscosity liquids.

Suitable starting compounds c2) for the process according to the invention are any desired diisocyanates having aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups which can be prepared by any desired method, for example. B. by phosgenation or phosgene-free way, for example by urethane cleavage can be produced. Suitable starting diisocyanates are for example those of the molecular weight range 140 to 400 g / mol, such as. For example, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane , 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,4-diisocyanato-3,3,5-trimethylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4- methylcyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1-isocyanato-1-methyl-4 (3) isocyanatomethylcyclohexane, 2,4'- and 4,4'- Diisocyanatodicyclohexylmethane, 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, 4,4'-diisocyanato-3,3'-dimethyldicyclohexylmethane, 4,4'-diisocyanato-3,3 ', 5,5'-tetramethyldicyclohexylmethane, 4,4'-diisocyanato-1,1'-bi (cyclohexyl), 4,4'-diisocyanato-3,3'-dimethyl-1,1'-bi (cyclohexyl), 4,4'-diisocyanato-2, 2 ', 5,5'-tetra-methyl-1,1'-bi (cyclohexyl), 1,8-diisocyanato-p-menthane, 1,3-diisocyanato-adamantane, 1,3-dimethyl-5,7- diisocyanatoadamantane, 1,3- and 1,4-bis (isocyanatomethyl) benzene, 1,3- and 1,4-bis (1-isocyanato-1-methyls ethyl) benzene (TMXDI), bis (4- (1-isocyanato-1-methylethyl) phenyl) carbonate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and also any desired mixtures these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate and naphthylene-1,5-diisocyanate and any mixtures of such diisocyanates. Other likewise suitable diisocyanates can be found in addition, for example, in Justus Liebigs Annalen der Chemie Volume 562 (1949), pp. 75-136 ,

When Starting component c2) preferred are the diisocyanates mentioned with aliphatically and / or cycloaliphatically bonded isocyanate groups.

Especially preferred starting components c2) for the inventive Processes are 1,6-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4'- and / or 4,4'-diisocyanatodicyclohexylmethane or any Mixtures of these diisocyanates.

to Preparation of the silane-containing polyisocyanate component C) particularly suitable allophanate polyisocyanates are the silane groups having hydroxyurethanes and / or hydroxyamides c1) with the diisocyanates c2) at temperatures of 40 to 200 ° C, preferably 60 to 180 ° C, while maintaining an equivalent ratio from isocyanate groups to isocyanate-reactive Groups of 4: 1 to 50: 1, preferably from 5: 1 to 30: 1, to Allophanatpolyisocyanaten implemented.

In this case, as "isocyanate-reactive groups" in addition to the hydroxyl groups of the compo component c1) and the urethane groups intermediately formed therefrom by NCO / OH reaction in the case of the use of hydroxyurethanes also include the urethane groups already contained herein, since these also react further under the reaction conditions to allophanate groups.

The preparation of the silane-containing allophanate polyisocyanates can be carried out uncatalysed as thermally induced allophanatization. However, suitable catalysts are preferably used to accelerate the allophanatization reaction. These are the usual known allophanatization catalysts, for example metal carboxylates, metal chelates or tertiary amines of the type described in US Pat GB-A 0 994 890 to alkylating agents described in the US-A 3,769,318 or strong acids, as described in the EP-A-000194 are described by way of example.

suitable Allophanatization catalysts are in particular zinc compounds, such as Zinc (II) stearate, zinc (II) n-octanoate, zinc (II) 2-ethyl-1-hexanoate, Zinc (II) naphthenate or zinc (II) acetylacetonate, tin compounds, such as Tin (II) n-octanoate, tin (II) 2-ethyl-1-hexanoate, tin (II) laurate, Dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, Dibutyltin dimaleate or dioctyltin diacetate, zirconium compounds, such as Zirconium (IV) -2-ethyl-1-hexanoate, zirconium (IV) neodecanoate, zirconium (IV) naphthenate or zirconium (IV) acetylacetonate, aluminum tri (ethylacetoacetate), Iron (III) chloride, potassium octoate, manganese cobalt or nickel compounds and strong acids, such as. Trifluoroacetic acid, Sulfuric acid, hydrogen chloride, hydrogen bromide, phosphoric acid or perchloric acid, or any mixtures of these catalysts.

Suitable, albeit less preferred, catalysts for preparing the alanphanate polyisocyanates containing silane groups which are particularly suitable as polyisocyanate component C) are also those compounds which, in addition to the allophanatization reaction, also catalyze the trimerization of isocyanate groups to form isocyanurate structures. Such catalysts are for example in the EP-A 0 649 866 Page 4, line 7 to page 5, line 15 described.

preferred Catalysts are zinc and / or zirconium compounds of the abovementioned The most preferred is the use of zinc (II) n-octanoate, Zinc (II) 2-ethyl-1-hexanoate and / or zinc (II) stearate, zirconium (IV) n-octanoate, Zirconium (IV) 2-ethyl-1-hexanoate and / or zirconium (IV) neodecanoate.

These Catalysts are used in the preparation of the polyisocyanate component C) particularly suitable silane-containing allophanate polyisocyanates, if any, in an amount of 0.001 to 5% by weight, preferably 0.005 to 1 wt .-%, based on the total weight of Reactants c1) and c2) are used and can both be added before the start of reaction as well as at any time of the reaction.

The silane-containing allophanate polyisocyanates are preferably prepared solvent-free. Optionally, however, it is also possible to use concomitant solvents which are inert towards the reactive groups of the starting components. Suitable solvents are, for example, the known conventional lacquer solvents, such as. Ethyl acetate, butyl acetate, ethylene glycol monomethyl or ethyl ether acetate, 1-methoxypropyl 2-acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene, White spirit, higher substituted aromatics, such as those under the names Solventnaphtha, Solvesso ^® , Isopar ^® , Nappar ^® (German EXXON CHEMICAL GmbH, Cologne, DE) and Shellsol ^® (Deutsche Shell Chemie GmbH, Eschbom, DE) are commercially available, but also solvents such as propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl and butyl ether acetate, N-methylpyrrolidone and N-methylcaprolactam, or any mixtures of such solvents.

In one possible embodiment of the process for preparing the silane-containing allophanate polyisocyanates C), the starting diisocyanate c2) or a mixture of different starting diisocyanates optionally under inert gas, such as nitrogen, and optionally in the presence of a suitable solvent of the type mentioned at a temperature between 20 and 100 ° C submitted. Subsequently, the hydroxy-functional starting compound c1) is added in the amount indicated above and the reaction temperature for the urethanization optionally by a suitable measure (heating or cooling) to a temperature of 30 to 120 ° C, preferably set from 50 to 100 ° C. Subsequent to the urethanization reaction, ie, when the complete conversion of isocyanate and hydroxyl groups theoretically corresponding NCO content is reached, the allophanatization example, without addition of a catalyst by heating the reaction mixture to a temperature of 140 to 200 ° C ge will be started. However, suitable catalysts of the abovementioned type are preferably used to accelerate the allophanatization reaction, temperatures ranging from 60 to 140.degree. C., preferably from 80 to 120.degree. C., being sufficient, depending on the nature and amount of the catalyst used.

In another possible embodiment of the method for preparing the silane-containing allophanate polyisocyanates C) the optionally used catalyst is either the silane component c1) and / or the diisocyanate component c2) already mixed before the actual implementation. In this case the intermediates form and react when used of hydroxyurethanes c1) in these already contained urethane groups spontaneously continue to the desired allophanate structure. at This type of one - step reaction will be the optionally the catalyst-containing starting diisocyanates c2) optionally under inert gas, such as, for example, nitrogen, and optionally in the presence of a suitable solvent of the type mentioned, usually for allophanatization optimum temperatures in the range of 60 to 140 ° C, preferably 80 to 120 ° C, and with the optionally the catalyst containing silane component c1) is reacted.

It but is also possible, the catalyst to the reaction mixture at any time during the urethanization reaction add. In this embodiment of the invention Process is for the expiring before the catalyst addition Pure urethanization reaction usually has a temperature in the range from 30 to 120 ° C, preferably from 50 to 100 ° C, set. After addition of a suitable catalyst, the Allophanatization reaction finally at temperatures from 60 to 140 ° C, preferably from 80 to 120 ° C, carried out.

Of the Course of the implementation of c1) with c2) can be replaced by z. B. titrimetric Determination of the NCO content to be followed. After reaching the desired NCO content, preferably when the Allophanatisierungsgrad (i.e., the percentage of NCO content that can be calculated from the NCO content) converted to Allophanatgruppen, from the hydroxyl groups of the component c1) intermediately forming and when using hydroxyurethanes c1) in these already contained urethane groups) of the reaction mixture at least 80%, more preferably at least 90%, most preferably after complete allophanatization, the reaction is stopped. This can be done with purely thermal reaction for example, by cooling the reaction mixture Room temperature. In the preferred concomitant use of a Allophanatization catalyst of the type mentioned becomes the reaction but generally by adding suitable catalyst poisons, for example Acid chlorides such as benzoyl chloride or Isophthaloyldichlorid, stopped.

Preferably The reaction mixture is then by thin film distillation under reduced pressure, for example at a pressure of below 10 mbar, preferably below 3 mbar, more preferably below 1 mbar mbar, under as gentle conditions as possible, for example at a temperature of 100 to 200 ° C, preferably from 120 to 180 ° C, of volatiles (excess monomeric diisocyanates, optionally in the preparation of Starting compounds A) used in excess cyclic Carbonates or lactones, optionally with solvents used and, in the absence of the use of a catalyst poison, if necessary active catalyst).

The incurred distillates, in addition to the unreacted monomers Starting diisocyanates c2), if appropriate, excess used cyclic carbonates or lactones c2) and optionally Mitverwendete solvents and waiving the Use of a catalyst poison optionally active catalyst can easily be used for re-oligomerization be used.

In another embodiment of the process for the preparation the silane-containing allophanate polyisocyanates C) the volatiles mentioned by extraction with suitable isocyanate-inert solvents, for example aliphatic or cycloaliphatic hydrocarbons, such as pentane, Hexane, heptane, cyclopentane or cyclohexane separated from the oligomerization.

Regardless of the type of workup, the particularly suitable silane-functional allophanate polyisocyanates in the form of clear, practically colorless resins which as a rule have color numbers of less than 200 APHA, preferably less than 100 APHA, more preferably less than 80 APHA, are obtained as the process products. an average NCO functionality of 2.0 to 5.0, preferably 2.4 to 4.8, more preferably 3.0 to 4.5, and an NCO content of 6.0 to 20.5 wt .-% , preferably 10.0 to 18.0 wt .-%, particularly preferably 12.0 to 17.0 wt .-%, have. When using selective allophanatization ka they are virtually free of by-products such as B. isocyanurates, ie that in addition to isocyanate functions in addition to at least one silane group is present in almost every molecule.

The Coating compositions according to the invention can optionally organic solvents D) and / or others Auxiliary and additive E) included.

suitable Solvents D) are, for example, those mentioned above, optionally in the preparation of the polyisocyanate component C) particularly suitable silane-containing allophanate polyisocyanates to be used with conventional inert lacquer solvent. If anything, such paint solvents come in the coating compositions of the invention in an amount of up to 50%, preferably up to 30%, especially preferably up to 10%, based on the total amount of the components A) to E) are used.

When Auxiliaries and additives E) can be, for example, curing catalysts, Fillers, dyes, pigments, matting agents, flame retardants, Hydrolysis protectants, microbicides, algicides, flow control agents, Antioxidants, light stabilizers, water scavengers, thixotropic carriers, Wetting agent or deaerator are used. These auxiliaries and additives E) are made according to the requirements the to be solved by the application of the coating Problems and their compatibility with component A), B) and / or C). Hydrous or strongly alkaline For example, reacting additives should not be the polyisocyanate component C) but the amine A) and / or optionally component B) be mixed.

Suitable curing catalysts E) for the coating compositions according to the invention are, for example, the compounds known from polyurethane chemistry for accelerating isocyanate reactions, such as. As the known tin or bismuth compounds and tertiary amines, such as those in "Kunststoff Handbuch 7, Polyurethanes" Carl-Hanser-Verlag, Munich-Vienna, 1984, pp. 97-98 , are described in detail. Such catalysts may be used, if at all, in amounts of up to 2% by weight, based on the weight of the binder consisting of the individual components A), optionally B) and C).

suitable Fillers are, for example, stone or plastic granules, Glass balls, sand or cork, if necessary in quantities of up to to 100 wt .-% based on that from the individual components A), optionally B) and C) existing binder mixture can be used.

Examples of suitable pigments are titanium dioxide, zinc oxide, iron oxides, chromium oxides or carbon blacks. A detailed overview of Pigments for paints gives that "Textbook of coatings and coatings, Volume II, pigments, fillers, dyes", Kittel, Verlag WA Colomb in Heenemann GmbH, Berlin-Oberschwandorf 1974, p 17-265 , The pigments mentioned by way of example may be used, if at all, in amounts of up to 100% by weight, based on the binder mixture consisting of the individual components A), if appropriate B) and C).

Matting agents, flame retardants, hydrolysis stabilizers, microbicides, algicides, leveling agents, antioxidants, light stabilizers, water scavengers, thixotropic agents, wetting agents or deaerating agents are also optionally used in the coating compositions according to the invention as auxiliaries and additives E) "Textbook of Paints and Coatings, Volume III., Solvents, Plasticizers, Additives, Intermediates", H. Kittel, Verlag WA Colomb in Heenemann GmbH, Berlin-Oberschwandorf, 1976, pp. 237-398 , described. Desiccants acting as water scavengers are, for example, in "Kunststoff Handbuch 7, Polyurethane", Carl-Hanser-Verlag, Munich - Vienna, 1983, p. 545 described in more detail. The total amount of such other auxiliaries and additives is generally up to 25 wt .-%, based on the consisting of the individual components A), optionally B) and C) binder.

The novel coating compositions are prepared by mixing the individual components A), C) and optionally B), D) and E), for example using the known dissolvers or vacuum dissolvers, which are often preferred in order to achieve extensive degassing of the coating compositions. When concomitant use of isocyanate-reactive group-containing components B), it is generally useful to combine them in a first step with the polyamines A) and optionally used solvents D) and optionally other auxiliaries and additives E) to form a storage-stable binder component and the Polyisocyanate component C), which may also optionally contain solvent D) and optionally further auxiliaries and additives E), as usual in two-component systems, to add immediately before application. The quantity ver Component A), optionally B) and C) are chosen so that each isocyanate-reactive group of components A) and optionally B) 0.7 to 2.0, preferably 0.8 to 1.6, particularly preferably 0 , 9 to 1.4 isocyanate groups of component C) omitted.

The novel coating compositions can be after methods known per se, for example by spraying, brushing, Dipping, flooding or with the help of rollers or squeegees on any substrates, such as As metals, plastics, wood or glass, one or more layers Instruct. The lower proportion required, if necessary, to be used organic solvent D) allows it in one operation Apply thick layers without bubbles.

The Harden coating agent according to the invention even at low temperatures, for example within the Temperature range from -20 to + 60 ° C, preferably from -10 to + 40 ° C to light and weather resistant Paint films characterized by a high hardness and abrasion resistance with high elasticity at the same time. You can however, if necessary, of course also at higher temperatures, for example, up to 140 ° C. be burned.

Especially the novel coating compositions are well suited for the production of coatings, in particular as Corrosion protection coatings, on metallic materials, as for example in the manufacture of vehicle bodies, machines, cladding, Drums or containers are used.

The to be coated substrates can before application the coating composition according to the invention with suitable Primers are provided. Because of her excellent direct liability for conventional polyaspartic acid systems critical metallic substrates, such. As zinc, aluminum or cold-rolled steel, when using the inventive Coating agent without loss of quality but also on the concomitant use of a primer layer are dispensed with. In Combination with the high layer thickness that can be applied in one operation this means for the user of the inventive Coating a significant reduction in painting times and thus a noticeable increase in productivity.

object The present invention is therefore also the use of the inventive Coating agent for coating substrates, in particular the use for direct coating of metallic substrates as well the use of the coating agent as a corrosion protective varnish. Consequently, therefore, from the inventive Coating obtained films and coated with these Substrates Subject of the present invention.

Examples

All Percentages are, unless stated otherwise, on the weight.

The determination of the NCO contents was carried out after DIN EN ISO 11909 ,

All viscosity measurements were carried out with a Physica MCR 51 Rheometer from Anton Paar Germany GmbH (Ostfildern) DIN EN ISO 3219 ,

The Hazen color numbers were taken on a LICO 400 colorimeter The company Hach Lange GmbH, Dusseldorf, determined.

The in the case of the starting compounds c1) indicated OH numbers from the theoretically resulting molecular weight of the ideal structure Calculated (1: 1 adduct).

starting compounds

Amine A1)

Polyaspartic acid ester, prepared according to EP-B 0 403 921 (Polyasparaginsäureester D)) by reacting 2 moles of diethyl maleate with 1 mol of 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (Laromin ^® C 260 Fa. BASF). Viscosity: about 1000 mPas Equivalent weight: 290 g / val

Amine A2)

Polyaspartic acid ester, prepared according to EP-B 0 403 921 (Polyaspartic acid esters I)) by reacting 2 moles of diethyl maleate with 1 mole of 4,4'-diaminodicyclohexylmethane. Viscosity: about 1000 mPas Equivalent weight: 276 g / val

Polyaldimine B)

Polyaldimine prepared according to DE-A 2 325 824 by reaction of 3 mol of isobutyraldehyde with 1 mol of 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (IPDA) and subsequent work-up by distillation of the reaction mixture. Viscosity: about 30 mPas Equivalent weight: 139 g / val

Preparation of the starting compounds C)

Silane-containing hydroxyurethane c1)

221 g (1.0 mol) of 3-aminopropyltriethoxysilane were added at room temperature submitted under dry nitrogen. This was added with stirring within 15 minutes 88 g (1.0 mol) of ethylene carbonate, wherein the mixture due to the released heat of reaction initially heated to 34 ° C, and then stirred without further heating for 18 hours at room temperature. An amine titration with 1N HCl showed a conversion of 99.8%.

2-Hydroxyethyl [3- (triethoxysilyl) propyl] urethane was obtained as a colorless liquid. Viscosity (23 ° C): 69 mPas OH number (calculated): 181 mg KOH / g Molecular weight (calculated): 309 g / mol

Silane-containing polyisocyanate component C)

1680 g (10.0 mol) of hexamethylene diisocyanate (HDI) were at a temperature of 80 ° C under dry nitrogen with 309 g (1.0 mol) the silane-containing hydroxyurethane c1) and 3 hours stirred until an NCO content of 40.1%, corresponding to one complete urethanization was achieved. Subsequently the reaction mixture was heated to 95 ° C and 0.5 g Zinc (II) -2-ethyl-1-hexanoate as an allophanatization catalyst added. Due to the exothermic reaction rose Temperature of the mixture up to 110 ° C on. After approx. 30 min the NCO content of the reaction mixture was 35.9%. The catalyst was deactivated by the addition of 1 g of benzoyl chloride and not converted monomeric HDI at a temperature of 130 ° C. and a pressure of 0.1 mbar separated in a thin-film evaporator.

This gave 789 g of a virtually colorless, clear allophanate polyisocyanate with the following characteristics: NCO content: 13.7% monomeric HDI: 0.03% Viscosity (23 ° C): 1270 mPas Color number (APHA): 21 Hazen NCO functionality: > 3 (calculated) Silane content: 9.6% (calculated as SiO ₃ , molar weight = 76 g / mol)

Silane group-free comparative polyisocyanate V)

Isocyanurate-containing HDI polyisocyanate, prepared on the basis of Example 11 of EP-A 0 330 966 , with the modification that 2-ethylhexanol instead of 2-ethyl-1,3-hexanediol as catalyst solvent was used. NCO content: 23.0% NCO functionality: 3.2 Monomeric HDI: 0.1% Viscosity (23 ° C): 1,200 mPas

Examples 1 and 2 (according to the invention and Comparison)

• ¹⁾ Molekularsieb, UOP GmbH, D-51368 Leverkusen, Deutschland
• ²⁾ Dispergieradditive/Entlüftungsmittel, Byk-Chemie GmbH, 46483 Wesel, Deutschland
• ³⁾ Pigment, Tronox Pigments GmbH, 42789 Krefeld, Deutschland
• ⁴⁾ Pigment, Lanxess, 51369 Leverkusen, Deutschland
• ⁵⁾ Pigment, Heubach GmbH & Co. KG, 38685 Langelsheim, Deutschland
• ⁶⁾ Füllstoff, Sachtleben Chemie GmbH, D-47198 Duisburg, Deutschland
• ⁷⁾ Rheologie Additiv, Cabot GmbH, 63457 Hanau, Deutschland
• ⁸⁾ Lichtschutzmittel, Ciba, Basel, Schweiz

From the raw materials listed in Table 1 below, an amino-functional binder component was prepared by predischarging for 10 minutes with the aid of a dissolver and subsequent grinding on a bead mill with cooling in the proportions indicated there. Table 1: Amine A1) 15.11 Parts by weight Amine A2) 22.82 Parts by weight UOP-L powder ¹⁾ 3.86 Parts by weight 1-methoxypropyl-2-acetate / butyl acetate (1: 1) 8.69 Parts by weight Byk ^® A 530, asf. ²⁾ 0.80 Parts by weight Disperbyk ^® 163, asf. ²⁾ 1.45 Parts by weight Tronox ^® R-KB-4 ³⁾ 14.15 Parts by weight Chrome oxide green GNM ⁴⁾ 9.81 Parts by weight Bayferrox ^® 415 ⁴⁾ 1.77 Parts by weight Heucophos ZPA ^{® 5)} 15.76 Parts by weight Barite EWO ⁶⁾ 3.53 Parts by weight Cab-O- ^Sil® TS 720 ⁷⁾ 1.45 Parts by weight Tinuvin ^® 292 ⁸⁾ 0.80 Parts by weight

• ¹⁾ Molecular Sieve, UOP GmbH, D-51368 Leverkusen, Germany
• ²⁾ Dispersing additives / deaerating agents, Byk-Chemie GmbH, 46483 Wesel, Germany
• ³⁾ Pigment, Tronox Pigments GmbH, 42789 Krefeld, Germany
• ⁴⁾ Pigment, Lanxess, 51369 Leverkusen, Germany
• ⁵⁾ Pigment, Heubach GmbH & Co. KG, 38685 Langelsheim, Germany
• ⁶⁾ Filler, Sachtleben Chemie GmbH, D-47198 Duisburg, Germany
• ⁷⁾ Rheology Additive, Cabot GmbH, 63457 Hanau, Germany
• ⁸⁾ Sunscreens, Ciba, Basel, Switzerland

to Production of a ready-to-use invention Coating agent of this binder component 45.46 parts by weight the silane-containing polyisocyanate component C), accordingly an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 1.1: 1 added and well incorporated.

To the Comparison was made in a second coating batch of the same binder component 27.08 parts by weight of the silane-free comparative polyisocyanate V), also according to an equivalent ratio from isocyanate groups to isocyanate-reactive Groups of 1.1: 1, added and also well incorporated.

The two so-formulated varnishes, which had comparable pot lives of about 2 hours, were applied to a degreased aluminum sheet and to cold-rolled steel using an airless spraying unit each in a wet film thickness of about 120 .mu.m and at room temperature (approx. 23 ° C) and a relative humidity of about 50%. The dry times after DIN 53 150 were comparable with T1 about 50 min and T6 about 2 hours also.

Significant differences were found in the adhesion properties of the two coatings. Like the results of cross hatch tests shown in Table 2 ISO 2409 show that possesses The present invention crosslinked with a silane-containing polyisocyanate coating compositions on both aluminum and cold rolled steel compared to a conventional, ie crosslinked with a silane-free polyisocyanate system significantly improved adhesion. Table 2: Cross-cut tests according to DIN EN ISO 2409 Example (according to the invention) Example 2 (comparison) Adhesive strength on aluminum after 12 h GT 0 GT 3 after 14d condensation ( DIN EN ISO 6270 ) GT 0 GT 5 Adhesive strength on cold rolled steel after 12 h GT 1 GT 1-2 after 14d condensation ( DIN EN ISO 6270 ) GT 3 GT 5

Examples 3 and 4 (according to the invention and Comparison)

• ¹⁾ Molekularsieb, UOP GmbH, D-51368 Leverkusen, Deutschland
• ²⁾ Schwebemittel, Elementis Specialties, 9000 Gent/Belgien
• ³⁾ Dispergieradditive/Entlüftungsmittel, Byk-Chemie GmbH, 46483 Wesel, Deutschland
• ⁴⁾ Pigment, Lanxess, 51369 Leverkusen, Deutschland
• ⁵⁾ Pigment, Tronox Pigments GmbH, 42789 Krefeld, Deutschland
• ⁶⁾ Füllstoff, Sachtleben Chemie GmbH, D-47198 Duisburg, Deutschland
• ⁷⁾ Rheologie Additiv, Cabot GmbH, 63457 Hanau, Deutschland
• ⁸⁾ Lichtschutzmittel, Ciba, Basel, Schweiz

From the raw materials listed in Table 3 below, an amino-functional binder component was prepared in the proportions specified therein by predispersing for 10 minutes with the aid of a dissolver and subsequent grinding on a bead mill with cooling. Table 3: Amine A1) 24.32 Parts by weight Polyaldimine B) 7.68 Parts by weight UOP-L powder ¹⁾ 3.26 Parts by weight butyl 3.34 Parts by weight Bentone 38, 10% digestion ²⁾ 3.76 Parts by weight Disperbyk ^® 110 ³⁾ 1.04 Parts by weight ^Byk® 085 ³⁾ 1.14 Parts by weight Chrome oxide green GNM ⁴⁾ 8.29 Parts by weight Bayferrox ^® 415 ⁴⁾ 1.48 Parts by weight Tronox ^® R-KB-4, ⁵⁾ 11.88 Parts by weight Barite EWO ⁶⁾ 31.58 Parts by weight Cab-O- ^Sil® TS 720 ⁷⁾ 1.51 Parts by weight Tinuvin ^® 292 ⁸⁾ 0.72 Parts by weight

• ¹⁾ Molecular Sieve, UOP GmbH, D-51368 Leverkusen, Germany
• ²⁾ Suspending agent, Elementis Specialties, 9000 Ghent / Belgium
• ³⁾ Dispersing additives / deaerating agents, Byk-Chemie GmbH, 46483 Wesel, Germany
• ⁴⁾ Pigment, Lanxess, 51369 Leverkusen, Germany
• ⁵⁾ Pigment, Tronox Pigments GmbH, 42789 Krefeld, Germany
• ⁶⁾ Filler, Sachtleben Chemie GmbH, D-47198 Duisburg, Germany
• ⁷⁾ Rheology Additive, Cabot GmbH, 63457 Hanau, Germany
• ⁸⁾ Sunscreens, Ciba, Basel, Switzerland

to Production of a ready-to-use invention Coating agent of this binder component was 37.66 parts by weight the silane-containing polyisocyanate component C), accordingly an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 1.1: 1 added and well incorporated.

For comparison, in a second coating batch of the same binder component 22,43 Parts by weight of Silangmppen-free comparative polyisocyanate V), also according to an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 1.1: 1, added and also well incorporated.

The two paints formulated in this way were applied to a degreased aluminum sheet and to cold-rolled steel with the aid of an airless spray coating in a wet film thickness of about 120 μm and at room temperature (about 23 ° C.) and a relative atmospheric humidity of approx. 50% cured. The dry times after DIN 53 150 were comparable with T1 about 80 min and T6 about 4 hours. The pot lives of the paint approaches was in both cases at about 6 hours.

As in Examples 1 and 2, clear differences in the adhesion properties of the two coatings also showed here. Table 4 shows the results of the cross hatch tests ISO 2409 listed. Thereafter, the inventive, crosslinked with a silane-containing polyisocyanate coating agent both on aluminum and on cold rolled steel compared to a conventional, ie crosslinked with a silane-free polyisocyanate system improved adhesion. Table 4: Cross-cut tests according to DIN EN ISO 2409 Example 1 (according to the invention) Example 2 (comparison) Adhesive strength on aluminum after 12 h GT 1 GT 3 Adhesive strength on cold rolled steel after 12 h GT 1 GT 4

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 0403921 A [0003, 0013]
• EP 0470461 A [0004]
• - EP 0531249 A [0004]
• - EP 1581575 A [0004]
• - EP 1277876 A [0004]
• - EP 1199320 A [0004]
• - EP 0689881 A [0005, 0013]
• EP 0816326A [0013]
• WO 2003/054049 [0049]
• - JP 2005015644A [0049]
• - EP 1273640 A [0049]
• EP 0994139 B [0049]
• EP 0596360A [0049]
• WO 02/058569 [0049]
• - EP 2014692A [0051]
• - SU 295764 A [0062]
• - US 4104296 A [0062]
• EP 0833830A [0062]
• WO 1998/018844 [0062]
• GB 0994890 A [0068]
• US 3769318A [0068]
• EP 0000194A [0068]
• - EP 0649866 A [0070]
• - EP 0403921 B [0100, 0101]
• - DE 2325824 A [0102]
• - EP 0330966 A [0107]

Cited non-patent literature

• - Justus Liebigs Annalen der Chemie Volume 562 (1949), pp. 75-136 [0063]
• "Kunststoff Handbuch 7, Polyurethanes" Carl-Hanser-Verlag, Munich-Vienna, 1984, pp. 97-98 [0085]
• - "Textbook of coatings and coatings, Volume II, pigments, fillers, dyes", Kittel, Verlag WA Colomb in Heenemann GmbH, Berlin-Oberschwandorf 1974, p. 17-265 [0087]
• - "Textbook of Paints and Coatings, Volume III., Solvents, Plasticizers, Additives, Intermediates", H. Kittel, Verlag WA Colomb in Heenemann GmbH, Berlin-Oberschwandorf, 1976, pp. 237-398 [0088]
• "Kunststoff Handbuch 7, Polyurethane", Carl-Hanser-Verlag, Munich-Vienna, 1983, p. 545 [0088]
• - DIN EN ISO 11909 [0096]
• - DIN EN ISO 3219 [0097]
• - DIN 53 150 [0111]
• - ISO 2409 [0112]
• - DIN EN ISO 6270 [0112]
• - DIN EN ISO 6270 [0112]
• - DIN 53 150 [0116]
• - ISO 2409 [0117]

Claims (10)

Coating composition comprising A) at least one amine of the formula (I)

in which X is an n-valent, isocyanate-inert radical, as obtained by removing the primary amino groups from an organic polyamine in the molecular weight range 60 to 6000 with n primary aliphatic and / or cycloaliphatically bonded amino groups, optionally one or more heteroatoms and / or further, isocyanate-reactive and / or inert at temperatures up to 100 ° C containing functional groups, R ¹ and R ^{2 are the} same or different organic radicals having 1 to 18 carbon atoms and n is an integer ≥ 1, B optionally further isocyanate-reactive components, C) a silane group-containing polyisocyanate component, D) optionally organic solvents and E) optionally further auxiliaries and additives, with the proviso that the components A), optionally B) and C) are present in such proportions that on each opposite isocyanates re active group of components A) and optionally B) 0.7 to 2.0 isocyanate groups of component C) are omitted. Coating composition according to Claim 1, characterized in that the amine A) used is polyaspartic acid esters which are obtained by reaction of a component of the formula (II) containing primary amino groups.

with fumaric acid esters and / or maleic acid esters of the formula (III) R ¹ OOC-CH = CH-COOR ² (III) wherein X and n in formula (II) and R ¹ and R ² in formula (III) have the meaning given in claim 1. Coating composition according to claim 2, characterized in that as the amine A) polyaspartic acid ester which can be used by reaction of 1,5-diamino-2-methylpentane, 2,4'- and / or 4,4'-diamino-dicyclohexylmethane and / or 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane were prepared with diethyl maleate. Coating composition according to claim 1, characterized in that as isocyanate-reactive component B) polyaldimines and / or polyketimines of the formula (V)

be used, in which R ³ and R ^{4 are the} same or different radicals and hydrogen or inert organic radicals, such as. B. hydrocarbon radicals having up to 8 carbon atoms, in particular alkyl radicals having 1 to 8 carbon atoms, and wherein the radicals R ³ and R ⁴ together with the carbon atom can form a 5- or 6-membered cycloaliphatic ring, with the proviso that the Radicals R ³ and R ^{4 are} not simultaneously hydrogen, and X has the meaning given in claim 1 and m stands for an integer ≥ 2. Coating composition according to claim 1, characterized in that as polyisocyanate component C) silane groups containing Allophanatpolyisocyanate be used by Implementation of c1) at least one of the reaction of aminosilanes silane groups obtainable with cyclic carbonates or lactones having hydroxyurethane and / or hydroxyamide with a molar excess based on the NCO-reactive groups of component c1) Amount of c2) at least one diisocyanate with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups and optionally subsequent removal of the unreacted diisocyanate excess were obtained. Coating composition according to claim 5, characterized in that as component c1) reaction products of aminosilanes of the general formula (VII)

in which R ⁵ , R ⁶ and R ^{7 are} identical or different radicals and are each a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic radical or an optionally substituted aromatic or araliphatic radical having up to 18 carbon atoms, optionally up to 3 Y is a linear or branched organic radical having at least 2 carbon atoms, which may optionally contain up to 2 imino groups (-NH-), and R ^{8 is} hydrogen, a saturated or unsaturated , linear or branched, aliphatic or cycloaliphatic or a ge

in which R ⁵ , R ² , R ⁷ and Y have the abovementioned meaning, be used with cyclic carbonates and / or lactones. Use of the coating compositions according to claim 1 for coating substrates. Use of the coating compositions according to claim 1 for direct coating of metallic substrates. Use of the coating compositions according to claim 1 as corrosion protection paint. With from coating compositions according to claim 1 of films obtained coated substrates.