BRPI0821745B1 - Coating agent with high scratch resistance and weather stability, coating process, and use - Google Patents

Description

COATING AGENT WITH HIGH RISK RESISTANCE AND WEATHER STABILITY, COATING PROCESS, AND, USE [0001] The present invention relates to coating agents containing [0002] (a) at least one compound containing reactive groups (A) , [0003] (b) at least one compound (B) with free and / or blocked isocyanate groups and [0004] (c) at least one catalyst (C) for crosslinking silane groups, [0005] where one or further components (A) and / or (B) and / or at least one other component of the coating agent contain hydrolyzable silane groups.

[0006] WO-A-01/98393 describes 2K coating agents, which contain a polyol as a binding component, as well as a cross-linking component, a polyisocyanate, which is partially functionalized with alkoxysilane groups. These coating agents are used as primers and are optimized for adhesion with metallic bases, especially aluminum bases. Basic lacquer-transparent lacquer superstructures can be applied to these coating agents as part of an OEM series or repair lacquer. With respect to scratch resistance and weathering stability, the coating agents according to WO 01/98393 are not optimized.

[0007] EP-A-0.994.117 describes moisture-curable mixtures, which contain a polyol component and a polyisocyanate component, which can be partially reacted with reacted monoalkoxysilylalkylamine to an aspartate. Coatings of these mixtures actually have a certain hardness, however, with respect to weathering stability and especially with respect to their resistance to

Petition 870190037071, of 17/04/2019, p. 9/15 / 41 risk, are only conditionally suitable for OEM applications.

[0008] US-A-2006/0217472 describes coating agents, which may contain a functional hydroxy acrylate, a low molecular weight polyol component, a polyisocyanate, as well as a functional amino alkoxysilyl component, preferably bisalcoxysilamine . Such coating agents are used as transparent lacquer in basic lacquer-transparent lacquer superstructures and lead to scratch resistant coatings. However, such coating agents are only very conditionally storable and the resulting coatings have poor weather stability, especially against ultraviolet radiation in the wet-dry cycle.

[0009] WO 2006/042585 describes clear lacquers, which are suitable for OEM series lacquering, which contain polyisocyanates as the main binding component, the isocyanate groups of which are preferably reacted in more than 90 mol% with bisalkoxysilylamines. Such transparent lacquers have excellent scratch resistance while being highly resistant to chemicals and weather. However, there is still a need to improve the stability to the weather, especially against the formation of cracks in ultraviolet radiation in the wet-dry cycle, by obtaining the high level of resistance to scratching.

[00010] EP-A-1,273,640 describes 2K coating agents, consisting of a polyol component and a cross-linking component, consisting of aliphatic and / or cycloaliphatic polyisocyanates, where 0.1 to 95 mol% , of the originally free isocyanate groups present is reacted with bisalkoxysilylamine These coating agents can be used for OEM series lacquering and after they have completely hardened, they show good scratch resistance while also good resistance to environmental actions. However, these coating agents tend particularly strongly towards post-crosslinking, which results in Petition 870180130797, of 17/09/2018, p. 15/60 / 41 directly after final thermal hardening - only insufficient resistance of the coatings to scratching. Likewise, the strong post-reticulation has a negative effect on weather stability, as there is a great risk of damage due to tension.

[00011] In the primary car lacquering, relatively high hardening temperatures can be applied, as the car body does not yet contain any temperature sensitive parts. Another situation occurs in the repair lacquer. When, for example, failures in the finished lacquered car require partial repair of the series finish or when minor repairs only part of the surface must be lacquered again, it is necessary to use lacquers, which harden at low temperatures, so as not to put at risk temperature sensitive parts such as tires and plastic parts. Silanized systems are able to be hardened at relatively low temperatures, however, the crosslinking of the isocyanate is generally satisfactory only at elevated temperatures.

[00012] In the case of partially silanized systems, which are additionally cross-linked with urethane formation through polyisocyanates, blocked phosphoric acid ester derivatives are often used as catalysts. Here, the acid effect of the phosphoric acid ester is neutralized by a basic component. As a rule, amines are used as a rule, such as, for example, triethylamine. After a certain temperature, the blockage is abolished, the phosphorus compounds cause an acid hydrolysis of the alkoxysilane compounds and the triethylamine leaves the lacquer due to its low vapor pressure. Here, an acid catalysis of the isocyanate-polyol reaction is generally not obtained.

Objective [00013] The objective of the present invention was to make coating agents available, especially for the transparent lacquer layer

Petition 870180130797, of 9/17/2018, p. 16/60 / 41 in OEM series lacquers and auto repair lacquers, which lead to a network stable to high-grade weather, where the unwanted formation of labile groups to hydrolysis and weather is suppressed as widely as possible, to ensure high resistance to acids. In addition, the coating agents must lead to coatings, which are resistant to scratching to a high degree already directly after thermal hardening and have a particularly high gloss after pressure loading. In addition, coatings and lacquers, especially transparent lacquers, must also be prepared in layer thicknesses of> 40 pm, without the occurrence of stress cracks. This is an essential condition for the use of coatings and lacquers, especially transparent lacquers, in the technologically and aesthetically demanding field of automotive series (OEM) lacquering.

[00014] In particular, transparent lacquers with high resistance must be made available, particularly against the formation of cracks, in the weather with ultraviolet radiation in the wet cycle in combination with excellent scratch resistance.

[00015] In addition, new coating agents must be preparable in a simple and very well reproducible manner and not cause any ecological problems during the application of the lacquer.

[00016] An essential objective of the present invention is to obtain, in the case of lacquers which are hardened by a hydrolysis of alkoxysilane compounds and additionally by the reaction of isocyanate groups with hydroxyl groups, a complete cross-linking at low temperatures. Surprisingly, it was found that this objective can be solved by applying bicyclic amines to block phosphoric acid catalysts.

Petition 870180130797, of 9/17/2018, p. 17/60 / 41

Resolution of the objective [00017] Therefore, the object of the present invention is coating agents of the type initially mentioned, in which the catalyst (C) is an amine-phosphoric acid compound with a pKb value> 3 and a boiling> 100 ^o C, especially phosphoric acid or phosphonic acid.

[00018] Advantageously, the amine is a bicyclic amine.

[00019] Other advantageous embodiments of the invention result from the subclaims.

[00020] The crosslinking of the coating agent according to the invention is carried out simultaneously by the reaction of the isocyanate groups and the hydrolysable silane groups. The silane groups can be a component of compound (A) and / or (B). But it is also possible that the coating agent contains another component, which is a support for the silane groups.

[00021] The determination of the pKb value is described in the annex.

[00022] The bicyclic amines to be added according to the invention, have a higher boiling point than, for example, triethylamine. Hereby, after unblocking, they remain in the lacquer layer and further catalyze the isocyanate-alcohol reaction. A suitable high-boiling tertiary amine is, for example, diazabicyclooctane (DABCO). The catalytic effect of these tertiary amines on the reaction of isocyanate groups with hydroxyl groups is itself known. However, based on the saline character of the phosphoric acid-amine ester complexes, it was surprising and unpredictable, that the crosslinking of the isocyanate with polyols, even at low temperatures, such as for example, 60 ^o C, is catalyzed in the same way as through free diazabicyclooctane.

[00023] Regarding the state of the art, it was surprising and unforeseeable for the technician, that the objectives, which served as the basis for this

Petition 870180130797, of 9/17/2018, p. 18/60 / 41 invention, could be solved with the aid of the coating agent according to the invention.

[00024] The components according to the invention, can be prepared in a particularly simple and very reproducible way and in the application of the lacquer do not offer any significant toxicological and ecological problems.

[00025] The coating agents according to the invention, provide new coatings and lacquers, especially transparent lacquers, which are highly scratch resistant and, unlike current highly cross-linked scratch resistant systems, are acid resistant. In addition, the coatings and lacquers according to the invention, especially the transparent lacquers, can also be prepared with layer thicknesses> 40 qm, without stress cracking. For this reason, coatings and lacquers according to the invention, especially transparent lacquers, can be used in the technologically and aesthetically demanding field of automotive series (OEM) lacquering. In this case, they stand out for their particularly high resistance to street washing and scratch resistance. In particular, the high scratch resistance of the coatings is given directly after the final hardening of the coatings, so that the coatings can be handled without problems directly after the final hardening. In addition, the resistance of the coatings according to the invention against the formation of cracks in ultraviolet radiation and wet-dry exchange in the CAM180 test (according to DIN EN ISO 11341 February 98 and DIN EN ISO 4892-2 November 00 ) and combination with high scratch resistance, is excellent.

[00026] Especially the coating and lacquering agents according to the invention, especially the transparent lacquering, are used in the field technologically and aesthetically particularly

Petition 870180130797, of 9/17/2018, p. 19/60 / 41 demanding of series car lacquering (OEM), mainly for the coating of plastic parts for passenger car bodies, especially for upper class passenger car bodies, such as, for example, for the production of ceilings, rear covers, bonnet, fenders, bumpers, airfoils, pedals, protective bars, side coverings and the like, as well as car repair lacquering.

[00027] Plastic parts usually consist of ASA, polycarbonates, mixtures of ASA and polycarbonates, polypropylene, polymethyl methacrylates or impact-modified polymethyl methacrylates, are used especially of mixtures of ASA and polycarbonates, preferably with a polycarbonate fraction> 40%, especially> 50%.

[00028] By ASA, in this case, we mean, in general, modified styrene / acrylonitrile polymers in terms of impact resistance, in which the graft copolymers of vinilaromatic compounds, especially styrene and vinyl cyanides, especially acrylonitrile, on rubbers. polyalkyl acrylates are present in a matrix of copolymers of especially styrene and acrylonitrile.

Description of the Invention [00029] Examples of suitable phosphorous catalysts (C) are phosphonic acid diesters and substituted diphosphonic acid diesters, preferably from the group, consisting of acyclic phosphonic acid diesters, cyclic phosphonic acid diesters, acyclic and phosphonic acid diesters cyclic diphosphonic acid diesters. Such catalysts are described, for example, in German patent application DE-A-102005045228.

[00030] Especially, however, phosphoric acid monoesters and substituted phosphoric acid diesters are employed as a catalyst, preferably of the group, consisting of acyclic phosphoric acid diesters and cyclic phosphoric acid diesters, particularly preferably,

Petition 870180130797, of 9/17/2018, p. 20/60

8/41 amine addition products of phosphoric acid mono- and diesters.

[00031] In this case, the acyclic phosphoric acid (C) diesters are specially selected from the group, consisting of acyclic phosphoric acid (C) diesters of the general formula (IV):

Ria-0

P (OJOH (IV) ·

R11-O [00032] in which the radicals Rio and Rn are selected from the group consisting of:

[00033] - alkyl group unsubstituted and substituted by 1 to 20, preferably 2 to 16 and especially 2 to 10 carbon atoms, cycloalkyl group with 3 to 20, preferably 3 to 16 and especially 3 to 10 carbon atoms and aryl group with 5 to 20, preferably 6 to 14 and especially 6 to 10 carbon atoms, [00034] - alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl arylcycloalkyl, cycloalkylyl groups, alkyl cycloalkyl alkyl, alkyl alkyl cycloalkyl, alkyl cycloalkyl, alkyl cycloalkyl, alkyl cycloalkyl, alkyl cycloalkyl, alkyl, cycloalkyl and aryl contained herein contain in each case the number of carbon atoms mentioned above and [00035] - unsubstituted and substituted radical of the type mentioned above, containing at least one, especially a heteroatom, selected from the group consisting of oxygen, sulfur atom, nitrogen atom, phosphorus atom and silicon atom, especially oxygen atom, sulfur atom and nitrogen atom and additionally can also represent hydrogen (partial esterification).

[00036] As examples of amine, with which phosphoric acid esters are blocked, in addition to DABCO can be mentioned, for example, Ndimethyl-benzylamine and N-methyl-morpholine.

Petition 870180130797, of 9/17/2018, p. 21/60 / 41 [00037] Catalysts are preferably employed in fractions of 0.01 to 20% by weight, particularly preferably in fractions of 0.1 to 10% by weight, in relation to the non-volatile components of the agent coating according to the invention. In this case, the quantity of the applied catalyst also has a certain influence on the crosslinking, since a lower efficiency of the catalyst can be partially offset by the correspondingly higher application quantities.

Structural units with hydrolyzable silane groups [00038] For the invention, it is essential that one or more components of the coating agent contain hydrolyzable silane groups. This includes especially coating agents, in which one or more components of the coating agent have at least partially one or more structural units that are the same or different from formula (I)

-X-Si-RxG3-x (I), [00039] with G = the same or different hydrolyzable groups, [00040] X = organic radical, especially linear and / or branched alkylene or cycloalkylene radical with 1 to 20 carbon atoms, particularly preferably X = alkylene radical having 1 to 4 carbon atoms, [00041] R = alkyl, cycloalkyl, aryl or aralkyl, where the carbon chain can be interrupted by non-adjacent oxygen, sulfur or NRa groups, with Ra = alkyl, cycloalkyl, aryl or aralkyl preferably R = alkyl radical, especially with 1 to 6 carbon atoms, [00042] x = 0 to 2, preferably 0 to 1, particularly preferably x = 0.

[00043] In this case, the structure of these silane radicals also has an influence on the reactivity and, therefore, also on the widest possible reaction during the hardening of the coating, that is, on the adjustment of a post-crosslinking index as low as possible (PCI).

Petition 870180130797, of 9/17/2018, p. 22/60 / 41 [00044] With respect to the compatibility and reactivity of silanes, silanes with 3 hydrolyzable groups are preferably used, that is, x = 0.

[00045] Hydrolyzable groups G can be selected from the group of halogens, especially chlorine and bromine, from the group of alkoxy groups, from the group of alkylcarbonyl groups and from the group of acyloxy groups. Alkoxy groups (OR ') are particularly preferred.

[00046] The respective preferred alkoxy radicals (OR ') can be the same or different, for the formation of the radicals it is decisive, however, to what extent they influence the reactivity of the hydrolysable silane groups. Preferably, R 'is an alkyl radical, especially with 1 to 6 carbon atoms. Particularly preferred are radicals R ', which increase the reactivity of the silane groups, that is, they represent good starting groups. So far, a methoxy radical is preferred compared to an ethoxy radical and this, in turn, is preferred compared to a propoxy radical. Particularly preferably, therefore, R '= ethyl and / or methyl, especially methyl.

[00047] In addition, the reactivity of organo-functional silanes can also be considerably influenced by the length of the X spacer between the silane functionality and the functional organic group, which serves for the reaction with the modifying component. For this purpose, mention is made, for example, of alpha silanes, which can be sold by Wacker and in which a methylene group, instead of the propylene group present in gamma silanes, is between the Si atom and the functional group. For the illustration it is mentioned that methacryloxymethyltrimethoxysilane (alpha silane, for example, commercial product GENIOSIL® XL 33 from Wacker) is preferably applied compared to methacryloxypropyltrimethoxysilane (gamma silane, for example, commercial product GENIOSIL® GF 31 from Wacker), for introduce the hydrolyzable silane groups into the coating agent.

[00048] Very common are spacers, which increase the reactivity of silanes, preferably compared with spacers, which

Petition 870180130797, of 9/17/2018, p. 23/60 / 41 decrease the reactivity of silanes.

[00049] In addition, the functionality of silanes also has an influence on the post-crosslinking index. In this case, functionality is understood as the number of radicals of formula (I) per molecule. By a monofunctional silane, therefore, are silanes, which in each case introduce a radical of formula (I) into the component to be modified by a silane molecule. In this case, a difunctional silane is understood as silanes, which in each case introduce two radicals of formula (I) into the component per silane molecule.

[00050] Particularly preferred are coating agents according to the invention, in which the components have been modified with a mixture of a mono- and a di-functional silane. As difunctional silanes, in this case, especially the functional amino disilanes of formula (IIa) described below are used and as monofunctional silanes, the silanes of formula (IIIa) described below.

[00051] Finally, non-functional substituents on organo functional silane, which are used for the introduction of structural units (I) or (II) or (III), can influence the reactivity of the hydrolysable silane group. Exemplarily, this is elucidated in the example of wide-open substituents, bulky in the amine function, which can reduce the reactivity of functional amino silanes. Given this foundation, N- (n-butyl) -3aminopropyltrimethoxysilane is preferred before N-cyclohexyl-3aminopropyltrimethoxysilane for the introduction of structural units (III).

[00052] Radicals, which increase the reactivity of silanes, preferably in relation to radicals, which decrease the reactivity of silanes, are very common.

[00053] The structural units of formula (I) can be introduced in different ways into the components of the coating agent. However, in different ways it is common, that the introduction of units

Petition 870180130797, of 9/17/2018, p. Structural 24/60 / 41 is carried out through a reaction of the functional groups of the components to be modified with complementary functional groups of the silane. Consequently, for example, the various possibilities for the introduction of the structural units (I) in the compound (A) which presents hydroxyl groups and possibly other reactive groups and / or in the compound (B) which is isocyanate groups are mentioned below.

[00054] Especially in the context of Michael's additions, for example, primary aminosilanes, such as 3aminopropyltriethoxysilane (for sale, for example, under the brand name Geniosil® GF 93 from the company Wacker Chemie), 3-aminopropyltrimethoxysilane (is available) for sale, for example, under the brand name Geniosil® GF 96 from the company Wacker Chemie), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (for sale, for example, under the brand name Geniosil® GF 9, as well as Geniosil® GF from Wacker Chemie), N- (2-aminoethyl) -3aminopropylmethyldimethoxysilane (for sale, for example, under the brand name Geniosil® GF 95 from Wacker Chemie) and the like.

[00055] Especially in the context of additions of functional isocyanate compounds, for example, secondary aminosilanes, such as, for example, bis- (2-trimethoxysilylethyl) amine, bis- (2triethoxysilylethyl) amine, bis- (3- triethoxysilylpropyl) amine (available for sale under the trade name Dynasylan® 1122 at Degussa), bis (3trimethoxysilylpropyl) amine (available for sale under the trade name Dynasylan® 1124 at Degussa), bis- (4-triethoxysilylbutyl) amine, N- (n- butyl) -3aminopropyltrimethoxysilane (is available under the trade name Dynasylan® 1124 at Degussa), N- (n-butyl) -3-aminopropyltriethoxysilane, N-cyclohexyl-3aminopropyltrimethoxysilane (is available under the trade name Geniosil® GF from Wacker Chemie), N-cyclohexyl-3-aminopropyltriethoxysilane, Ncyclohexylaminomethylmethyldiethoxysilane (is available from Wacker Chemie under the trade name Geniosil® XL 924), N-

Petition 870180130797, of 9/17/2018, p. 25/60 / 41 cyclohexylaminomethyltriethoxysilane (is available from Wacker Chemie under the brand name Geniosil® XL 926), N-phenylaminomethyltrimethoxysilane (is available from Wacker Chemie under the brand name Geniosil® XL 973) and the like.

[00056] Functional epoxy silanes can be especially used for the addition to functional carboxylic acid or functional anhydride compounds. Examples of suitable functional epoxy silanes are 3glycidyloxypropyltrimethoxysilane (can be obtained from Degussa under the trade name Dynasylan® GLYMO), 3-glycidyloxypropyltriethoxysilane (is available from Degussa under the trade name Dynasylan® GLYEO) and the like.

[00057] Functional anhydride silanes can be especially used for addition to functional epoxy compounds. For example, for a silane with anhydride functionality, mention the propylsuccinic acid 3 (triethoxysilyl) anhydride (it is available from Wacker Chemie under the trade name Geniosil® GF 20).

[00058] Such silanes can be used in the context of Michael reactions or also in the context of catalyzed reactions with metals. For example, 3-methacryloxypropyltrimethoxysilane is mentioned (it is for sale, for example, by Degussa under the trade name Dynasylan® MEMO or by Wacker Chemie under the trade name Geniosil® GF 31), 3methacryloxypropyltriethoxysilane, vinyltrimethoxysilane (is on sale, among others, by Wackack Chemie by the trade name Geniosil® XL 10), vinildimethoxymethylsilane (is for sale, among others, by Wacker Chemie by the trade name Geniosil® XL 12), vinyltriethoxysilane (is for sale, among others, by Wacker Chemie by the trade name Geniosil® XL 56 ), (methacryloxymethyl) methyldimethoxysilane (is available, among others, from Wacker Chemie under the trade name Geniosil® XL 32), methacryloxymethyltrimethoxysilane (is available, among others, from Wacker Chemie under the trade name Geniosil® XL 33),

Petition 870180130797, of 9/17/2018, p. 26/60 / 41 (methacryloxymethyl) methyldiethoxysilane (is available, among others, from Wacker Chemie under the trade name Geniosil® XL 34), methacryloxymethyltriethoxysilane (is available, among others, from Wacker Chemie under the trade name Geniosil® XL 36).

[00059] Silanes with isocyanate or carbamate function are used in the context of reactions with functional hydroxy compounds. Examples of silanes with an isocyanate function are described, for example, in WO 07/03857.

[00060] Suitable Isocianatoalquiltrialcoxissilanos are, for example, isocianatopropiltrimetoxissilano, isocianatopropilmetildimetoxissilano, isocianatopropilmetildietoxissilano, isocianatopropiltrietoxissilano, isocianatopropiltriisopropoxissilano, isocianatopropilmetildi-isopropoxissilano, isocianatoneohexiltrimetoxissilano, isocianatoneohexildimetoxissilano, isocianatoneohexildietoxissilano, isocianatoneohexiltrietoxissilano, isocianatoneohexiltriisopropoxissilano, isocianatoneohexildi-isopropoxissilano, isocianatoisoamiltrimetoxissilano, isocianatoisoamilmetildimetoxissilano, isocianatoisoamilmetildietoxissilano, isocianatoisoamiltrietoxissilano, and isocianatoisoamiltriisopropoxissilano isocianatoisoamilmetildi- isopropoxysilane. Many isocyanatoalkyltri- and -dialcoxysilanes are commercially available, for example, under the name SILQUEST® from OSi Specialties, Inc., a venture by Witco Corporation.

[00061] Isocyanatopropylalkoxysilane is preferably of a high degree of purity, especially at least 95% and is preferably free of additives, such as transesterification catalysts, which can lead to unwanted side reactions.

[00062] Especially methyldimethoxysilane (isocyanatomethyl) is used (is available from Wacker-Chemie under the brand name Geniosil® XL 42), 3-isocyanatopropyltrimethoxysilane (is available

Petition 870180130797, of 9/17/2018, p. 27/60 / 41 sold by Wacker-Chemie under the brand name Geniosil® XL 40) and Ndimethoxy (methyl) silylmethyl-O-methyl-carbamate (is available for sale by WackerChemie under the brand name Geniosil® XL 65).

[00063] Especially preferred according to the invention are coating agents, containing at least one compound (A) containing hydroxyl groups, as well as at least one compound (B) containing isocyanate groups, which are characterized by the fact that one or more more components of the coating agent have as additional functional components, between [00064] between 2.5 and 97.5 mol%, in relation to the total structural units (II) and (III), of at least one structural unit of the formula (II)

-N (X-SiR''x (OR ') 3-x) n (X'-SiR''y (OR') 3-y) m (II), [00065] where [00066] R '= hydrogen, alkyl or cycloalkyl, where the carbon chain can be interrupted by non-adjacent oxygen, sulfur or NRa groups, with Ra = alkyl, cycloalkyl, aryl or aralkyl, preferably R '= ethyl and / or methyl, [00067] X , X '= linear and / or branched alkylene or cycloalkylene radical with 1 to 20 carbon atoms, preferably X, X' = alkylene radical with 1 to 4 carbon atoms, [00068] R '' = alkyl, cycloalkyl, aryl or aralkyl, where the carbon chain can be interrupted by non-adjacent oxygen, sulfur or NRa groups, with Ra = alkyl, cycloalkyl, aryl or aralkyl, preferably R '' = alkyl radical, especially with 1 to 6 carbon atoms, [ 00069] n = 0 to 2, m = 0 to 2, m + n = 2, as well as x, y = 0 to 2 [00070] and [00071] between 2.5 and 97.5 mol%, with respect to to all

Petition 870180130797, of 9/17/2018, p. 28/60 / 41 structural units (II) and (III), of at least one structural unit of the formula (III)

-Z- (X-SiR''x (OR ') 3-x) (III), [00072] where [00073] Z = -NH-, -NR-, -O-, with [00074] R = alkyl, cycloalkyl, aryl or aralkyl, where the carbon chain can be interrupted by non-adjacent oxygen, sulfur or NRa groups, with Ra = alkyl, cycloalkyl, aryl or aralkyl, [00075] x = 0 to 2 and [00076] X, R ', R' 'have the meanings indicated in formula (II).

[00077] Coating agents are particularly preferred, in which one or more components of the coating agent have between 5 and 95 mol%, especially between 10 and 90 mol%, particularly preferably between 20 and 80 mole% and most particularly preferably between 30 and 70 mole%, in each case in relation to the totality of the structural units (II) and (III), of at least one structural unit of the formula (II) and between 5 and 95 mol%, especially between 10 and 90 mol%, particularly preferably between 20 and 80 mol% and most particularly preferably between 30 and 70 mol%, in each case in relation to all structural units (II) and (III) of at least one structural unit of the formula (III).

The compound (A) containing hydroxyl groups [00078] As compound (A) containing hydroxyl groups, preferably both low molecular weight polyols, as well as oligo- and / or polymeric polyols.

[00079] As low molecular weight polyols, for example, diols are used, such as preferably ethylene glycol, neopentyl glycol, 1,2propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3 -butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4 Petition 870180130797, of 9/17/2018, p. 29/60 / 41 cyclohexanedimethanol and 1,2-cyclohexanedimethanol, as well as polyols, such as preferably trimethylolethane, trimethylolpropane, trimethylol-hexane,

1,2,4-butanotriol, pentaerythritol, as well as dipentaerythritol.

[00080] Preferably, such low molecular weight polyols are added in fractions subordinate to the polyol (A) oligoe / or polymeric component.

[00081] The preferred (A) oligo- and / or polymeric polyols have an average molecular weight Mw> 500 Dalton, measured by means of GPC (gel permeation chromatography), preferably between 800 and 100,000 Dalton, especially between 1,000 and 50,000 Dalton. Particularly preferred are polyester polyols, polyurethane polyols, polysiloxane polyols and especially polyacrylate polyols and / or polymethacrylate polyols, as well as their copolymers, hereinafter polyacrylate polyols. Polyols preferably have an OH number of 30 to 400 mg KOH / g, especially between 100 and 300 KOH / g. The glass transition temperatures, measured by DSC (Differential-Thermoanalyse), of the polyols are preferably between -150 and 100 ^o C, particularly preferably between -120 ^o C and 80 ^o C.

[00082] Suitable polyester polyols are described, for example, in EP-A-0.994.117 and EP-A-1,273,640. Polyurethane polyols are preferably prepared by reacting polyester polyol prepolymers with suitable di- or polyisocyanates and are described, for example, in EP-A-1,273,640. Suitable polysiloxane polyols are described, for example, in WO-A-01/09260, where the polysiloxane polyols cited therein can preferably be used in combination with other polyols, especially those with higher glass transition temperatures.

[00083] As a rule, the preferred polyacrylate polyols in a very particular way according to the invention, are copolymers and preferably have average molecular weight Mw between 1,000

Petition 870180130797, of 9/17/2018, p. 30/60 / 41 and 20,000 Dalton, especially between 1,500 and 10,000 Dalton, in each case measured by gel permeation chromatography (GPC) against a polystyrene standard. The glass transition temperature of the copolymers is, as a rule, between -100 and 100 ^o C, especially between -50 and 80 ^o C (measured by means of DSC measurement). Polyacrylate polyols preferably have an OH number of 60 to 250 mg KOH / g, especially between 70 and 200 KOH / g, as well as an acid number of 0 to 30 mg KOH / g.

[00084] The hydroxyl index (OH index) indicates, how many mg of potassium hydroxide are equivalent to the amount of acetic acid, which is bound by 1 g of substance in acetylation. During the determination, the sample is boiled with acetic acid-pyridine anhydride and the resulting acid is titrated with potassium hydroxide solution (DIN 53240-2). The acidity index here indicates the index of mg of potassium hydroxide, which is used to neutralize 1 g of the respective compound in component (b) (DIN EN ISO 2114).

[00085] As monomeric composition elements containing hydroxyl groups, hydroxyalkyl acrylates and / or hydroxyalkyl methacrylates are preferably employed, such as especially 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate , 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, as well as especially 4-hydroxybutyl acrylate and / or 4-hydroxybutyl methacrylate.

[00086] As other monomeric composition elements for polyacrylate polyols, alkyl methacrylates and / or alkyl methacrylates are preferably employed, such as preferably ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, acrylate isopropyl, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, methacrylate

Petition 870180130797, of 9/17/2018, p. 31/60 / 41 of tert-butyl, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, 3,3,5-trimethylhexyl acrylate, 3,3,5-trimethylhexyl methacrylate, stearyl acrylate, stearyl methacrylate, lauryl acrylate or lauryl methacrylate, cycloalkyl acrylates and / or cycloalkyl methacrylates, such as cyclopentyl acrylate, cyclopentyl methacrylate, cyclopentyl acrylate isobornyl, isobornyl methacrylate or especially cyclohexyl acrylate and / or cyclohexyl methacrylate.

[00087] As other monomeric compositional elements for polyacrylate polyols, vinylaromatic hydrocarbons, such as viniltoluene, alpha-methylstyrene or especially styrene, amides or nitriles of acrylic or methacrylic acid, vinyl ester or vinyl ether, as well as in subordinate amounts, especially acrylic and / or methacrylic acid.

[00088] In another embodiment of the invention, compound A containing hydroxyl groups has structural units of formula (I) and / or formula (II) and / or formula (III), in addition to hydroxyl groups.

[00089] Structural units of formula (II) can be introduced into compound (A) through the incorporation of monomer units with those structural units or through the reaction of polyols, which have other functional groups, with a compound of formula (IIa) HN (X-SiRx (OR ') 3-x) n (X'-SiRy (OR') 3-y) m (IIa), [00090] where the substituents have the meaning mentioned above. For the reaction of the polyol with the compound (IIa), it has correspondingly other functional groups, which react with the secondary amino group of the compound (IIa), such as especially acidic or epoxy groups. Preferred compounds (IIa) according to the invention, are bis (2ethyltrimethoxysilyl) amine, bis (3-propyltrimethoxysilyl) amine, bis (4Petition 870180130797, of 17/09/2018, page 32/60 / 41 butyltrimethoxysilyl) amine, bis (2-ethyltriethoxysilyl) amine, bis (3-propyltriethoxysilyl) amine and / or bis (4-butyltriethoxysilyl) amine. Bis (3-propyltrimethoxysilyl) amine is particularly preferred. Such aminosilanes are available, for example, under the brand name DYNASYLAN® by DEGUSSA or Silquest® by OSi.

[00091] Monomeric composition elements, which carry the structural elements (II), are preferably reaction products of acrylic acid and / or methacrylic or acrylates and / or alkyl methacrylates containing epoxy groups with the compounds (IIa) mentioned above .

[00092] Structural units of formula (III) can be introduced into compound (A) through the incorporation of monomer units with those structural units or through the reaction of polyols, which have other functional groups, with a compound of formula (IIIa) HZ - (X-SiRx (OR ') 3-x) (IIIa), [00093] where the substituents have the meaning mentioned above. For the reaction of the polyol with the compound (IIIa), it has correspondingly other functional groups, which react with the -ZH functional group of the compound (IIIa), such as especially acidic, epoxy or ester groups. Preferred compounds (IIIa) according to the invention are omega-aminoalkyl- or omega-hydroxyalkyltrialoxysilanes, such as preferably 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminoyltroxymethylsilane, 4-aminoyl hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane. Particularly preferred compounds (IIIa) are N- (2- (trimethoxysilyl) ethyl) alkylamines, N- (3 (trimethoxysilyl) propyl) alkylamines, N- (4-trimethoxysilyl) butyl) alkylamines, N (2- (triethoxysilyl) ethyl) alkylamines, N- (3- (triethoxysilyl) propyl) alkylamines and / or

Petition 870180130797, of 9/17/2018, p. 33/60 / 41

N- (4- (triethoxysilyl) butyl) alkylamines. N- (3- (trimethoxysilyl) propyl) butylamine is particularly preferred. Such aminosilanes are available, for example, under the brand name DYNASYLAN® by DEGUSSA or Silquest® by OSI.

[00094] Monomeric composition elements, which carry structural elements (III) are preferably reaction products of acrylic acid and / or methacrylic or acrylates and / or alkyl methacrylates containing epoxy groups, as well as in the case of hydroxy alkoxylsilyl compounds alkyl ester and / or methacrylate transesterification products, especially with the hydroxy and / or amino functional alkoxysilyl (IIIa) compounds mentioned above.

Compounds (B) containing isocyanate groups [00095] The coating agents according to the invention contain as component (B) one or more compounds with free isocyanate groups, that is, deblocked and / or blocked. Preferably, the coating agents according to the invention contain compounds (B) with free isocyanate groups. The free isocyanate groups of compounds B containing isocyanate groups, however, can also be used in blocked form. This is preferably the case when the coating agents according to the invention are used as one-component systems.

[00096] The di- and / or polyisocyanate which serve as basic bodies for the compounds (B) containing isocyanate groups preferably employed according to the invention, are preferably unsubstituted aromatic, aliphatic, cycloaliphatic and / or heterocyclic polyisocyanates or substituted, per se known. Examples of preferred polyisocyanates are:

2,4-toluylenediisocyanate, 2,6-toluylenediisocyanate, diphenylmethan-4,4'-diisocyanate, diphenylmethan-2,4'-diisocyanate, p-phenylenediisocyanate, biphenyldiisocyanates, 3,3'-dimethyl -4,4'-diphenylenediisocyanate, tetramethylen-1,4-diisocyanate, hexamethylen-1,6-diisocyanate, 2,2,4-trimethylhexan-1,6-diisocyanate, isophoronediisocyanate, Ethylenediisocyanate, 1,12-dodecanediPetition 870180130797, of 17/09/2018, p. 34/60 / 41 isocyanate, cyclobutan-1,3-diisocyanate, cyclohexan-1,3-diisocyanate, cyclohexan-1,4-diisocyanate, methylcyclohexildi-isocyanates, hexahydrotoluene-

2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylen-1,3-diisocyanate, hexahydrophenylen-1,4-diisocyanate, perhydrodiphenylmethan-2,4'-diisocyanate, 4,4'- methylenedicyclohexyldiisocyanate (eg Desmodur® W from Bayer AG), tetramethylxylyldiisocyanates (eg TMXDI® from American Cyanamid) and mixtures of the polyisocyanates mentioned above.

[00097] Preferred polyisocyanates, moreover, are the biuret dimers and isocyanurate trimers of the diisocyanates mentioned above.

[00098] Particularly preferred polyisocyanates are hexamethylen-1,6-diisocyanate, isophoronediisocyanate and 4,4'methylene dicyclohexyldiisocyanate, their biuret dimers and / or isocyanurate trimers.

[00099] In another embodiment of the invention, polyisocyanates are polyisocyanate prepolymers with urethane structural units, which are obtained by reacting polyols with a stoichiometric excess of the polyisocyanates mentioned above. Such polyisocyanate prepolymers are described, for example, in US-A-4,598,131.

[000100] The compounds (B) containing isocyanate groups functionalized with the structural units (II) and (III) in a very particular way according to the invention, are preferably prepared by the reaction of the mentioned di- and / or polyisocyanates above with the compounds (IIa) and (IIIa) mentioned above, where [000101] between 2.5 and 90 mol%, preferably 5 to 85 mol%, particularly preferably 7.5 to 80 mol% , of the isocyanate groups in the basic polyisocyanate body, are reacted with at least one compound (IIa) and between [000102] between 2.5 and 90 mol%, preferably 5 to 85 mol%, particularly preferably 7 , 5 to 80 mol%, of the isocyanate groups

Petition 870180130797, of 9/17/2018, p. 35/60 / 41 in the basic polyisocyanate body are reacted with at least one compound (IIIa).

[000103] The total fraction of the isocyanate groups reacted with the compounds (IIa) and (IIIa) is found in the polyisocyanate compound (B) between 5 and 95 mol%, preferably between 10 and 90 mol%, of particularly preferably, between 15 and 85 mol% of the isocyanate groups in the basic polyisocyanate body. Especially with a high degree of silanization, that is, when a high fraction of the isocyanate groups, especially at least 50 mol%, has been reacted with the compounds (IIa) / (IIIa), the isocyanate groups are advantageously reacted with a mixture compounds (IIa) and (IIIa).

[000104] Particularly preferred compounds (IIa) are bis (2ethyltrimethoxysilyl) amine, bis (3-propyltrimethoxysilyl) amine, bis (4butyltrimethoxysilyl) amine, bis (2-ethyltriethoxysilyl) amine, bis (3-propyltriethoxysilyl) amine and / or (or 4-butyltriethoxysilyl) amine. Bis (3-propyltrimethoxysilyl) amine is particularly preferred. Such aminosilanes are for sale, for example, under the brand name DYNASYLAN® by DEGUSSA or Silquest® by OSI.

[000105] Preferred compounds (IIIa) are 2aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 3aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 2-hydroxyethyltriethyl, 3-hydroxyethyltrimethoxy

3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane.

[000106] Particularly preferred compounds (IIIa) are N- (2 (trimethoxysilyl) ethyl) alkylamines, N- (3- (trimethoxysilyl) propyl) alkylamines, N (4- (trimethoxysilyl) butyl) alkylamines, N- (2- ( triethoxysilyl) ethyl) alkylamines, N (3- (triethoxysilyl) propyl) alkylamines and / or N- (4- (triethoxysilyl) butyl) alkylamines.

Petition 870180130797, of 9/17/2018, p. 36/60 / 41

N- (3- (trimethoxysilyl) propyl) butylamine is particularly preferred. Such aminosilanes are for sale, for example, under the brand name DYNASYLAN® by DEGUSSA or Silquest® by OSI.

[000107] Compounds (B) containing very particularly preferred isocyanate groups are reaction products of hexamethylen-1,6-diisocyanate and / or isophoronediisocyanate and / or its isocyanurate trimers with bis (3-propyltrimethoxysilyl) amine and N- ( 3- (trimethoxysilyl) propyl) butylamine. The reaction of the compounds (B) containing isocyanate groups with the compounds (IIa) and (IIIa), is preferably carried out in an atmosphere of inert gas at temperatures of maximum 100 ^o C, preferably of maximum 60 ^o C.

[000108] The free isocyanate groups of compounds B containing isocyanate groups can also be used in blocked form. This is preferably the case when the coating agents according to the invention are used as one-component systems. For blocking, in principle, each of the coating agents applicable for blocking polyisocyanates can be applied with a sufficiently low release temperature. Such blocking agents are well known by the technician. Preferably, blocking agents are employed, as described in EP-A-0.626.888 and EP-A-0.692.007.

The combination of components A and B, as well as other components of the coating agent [000109] The weight fraction of compounds A containing hydroxyl groups to be used, in relation to the weight fraction of compounds B containing isocyanate groups, depends on the equivalent weight of polyol hydroxy and the equivalent weight of the free isocyanate groups of polyisocyanate B.

[000110] It is preferable that, in the coating agent according to the invention, one or more components have between 2.5 to 97.5 mol%, based on the sum of the structural units (II) and (III), of at least one structural unit (II) and between 2.5 and 97.5 mol%, in relation to the sum of the

Petition 870180130797, of 9/17/2018, p. 37/60 / 41 structural units (II) and (III), of at least one structural unit (III).

[000111] The coating agents according to the invention preferably contain between 2.5 and 97.5% by weight, particularly preferably between 5 and 95% by weight, most particularly preferably between 10 and 90% % by weight, especially between 20 and 80% by weight, based on the rate of non-volatile substances in the coating agent, of the compounds (A) containing hydroxyl groups and preferably between 2.5 and 97.5% by weight, so particularly preferred, between 5 and 95% by weight, most particularly preferably between 10 and 90% by weight, especially between 20 and 80% by weight, in relation to the rate of non-volatile substances in the coating agent, of the compounds ( B) containing isocyanate groups.

[000112] Regarding the sum of the functional groups decisive for crosslinking in the coating agent according to the invention, formed from the fractions of the hydroxyl and isocyanate groups, as well as the fractions of the structural elements (I) and / or (II) and / or (III), are the structural elements (I) and / or (II) and / or (III) preferably in fractions of 2.5 to 97.5 mol%, particularly preferably between 5 and 95% in mol and most particularly preferably between 10 and 90 mol%.

[000113] In another embodiment of the invention, the structural elements (I), (II) and / or (III) can additionally also be a component of one or more other components (D) that are distinguished from the components (A ) and (B), in which the criteria mentioned above must be used. For example, as component (D), oligomers or polymers with alkoxysilyl groups can be used, such as, for example, the poly (meth) acrylates mentioned in US-A-4,499 patent (s). 150, US-A-4,499,151 or EP-A-0.571.073 as supports for structural elements (III) or the compounds mentioned in WO-A-2006/042585 as supports for structural elements (II). As a rule, these components (D) are used in fractions of up to 40% by weight, preferably up to 30% by weight, so

Petition 870180130797, of 9/17/2018, p. 38/60 / 41 is particularly preferred, up to 25% by weight, with respect to the non-volatile components of the coating agent.

[000114] The weight fractions of polyol A and polyisocyanate B are preferably selected in such a way that the molar equivalent ratio of the unreacted isocyanate groups of the compounds (B) containing isocyanate to the hydroxyl groups of the compounds (A) containing hydroxyl groups are between 0.9: 1 and 1: 1.1, preferably between 0.95: 1 and 1.05: 1, particularly preferably between 0.98: 1 and 1.02: 1.

[000115] In the case of mono-component coating agents, then compounds (B) containing isocyanate groups are selected, whose free isocyanate groups are blocked with the coating agents described above.

[000116] In the preferred two-component (2K) coating agents according to the invention, shortly before application of the coating agent, a lacquer component containing the compound (A) containing hydroxyl groups, as well as other components described below. next, it is mixed in a known way with another lacquer component, containing the compound (B) containing isocyanate groups and possibly other components described below, being, as a rule, the lacquer component, which contains the compound ( A), contains the catalyst as well as a part of the solvent.

[000117] As solvents for the coating agents according to the invention, those which are chemically inert in the coating agent compared to compounds (A) and (B) and which do not react as (A) and (B) in the hardening of the coating agent. Examples of such solvents are aliphatic and / or aromatic hydrocarbons, such as toluene, xylene, solvent naphtha, Solvesso 100 or Hydrosol® (ARAL company), ketones, such as acetone, methyl ethyl ketone or methyl amyl ketone, esters, such as ethyl acetate, acetate butyl, acetate

Petition 870180130797, of 9/17/2018, p. 39/60 / 41 pentyl or ethyl ethyloxy propionate, ethers or mixtures of the solvents mentioned above. Preferably, aprotic solvents or solvent mixtures have a water rate of at most 1% by weight, particularly preferably at most 0.5% by weight, relative to the solvent.

[000118] In addition to compounds (A), (B) and (D), other ligands (E) can also be used, which preferentially react with the hydroxyl groups of compound (A) and / or with the free isocyanate groups of the compound (B) and / or with the alkoxysilane groups of compounds (A), (B) and / or (D) and can form network points.

[000119] For example, as component (E) aminoplast resins and / or epoxy resins can be used. The usual and known amino acid resins are included, whose methylol and / or methoxymethyl groups can be partially de-functionalized by means of carbamate or allophanate groups. Such crosslinking agents are described in patent reports USA-4,710,542 and EP-B-0.245,700, as well as in the article by B. Singh et al., Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry in Advanced Organic Coatings Science and Technology Series 1991, volume 13, pages 193 to 207.

[000120] As a rule, such components (E) are used in fractions of up to 40% by weight, preferably up to 30% by weight, particularly preferably up to 25% by weight, in relation to the non-volatile components of the agent of coating.

[000121] Furthermore, the coating agent according to the invention may contain at least one lacquer additive which is usual and known in effective amounts, that is, in amounts preferably preferably up to 30% by weight, particularly preferably up to 25% by weight and especially up to 20% by weight, in each case in relation to the non-volatile components of the coating agent.

Petition 870180130797, of 9/17/2018, p. 40/60 / 41 [000122] Examples of suitable lacquer additives are:

[000123] - especially ultraviolet absorbers;

[000124] - especially sun protection agents, such as HALS compounds, benzotriazoles or oxalanilides;

[000125] - antioxidants;

[000126] - straightening additives;

[000127] - polymerization inhibitors;

[000128] - defoamers;

[000129] - reactive diluents, as they are generally known in the prior art, which are preferably inert in relation to the -Si (OR) 3 groups.

[000130] - humectants, such as siloxanes, fluorinated compounds, carboxylic acid semesters, phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes;

[000131] - adhesion promoters such as tricyclodecanedimethanol;

[000132] - course agents;

[000133] - auxiliary film-forming agents, such as cellulose derivatives;

[000134] - filling materials, such as, for example, nanoparticles based on silicon dioxide, aluminum oxide or zirconium oxide; in addition, reference is still made to Rompp Lexikon Lacke und Druckfarben Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252;

[000135] - rheology controlling additives, such as additives known from WO 94/22968, EP-A-0.276,501, EP-A0.249.201 or WO 97/12945; cross-linked polymeric microparticles, such as are published, for example, in EP-A-0.008.127; inorganic layer silicates, such as aluminum-magnesium silicates, sodium-magnesium and sodium-magnesium-fluorine-lithium layer silicones of the montmorillonite type; silicic acids such as aerosils; or synthetic polymers with ionic groups and / or

Petition 870180130797, of 9/17/2018, p. 41/60 / 41 of associative effect, such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone, styrene-anhydride copolymers of maleic acid or ethylene-maleic acid anhydride and their derivatives or ethoxylated urethanes hydrophobically modified or polyacrylates;

[000136] - and / or flame protection agents.

[000137] In another embodiment of the invention, the agent according to the invention, can still contain other pigments and / or fillers and serve for the preparation of pigmented topcoats. The pigments and / or fillers used for this purpose are known to the technician.

[000138] Since the coatings according to the invention, prepared from the coating agents according to the invention, also adhere strongly to electro-immersion lacquers, filling lacquers, already hardened basic lacquers or the usual transparent lacquers and well-known, they are excellently suited, in addition to the use in car serial lacquering (OEM) for car repair lacquering or the risk-resistant modular finish of already lacquered car bodies.

[000139] The application of the coating agents according to the invention, can be carried out using all the usual application methods, such as, for example, spraying, application with rasquilha, spreading, casting, immersion, soaking, instillation or lamination . In that case, the substrate to be coated can rest as such, and the device or application installation is moved. However, the substrate to be coated, especially a coil, can also be moved, and the application installation rests relative to the substrate or is moved properly.

[000140] Preferably, spray application methods are used, such as, for example, spraying with compressed air,

Petition 870180130797, of 9/17/2018, p. 42/60 / 41 airless spraying, high speed, electrostatic spray application (ESTA), possibly associated with hot spray application, such as, for example, hot spray hot-air.

[000141] The hardening of the coating agents used according to the invention, can be carried out after a certain time of rest. The resting time serves, for example, for the elapsing and degassing of the lacquer layers or for evaporating volatile components, such as solvents. The resting time can be supported and / or reduced by the application of high temperatures and / or reduced atmospheric humidity, provided that no damage or changes to the lacquer layers occur, for example, a premature full crosslinking.

[000142] The thermal hardening of the coating agents does not present any methodical particularities, but rather, it is carried out by usual and known methods, such as heating in a circulating air oven or radiation with infrared lamps. Here, thermal hardening can also be carried out in stages. Another preferred method of hardening is hardening with near infrared (NIR radiation). Advantageously, the thermal curing is carried out at a temperature of 30 to 200 ^o C, particularly preferably 40 to 190 ^o C and especially 50 to 180 ^o C over a period of 1 minute to 10 hours, particularly preferably , 2 minutes up to 5 hours and especially 3 minutes up to 3 hours, and at temperatures used for car repair lacquering, which are preferably between 30 and 90 ^o C, longer hardening periods can also be used.

[000143] The coating agents according to the invention, provide new hardened coatings, especially lacquers, especially transparent lacquers, molded parts, especially molded optical parts and cantilever films, which are highly scratch resistant and are especially stable to chemicals and the weather.

Petition 870180130797, of 9/17/2018, p. 43/60 / 41

In particular, coatings and lacquers according to the invention, especially transparent lacquers, can also be produced in layer thicknesses> 40 qm, without the occurrence of stress cracks.

[000144] Therefore, the coating agents according to the invention, are excellently suitable as decorative, protective and / or effect-giving coatings, highly resistant to scratching and lacquering of the bodies of locomotion vehicles (especially vehicles, such as motorcycles , buses, trucks or passenger cars) or parts thereof; of constructions in the internal and external area; furniture, windows and doors; molded plastic parts, especially CDs and windows, small industrial parts, reels, containers and packaging; white goods; of films; optical, electrical and mechanical construction parts, as well as hollow glass bodies and objects for daily use.

[000145] The coating agents according to the invention and lacquers, especially transparent lacquers, are especially used in the particularly demanding technological and aesthetic field of automotive series lacquering (OEM), as well as car repair lacquering. Particularly preferred, the coating agents according to the invention are used in multistage coating processes, especially in the process, in which a pigmented basic lacquer layer is initially applied to a possibly pre-coated substrate and then a layer with the coating agents according to the invention.

[000146] It is possible to use both basic lacquers dilutable with water, as well as basic lacquers based on organic solvents. Suitable basic lacquers are described, for example, in EP-A-0.692.007 and in the documents listed there in column 3, line 50 and following. Preferably, the applied basic lacquer is initially dried, that is, it is removed from the basic lacquer film in a

Petition 870180130797, of 9/17/2018, p. 44/60 / 41 evaporation phase, at least part of the organic solvent, respectively, from the water. Drying is preferably carried out at temperatures from room temperature up to 80 ^o C. After drying, the coating agent according to the invention is applied. Thereafter, the two-layer lacquer is preferably kiln dried under the conditions used in series car lacquering, at temperatures of 30 to 200 ^o C, particularly preferably 40 to 190 ° C and especially 50 to 180 ^o C, for a period of 1 minute to 10 hours, particularly preferably 2 minutes to 5 hours and especially 3 minutes to 3 hours, and at temperatures applied for car repair lacquering, which are preferably between 30 and 90 ^o C , longer hardening periods can also be applied.

[000147] The layers produced with the coating agent according to the invention, stand out mainly for their particularly high resistance to chemicals and weather, as well as for a very good resistance to street washing and scratch resistance, especially by an excellent combination of scratch resistance and weather stability against ultraviolet radiation in the wet-dry cycle.

[000148] In another preferred embodiment of the invention, the coating agent according to the invention is used as a clear transparent lacquer for coating plastic substrates, especially transparent plastic substrates. In this case, the coating agents contain ultraviolet absorbers, which in quantity and type are also coated on the effective ultraviolet protection of the plastic material substrate. Here too, coating agents stand out for their outstanding combination of scratch resistance and weather resistance against ultraviolet radiation in the wet-dry cycle. Plastic substrates coated in this way are preferably used to replace glass components in the construction of

Petition 870180130797, of 9/17/2018, p. 45/60 / 41 automobiles, where the plastic material substrates preferably consist of polymethyl methacrylate or polycarbonate.

Preparation examples [000149] Silanized hardener 1:

[000150] Preparation:

[000151] - pos 1: 57.30 g (0.100 mol) of HDI polyisocyanurate (hexamethyl-1,6-diisocyanate), Basonat® HI 100 [000152] - pos 2: 63.74 g of naphtha solvent (aromatic hydrocarbon mixture) [000153] - pos 3: 51.23 g (0.150 mol) of bis- [3- (trimethoxysilyl) propyl] -amine, Dynasylan 1124® [000154] Execution:

[000155] In a 250 mg tritubulated flask with stirring magnet, internal thermometer and drip funnel, pos 1 and 2 are previously introduced. The colorless, clear solution is stirred at room temperature under a refluxing nitrogen atmosphere. Pos 3 is slowly added to the drops, so that the temperature does not exceed 60 ^o C. After the completion of pos 3, there is a yellowish, clear solution. The temperature is 56 ^o C and, using a heating and oil bath stirring plate, is kept at 50-60 ^o C for 4 hours. The determination of the free isocyanate rate is carried out through titration. The product is sieved with a 31 qm sieve.

[000156] characteristic indexes:

theoretical: nfA [%] 63.00 theoretical NCO rate in relation to nfA [%] 5.81 degree of blockade of groups NCO [%] 50 viscosity [mPas] 70

[000157] Silanized hardener 2:

Petition 870180130797, of 9/17/2018, p. 46/60 / 41 [000158] Preparation:

[000159] - pos 1: 57.30 g (0.100 mol) of HDI polyisocyanurate (hexamethyl-1,6-diisocyanate), Basonat® HI 100 [000160] - pos 2: 62,70 g of naphtha solvent (aromatic hydrocarbon mixture) [000161] - pos 3: 25.62 g (0.075 mol) of bis- [3- (trimethoxysilyl) propyl] -amine, Dynasylan 1124® [000162] - pos 4: 17.65 g (0.075 mol) of N- [3- (trimethoxysilyl) propyl] -butylamine Dynasylan 1189® [000163] Execution:

[000164] In a 250 mg tritubulated flask with stirring magnet, internal thermometer and drip funnel, pos 1 and 2 are previously introduced. The colorless, clear solution is stirred at room temperature under a nitrogen and reflux atmosphere. A mixture of pos 3 and 4 is slowly added to the drops, so that the temperature does not exceed 60 ^o C. After the completion of pos 3 and 4, there is a clear, slightly yellow solution. The temperature is 56 ^o C and, using a heating and oil bath stirring plate, is kept at 50-60 ^o C for 4 hours. The determination of the free isocyanate rate is carried out through titration. The product is sieved through a 31 pm sieve.

[000165] characteristic indexes:

theoretical: nfA [%] 63.00 theoretical NCO rate in relation to nfA [%] 6.3 degree of blockade of groups NCO [%] 50

[000166] Through the simultaneous use of bis- and monosilanamines, a better risk resistance is obtained with simultaneously good weather properties. Compared to compounds

Petition 870180130797, of 9/17/2018, p. 47/60 / 41 pure bisilanes, an improvement is obtained with respect to the premature formation of cracks in the fast weather and the necessary resistance to risk.

Phosphoric acid ester catalyst:

Triethylamine-based catalyst:

[000167] Preparation:

[000168] - pos 1: 10.62 g (0.105 mol) of triethylamine [000169] - pos 2: 32.24 g (0.100 mol) of bis (2-ethylhexyl) phosphate [000170] - pos 3: 10.00 g (0.100 mol) of methylisobutyl ketone [000171] - pos 4: 10.00 g (0.113 mol) of ethyl acetate [000172] In a 100 ml tritubulated flask, positions 2, 3 and 4 are previously introduced. The colorless, clear liquid is stirred at room temperature under a nitrogen atmosphere. Pos 1 is slowly added to the drops, so that the temperature does not exceed 45 ^o C. After the completion of pos 1, there is a colorless, clear solution. The temperature is 40 ^o C and maintained for 3 hours by means of a heating shaker and oil bath. Then, the solvent (pos 3 and 4) is distilled by means of a rotary evaporator at 65 ^o C and 20 mbar. A colorless, clear solution is obtained. The yield is 40.20 g (94%). Then, adjust to a nfA of 25% with isopropanol. (nfA = non-volatile fraction, determined by weighing after 1 hour at 130 ^o C).

characteristic indices:

[000173] - viscosity η [mPas]: 124.7 mPas, T = 23.0 ^o C [000174] - refractive index n: nD ²⁰ = 1.4488 [000175] - acidity index SZ [mg KOH / g]: 144 mg KOH / g [000176] - pH value: pH = 6; T = 24 ^o C.

DABCO-based catalyst:

[000177] Preparation:

[000178] - pos 1: 11,78 g (0,105 mol) of 1,4 diazabicyclo (2,2,2) octane [DABCO Crystal] [000179] - pos 2: 32,24 g (0,100 mol) of bis phosphate (2-ethylhexyl)

Petition 870180130797, of 9/17/2018, p. 48/60 / 41 [000180] - pos 3: 10.00 g (0.100 mol) of methylisobutyl ketone [000181] - pos 4: 20.00 g (0.226 mol) of ethyl acetate [000182] Execution:

[000183] In a 100 ml tritubulated flask, pos 1, 3 and 4 are previously introduced. Pos 1 is stirred at 44 ^o C under nitrogen and reflux and dissolved. Pos 2 is slowly added to the drops, so that the temperature does not exceed 50 ^o C. After the completion of pos 1, there is a clear, slightly yellow solution. The temperature is 48 ^o C and by means of a heating and oil bath stirring plate. it is kept for 3 hours at 40 ^o C. Then, the solvent (pos 3 and 4) is distilled by means of rotary evaporator at 65 ^o C and 20 mbar. A gelatinous, white mass is obtained, which solidifies at room temperature. The yield is 41.00 g (93%).

[000184] Characteristic indices:

[000185] - acidity index SZ [mg KOH / g]: 134 mg KOH / g [000186] - pH value: pH = 7; T = 24 ^o C.

[000187] Formulation:

pos product fA m revenue% in m binder 1 OHZ polyacrylate 156 mg KOH / g, (52.40 + 1.0% solvent mixture) 17.26 32.94 2 solvent naphtha 12 3 catalyst X X X hardener

Petition 870180130797, of 9/17/2018, p. 49/60 / 41

4 HDI isocyanurate modified (silanized hardener in the preparation example) NCO rate: 5.81 + 1.00% (at 63.00 + 2.00% in solvent naphtha) 34.69 55.06 total sum 51.95 100.00 viscosity of processing about 50s (ISO 4)

[000188] X represents catalyst based on DABCO: 0.28 [000189] X represents catalyst based on triethylamine: 0.26

Attachment

Determination of the pKb value:

1. Summary [000190] The dissociation constant (pK _a ) of the test substance at 23 ^o C and a concentration of the test substance of approximately 0.01 m makes:

[000191] pKa = 9.90 + 0.06

2. Experimental [000192] Literature:

[000193] The determination is made based on the OECD GUIDELINE FOR TESTING OF CHEMICALS, 112 (1981) Dissoziation Constants in Water, as well as the monograph:

[000194] A. Albert, E.P. Serjeant, Determination of Ionization Constants, chapter 2: Determination of ionization constants by potentiometric titration using a glass electrode, Chapman and Hall, London (1984).

[000195] Principle:

For the ionization of a base in water [000196], the dissociation constant Kb can be indicated:

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Β + HO _ν ^s ΒΗ * + CH 'ΒΗ * ILO

Kh = ------------- ^a B H20 [000197] Here, ^a represents the activities of each species in mol / 1.

[000198] In diluted solutions, the activity of a species approximately corresponds to its concentration c in mol / 1. In addition, Ή2Ο can be considered as constant. In this way, it results:

= βΗ * 'OH —---- ^and B [000199] The dissociation constant is also often indicated in the form of a negative logarithm.

'B pKt »- pOH + log ---- ΐΗ * [000200] When using the ionization constant of the

BH ’H * + B [000201] conjugated, must be formulated:

[000202] using the formulas [000203] pOH + pH = 14 [000204] pK _b + pK _a = 14 [000205] the ionization constant pK _a can be determined using the following equation:

^and BH ⁺ pK „= pH + log ---- Petition 870180130797, of 17/09/2018, p. 51/60

39/41 [000206] The pK _a value can be determined, among others, titrimetrically.

[000207] For this purpose, the test substance (for example, base B) is dissolved in water. In this case, the concentration should not make more than 0.01 mol / 1. When the substance is only slightly dissolved, small fractions of a water-miscible solvent (for example, isopropanol) are added. The test solution is titrated with a dimensional acid solution. In that case, the temperature should be between 20 ° C and 25 ° C and maintained at + 1 ° C. The assessment is carried out according to the following formula:

'MH +' OH - ^and H * pKa ~ pH + log ------------------------ ^C S - ^C MH-'OH · + ^C IT [000208] In this case, they mean:

[000209] pK ^a = negative logarithm of the dissociation constant [000210] pH = negative logarithm of H ⁺ ions activity (approximately H ⁺ ion concentration), in which it is worth:

[000211] pH = -log Ή ⁺ [000212] Ή ⁺ = concentration of H ⁺ ions in mol / 1 (calculated from the measured pH value. While the pH value is above 7, ^C H ⁺ can be neglected in the calculation of the result).

[000213] ΌΗ = concentration of OH ions ^- in mol / 1 (calculated from the measured pH value: pH + pOH = 14. While the pH value is below 7, Ή 'can be neglected when calculating the result) .

[000214] ^C S = the crude concentration of the test substance determined by the initial weight in the test solution in mol / 1 (concentration of the substance) [000215] ^C MH = concentration of the titrating agent MH and mol / 1, where M , as a rule, is a halogen (for example, Cl, Br and others).

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1ÔÚÔ 'MH = Vc't · ------------ Vp + V1OOT [000216] V = titration agent consumption in 1 [000217] c = measurement concentration of the titrating agent in mol / 1 [000218] t = title p & oo [000219] Vp = volume of ε ___________ il when adding ^C S [000220] The expression vp + v 1000 can be fixed at approximately 20 [000221] when the consumption of the titrating agent amounts to no more than 5 ml and Vp makes about 47 - 48 ml (for example, 47.5 ml).

2.1 Devices [000222] 2.1.1 Scale: Mettler AT 261 Wag 17 [000223] 2.1.2 Titrator: Metrohm DMS Titrino 716 with 10 ml of exchange unit W 20 [000224] 2.1.3 Combined glass electrode: Metrohm 6.0203. 100

EG 10

2.2 Reagents [000225] 2.2.1 Measuring solution: hydrochloric acid, [000226] concentration of the quantity of substance c (HCl) = 0.1 mol / 1, manufacturer: Bernd Kraft, article no. 1044. title t = 1, 0016, title n ° 98/08/32 [000227] 2.2.2 water, deionized, BASF (ELGA-Maxima pure water installation)

2.3 Procedure [000228] Approximately 0.09 g of the test substance is exactly weighed (compare paragraph 2) and dissolved in 47.5 ml of water (2.2.2) under magnetic stirring. The solution obtained with a ^C S concentration of about

Petition 870180130797, of 9/17/2018, p. 53/60 / 41

0.01 M is then added step by step in each case with equal volumes of hydrochloric acid (2.2.1). The pH value obtained is determined and evaluated in tabular form using the formula mentioned in paragraph 2.

[000229] Measuring temperature = 23 ^o C.

Claims (17)

1. Coating agent, characterized by the fact that it contains (a) at least one binder (A) containing hydroxyl groups, (b) at least one cross-linking agent (B) containing free and / or blocked isocyanate groups, which can react with the hydroxyl groups of the linker (A) under crosslinking and (c) at least one catalyst (C) for crosslinking silane groups, in which one or more components (A) and / or (B) and / or at least one other component of the coating agent contains hydrolysable silane groups, where the catalyst (C) is a phosphoric acid and / or phosphonic acid compound blocked with a bicyclic amine which has a pKb value> 3 and a boiling point> 100 ^o C . Coating agent according to claim 1, characterized in that the catalyst (C) is selected from the group of phosphoric acid monoesters and substituted phosphoric acid diesters, preferably from the group, consisting of acyclic phosphoric acid diesters and cyclic phosphoric acid diesters. Coating agent according to claim 2, characterized in that the catalyst (C) is selected from the group of amine-blocked partial phosphoric acid ethylhexyl esters and amine-blocked partial phenyl esters, especially bis (ethylhexyl) esters of phosphoric acid blocked with amine. Coating agent according to any one of claims 1 to 3, characterized in that the bicyclic amine is diazabicyclooctane. Coating agent according to any one of claims 1 to 3, characterized in that one or more components of the coating agent have at least partially one or more Petition 870190037071, of 17/04/2019, p. 10/15 2/5 same or different structural units of formula (I) -X-Si-R _x G3- _x (I) with G = identical or different hydrolyzable groups, especially G = alkoxy group (O R '), where R' is an alkyl radical containing 1 to 6 carbon atoms X = organic radical, especially linear and / or branched alkylene or cycloalkylene radical with 1 to 20 carbon atoms, most particularly preferred X = alkylene radical with 1 to 4 carbon atoms, R '' = alkyl, cycloalkyl, aryl or aralkyl, where the carbon chain can be interrupted by non-adjacent oxygen, sulfur or NRa groups, with Ra = alkyl, cycloalkyl, aryl or aralkyl, preferably R '' = radical alkyl, especially with 1 to 6 carbon atoms, x = 0 to 2, preferably 0 to 1, particularly preferably, x = 0. Coating agent according to any one of claims 1 to 5, characterized in that one or more components of the coating agent have between 2.5 and 97.5 mol%, in relation to the total structural units ( II) and (III), of at least one structural unit of formula (II) -N (X-SiR''x (OR ') 3-x) n (X'-SiR''y (OR') 3-y) m (II), in which R '= hydrogen, alkyl or cycloalkyl, where the carbon chain can be interrupted by non-adjacent oxygen, sulfur or NRa groups, with Ra = alkyl, cycloalkyl, aryl or aralkyl, preferably R' = ethyl and / or methyl, X, X '= linear and / or branched alkylene or cycloalkylene radical with 1 to 20 carbon atoms, preferably X, X' = alkylene radical with 1 to 4 carbon atoms, Petition 870190037071, of 17/04/2019, p. 11/15 3/5 R '' = alkyl, cycloalkyl, aryl or aralkyl, where the carbon chain can be interrupted by non-adjacent oxygen, sulfur or NRa groups, with Ra = alkyl, cycloalkyl, aryl or aralkyl, preferably R '' = radical alkyl, especially with 1 to 6 carbon atoms, n = 0 to 2, m = 0 to 2, m + n = 2, as well as x, y = 0 to 2 and between 2.5 and 97.5 mol%, in relation to the total structural units (II) and (III), of at least one structural unit of the formula (III) -Z- (X-SiR''x (OR ') 3-x) (III), in which Z = -NH-, -NR-, -O-, with R = alkyl, cycloalkyl, aryl or aralkyl, where the carbon chain can be interrupted by non-adjacent oxygen, sulfur or NRa groups, with Ra = alkyl, cycloalkyl, aryl or aralkyl, x = 0 to 2 and X, R ', R' 'have the meanings indicated in formula (II). Coating agent according to claim 6, characterized in that one or more components of the coating agent have between 5 and 95 mol%, especially between 10 and 90 mol%, particularly preferably between 20 and 80% by mol and in a very particular way, between 30 and 70% by mol, in each case in relation to the totality of the structural units (II) and (III), of at least one structural unit of the formula (II) and between 5 and 95 mol%, especially between 10 and 90 mol%, particularly preferably between 20 and 80 mol% and very particularly between 30 and 70 mol%, in each case in relation to all structural units (II) and (III) of at least one structural unit of the formula (III). Coating agent according to claim 6 or 7, Petition 870190037071, of 17/04/2019, p. 12/15 4/5 characterized by the fact that the structural elements (II) and (III) are present in fractions of 2.5 to 97.5 mol%, preferably from 5 to 95 mol%, particularly preferably between 10 and 90 mol%, in each case in relation to the sum of the functional groups suitable for crosslinking in the coating agent, formed from the fractions of the hydroxyl and isocyanate groups, as well as the fractions of the structural elements (II) and (III). Coating agent according to claim 5 or 6, characterized in that the polyisocyanate (B) has the structural units (I) or (II) or (III). 10. Coating agent according to claim 9, characterized in that in the polyisocyanate (B) between 2.5 and 90 mol%, the isocyanate groups in the basic polyisocyanate body are reacted to form structural units (II) and between 2.5 and 90 mol%, of the isocyanate groups in the basic polyisocyanate body are reacted to form structural units (III) and the total fraction of the isocyanate groups reacted to form the structural units (II) and (III) in the basic polyisocyanate body is between 5 and 95 mol%. Coating agent according to claim 9 or 10, characterized in that the basic polyisocyanate body is selected from the group 1,6-hexamethylenediisocyanate, isophoronodiisocyanate and 4,4'-methylenedicyclohexildiisocyanate , the polyisocyanate biuret dimers mentioned above and / or the polyisocyanates isocyanurate trimers mentioned above. Coating agent according to any one of claims 1 to 11, characterized in that the binder (A) containing hydroxyl groups contains at least one poly (meth) acrylate polyol. 13. Coating agent according to any of the Petition 870190037071, of 17/04/2019, p. 13/15 5/5 claims 1 to 12, characterized in that the catalyst (C) is contained in it in an amount of 0.1 to 10% by weight, preferably 0.1 to 3% by weight, in relation to the solid content of the coating agent. 14. Multistage coating process, characterized in that a pigmented basic lacquer layer and then a coating agent layer as defined in any of claims 1 to 13 are applied to a possibly pre-coated substrate. 15. Multistage coating process according to claim 14, characterized by the fact that after the application of the pigmented basic lacquer layer, the applied basic lacquer is initially dried at room temperature temperatures up to 80 ^o C and after application of the coating agent as defined in any one of claims 1 to 13 is cured at temperatures of 30 to 200 ^o C for a time of 1 minute to 10 hours. 16. Multistage coating process according to claim 14 or 15, characterized by the fact that it is for car lacquering and car repair lacquering. 17. Use of coating agents as defined in any one of claims 1 to 13, characterized in that it is a clear lacquer.