The present invention relates to a process for preparing a thin film on a substrate based on a first precursor composition (FPC) and a second precursor composition (SPC), wherein the first precursor composition (FPC) contains particles, an article comprising said thin film, a composition comprising said first precursor composition (FPC) and second precursor composition (SPC), a kit-of-parts comprising said first precursor composition (FPC) in a first vessel and said second precursor composition (SPC) in a second vessel, the use of said composition or said kit-of-parts for preparing a thin film on a substrate and for preparing an optical or electrical coating.

Background of the invention

For many applications, such as touch panel displays, solar panel screens, and windows it is important to be able to keep the surface clear from stains for hygienic and visual appearance reasons as well as to be able to use the device with its best potential. It is equally important to be able to maintain this performance through-out the lifetime of the device or application. Easy-to-clean (E2C) properties with abrasion resistance have been often demonstrated by using fluorinated materials to achieve both hydrophobic and oleophobic coating. These fluorinated materials are often functionalized with siloxane groups to improve adhesion e.g. to glass substrates. A good example of such material is siloxane functionalized perfluoropolyether which has been shown to give good E2C properties along with abrasion resistance. However, these types of materials can typically use only certain types of solvents, namely fluorosolvents, for dilution which makes these materials highly expensive along with the production costs. Even in case a complete avoidance of fluorosolvents may not be possible, at least a reduction of the amount of fluorosolvents needed is, thus, desirable, e.g. by using mixtures of fluorosolvents with non-fluorosolvents. Furthermore, these types of materials are typically used to produce monolayer coatings. The monolayer coating in principle mimics the hardness of the underlying substrate. Such monolayer coatings typically suffer also from poor long-term thermal stability especially when exposed to high temperatures, especially when exposed to humidity. Moreover, these monolayer coatings cannot pass severe abrasion resistance conditions and retain long-term use life. Thus, coatings are required with excellent E2C properties, high hardness and high durability which can maintain these properties over abrasion and environmental conditions. Such coatings should be usable on both smooth and rough substrate surfaces and on different types of substrates such as glass, ceramic, and/or metal. Furthermore, an improvement of the hardness of the surface the coating is applied to is desirable. Moreover, this should be achieved by using single layer film on the substrate without the need of specific additional primer layers.

WO 2020/099290 Al discloses E2C coatings based on cured product of a polymerized metal or metalloid component and a fluoropolyether silane component. Said E2C coating shows a good balance of properties regarding hardness, abrasion resistance, surface cleanability and optical properties. Thus, the E2C coating of WO 2020/099290 Al form a good basis for further improvement.

It has surprisingly been found that the abrasion resistance and corrosion resistance of the coatings of WO 2020/099290 Al can be further improved by introducing particles into the polymerization mixture of the first precursor composition (FPC). It has been known in the art that the presence of particles in an E2C coating increases abrasion resistance. It has been found that introducing the particles into the first precursor composition (FPC) together with the one or more metal or metalloid compound and polymerize said one or more metal or metalloid compound in the presence of the particles show better abrasion resistance and corrosion resistance compared to E2C coatings without particles and to E2C coatings in which the particles or other known additives for improving abrasion resistance are introduced to the composition just before coating.

Summary of the invention

The present invention relates to a process for preparing a thin film on a substrate, the process comprising the steps of a) preparing a first precursor composition (FPC) in a first vessel, the preparation comprising the following steps: al) providing one or more metal or metalloid compound(s) according to the following formula (I)

M^OR^nR^ (I) wherein

M ¹ is a metal or metalloid with a valence z;

R ¹ is each independently selected from a Ci to Cio organyl or organoheteryl group;

R ² is each independently selected from a Ci to C20 organyl, organoheteryl, fluorinated organyl or fluorinated organoheteryl group, wherein the fluorinated organyl or fluorinated organoheteryl group is not a fluoropolyether group; n is 1 to z; m is z— 1 to 0; and n+m is z; a2) at least partially hydrolyzing the M^OR^-moieties and polymerizing the one or more metal or metalloid compound according to formula (I) in a first solvent; a3) optionally exchanging the first solvent used in step a2) by one or more second solvent(s); b) preparing a second precursor composition (SPC) in a second vessel, the preparation comprising the following steps: bl) providing a fluoropolyether silane comprising hydrolysable groups (PFS) , which differs from the one or more metal or metalloid compound(s) according to formula (I) at least in the presence of a fluoropolyether group; c) mixing the first precursor composition (FPC) obtained in step a) with the second precursor composition (SPC) obtained in step b) to obtain a composition; d) forming a thin layer from the composition obtained in step c) on the substrate; e) optionally partially or completely removing solvent, if present, after step d); f) curing the intermediate product obtained in step e), if present, or step d), if step e) is not present, thereby obtaining a thin film, characterized in that in step a) additionally particles selected from phosphorous- based particles, oxides, quantum dots or metals are added to the one or more metal or metalloid compound(s) of formula (I) in process step al) and the particles are present during hydrolyzing and polymerizing step a2).

Further, the present invention relates to an article, preferably a coated optical or electrical article, comprising the thin film obtainable by the process as described above or below.

Still further, the present invention relates to a composition comprising a first precursor composition (FPC) and a second precursor composition (SPC), the first precursor composition (FPC) comprising particles selected from phosphorous-based particles, oxides, quantum dots or metals and a polymerized metal or metalloid compound according to formula (I)

M^OR^nR^ (I) wherein

M ¹ is a metal or metalloid with a valence z;

R ¹ is each independently selected from a Ci to Cio organyl or organoheteryl group;

R ² is each independently selected from a Ci to C20 organyl, organoheteryl, fluorinated organyl or fluorinated organoheteryl group, wherein the fluorinated organyl or fluorinated organoheteryl group is not a fluoropolyether group; n is 1 to z-1; m is 1 to z-1; and n+m is z, whereby the polymerization is effected by at least partial hydrolyzing of the M^OR^-moieties in the presence of the particles in a first solvent; and the second precursor composition (SPC) comprising a fluoropolyether silane comprising hydrolysable groups (PFS) , which differs from the polymerized metal or metalloid compound according to formula (I) at least in the presence of a fluoropoly ether group.

Further, the present invention relates to a kit-of-parts comprising a first precursor composition (FPC) in a first vessel and a second precursor composition (SPC) in a second vessel, the first precursor composition (FPC) comprising particles selected from phosphorous-based particles, oxides, quantum dots or metals and a polymerized metal or metalloid compound according to formula (I)

M^OR^nR^ (I) wherein

M ¹ is a metal or metalloid with a valence z;

R ¹ is each independently selected from a Ci to Cio organyl or organoheteryl group;

R ² is each independently selected from a Ci to C20 organyl, organoheteryl fluorinated organyl or fluorinated organoheteryl group, wherein the fluorinated organyl or fluorinated organoheteryl group is not a fluoropolyether group; n is 1 to z-1; m is 1 to z-1; and n+m is z, whereby the polymerization is effected by at least partial hydrolyzing the M^OR ¹ )- moieties in the presence of the particles in a first solvent; and the second precursor composition (SPC) comprising a fluoropolyether silane comprising hydrolysable groups (PFS), which differs from the polymerized metal or metalloid compound according to formula (I) at least in the presence of a fluoropoly ether group.

Additionally, the present invention relates to the use of the composition or the kit-of- parts both as described above or below for preparing a thin film on a substrate. Finally, the present invention relates to the use of the composition or the kit-of-parts both as described above or below for preparing a coating on an optical or electrical article.

The thus obtained coatings provide superior hardness, abrasion resistance and excellent surface cleanability. The coating can further enhance the optical properties of display device. Furthermore, the usage of an excess of fluorine containing solvents can be avoided and applicability with wider deposition equipment range is achieved. Moreover, the composition can be applied by conventional methods and cured at low temperature. The composition provides improved adhesion without the need of using additional adhesion promotion layers for multiple substrate surfaces. It has also superior thermal and long-term performance stability (meaning use life stability as a thicker physical coating rather than thin monolayer on substrate) and is cost effective due to lower fluorine solvent content and fluorine content. In view of these properties the inventive coatings are comparable to the coatings of WO 2020/099290 Al. Further, the coatings, in which the particles are present during the hydrolysis and polymerization of the metal or metalloid compound in the first precursor composition (FPC), show an improved abrasion resistance and corrosion resistance compared to E2C coatings without particles and to E2C coatings in which the particles or other known additives for improving abrasion resistance are introduced to the composition just before coating.

Detailed description of the invention

The following definitions apply in the present invention unless explicitly mentioned to the contrary.

An organyl group is an organic substituent group, having one free valence at a carbon atom. An organoheteryl group is an organic substituent group, having one free valence at an atom different from a carbon atom.

A fluorinated organyl group or fluorinated organoheteryl group is an organyl group or organoheteryl group as defined above, in which at least one hydrogen atom is replaced by fluorine. Fluoropolyether groups do not fall under the definition of a fluorinated organyl group or fluorinated organoheteryl group.

First precursor composition

As outlined above, the first precursor composition (FPC) is prepared in a first vessel, the preparation comprising the following steps: al) providing one or more metal or metalloid compound(s) according to the following formula (I)

M^OR^nR^ (I) wherein

M ¹ is a metal or metalloid with a valence z;

R ¹ is each independently selected from a Ci to Cio organyl or organoheteryl group;

R ² is each independently selected from a Ci to C20 organyl, organoheteryl, fluorinated organyl or fluorinated organoheteryl group, wherein the fluorinated organyl or fluorinated organoheteryl group is not a fluoropolyether group; n is 1 to z; m is z— 1 to 0; and n+m is z; a2) at least partially hydrolyzing the M^OR^-moieties and polymerizing the one or more metal or metalloid compound according to formula (I) in a first solvent; a3) optionally exchanging the first solvent used in step a2) by one or more second solvent(s), characterized in that in step a) additionally particles are added to the one or more metal or metalloid compound(s) of formula (I) in process step al) and the particles are present during hydrolyzing and polymerizing step a2).

The particles are selected from phosphorus-based particles, oxides, quantum dots or metals.

Suitable phosphorus-based particles are phosphorus containing dendrimer particles, such as polyphosphazenes and polyphosphoesters, black phosphorus particles, metal phosphite particles, such as N12P, RI12P, PdsP, CdsP2, ZnsP2, CuiP, CoP or FeP, and metal phosphate particles, such as CaPCh, MnPCh, MgPCh or ZrPCh.

Suitable oxides are inorganic oxides, more preferably metal or metalloid oxides such as ZrCh, SiCh, TiCh, AI2O3, Fe2Os, FesCh, Ta2Os, ZnO, aluminosilicates or mixtures thereof, preferably ZrCh, SiCh, TiCh or mixtures thereof, most preferably ZrCh.

Suitable metal particles are particles of Ag, Au, Cu, Fe, Pt and FePt.

Preferred are oxides, more preferably metal or metalloid oxides such as ZrCh, SiCh, TiCh, AI2O3, Fe2O3, FesC , ZnO, Ta2Os, aluminosilicates or mixtures thereof, preferably ZrO2, SiO2, TiO2 or mixtures thereof, most preferably ZrO2.

The particles preferably have an average particle size of from 0.1 to 100 nm, more preferably from 0.5 to 50 nm, most preferably from 0.7 to 25 nm.

Thus, the particles preferably are nanoparticles.

In step al) up to five different metal or metalloid compounds according to formula (I) may be provided, usually, not more than three different metal or metalloid compounds according to formula (I) are provided.

It is preferred that one or two, preferably two different metal or metalloid compound(s) according to formula (I) are provided.

Preferably, in a first embodiment the one or more metal or metalloid compound(s) according to formula (I) is/are free from fluorine. Thus, in case more than one metal or metalloid compound(s) according to formula (I) are provided they are preferably all free from fluorine. More preferably no fluorine containing compound except optionally fluorine containing solvents is/are present during the preparation of the first precursor composition (FPC) before step c) is accomplished, even more preferably, in case solvents are present, the amount of fluorine-containing solvents based on the total weight of the solvents present is equal or less than 75 weight % is present and most preferably no fluorine containing compound including fluorine containing solvents are present during the preparation of the first precursor composition (FPC) before step c) is accomplished.

Preferably, in a second embodiment one or more of the one or more metal or metalloid compound(s) according to formula (I) comprise at least one fluorine atom in the R ² residue of formula (I). Thus, in the second embodiment one or more, such as 1, 2 or three metal or metalloid compound(s) according to formula (I) contain one or more fluorine atoms in the R ² residue of formula (I).

M ¹ is preferably selected from Si, Ge, Sb, Ti, Zr, Al, Sn, Se, Cr or Ni, more preferably from Si, Ti, Zr, Ge, Sb, and most preferably M ¹ is Si.

R ¹ is each independently selected from a Ci to Cio organyl or organoheteryl group.

In case heteroatoms are present in the organyl group of R ¹ they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.

Preferred groups OR ¹ are alkoxy, acyloxy and aryloxy groups.

The heteroatom of the organoheteryl group of R ¹ bound to the oxygen atom bound to M ¹ is usually different from O. The heteroatom(s) present in the organoheteryl group of R ¹ are preferably selected from N, O, P or S, more preferably selected from N and O.

The total number of heteroatoms, if present, in R ¹ is usually not more than five, preferably not more than three.

Preferably R ¹ is a Ci to Cio organyl group containing not more than three heteroatoms, more preferably R ¹ is a Ci to Cio hydrocarbyl group, even more preferably a Ci to Cio linear, branched, or cyclic alkyl group.

Preferably the total number of carbon atoms present in R ¹ according to any one of the above variants is 1 to 6, more preferably 1 to 4.

R ² is each independently selected from a Ci to C20 organyl or organoheteryl group in the first embodiment or is each independently selected from a Ci to C20 organyl, organoheteryl, fluorinated organyl or fluorinated organoheteryl group in the second embodiment.

In case heteroatoms are present in the organyl group of R ² they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.

The heteroatom of the organoheteryl group of R ² bound to M ¹ is usually different from O.

The heteroatom(s) present in the organoheteryl group of R ² are preferably selected from N, O, P or S, more preferably selected from N and O.

The total number of heteroatoms, if present, in R ² is usually not more than eight, preferably not more than five and most preferably not more than three. In the first embodiment, preferably R ² is a Ci to C20 organyl group containing not more than three heteroatoms, more preferably R ² is a Ci to C20 hydrocarbyl group, even more preferably a Ci to C20 linear, branched or cyclic alkyl group.

In the second embodiment, preferably R ² is a Ci to C20 organyl group and/or fluorinated organyl groups containing not more than three heteroatoms, more preferably R ² is a Ci to C20 hydrocarbyl group, even more preferably a Ci to C20 linear, branched or cyclic alkyl group.

The fluorinated organyl groups preferably comprises from 1 to 30 fluorine atoms, more preferably from 3 to 17 fluorine atoms.

The fluorinated organyl or fluorinated organoheteryl group is not a fluoropoly ether group.

Preferably the total number of carbon atoms present in R ² according to any one of the above variants is 1 to 15, more preferably 1 to 12 and most preferably 1 to 10.

Preferably n is at least 2. In case the valence z of the metal or metalloid M ¹ is 4 or more, n is preferably at least 3.

Preferably, in at least one compound according to formula (I) each R ¹ and R ² , if present, are the same. Hence, R ¹ and R ² may still be different.

More preferably, in each compound according to formula (I) each respective R ¹ and R ² , if present, are the same. Thus, in case more than one compound according to formula (I) is used R ¹ of one compound according to formula (I) may still be different from R ¹ of another compound according to formula (I).

In case more than one compound according to formula (I) is provided in step al), preferably in at least one compound according to formula (I) n = z whereas in at least one other compound according to formula (I) n < z. Suitable fluorine-free compounds according to formula (I) are, for example triethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, diethyl-diethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-butyltriethoxysilane, methyldiethoxyvinylsilane, phenyltrimethoxy silane, phenantrene-9-tri ethoxy silane, vinyltrimethoxy silane, 3- gly ci doxy propy Itrimethoxy sil ane, 3 -gly ci doxy propy 1 tri ethoxy si 1 ane, 3 - glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, aminopropyltrimethoxysilane, n-hexyltrimethoxysilane, propyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, mercaptpropyltrimethoxysilane, mercaptpropyl methyldimethoxysilane, acryloxypropyltrimethoxysilane, allyltrimethoxysilane, epoxy cyclohexylethyltrimethoxysilane, methyltrimethoxysilane (MTMOS), methyltri ethoxy sil ane (MTEOS), dimethyldiethoxysilane (DMDEOS), phenyl triethoxysilane (PTEOS), phenylmethyldimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methoxytrimethylsilane, ethoxy -trimethylsilane, n-propoxytrimethylsilane, methoxydimethylethylsilane, ethoxydimethyl-ethylsilane, n- propoxy dimethylethylsilane, methoxy dimethylvinylsilane, ethoxy dimethyl- vinylsilane, n-propoxy dimethylvinylsilane, trimethoxymethylsilane, triethoxymethylsilane and mixtures thereof.

Suitable fluorine containing compounds are 1H,1H,2H,2H- Perfluorooctyltri ethoxy silane, (Heptadecafluoro- 1 , 1 ,2,2-tetra- hydrodecyl)trimethoxysilane, tridecafluorotriethoxysilane, 1H, 1H, 2H, 2H- perfluorodecyltrimethoxysilane, pentafluorostyrenyltrimethoxysilane, trimethoxy(3,3,3-trifluoropropyl)silane, perfluorododecyl- 1H,1H,2H,2H- triethoxysilane, perfluorotetradecyl- 1H, lH,2H,2H-triethoxysilane, [(4- trifluoromethyl)-2,3,5,6-tetrafluorophenyl]triethoxysilane, Poly(methyl-3,3,3- trifluoropropylsiloxane) and mixtures thereof.

Especially preferred are tetraethoxysilane and methacryloxypropyltrimethoxysilane. The weight ratio of the one or more metal or metalloid compound(s) of formula (I) and the particles in process step al) is preferably from 10: 1 to 1 : 1, more preferably from 8: 1 to 2 : 1 , most preferably from 6: 1 to 4 : 1.

In one embodiment in process step al) additionally one or more compound(s) according to the following formula (II) may be provided

R ⁷ t (OR ⁶ )s’M ² -Y-M ² (OR ⁶ ) _s R ⁷ t

(II) wherein

M ² , M ² are the same or different and are each independently selected from a metal or metalloid with a valence x;

Y is a divalent linking group;

R ⁶ , R ⁶ are the same or different and are each independently selected from a Ci to Cio organyl or organoheteryl group;

R ⁷ , R ⁷ are the same or different and are each independently selected from a Ci to C20 organyl or organoheteryl group; s, s’ are the same or different and are each independently selected from 1 to x-1; t, t’ are the same or different and are each independently selected from is x-2 to

0; s+t is x-1; and s’+t’ is x-1.

In step al), if present, up to five different compounds according to formula (II) may be provided, usually, not more than three different compounds according to formula (II) are provided.

It is preferred that, if present, one or two different, preferably one compound(s) according to formula (II) are provided.

In one preferred embodiment no compound according to formula (II) is provided. M ² and M ² are preferably independently selected from Si, Ge, Sb, Ti, Zr, Al, Sn, Se, Cr, or Ni, more preferably independently selected from Si, Ti, Zr, Ge, Sb, and most preferably M ² and M ² are Si.

Preferably M ² and M ² are the same.

Y preferably is selected from a Ci to C20 organyl or organoheteryl group, more preferably is selected from a Ci to C20 hydrocarbyl group, even more preferably is selected from a Ci to C20 linear or branched or cyclic alkyl group or a Ce to C20 aryl group.

R ⁶ , R ⁶ ’ are the same or different and are each independently selected from a Ci to C10 organyl or organoheteryl group.

In case heteroatoms are present in the organyl group of R ⁶ and/or R ⁶ they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.

Preferred groups OR ⁶ and/or OR ⁶ are alkoxy, acyloxy and aryloxy groups.

The heteroatom of the organoheteryl group of R ⁶ and/or R ⁶ bound to the oxygen atom bound to M ¹ is usually different from O.

The heteroatom(s) present in the organoheteryl group of R ⁶ and/or R ⁶ are preferably selected from N, O, P or S, more preferably selected from N and O.

The total number of heteroatoms, if present, in R ⁶ and/or R ⁶ is usually not more than five, preferably not more than three.

Preferably R ⁶ and/or R ⁶ is a Ci to C10 organyl group containing not more than three heteroatoms, more preferably R ⁶ and/or R ⁶ is a Ci to C10 hydrocarbyl group, even more preferably a Ci to C10 linear, branched or cyclic alkyl group. Preferably the total number of carbon atoms present in R ⁶ and/or R ⁶ according to any one of the above variants is 1 to 6, more preferably 1 to 4.

Preferably R ⁶ andR ⁶ are the same.

R ⁷ , R ⁷ is each independently selected from a Ci to C20 organyl or organoheteryl group.

In case heteroatoms are present in the organyl group of R ⁷ and/or R ⁷ they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.

The heteroatom of the organoheteryl group of R ⁷ and/or R ⁷ bound to M ¹ is usually different from O.

The heteroatom(s) present in the organoheteryl group of R ⁷ and/or R ⁷ are preferably selected from N, O, P or S, more preferably selected from N and O.

The total number of heteroatoms, if present, in R ⁷ and/or R ⁷ is usually not more than eight, preferably not more than five and most preferably not more than three.

Preferably R ⁷ and/or R ⁷ is a Ci to C20 organyl group containing not more than three heteroatoms, more preferably R ⁷ and/or R ⁷ is a Ci to C20 hydrocarbyl group, even more preferably a Ci to C20 linear, branched, or cyclic alkyl group.

Preferably the total number of carbon atoms present in R ⁷ and/or R ⁷ according to any one of the above variants is 1 to 15, more preferably 1 to 10 and most preferably 1 to 6.

Preferably R ⁷ andR ⁷ are the same. Preferably s and/or s’ is at least 2. In case the valence z of the metal or metalloid M ² and/or M ² is 4 or more, s and/or s’ is preferably at least 3.

Suitable compounds according to formula (II) are, for example 1,2- bis(trimethoxysilyl)methane, 1 ,2-bis(triethoxysilyl)methane, 1 ,2- bis(trimethoxysilyl)ethane, 1 ,2-bis(triethoxysilyl)ethane, 1 -(dimethoxymethylsilyl)- 1 -(trimethoxy silyl)methane, 1 -(di ethoxymethyl silyl)- 1 -(tri ethoxy silyl)m ethane, 1 - (trimethoxymethylsilyl)-2-(dimethoxysilyl)ethane, l-(dimethoxymethylsilyl)-2- (trimethoxysilyl)ethane, l-(diethoxymethylsilyl)-2-(triethoxysilyl)ethane, bi s(dimethoxy methyl silyl)methane, bis(diethoxymethylsilyl)methane, 1,2- bis(dichloromethylsilyl)ethane, l,2-bis(trichlorosilyl)ethane, 1,2- bis(dimethoxy methyl silyl)ethane, l,2-bis(diethoxymethylsilyl)ethane, 1,2- bis(trimethoxysilyl)benzene, l,2-bis(triethoxysilyl)benzene, 1,3- bis(trimethoxysilyl)benzene, l,3-bis(triethoxysilyl)benzene, 1,4- bis(trimethoxysilyl)benzene, l,4-bis(triethoxysilyl)benzene, 4,4'-Bis(triethoxysilyl)- l,l'-biphenyl, 1,4-Bis(triethoxysilyl)benzene, and 1,3-Bis(triethoxysilyl)benzene and combinations thereof.

It is preferred that in step al) the one or more, preferably one or two, most preferably two metal or metalloid compounds according to formula (I), the particles and optionally, if present, the one or more compound(s) according to formula (II) are mixed in a first solvent, preferably a first organic solvent.

Suitable solvents as first solvent are alcohols, preferably containing 1 to 6 carbon atoms, e.g. methanol, ethanol, propanol, butanol, ether alcohols such as propyleneglycolmonomethylether, ketones, such as acetone, esters, such as propyleneglycolmonomethyletheracetate, ethyl acetate, methylformate and ethers; such as diethyl ether, THF, preferably alcohols or ketones.

Especially preferred are methanol, ethanol, propanol, butanol, and acetone, most preferred are ethanol and acetone. A mixture of up to five organic solvents may be used, preferably not more than three organic solvents are used and most preferable only one organic solvent is used.

Preferably, as outlined above, the organic solvent(s) used during the preparation of the first precursor composition is fluorine free.

In step al) the temperature is preferably from 10 to 50°C, more preferably from 15 to 30°C.

It is preferred that the weight ratio of the one or more metal or metalloid compound(s) of formula (I) and the particles in process step al) is from 10: 1 to 1 : 1, preferably from 8: 1 to 2: 1, more preferably from 6: 1 to 4: 1.

The at least partial hydrolysis and polymerization in step a2), in the presence of the particles and optionally one or more compound(s) of formula (II), is preferably accomplished under acidic or basic conditions, usually using a catalyst, such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, formic acid, triflic acid, perfluorobutyric acid or another mineral or organic acid or a base, more preferably a mineral acid such as HNO3.

In case an acid is used the concentration of the acid is preferably 0.01 mol/1 to 1.0 mol/1, more preferably 0.05 mol/1 to 0.2 mol/1. The acid is usually dissolved in water or in a mixture of water and the first solvent as defined above. In the case that a first solvent is present in step al) the first solvent in the mixture can be the same as or different from the first solvent present in step al). It is preferred that the first solvent in the mixture is the same as the first solvent present in step al).

The at least partial hydrolysis and polymerization in step a2) is preferably accomplished at a temperature between 50 and 150°C, more preferably 55 - 100°C. The at least partial hydrolysis and polymerization in step a2) is preferably accomplished for 0.5 to 10 hours, preferably 1.0 to 5.0 hours.

During the at least partial hydrolysis polymerization in step a2) a basic substance, e.g. an amine, such as a Ci to C4-trialkylamine may be added.

Preferably the molecular weight of the product of step a2) is 500 g/mol to 6000 g/mol, more preferably 800 g/mol to 4000 g/mol.

It is preferred that after step a2) an additional step a3) is accomplished. a3) exchanging the first solvent or solvents used in step a2) by one or more second solvents.

Exchanging the solvents denotes that the first and second solvent or solvent mixture present before and after the solvent exchange are different. Usually, at least the water present in the at least partial hydrolysis in step a2) is removed by the solvent exchange.

Thus, for example, the water and the first solvent, e.g. ketone or alcohol, used in the at least partial hydrolysis in step a2) is/are replaced by a second solvent.

The second solvent is preferably different from the first solvent.

Suitable solvents are alcohols, preferably containing 1 to 6 carbon atoms, e.g. methanol, ethanol, propanol, butanol, ether alcohols such as propyleneglycolmonomethylether, ketones, such as acetone, esters, such as propyleneglycolmonomethyletheracetate, ethyl acetate, methylformate and ethers; such as diethyl ether, THF, preferably ether alcohols.

Especially preferred is propyleneglycolmonomethylether. In step a3) the temperature is preferably from 10 to 50°C, more preferably from 15 to 30°C.

The solids content of the first precursor composition is preferably 1.0 to 25 wt.% based on the entire first precursor composition, more preferably 5 to 20 wt.% based on the entire first precursor composition.

Second precursor composition

As outlined above, the second precursor composition (SPC) is prepared in a second vessel, the preparation comprising the following step: bl) providing a fluoropolyether silane comprising hydrolysable groups (PFS), which differs from the one or more metal or metalloid compound(s) according to formula (I) at least in the presence of a fluoropoly ether group.

The fluoropoly ether silane comprising hydrolysable groups (PFS) is preferably selected from compounds according to the following formula (III)

R ⁵ -R ^F -Q-Si(OR ³ )oR ⁴ _P (III) wherein

R ^F is a fluoropolyether group;

Q is a divalent linking group;

R ³ is each independently selected from a Ci to Cio organyl or organoheteryl group;

R ⁴ is each independently selected from a Ci to C20 organyl or organoheteryl group; o is 1, 2 or 3; p is 0, 1 or 2; o+p is 3; and

R ⁵ is H, C _X F2X+I with x being 1 to 10 or -Q-Si(OR ³ ) _o R ⁴ _P , with Q, R ³ , R ⁴ , o and p as defined above, whereby in each occurrence Q, R ³ , R ⁴ , o and p being present may be the same or different. R ³ is each independently selected from a Ci to Cio organyl or organoheteryl group.

In case heteroatoms are present in the organyl group of R ³ they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.

Preferred groups OR ³ are alkoxy, acyloxy and aryloxy groups.

The heteroatom of the organoheteryl group of R ³ bound to the oxygen atom bound to M ¹ is usually different from O.

The heteroatom(s) present in the organoheteryl group of R ³ are preferably selected from N, O, P or S, more preferably selected from N and O.

The total number of heteroatoms, if present, in R ³ is usually not more than five, preferably not more than three.

Preferably R ³ is a Ci to Cio organyl group containing not more than three heteroatoms, more preferably R ³ is a Ci to Cio hydrocarbyl group, even more preferably a Ci to Cio linear, branched or cyclic alkyl group.

Preferably the total number of carbon atoms present in R ³ according to any one of the above variants is 1 to 6, more preferably 1 to 4.

R ⁴ is each independently selected from a Ci to C20 organyl or organoheteryl group

In case heteroatoms are present in the organyl group of R ⁴ they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.

The heteroatom of the organoheteryl group of R ⁴ bound to Si is usually different from O. The heteroatom(s) present in the organoheteryl group of R ⁴ are preferably selected from N, O, P or S, more preferably selected from N and O.

The total number of heteroatoms, if present, in R ⁴ is usually not more than eight, preferably not more than five and most preferably not more than three.

Preferably R ⁴ is a Ci to C20 organyl group containing not more than three heteroatoms, more preferably R ⁴ is a Ci to C20 hydrocarbyl group, even more preferably a Ci to C20 linear, branched or cyclic alkyl group.

Preferably the total number of carbon atoms present in R ⁴ according to any one of the above variants is 1 to 15, more preferably 1 to 10 and most preferably 1 to 6. o is preferably 1 to 3, more preferably 2 or 3 and most preferably 3 p is preferably 0 to 2, more preferably 0 or 1 and most preferably 0. o + p is 3.

The fluoropoly ether group R ^F usually has a molecular weight of 150 to 10,000 g/mol, more preferably 250 to 5,000 g/mol and most preferably 350 to 2,500 g/mol.

In the fluoropolyether group R ^F not all hydrogen atoms may be replaced by fluorine. In case hydrogen atoms are present in the fluoropolyether group R ^F the molecular ratio fluorine/hydrogen is preferably at least 5, more preferably at least 10. More preferably, the fluoropolyether group R ^F is a perfluoropoly ether group.

The fluoropolyether group R ^F may be a linear or branched group, preferably is a linear group.

The repeating units of the fluoropolyether group R ^F are preferably Ci to Ce fluorinated dialcohols, more preferably Ci to C4 fluorinated dialcohols and most preferably Ci to C3 fluorinated dialcohols. Preferable monomers of the fluoropoly ether group R ^F are perfluoro- 1,2-propylene glycol, perfluoro-l,3-propylene glycol, perfluoro- 1,2-ethylene glycol and difluoro- 1,1 -dihydroxy-methane, preferably perfluoro- 1,3 -propylene glycol, perfluoro- 1,2- ethylene glycol and difluoro-methanediol.

The latter monomer, difluoro- 1,1 -dihydroxy-methane, may be obtained by oxidizing poly(tetrafluoroethylene).

Preferred structures for a divalent perfluoropolyether group include -CF2O(CF2O)m(C2F4O)pCF2- wherein an average value for m and p is 0 to 50, with the proviso that m and p are not simultaneously zero,

-CF(CF3)O(CF(CF3)CF ₂ O) _P CF(CF3)-,

-CF2O(C2F ₄ O) _P CF2-, and

-(CF2)3O(C4F ₈ O)p(CF2)3- wherein an average value for p is 3 to 50.

Of these, particularly preferred structures are -CF2O(CF2O)m(C2F ₄ O)pCF2 , -CF2O(C2F ₄ O) _P CF2-, and -CF(CF3)(OCF2(CF3)CF)pO(CF2)mO(CF(CF3)CF ₂ O)pCF(CF3)-.

Preferred structures for a monovalent perfluoropolyether group, include CF3CF2O(CF2O)m(C2F ₄ O)pCF2-,

CF ₃ CF2O(C2F ₄ O)pCF2-,

CF3CF2CF2O(CF(CF3)CF ₂ O) _P CF(CF3)-, or combinations thereof, where an average value for m and p is 0 to 50 and m and p are not independently 0. Especially preferable are fluoropolyether groups R ^F are selected from - CF2O- [C2F4O]m- [CF2O]n- with 1 < n < 8 and 3 < m < 10

R-[C3FeO] _n - with n = 2 to 10 and R being a linear or branched, preferably linear, perfluorinated C2 or Cs-alcohol, preferably Cs-alcohol;

The divalent linking group Q links the perfluorpolyether with the silicon-containing group.

Q is usually having a molecular weight of not more than 500 g/mol, more preferably not more than 250 g/mol and most preferably not more than 150 g/mol. Examples for divalent linking groups are amide-containing groups and alkylene groups.

Fluoropolyether silane compounds comprising hydrolysable groups can be commercially available without public knowledge of their exact chemical structure.

Suitable commercially available fluoropolyether silane comprising hydrolysable groups are, for example Fluorolink S10 (CAS no. 223557-70-8, Solvay), Optool™ DSX (Daikin Industries), Shin-Etsu Subelyn™ KY-1900 (Shin-Etsu Chemical) and Dow Corning® 2634 (CAS no. 870998-78-0).

During the preparation of the second precursor composition (SPC) organic solvents may be used.

Preferably, the solvent(s) is/are selected from alcohols, preferably containing 1 to 6 carbon atoms, e.g. methanol, ethanol, propanol, butanol, ether alcohols such as propyleneglycolmonomethylether, ethylene glycol, ketones, esters, such as ethyl acetate, methylformate, ethers, such as partially or completely fluorinated ethers, partially or completely fluorinated hydrocarbons, particularly preferred are alcohols, preferably containing 1 to 6 carbon atoms, e.g. methanol, ethanol, propanol, butanol, ether alcohols such as propyleneglycolmonomethylether, partially or completely fluorinated ethers, ethylene glycol, or mixtures thereof, most preferred are ether alcohols such as propyleneglycolmonomethylether, partially or completely fluorinated ethers, ethylene glycol, or mixtures thereof, e.g. methoxynonafluor obutane, methyl -nonaflurobuty 1 ether, methyl -nonafluor oi sobuty 1 ether, ethoxy-nonafluorobutane, isopropyl alcohol, ethanol, propyleneglycolmonomethylether and/or ethylene glycol.

In case solvents are present, during the preparation of the second precursor composition (SPC) the amount of fluorine-containing solvents based on the total weight of the solvents present is equal or less than 90 wt.%, more preferably equal or less than 80 wt.%, and most preferably equal or less than 75 vol.%.

Suitable fluorine-containing solvents are, for example, partially or completely fluorinated hydrocarbons, partially or completely fluorinated ethers or mixtures thereof e.g. methyl-nonafluorobutylether, methyl-nonafluoroisobutylether and ethoxy-nonafluorobutane.

The solids content of the second precursor composition is preferably 0.2 to 100 wt.% based on the entire first precursor composition, more preferably 0.3 to 20 wt.% based on the entire second precursor composition.

The preparation of the second precursor composition is preferably accomplished within a temperature range of 0 to 75°C, more preferably within a temperature range of 20 to 50°C.

During step c) the first precursor composition (FPC) is mixed with the second precursor composition (SPC) to obtain a composition. The first precursor composition (FPC) and the second precursor composition (SPC) are preferably mixed by adding the two compositions into a vessel, such as a flask, and stirring the combined compositions.

Upon combining the two precursor compositions, a reaction may take place. However, this reaction is different from the curing reaction. The second precursor composition silane groups react with the first precursor composition silane groups to form a pre-polymer ready for coating deposition.

Additional organic solvents may be added during step c) in order to obtain the desired final solids content.

The amount of fluorine-containing solvents used in the final formulation, based on the total weight of the solvents present, is equal or less than 90 wt.%, more preferably equal or less than 80 wt.%, and most preferably equal or less than 75 vol.%.

Preferably, the solvent(s) which may be added are selected from alcohols, preferably containing 1 to 6 carbon atoms, e.g. methanol, ethanol, propanol, butanol, ether alcohols such as propyleneglycolmonomethylether, ethylene glycol, ketones, esters, such as ethyl acetate, methylformate, ethers, such as partially or completely fluorinated ethers, particularly preferred are alcohols, preferably containing 1 to 6 carbon atoms, e.g. methanol, ethanol, propanol, butanol, ether alcohols such as propyleneglycolmonomethylether, partially or completely fluorinated ethers, ethylene glycol, or mixtures thereof, most preferred are ether alcohols such as propyleneglycolmonomethylether, partially or completely fluorinated ethers, ethylene glycol, or mixtures thereof, e.g. methoxy-nonafluorobutane, methyl- nonaflurobuty 1 ether, methyl -nonafluor oi sobutyl ether, ethoxy -nonafluorobutane, ethylacetate, n-hexane, n-pentane, isopropyl alcohol, ethanol, butanol, propyleneglycolmonomethylether, propylene glycol. In step c) the weight ratio between the solids contents of the first precursor composition (FPC) and the solids content of the second precursor composition (SPC) is preferably between 100: 1.0 to 0.5:1.0, preferably between 80: 1.0 to 1.0:1.0, more preferably between 60: 1.0 to 1.5: 1.0.

Furthermore, usual additives used for coating compositions for thin films may be added during step c). Such usual additives include, for example, surfactants, levelling agents, processing aids, antistatic agents, antioxidants, water and oxygen scavengers, catalysts, photoinitators or mixtures thereof. Preferably, due to the presence of particles in the first precursor composition, no further particles are added during step c).

The solids content of the composition obtained after step c) is preferably 0.1 to 10 wt.% based on the entire composition, more preferably 0.1 to 5 wt.% based on the entire composition.

Preferably, the fluorine content of the solids content of the composition obtained after step c) is 0.005 to 0.3 wt.%, preferably between 0.01 to 0.1 wt.% based on the total formulation composition obtained after step c).

Preferably, the fluorine content of the solids content of the composition obtained after step c) is 0.1 to 17.5 wt.%, preferably between 0.2 to 15 wt.% based on the total solids content of the composition obtained after step c).

Usually and preferably the solids content after step c) remains unchanged until step d) is accomplished.

The temperature during step c) preferably does not exceed 75°C, more preferably does not exceed 50°C and is usually below 35°C. The reaction time is usually below 24h, preferably 6 to 15 hours.

In step d) a thin layer from the composition obtained in step c) on the substrate is formed.

Suitable substrates include ceramics, glass, metals, natural and man-made stone, polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), paints (such as those on acrylic resins), powder coatings (such as polyurethane or hybrid powder coatings), wood and fibrous substrates (such as textile, leather, carpet, paper). Preferably, the substrate is selected from ceramics, glass, metals, polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), natural and man-made stone, more preferably from metals, ceramics, glass and polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate).

Step d) is preferably effected by dip coating, slot coating, combined slot+spin coating, spin coating, spray coating, ink-jet printing, curtain coating, roller coating, roll-to-roll coating, screen printing or using a bar, a brush or by rubbing, more preferably by spray coating, slot coating, dip coating, spin coating, most preferably spray coating and spin coating (to mention few typical liquid phase deposition methods but not limited to these). Such methods are known in the art.

The temperature during step d) preferably does not exceed 75°C, more preferably does not exceed 50°C and most preferably does not exceed 35°C. The temperature of the substrate during step d) preferably does not exceed 100°C, more preferably does not exceed 50°C and most preferably does not exceed 35°C. In some cases, it might be preferable to make deposition on pre-heated substrate. After forming the thin layer on the substrate in step d) and before curing the intermediate product in step f) a pattern can be formed into the thin film to form surface structures and patterns. Suitable methods for pattern forming are nanoimprinting, embossing, roll-to-roll, gravure, flexo-graphic, roller, ink-jet, screenprinting, spray and or UV lithography is used as patterning process) is used the form surface structures (nano-scale or micro or millimeter scale).

The purpose of the pattern forming is to produce additional optical, physical or chemical properties to the thin film.

In case solvent(s) are present in step d) in step e) the solvent(s) are preferably partially or completely removed. Step e) is optional and not typically necessary. There are differences between the deposition method and manufacturing line specifications.

In addition to temperature, also vacuum dry step can be optionally applied to promote the evaporation of the solvent(s). If vacuum dry step is used, typically it is applied first and followed by the thermal pre-cure. Usually, the removal is accomplished at a pressure of 50 to 200 kPa and/or followed by thermal cure at a temperature of 50 to 150 °C, preferably the removal is accomplished at a pressure of 90 to 115 kPa and/or followed by thermal cure at a temperature of 60 to 100 °C.

The optional thermal pre-cure is usually effected by exposure to heat, e.g. by using a convection oven, hot plate or IR irradiation. The optional vacuum dry is carried out by specific equipment capable to remove solvents by applying high vacuum in specific chamber in which the coated substrate is loaded.

In step f) the intermediate product obtained in step e), if present, or step d), if step e) is not present, is cured.

The curing is usually effected by exposure to heat, e.g. by using a convection oven, hot plate or IR irradiation. Optionally also combined thermal and UV cure process can be used.

The temperature used for curing usually does not exceed 300°C preferably does not exceed 250°C and most preferably does not exceed 150°C or does not exceed 80°C.

The curing time is usually 10 min to 5.0 hours, preferably 20 min to 3.0 hours, and most preferably 5 min to 1.0 hour.

The total fluorine content of the final thin film obtained after step f) is preferably from 0.2 to 15 wt.-% based on the total weight of the monomers in the thin film.

The total particles content of the final thin film obtained after step f) is preferably from 5 to 15 wt.-% based on the total weight of the monomers in the thin film.

The thickness of the thin film after step f) is preferably 15.0 to 120 nm, more preferably 30 to 100 nm.

The film preferably has a pencil hardness (PEHA) of at least 7H, preferably at least 8H, most preferably at least 9H. The film preferably has an initial water contact angle of at least 110°, preferably at least 115°, most preferably at least 120°, when measured on a stainless steel substrate (grade 304) with a hairline surface finishing.

In some embodiments the film preferably has an initial water contact angle of at least 130°, when applied on a stainless steel substrate (grade 304) with a hairline surface finishing.

The film preferably has a water contact angle after 200 cycle steel wool abrasion of at least 100°, more preferably at least 110° and most preferably at least 120° when applied onto a stainless steel substrate (grade 304) with a hairline surface finishing.

The film preferably has a water contact angle after 2000 cycle steel wool abrasion of at least 90°, more preferably at least 100° and most preferably at least 105° when applied onto a stainless steel substrate (grade 304) with a hairline surface finishing.

A “salt fog test” treated film preferably has a water contact angle of at least 100°, more preferably at least 110° and most preferably at least 120° when applied onto a stainless steel substrate (grade 304) with a hairline surface finishing.

Article

The present invention is furthermore directed to an article, preferably a coated optical or electrical article, comprising the thin film obtainable by the process according to the present invention.

The article may be a touch panel display, such as a handheld touch panel display or other interactive touch screen device, a solar panel or a window or other glazing in general, mobile phone and computer metal casing and other metal surfaces.

Suitable materials for the articles which comprises the thin film obtainable by the process according to the invention include ceramics, glass, metals, natural and man- made stone, polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), paints (such as those on acrylic resins), powder coatings (such as polyurethane or hybrid powder coatings), wood and fibrous substrates (such as textile, leather, carpet, paper). Preferably, the material for the article is selected from ceramics, glass (for example boroslicate glass, sodalime glass, aluminoslicate glass, or any other glass type), metals (such as aluminum, steel etc.), polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), natural and man-made stone, more preferably from metals, ceramics, glass and polymeric materials (such as poly(meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate).

Thickness and shape of the article may vary case by case and can be flat, 2D or 3D shape.

The article can have chemical, physical and/or mechanical surface treatments before the thin film is applied to the article such as deposited onto the article.

In case of metal, for example aluminum, the article can be polished, anodized, colored, or coated with other coating(s) prior to material deposition.

Glass can be non-tempered, thermally, or chemically tempered and it can have different surface preparations including polishing, grinding, washing using various different surface treatment agents (alkaline or acidic).

Furthermore, the article can be either flat or can have a surface texture (example etched glass surface or anodized aluminium surface) in it or other layers on the article can provide the texturing/corrugated surface or no surface texture in it. In case of glass the surface can be textured by using etching [e.g. to produce antiglare (AG) effect on glass] or by applying coating layer to provide the AG effect.

The thin film can be directly applied onto the article as such that at least one surface of the article is in direct contact with the thin film.

The thin film can also be applied onto an intermediate layer as such that the inner surface of the intermediate layer is in direct contact with at least one surface of the article. The thin film is then in direct contact with the outer surface of the intermediate layer. The intermediate layer can have mechanical, physical, chemical, or optical function in connection with the material coating layer. The intermediate layer can be actual physical coating layer or can be a modification on molecular and or atomic level in the article in the area of the surface which is in direct contact with the intermediate layer.

Preferred variants and embodiments of the process of the present invention are also preferred variants and embodiments of the article according to the present invention.

The present invention is further directed to a composition comprising a first precursor composition (FPC) and a second precursor composition (SPC), the first precursor composition (FPC) comprising particles selected from phosphorous-based particles, oxides, quantum dots or metals and a polymerized metal or metalloid compound according to formula (I)

M^OR^nR^ (I) wherein

M ¹ is a metal or metalloid with a valence z;

R ¹ is each independently selected from a Ci to Cio organyl or organoheteryl group; R ² is each independently selected from a Ci to C20 organyl, organoheteryl, fluorinated organyl or fluorinated organoheteryl group, wherein the fluorinated organyl or fluorinated organoheteryl group is not a fluoropolyether group; n is 1 to z-1; m is 1 to z-1; and n+m is z, whereby the polymerization is effected by at least partial hydrolyzing of the M^OR^-moieties in the presence of the particles in a first solvent; and the second precursor composition (SPC) comprising a fluoropolyether silane comprising hydrolysable groups (PFS), which differs from the polymerized metal or metalloid compound according to formula (I) at least in the presence of a fluoropoly ether group.

Preferred features of the process according to the present invention are also preferred features of the composition of the present invention.

This composition is surprisingly stable at room temperature and slightly elevated temperature (up to 40°C).

The composition usually has a shelf life, determined as described in the experimental part of, of at least 6 months.

Kit-of-parts

The present invention is furthermore directed to a kit-of-parts comprising a first precursor composition (FPC) in a first vessel and a second precursor composition (SPC) in a second vessel, the first precursor composition (FPC) comprising particles selected from phosphorous-based particles, oxides, quantum dots or metals and a polymerized metal or metalloid compound according to formula (I)

M^OR^nR^ (I) wherein M ¹ is a metal or metalloid with a valence z;

R ¹ is each independently selected from a Ci to Cio organyl or organoheterylfluorinated organyl or fluorinated organoheteryl group;

R ² is each independently selected from a Ci to C20 organyl, organoheteryl, fluorinated organyl or fluorinated organoheteryl group, wherein the fluorinated organyl or fluorinated organoheteryl group is not a fluoropolyether group; n is 1 to z-1; m is 1 to z-1; and n+m is z, whereby the polymerization is effected by at least partial hydrolyzing the M^OR ¹ )- moieties in the presence of the particles in a first solvent; and the second precursor composition (SPC) comprising a fluoropolyether silane comprising hydrolysable groups (PFS), which differs from the polymerized metal or metalloid compound according to formula (I) at least in the presence of a fluoropoly ether group.

Preferred features of the process and the composition according to the present invention are also preferred features of the kit-of-parts of the present invention.

Use

The present invention is furthermore directed to the use of the composition or the kit- of-parts according to the present invention for preparing a thin film on a substrate.

The present invention is furthermore directed to the use of the composition or the kit- of-parts according to the present invention for preparing an optical or electrical coating.

Preferred features of the process, the composition, the kit-of-parts, the thin film, the substrate and the optical or electrical coating according to the present invention are also preferred features of the use of the present invention. Experimental part

Measuring methods

Molecular weight

The gel permeation chromatographic system consisted of a GPC apparatus equipped with a Waters 1515 isocratic HPLC pump and a Waters 2414 refractive index detector. The polysiloxanes (0.20 g, 50% solid content) were dissolved in THF (HPLC grade; 2.30 g). The analyte injection volume was 100 pL, the flow was 0.70 mL min' ¹ , and the column temperature was set to 40 °C. Four polysterene exclusionbased columns were used. The mobile phase was THF (HPLC grade). The weightaverage molecular weight (Mw) of the polymers were determined using internal standards, e.g. two series of polystyrenes (Serie A: 5 polystyrenes with r = 120 000 g mol' ¹ , 42 400 g mol' ¹ , 10 700 g mol' ¹ , 2 640 g mol' ¹ , 474 g mol' ¹ and Serie B: 4 polymers with Mr = 193 000 g mol' ¹ , 16 700 g mol' ¹ , 6 540 g mol' ¹ , 890 g mol' ¹ ).

Solids content analysis measurement)

The solid content of the polymers was determined using a Mettler Toledo HB43 instrument. The polymeric solution (0.9 - 1.1 g) to analyzed was placed in a measuring tray (disposable weighing/drying pan in aluminum). The aluminum pan was then heated by a halogen lamp for 10 min from room temperature to T = 160 °C. The mass of solid polymer present in the analyzed polymeric solution was determined after evaporation of the solvents.

Shelf-life determination

See material example 1A data for actual measurement data. Material shelf life is determined by following material process/application result stability/repeatability as cured film. The values monitored from cured film are film thickness and abrasion performance. The film thickness is characterized by usingFilmetrix F20. Measurements are performed using Gorilla Glass 4 and metal and silicon wafer (Diameter: 150 mm, Type/Dopant: P/Bor, Orientation: <l-0-0>, Resistivity: 1-30 Q cm, Thickness: 675+/-25 pm, TTV: <5 pm, Particle: <20 @ 0.2 pm, Front Surface: Polished, Back Surface: Etched, Flat: l SEMI Standard) as substrates. Material film depositions are done by using spray coating, the material film is spray coated on pre-treated (plasma) glass substrate (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm2), followed by thermal cure example at 150°C for 60 min.

Pencil hardness (PEHA)

Film is prepared on pretreated (plasma) glass or anodized aluminum or hairline substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm2), followed by thermal cure example at 150°C for 60 min (for glass) and at 80°C for 60 min (for anodized aluminium). The pencil hardness is determined according to ASTM standard D3363-00 using a Elcometer pencil hardness tester.

Water contact angle (CA)

Film is prepared on pretreated (plasma) glass or anodized aluminum substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm ² ), followed by thermal cure example at 150°C for 60 min (for glass and ceramic) and at 80°C for 60 min (for anodized aluminium). The static contact angle measurement is performed by optical tensiometer using distilled water, 4 pl droplet size, three measurement points average is recorded as the measurement result value and Young-Laplace equation is used as the numerical method to describe the contour of the drop (Tool: Attension Theta optical tensiometer). Also other liquids can be used in addition to water, such as di-iodomethane and hexadecane, to characterize the surface.

Abrasion

Film is prepared on pretreated (plasma) glass, anodized aluminum, or ceramic substrate by using a spray tool (Typical spray process: Scan speed: 300 mm/s; Pitch: 50 mm; Gap: 100 mm; Flow rate: 5-6 ml/min; Atomization air pressure: 5 kg/cm ² ), followed by thermal cure example at 150°C for 60 min (for glass and ceramic) and at 80°C for 60 min (for anodized aluminium and other metal). Abrasion testing is carried out using Bon Star steel wool #0000, 1kg load, Ixlcm head (non-metal substrate) or 2x2 cm (metal substrate), 2-inch stroke, 60c/min speed. (Tools: Taber linear abraser, 5750). Abrasion test evaluation criteria: Initial water contact angle, water contact angle measurement at 1000 cycle intervals (up to 8000 cycles) and visual inspection for surface damage / visual scratch inspection at 1000 cycle intervals (up to 8000 cycles). Water contact angle is measured according to water contact angle measurement method and visual inspection is done under microscope inspection and green and red-light quality lamp inspection. In addition to steel wool, also Cotton Cloth and Minoan Eraser are used to test the abrasion performance.

Chemical resistance Test (Salt fog test)

The coated samples were placed in a_Weiss SC/KWT 1000 salt mist chamber. The salt mist consisted of a 5 wt.-% neutral salt mist made from NaCl (purity 99%) and DI-H2O. The reference standard was based on IECZEN 60068-2- 11 : 2002. The standards marked have been only used as guidance; severity, duration but other parameters may be customized. The test duration was of 24h, 48h and 96h.

Synthesis examples:

Abbreviations of components:

TEOS tetraethoxy silane

MEMO methacryloxypropyltrimethoxysilane

PGME propyleneglycolmonomethylether

Novec 7100 mixture of isomers of methoxy-nonafluorobutane, commercially available from 3M

DSX OPTOOL DSX E (fluoropolyether silane), commercially available from Daikin

PGMEA propyleneglycolmonomethyletheracetate BYK 333 silicon-containing surface additive, commercially available from BYK U375 Miramer U375, commercially available from Miwon

U307 Miramer U307, commercially available from Miwon

PU250NT Miramer PU250NT, commercially available from Miwon

PU3280NT Miramer PU3280NT, commercially available from Miwon

PU620NT Miramer PU620NT, commercially available from Miwon

PU2100NT Miramer PU2100NT, commercially available from Miwon

M4004M Miramer M4004M, commercially available from Miwon

UD509 OPTOOL UD509 (XXX), commercially available from Daikin

SCO 19 is a fluoropoly ether compound dissolved in a mixture comprising 1- ethoxy-l,l,2,3,3,3-hexafluoro-2-(trifluoromethyl)propane and 1- ethoxy-1, 1,2,2,3,3,4,4,4-nonafluorobutane, commercially available from Shin-Etsu

Example 1 (inventive)

In a 500 mL round bottom flask, TEOS (43,46 g) and ZrCh (8,1 g; 50% solid content in PGMEA) were mixed in acetone (136,08 g). The reaction mixture was heated at T = 60 C and nitric acid (0.1M; 29,98 g) was added dropwise and the reaction mixture was stirred at T = 60 C for additional 2 h. Then, the reaction mixture was cooled to room temperature and PGME (150 g) was added. Solvent exchange procedure from acetone to PGME was performed under low pressure giving a final material with a solid content of 15,98 %. The solid content was adjusted to 10% by addition of more PGME.

Formulation 1 A (inventive)

The polymer of example 1 (10% solid content in PGME, 6 g), dipropylene glycol (3,72 g), PGME (65,68 g), Novec 7100 (37,45 g) and DSX (diluted to 0,4% in Novec 7100; 37,5 g) and BYK 333 (0,06 g) are mixed before process testing.

Formulation IB (inventive) The polymer of example 1 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g) are mixed before process testing.

In a 500 mL round bottom flask, TEOS (43 g), MEMO (5,7 g) and ZrO2 (9,74 g; 50% solid content in PGMEA) were mixed in acetone (136 g). Nitric acid (0.1M; 32,22 g) was added dropwise and the reaction mixture was stirred at T = 60 C for 2h. Then, the reaction mixture was cooled to room temperature and PGME (116 g) was added. Solvent exchange procedure from acetone to PGME was performed under low pressure giving a final material with a solid content of 14,14 %. The solid content was adjusted to 10% by addition of PGME.

Formulation 2A (inventive)

The polymer of example 2 (10% solid content in PGME, 6 g), dipropylene glycol (3,72 g), PGME (65,68 g), Novec 7100 (37,45 g) and DSX (diluted to 0,4% in Novec 7100; 37,5 g) and BYK 333 (0,06 g) are mixed before process testing.

Formulation 2B (inventive)

The polymer of example 2 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g) are mixed before process testing.

In a 500 mL round bottom flask, TEOS (43 g) and MEMO (5,7 g) were mixed in acetone (136 g). Nitric acid (0.1M; 32,22 g) was added dropwise and the reaction mixture was stirred at T = 60 C for 2h. Then, the reaction mixture was cooled to room temperature and PGME (121 g) was added. Solvent exchange procedure from acetone to PGME was performed under low pressure giving a final material with a solid content of 14,14 %.

Formulation 3B The polymer of example 3 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g) are mixed together before process testing.

In a 10L reactor, TEOS (519,72 g) is mixed with acetone (1600 g). Nitric acid (0,lM; 353,28 g) is added dropwise and the reaction mixture is refluxed for 2h. PGME (1600 g) is added and solvent exchange procedure from acetone to PGME is performed under low pressure. The solid content of the final product is adjusted to 10% by addition of extra PGME.

Formulation 4Aa (comparative)

The polymer of example 4 (10% solid content in PGME, 6 g), dipropylene glycol

(3,72 g), PGME (65,68 g), Novec 7100 (37,45 g) and DSX (diluted to 0,4% in Novec

7100; 37,5 g) and BYK 333 (0,06 g) and ZrO2 in PGMEA (10% of solid content) are mixed before process testing.

Formulation 4 Ab

The polymer of example 4 (10% solid content in PGME, 6 g), dipropylene glycol (3,72 g), PGME (65,68 g), Novec 7100 (37,45 g) and DSX (diluted to 0,4% in Novec 7100; 37,5 g) and BYK 333 (0,06 g) and ZrO2 in PGMEA (5% of solid content) are mixed before process testing.

Formulation 4Ba

The polymer of example 4 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g), U375 (10% of solid content) are mixed before process testing.

Formulation 4Bb

The polymer of example 4 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g), U307 (10% of solid content) are mixed before process testing.

Formulation 4Bc The polymer of example 4 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g), PU250NT (10% of solid content) are mixed before process testing. Formulation 4Bd (comparative)

The polymer of example 4 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g), PU3280NT (10% of solid content) are mixed before process testing. Formulation 4Be (comparative)

The polymer of example 4 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g), PU620NT (10% of solid content) are mixed before process testing. Formulation 4Bf (comparative)

The polymer of example 4 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g), PU2100NT (10% of solid content) are mixed before process testing. Formulation 4Bg (comparative)

The polymer of example 4 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g), M4004M (10% of solid content) are mixed before process testing. Formulation 4Bh (comparative)

The polymer of example 4 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g), UD509 (0,05% of solid content) are mixed before process testing. Formulation 4Bi (comparative)

The polymer of example 4 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and SC19 (0,05% of solid content) are mixed before process testing.

Formulation 4Bj (comparative) The polymer of example 4 (10% solid content in PGME, 11,25 g), ethylene glycol (3,72 g), PGME (60,18 g), Novec 7100 (55,95 g) and SC19 (0,07% of solid content) are mixed before process testing.

Formulation 4C (comparative)

The polymer of example 4 (10% solid content in PGME, 18,75 g), ethylene glycol (3,72 g), PGME (53,78 g), Novec 7100 (55,7 g) and DSX (diluted to 0,4% in Novec 7100; 18,75 g) are mixed before process testing.

Process conditions and

Glass substrate must be free of stains, debris and any greasiness prior to coating; It is very important to get good wetting of the glass surface (glass surface water contact angle should be <5° prior coating; to ensure excellent coating performance and visual quality);

Step 1 : Liquid alkaline or acidic glass clean solution; non-foaming cleaning agent to be used in glass clean machinery;

Step 2: DI water clean step in glass clean machinery;

Step 3: Plasma/Corona treatment (If possible make water contact angle check <5°, as quality check) (In case of glass either a liquid clean and/or plasma clean steps can be used);

Optimize spray parameters to target cured film thickness of 40-100 nm; handle substrates with care not to damage wet coating when transfering to thermal cure; Step 5: Curing temperature 80-250°C; Curing time 30-60 minutes; no special atmosphere

Step 4: Spray Process; Optimize spray parameters to target cured film thickness of 40-100 nm;

Curing conditions: handle substrates with care not to damage wet coating when transfering to thermal cure;

Step 5: Curing temperature 200°C; Curing time 60 minutes; no special atmosphere Application examples:

Films are prepared on hairline and dark mirror substrates as described above.

The initial water contact angles and the water contact angles of the cured films after the abrasion test are shown in Table 1. Table 1 : water contact angles of cured films after abrasion test n.d. = not determined The cured films of formulations 2B, 4Ba and 4C all coated onto a hairline substrate we subjected to the salt fog text. The visual quality before and after the test were observed and the water contact angles (WCA) after the salt fog test were determined. The results are listed in Table 2.

Table 2: Results of salt fog test