DE102013213835A1 - Crosslinkable compositions based on phenylsilicone resins and organyloxysilane-terminated polymers - Google Patents

Abstract

The invention relates to crosslinkable compositions comprising (A) 100 parts by weight of compounds (A) of the formula Y - [(CR 1 2) b-SiRa (OR 2) 3-a] x (I), (B) more than 50 parts by weight of silicone resins containing units of Formula R3c (R4O) dR5 eSiO (4-cde) / 2 (II), (C) at least 0.1 part by weight of organosilicon compounds other than component (B) containing units of the formula DfSi (OR7) gR8h (III), all Radicals and indices of the meaning given in claim 1, (D) at least 0.05 part by weight of antioxidants and (E) at least 0.05 part by weight of UV absorber, process for their preparation and their use.

Description

The invention relates to crosslinkable compositions, in particular coatings containing silane-crosslinking prepolymers and phenylsilicone resins, processes for their preparation and their use.

Silicone resin coatings have some outstanding properties over coatings consisting solely of organic binders, e.g. a good weather resistance, corrosion resistance or a high abrasion resistance. In addition, the liquid coatings before their curing usually low solvent or free and also very beneficial from a toxicological point of view, u.a. they are not sensitizing.

However, the known, crosslinked silicone resin coatings also have disadvantages. Due to the high three-dimensional cross-linking density, the flexibility is usually low, which is first expressed by poorer impact resistance in the so-called impact test and moderate results in the mandrel bending test. The coatings often harden and lose further flexibility.

In principle, mixing systems consisting of silicone resins and silane-crosslinking polymers, as in WO 2013/026654 offer significant advantages, since they can in principle combine the advantages of pure silicone resins and organic polymers together. For weathering exposed, colored coatings, however, such systems are not due to their lack of UV resistance or at least only very partially suitable.

The object of the invention is therefore to provide coating formulations which avoid the disadvantages of the prior art.

• (A) 100 Gewichtsteile Verbindungen (A) der Formel Y-[(CR¹ ₂)_b-SiR_a(OR²)_3-a]_x (I), wobei Y einen x-wertigen, über Stickstoff, Sauerstoff, Schwefel oder Kohlenstoff gebundenen Polymerrest bedeutet, R gleich oder verschieden sein kann und einen einwertigen, gegebenenfalls substituierten, SiC-gebundenen Kohlenwasserstoffrest darstellt, R¹ gleich oder verschieden sein kann und Wasserstoffatom oder einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest darstellt, der über Stickstoff, Phosphor, Sauerstoff, Schwefel oder Carbonylgruppe an das Kohlenstoffatom angebunden sein kann, R² gleich oder verschieden sein kann und Wasserstoffatom oder einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest darstellt, x eine ganze Zahl von 1 bis 10, bevorzugt 1, 2 oder 3, besonders bevorzugt 1 oder 2, ist, a gleich oder verschieden sein kann und 0, 1 oder 2, bevorzugt 0 oder 1, ist und b gleich oder verschieden sein kann und eine ganze Zahl von 1 bis 10, bevorzugt 1, 3 oder 4, besonders bevorzugt 1 oder 3, insbesondere 1, ist,
• (B) mehr als 50 Gewichtsteile Siliconharze enthaltend Einheiten der Formel R³ _c(R⁴O)_dR⁵ _eSiO_(4-c-d-e)/2 (II), wobei R³ gleich oder verschieden sein kann und Wasserstoffatom, einen einwertigen, SiC-gebundenen, gegebenenfalls substituierten aliphatischen Kohlenwasserstoffrest oder einen zweiwertigen, gegebenenfalls substituierten, aliphatischen Kohlenwasserstoffrest, der zwei Einheiten der Formel (II) verbrückt, bedeutet, R⁴ gleich oder verschieden sein kann und Wasserstoffatom oder einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest bedeutet, R⁵ gleich oder verschieden sein kann und einen einwertigen, SiC-gebundenen, gegebenenfalls substituierten aromatischen Kohlenwasserstoffrest bedeutet, c 0, 1, 2 oder 3 ist, d 0, 1, 2 oder 3, bevorzugt 0, 1 oder 2, besonders bevorzugt 0 oder 1, ist und e 0, 1 oder 2, bevorzugt 0 oder 1, ist, mit der Maßgabe, dass die Summe aus c + d + e kleiner oder gleich 3 ist, in mindestens einer Einheit e verschieden 0 ist und in mindestens 40 % der Einheiten der Formel (II) die Summe c + e gleich 0 oder 1 ist,
• (C) mindestens 0,1 Gewichtsteile von Komponente (B) verschiedenen Organosiliciumverbindungen enthaltend Einheiten der Formel D_fSi(OR⁷)_gR⁸ _h (III), worin D gleich oder verschieden sein kann und einen einwertigen SiC-gebundenen organischen Rest mit mindestens zwei Kohlenstoffatomen, der kein nicht direkt an eine Carbonylgruppe gebundenes Stickstoffatom aufweist, bedeutet, R⁷ gleich oder verschieden sein kann und Wasserstoffatom oder gegebenenfalls substituierte Kohlenwasserstoffreste bedeutet, R⁸ gleich oder verschieden sein kann und gegebenenfalls substituierte Kohlenwasserstoffreste bedeutet, f 0, 1, 2 oder 3, bevorzugt 1, ist, g 0, 1, 2, 3 oder 4, bevorzugt 1, 2 oder 3, besonders bevorzugt 2 oder 3, ist und h 0, 1, 2 oder 3, bevorzugt 1 oder 0, ist, mit der Maßgabe, dass die Summe aus f + g + h gleich 4 ist,
• (D) mindestens 0,05 Gewichtsteile Antioxidantien und
• (E) mindestens 0,05 Gewichtsteile UV-Absorber.

The invention relates to crosslinkable compositions containing

• (A) 100 parts by weight of compounds (A) of the formula Y - [(CR ¹ ₂ ) _b -SiR _a (OR ² ) _3-a ] _x (I), wherein Y is an x-valent, bound via nitrogen, oxygen, sulfur or carbon polymer residue, R may be the same or different and represents a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, R ^{1 may be the} same or different and is hydrogen atom or a monovalent is optionally substituted hydrocarbon radical which may be attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group, R ^{2 may be} identical or different and represents hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, x is an integer from 1 to 10 , preferably 1, 2 or 3, more preferably 1 or 2, a, may be the same or different and 0, 1 or 2, preferably 0 or 1, and b may be the same or different and an integer from 1 to 10 , preferably 1, 3 or 4, particularly preferably 1 or 3, in particular 1,
• (B) more than 50 parts by weight of silicone resins containing units of the formula R ³ _c (R ⁴ O) _d R ⁵ _e SiO _{(4-cde) / 2} (II), wherein R ^{3 may be the} same or different and is hydrogen atom, a monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon radical or a divalent, optionally substituted, aliphatic hydrocarbon radical bridging two units of formula (II), R ^{4 may be the} same or different R ^{5 is the} same or different and is a monovalent, SiC-bonded, optionally substituted aromatic hydrocarbon radical, c is 0, 1, 2 or 3, d is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and e is 0, 1 or 2, preferably 0 or 1, with the proviso that the sum of c + d + e is less than or equal to 3, is different in at least one unit e, and in at least 40% of the units of the formula (II) the sum c + e is 0 or 1,
• (C) at least 0.1 part by weight of component (B) different organosilicon compounds containing units of the formula D _f Si (OR ⁷ ) _g R ⁸ _h (III), wherein D may be the same or different and is a monovalent SiC-bonded organic radical having at least two carbon atoms which does not have a nitrogen atom not directly bonded to a carbonyl group, R ^{7 may be the} same or different and is hydrogen or optionally substituted hydrocarbon radicals, R ⁸ may be the same or different and is optionally substituted hydrocarbon radicals, f is 0, 1, 2 or 3, preferably 1, g is 0, 1, 2, 3 or 4, preferably 1, 2 or 3, particularly preferably 2 or 3 and h is 0, 1, 2 or 3, preferably 1 or 0, with the proviso that the sum of f + g + h is 4,
• (D) at least 0.05 parts by weight of antioxidants and
• (E) at least 0.05 part by weight of UV absorber.

• (F) mindestens 0,1 Gewichtsteile Farbmittel.

Preferably, the formulation according to the invention additionally contains

• (F) at least 0.1 parts by weight of colorant.

The invention is based on the surprising discovery that the addition of an organosilicon compound (C) of the formula (III) leads to a significant improvement in the storage stability of the resulting uncrosslinked coating.

Furthermore, the invention is based on the surprising discovery that the addition of an organosilicon compound (C) of the formula (III) additionally leads to a significant improvement in the UV resistance of the resulting coating, if the coating additionally contains at least one or more antioxidants and one or more UV Absorber contains. Particularly surprising was the fact that the UV stability can be increased even further, if the mixture according to the invention additionally contains one or more pigments, which is why this represents a particularly preferred embodiment of the invention.

Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl; Hexyl radicals, such as the n-hexyl radical; Heptyl radicals, such as the n-heptyl radical; Octyl radicals such as the n-octyl radical, iso-octyl radicals and the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; Alkenyl radicals such as the vinyl, 1-propenyl and 2-propenyl radicals; Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radicals; Alkaryl radicals, such as o-, m-, p-tolyl radicals; Xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.

Examples of substituted radicals R are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2',2',2'-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, and haloaryl radicals, such as , m- and p-chlorophenyl.

The radicals R are preferably monovalent hydrocarbon radicals having 1 to 6 carbon atoms which are optionally substituted by halogen atoms, particularly preferably alkyl radicals having 1 or 2 carbon atoms, in particular the methyl radical.

Examples of radicals R are hydrogen atom, the radicals indicated for R ¹ and optionally substituted hydrocarbon radicals bonded to the carbon atom via nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl group.

Radical R ¹ is preferably hydrogen atom and hydrocarbon radicals having 1 to 20 carbon atoms, in particular hydrogen atom.

Examples of radical R ² are hydrogen atom or the examples given for radical R.

The radicals R ^{2 are} preferably hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms optionally substituted by halogen atoms, more preferably alkyl radicals having 1 to 4 carbon atoms, in particular the methyl and ethyl radical.

For the purposes of the present invention, polymers which are based on the polymer radical Y are all polymers in which at least 50%, preferably at least 70%, particularly preferably at least 90%, of all bonds in the main chain carbon-carbon, carbon Nitrogen or carbon-oxygen bonds are.

Polymer residue Y is preferably an organic polymer residue which, as polymer chain, comprises polyoxyalkylenes, such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer and polyoxypropylene-polyoxybutylene copolymer; Hydrocarbon polymers, such as polyisobutylene, polyethylene or polypropylene and copolymers of polyisobutylene with isoprene; polyisoprenes; polyurethanes; Polyester; polyamides; polyacrylates; polymethacrylates; and polycarbonates and which preferably have O -OC (OO) -NH-, -NH-C (OO) O-, -NH-C (OO) -NH-, -NR'-C (OO) - NH-, NH-C (= O) -NR'-, -NH-C (= O) -, -C (= O) -NH-, -C (= O) -O-, -OC (= O ), -OC (= O) -O-, -SC (= O) -NH-, -NH-C (= O) -S-, -C (= O) -S-, -SC (= O ) -, -SC (= O) -S-, -C (= O) -, -S-, -O- and -NR'- to the group or groups - [(CR ¹ 2) _b -SiR _a (OR ² ) _3-a ], where R 'may be identical or different and has a meaning given for R or represents a group -CH (COOR ") - CH ₂ -COOR", in which R "is identical or may be different and has a meaning given for R.

Examples of radicals R 'are cyclohexyl, cyclopentyl, n- and iso-propyl, n-, iso- and t-butyl, the various sterioisomers of the pentyl radical, hexyl radical or heptyl radical and the phenyl radical.

Particularly preferably, radical Y in formula (I) is polyacrylates, polyesters or polyoxyalkylene radicals.

The component (A) can have the groups attached in the described manner - [(CR ¹ ₂ ) _b -SiR _a (OR ² ) _3-a ] at arbitrary positions in the polymer, such as chain-connected and / or terminal, preferably chain-chain and terminal, more preferably terminal.

The end groups of the compounds (A) used according to the invention are preferably those of the general formula -OC (= O) -NH- (CR ¹ ₂ ) _b -SiR _a (OR ² ) _3-a (IV), where the radicals and indices have one of the meanings given above.

In a particularly preferred embodiment of the invention, component (A) is silane-terminated polyethers, polyacrylates or polyesters having dimethoxymethylsilyl, trimethoxysilyl, in each case attached via --OC (= O) -NH- (CR ¹ ₂ ) _b groups. Diethoxymethylsilyl or triethoxysilyl end groups, wherein R ¹ and b have one of the meanings given above.

The average molecular weights M _{n of} the compounds (A) are preferably at least 400 g / mol, more preferably at least 600 g / mol, in particular at least 800 g / mol and preferably at most 30,000 g / mol, particularly preferably at most 19,000 g / mol.

The number average molecular weight M _n was determined by means of Size Exclusion Chromatography (SEC) against polystyrene standard, in THF, at 60 ° C., flow rate 1.2 ml / min and detection with RI (refractive index detector) on a column set Styragel HR3- HR4-HR5-HR5 from Waters Corp. USA with an injection volume of 100 μl.

The viscosity of the compounds (A) is preferably at least 100 mPas, preferably at least 250 mPas, more preferably at least 500 mPas, and preferably at most 100,000 mPas, preferably at most 50,000 mPas, each measured at 20 ° C.

In the context of the present invention, the viscosity is determined using a Brookfield rotational viscometer.

The compounds (A) used according to the invention are commercially available products or can be prepared by methods customary in chemistry.

The preparation of the polymers (A) can be carried out by various known methods, such as addition reactions, e.g. hydrosilylation, Michael addition, Diels-Alder addition or reactions between isocyanate-functional compounds with compounds having isocyanate-reactive groups.

In a first particularly preferred embodiment of the invention, component (A) contains as polymer radicals Y linear or branched polyoxyalkylene radicals, more preferably polyoxyethylene radicals, polyoxypropylene radicals or polyoxytetramethylene radicals, in particular polyoxypropylene radicals whose chain ends preferably via -OC (= O) -NH- to the group or Groups - [(CR ¹ ₂ ) _b -SiR _a (OR ² ) _3-a ] are bonded, wherein the radicals and indices have one of the meanings mentioned above. Preferably, at least 85%, particularly preferably at least 90%, especially at least 95%, of all chain ends via -OC (= O) -NH- to the group - [(CR ¹ ₂ ) _b -SiR _a (OR ² ) _{3- a} ] bound. The polyoxyalkylene radicals Y preferably have average molecular weights M _n of 4000 to 30 000 g / mol, preferably from 8000 to 20 000 g / mol. Suitable processes for preparing a corresponding component (A) as well as examples of the component (A) itself are known and inter alia in EP 1 535 940 B1 (Paragraphs [0005] - [0025] and Examples 1-3 and Comparative Example 1-4) or EP 1 896 523 B1 (Paragraphs [0008] - [0047]), which are to be included in the disclosure of the present application. Corresponding silane-terminated polymers are also commercially available, for example under the name GENIOSIL® ^® STP-E from. Wacker Chemie AG.

If component (A) is a different type of compound of formula (I), mixtures comprising both compounds (A1) having end groups of formula (IV) wherein b = 1 and R ¹ = H and a = 0 or 1, as well as compounds (A2) having end groups of the formula (IV) in which b = 3 and R ¹ = H and a = 0 is preferred.

The compositions of the invention preferably contain compounds (A) in concentrations of at most 60% by weight, more preferably at most 50% by weight, and preferably at least 10% by weight, particularly preferably at least 20% by weight.

Based on 100 parts by weight of component (A), the compositions according to the invention preferably contain at least 60 parts by weight, more preferably at least 80 parts by weight, in particular at least 100 parts by weight, of component (B). Based on 100 parts by weight of component (A), the compositions of the invention preferably contain at most 1000 parts by weight, more preferably at most 500 parts by weight, especially at most 300 parts by weight, component (B).

Components (B) preferably consists of at least 90% by weight of units of the formula (II). Particularly preferably, component (B) consists exclusively of units of the formula (II).

Examples of radicals R ³ are the aliphatic examples given above for R. However, radical R ³ may also be divalent aliphatic radicals which connect two silyl groups of the formula (II) with one another, for example alkylene radicals having 1 to 10 carbon atoms, such as methylene, ethylene, propylene or butylene radicals.

However, radical R ³ is preferably monosubstituted SiC-bonded aliphatic hydrocarbon radicals having 1 to 18 carbon atoms which are optionally substituted by halogen atoms, particularly preferably aliphatic hydrocarbon radicals having 1 to 6 carbon atoms, in particular the methyl radical.

Examples of radical R ⁴ are hydrogen atom or the examples given for radical R.

Radical R ⁴ is preferably hydrogen or optionally halogen-substituted alkyl radicals having 1 to 10 carbon atoms, particularly preferably alkyl radicals having 1 to 4 carbon atoms, in particular the methyl and ethyl radical.

Examples of radicals R ⁵ are the aromatic radicals given above for R.

The radical R ⁵ is preferably SiC-bonded aromatic hydrocarbon radicals having 1 to 18 carbon atoms, optionally substituted by halogen atoms, such as, for example, ethylphenyl, toluyl, xylyl, chlorophenyl, naphthyl or styryl radicals, particularly preferably the phenyl radical.

Silicone resins are preferably used as components (B) in which at least 90% of all radicals R ^{3 is} methyl, at least 90% of all radicals R ^{4 is} methyl, ethyl, propyl or isopropyl and at least 90% of all radicals R ^{5 is} phenyl stand.

Silicone resins (B) which have at least 40%, particularly preferably at least 60%, of units of the formula (II) in which c is 0, in each case based on the total number of units of the formula (II), are preferably used according to the invention.

Silicone resins (B) are preferably used which, based in each case on the total number of units of the formula (II), have at least 70%, particularly preferably at least 80%, of units of the formula (II) in which d is 0 or 1 stands.

Silicone resins (B) are preferably used which, based in each case on the total number of units of the formula (II), have at least 20%, particularly preferably at least 40%, of units of the formula (II) in which e is 1. It is possible to use silicone resins (B) which have exclusively units of the formula (II) in which e is 1, but particularly preferably at least 10%, particularly preferably at least 20%, at most 60%, particularly preferably at most 80%, the units of the formula (II) have an e of 0.

Silicone resins (B) are preferably used which, based in each case on the total number of units of the formula (II), have at least 50%, particularly preferably at least 70%, in particular at least 80% of units of the formula (II) in which the sum c + e is equal to 1.

In a particularly preferred embodiment of the invention, component (B) used are silicone resins which, based in each case on the total number of units of the formula (II), have at least 20%, particularly preferably at least 40%, of units of the formula (II) where e is 1 and c is 0. Preferably, at most 40%, particularly preferably at most 70%, of all units of the formula (II) have a d different from 0.

In a further particularly preferred embodiment of the invention, component (B) used are silicone resins which, based in each case on the total number of units of the formula (II), have at least 20%, particularly preferably at least 40%, units of the formula (II) in which e is the value 1 and c is the value 0 and which furthermore have at least 1%, preferably at least 10%, of units of the formula (II) in which c is 1 or 2, preferably 1, and e is 0 stands.

Examples of the silicone resins (B) used according to the invention are organopolysiloxane resins which are essentially, preferably exclusively, composed of (Q) units of the formulas SiO _4/2 , Si (OR ⁴ ) O _3/2 , Si (OR ⁴ ) ₂ O _{2 / 2} and Si (OR ⁴ ) ₃ O _1/2 , (T) units of the formulas PhSiO _3/2 , PhSi (OR ⁴ ) O _2/2 , PhSi (OR ⁴ ) ₂ O _1/2 , MeSiO _{3 / 2} , MeSi (OR ⁴ ) O _2/2 and MeSi (OR ⁴ ) ₂ O _1/2 (D) units of the formulas Me ₂ SiO _2/2 , Me ₂ Si (OR ⁴ ) O _1/2 , Ph ₂ SiO _2/2 and Ph ₂ Si (OR ⁴ ) O _1/2 , MePhSiO2 _{/ 2} and MePhSi (OR ⁴ ) O _1/2 and (M) units of the formula Me ₃ SiO _1/2 where Me is is a methyl radical, Ph is a phenyl radical and R ^{4 is} hydrogen or optionally halogen atoms substituted alkyl radicals having 1 to 10 carbon atoms, more preferably hydrogen or alkyl radicals having 1 to 4 carbon atoms, wherein the resin per mole of (T) units 0- 2 mole (Q) units, 0-2 mole (D) units and 0-2 mole (M) units.

Preferred examples of the silicone resins (B) used according to the invention are organopolysiloxane resins which consist essentially, preferably exclusively, of T units of the formulas PhSiO _3/2 , PhSi (OR ⁴ ) O _2/2 and PhSi (OR ⁴ ) ₂ O _{1 / 2} , T units of the formulas MeSiO _3/2 , MeSi (OR ⁴ ) O _2/2 and MeSi (OR ⁴ ) ₂ O _1/2 and D units of the formulas Me ₂ SiO _2/2 and Me ₂ Si (OR ⁴ ) O _1/2 , wherein Me is a methyl radical, Ph is a phenyl radical and R ^{4 is} hydrogen or optionally substituted by halogen atoms substituted alkyl radicals having 1 to 10 carbon atoms, more preferably hydrogen or alkyl radicals having 1 to 4 carbon atoms, with a molar ratio of (T) to (D) units of 0.5 to 2.0.

Among these examples, silicone resins (B) are particularly preferred whose units of the formula (II) to at least 50%, preferably at least 70%, in particular at least 85% of T units of the formulas PhSiO _3/2 , PhSi (OR ⁴ ) O _{2 / 2} , PhSi (OR ⁴ ) ₂ O _1/2 , Me SiO _3/2 , MeSi (OR ⁴ ) O _2/2 and MeSi (OR ⁴ ) ₂ O _1/2 , these silicone resins (B) being at least 30%, preferably at least 40%, in particular at least 50% T units of the formulas PhSiO _3/2 , PhSi (OR ⁴ ) O _2/2 and PhSi (OR ⁴ ) ₂ O _1/2 and at least 10%, preferably at least 15 %, in particular at least 20% T units of MeSiO _3/2 , MeSi (OR ⁴ ) O _2/2 and MeSi (OR ⁴ ) ₂ O _1/2 . The content of hydroxyl groups in these silicone resins (B) is preferably below 1 wt .-%, more preferably below 0.5 wt .-%, in particular below 0.35 wt .-%.

The silicone resins (B) used according to the invention preferably have a number average molecular weight M _n of at least 500 g / mol and more preferably of at least 600 g / mol. The average molecular weight M _n is preferably at most 400,000 g / mol, more preferably at most 100,000 g / mol, in particular at most 50,000 g / mol.

The silicone resins (B) used according to the invention may be both solid and liquid at 23 ° C. and 1000 hPa, with silicone resins (B) preferably being liquid.

The silicone resins (B) can be used both in pure form and in the form of a solution in a suitable solvent (L).

Substances such as ethers (eg diethyl ether, methyl t-butyl ether, ether derivatives of glycol, THF), esters (eg ethyl acetate, butyl acetate, methoxypropyl acetate, glycol esters), hydrocarbons (eg pentane, cyclopentane, hexane, cyclohexane, Heptane, octane or else long-chain branched and unbranched alkanes), ketones (for example acetone, methyl ethyl ketone), aromatics (for example toluene, xylene, ethylbenzene, chlorobenzene) or alcohols (for example methanol, ethanol, glycol, propanol, isopropanol, glycerol, Butanol, iso-butanol, t-butanol) serve.

Preferably, however, silicone resins (B) are used, which are free of organic solvents (L).

The silicone resins (B) used according to the invention are commercially available products or can be prepared by methods customary in silicon chemistry.

Based on 100 parts by weight of component (A), the compositions of the invention preferably contain at least 0.5 parts by weight, more preferably at least 3 parts by weight, in particular at least 5 parts by weight, of component (C). Based on 100 parts by weight of component (A), the compositions according to the invention preferably contain at most 100 parts by weight, more preferably at most 50 parts by weight, in particular at most 20 parts by weight, of component (C).

The optionally used organosilicon compounds (C) according to the invention may be both silanes, i. Compounds of formula (III) with f + g + h = 4, as well as siloxanes, i. Compounds containing units of formula (III) with f + g + h <3, which are preferably silanes.

Examples of optionally substituted hydrocarbon radicals R ⁷ are the examples given for radical R.

The radicals R ⁷ is preferably a hydrogen atom and an optionally halogen-substituted hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably a hydrogen atom and hydrocarbon radicals having 1 to 10 carbon atoms, in particular methyl and ethyl radicals.

Examples of radical R ⁸ are the examples given for R. The radical R ⁸ is preferably hydrocarbon radicals optionally substituted by halogen atoms having 1 to 18 carbon atoms, more preferably hydrocarbon radicals having 1 to 5 carbon atoms, in particular the methyl radical.

Examples of radicals D are alkyl groups having 2 to 22 carbon atoms, vinyl group, allyl group, glycidoxypropyl group, (meth) acrylatopropyl group, (meth) acrylatomethyl group, 3- (O-methylcarbamato) propyl group, O-methylcarbamato-methyl group, maleic anhydride, an over a urea group bound to the Si atom of a propyl or methyl radical or a maleic anhydride group bonded to the Si atom via a propyl or methyl radical.

Preferred radicals D represent the vinyl group, allyl group, methylcarbamato) -propyl group and the O-methylcarbamato-methyl group.

Examples of silanes of the formula (III) used according to the invention are alkylsilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, i- or n-octyltrimethoxysilane, i- or n-octyltriethoxysilane, decyltrimethoxysilane, dodecyltetramethoxysilane, tetradecytrimethoxysilane or hexadecyltrimethoxysilane, epoxysilanes, such as glycidoxypropyltrimethoxysilanes, Glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane or glycidoxypropylmetyldiethoxysilane, 2- (3-triethoxysilylpropyl) -maleic anhydride, N- (3-trimethoxysilylpropyl) -urea, N- (3-triethoxysilylpropyl) -urea, N- (trimethoxysilylmethyl) -urea, N- (Methyldimethoxysilymethyl) urea, N- (3-triethoxysilylmethyl) urea, N- (3-methyldiethoxysilylmethyl) urea, O-methylcarbamatomethyl-methyldimethoxysilane, O-methylcarbamatomethyltrimethoxysilane, O-ethylcarbamatomethyl-methyldiethoxysilane, O-ethylcarbamatomethyltriethoxysilane, 3 - (O-Methylcarbam ato) -propyl-methyldimethoxysilane, 3- (O-methylcarbamato) -propyltrimethoxysilane, 3- (O-ethylcarbamato) -propyl-methyldiethoxysilane, 3- (O-ethylcarbamato) -propyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, methacryloxymethyltrimethoxysilane , methacryloxymethyl-methyldimethoxysilane, methacryloxymethyl triethoxysilane, methacryloxymethyl-methyldiethoxysilane, 3-acryloxypropyl trimethoxy silane, acryloxymethyl trimethoxy silane, acryloxymethyl methyldimethoxysilane, acryloxymethyl triethoxysilane and acryloxymethyl methyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane and allylmethyldimethoxysilane optionally in admixture with their partial condensates.

The partial condensates of the silanes of the formula (III) which may be present in component (C) are preferably those having 2 to 10 silicon atoms.

The component (C) used according to the invention is preferably one or more of the listed allyl, vinyl and carbamate-functional silanes, where O-methylcarbamatomethylmethyldimethoxysilane, O-methylcarbamatomethyltrimethoxysilane, 3- (O-methylcarbamato) propyl trimethoxysilane or vinyltrimethoxysilane are particularly preferred.

The silanes (C) used according to the invention are commercially available products, or they can be prepared by methods customary in silicon chemistry.

The antioxidants (D) used according to the invention may be any and all known antioxidants. Component (D) is preferably radical scavengers, particularly preferably so-called HALS types (hindered amine light stabilizers), which are preferably derived from 2,2,6,6-tetramethylpiperidine. Examples of component (D) are commercially available under the trade name TINUVIN ^® (BASF SE) compounds obtainable.

Component (D) is preferably used in amounts of from 0.1 to 5 parts by weight, particularly preferably from 0.2 to 2 parts by weight, in each case based on 100 parts by weight of component (A).

The UV absorbers (E) used according to the invention may be any UV adsorbers known to date.

Component (E) is preferably 2-hydroxybenzophenones, 2-hydroxyphenylbenzotriazoles, 2-hydroxyphenyltriazines or oxalanilides. These compounds are commercially available, eg under the trade name TINUVIN ^® (BASF SE).

Component (E) is preferably used in amounts of from 0.1 to 5 parts by weight, more preferably from 0.2 to 2 parts by weight, in each case based on 100 parts by weight of component (A).

The optionally used colorants (F) may be all pigments or dyes which have hitherto been used in coating compositions. For this purpose, see e.g. on textbook of paints and coatings Part 5, Hans Kittel, Jürgen Spille, 2nd edition, Hirzel Verlag referenced.

The colorants (F) can be used both in pure form as well as in the form of a mixture with liquid media.

The optionally used colorants (F) may be pigments or dyes. Pigments are a practically insoluble substance in the application medium, which are used as colorants and possibly because of their corrosion-inhibiting or magnetic properties. Dye is a colorant soluble in the application medium.

• – anorganische Erdpigmente wie Kreide, Ocker, Umbra und Grünerde,
• – Weißpigmente wie Oxide (TiO₂, ZrO₂, SnO₂, Zinkweiß ZnO), Carbonate ((2PbCO₃ Pb(OH)₂ (Bleiweiß), 2ZnCO₃ 3Zn(OH)₂, Sulfide, (ZnS, ZnS + BaSO₄ (Litopone)), Sulfate (2PBSO₄ Pb(OH)₂),
• – Schwarzpigmente (Pigmentruße (Gas-, Furnace-Flammruße), Eisenoxidschwarz und verschiedene oxidische Mischphasenpigmente wie Spinellschwarz),
• – Anorganische Buntpigmente wie Eisenoxidpigmente (Eisenoxidgelb, Eisenoxidrot-, Eisenoxidschwarz-, Eisenoxidbraun-Pigmente, transparente Eisenoxid-Pigmente), Chromoxidpigmente (Chromoxidgrün, Chromoxidhydratgrün), Oxidische Mischphasenpigmente (Nickeltitangelb, Chromtitangelb, Cobaltgrün, Cobaltblau, Zinkeisenbraun, Chromeisenbraun, Eisenmanganschwarz, Spinellschwarz), Cadmiumpigmente (Cadmiumgelb, -orange,-rot), Chromatpigmente (Chromgelb, Molybdatoorange, Molybdatorot, Chromorange, Chromrot, Chromgrün, Chromechtgrün), Bismutvanadat-Pigmente, Eisenblau-Pigmente, Ultramarin-Pigmente,
• – Organische Buntpigmente wie z.B. Azo-Pigmente, Monoazopigmente (Acetoacetarylid, Benzimidazolon, Naphtol AS, verlackte ß-Naphtholfarbstoffe), Disazopigmente (Azokondensationspigmente, Dipyrazolon), polycyclische Pigmente (Chinaridon, Dioxazin, Perylen, Diketo-Pyrrolo-Pyrrol, Isoindolin), Metallkomplexpigmente (Cu-Phthalocyanine),
• – Metalleffektpigmente wie Aluminium (typischerweise plättchenförmig mit Formfaktoren (Dicke zu Durchmesser) von 1:50 bis 1:500. Sowohl sog. „leafing“ als auch „nonleafing“ Typen können eingesetzt werden), Cu/Sn-, Cu/Al, Cu oder Cu/Zn-Legierungen,
• – Perglanz- und Interferenzpigmente, wie beschichteten Glimmer, Kieselsäure oder Aluminium oder transparente Flüssigkristallpigmente,
• – Korrosionsschutzpigmente (F) wie bleihaltige Korrosionsschutzpigmente (Bleimennige), Chromathaltige Korrosionsschutzpigmente (verschiedene Zinkchromate und Strontiumchromat), Phosphathaltige Korrosionsschutzpigmente (Zinkphosphate, Chromphosphat, Aluminiumtripohsphate, Calcium-Magnesium-Phosphate, Bariumphosphat, Aluminiumzinphosphat, metallische Korrosionsschutzpigmente wie Zinkstaub, sonstige Korrosionsschutzpigmente (Modifikationen der phosphathaltigen Korrosionsschutzpigmente durch Molybdate, Wolframate, Zirkonate oder Vanadate), Eisenglimmer, organische Korrosionsinhibitoren wie Zinksalze der 5-Nitrophthalsäure und
• – Leitfähige Pigmente wie Ruße, Kohlenstoffnanoröhren, mit Sb dotiertes SnO₂,

wobei viele der anorganischen Pigmente auch als Füllstoffe fungieren und umgekehrt. Examples of optionally used colorants (F) are

• - inorganic earth pigments such as chalk, ocher, umber and green soil,
• - white pigments such as oxides (TiO ₂ , ZrO ₂ , SnO ₂ , zinc white ZnO), carbonates ((2PbCO ₃ Pb (OH) ₂ (lead white), 2ZnCO ₃ 3Zn (OH) ₂ , sulfides, (ZnS, ZnS + BaSO ₄ ( Litopone)), sulfates (2PBSO ₄ Pb (OH) ₂ ),
• Black pigments (carbon blacks (gas blacks, furnace blacks), black iron oxide and various oxide mixed phase pigments such as spinel black),
• Inorganic colored pigments such as iron oxide pigments (iron oxide yellow, iron oxide red, iron oxide black, iron oxide brown pigments, transparent iron oxide pigments), chromium oxide pigments (chrome oxide green, chrome oxide hydrate green), mixed oxide oxide pigments (nickel titanium yellow, chrome titanium yellow, cobalt green, cobalt blue, zinc iron brown, chrome iron brown, iron manganese black, spinel black) , Cadmium pigments (cadmium yellow, orange, red), chromate pigments (chrome yellow, molybdate orange, molybdate red, chrome orange, chrome red, chrome green, chrome green), bismuth vanadate pigments, iron blue pigments, ultramarine pigments,
• - Organic colored pigments such as azo pigments, monoazo pigments (acetoacetarylide, benzimidazolone, Naphtol AS, laked ß-naphthol dyes), disazo pigments (azo condensation pigments, dipyrazolone), polycyclic pigments (quinaridone, dioxazine, perylene, diketo-pyrrolo-pyrrole, isoindoline), metal complex pigments (Cu-phthalocyanines),
• Metallic effect pigments such as aluminum (typically platelet-shaped with shape factors (thickness to diameter) of 1:50 to 1: 500. Both so-called "leafing" and "nonleafing" types can be used), Cu / Sn, Cu / Al, Cu or Cu / Zn alloys,
• Pearlescent and interference pigments, such as coated mica, silica or aluminum or transparent liquid-crystal pigments,
• - Anticorrosive pigments (F) such as lead anticorrosive pigments (lead names), chromate anticorrosion pigments (various zinc chromates and strontium chromate), phosphate anticorrosion pigments (zinc phosphates, chromium phosphate, aluminum triphosphates, calcium magnesium phosphates, barium phosphate, aluminum zinc phosphate, metallic anticorrosive pigments such as zinc dust, other anticorrosive pigments (modifications of phosphate-containing anticorrosion pigments by molybdate, tungstates, zirconates or vanadates), iron mica, organic corrosion inhibitors such as zinc salts of 5-nitrophthalic acid and
• Conductive pigments such as carbon blacks, carbon nanotubes, Sb-doped SnO ₂ ,

many of the inorganic pigments also function as fillers and vice versa.

The optionally used colorants (F) are preferably pigments.

Based on 100 parts by weight of component (A), the compositions according to the invention preferably contain at least 5 parts by weight, more preferably at least 10 parts by weight, in particular at least 50 parts by weight, of component (F). Based on 100 parts by weight of component (A), the compositions according to the invention preferably contain at most 600 parts by weight, more preferably at most 400 parts by weight, in particular at most 250 parts by weight, of component (F).

In addition to the components (A), (B), (C) and (D), (E) and optionally (F) used, the compositions according to the invention may contain all other substances which have hitherto been used in crosslinkable compositions and which are different to components (A) to (F), such as basic nitrogen-containing organosilicon compound (G), fillers (H), catalyst (I), additives (J) and additives (K).

Component (G) is preferably organosilicon compounds containing units of the formula E _i Si (OR ⁹ ) _j R ¹⁰ _k O _{(4-ijk) / 2} (V), wherein
R ^{9 may be the} same or different and is hydrogen or optionally substituted hydrocarbon radicals,
R ^{10 may be the} same or different and represents a monovalent, optionally substituted, SiC-bonded, nitrogen-free organic radical,
E may be the same or different and is a monovalent, SiC-bonded radical having a nitrogen atom not bonded directly to a carbonyl group,
i is 0, 1, 2 or 3, preferably 1,
j is 0, 1, 2, 3 or 4, preferably 1, 2 or 3, particularly preferably 2 or 3, and
k is 0, 1, 2 or 3, preferably 1 or 0,
with the proviso that the sum of i + j + k is less than or equal to 4 and at least one residue E is present per molecule.

In a preferred embodiment of the invention, the compositions according to the invention in addition to the components (A) to (E), preferably (A) to (F), also contain at least one further component (G) corresponding to the formula (V).

The organosilicon compounds (G) optionally used according to the invention may be both silanes, i. Compounds of formula (V) with i + j + k = 4, as well as siloxanes, i. Compounds containing units of formula (V) with i + j + k <3, which are preferably silanes.

Examples of optionally substituted hydrocarbon radicals R ⁹ are the examples given for radical R.

The radicals R ⁹ is preferably a hydrogen atom and an optionally halogen-substituted hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably a hydrogen atom and hydrocarbon radicals having 1 to 10 carbon atoms, in particular methyl and ethyl radicals.

Examples of radical R ¹⁰ are the examples given for R.

The radical R ¹⁰ is preferably hydrocarbon radicals optionally substituted by halogen atoms having 1 to 18 carbon atoms, particularly preferably hydrocarbon radicals having 1 to 5 carbon atoms, in particular the methyl radical.

Examples of radicals E are radicals of the formulas H ₂ N (CH ₂ ) ₃ -, H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -, H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH ( CH ₂ ) ₃ -, H ₃ CNH (CH ₂ ) ₃ -, C ₂ H ₅ NH (CH ₂ ) ₃ -, C ₃ H ₇ NH (CH ₂ ) ₃ -, C ₄ H ₉ NH (CH ₂ ) ₃ -, C ₅ H ₁₁ NH (CH ₂ ) ₃ -, C ₆ H ₁₃ NH (CH ₂ ) ₃ -, C ₇ H ₁₅ NH (CH ₂ ) ₃ -, H ₂ N (CH ₂ ) ₄ -, H ₂ N-CH ₂ -CH (CH 3) -CH ₂ -, H ₂ N (CH ₂ ) ₅ -, cyclo-C ₅ H ₉ NH (CH ₂ ) ₃ -, cyclo-C ₆ H ₁₁ NH (CH ₂ ) ₃ -, phenyl-NH (CH ₂ ) ₃ -, (CH ₃ ) ₂ N (CH ₂ ) ₃ -, (C ₂ H ₅ ) ₂ N (CH ₂ ) ₃ -, (C ₃ H ₇ ) ₂ N (CH ₂ ) ₃ -, (C ₄ H ₉ ) ₂ N (CH ₂ ) ₃ -, (C ₅ H ₁₁ ) ₂ N (CH ₂ ) ₃ -, (C ₆ H ₁₃ ) ₂ N (CH ₂ ) ₃ -, (C ₇ H ₁₅ ) ₂ N (CH ₂ ) ₃ -, H ₂ N (CH ₂ ) -, H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) -, H ₂ N (CH ₂ ) ₂ NH (CH _{2) 2} NH (CH ₂₎ -, H ₃ CNH (CH ₂₎ -, C ₂ H ₅ NH (CH ₂₎ -, C ₃ H ₇ NH (CH ₂₎ -, C ₄ H ₉ NH (CH ₂₎ - C ₅ H ₁₁ NH (CH ₂ ) -, C ₆ H ₁₃ NH (CH ₂ ) -, C ₇ H ₁₅ NH (CH ₂ ) -, cyclo-C ₅ H ₉ NH (CH ₂ ) -, cyclo- C ₆ H ₁₁ NH (CH ₂ ) -, phenyl-NH (CH ₂ ) -, (CH ₃ ) ₂ N (CH ₂ ) -, (C ₂ H ₅ ) ₂ N (CH ₂ ) -, (C ₃ H _{7) 2} N (CH ₂₎ -, (C ₄ H _{9) 2} N (CH ₂₎ -, (C ₅ H _{11) 2} N (CH ₂₎ -, (C ₆ H _{13) 2} N (CH ₂₎ -, (C ₇ H _{15) 2} N (CH ₂₎ -, (CH ₃ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₃ -, (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₃ -, (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ NH (CH ₂ ) ₃ - and (C ₂ H ₅ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ NH (CH ₂ ) ₃ - as well as reaction products of the above-mentioned primary amino groups Compounds containing reactive double bonds or epoxide groups with respect to primary amino groups.

Preferably, the radical E is the H ₂ N (CH ₂ ) ₃ -, H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ - and cyclo-C ₆ H ₁₁ NH (CH ₂ ) ₃ radical.

Examples of the silanes of the formula (V) which may be used according to the invention are H ₂ N (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ , H ₂ N (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ , H ₂ N (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ - Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OH) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OH) ₂ CH ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ , cycloC ₆ H ₁₁ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , cyclo-C ₆ H ₁₁ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ , cyclo-C ₆ H ₁₁ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ , cyclo-C ₆ H ₁₁ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ , cyclo-C ₆ H ₁₁ NH (CH ₂ ) ₃ -Si (OH) ₃ , cyclo-C ₆ H ₁₁ NH (CH ₂ ) ₃ -Si (OH) ₂ CH ₃ , phenyl-NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , phenyl-NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ , phenyl-NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ , Phenyl-NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ , phenyl-NH (CH ₂ ) ₃ -Si (OH) ₃ , phenyl-NH (CH ₂ ) ₃ -Si (OH) ₂ CH ₃ , HN ((CH ₂ ) ₃ -Si (OCH ₃ ) ₃ ) ₂ , HN ((CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ ) ₂ , HN ((CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ ) ₂ , HN ((CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ ) ₂ , cyclo-C ₆ H ₁₁ NH (CH ₂ ) -Si (OCH ₃ ) ₃ , cyclo-C ₆ H ₁₁ NH (CH ₂ ) -Si (OC ₂ H ₅ ) ₃ , cycloC ₆ H ₁₁ NH (CH ₂ ) -Si (OCH ₃ ) ₂ CH ₃ , cycloC ₆ H ₁₁ NH (CH ₂ ) -Si (OC ₂ H ₅ ) ₂ CH ₃ , cycloC ₆ H ₁₁ NH (CH ₂ ) -Si (OH) ₃ , cycloC ₆ H ₁₁ NH (CH ₂ ) -Si (OH) ₂ CH ₃ , Phenyl-NH (CH ₂ ) -Si (OCH ₃ ) ₃ , phenyl-NH (CH ₂ ) -Si (OC ₂ H ₅ ) ₃ , phenyl-NH (CH ₂ ) -Si (OCH ₃ ) ₂ CH ₃ , phenyl -NH (CH ₂ ) -Si (OC ₂ H ₅ ) ₂ CH ₃ , phenyl-NH (CH ₂ ) -Si (OH) ₃ and phenyl-NH (CH ₂ ) -Si (OH) ₂ CH ₃ and their partial hydrolysates where H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ , cycloC ₆ H ₁₁ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , cycloC ₆ H ₁₁ NH ( CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ and cyclo-C ₆ H ₁₁ NH (CH ₂ ) _3- Si (OCH ₃ ) ₂ CH ₃ and in each case their partial hydrolysates are preferred and H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH ( CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ , cycloC ₆ H ₁₁ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , cycloC ₆ H ₁₁ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ and each of their partial hydrolysates are particularly preferred.

The organosilicon compounds (G) which may optionally be used according to the invention may, inter alia, assume the function of an adhesion promoter but also of a curing catalyst or cocatalyst in the compositions according to the invention.

The organosilicon compounds (G) which may optionally be used according to the invention are commercially available products or can be prepared by processes customary in chemistry.

If the compositions according to the invention contain component (G), these are amounts of preferably 0.1 to 50 parts by weight, more preferably 0.5 to 25 parts by weight, in each case based on 100 parts by weight of component (A). The compositions of the invention preferably contain component (G).

The fillers (H) optionally used in the compositions according to the invention may be any, hitherto known fillers which are different from (F).

• – Carbonate (natürliche Kreide, Calcit, Aragonit oder gefälltes Calciumcarbonat), Dolomite (natürlich vorkommende Calcium-Magnesiumcarbonate),
• – natürliche Siliciumdioxide (Quarzmehl), amorphe natürliche Kieselsäuren, pyrogene Kieselsäuren, gefällte Kieselsäuren,
• – Silikate wie Talkum, Kaolin, Glimmer (Mica)
• – Sulfate wie natürlich vorkommender Schwerspat oder gefälltes Bariumsulfat (Blanc fixe)
• – Metalloxidpulver, wie Aluminium-, Titan-, Eisen- oder Zinkoxide bzw. deren Mischoxide,
• – Siliciumnitrid, Siliciumcarbid, Bornitrid,
• – Glas- und Kunststoffpulver, wie Polyacrylnitrilpulver;
• – Ruß, wie Furnace- und Acetylenruß
• – Silicium-Aluminium-Mischoxide großer BET-Oberfläche; Aluminiumtrihydroxid,
• – hohlkugelförmiger Füllstoffe, wie keramische Mikrokugel, wie z.B. solche erhältlich unter der Handelsbezeichnung Zeeospheres^TM bei der Fa. 3M Deutschland GmbH in D-Neuss,
• – elastische Kunststoffkugeln, wie etwa solche erhältlich unter der Handelsbezeichnung EXPANCEL^® bei der Fa. AKZO NOBEL, Expancel in Sundsvall, Schweden, oder Glaskugeln;
• – faserförmige Füllstoffe, wie Asbest sowie Kunststofffasern.

Examples of fillers (H) are

• Carbonates (natural chalk, calcite, aragonite or precipitated calcium carbonate), dolomite (naturally occurring calcium-magnesium carbonates),
• - natural silicas (quartz powder), amorphous natural silicas, fumed silicas, precipitated silicas,
• - silicates such as talc, kaolin, mica (mica)
• - sulphates such as naturally occurring barite or precipitated barium sulphate (Blanc fixe)
• Metal oxide powders, such as aluminum, titanium, iron or zinc oxides or their mixed oxides,
• Silicon nitride, silicon carbide, boron nitride,
• Glass and plastic powders, such as polyacrylonitrile powder;
• - Carbon black, such as furnace and acetylene black
• - silicon-aluminum mixed oxides of large BET surface area; aluminum trihydrate,
• Hollow spherical fillers, such as ceramic microspheres, such as those available under the trade name Zeeospheres ^™ from the company 3M Deutschland GmbH in D-Neuss,
• . - elastic plastic spheres, such as those available under the trade name Expancel ^® at AKZO NOBEL, Expancel in Sundsvall, Sweden, or glass beads;
• - fibrous fillers, such as asbestos and plastic fibers.

The fillers mentioned can be rendered hydrophobic, for example by treatment with organosilanes or siloxanes or with stearic acid or by etherification of hydroxyl groups to alkoxy groups.

Based on 100 parts by weight of component (A), the compositions according to the invention preferably contain at least 5 parts by weight, more preferably at least 10 parts by weight, in particular at least 50 parts by weight, of component (H). Based on 100 parts by weight of component (A), the compositions according to the invention preferably contain at most 600 parts by weight, more preferably at most 400 parts by weight, in particular at most 250 parts by weight, of component (H).

The catalysts (I) optionally used in the compositions according to the invention may be any, hitherto known catalysts for compositions which cure by silane condensation.

Examples of metal-containing curing catalysts (I) are organic titanium and tin compounds, for example, titanic acid esters such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and titanium tetraacetylacetonate; Tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxides, and corresponding dioctyltin compounds.

Examples of metal-free curing catalysts (I) are basic compounds, such as triethylamine, tributylamine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8- Diazabicyclo [5.4.0] undec-7-ene, N, N-bis (N, N-dimethyl-2-aminoethyl) methylamine, N, N-dimethylcyclohexylamine, N, N-dimethylphenylamine, 1,1,3, 3-tetramethylguanidine and N-ethylmorpholine. Particularly preferred are 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,1,3,3-tetramethylguanidine.

Also, as the catalyst (I), acidic compounds such as phosphoric acid and its esters, toluenesulfonic acid, sulfuric acid, nitric acid or organic carboxylic acids, e.g. Acetic acid and benzoic acid.

If the compositions according to the invention comprise catalysts (I), these are amounts of preferably 0.01 to 20 parts by weight, more preferably 0.05 to 5 parts by weight, based in each case on 100 parts by weight of component (A).

The catalyst (I) is particularly preferably a basic compound, particularly preferably strongly basic compounds having a pK _B value> 11, for example 1,5-diazabicyclo [4.3.0] non-5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene, N, N-bis (N, N-dimethyl-2-aminoethyl) methylamine, 1,1,3,3-tetramethylguanidine and other guanidine derivatives.

The compositions of the invention preferably comprise basic catalysts (I), in particular strongly basic catalysts having a pK _B value> 11, in amounts of at least 0.01, more preferably in amounts of at least 0.1 parts by weight, particularly preferably 0.05 to 5 Parts by weight, based in each case on 100 parts by weight of component (A).

The additives (J) optionally used in the compositions according to the invention may be any additives known hitherto known for silane-crosslinking systems.

The additives (J) optionally used according to the invention are preferably deaerators, leveling agents and fungicides.

If the compositions of the invention contain additives (J), they are amounts of preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, in each case based on 100 parts by weight of component (A).

The additives (K) optionally used according to the invention are preferably plasticizers, rheology additives, flame retardants and organic solvents.

Examples of plasticizers (K) are phthalic acid esters (eg dioctyl phthalate, diisooctyl phthalate and diundecyl phthalate), perhydrogenated phthalic acid esters (eg 1,2-cyclohexanedicarboxylic acid diisononyl ester and 1,2-cyclohexanedicarboxylic acid dioctyl ester) adipic acid esters (eg dioctyl adipate), benzoic acid esters, glycol esters, esters of saturated alkanediols (eg 2 , 2,4-trimethyl-1,3-pentanediol monoisobutyrate and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate), phosphoric acid esters, sulfonic acid esters, polyesters, polyethers (for example polyethylene glycols and polypropylene glycols having molar masses of preferably from 1000 to 10000 daltons), Polystyrenes, polybutadienes, polyisobutylenes, paraffinic hydrocarbons and high molecular weight, branched hydrocarbons, wherein preferably no plasticizers (K) are used.

The rheology additives (K) are preferably cellulose derivatives (e.g., alkyl cellulose, hydroxyalkyl cellulose), derivatives of heteropolysaccarides (e.g., xanthan), polyacrylates, polyether polyols, and polyurethane derivatives. These include associative thickeners, e.g. hydrophobically modified PUR thickeners, products of the type (HASE (hydrophobically modified alkali soluble emulsions (acrylic ester copolymers) or HMHEC (hydrophobically modified hydroxyethyl cellulose) and thixotropic agents (modified phyllosilicates (eg hectorite, bentonite), fumed silica, polyurea derivatives and derivatives of hydrogenated castor oil ) and Sag Control Agents (low molecular weight, semi-crystalline urea-based organic compounds or microgels of acrylate copolymer microparticles.

Examples of organic solvents (K) are the compounds already mentioned above as solvent (L).

If the compositions according to the invention contain components (K), these are in each case amounts of preferably 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, in particular 2 to 70 parts by weight, in each case based on 100 parts by weight of component (A).

• (A) 100 Gewichtsteile Verbindungen der Formel (I),
• (B) 100 bis 500 Gewichtsteile Siliconharze enthaltend Einheiten der Formel (II),
• (C) 0,5 bis 20 Gewichtsteile Silane der Formel (III),
• (D) 0,1 bis 5 Gewichtsteile Antioxidantien,
• (E) 0,1 bis 5 Gewichtsteile UV-Absorber,
• (F) 0,1 bis 250 Gewichtsteile Pigmente, gegebenenfalls
• (G) 0,5 bis 10 Gewichtsteile Stickstoff aufweisende Verbindung, gegebenenfalls
• (H) Füllstoffe, gegebenenfalls
• (I) Katalysatoren, gegebenenfalls
• (J) Additive und gegebenenfalls
• (K) Zuschlagstoffe.

The compositions of the invention are preferably those containing

• (A) 100 parts by weight of compounds of the formula (I)
• (B) 100 to 500 parts by weight of silicone resins containing units of the formula (II),
• (C) 0.5 to 20 parts by weight of silanes of the formula (III),
• (D) 0.1 to 5 parts by weight of antioxidants,
• (E) 0.1 to 5 parts by weight of UV absorber,
• (F) 0.1 to 250 parts by weight of pigments, optionally
• (G) 0.5 to 10 parts by weight of nitrogen-containing compound, if appropriate
• (H) fillers, optionally
• (I) catalysts, optionally
• (J) additives and optionally
• (K) aggregates.

In addition to the components (A) to (K), the compositions according to the invention preferably contain no further component which has a content of Si-bonded hydroxyl groups of at least 1% by weight, more preferably of at least 0.5% by weight, in particular of at least 0.35 wt .-%, having.

The compositions according to the invention preferably contain no further components apart from the components (A) to (K).

The components used according to the invention may each be one type of such a component as well as a mixture of at least two types of a respective component.

The compositions according to the invention are preferably formulations having viscosities of preferably 500 to 1,000,000 mPas, more preferably from 1,000 to 500,000 mPas, in particular from 1,000 to 20,000 mPas, in each case at 20 °.

The preparation of the compositions according to the invention can be carried out according to any desired and known manner, such as by methods and mixing methods, as are customary for the preparation of moisture-curing compositions. The order in which the various components are mixed together can be varied as desired.

Another object of the present invention is a process for preparing the composition according to the invention by mixing the individual components in any order.

This mixing can be carried out at room temperature and the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa. If desired, however, this mixing may also be carried out at higher temperatures, e.g. at temperatures in the range of 30 to 130 ° C. Furthermore, it is possible to mix temporarily or constantly under reduced pressure, e.g. at 30 to 500 hPa absolute pressure to remove volatile compounds and / or air.

The mixing according to the invention is preferably carried out with exclusion of moisture.

The process according to the invention can be carried out continuously or batchwise.

The compositions according to the invention are preferably one-component masses which can be stored under exclusion of water and can be crosslinked at room temperature on the admission of water. However, the compositions according to the invention can also be part of two-component crosslinking systems in which components (A) to (K) are divided into two components. Alternatively, OH-containing compounds, such as water, may also be added in a second component.

For the crosslinking of the compositions of the invention, the usual water content of the air is sufficient. The crosslinking of the compositions of the invention is preferably carried out at room temperature. It may, if desired, also be at higher or lower temperatures than room temperature, e.g. at -5 ° to 15 ° C or at 30 ° to 50 ° C and / or in excess of the normal water content of the air in excess of concentrations of water.

Preferably, the crosslinking is carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.

Another object of the invention are moldings prepared by crosslinking of the compositions of the invention.

The moldings according to the invention are preferably coatings.

Another object of the invention is a process for the preparation of coatings, characterized in that the composition according to the invention is applied to the substrate to be coated and allowed to crosslink.

The substrates used according to the invention may be any and all known substrates, e.g. Metals, in particular steel or aluminum, plastics, wood or mineral surfaces, which may also be primed.

The application of the compositions according to the invention to the substrates to be coated can be carried out in any suitable and widely known manner for the production of coatings from liquid substances, for example by brushing, dipping, brushing, pouring, spraying, rolling, printing, knife or doctor blade Coating, padding, extrusion or spraying.

The layer thickness on the substrates coated according to the invention after crosslinking is preferably 5 to 250 μm, more preferably 10 to 100 μm.

The compositions of the invention have the advantage that they are easy to prepare.

The crosslinkable compositions of the invention have the advantage that they are characterized by a very high storage stability and a high crosslinking rate.

Furthermore, the crosslinkable compositions according to the invention have the advantage that they have an excellent adhesion profile and excellent impact strength.

Furthermore, the crosslinkable compositions according to the invention have the advantage that they are easy to process.

Another advantage of the compositions of this invention is the option of selecting low viscosity component (B) compositions having a low viscosity, i. a very good processability, without having to add large amounts of unwanted solvents and / or plasticizers for this purpose often.

In the examples described below, all viscosity data refer to a temperature of 25 ° C. Unless otherwise specified, the examples below are at a pressure of the surrounding atmosphere, ie at about 1000 hPa, and at room temperature, ie at about 23 ° C, or at a temperature resulting from combining the reactants at room temperature without additional heating or cooling, and performed at a relative humidity of about 50%. Furthermore, all parts and percentages are by weight unless otherwise specified.

In the following examples the following substances were used:
GENIOSIL ^® STP E10: Silane-terminated polypropylene glycol having an average molecular weight (M _n) of 12,000 daltons and end groups of the formula -OC (= O) -NH-CH ₂ -SiCH ₃ (OCH _{3) 2} (commercially available from Wacker Chemie AG , D-Munich);
GENIOSIL XL63 ^®: N-trimethoxysilylmethyl-O-methylcarbamate CAS [23432-62-4];
SILRES ^® IC 368: A solvent-free, liquid phenylsilicone, the weight of phenylfunktionellen T units (60-65 wt .-%) and methyl t-functional units (18-22 wt .-%) and dimethylfunktionellen D units (2-4. -%), has a content of methoxy groups of 12-16 wt .-% and an average molecular weight of 800-1300 daltons (commercially available from Wacker Chemie AG, D-Munich);
TINUVIN ^® 123, 292, 400: stabilizers (commercially available under the name of BASF SE, Germany);
GENIOSIL® ^® GF91: N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (commercially available from Wacker Chemie AG, Munich, Germany.);
GENIOSIL® ^® XL10: vinyltrimethoxysilane (commercially available from Wacker Chemie AG, Munich, Germany.).

example 1

Production of a red pigmented varnish

49.2 g phenylsilicone SILRES ^® IC 368 are 16.4 g polypropylene glycol silanterminiertem GENIOSIL ^® STP-E10 and 1.70 g N-trimethoxysilylmethyl-O-methylcarbamate GENIOSIL ^® XL offset 63 and thoroughly mixed in a steel vessel. The homogeneous mixture is now in a dissolver "Dispermat" Fa. VMA Getzmann equipped with a disc (diameter 4.5 cm) and grinding beads of zirconia (diameter 1.7-2.4 mm, commercially available from Fa. VMA Getzmann , Germany), at about 25 ° C with 0.8 g of highly dispersed silicic acid (commercially available under the name HDK ^® H13L from Wacker Chemie AG), 6.2 g of red pigment (commercially available under the name "Irgazin Red 2030" at BASF SE, Germany), 12.8 g of barium sulfate (Blanc Fixe N, commercially available from Sachtleben Chemie GmbH, Germany), 7.0 g of butyl acetate, 0.5 g of UV absorber 2-hydroxyphenyl-s-triazine (commercially available under "TINUVIN 400" at BASF SE, Germany) and 1.0 g of solvent-free, non-basic aminoether, a so-called "hindered amine light stabilizer (HALS)" (commercially available under "TINUVIN 123" from BASF SE, Germany ) and dispersed at 4000 rpm for 30 minutes. The base paint thus obtained was then immediately before application with 1.7 g of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane GENIOSIL GF91 ^® and 3.2 g of a 10 wt .-% solution of 1,8-diazabicyclo [5.4 .0] undec-7-ene in n-butanol and mixed with a spatula.

The red paint was applied with a doctor blade (wet film thickness 100 μm) on steel and aluminum sheets (type: Q-Lab Corporation Al-36 or S-36). It was tack-free after 55 minutes and had the following properties after 7d:
Layer thickness: 31 μm
Cross-cut test ( DIN EN ISO 2409 ): 0
Pencil hardness ( ISO 15184 ): HB
Mandrel bending test ( DIN EN ISO 1519 ): <4mm
Pendulum damping test ( DIN EN ISO 1522 ): 53
Solvent resistance:> 200 double rubs with a cotton bud impregnated with methyl ethyl ketone without change
Impact test ( ASTM D2894-93 ): 70 inches / pound

A test sheet with the surface coating was tested in a QUV rapid weathering device from the company Pausch Messtechnik, Germany, a QUV-B (313nm) test ASTM 154 Cycle 3 subjected. After the time intervals mentioned below, the sheet was removed and examined for the gloss and the color location or the color deviation. The following values were obtained: Time in [h] 0 72 240 500 750 1120 1500 2000 Gloss units [60 °] 80.5 74.3 72.9 71.2 70.1 68.4 65.9 59.8

The gloss units were determined with a spectrometer Spektromaster 565-45 from Erichsen at a 60 ° angle. After 2000 h in the QUV-B test, 75% gloss retention of the initial value was obtained.

Example 2

(Preparation of a white pigmented varnish)

71.5 g phenylsilicone SILRES ^® IC 368 are added with 38.5 g GENIOSIL ^® STP-E10 and 2.80 g GENIOSIL ^® XL 63 thoroughly mixed in a steel vessel. The homogeneous mixture is now in a dissolver "Dispermat" Fa. VMA Getzmann equipped with a disc (diameter 4.5 cm) and grinding beads of zirconia (diameter 1.7-2.4 mm, commercially available from Fa. VMA Getzmann , Germany), at about 25 ° C with 40.0 g KRONOS 2360 (white pigment, commercially available from KRONOS Inc., USA), 16.0 g barium sulfate (Blanc Fixe N, commercially available from Sachtleben Chemie GmbH, Germany) , 26.7 g of butyl acetate, 0.5 g of TINUVIN 400 (UV absorber, 2-hydroxyphenyl-s-triazine, commercially available from BASF SE, Germany) and 2.0 g of TINUVIN 123 (solvent-free, non-basic aminoether, a so-called "hindered amine light stabilizer (HALS)", commercially available from BASF SE, Germany) and dispersed at 4000 revolutions per minute for 30 min. This stock was then mixed immediately before application with 2.8 g of GENIOSIL ^® GF91 and 1.1 g of a 10% solution of 1,8-diazabicyclo [5.4.0] undec-7-ene in n-butanol and mixed with a spatula ,

The white paint was applied with a doctor blade (wet film thickness 100 μm) on steel and aluminum sheets (type: Q-Lab Corporation Al-36 or S-36). It was tack-free after 40 minutes and had the following properties after 7d:
Layer thickness: 24 μm
Cross-cut test ( DIN EN ISO 2409 ): 1
Pencil hardness ( ISO 15184 ): F
Mandrel bending test ( DIN EN ISO 1519 ): <4mm
Pendulum damping test ( DIN EN ISO 1522 ): 52
Solvent resistance:> 200 double rubs with a cotton bud impregnated with methyl ethyl ketone without change
Impact test ( ASTM D2894-93 ):> 800 inch / pound

A test sheet with the surface coating was tested in a QUV rapid weathering device from the company Pausch Messtechnik, Germany, a QUV-B (313nm) test ASTM 154 Cycle 3 subjected. After the time intervals mentioned below, the sheet was removed and examined for the gloss and the color location or the color deviation. The following values were obtained: Time in [h] 0 72 240 500 750 1000 1500 2000 Gloss units [60 °] 91.5 88.3 84.5 78.8 74 69 58 39

The color shift delta E was 0.7 after 2000 h. The gloss units or the chromaticity coordinates were determined with a spectrometer Spektromaster 565-45 from Erichsen at a 60 ° angle.

A sample plate with the surface coating was used in a QUV rapid weathering device from the company Pausch Messtechnik, Germany, a QUV-A (340 nm) test after ASTM G-154 Subjected to cycle 1. After the time intervals mentioned below, the sheet was removed and examined for the gloss and the color location or the color deviation. The following values were obtained: Time in [h] 0 72 240 500 750 1000 1500 2000 Gloss units [60 °] 92.2 88.4 86.7 84.7 83.8 81.5 80.8 78

The color shift delta E was 0.5 after 2000 h. The gloss units or the chromaticity coordinates were determined with a spectrometer Spektromaster 565-45 from Erichsen at a 60 ° angle.

Example 3

heat resistance

The paint prepared in Example 2 was applied to a steel sheet and dried at room temperature (RT). The dry film thickness was 35 μm, the gloss 90.4 gloss units. The test sheet was exposed to a temperature of 200 ° C for 1 h. The coating did not show any damage, e.g. Cracks or chipping on. The gloss was 85.5 gloss units and the color shift deltaE 1.8.

The gloss units or the chromaticity coordinates were determined with a spectrometer Spektromaster 565-45 from Erichsen at a 60 ° angle.

Example 4

storage stability

65 g SILRES ^® 368 were mixed with 35 g GENIOSIL ^® STP-E10 and treated with the substances of Table 1 below. The viscosity of the resulting mixture was examined.

The viscosities were determined using a commercially available Brookfield viscometer.

Mix 1 and 3 do not dry to a tack-free film within 72 hours. Mixtures 2 and 4 dry to a tack-free film within 5 hours. Mixture 4 has a significantly better storage stability than mixture 2.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2013/026654 [0004]
• EP 1535940 B1 [0030]
• EP 1896523 B1 [0030]

Cited non-patent literature

• DIN EN ISO 2409 [0139]
• ISO 15184 [0139]
• DIN EN ISO 1519 [0139]
• DIN EN ISO 1522 [0139]
• ASTM D2894-93 [0139]
• ASTM 154 [0140]
• DIN EN ISO 2409 [0143]
• ISO 15184 [0143]
• DIN EN ISO 1519 [0143]
• DIN EN ISO 1522 [0143]
• ASTM D2894-93 [0143]
• ASTM 154 [0144]
• ASTM G-154 [0146]

Claims (10)

Crosslinkable compositions comprising (A) 100 parts by weight of compounds (A) of the formula Y - [(CR ¹ ₂ ) _b -SiR _a (OR ² ) _3-a ] _x (I), wherein Y is an x-valent, bound via nitrogen, oxygen, sulfur or carbon polymer residue, R may be the same or different and represents a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, R ^{1 may be the} same or different and is hydrogen atom or a monovalent is optionally substituted hydrocarbon radical which may be attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group, R ^{2 may be} identical or different and represents hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, x is an integer from 1 to 10 is, a is the same or different and is 0, 1 or 2 and b may be the same or different and is an integer from 1 to 10, (B) more than 50 parts by weight of silicone resins containing units of the formula R ³ _c (R ⁴ O) _d R ⁵ _e SiO _{(4-cde) / 2} (II), wherein R ^{3 may be the} same or different and is hydrogen atom, a monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon radical or a divalent, optionally substituted, aliphatic hydrocarbon radical bridging two units of formula (II), R ^{4 may be the} same or different R ^{5 is the} same or different and is a monovalent, SiC-bonded, optionally substituted aromatic hydrocarbon radical, c is 0, 1, 2 or 3, d is 0, 1, 2 or 3 and e is 0, 1 or 2, with the proviso that the sum of c + d + e is less than or equal to 3, is different in at least one unit e and 0 in at least 40% of the units of the formula (II) the sum c + e is 0 or 1, (C) at least 0.1 part by weight of component (B) different organosilicon compounds containing unit th of the formula D _f Si (OR ⁷ ) _g R ⁸ _h (III), wherein D may be the same or different and is a monovalent SiC-bonded organic radical having at least two carbon atoms which does not have a nitrogen atom not directly bonded to a carbonyl group, R ^{7 may be the} same or different and is hydrogen or optionally substituted hydrocarbon radicals, R ⁸ may be the same or different and is optionally substituted hydrocarbon radicals, f is 0, 1, 2 or 3, g is 0, 1, 2, 3 or 4 and h is 0, 1, 2 or 3, with the proviso that the sum from f + g + h is 4, (D) at least 0.05 parts by weight of antioxidants and (E) at least 0.05 parts by weight of UV absorber. Crosslinkable compositions according to Claim 1, characterized in that radical Y in formula (I) is polyacrylate, polyester or polyoxyalkylene radicals. Crosslinkable compositions according to Claim 1 or 2, characterized in that they additionally also contain (F) at least 0.1 part by weight of colorant. Crosslinkable compositions according to Claim 3, characterized in that the colorants (F) are pigments. Crosslinkable compositions according to one or more of claims 1 to 4, characterized in that they additionally contain component (G). Crosslinkable compositions according to one or more of Claims 1 to 5, characterized in that they are (A) 100 parts by weight of compounds of the formula (I), (B) 100 to 500 parts by weight of silicone resins containing units of the formula (II) (C) 0.5 to 20 parts by weight of silanes of the formula (III), (D) 0.1 to 5 parts by weight of antioxidants, (E) 0.1 to 5 parts by weight of UV absorber, (F) 0.1 to 250 parts by weight of pigments , optionally (G) 0.5 to 10 parts by weight of nitrogen-containing compound, optionally (H) fillers, optionally (I) catalysts, optionally (J) additives and optionally (K) additives.  A process for preparing the compositions according to one or more of claims 1 to 6 by mixing the individual components in any order.  Shaped body produced by crosslinking of the compositions according to one or more of claims 1 to 6 or prepared according to claim 7. Shaped body according to claim 8, characterized in that they are coatings. A process for the production of coatings, characterized in that the compositions according to one or more of claims 1 to 6 or prepared according to claim 7 are applied to the substrate to be coated and crosslinked.