WO2025040760A1

WO2025040760A1 - Coating compositions

Info

Publication number: WO2025040760A1
Application number: PCT/EP2024/073595
Authority: WO
Inventors: Philip Alexander KENSBOCK; Thorsten FELDER; Jan Engelhardt; Christoph Hilgers; Max CONRAD; Annika FUHRMANN; Jörg-Walter Hermann; Anita Witossek
Original assignee: Momentive Performance Materials Gmbh
Priority date: 2023-08-24
Filing date: 2024-08-22
Publication date: 2025-02-27

Abstract

The present invention relates to a new coating composition, comprising colloidal metal oxides with a specific modification, a process for the manufacture of the coating compositions, the specific modified colloidal metal oxides, a process for preparing coated articles with the new coating, and coated articles obtained by the process.

Description

COATING COMPOSITIONS

FIELD OF THE INVENTION

[0001] The present invention relates to a new coating composition, comprising a colloidal metal compound A), a partial condensate B) of at least one hydrolysable silane, one or both of which are modified with a specific modifier component C), a process for the manufacture of the coating compositions, specific modified colloidal metal compounds AM) and modified partial condensates BM), a process for preparing coated articles with the new coating composition, and coated articles obtained by the coating process. The coating compositions provide superior surface properties of the dried or cured coating compositions. In particular, the coatings made by drying or curing the coating compositions on a substrate are resistant to oil, grease, fouling (anti-fouling properties), graffities, water (weather) and dust (abrasion) and have improved properties such as repulsion of liquids containing dirt, lower dirt accumulating on their surface, scratch resistance, weathering-stability, transparency and the like. BACKGROUND

[0002] Dirt pick-up resistance is highly sought by end users, and significant resources have been committed by paint manufacturers to improve it.

[0003] Easy-to-clean coatings are defined by reduced dirt accumulation on the surface or by simplified cleaning compared to a reference coating without easy-to-clean properties. An Easy- to-Clean coating shows resistance to various types of outdoor contaminants, such as oil, grease, graffities, water or dust-based.

[0004] In literature coatings often achieve this property by creating an omniphobic surface based on a sol-gel formulation (see e.g. Omniphobic surfaces: state-of-the-art and future perspectives, Salimi, Esmaeil, Journal of Adhesion Science and Technology, 2019, Pages 1369-1379). This can be achieved by various methods, such as a hydrophobic topcoat, a rough surface structure similar to a lotus leaf. However, an easier approach uses hydrophobic building blocks and by this is creating a hydrophobic/omniphobic coating formulation. The great advantage of the latter solution is the transparency and the stability against mechanical and weathering influences. Furthermore, the applicability of a system with as few layers as possible using conventional coating methods is a major argument for the modification of existing paint systems.

[0005] US9028603B2 relates to a xerogel film exhibiting antifouling properties using long- chain alkyltrialkoxysilanes, short-chain alkyltrialkoxysilanes, aminoalkyltrialkoxysilanes, alkylaminoalkyltrialkoxysilanes, dialkylaminoalkyltrialkoxysilanes, and perfluororalkyltrialkoxysilanes as sol-gel precursors. WO2007126432A1 relates to a method of applying Lotus Effect materials as a (superhydrophobicity) protective coating for various system applications, as well as the method of fabricating/preparing Lotus Effect coatings. US9353268B2 discloses abrasion resistant, persistently hydrophobic and oleophobic, anti- reflective and anti-soiling coatings for glass, which is formed by combinations of hydrolyzed silane-base precursors through sol-gel processes. W02017012714A relates to asymmetrically substituted polyorganosiloxanes. WO2021154504A1 relates to a coating composition comprising an organic binder and a polyorganosiloxane, optionally with a hardener. WO2021154501 A1 relates to a coating composition including an organic binder and a combination of a hydrolyzable or hydrolyzed polysiloxane and an epoxy-functional polysiloxane optionally with a hardener.

[0006] EP2281857A1 discloses a silicone composition silicone coating composition comprising a hydrolytic condensate obtainable by (co)hydrolytic condensation of at least one alkoxysilanes and partial hydrolytic condensates thereof, the alkoxysilanes may include fluoroalkylsilanes. LIS6162498 relates to a process for providing a metallic surface with a vitreous layer wherein a coating composition is used which is prepared from hydrolyzing and polycondensing one or more silanes such as fluorinated silanes. There is no disclosure of functional alkyl substituted polysiloxanes in these patents, and the use of such fluorinated silanes is also not preferred with regard to increasing concerns about the use of so-called PFAS.

[0007] LIS2016340551 A1 discloses a coating composition coating composition for enhancing light transmittance, comprising (A) a polysiloxane resin, and (B) inorganic particles. Among the polysiloxane resins there are also mentioned siloxane oligomers of formula (II) and (III) such as Dow Corning 3074 that have hydroxy or alkoxy substitution at terminal siloxy groups. But again, there is no disclosure or pointer to functional alkyl-substituted polysiloxanes, since these siloxane oligomers can have only methyl or phenyl substituents. Also, coatings made with such siloxane oligomers tend to be relatively soft (composition e, example 12 having enhanced flexibility).

SUMMARY OF THE INVENTION

[0008] The present invention provides, in particular, easy-to-clean, dirt-repellent hardcoat compositions which can be applied directly or with a primer undercoat, in particular, on plastic substrates such as polycarbonate, poly(methyl methacrylate) (PMMA) and others having improved properties such as repulsion of liquids containing dirt, lower dirt accumulating on their surface, scratch resistance, anti-fouling properties, graffiti resistance, grease resistance, weathering-stability, transparency and the like.

[0009] In accordance with the present invention there is provided a coating composition, comprising:

A) one or more colloidal metal compounds A) selected from A1) metal oxides and A2) metal fluorides, preferably from A1) metal oxides,

B) one or more partial condensates of at least one hydrolysable silane E), wherein components

A) or

B) or

A) and B) are modified with

C) one or more compounds, selected from the group consisting of

C1) polyorganosiloxanes of the formula (I):

M_aDbTcQ_d (I) wherein

M, D T and Q each represent siloxy units, and wherein

M is selected from M¹ = RsSiOi/2, M² = R_PR¹(3-_P)SiOi/2, and M³ = R_PR²<3-_P)SiOi/2,

D is selected from D¹ = R2SiC>2/2, D² = R_qR¹(2-q)SiC>2/2, and D³ = R_qR²(2-q)SiC>2/2,

T is selected from T¹ = RSiOs/2, T² = R¹SiC>3/2, and T³ = R²SiC>3/2,

Q=SiO4/2, wherein

R independently is the same or different, and is an organic group, preferably alkyl, more preferably methyl,

R¹ independently is an organic group different from R and R² and comprising at least one hydrolysable silyl group, preferably R¹ is alkyl having two or more carbon atoms, substituted with a hydrolysable silyl group, preferably of the formula:

RxR⁴(3-x)Si- wherein

R is as defined above,

R⁴ is a hydrolysable group, preferably selected from alkoxy, acetoxy, halogen, preferably chlorine, ketoximo, most preferably R⁴ is alkoxy with 1 to 6 carbon atoms, in particular, methoxy, and x is 0 to 2, preferably 0,

R² independently is an organic group different from R and R¹, selected from optionally substituted alkyl, preferably optionally substituted alkyl having 2 or more carbon atoms, or optionally substituted alkyl having 4 or more carbon atoms, or optionally substituted alkyl having 6 or more carbon atoms, preferably R² is selected from the group consisting of unsubstituted alkyl having two or more carbon atoms, preferably unsubstituted alkyl having 4 or more carbon atoms, more preferably unsubstituted alkyl having 6 or more carbon atoms, alkyl, preferably alkyl having 2 or more carbon atoms, substituted with acyloxy, such as alkylcarbonyloxy, preferably branched alkylcarbonyloxy, and alkyl substituted with one or more halogen atoms, preferably fluorine atoms, p is independently 0 to 2, preferably 2, q is independently 0 or 1 , preferably 1 , with the provisos that in the polyorganosiloxanes of the formula (I): there are at least at least two siloxy units M², or there is at least one siloxy unit M² and at least one siloxy unit M³, or there is at least one siloxy unit D² and at least one siloxy unit D³, or there is at least one siloxy unit D² and at least one siloxy unit M³, or there is at least one siloxy unit M² and at least one siloxy unit D³, and preferably there are at least one, more preferably at least 3, more preferably at least 5 siloxy units D¹, wherein each siloxy unit is as defined above, and the indices in formula (I) represent the average numbers of the siloxy units M, D, T and Q as defined above, which may be distributed blockwise or randomly in the polyorganosiloxanes, and which may be identical or different, and are a = 2 to 10, preferably 2, b = 2 to 50, preferably 2 to 40, more preferably 2 to 30, more preferably 2 to 25, more preferably about 5 to about 20, c = 0 to 10, preferably 0, d = 0 to 1 , preferably 0, and

D) at least one solvent.

[0010] In the specification and claims herein, the following terms and expressions are to be understood as indicated.

[0011] The singular forms "a," "an," and "the" include the plural, and reference to a numerical value includes at least that particular value, unless the context clearly dictates otherwise. “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

[0012] Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about”, is not to be limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. [0013] All methods described herein may be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illustrate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed.

[0014] No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0015] The terms, "comprising," "including," "containing," "characterized by," and grammatical equivalents thereof are inclusive or open-ended terms that do not exclude additional, unrecited elements or method steps, but will also be understood to include the more restrictive terms "consisting of" and "consisting essentially of.”

[0016] It will be further understood that any compound, material or substance which is expressly or implicitly disclosed in the specification and/or recited in a claim as belonging to a group of structurally, compositionally and/or functionally related compounds, materials or substances includes individual representatives of the group and all combinations thereof.

[0017] As used herein an organic group means any aromatic or aliphatic group, such as optionally substituted aryl, alkenyl or alkyl groups.

[0018] As used herein, the term "alkyl" means preferably any monovalent, saturated straight, branched or cyclic hydrocarbon group. Examples include of methyl, ethyl n-propyl, n-butyl, n- pentyl, n-hexyl, n-heptyl or n-octyl groups, branched alkyl groups containing from 3 to 22 carbon atoms, such as iso-propyl, iso-butyl, tert-butyl, iso-pentyl, tert-pentyl, neo-pentyl and 2- ethylhexyl groups, and cyclic alkyl groups containing from 3 to 22 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups. Most preferably alkyl is methyl for R.

[0019] The term alkoxy means preferably any of the before mentioned alkyl groups, which are subsituted and bound via an oxygen atom (i.e. alkyl-O-). For R⁴ being alkoxy is preferably methoxy.

[0020] As used herein, the term “hydrolysable silyl group” refers to a silyl group which is easily cleavable by the addition of water, hydroxide anions, an alcohol, or an alkoxide anions. In case of water or alcohols, in particular, under acidic or basic conditions, the group is easily cleavable. The term “hydrolysable” indicates the groups which are not bonded to the silicon atom by a C-Si bond, but by an Si-X bond, wherein X is Cl, Br or I, an Si-0 bond, as is the case in hydroxy, hydrocarbylcarbonyloxy (preferably acetoxy), hydrocarbyloxy (preferably alkoxy) groups and ketoximo (-ON=CR2) groups (preferably dialkylketoximo groups), an Si-N bond, an Si-S bond or an Si-H bond. A preferred “hydrolysable silyl group” is a group of the formula:

RxR⁴(3-x)Si- wherein R is as defined above, R⁴ is a hydrolysable group as defined before, preferably selected from alkoxy groups, preferably methoxy, ethoxy, acetoxy groups, and halogen, preferably chlorine, and x is 0 to 2, preferably 0.

[0021] In a preferred embodiment of the coating composition according to the invention c and d are 0, that is, the polyorganosiloxanes C1) of the formula (I) essentially do not comprise branching siloxy units T and Q and are preferably linear polyorganosiloxanes.

[0022] In a further preferred embodiment of the coating composition according to the invention the polysiloxanes C1) are selected from the formula

MDbM (la), wherein

M, D, and b are as defined above, preferably b is about 5 to about 20, more preferably b is about 5, about 10 or about 20, with the provisos that there are two M² siloxy units, or there is one siloxy unit M² and one siloxy unit M³, or there is at least one unit siloxy D² and at least one siloxy unit D³, or there is at least one unit siloxy D² and at least one siloxy unit M³, or there is at least one siloxy unit M² and at least one siloxy unit D³, and preferably there is at least one siloxy unit D¹, wherein M², M³, D¹, D² and D³ are each as defined above.

[0023] In a further preferred embodiment of the coating composition according to the invention the polysiloxanes C1) are selected from the formulas (lb) to (le):

M²D_bM³ (lb), wherein

M², D, b and M³ are as defined above, preferably b is about 5 to about 20, more preferably b is about 5 to 20, more preferably b is about 5, about 10 or about 20, preferably D is D¹, that is R₂SiO₂/₂, wherein R is as defined above,

M²D_bM² (Ic), wherein

M², D, and b are as defined above, preferably b is about 5 to about 20, more preferably b is about 5, about 10 or about 20, MDbM (Id) wherein

M, D, and b are as defined above, preferably b is about 5 to about 20, more preferably b is about 5, about 10 or about 20, with the provisos that

D in formula (Id) comprises at least one siloxy unit D², and that M in formula (Id) comprises at least one siloxy unit M³ or that D in formula (Id) comprises at least one siloxy unit D³, or

D in formula (Id) comprises at least one siloxy unit D², and that M in formula (Id) comprises at least one siloxy unit M³ and that D in formula (Id) comprises at least one siloxy unit D³, wherein D, D², D³, M and M³ are as defined above, and

M³[(D¹)bi(D²)b₂(D³)b₃]M³ (le)

Wherein

M³, D¹, D², and D³ are as defined above, the siloxy units D¹, D² and D³ can be distributed blockwise or randomly in the polyorganosiloxane, and wherein b1 is from 0 to 10, b2 is from 1 to 5, and b3 is from 0 to 10 and the sum of b1+b2+b3 is from 2 to 30.

In a further preferred embodiment of the coating composition according to the invention the polysiloxanes C1) are selected from the formulas:

M² ₂D¹5,

M² ₂D¹ ,

M² ₂D¹ ₂₀,

M²D¹ ₃M³,

M²D¹ ₅M³,

M²D¹ M³,

M²D¹ ₂₀M³,

M³ ₂D¹ ₆D³ ₄D² ₂ wherein M², M³, D¹, D², and D³ are as defined above.

[0024] In a further preferred embodiment of the coating composition according to the invention the polysiloxanes C1) comprise at least one D¹ unit.

[0025] In a further preferred embodiment of the coating composition according to the invention the polyorganosiloxanes C1) of the formula (I) comprise (preferably consist of): at least two siloxy units M², or at least one siloxy unit M² and at least one siloxy unit M³, and at least one, more preferably at least about 3, or at least about 5 siloxy units D¹, or 2 to 20, or 3 to 20, or 5 to 20 siloxy units D¹.

[0026] In a further preferred embodiment of the coating composition according to the invention R⁴ is selected from alkoxy groups, preferably methoxy, ethoxy, and most preferably R⁴ is methoxy.

[0027] In a further preferred embodiment of the coating composition according to the invention the colloidal metal compounds A) are selected from the group consisting of oxides A1) and fluorides A2) of metals such as aluminum, cerium, silicon, titanium, zirconium, tantalum, tungsten, hafnium, tin, zinc, ytterbium and yttrium, preferably from metal oxides A1) of such metals, still more preferably from silicas. Most preferred the colloidal metal compound A) is selected from silicas.

[0028] Colloidal silica is generally used in the form of an aqueous-organic dispersion. Silica dispersions which can be employed are exemplified for example in EP1087001.

[0029] In a further preferred embodiment of the coating composition according to the invention the colloidal metal compounds A) are selected from metal fluorides A2), preferably of alkali metals such as lithium, sodium, potassium etc., alkaline earth metals, such as magnesium, calcium, strontium, barium, main group metals such as aluminium, boron, transition metal compounds such as period 4 transition metals: scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn), period 5 transition metals: yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and cadmium (Cd), period 6 transition metals: lanthanum (La), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg), lanthanides, such as cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium and mixed metal fluorides such as CaAIFs, MgAhFs etc. Preferred metal fluorides A2) include fluorides of aluminum, cerium, silicon, titanium, zirconium, tantalum, tungsten, hafnium, tin, zinc, ytterbium and yttrium and mixed metal fluorides thereof.

[0030] In a further preferred embodiment of the coating composition according to the invention the solvent D) is selected from the group consisting of water D1) and organic solvents D2).

[0031] In a further preferred embodiment of the coating composition according to the invention the solvent D) comprises water D1) and one or more organic solvents D2). Preferred organic solvents include alkyl acetates such as ethylacetate, alkyl ethers, glycolethers such as 1- methoxy-2-propanol, 2-propoxyethanol, ketones and aldehydes such as acetone, 4-hydroxy- 4-methylpentan-2-one and alcohols such as C1-C6 alcohols, preferably C3-C4 alcohols such as n-butanol, isopropanol, etc. [0032] Preferably the content of the solvents D) based on the total weight of the composition is from 50 to 95 wt.-%, preferably 60 to 90 wt.-%, still more preferably from 65 to 85 wt.-%.

[0033] Preferably the ratio of water D1) and organic solvents D2) is in the range of 0 (zero) (no water) to 1 : 20, preferably 0 to 1 : 15.

[0034] The component B), that is, one or more partial condensates of at least one hydrolysable silane E) is a product that is obtained by the hydrolysis and condensation reaction of one hydrolysable silane E). In this respect the term “partial” is to be understood that not all of the hydrolysable groups are hydrolysed or condensed to Si-O-Si linkages, in particular, so that the partial condensate is still capable of reacting or condensing with in particular the colloidal metal compounds A), such as in particular with the silica particles and with the modifying component C). In practice this is achieved by controlling the partial hydrolysis and condensation in a targeted manner for example: by concentration ratios, temperature, reaction time, catalysts etc. Depending on these conditions and the hydrolysable silane E) the partial condensates can comprise a variety of structures, and can range from structures having for example a number average molecular weight of less than 1000 to particles having an average particle size in the range of from 1 nanometer (nm) to greater 6 microns as measured by light scattering. In general, the hydrolysis and condensation results in a product having a mixture of products. One of ordinary skill in the art can modify the reaction conditions to favor lower molecular weight products or to favor larger organosilane condensates. In the present invention it is assumed that upon curing these partial condensates form three-dimensional networks with the colloidal metal compounds A), which are modified in its properties by the addition and incorporation of the modifying component C), leading to the excellent properties of the resulting cured coatings, such as, a mechanically stable, omniphobic surface, easy-to-clean and dirtrepellent properties, low roll-off angle of water in at least 1100 h of artificial weathering, durability of these properties as evidenced in particular by the artificial weathering test using ASTM Gmod 155 (1100h ~ 1 year Florida Weathering on transparent PC substrates) and at the same time high abrasion resistance , and low haze.

[0035] The partial organosilane condensate B) can be formed from several hydrolysis methods which are done in the presence of water and optionally, an acid catalyst can be added to the reaction to help accelerate the hydrolysis. Solvents are also optional present in the formation of the partial organosilane condensate B).

[0036] The component B) thus includes one or more condensates of at least one hydrolysable silane E) which are obtained by the hydrolysis and condensation reaction of one hydrolysable silane E).

[0037] The formation of the partial organosilane condensate B) is preferably carried out in the presence of the component A) by adding one or more hydrolysable silanes E) to an aqueous suspension of the colloidal metal compounds A), and then subjecting the resulting mixture preferably in the presence of an acid catalyst such as acetic acid to hydrolysis and condensation for example at about room temperature for several hours up to several weeks (ageing). Prior, during or subsequent to this reaction one or more modifying compounds C) can be added. Without being bound to theory it is assumed that the compounds C) react with partial organosilane condensate B) and/or, preferably and with the colloidal metal compounds

A), thereby providing the beneficial properties in particular to the surface of the coatings as described herein. The hydrolysable silane E) which is used in the formation of the partial organosilane condensate B) is preferably selected from the formula (III):

R⁶zR⁴ ₍₄-z)Si (III) wherein R⁴ is as defined above, R⁶ is selected preferably from the group consisting of an optionally substituted aliphatic group, preferably an optionally substituted alkyl group, more preferably a methyl, an ethyl or propyl group, aryl, preferably phenyl, and alkenyl, preferably vinyl, and z is 0 to 3, preferably z is 1 to 3, more preferably z is 1 .

[0038] For example R⁶ can be selected from an unsubstituted alkyl group having 1 to 20 carbon atoms, an organic group having 1 to 20 carbon atoms which might be also substituted with one or more functional groups, such as, for example, epoxide, carbamate, urea, isocyanate, hydroxyl, vinyl, blocked isocyanate or a combination thereof. The addition of such functional groups can help to provide another crosslinkable group so that the partial organosilane condensate B) which might be helpful in certain circumstances. But preferably in formula (III) R⁶ is an unsubstituted alkyl group, and most preferably methyl.

[0039] As to the preferred hydrolyable groups R⁴ it can be referred to the to those indicated for the compounds C1) above, that is, preferred hydrolyable groups R⁴ in formular (III) include in particular, alkoxy, acetoxy, halogen, preferably chlorine, ketoximo, most preferably R⁴ is alkoxy with 1 to 6 carbon atoms, in particular, methoxy.

[0040] Usually the hydrolysable silane E) is different from the optional hydrolysable fluoroorganosilanes or a hydrolysed and condensed product of such hydrolysable fluoroorganosilanes as component F) in that the hydrolysable silane E) does not comprise any fluorine atoms.

[0041] In a preferred embodiment R⁴ - and this includes all definitions for components C) and

B) and E) - is selected from alkoxy and chlorine, preferably alkoxy, more preferably C1-C6 alkoxy, more preferably methoxy or ethoxy, most preferably methoxy.

[0042] In a preferred embodiment of formula (III) R⁶ is selected form preferably unsubstituted alkyl groups and alkyl groups substituted with at least one UV stabilizing group, such as aromatic groups comprising a benzophenone moiety. If R⁶ is an alkyl group with at least one UV stabilizing / absorbing group such hydrolysable silane E) is usually used in minor amount in combination with further hydrolysable silanes E) which form the major part of the partial organosilane condensate B). A preferred silane with an UV stabilizing group is a silylated hydroxybenzophenon, preferably of the formula:

wherein in this particular formula each R is independently a substituted or unsubstituted monocyclic or polycyclic aromatic radical, R¹ is carbon is or a linear or branched aliphatic chain having less than 10 carbons and R² is a C1-6 alkyl group. Often, however, the silylated agent is a 4,6-dibenzoyl-2-(3-trialkoxysilylalkyl) resorcinol and preferably 4,6-dibenzoyl-2-(3- triethoxysilylpropyl) resorcinol

Alternatively, silylated hydroxybenzophenone UV-Absorbers, preferably of the formula

can be used as UV stabilizing group. The UV stabilizing group protects an underlaying plastic substrate from premature UV-degradation. [0043] In a preferred embodiment compound B) is a (partially) condensed product of the hydrolysable silanes E) and is obtained by hydrolysis and condensation of hydrolysable silanes E), preferably of the hydrolysable silanes E) of formula (III), as defined above.

[0044] Preferred hydrolysable silanes E) are selected from the group consisting of tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, dimethoxydimethylsilane, diethoxydimethylsilane, dimethyldichlorosilane, methyldichlorosilane, methyltrichlorosilane, phenyltricholorosilane, silicone tetrachloride, vinyltrichlorosilane, cyclohexyldimethoxymethylsilane, dimethoxymethyloctylsilane, diethoxymethylvinylsilane, chloromethyl(diisopropoxy)methylsilane, dimethoxymethylphenylsilane, diethoxydiphenylsilane, trimethoxypropylsilane, isobutyltrimethoxysilane, octyltrimethoxysilane, octadecyltrimethoxysilane, isobutyltriethoxysilane, octyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, (3-chloropropyl)trimethoxysilane, chloromethyltriethoxysilane, tris(2-methoxyethoxy)vinylsilane, 3- glycidoxypropyltrimethoxysilane, diethoxy(3-glycidoxypropyl)methylsilane, trimethoxy[2-(7- oxabicyclo[4.1.0]-hept-3-y I) ethy l]si lane, chlorotrimethoxysilane, chlorotriethoxysilane, chlorotris(1 ,3-dimethylbutoxy)-silane, dichlorodiethoxysilane, 3-(triethoxysilyl)-propionitrile, 4- (triethoxysilyl)-butyronitrile, 3-(triethoxysilyl)-propylisocyanate, 3-(triethoxysilyl)- propylthioisocyanate, phenyltriethoxysilane, 1 ,3,5,7-tetraethoxy-1 ,3,5,7- tetramethylcyclotetrasiloxane, 1 ,3,5,7-tetramethyl-1 ,3,5,7-tetrapropoxycyclotetrasiloxane, 1 ,3,5,7-tetraisopropoxy-1 ,3,5,7-tetramethylcyclotetrasiloxane, 1 ,3,5,7-tetrabutoxy-1 ,3,5,7- tetramethylcyclotetrasiloxane, 1 ,3,5,7,9-pentaethoxy-1 , 3, 5,7,9- pentamethylcyclopentasiloxane, 1 ,3-diethoxytetramethyldisiloxane, 1 ,3- dimethoxytetramethyldisiloxane, 1 , 1 ,3,3-tetramethyl-1 ,3-dichlorodisiloxane, 1 ,2- bis(methyldichlorosilyl)ethane, diacetoxydiphenylsilane, methyltris(ethylmethylketoxime)silane, bis(ethylmethylketoxime)methylisopropoxysilane, bis(ethylmethylketoxime)ethoxymethylsilane, 2-(3,4-epoxycyclohexylethyl)trimethoxysilane, methyltriisopropenoxysilane, ethyltriacetoxysilane, methyltriacetoxysilane, diacetoxydimethylsilane, triacetoxyvinylsilane, tetraacetoxysilane, and diacetoxymethylphenylsilane and combinations thereof. [0045] Most preferred the hydrolysable silane E) is methyltrimethoxysilane. [0046] If the colloidal metal compounds A) are present during the formation of the partial condensates B) from the hydrolysable silanes E), it is possible that the colloidal metal compounds A) react with the partial condensates B) leading to modified colloidal metal compounds A) or in turn to modified partial condensates B). It is assumed that such reaction will also take place during curing of the coating composition leading to the three-dimensional networks as mentioned above. [0047] In a further preferred embodiment of the coating composition according to the invention the colloidal metal oxides A1) are further modified with one or more compounds E) and the condensation products thereof. [0048] In a further preferred embodiment of the invention the coating composition is obtained from the components A), B) and D) in the following wt.-ratios: 5 to 90 wt.-% of component A), more preferably 15 to 80 wt.-% of component A), more preferably 20 to 50 wt.-% of component A),

> 0 to 94.9 wt.-% of component B), more preferably 10 to 84.9 wt.-% of component B), more preferably 20 to 74.9 wt.-% of component B), or more preferably 50 to 94.9 wt.-% of component B), and

0.1 to 10 wt.-% of component C), based on the total weight of the components A), B) and C).

[0049] As regards the component B) it is understood that its wt-percentages to a first approximation corresponds to the amount of the hydrolysable silanes E) of which the component B) is formed, considering the loss of weight by formation of, in particular, alkanols such as methanol from the condensation of alkoxy groups such as methoxy in the hydrolysis and condensation step.

[0050] In a further preferred embodiment of the coating composition of the invention the weight ratio of component A) to component B) is about 10:1 to 1 :20, preferably 2:1 to 1 :5.

[0051] In a further preferred embodiment of the coating composition of the invention the weight ratio of A) to B) is about 300: 1 to 10: 1 , preferably 200: 1 to 20: 1.

[0052] In a further preferred embodiment of the coating composition of the invention the weight ratio of component A) to component C) is about 300: 1 to 10: 1 , preferably 200: 1 to 20: 1

[0053] In a further preferred embodiment of the coating composition of the invention the weight ratio of component B) to component C) is about 300:1 to 1 :1 , preferably 200:1 to 2:1.

[0054] In a further preferred embodiment of the coating composition of the invention the amount of component C) added is in the range of about 0.01 to about 15 wt.-%, preferably 0.05 to 12 wt.-%, more preferably 0.1 to 10 wt.-% based on the entire solid content of the coating composition.

[0055] In a further preferred embodiment of the coating composition of the invention the weight ratio of the solvent D) to the remainder of the coating composition (i.e. components A), B), and C) and optional F) as defined below) is in the range (D) : E A) + B) + C) + F)) of 50 to 95 : 5 to 50, more preferably 60 to 90 to 40 : 10 to 40, still more preferably 65 to 85 : 15 to 35, most preferably about 75 : about 25.

[0056] In a further preferred embodiment of the coating composition of the invention the solid content (determined by Test method: ASTM D2369-20) is in the range of 5 to 40 wt.-%, preferably 5 to 35 wt.-%, more preferably 10 to 30 wt.-%, more preferably 15 to 25 wt.-%.

[0057] In a further preferred embodiment of the coating composition of the invention the colloidal metal compounds A) are incorporated as aqueous dispersions into the coating compositions as mentioned before.

[0058] In a further preferred embodiment of the coating composition of the invention the colloidal metal compounds A) have a particle size distribution wherein at least 40%, or at least 60%, or at least 80%, or at least 90% of the particles in the particle size distribution are between 1 to 1000 nm, or between 5 to 500 nm, or between 10 to 250 nm, the particle size distribution is preferably determined in accordance with ASTM E2490-09 (2015), Standard Guide for Measurement of Particle Size Distribution of Nanomaterials in Suspension by Dynamic Light Scattering (DLS).

[0059] In a further preferred embodiment of the coating composition of the invention the colloidal metal compounds A) have a particle size distribution with a d50 between 1 nm to 250 nm, or 2 nm to 100 nm, or 5 nm to 80 nm.

[0060] In a further preferred embodiment of the coating composition of the invention the coating composition has a pH in the range of 4 to 6.5.

[0061] In a further preferred embodiment of the coating composition of the invention the organic solvent D2) is preferably selected from aliphatic alcohols, such as n-butanol (1- butanol), isopropanol (or 2-propanol), 1-methoxy-2-propanol, aliphatic ethers, aliphatic esters, such as alkyl acetates, such as C1-C4 alkyl acetates including methyl acetate, ethyl acetate, n- propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, and sec-butyl acetate and the like. More preferably the organic solvents are alkanols with 2 to 4 carbon atoms, such as n-butanol or isopropanol and mixtures thereof.

[0062] In a further preferred embodiment of the coating composition of the invention the coating composition comprises one of more additive components F), preferably selected from: a. one or more fillers, b. one or more pigments, c. one or more flow control or levelling agents, d. one or more foam control agents, e. one or more antimicrobial and biocidal additives, f. one or more surface-active agents such as wetting and dispersion additives, g. one or more rheology modifiers, h. one or more corrosion inhibitors, i. one or more light stabilizers, such as UV absorbers, j. one or more catalysts, such as acids, k. one or more pH adjusting agents, such as acids, bases or buffers, l. one or more adhesion promotors such as organosilane adhesion promoters, organotitanate adhesion promoters, zirconate adhesion promoters, zircoaluminate adhesion promoters, alkyl phosphate esters, chrome complexes, amines, acrylic resins derived from acrylic acid, methacrylic acid and acrylate monomers such as butyl acrylate and or methacrylate monomers such as methyl methacrylate, hydroxy-functional acrylate resins such as those obtained by copolymerizing hydroxyacrylate monomers such as 2- hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc. m. one or more hydrolysable fluoroorganosilanes which are selected from the formula (II):

R⁵ _yR⁴(4-y)Si (II) wherein R⁴ is as defined above, and R⁵ is selected from an aryl group substituted with at least one fluorine substituent and an alkyl group substituted with at least one fluorine atom, preferably an alkyl group substituted with at least one fluorine atom, more preferably an alkyl group, preferably an ethyl group, substituted with a perfluoroalkyl group, and y is 1 to 3, preferably 1 , or a hydrolysed and condensed product of such hydrolysable fluoroorganosilanes which are obtained by hydrolysis and condensation of hydrolysable fluoroorganosilanes, preferably of the fluoroalkylsilanes or fluoroarylsilanes of the formula (II) defined before.

Preferred hydrolysable fluoroorgano silanes are as follows:

wherein

R⁴ are as defined above and preferably are alkoxy, more preferably methoxy or ethoxy, most preferably are methoxy, and

R¹⁵ is selected from aryl substituted by at least one fluorine atom or alkyl substituted by at least one fluorine atom, preferably from alkyl substituted by at least one fluorine atom, preferably

wherein

R¹⁶ is selected from perfluoroalkyl groups such as trifluoromethyl, 1 , 1 ,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl, 1 , 1 ,2,2,3,3,4,4,4-nonafluorobutyl, and

1 , 1 ,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl, and the hydrolysis and condensation products thereof.

[0063] Preferably the coating composition according to the invention does not comprise hydrolysable fluoroorganosilanes or hydrolysed and condensed products of such hydrolysable fluoroorganosilanes. [0064] Said additive components F) do not include any of the other components A) to E) and are different therefrom respectively.

[0065] In a further preferred embodiment of the coating composition of the invention the compounds C1) are selected from a, co-substituted dimethylpolysiloxanes of the formula (IV):

(IV), wherein R⁷ and R⁸ can be the same or different and are independently selected from optionally substituted alkyl groups, with the provisos one of R⁷ and R⁸ is an optionally substituted alkyl group having two or more carbon atoms and the other of R⁷ and R⁸ is an alkyl group which is substituted with at least one hydrolysable silyl group as defined above, and n is about 2 to about 50, preferably about 2 to about 40, more preferably about 2 to about 30, more preferably about 2 to about 25,

[0066] In a further preferred embodiment of the coating composition of the invention in the a, co-substituted dimethylpolysiloxanes of the formula (IV):

(i) R⁷ is alkyl substituted with at least one hydrolysable silyl group and R⁸ is alkyl substituted with a branched alkylcarbonyloxy group, or

(ii) R⁷ is alkyl substituted with at least one hydrolysable silyl group and R⁸ is C3 to C18 alkyl, or

(iii) R⁷ is alkyl substituted with at least one hydrolysable silyl group and R⁸ is C3 to C18 alkyl group having one of more fluorine atoms, or

(iv) R⁷ and R⁸ are each ethyl substituted with at least one hydrolysable silyl group.

[0067] In a further preferred embodiment of the coating composition of the invention the compounds B1) are selected from the following formulas:

wherein n is as defined above, preferably n is about 3 to about 20, preferably about 3, about 5, about 10 or about 20,

R⁴ are as defined above and preferably are alkoxy, more preferably methoxy or ethoxy, most preferably are methoxy,

R¹⁰ are independently CHs or H,

R⁹ are independently isobutyl or C₂H₅ or CH₃ or H,

[0068]

R¹¹ and R¹² are independently linear or branched alkyl groups, having a total number of carbon atoms from 2 (pivalic acid residue) to 7 (versatic or neodecanoic acid residue), [0069]

wherein n is as defined above, preferably n is about 3 to about 20, preferably about 3, about 5, about 10 or about 20, and

R⁴ are as defined above and preferably are alkoxy, more preferably methoxy or ethoxy, most preferably are methoxy, [0070]

R¹³ is selected from linear alkyl C3 to C18 alkyl, preferably linear C4 or C12 alkyl,

[0071]

R¹⁴ is selected from linear alkyl C3 to C18 alkyl having at least one fluorine substituent, more preferably n is about 10 and R¹⁴ is ethyl substituted by a perfluoroalkyl group, preferably a perfluorohexyl group, [0072]

wherein n is as defined above, preferably n is about 3 to about 50, more preferably about 3, about 5, about 10, about 20 or about 50, and still more preferably n is about 5, about 10 or about 20, and

R⁴ are as defined above and preferably are alkoxy, more preferably methoxy or ethoxy, most preferably are methoxy, [0073]

wherein

R¹¹ and R¹² are independently defined as above, preferably R¹¹ and R¹² have in total 7 carbon atoms, and p is from about 2 to about 10, preferably about 6, q is from about 2 to about 8, preferably about 4, and r is from about 1 to about 5, preferably about 2.

[0074] The polyorganosiloxanes of the formula (I) (component C1)) can be prepared in particular according to the processes described in WO2021154504A1 and WO2021154501 A1 , which are fully included herein by reference.

[0075] In a particular preferred process, the polyorganosiloxanes of the formula (I) are prepared starting from the corresponding SiH-terminated polysiloxanes which are obtained in particular by the acid-catalyzed equilibration reaction as is known in the art, which are then reacted with alkenyl compounds providing the organic group R¹ comprising the at least one hydrolysable silyl group and alkenyl compounds providing the organic group R² in transition metal (in particular platinum) catalyzed hydrosilylation reaction as is well-known to the skilled person in the art. As is also well-known to a skiled person in the art the hydrosilylation reaction products C1) obtained are statistical mixtures of symmetric and asymmetric polysiloxanes.

[0076] In particular, compounds of the formula (la)

MaD cQd (la) wherein M, D, T, Q, a, b, c and d are as defined above, but wherein at least two siloxy units are selected from hydrogen-functional siloxy units M^H, D^H and T^H, wherein in particular, M^H is HR₂SiOi/₂, D^H is HRSiC>2/2, and

T^H is HSiO₃/₂ are reacted with the corresponding alkenyl compounds. For example, the compounds of the formula

can be prepared by reacting the underlying a, co-hydrogen substituted dimethylpolysiloxanes of the formula:

subsequently with the vinyl compounds:

in any order, wherein each substituent R⁴, R¹¹ and R¹² and the index n is as defined above, in the presence of a transition metal hydrosilylation catalyst, preferably a platinum metal complex catalyst.

[0077] The underlying hydrogen-functional starting polysiloxanes can be prepared for example by equilibration reaction at elevated temperatures from cyclic siloxanes such as octamethylcyclotetrasiloxane and tetramethyldisiloxane in the presence of an acid catalyst such as perfluoro-n-butanoic acid. [0078] The present invention further relates to the preferred process for the manufacture of the coating compositions according to the invention comprising the steps of (in any possible order): a) Providing one or more aqueous dispersions of one or more colloidal metal compounds such as colloidal metal oxides A), b) Adding one or more compounds C) as defined above, c) Adding one or more compounds E) as defined above, d) Optionally adding one or more pH adjusting agents, e) Optionally adding one or more additive components F) as mentioned above, f) Optionally distilling off of alcohols and water, g) Optionally subjecting the reaction mixture to treating at room temperature (25°C) or heating above room temperature, h) Adding one or more solvents D) as defined above, i) Subjecting the resulting dispersion to gel formation at room temperature or above room temperature (25°C).

[0079] It is possible within the scope of this process to change the order of steps a) to i) into any suitable order.

[0080] For example, in a preferred process of the invention, in a first step one or more hydrolysable silanes E) are added to an aqueous dispersion of the colloidal metal compounds A) and subjected to in the presence of an acid catalyst at room temperature (23°) or above, thereby forming one or more partial condensates B). During such step also condensation reactions of the colloidal metal compounds A) with the partial condensates B) or the hydrolysable silanes E) may take place. One or more solvents D) can be added, and optionally further components E) and solvents D) can be added and the mixture optionally can be aso heated in vacuo with the removal of water and alcohol formed during hydrolysis and condensation. Preferably subsequently additional solvents and one or more components C),that is C1), can be added and the resulting mixture is aged for several hours (e.g. 2 to 24 hours) to several days (e.g. 1 to 40 days) at room temperature (23°) or elevated temperatures. Finally, further acid and further solvents D) can be added and a suitable solid content is thereby adjusted as mentioned before.

[0081] In a further aspect of the invention, it relates to a modified colloidal metal compound AM), preferably metal oxides, more preferably silica, which is obtained by modifying (reacting) the colloidal metal compound A) with one or more compounds C) as defined above.

[0082] In a further aspect of the invention, it relates to a modified partial condensate BM) of at least one hydrolysable silane E), which is obtained by modifying the partial condensate of at least one hydrolysable silane E) with one or more compounds C) as defined above. [0083] It is also possible to prepare the partial condensate B) from the one or more hydrolysable silanes E) in a separate production step and then combine the colloidal metal compound A) dispersion with such partial condensate B) and the one or more compounds C) as defined above. Likewise it is possible to subject the colloidal metal compound A) and the partial condensate B) to the reaction with the one or more compounds C) separately and then to combine the reaction products to form the coating composition of the invention. In such processes solvents D) can be added at any suitable step.

[0084] In a still further aspect of the invention, a process for preparing a coated article is provided by a coating process which comprises the steps of a) Providing the coating composition according to the invention onto the surface of a substrate, and b) Drying the coating composition on such substrate to obtain a coated article.

[0085] This process is preferably used to provide coated articles, wherein the substrate is selected from transparent and non-transparent substrates, such as wood, painted surfaces, leather, ceramics, textiles, metal, glass, plastic, composite substrates of them with or without an organic or inorganic base coating, preferably selected from plastic substrates, more preferably from polycarbonate substrates, acrylic polymers such as poly(methyl methacrylate), polyethylene, polypropylene or polyesters such as poly(ethylene terephthalate), poly(butylene terephthalate), polyamide, polyimide, acrylonitrile-styrene copolymer, styrene acrylonitrilebutadiene copolymer, polyvinyl chloride, butyrate- substrates and the like, wherein such substrates can be in any form, such as in the form of sheets, foils or mouldings. Most preferably polycarbonate is used as a substrate.

[0086] The process for preparing the coated articles usually comprise a process step selected from a. Spray coating, b. Flow coating, c. Roll coating, and d. Dip coating.

[0087] The preferred coating process is spray-coating.

[0088] In the process for preparing the coated articles according to the invention, the drying step is preferably carried out at a temperature of about 30 to 200°C, preferably at temperature of about 100 to about 160°C.

[0089] In the process for preparing a coated article according to the invention, the coating composition is preferably provided in an amount of up to 50 g per m² of the substrate such as from 4 to 50g per m² of the substrate.

[0090] The process for preparing the coated article according to the invention can be used to provide a coating onto a substrate which has a primer coating or which has no primer coating. In case the substrate has no primer coating the coating composition of the invention preferably comprises as additive component E) m., as defined above, that is, one or more adhesion promotors, in particular, one or more adhesion promoting binder resins, in particular acrylate resins as defined above, such as poly(meth)acrylate binder resins, in particular, hydroxyfunctional acrylate resins, such as hydroxy-functional poly(meth)acrylate binder resins Such additional adhesion promoting binder resins can be added to the coating composition in an amount of e.g. 0.01 to 6 wt-% based on the total weight of the coating composition.

[0091] In case the substrate, in particular, the plastic substrate has primer coating such primer coating is preferably a poly(methyl methacrylate) (PMMA) resin coating.

[0092] The present invention further relates to coated articles obtained by the process according to the invention as described above. Such coated articles may have a single layer or multiple layer coatings which comprise the dried coating composition of the invention as one of the layers.

[0093] Preferably the coated articles comprise the dried coating composition obtained by drying the coating composition of the invention as the outer layer (top coat).

[0094] The dried coating composition of the invention may have a thickness in the range of 1 to 50 pm, preferably 1.5 to 40 pm; more preferably 2 to 25 pm, more preferably 3 to 25 pm, more preferably 4 to 16 pm.

[0095] As shown in the following examples the present invention provides a coating composition which provides a coating with superior surface properties. In particular, the coatings made by drying the coating compositions on a substrate are resistant to oil, water (weather) and dust (abrasion) and have improved properties such as repulsion of liquids containing dirt, anti-graffity properties, lower dirt accumulating on their surface, scratch resistance, weathering-stability, transparency and the like.

[0096] While the invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made, and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed as the best mode contemplated for carrying out this invention but that the invention will include all embodiments falling within the scope of the appended claims. SUMMARY OF THE PREFERRED EMBODIMENTS

In the following the preferred embodiments of the invention are summarized:

1. Embodiment

A coating composition, comprising

A) or

B) or

A) and B) are modified with

C) one or more compounds, different from B), selected from the group consisting of

C1) polyorganosiloxanes of the formula (I):

M_aDbTcQ_d (I) wherein

M, D T and Q each represent siloxy units, and wherein

T is selected from T¹ = RSiOs/2, T² = R¹SiC>3/2, and T³ = R²SiC>3/2,

Q=SiO4/2, wherein

RxR⁴(3-x)Si- wherein R is as defined above, R⁴ is a hydrolysable group, preferably selected from alkoxy, acetoxy, halogen, preferably chlorine, and ketoximo, and x is 0 to 2, preferably 0,

R² independently is an organic group different from R and R¹, selected from optionally substituted alkyl, preferably optionally substituted alkyl having 2 or more carbon atoms, or optionally substituted alkyl having 4 or more carbon atoms, or optionally substituted alkyl having 6 or more carbon atoms, preferably R² is selected from the group consisting of unsubstituted alkyl having two or more carbon atoms, preferably unsubstituted alkyl having 4 or more carbon atoms, more preferably unsubstituted alkyl having 6 or more carbon atoms, alkyl, preferably alkyl having 2 or more carbon atoms, substituted with acyloxy, such as alkylcarbonyloxy, preferably branched alkylcarbonyloxy, and alkyl substituted with one or more halogen atoms, preferably fluorine atoms, p is independently 0 to 2, preferably 2, q is independently 0 or 1 , preferably 1 , with the provisos that in the polyorganosiloxanes of the formula (I): there are at least at least two siloxy units M², or there is at least one siloxy unit M² and at least one siloxy unit M³, or there is at least one siloxy unit D² and at least one siloxy unit D³, or there is at least one siloxy unit D² and at least one siloxy unit M³, or there is at least one siloxy unit M² and at least one siloxy unit D³, and preferably there are at least one, more preferably at least 3, more preferably at least 5 siloxy units D¹, wherein each siloxy unit is as defined above, and the indices in formula (I) represent the average numbers of the siloxy units M, D, T and Q as defined above, which may be distributed blockwise or randomly in the polyorganosiloxanes, and which may be identical or different, and are a = 2 to 10, preferably 2, b = 2 to 50, preferably 2 to 40, more preferably 2 to 30, more preferably 2 to 25, c = 0 to 10, preferably 0, d = 0 to 1 , preferably 0,

D) at least one solvent.

2. Embodiment

A coating composition according to the previous embodiment 1 , wherein c and d are 0.

3. Embodiment

A coating composition according to any of the previous embodiments, wherein the polysiloxanes C1) are selected from the formula (la): MDbM (la), wherein

M, D, and b are as defined above, preferably b is about 5, about 10 or about 20, with the provisos that there are two M² siloxy units, or there is one siloxy unit M² and one siloxy unit M³, or there is at least one unit siloxy D² and at least one siloxy unit D³, or there is at least one unit siloxy D² and at least one siloxy unit M³, or there is at least one siloxy unit M² and at least one siloxy unit D³, and preferably there is at least one siloxy unit D¹, wherein M², M³, D¹, D² and D³ are each as defined above.

4. Embodiment

A coating composition according to embodiment 1 , wherein the polysiloxanes C1) are selected from the formulas (lb) to (le): M²D_bM³ (lb), wherein

M², D, b and M³ are as defined above, preferably b is about 5, about 10 or about 20, preferably D is D¹ being R2SiO2/2, wherein R is as defined above, M²D_bM² (Ic), wherein

M², D, and b are as defined above, preferably b is about 5, about 10 or about 20, MD_bM (Id) wherein

M, D, and b are as defined above, preferably b is about 5, about 10 or about 20, with the provisos that

D in formula (Id) comprises at least one siloxy unit D², and that M in formula (Id) comprises at least one siloxy unit M³ and that D in formula (Id) comprises at least one siloxy unit D³, wherein D, D², D³, M and M³ are as defined above, and M³[(D¹)bi(D²)b2(D³)_b3]M³ (le) wherein

5. Embodiment

A coating composition according to any of embodiments 1 to 4, wherein the polysiloxanes C1) are selected from the formulas

M² ₂D¹5, M² ₂D¹ , M² ₂D¹20,

M²D¹ ₃M³,

M²D¹ ₅M³,

M²D¹ M³,

M²D¹2OM³,

M³ ₂D¹6D³ ₄D²2 wherein M², M³, D¹, D², and D³ are as defined above.

6. Embodiment

A coating composition according to any of embodiments 1 to 5, wherein the polysiloxanes C1) comprise at least one D¹ unit.

7. Embodiment

A coating composition according to any of the previous embodiments, wherein the polyorganosiloxanes C1) of the formula (I) comprise (preferably consist of): at least two siloxy units M², or at least one siloxy unit M² and at least one siloxy unit M³, and at least one, more preferably at least 3, more preferably at least 5 siloxy units D¹.

8. Embodiment

A coating composition according to any of the previous embodiments, wherein the colloidal metal compounds A) are selected from the group consisting of oxides A1) and fluorides A2) of aluminum, cerium, silicon, titanium, zirconium, tantalum, tungsten, hafnium, tin, zinc, ytterbium and yttrium.

9. Embodiment

A coating composition according to any of the previous embodiments, wherein the colloidal metal compound A) is selected from metal oxides A1), preferably from silicas.

10. Embodiment

A coating composition according to any of the previous embodiments, wherein the colloidal metal compound A) is selected from metal fluorides A2), preferably from metals selected from aluminum, cerium, silicon, titanium, zirconium, tantalum, tungsten, hafnium, tin, zinc, ytterbium and yttrium.

11. Embodiment

A coating composition according to any of the previous embodiments, wherein the solvent D) is selected from the group consisting of water D1) and organic solvents D2).

12. Embodiment

A coating composition according to any of the previous embodiments, wherein the solvent D) comprises water D1) and organic solvents D2).

13. Embodiment A coating composition according to any of the previous embodiments, wherein the hydrolysable silane E) is selected from the formula (III): R⁶zR⁴(4-_z)Si (III) wherein R⁴ is as defined above, R⁶ is selected from the group consisting of an optionally substituted aliphatic group, preferably an optionally substituted alkyl group, more preferably a methyl, an ethyl or propyl group, aryl, preferably phenyl, and alkenyl, preferably vinyl, and z is 0 to 3, preferably z is 1 to 3, more preferably z is 1.

14. Embodiment

A coating composition according to any of the previous embodiments, wherein the hydrolysable silane E) does not comprise fluorine.

15. Embodiment

A coating composition according to any of the previous embodiments, wherein R⁴ is selected from alkoxy and chlorine, preferably alkoxy, more preferably C1-C6 alkoxy, more preferably methoxy or ethoxy, most preferably methoxy.

16. Embodiment

A coating composition according to the previous embodiment, wherein R⁶ in formula (III) is selected from alkyl groups and alkyl groups substituted with at least one UV stabilizing group, such as aromatic groups comprising a benzophenone moiety.

17. Embodiment

A coating composition according to any of the previous embodiments, wherein compound B) is a condensed product of the hydrolysable silanes E) and is obtained by hydrolysis and condensation of hydrolysable silanes E), preferably of the hydrolysable silanes E) of formula (III), as defined above.

18. Embodiment

A coating composition according to any of the previous embodiments, wherein compound E) is selected from the group consisting of tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, dimethoxydimethylsilane, diethoxydimethylsilane, dimethyldichlorosilane, methyldichlorosilane, methyltrichlorosilane, phenyltricholorosilane, silicone tetrachloride, vinyltrichlorosilane, cyclohexyldimethoxymethylsilane, dimethoxymethyloctylsilane, diethoxymethylvinylsilane, chloromethyl(diisopropoxy)methylsilane, dimethoxymethylphenylsilane, diethoxydiphenylsilane, trimethoxypropylsilane, isobutyltrimethoxysilane, octyltrimethoxysilane, octadecyltrimethoxysilane, isobutyltriethoxysilane, octyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, (3-chloropropyl)trimethoxysilane, chloromethyltriethoxysilane, tris(2-methoxyethoxy)vinylsilane, 3- glycidoxypropyltrimethoxysilane, diethoxy(3-glycidoxypropyl)methylsilane, trimethoxy[2-(7- oxabicyclo[4.1.0]-hept-3-y I) ethy l]si lane, chlorotrimethoxysilane, chlorotriethoxysilane, chlorotris(1 ,3-dimethylbutoxy)-silane, dichlorodiethoxysilane, 3-(triethoxysilyl)-propionitrile, 4- (triethoxysilyl)-butyronitrile, 3-(triethoxysilyl)-propylisocyanate, 3-(triethoxysilyl)- propylthioisocyanate, phenyltriethoxysilane, 1 ,3,5,7-tetraethoxy-1 ,3,5,7- tetramethylcyclotetrasiloxane, 1 ,3,5,7-tetramethyl-1 ,3,5,7-tetrapropoxycyclotetrasiloxane, 1 ,3,5,7-tetraisopropoxy-1 ,3,5,7-tetramethylcyclotetrasiloxane, 1 ,3,5,7-tetrabutoxy-1 ,3,5,7- tetramethylcyclotetrasiloxane, 1 ,3,5,7,9-pentaethoxy-1 , 3, 5,7,9- pentamethylcyclopentasiloxane, 1 ,3-diethoxytetramethyldisiloxane, 1 ,3- dimethoxytetramethyldisiloxane, 1 , 1 ,3,3-tetramethyl-1 ,3-dichlorodisiloxane, 1 ,2- bis(methyldichlorosilyl)ethane, diacetoxydiphenylsilane, methyltris(ethylmethylketoxime)silane, bis(ethylmethylketoxime)methylisopropoxysilane, bis(ethylmethylketoxime)ethoxymethylsilane, 2-(3,4-epoxycyclohexylethyl)trimethoxysilane, methyltriisopropenoxysilane, ethyltriacetoxysilane, methyltriacetoxysilane, diacetoxydimethylsilane, triacetoxyvinylsilane, tetraacetoxysilane, and diacetoxymethylphenylsilane, and preferably E) is methyltrimethoxysilane.

19. Embodiment

A coating composition according to any of the previous embodiments, wherein the component A) is modified with at least one hydrolysable silane E) as defined above.

20. Embodiment

A coating composition according to any of the previous embodiments, which is obtained from the components A), B) and C) in the following wt.-ratios: about 5 to about 90 wt.-% of component A),

> 0 to about 94.9 wt.-% of component B), more preferably about 50 to about 94.9 wt.-% of component B), and about 0.1 to about 10 wt.-% of component C), based on the total weight of the components A), B) and C).

21. Embodiment

A coating composition according to any of the previous embodiments, wherein the weight ratio of component A) to component B) is about 10:1 to about 1 :20, preferably about 2:1 to about 1 :5.

22. Embodiment

A coating composition according to any of the previous embodiments, wherein the weight ratio of component A) to component C) is about 300:1 to about 10:1 , preferably about 200: 1 to about 20: 1 .

23. Embodiment

A coating composition according to any of the previous embodiments 16 to 23, wherein the weight ratio of component B) to component C) is about 300: 1 to about 1 :1 , preferably about 200: 1 to about 2: 1.

24. Embodiment

A coating composition according to any of the previous embodiments, wherein the weight ratio of the solvent D) to the remainder of the coating composition (i.e. components A), B), and C) and optional F) as defined below) is in the range (D) : E A) + B) + C) + F)) of about 50 to about 95 : about 5 to about 50, more preferably about 60 to about 90 to about 40 : about 10 to about 40, still more preferably about 65 to about 85 : about 15 to about 35, most preferably about 75 : about 25.

25. Embodiment

A coating composition according to any of the previous embodiments, wherein the solid content (determined by Test method: ASTM D2369-20) is in the range of about 5 to about 40 wt.-%, preferably about 10 to about 30 wt.-%.

26. Embodiment

A coating composition according to any of the previous embodiments, wherein the colloidal metal compounds A) are incorporated as aqueous dispersions into the coating compositions.

27. Embodiment

A coating composition according to any of the previous embodiments, wherein the colloidal metal compounds A) have a particle size distribution wherein at least 40%, or at least 60%, or at least 80%, or at least 90% of the particles in the particle size distribution are between about 1 to about 1000 nm, or between about 5 to about 500 nm, or between about 10 to about 250 nm, the particle size distribution is preferably determined in accordance with ASTM E2490-09 (2015), Standard Guide for Measurement of Particle Size Distribution of Nanomaterials in Suspension by Dynamic Light Scattering (DLS).

28. Embodiment

A coating composition according to any of the previous embodiments, wherein the colloidal metal compounds A) have a particle size distribution with a d50 between about 1 nm to about 250 nm, or about 5 nm to about 100 nm, or about 10 nm to about 80 nm.

29. Embodiment

A coating composition according to any of the previous embodiments, having a pH in the range of about 4 to about 6.5.

30. Embodiment

A coating composition according to any of the previous embodiments, wherein the organic solvent D2) is selected from aliphatic alcohols, such as methanol, n-butanol, isopropanol, alkyl acetates, such as C 1-C4 alkyl acetates including methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, aliphatic ethers, and glycolethers, such as C1-C4 glycolethers including 2-methoxyethanol, 2-ethoxyethanol, 2- propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 2-(2-methoxyethoxy)ethanol and (2- (2-ethoxyethoxy)ethanol.

31. Embodiment

A coating composition according to any of the previous embodiments, further comprising one of more additive components F), preferably selected from: a. one or more fillers, b. one or more pigments, c. one or more flow control or levelling agents, d. one or more foam control agents, e. one or more antimicrobial and biocidal additives, f. one or more surface-active agents such as wetting and dispersion additives, g. one or more rheology modifiers, h. one or more corrosion inhibitors, i. one or more light stabilizers, such as UV absorbers, j. one or more catalysts, such as acids, k. one or more pH adjusting agents, such as acids, bases or buffers, l. one or more adhesion promotors such as organosilane adhesion promoters, organotitanate adhesion promoters, zirconate adhesion promoters, zircoaluminate adhesion promoters, alkyl phosphate esters, chrome complexes, amines, acrylic resins derived from acrylic acid, methacrylic acid and acrylate monomers such as butyl acrylate and or methacrylate monomers such as methyl methacrylate, hydroxyfunctional acrylate resins such as those obtained by copolymerizing hydroxyacrylate monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc., m. one or more hydrolysable fluoroorganosilanes or a hydrolysed and condensed product of such hydrolysable fluoroorganosilanes which are obtained by hydrolysis and condensation of hydrolysable fluoroorganosilanes such as those shown before.

32. Embodiment

A coating composition according to any of the previous embodiments, wherein the compounds C1) are selected from a, co-substituted dimethylpolysiloxanes of the formula (IV):

(IV), wherein R⁷ and R⁸ can be the same or different and are independently selected from optionally substituted alkyl groups, with the provisos that one of R⁷ and R⁸ is an optionally substituted alkyl group having two or more carbon atoms and the other of R⁷ and R⁸ is an alkyl group which is substituted with at least one hydrolysable silyl group as defined above, and n is about 2 to about 50, preferably about 2 to about 40, more preferably about 2 to about 30, more preferably about 2 to about 25.

33. Embodiment

A coating composition according to the previous embodiment, wherein in the a, co -substituted dimethylpolysiloxanes of the formula (IV):

34. Embodiment

A coating composition according to any of the previous embodiments, wherein the compounds C1) are selected from the following formulas:

wherein n is as defined above, preferably n is about 3 to about 20, preferably about 3, about 5, about

10 or about 20,

R¹⁰ are independently CHs or H,

R⁹ are independently isobutyl or C₂H₅ or CH₃ or H,

R¹¹ and R¹² are independently linear or branched alkyl groups, having a total number of carbon atoms from 2 (pivalic acid residue) to 7 (versatic or neodecanoic acid residue),

R¹³ is selected from linear alkyl, preferably linear C3 to C18 alkyl, preferably linear C4 or C12 alkyl, or R¹³ is branched alkyl, preferably branched C4 to C12 alkyl, derived from corresponding alpha-olefins such as oligomerization products of 1-butene, 2-butene, 2-methylbut-1-ene, 2- methylbut-2-ene,

wherein n is as defined above, preferably n is about 3 to about 20, preferably about 3, about 5, about 10 or about 20, and R⁴ are as defined above and preferably are alkoxy, more preferably methoxy or ethoxy, most preferably are methoxy,

R¹⁴ is selected from linear alkyl, preferably linear C3 to C18 alkyl having at least one fluorine substituent, more preferably n is about 10 and R¹⁴ is ethyl substituted by a perfluoroalkyl group, preferably a perfluorohexyl group,

wherein

35. Embodiment

A process for the manufacture of the coating compositions according to any of the previous embodiments comprising (in any order): a) Providing one or more aqueous dispersions of one or more colloidal metal compounds such as colloidal metal oxides A), b) Adding one or more compounds C) as defined above, c) Adding one or more compounds E) as defined above, d) Optionally adding one or more pH adjusting agents, e) Optionally adding one or more additive components F) as mentioned above, f) Optionally distilling off of alcohols and water, g) Optionally subjecting the reaction mixture to treating at room temperature (25°C) or heating above room temperature, h) Adding one or more solvents D) as defined above, i) Subjecting the resulting dispersion to gel formation.

36. Embodiment

Modified colloidal metal compounds AM), preferably metal oxides, more preferably silica, which is obtained by modifying the colloidal metal compound A) with one or more compounds C) as defined above.

37. Embodiment

Modified partial condensates BM) of at least one hydrolysable silane E), which is obtained by modifying the partial condensate of at least one hydrolysable silane E) with one or more compounds C) as defined above.

38. Embodiment

A process for preparing a coated article by a coating process which comprises a) Providing the coating composition according to any of the previous embodiments onto the surface of a substrate, and b) Drying the coating composition on such substrate to obtain a coated article.

39. Embodiment

A process for preparing a coated article according to the previous embodiment, wherein the substrate is selected from transparent and non-transparent substrates, such as wood, painted surfaces, leather, ceramics, textiles, metal, glass, plastic, composite substrates of them with or without an organic or inorganic base coating, preferably selected from plastic substrates, more preferably from polycarbonate substrates, acrylic polymers such as poly(methyl methacrylate), polyethylene, polypropylene or polyesters such as poly(ethylene terephthalate), poly(butylene terephthalate), polyamide, polyimide, acrylonitrile-styrene copolymer, styrene acrylonitrile-butadiene copolymer, polyvinyl chloride, butyrate- substrates and the like, wherein such substrates can be in any form, such as in the form of sheets, foils or mouldings.

40. Embodiment

A process for preparing a coated article according to the previous embodiments, wherein the coating composition is provided onto the substrate by a. Spray coating, b. Flow coating, c. Roll coating, or d. Dip coating.

41. Embodiment

A process for preparing a coated article according to the previous embodiments, wherein the drying step is carried out at a temperature of about 30 to about 200°C, preferably at temperature of about 85°C to about 160°C.

42. Embodiment

A process for preparing a coated article according to the previous embodiments, wherein the coating composition is provided in an amount of up to about 50 g per m².

43. Embodiment

A process for preparing a coated article according to any of the previous embodiments, wherein the coating composition is provided onto a substrate which has a primer coating or which has no primer coating.

44. Embodiment

A process for preparing a coated article according to any of the previous embodiments, wherein the coating composition is provided onto a substrate which has a primer coating, where such primer coating preferably is selected from the group consisting of acrylic resins, such as a poly(methyl methacrylate) resins and polyurethane resins.

45. Embodiment

A coated article obtained by the process according to any of the previous embodiments.

46. Embodiment

Coated articles having a single layer or multiple layer coating comprising the dried coating composition as defined in any of the previous embodiments as one layer.

47. Embodiment

Coated articles comprising the dried coating composition obtained by drying the coating composition as defined in any of the previous embodiments as the outer layer (top coat).

48. Embodiment

Coated articles according to the previous embodiments comprising the dried coating composition as defined in any of the previous embodiments in a thickness of about 1 to about 50 pm, preferably about 1 to about 25 pm. EXAMPLES

Preparation examples component C1)

[0097] The compounds C1) with two different terminal functional groups used in this invention were made in a three-step process: In the first step, a polysiloxane with SiH terminal groups is made by acid-catalyzed equilibration reaction or in case of preparation examples 3-6 according to a process described in W02017012714. In the second step, one of the SiH terminal groups is equipped with a preferably vinyl-functional alkoxy silane in a hydrosilylation catalyst supported reaction. Finally, the remaining SiH-terminal group of the polysiloxane is reacted in a hydrosilylation reaction with a vinyl- or allyl functional group. As is known by the skilled person in the art the hydrosilylation reaction products will be statistical mixtures of symmetric and asymmetric polysiloxanes the major asymmetric product will be depicted.

[0098] The compounds C1) with the same terminal functional group, were made in a two-step process: In the first step, a polysiloxane with SiH terminal groups is made by acid-catalyzed equilibration reaction. In the second step, the SiH terminal groups were equipped with an alkoxy silane in a hydrosilylation catalyst supported reaction.

Representative example for the synthesis of Si-H terminated polydimethylsiloxanes M^HD_XM^H:

Preparation Example 1 : Silicone hydride fluids - M^HDn.2M^H

[0099] A silicone hydride fluid having a structure of M^HDn.2M^H (SiH = 6 wt%, linear structure) was prepared in an equilibration reaction at 70° for 4 hrs. from octamethylcyclotetrasiloxane (1187.0 g, 4.0 mol), tetramethyldisiloxane (215.0 g, 1.6 mol) and perfluoro-n-butanoic acid (1000 ppm) as the catalyst. At the end of the reaction time, acid neutralization was performed at 70 °C through the addition of sodium bicarbonate (14.0 g) and water (1.4 g). The crude product was filtered yielding in 1505.0 g of a colorless liquid. Low volatiles were removed in vacuo. The structure and the SiH content were determined by ¹H- and ²⁹Si-NMR.

[0100] Si-H terminated polydimethylsiloxanes of the structure M^HD_XM^H with different chain lengths x were prepared accordingly.

Representative example for the synthesis of mono-functionalized polydimethylsiloxanes M² D_XM^H: Preparation Example 2: M²Dn.2M^H (a-(3-trimethoxysilyl)ethyl-functionalized polysiloxane)

(with M=M² with R¹ = ethyl substituted with trimethoxysilyl)

[0101] M^HDII.2M^H (400.0 g, 0.4 mol) was dissolved in xylene (70.0 g) and heated to 80°C. Vinyltrimethoxysilane (61.4 g, 0.4 mol) was added slowly to the mixture in the presence of tris(triphenylphosphine)rhodium(l) chloride (175 ppm) as the catalyst. The reaction mixture was further heated for 5.5 hrs. at 80°C. The cure product dissolved in xylene was received as pale yellowish liquid in 0.530 g yield. Solvent was finally removed in vacuo. The structure was confirmed by ¹H- and ²⁹Si-NMR.

Representative examples for the synthesis of a, co bi-functionalized polydimethylsiloxanes M² D_XM³:

Preparation Example 3: M²Dn.2M³ (with M=M² with R¹ = ethyl substituted with trimethoxysilyl and M=M³ with R² = ethyl substituted with branched alkyl carbonyloxy)

[0102] M²DII.2M^H (with M² = ethyl substituted with trimethoxysilyl)(260.0 g, 0.23 mol), the vinylic monomer VeoVa 9:

(with R^a and R^b having 6 carbon atoms in total), (43.0 g, 0.23 mol, vinyl ester of Versatic™ acid 9, supplier Hexion Inc. corresponding to M³) and Karstedt Catalyst (10 ppm, platinum(O) - 1 ,3-Divinyltetramethyldisiloxane Complex) were dissolved in xylene (15.0 g) and heated to 80°C for 5 hrs. After the removal of the solvent, the product (311.0 g) was received as clear yellow to light-brownish liquid. The target product was confirmed by ¹H- and ²⁹Si-NMR.

Preparation Example 4: M²Dn.2M³ (with M=M² with R¹ = ethyl substituted with trimethoxysilyl and M=M³ with R² = ethyl substituted with branched alkyl carbonyloxy)

[0103] M²DII.2M^H (with M² with R¹ = ethyl substituted with trimethoxysilyl) (270.0 g, 0.24 mol), the vinylic monomer VeoVa 10: o C H₃ o—c— C— R^a

H₂C=CH ■ Ih

(with R^a and R^b having 7 carbon atoms in total),

(48.1 g, 0.24 mol, vinyl ester of Versatic™ acid 10, supplier Hexion Inc. corresponding to M³) and Karstedt Catalyst (10 ppm, platinum(O) - 1 ,3-Divinyltetramethyldisiloxane Complex) were dissolved in xylene (16.0 g) and heated to 80°C for 5 hrs. After the removal of the solvent from the crude (324.0 g) in valuo, the product was received as yellow to brownish clear liquid. The product structure was confirmed by ¹H- and ²⁹Si-NMR.

Preparation Example 5: M²Dio.gM³ (with M=M² with R¹ = ethyl substituted with trimethoxysilyl and M=M³ with R² = ethyl substituted with branched alkyl carbonyloxy)

[0104] M²Dio.gM^H (with M² with R¹ = ethyl substituted with trimethoxysilyl) (53.3 g, 0.04 mol), vinylpivalat: o C H3

O C — C — C Hj

H₂C=C H^/ C H₃

(4.6 g, 0.04 mol) and Lamoreaux catalyst (10 ppm, 3.3 wt% solution in toluene) were dissolved in xylene (2.9 g) and heated to 133°C for 3.0 hrs. Completion of the reaction was indicated by titration with a butanolic KOH solution through observing the absence of a H2 evolution. The product structure was confirmed by ¹H-NMR.

Preparation Example 6: M²Dio.gM³⁽ (with M=M² with R¹ = ethyl substituted with trimethoxysilyl and M=M³ with R² = ethyl substituted with branched alkyl carbonyloxy)

[0105] M²Dio.gM^H (with M² with R¹ = ethyl substituted with trimethoxysilyl) (80.0 g, 0.07 mol), vinyl 2-ethylhexanoate:

(10.3 g, 0.06 mol) and Lamoreaux catalyst (10 ppm, 3.3 wt% solution in toluene) were dissolved in xylene (13.6 g) and heated to 130°C for 16.0 hrs. Completion of the reaction was indicated by titration with an alcoholic KOH solution through observing the absence of a H2 evolution. The product structure was confirmed by ¹H-NMR.

Preparation Example 7: M²Dn.6M³ (with M=M² with R¹ = ethyl substituted with trimethoxysilyl and M=M³ with R² = fluoroalkyl)

[0106] M²DII.6M^H (with M² with R¹ = ethyl substituted with trimethoxysilyl) (50.0 g, 0.04 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoroct-1-en: /CF₂-CF₃ CF2-CF2

CF2-CF2

/

H₂C=C H

(18.2 g, 0.05 mol) and Lamoreaux catalyst (10 ppm, 3.3 wt% solution in toluene) were heated to 120°C for 7.0 hrs. The structure of the brownish product was confirmed by ¹H-NMR and was further used without purification.

Representative example for the synthesis of di-alkoxyvinyl terminated polydimethylsiloxanes M²D_XM²:

Preparation Example 8: M²DeM² (with M=M² with R¹ = ethyl substituted with trimethoxysilyl) [0107] The silicone hydride fluid of the structural composition M^HDeM^H was made according to preparation procedure described in Example 1.

[0108] M^HDeM^H (200.0 g, 0.35 mol) was heated to 80°C and Lamoreaux catalyst (30 ppm, 3.3 wt% solution in toluene) was added. Subsequently, vinyltrimethoxysilane (118.0 g, 0.80 mol) was dropwise added during a period of 40 mins and the mixture was heated for 1 hr at 120°C. Completion of the reaction was indicated by titration with an alcoholic KOH solution through observing the absence of a H2 evolution. The product structure was confirmed by ¹H-NMR.

Coating composition examples

Base coating formulation

[0109] In a glass bottle equipped with a stirrer, 406 grams (g) of methyltrimethoxysilane was mixed with 2.5 g of acetic acid. In a separate vessel, 251 g of a silica sol (LUDOX AS, DuPont Co.) was mixed with 83 g of deionized water to reduce the silica level to 30 wt.%. The diluted silica sol was then added, with stirring, to the acidified methyltrimethoxysilane and stirring was continued for 4 hours at room temperature. An additional 25.2 g of acetic acid (1.8% of final reaction mixture) was added and stirring was continued for 3 hours to effect hydrolysiscondensation.

[0110] The mixture was diluted with 700 g of a 1 :1 mixture of 2-propanol and 1 -butanol, producing a solution having a pH of 5 to 6. Then, 70 g of a 53 wt.-% solution of a silylated hydroxybenzophenone in methanol was added. The resulting solution, containing about 22 wt.-% resin solids, was allowed to be kept for 3 weeks at room temperature (22-24°C).

[0111] After this, 3.2 wt.-% of JONCRYL 587 acrylic copolymer were added to the above treated solution based on the total solid content (22 wt.-%). To ensure effective solubilization of the Joncryl 587 additive, the whole solution was heated at 60°C for 2-3 hours. After cooling down the solution to room temperature, it was filtered with a paper filter to obtain a base coat formulation.

[0112] Inventive examples were obtained by adding about 1 wt.-% of the component C) based on the solids content of the coating formulation to the above base coat formulation before the above mentioned 3 weeks storage step at room temperature (22-24°C). The base coat formulation without addition of component C) was taken as comparative example 1 .

Example 1

[0113] Component C1) of Preparation Example 4: M²Dn.2M³ (with M=M² with R¹ = ethyl substituted with trimethoxysilyl and M=M³ with R² = ethyl substituted with branched alkyl carbonyloxy).

Coating Examples

Bisphenol A polycarbonate panels, 10.5 x 25.0 x 0.32 centimeters (cm), were flow coated with the coating compositions and air dried for 15 minutes. The coatings were then cured by heating in an air-circulated convection oven at 130°C for 45 min. The resulting optically clear hardcoats were 5-8 microns thick.

Example 2

Component C1) was added to commercially available Momentive Performance Materials coating products, namely SilFORT™ AS4700F, SilFORT™ PHCXH100 and SilFORT™ PHC587B. All coatings are prepared with the process described for the base coat formulation mentioned before, applied by flow, spray or dip coating and cured at 128 ± 2°C for 30 minutes part surface temperature. Preferred substrate for latter coatings is polycarbonate, e.g. Makrolon® AL2447 or AL2647 (Covestro AG). For the coating SilFORT™ AS4700F the primer SilFORT™ SHP470FT2050 is applied first to ensure sufficient adhesion on polycarbonate. The coatings AS4700F, PHCXH100 and PHC587B have a solids content of 25-26% determined with a halogen dryer at 160°C for 15 minutes. Typical coating sample quantity for the solids determination is 7-9 gram wet coating. 1% of component C1) based on the solids content of the coating solution is added to each product. The modified coatings are heat treated for 24 hours at 60°C. In Table 1 contact angles measured with a method aligned with ISO 19403- 1 :2017 are shown. Tab. 1 : Contact angle data (ISO 19403-1 :2017) of commercially available SilFORT™ coatings with and without the addition of component C1)

*based on the solids content of the coatings Example 3 (3-1 to 3-12)

[0114] Various compounds C) as shown in Table 2 were prepared analogously to the preparation examples and used to prepare coating compositions according to the invention according to the procedures of Example 1 or Example 2. The concentration of the components C) was about 1 wt-% based on the solid content of the coating compositions. The water contact angle was measured aligned with ISO 19403-1 :2017. The abrasion resistance has been measured with the taber abrasion test aligned with ASTM D 1044 and ISO 9352. The weathering-stability study has been conducted via artificial weathering using ASTM Gmod 155 (1100h ~ 1 year outdoor weathering Florida Weathering on transparent PC substrates). Light Transmission measurements were conducted aligned with ASTM D 1003.

Table 2 - Tests of Various Compounds C1)

[0115] As shown in table 2, the coating compositions of the invention show good weather stability (e.g. water contact angle > 90°), high light transmission (>90%), high mechanical stability (< 5 A haze after tested via the taber abrasion test). Particular good properties were achieved in example 3-2. Also, the coating compositions according to the invention are at least as good as those of reference examples 3-7 and 3-8 based on fluorosilanes and therefore make it possible to replace them, thereby avoiding such undesirable PFAS compounds. Example 4 (Weathering Tests - Water Contact Angle)

[0116] The coating compositions of example 1 , and comparative example 1 were subjected to an artificial weathering test on transparent PC (polycarbonate) substrates. The coating compositions of example 1 still show a water contact angle of > 90° after 2200 h of artificial weathering using ASTM Gmod 155 (1100h ~ 1 year Florida Weathering on transparent PC substrates) and has a much higher contact angle over the entire weathering period than comparative example 1.

Example 5 (Weathering Tests - Water Roll-off Angle)

[0117] The coating compositions of example 1 and comparative example 1 were subjected to an artificial weathering test on transparent PC (polycarbonate) substrates. The rolling behavior is also of elementary importance for the repulsion of liquids containing dirt. If the solutions and dispersions roll off at a smaller angle, the probability of dirt accumulating on the surface is lower. The formulation of example 1 has a much lower roll-off angle of water in the first 1100 h of artificial weathering compared to comparative example 1.

Example 6 (Dirt application Test)

[0118] To complete the proof of principles of the easy-to-clean coating compositions of the present invention, the following tests are carried out to determine whether the surface is actually dirt-repellent. For this purpose, the coating is repeatedly soiled with an ANNEX 4 standard dirt solution (2.1.2) by flooding, spraying or dipping. After a one-hour baking time at 90°C, the coating is then cleaned by flooding or spraying with power water. This cycle is repeated up to 20 times and then the contact angle, haze and surface coverage are determined by image analysis with the software Imaged via grey value analysis. As a result example 1 had a much better dirt repellency (0.8 % dirt coverage on the surface) than comparative example 1 (2.4 % dirt coverage on the surface).

Example 7

[0119] The surface coverage with standard dirt after several staining and cleaning cycles shows significant advantages of the coating compositions of example 1. The surface coverage is lower (<0.1 %) than for the coating compositions of comparative example 1 (>1%).

[0120] The water contact angle for the coating compositions of example 1 remains at hydrophobic values of 97° while with the coating composition of comparative example 1 the water contact angle decreased after 20 cycles to 87° - 91 °. Furthermore, the coating compositions of example 1 guarantees after 20 cycles a light transmission of -90%, while the comparative coating compositions show a decrease to 85%.

Claims

1. Coating composition, comprising

A) or

B) or

A) and B) are modified with

C1) polyorganosiloxanes of the formula (I):

MaD cQd

wherein

M, D T and Q each represent siloxy units, and wherein

M is selected from M¹ = RaSiOi/2, M² = R_PR¹(3-_P)SiOi/2, and M³ = R_PR²<3-_P)SiOi/2, D is selected from D¹ = R2SiC>2/2, D² = R_qR¹(2-q)SiC>2/2, and D³ = R_qR²(2-q)SiC>2/2, T is selected from T¹ = RSiOs/2, T² = R¹SiC>3/2, and T³ = R²SiC>3/2, Q=SiO4/2, wherein

R² independently is an organic group different from R and R¹, selected from optionally substituted alkyl, preferably optionally substituted alkyl having 2 or more carbon atoms, or optionally substituted alkyl having 4 or more carbon atoms, or optionally substituted alkyl having 6 or more carbon atoms, preferably R² is selected from the group consisting of unsubstituted alkyl having two or more carbon atoms, preferably unsubstituted alkyl having 4 or more carbon atoms, more preferably unsubstituted alkyl having 6 or more carbon atoms, alkyl, preferably alkyl having 2 or more carbon atoms, substituted with acyloxy, such as alkylcarbonyloxy, preferably branched alkylcarbonyloxy, and alkyl substituted with one or more halogen atoms, preferably fluorine atoms, p is independently 0 to 2, preferably 2, q is independently 0 or 1 , preferably 1 , with the provisos that in the polyorganosiloxanes of the formula (I): there are at least at least two siloxy units M², or there is at least one siloxy unit M² and at least one siloxy unit M³, or there is at least one siloxy unit D² and at least one siloxy unit D³, or there is at least one siloxy unit D² and at least one siloxy unit M³, or there is at least one siloxy unit M² and at least one siloxy unit D³, and preferably there are at least one, more preferably at least 3, more preferably at least 5 siloxy units D¹, wherein each siloxy unit is as defined above, and the indices in formula (I) represent the average numbers of the siloxy units M, D, T and Q as defined above, which may be distributed blockwise or randomly in the polyorganosiloxanes, and which may be identical or different, and are a = 2 to 10, preferably 2, b = 2 to 50, preferably 2 to 40, more preferably 2 to 30, more preferably 2 to 25, c = 0 to 10, preferably 0, d = 0 to 1 , preferably 0, and

D) at least one solvent.

2. Coating composition according to any of the previous claims, wherein the polysiloxanes C1) are selected from the formula (la):

MDbM (la), wherein M, D, and b are as defined above, preferably b is about 5, about 10 or about 20, with the provisos that there are two M² siloxy units, or there is one siloxy unit M² and one siloxy unit M³, or there is at least one unit siloxy D² and at least one siloxy unit D³, or there is at least one unit siloxy D² and at least one siloxy unit M³, or there is at least one siloxy unit M² and at least one siloxy unit D³, and preferably there is at least one siloxy unit D¹, wherein M², M³, D¹, D² and D³ are each as defined above.

3. Coating composition according to claim 1 , wherein the polysiloxanes C1) are selected from the formulas (lb) to (le):

M²D_bM³ (lb), wherein

M², D, b and M³ are as defined above, preferably b is about 5, about 10 or about 20, preferably D is D¹ being R2SiO2/2, wherein R is as defined above,

M²D_bM² (Ic), wherein

M², D, and b are as defined above, preferably b is about 5, about 10 or about 20,

MD_bM (Id) wherein

D in formula (Id) comprises at least one siloxy unit D², and that M in formula (Id) comprises at least one siloxy unit M³ or that D in formula (Id) comprises at least one siloxy unit D³, or D in formula (Id) comprises at least one siloxy unit D², and that M in formula (Id) comprises at least one siloxy unit M³ and that D in formula (Id) comprises at least one siloxy unit D³, wherein D, D², D³, M and M³ are as defined above, and

M³[(D¹)bi(D²)b₂(D³)b₃]M³ (le) wherein

4. A coating composition according to any of the previous claims, wherein the polysiloxanes C1) are selected from the formulas

M² ₂D¹ ₅, M² ₂D¹ , M² ₂D¹ ₂₀, M²D¹ ₃M³, M²D¹ ₅M³, M²D¹IOM³, M²D¹ ₂₀M³, M³ ₂D¹ ₆D³ ₄D² ₂ wherein M², M³, D¹, D², and D³ are as defined above.

5. A coating composition according to any of the previous claims, wherein the polysiloxanes C1) comprise at least one D¹ unit.

6. A coating composition according to any of the previous embodiments, wherein the polyorganosiloxanes C1) of the formula (I) comprise (preferably consist of): at least two siloxy units M², or at least one siloxy unit M² and at least one siloxy unit M³, and at least one, more preferably at least 3, more preferably at least 5 siloxy units D¹.

7. Coating composition according to any of the previous claims, wherein the colloidal metal compound A) is selected from metal oxides A1), preferably from silicas.

8. Coating composition according to any of the previous claims, wherein the solvent D) is selected from the group consisting of water D1) and organic solvents D2).

9. Coating composition according to any of the previous claims, wherein the hydrolysable silane E) is selected from the formula (III): R⁶zR⁴(4-_z)Si (III) wherein R⁴ is as defined above, R⁶ is selected from the group consisting of an optionally substituted aliphatic group, preferably an optionally substituted alkyl group, more preferably a methyl, an ethyl or propyl group, aryl, preferably phenyl, and alkenyl, preferably vinyl, and z is 0 to 3, preferably z is 1 to 3, more preferably z is 1.

10. Coating composition according to any of the previous claims, wherein the hydrolysable silane E) does not comprise fluorine.

11. Coating composition according to any of the previous claims, wherein R⁴ is selected from alkoxy and chlorine, preferably alkoxy, more preferably C1-C6 alkoxy, more preferably methoxy or ethoxy, most preferably methoxy.

Coating composition according to claim 9, wherein R⁶ in formula (III) is selected from alkyl groups and alkyl groups substituted with at least one UV stabilizing group, such as aromatic groups comprising a benzophenone moiety.

13. Coating composition according to any of the previous claims, wherein compound B) is a condensed product of the hydrolysable silanes E) and is obtained by hydrolysis and condensation of hydrolysable silanes E), preferably of the hydrolysable silanes E) of formula (III), as defined above.

Coating composition according to any of the previous claims, wherein compound E) is selected from the group consisting of tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, dimethoxydimethylsilane, diethoxydimethylsilane, dimethyldichlorosilane, methyldichlorosilane, methyltrichlorosilane, phenyltricholorosilane, silicone tetrachloride, vinyltrichlorosilane, cyclohexyldimethoxymethylsilane, dimethoxymethyloctylsilane, diethoxymethylvinylsilane, chloromethyl(diisopropoxy)methylsilane, dimethoxymethylphenylsilane, diethoxydiphenylsilane, trimethoxypropylsilane, isobutyltrimethoxysilane, octyltrimethoxysilane, octadecyltrimethoxysilane, isobutyltriethoxysilane, octyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, (3- chloropropyl)trimethoxysilane, chloromethyltriethoxysilane, tris(2- methoxyethoxy)vinylsilane, 3-glycidoxypropyltrimethoxysilane, diethoxy(3- glycidoxypropyl)methylsilane, trimethoxy[2-(7-oxabicyclo[4.1 .0]-hept-3-y l)ethy l]si lane, chlorotrimethoxysilane, chlorotriethoxysilane, chlorotris(1 ,3-dimethylbutoxy)-silane, dichlorodiethoxysilane, 3-(triethoxysilyl)-propionitrile, 4-(triethoxysilyl)-butyronitrile, 3- (triethoxysilyl)-propylisocyanate, 3-(triethoxysilyl)-propylthioisocyanate, phenyltriethoxysilane, 1 ,3,5,7-tetraethoxy-1 ,3,5,7-tetramethylcyclotetrasiloxane,

1.3.5.7-tetramethyl-1 ,3,5,7-tetrapropoxycyclotetrasiloxane, 1 ,3,5,7-tetraisopropoxy-

1.3.5.7-tetramethylcyclotetrasiloxane, 1 ,3,5,7-tetrabutoxy-1 ,3,5,7- tetramethylcyclotetrasiloxane, 1 ,3,5,7,9-pentaethoxy-1 , 3, 5,7,9- pentamethylcyclopentasiloxane, 1 ,3-diethoxytetramethyldisiloxane, 1 ,3- dimethoxytetramethyldisiloxane, 1 , 1 ,3, 3- tetramethyl- 1 ,3-dichlorodisiloxane, 1 ,2- bis(methyldichlorosilyl)ethane, diacetoxydiphenylsilane, methyltris(ethylmethylketoxime)silane, bis(ethylmethylketoxime)methylisopropoxysilane, bis(ethylmethylketoxime)ethoxymethylsilane, 2-(3,4- epoxycyclohexylethyl)trimethoxysilane, methyltriisopropenoxysilane, ethyltriacetoxysilane, methyltriacetoxysilane, diacetoxydimethylsilane, triacetoxyvinylsilane, tetraacetoxysilane, and diacetoxymethylphenylsilane, and preferably E) is methyltrimethoxysilane.

15. Coating composition according to any of the previous embodiments, wherein the component A) is modified with at least one hydrolysable silane E) as defined above.

16. Coating composition according to any of the previous claims, which is obtained from the components A), B) and C) in the following wt.-ratios: about 5 to about 90 wt.-% of component A),

> 0 to about 94.9 wt.-% of component B), more preferably about 50 to about 94.9 wt.- % of component B), and about 0.1 to about 10 wt.-% of component C), based on the total weight of the components A), B) and C), and preferably the weight ratio of component A) to component B) is about 10:1 to about 1:20, preferably about 2:1 to about 1:5, and/or the weight ratio of component A) to component C) is about 300: 1 to about 10: 1 , preferably about 200:1 to about 20:1 and/or the weight ratio of component B) to component C) is about 300: 1 to about 1 :1, preferably about 200: 1 to about 2:1.

17. A coating composition according to any of the previous claims, wherein the weight ratio of component A) to component B) is about 10:1 to about 1:20, preferably about 2:1 to about 1:5.

18. A coating composition according to any of the previous embodiments 15 to 17, wherein the weight ratio of component B) to component C) is about 300:1 to about 1:1 , preferably about 200: 1 to about 2: 1.

19. Coating composition according to any of the previous claims, wherein the compounds C1) are selected from a, co-substituted dimethylpolysiloxanes of the formula (IV):

20. A coating composition according to any of the previous claims, wherein the weight ratio of the solvent D) to the remainder of the coating composition (i.e. components A), B), and C) and optional F) as defined above) is in the range (D) : L ( A) + B) + C) + F) ) of about 50 to about 95 : about 5 to about 50, more preferably about 60 to about 90 to about 40 : about 10 to about 40, still more preferably about 65 to about 85 : about 15 to about 35, most preferably about 75 : about 25.

21. A coating composition according to any of the previous claims, wherein the solid content (determined by Test method: ASTM D2369-20) is in the range of about 5 to about 40 wt.-%, preferably about 10 to about 30 wt.-%.

22. A coating composition according to any of the previous claims, wherein the colloidal metal compounds A) are incorporated as aqueous dispersions into the coating compositions.

23. A coating composition according to any of the previous claims, wherein the colloidal metal compounds A) have a particle size distribution wherein at least 40%, or at least 60%, or at least 80%, or at least 90% of the particles in the particle size distribution are between about 1 to about 1000 nm, or between about 5 to about 500 nm, or between about 10 to about 250 nm.

24. A coating composition according to any of the previous claims, wherein the colloidal metal compounds A) have a particle size distribution with a d50 between about 1 nm to about 250 nm, or about 5 nm to about 100 nm, or about 10 nm to about 80 nm.

25. A coating composition according to any of the previous embodiments, having a pH in the range of about 4 to about 6.5.

26. A coating composition according to any of the previous claims, wherein the organic solvent D2) is selected from aliphatic alcohols, such as methanol, n-butanol, isopropanol, alkyl acetates, such as C 1-C4 alkyl acetates including methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, aliphatic ethers, and glycolethers, such as C1-C4 glycolethers including 2- methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1 -methoxylpropanol, 2-(2-methoxyethoxy)ethanol and (2-(2-ethoxyethoxy)ethanol.

27. A coating composition according to any of the previous claims, further comprising one of more additive components F), preferably selected from: a. one or more fillers, b. one or more pigments, c. one or more flow control or levelling agents, d. one or more foam control agents, e. one or more antimicrobial and biocidal additives, f. one or more surface-active agents such as wetting and dispersion additives, g. one or more rheology modifiers, h. one or more corrosion inhibitors, i. one or more light stabilizers, such as UV absorbers, j. one or more catalysts, such as acids, k. one or more pH adjusting agents, such as acids, bases or buffers, l. one or more adhesion promotors such as organosilane adhesion promoters, organotitanate adhesion promoters, zirconate adhesion promoters, zircoaluminate adhesion promoters, alkyl phosphate esters, chrome complexes, amines, acrylic resins derived from acrylic acid, methacrylic acid and acrylate monomers such as butyl acrylate and or methacrylate monomers such as methyl methacrylate, hydroxy-functional acrylate resins such as those obtained by copolymerizing hydroxyacrylate monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc., m. one or more hydrolysable fluoroorganosilanes or a hydrolysed and condensed product of such hydrolysable fluoroorganosilanes which are obtained by hydrolysis and condensation of hydrolysable fluoroorganosilanes.

28. A coating composition according to any of the previous claims, wherein the compounds C1) are selected from a, co-substituted dimethylpolysiloxanes of the formula (IV):

wherein R⁷ and R⁸ can be the same or different and are independently selected from optionally substituted alkyl groups, with the provisos that one of R⁷ and R⁸ is an optionally substituted alkyl group having two or more carbon atoms and the other of R⁷ and R⁸ is an alkyl group which is substituted with at least one hydrolysable silyl group as defined above, and n is about 2 to about 50, preferably about 2 to about 40, more preferably about 2 to about 30, more preferably about 2 to about 25.

29. A coating composition according to the previous claim, wherein in the a, co-substituted dimethylpolysiloxanes of the formula (IV):

30. A coating composition according to any of the previous claims, wherein the compounds C1) are selected from the following formulas:

R¹⁰ are independently CHs or H,

R⁹ are independently isobutyl or C₂H₅ or CH₃ or H,

R¹³ is selected from linear alkyl, preferably linear C3 to C18 alkyl, preferably linear C4 or C12 alkyl, or R¹³ is branched alkyl, preferably branched C4 to C12 alkyl, derived from corresponding alpha-olefins such as oligomerization products of 1 -butene, 2-butene, 2- methylbut-1-ene, 2-methylbut-2-ene,

wherein

31. A process for the manufacture of the coating compositions according to any of the previous claims comprising (in any order): a) Providing one or more aqueous dispersions of one or more colloidal metal compounds such as colloidal metal oxides A), b) Adding one or more compounds C) as defined above, c) Adding one or more compounds E) as defined above, d) Optionally adding one or more pH adjusting agents, e) Optionally adding one or more additive components F) as mentioned above, f) Optionally distilling off of alcohols and water, g) Optionally subjecting the reaction mixture to treating at room temperature (25°C) or heating above room temperature, h) Adding one or more solvents D) as defined above, i) Subjecting the resulting dispersion to gel formation.

32. Modified colloidal metal compounds AM), preferably metal oxides, more preferably silica, which is obtained by modifying the colloidal metal compound A) with one or more compounds C) as defined above.

33. Modified partial condensates BM) of at least one hydrolysable silane E), which is obtained by modifying the partial condensate of at least one hydrolysable silane E) with one or more compounds C) as defined above.

34. A process for preparing a coated article by a coating process which comprises a) Providing the coating composition according to any of the previous claims onto the surface of a substrate, and b) Drying the coating composition on such substrate to obtain a coated article.

35. A process for preparing a coated article according to the previous claim, wherein the substrate is selected from transparent and non-transparent substrates, such as wood, painted surfaces, leather, ceramics, textiles, metal, glass, plastic, composite substrates of them with or without an organic or inorganic base coating, preferably selected from plastic substrates, more preferably from polycarbonate substrates, acrylic polymers such as poly(methyl methacrylate), polyethylene, polypropylene or polyesters such as poly(ethylene terephthalate), poly(butylene terephthalate), polyamide, polyimide, acrylonitrile-styrene copolymer, styrene acrylonitrile-butadiene copolymer, polyvinyl chloride, butyrate- substrates and the like, wherein such substrates can be in any form, such as in the form of sheets, foils or mouldings.

36. A process for preparing a coated article according to the previous claims, wherein the coating composition is provided onto the substrate by a. Spray coating, b. Flow coating, c. Roll coating, or d. Dip coating.

37. A process for preparing a coated article according to the previous claims, wherein the drying step is carried out at a temperature of about 30 to about 200°C, preferably at temperature of about 85°C to about 160°C.

38. A process for preparing a coated article according to the previous claims, wherein the coating composition is provided in an amount of up to about 50 g per m².

39. A process for preparing a coated article according to any of the previous embodiments, wherein the coating composition is provided onto a substrate which has a primer coating or which has no primer coating.

40. A process for preparing a coated article according to any of the previous embodiments, wherein the coating composition is provided onto a substrate which has a primer coating, wherein such primer coating preferably is selected from the group consisting of acrylic resins, such as a poly(methyl methacrylate) resins and polyurethane resins.

41. A coated article obtained by the process according to any of the previous claims.