TWI859811B - Flexible multi-layered polysiloxane hard coating - Google Patents

Abstract

The present invention relates to a layered structure comprising a flexible or bendable substrate layer (A), a first polysiloxane based coating layer (B) and a second coating layer (C) comprising a fluoropolyether compound, a method for preparing said layered structure and the use of said layered structure for flexible electronics applications.

Description

Flexible multi-layer polysiloxane hardcoat

The present invention relates to a layered structure comprising a flexible or bendable substrate layer (A), a first coating layer based on polysiloxane (B) and a second coating layer (C) comprising a fluoropolyether compound, a method for preparing the layered structure, and a use of the layered structure in flexible electronic applications.

Transparent plastics have been widely used as core materials in the optical and transparent display industries. Specifically, transparent plastics such as PET (polyethylene terephthalate), PI (polyimide), PC (polycarbonate) or PMMA (polymethyl methacrylate) have been used in flexible electronic applications including displays, optical lenses, transparent panels and the automotive industry as a lightweight alternative to glass due to their high light transmittance and suitable refractive index properties. However, these plastics have the disadvantage of low wear resistance because they have a lower surface hardness than glass.

In order to increase the wear resistance and photopatternability, it is suggested to use a flexible and bendable hard coating film. Suitable flexible hard coatings are, for example, polysiloxane-based flexible hard coatings as disclosed in WO 2019/193258.

Hard coatings have the disadvantage of reducing the visibility of, for example, displays due to increased light reflection. In order to reduce light reflection, antireflective coatings have been proposed as an additional layer on top of the hard coating in a multi-layer approach.

For example, WO 2006/082701A1 discloses a two-layer coating on a transparent plastic film substrate, which has a first hard coating layer from a material containing a curable compound containing a (meth)acrylate group and a reactive polysilicone containing a (meth)acrylate group, and a second anti-reflective (low-refractive) coating layer from a material containing a compound containing a siloxane component.

Other two-layer approaches of hard coating and low refractive layer are suggested in, for example, US 11,046,827 B2 and KR 2004-0076422A.

Even a three-layer coating of a hard coating layer, a high-refractive layer and a low-refractive layer has been proposed, for example, in JP 2001-293818A.

Such multi-layer methods have the disadvantages of reduced scratch resistance and refractive index mismatch, which results in a strong rainbow pattern as discussed in, for example, CN 206270519 U. The reason for the poor scratch resistance may be that the hard coating layer used to improve the scratch resistance is usually an inner layer in direct contact with the plastic substrate and has relatively weak adhesion to the low-refractive outer layer.

When a low refractive layer is applied as an inner layer and a hard coating layer as an outer layer as discussed in TW 2009-16818 A, the coating exhibits good scratch resistance and a low rainbow pattern, but the high reflectivity problem is not solved.

Therefore, there is a need in this art for flexible coatings on transparent plastic substrates that are flexible and exhibit an improved balance of properties in terms of mechanical properties (such as scratch resistance) and optical properties (such as low refractive index) for reducing light reflection.

In the present invention, a multi-layer coating is proposed which shows such an improved balance of properties. The multi-layer coating comprises a coating based on polysiloxane and a coating comprising a fluoropolyether compound, wherein the inner layer is a flexible hard coating based on polysiloxane and the second layer is an anti-reflective layer.

The present invention relates to a layered structure, which comprises (A) a substrate layer; (B) a first coating layer coated on at least one surface of the substrate layer (A), and (C) a second coating layer coated on at least one surface of the first coating layer (B), so that the second coating layer (C) is in adhesive contact with at least one surface of the first coating layer (B), wherein the first coating layer (B) comprises a first siloxane polymer (B-1); the second coating layer (C) comprises a fluoropolyether compound; and the substrate layer (A) is flexible, bendable, or both.

In addition, the present invention relates to a method for manufacturing a layered structure as described above or below, which comprises the following steps: ●   Providing a first composition comprising at least two different silane monomers, wherein at least one of the silane monomers comprises an active group capable of achieving crosslinking with an adjacent siloxane polymer; ●   Subjecting the first composition to at least partial hydrolysis of the monomers to form a composition comprising a first siloxane polymer (B-1); ●   Providing a second composition comprising a fluoropolyether compound; ●   Providing a flexible or bendable substrate or both; ●   Depositing the first composition onto at least one surface of the substrate to form a first coating (B); ●  Crosslinking the siloxane polymer chains of the first coating layer (B) to obtain a first coating layer (B) comprising a crosslinked siloxane polymer in adhesive contact with the at least one surface of the substrate; ●   Depositing the second component onto the first coating layer (B) to form a second coating layer (C) in adhesive contact with the first coating layer (B); ●   Curing the second component of the second coating layer (C) to obtain a cured second coating layer (C) in adhesive contact with the first coating layer (B).

The multi-layer coating of the present invention exhibits good inter-layer adhesion, resulting in an improved balance of properties in terms of mechanical properties (especially scratch resistance) and optical properties (especially low refractive index).

In a specific embodiment, a further third coating layer is applied onto the second coating layer, which further improves the mechanical properties of the multi-layer coating.

In the specific example, the present invention relates to a layered structure, which comprises: (A) a substrate layer; (B) a first coating layer coated on at least one surface of the substrate layer (A); (C) a second coating layer coated on at least one surface of the first coating layer (B), such that the second coating layer (C) is in contact with at least one surface of the first coating layer (B); and (D) a third coating layer (D) coated on at least one surface of the second coating layer (C), such that the third coating layer (D) is in contact with at least one surface of the second coating layer (C), wherein the first coating layer (B) comprises a first siloxane polymer (B-1); The second coating layer (C) comprises a fluoropolyether compound; and the substrate layer (A) is flexible, bendable, or both.

Furthermore, in the specific embodiment, the present invention relates to a method for producing a layered structure as described above or below, comprising the following steps: ●   Providing a first composition comprising at least two different silane monomers, wherein at least one of the silane monomers comprises an active group capable of achieving crosslinking with an adjacent siloxane polymer; ●   Subjecting the first composition to at least partial hydrolysis of the monomers to form a composition comprising a first siloxane polymer (B-1); ●   Providing a second composition comprising a fluoropolyether compound; ●   Providing a third composition comprising a siloxane polymer and, if appropriate, a fluoropolyether compound; ●   Providing a flexible or bendable substrate or both; ●  Depositing the first component onto at least one surface of the substrate to form a first coating layer (B); ●   Crosslinking the siloxane polymer chains of the first coating layer (B) to obtain a first coating layer (B) comprising a crosslinked siloxane polymer in adhesive contact with the at least one surface of the substrate; ●   Depositing the second component onto the first coating layer (B) to form a second coating layer (C) in adhesive contact with the first coating layer (B); ●   Curing the second component of the second coating layer (C) to obtain a cured second coating layer (C) in adhesive contact with the first coating layer (B); ●  Depositing the third composition onto the second coating layer (C) to form a third coating layer (D) in adhesive contact with the second coating layer (C); ●   Crosslinking the siloxane polymer chains of the third coating layer (D) to obtain a third coating layer (D) comprising one or more crosslinked siloxane polymers in adhesive contact with the second coating layer (C).

Finally, the invention relates to the use of a layered structure as described above or below in flexible electronic applications, including displays, optical lenses, transparent panels and in the automotive industry, in particular as a lightweight alternative to glass.

Various illustrative and non-limiting embodiments both as to construction and methods of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific illustrative embodiments when read in conjunction with the accompanying drawings.

The verbs "comprise" and "include" are used in this document as open limitations that neither exclude nor require the existence of unrecited features. The features recited in the appendices are freely combinable with each other unless expressly stated otherwise.

The present invention provides a layered structure, wherein the substrate layer (A) has at least two layers comprising a siloxane polymer. The layered structure is "bendable", meaning that it can bend around an axis having a radius of curvature without breaking.

As described in WO 2019/193258, the bending properties can be tested using a test involving folding the layered structure inward or outward about a central axis.

Substrate layer (A) The substrate layer (A) may be any type of substrate, such as glass, quartz, silicon, silicon nitride, polymer, metal and plastic or mixtures thereof. In addition, the substrate layer (A) may also include a plurality of different surfaces, such as different oxides, doped oxides, semi-metals and the like or mixtures thereof.

Suitable polymers are, for example, thermoplastic polymers such as polyolefins, polyesters, polyamides, polyimides, polycarbonates, acrylic polymers such as poly(methyl methacrylate) and custom-designed polymers.

Particularly preferred polymers are polymethyl methacrylate (PMMA), polyethylene terephthalate (PET) and colorless polyimide (CPI).

The substrate layer (A) can be the outermost layer of the device or an inner layer of a single stack. The substrate layer (A) can be coated on one side or both sides.

The substrate layer (A) preferably has a thickness of 10 to 500 µm, more preferably 20 to 400 µm.

The substrate layer (A) is flexible, bendable or both, so that it can bend around a mandrel having a first minimum radius of curvature without breaking. The layered structure of the present invention is particularly capable of bending around a mandrel having a second minimum radius of curvature without breaking, the first minimum radius of curvature being less than or equal to the second minimum radius of curvature.

At least one surface of the substrate layer (A) may be modified before depositing the first composition on at least one surface of the substrate to form the first coating layer (B).

At least one surface of the substrate layer (A) may be physically or chemically modified.

Suitable for physical modification such as plasma treatment, corona treatment or similar treatment.

A suitable chemical modification may be a chemical cleaning process for cleaning at least one surface of the substrate layer (A).

At least one surface is preferably activated by means of physical or chemical modification to promote adhesion between the substrate layer (A) and the first coating layer (B).

In one embodiment, the optional coating composition is deposited on at least one surface of the substrate layer (A), so that the optional additional coating is formed on at least one surface of the substrate layer (A). The optional additional coating is then in adhesive contact with at least one surface of the substrate layer (A) on one side and in adhesive contact with the first coating (B) on the other side.

In this context, "adhesive contact" means that there are no other coating layers or adhesive layers between the substrate layer (A) and the optional additional coating layer and between the optional additional coating layer and at least one surface of the first coating layer (B).

The optional additional coating may have a thickness of 5 to 300 nm or a thickness of 300 nm to 5 µm.

In certain cases, the optional additional coating is typically applied, for example, to promote adhesion between the substrate layer (A) and the first coating layer (B), to wet the first coating layer (B), to promote the optical performance of the layered structure, or to promote the mechanical performance of the layered structure.

However, preferably, no optional additional coating layer is applied between the substrate layer and the first coating layer (B).

First coating layer (B) The first coating layer (B) is coated on at least one surface of the substrate layer (A) so that the first coating layer (B)

Preferably, the first coating layer (B) is in adhesive contact with at least one surface of the substrate layer (A). Therefore, the first coating layer (B) is usually an inner layer of a multi-layer coating layer having adhesive contact with at least one surface of the substrate layer (A). In this context, "adhesive contact" means that there are no other coating layers or adhesive layers between the substrate layer (A) and at least one surface of the first coating layer (B).

The first coating layer (B) preferably has a thickness of 1 to 50 µm, more preferably 2 to 20 µm, and more preferably 3 to 10 µm.

The first coating layer (B) includes a first siloxane polymer (B-1).

The first siloxane polymer (B-1) comprises monomer units selected from at least two different silane monomers, wherein at least one of the silane monomers comprises a reactive group capable of achieving crosslinking with adjacent siloxane polymer chains, and wherein the adjacent siloxane polymer chains are crosslinked via the reactive group.

The first siloxane polymer (B-1) may comprise monomer units selected from 2 to 10, such as 2 to 6, preferably 2 to 4 different silane monomers. "Different" in this context means that the silane monomers differ in at least one chemical moiety.

The reactive group is preferably an epoxy group, an alicyclic epoxy group (such as a glycidyl group), a vinyl group, an allyl group, an acrylate group, a methacrylate group, a silyl group, and a combination thereof.

Thus, epoxy, alicyclic epoxy (e.g., glycidyl), vinyl, allyl, acrylate, methacrylate groups are capable of crosslinking with adjacent siloxane polymer chains when initiated thermally or by radiation, preferably in the presence of a suitable initiator (e.g., a thermal or free radical initiator).

Suitable thermal or free radical initiators are preferably selected from triamyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile), benzoyl peroxide, 2,2-bis(tertiary butylperoxy)butane, 1,1-bis(tertiary butylperoxy)cyclohexane, 2,2'-azobisisobutyronitrile (AIBN), 2,5-bis(tertiary butylperoxy)-Z,S-dimethylhexane, 2,5-bis(tertiary butylperoxy)-2,5- Dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, isopropyl hydroperoxide, cyclohexanone peroxide, diisopropyl peroxide, lauryl peroxide, 2,4-pentanedione peroxide, peracetic acid or potassium persulfate. Particularly preferred is 2,2'-azobisisobutyronitrile (AIBN).

Silane groups are capable of crosslinking with carbon-carbon double bonds (such as _{vinyl or allyl) of adjacent siloxane polymer chains during hydrosilylation, preferably in the presence of a suitable catalyst (such as platinum (Pt)-based catalysts, such as Speier's catalyst (H2PtCl6.H2O )} , Karstedt's catalyst (Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution) or rhodium (Rh)-based catalysts, such as tris(triphenylphosphine)rhodium(I) chloride).

In a specific example, the molar ratio between the monomer containing the first reactive group, e.g., selected from epoxy, alicyclic epoxy (e.g., glycidyl), vinyl and allyl, and the monomer containing the second reactive group, e.g., selected from acrylate and methacrylate, ranges from 1:100 to 100:1, specifically 1:10 to 10:1, e.g., 5:1 to 1:2 or 3:1 to 1:1.

In some specific examples, the component containing the second reactive group is also selected from compounds containing acrylates and methacrylates other than silane monomers, such as tetraethylene glycol diacrylate, trihydroxymethylpropane triacrylate, pentaerythritol triacrylate, ditrimethylpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and combinations thereof.

In some embodiments, the reactive group or groups will be present at a concentration of about 1 to about 35% based on the molar fraction of the monomer.

Suitable silane monomers are preferably represented by formula (I): R ¹ _a SiX _4-a （I） wherein R ¹ is selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxide, allyl, vinyl and alkoxy, and an aromatic group having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X is a hydrolyzable group or a hydrocarbon residue; and a is an integer of 1 to 3.

The hydrolyzable group is especially an alkoxy group (see formula II).

^R1 and/or the alkoxy group of the hydrolyzable group X may be the same or different and are preferably selected from the group having the following formula ^-OR2 (II) wherein ^R2 represents a linear or branched alkyl group having 1 to 10, preferably 1 to 6 carbon atoms and optionally presents one or two substituents selected from the group consisting of halogen, hydroxyl, vinyl, epoxy and allyl. The most preferred are methoxy and ethoxy.

Particularly preferred are di-, tri- or tetraalkoxysilanes containing alkoxy groups according to formula (II).

Particularly suitable silane monomers are selected from the group consisting of tetraethoxysilane (TEOS), tetramethoxysilane (TMS), methyltriethoxysilane (MTEOS), methyltrimethoxysilane (MTMS), dimethyldiethoxysilane (DMDEOS), dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPDMS), 3-(trimethoxysilyl)propylmethacrylate (MEMO), 3-(triethoxysilyl)propylmethacrylate Ester, 5-(bicycloheptenyl)triethoxysilane (BCHTEOS), (3-glycidyloxypropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane (GPTMS), (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane (F17), (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane, 1H,1H,2H,2H-perfluorododecyltriethoxysilane, 1H,1H,2H,2H-perfluorododecyltriethoxysilane Alkyl trimethoxysilane, 1H,1H,2H,2H-perfluorooctyl triethoxysilane, 1H,1H,2H,2H-perfluorooctyl trimethoxysilane (F13), 1H,1H,2H,2H-perfluoropentyl triethoxysilane, 1H,1H,2H,2H-perfluoropentyl trimethoxysilane, 1H,1H,2H,2H-perfluorotetradecyl triethoxysilane, 1H,1H,2H,2H-perfluorotetradecyl trimethoxysilane, allyl trimethoxysilane (al lylTMS), allyl triethoxysilane (allylTEOS), vinyl trimethoxysilane, vinyl triethoxysilane, (3-glycidyloxypropyl) dimethoxymethyl silane (Me-GPTMS), methacryloxypropyl methyl dimethoxy silane (Me-MEMO), phenyl methyl dimethoxy silane (PMDMS), bis [(2,2,3,3,4,4-hexafluorobutyl) propionate] -3-aminopropyl trimethoxy silane or a mixture thereof.

The silane monomer is preferably selected from the group consisting of phenylmethyldimethoxysilane (PMDMS), 3-(trimethoxysilyl)propylmethacrylate (MEMO) and (3-glycidyloxypropyl)trimethoxysilane (GPTMS).

The silane monomers are preferably present in the siloxane polymer in a molar amount of 50 to 100 mol %, preferably 50 to 99 mol %, and more preferably 65 to 97 mol %.

In one embodiment, the at least two different silane monomers of the first siloxane polymer (B-1) include at least one bissilane.

Suitable bissilanes are preferably represented by the formula (III): (R ³ ) ₃ Si-Y-Si(R ⁴ ) ₃ , (III) wherein R ³ and R ⁴ are independently selected from hydrogen and a group consisting of a linear or branched alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an (alkyl)acrylate group, an epoxide group, an allyl group, a vinyl group, an alkoxy group and an aryl group having 1 to 6 rings, and wherein the group is substituted or unsubstituted; and Y is a linking group selected from divalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, -O-alkylene-O-; -O-arylene-O-; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z ¹ C(═O)Z ² -alkylene, arylene-Z ¹ C(=O)Z ² -arylene and -O-alkylene-Z ¹ C(=O)Z ² -phenylene-O-; -O-arylene-Z ¹ C(=O)Z ² -arylene-O-, wherein Z ¹ and Z ² are independently selected from a direct bond or -O-.

In divalent "alkylene" groups and other similar aliphatic groups, the alkyl residue (or the residue derived from the alkyl part) represents 1 to 10, preferably 1 to 8, or 1 to 6 or even 1 to 4 carbon atoms, examples include ethylene and methylene and propylene.

"Arylene" represents an aromatic divalent radical typically containing 1 to 3 aromatic rings and 6 to 18 carbon atoms. Such radicals are exemplified by phenylene (e.g., 1,4-phenylene and 1,3-phenylene) and biphenylene as well as naphthylene or anthracenylene.

The alkylene group and the arylene group may be substituted with 1 to 5 substituents selected from the group consisting of a hydroxyl group, a halogen group, a vinyl group, an epoxy group and an allyl group as well as an alkyl group, an aryl group and an aralkyl group, as the case may be.

Preferred alkoxy groups contain 1 to 4 carbon atoms. Examples are methoxy and ethoxy.

The term "phenyl" includes substituted phenyl groups, such as phenyltrialkoxy groups, especially phenyltrimethoxy or triethoxy groups, and perfluorophenyl groups. The phenyl group and other aromatic or alicyclic groups can be coupled directly to the silicon atom, or they can be coupled to the silicon atom via a methylene or ethylene bridge.

Exemplary bissilanes include 1,2-bis(triethoxysilyl)ethane (BTESE), 1,2-bis(trimethoxysilyl)ethane (MEOS), and mixtures thereof.

Preferably, the bissilane is present in the siloxane polymer in a molar amount of 0 to 50 mol %, preferably 1 to 50 mol %, and more preferably 3 to 35 mol %.

Particularly preferably, at least two silane monomers are selected from the group consisting of 1,2-bis(triethoxysilyl)ethane (BTESE), phenylmethyldimethoxysilane (PMDMS), 3-(trimethoxysilyl)propylmethacrylate (MEMO) and (3-glycidyloxypropyl)trimethoxysilane (GPTMS), or a mixture of two or more thereof.

The first composition comprising the siloxane polymer (B-1) is preferably formed by a method comprising the following steps: ●   Mixing at least two different silane monomers, preferably as described above or below, in a first solvent to form a mixture; ●   Subjecting the mixture to at least partial hydrolysis of the monomers in the presence of a catalyst, thereby causing the hydrolyzed monomers to at least partially polymerize and crosslink; ●   Optionally replacing the first solvent with a second solvent; ●   Optionally crosslinking the mixture by hydrosilylation, heat or radiation initiation.

The first solvent is preferably selected from the group consisting of acetone, tetrahydrofuran (THF), toluene, 1-propanol, 2-propanol, methanol, ethanol, water ( _H2O ), cyclopentanone, acetonitrile, propylene glycol propyl ether, methyl tertiary butyl ether (MTBE), propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether (PGME) and propylene glycol propyl ether (PnP).

At least two different silane monomers may be mixed in a first solvent at any suitable temperature to dissolve the silane monomers. Typically, room temperature is sufficient.

In the next process step, the mixture undergoes at least partial hydrolysis in the presence of a catalyst.

Suitable catalysts are acidic catalysts, alkaline catalysts or other catalysts.

The acidic catalyst is preferably selected from nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), formic acid (HCOOH), hydrochloric acid (HCl), sulfonic acid, hydrogen fluoride (HF), acetic acid (CH ₃ COOH), trifluoromethanesulfonic acid or p-toluenesulfonic acid. Particularly preferred acidic catalysts are nitric acid (HNO ₃ ), hydrochloric acid (HCl) and formic acid (HCOOH).

The alkaline catalyst is preferably selected from triethylamine (TEA), ammonium hydroxide (NH ₄ OH), tetraethylammonium hydroxide (TEAH), tetramethylammonium hydroxide (TMEA), 1,4-diazabicyclo[2.2.2]octane, imidazole and diethylenetriamine.

Other catalysts are preferably selected from 2,2,3,3,4,4,5,5-octafluoropentyl acrylate, poly(ethylene glycol) 200, poly(ethylene glycol) 300 and n-butyl melamine formaldehyde resin.

The hydrolysis step is preferably carried out at a temperature of 20 to 80°C for 1 to 24 hours, such as overnight at room temperature.

During the hydrolysis step, the silane monomers are at least partially hydrolyzed. The at least partially hydrolyzed silane monomers are then at least partially polymerized, preferably by condensation polymerization and crosslinking to form a siloxane polymer.

The polysiloxanes typically have a relatively low molecular weight in the range of about 500 to 2000 g/mol.

According to a preferred embodiment, subjecting the mixture to at least partial hydrolysis comprises refluxing. Typical reflux time is 2 hours.

After the hydrolysis step, in an optional further process step, the first solvent may be replaced with a second solvent. The optional solvent replacement is advantageous because it helps remove water and alcohol formed during the hydrolysis of the silane monomers. In addition, it improves the properties of the final siloxane polymer solution when used as a coating on a substrate.

The second solvent is preferably selected from the group consisting of propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), 1-ethanol, 2-ethanol (IPA), acrylonitrile diacetone alcohol (DAA) or propylene glycol n-propyl ether (PnP).

The mixture comprising the siloxane polymer may be further subjected to a crosslinking step after the hydrolysis step. Thereby, the siloxane polymer is preferably at least partially crosslinked by hydrosilylation, heat or radiation.

In this context, the term "partially crosslinked" means that the polymer is capable of further crosslinking under conditions that are favorable for crosslinking. In practice, the polymer still contains at least some reactive crosslinking groups after the first polymerization step. Further crosslinking that typically occurs after the partially crosslinked composition is deposited on a substrate will be described below.

The siloxane polymers are preferably at least partially crosslinked by hydrosilylation, heat or radiation using a catalyst as described above.

Thus, thermal crosslinking is preferably performed at a temperature in the range of about 30°C to 200°C.

Typically the crosslinking is carried out under refluxing conditions of the solvent.

In order to improve the resolution of the material when used in photolithography, the siloxane polymer can be partially crosslinked during polymerization, especially during or immediately after condensation polymerization, as appropriate. Various methods can be used to achieve the crosslinking. For example, a crosslinking method can be used in which two chains are joined via reactive groups that do not affect any active groups intended for UV photolithography. For example, hydrosilylation, such as using a proton on one chain to react with a double bond on another chain, will achieve the desired type of crosslinking. Another example is crosslinking via double bonds or epoxy groups.

Different reactive groups are preferred for crosslinking and for photolithography. Thus, crosslinking of siloxane polymers can be achieved using free radical initiators and photoacid generators with reactive groups having double bonds or epoxy groups or both, such as epoxy, vinyl or allyl or methacrylate groups.

Epoxy groups can be used for UV lithography, and vice versa. The proportion of reactive groups required for crosslinking is generally less than that required for UV lithography, for example, about 0.1 to 10 mol % based on monomer for crosslinking and about 5 to 50 mol % based on monomer for UV lithography.

The amount of initiator added to the reaction mixture/solution is generally about 0.1 to 10 wt %, preferably about 0.5 to 5 wt %, based on the total weight of the siloxane polymer.

Due to partial crosslinking, the molecular weight will typically be 2 to 10 times higher. Thus, with a molecular weight in the range of about 500 to 2000 g/mol, crosslinking will increase it to more than 3000 g/mol, preferably to 4000 to 20000 g/mol.

Optionally, the resulting free Si-OH groups present in the backbone of the siloxane polymer can be protected by end-capping. For end-capping, the free Si-OH groups are reacted with silanes such as methyldichlorofluorosilane ( _Cl2FSiCH3 , methylfluorodimethoxysilane ((MeO) _2SiFCH3 ), 3 _- chloropropyltrimethoxysilane (Cl( _CH2 ) _3Si (OMe) ₃ ), ethyltrimethoxysilane (ETMS) or trimethylchlorosilane ( _ClSiMe3 ) in the presence of a catalyst such as triethylaluminum (TEA) or imidazole. The amount of catalyst varies in _the range of 1.5 to 2 wt% of the total solids. The reaction time varies in the range of 40 to 45 min.

Other additives typically incorporated into the first composition comprising the siloxane polymer (B-1) include chemicals that can further modify the final surface properties of the coated and cured film or improve the wetting/adhesion properties of the coating (B) to the substrate layer (A) or other coatings (C) or improve the coating drying and packaging behavior during deposition and drying to achieve good visual quality.

Such additives may be surfactants, defoamers, antifouling agents, wetting agents, etc. Examples of such additives include: BYK-301, BYK-306, BYK-307, BYK-308, BYK-333, BYK-051, BYK-036, BYK-028, BYK-057A, BYK-011, BYK-055, BYK-036, BYK-067A, BYK-088, BYK -302, BYK-310, BYK-322, BYK-323, BYK-33l, BYK-333, BYK-341, BYK-345, BYK-348, BYK-370, BYK-377, BYK-378, BYK-381, BYK-390, BYK-3700, all of the above can be purchased from BYK.

The additive is preferably present in an amount of 0.01 to 5 wt %, more preferably 0.1 to 1 wt %, based on the total weight of the solids.

Before further condensation, excess water is preferably removed from the material, and it is possible at this stage to change the solvent to another synthesis solvent if necessary. This other synthesis solvent may serve as the final processing solvent or one of the final processing solvents for the siloxane polymer. Residual water and alcohol and other by-products may be removed after the further condensation steps are completed. Additional processing solvents may be added during the formulation steps to form the final processing solvent combination. Additives such as thermal initiators, radiation sensitive initiators, sensitizers, surfactants and other additives may be added before the final filtration of the siloxane polymer. After formulating the composition, the polymer is ready to be processed, for example in roll-to-roll film deposition or in a lithography process.

By adjusting the hydrolysis and condensation conditions, the concentration/content of groups capable of deprotonation (e.g., OH-groups) and any residual groups left from the silane precursor of the siloxane polymer composition (e.g., alkoxy groups) can be controlled, and the final molecular weight of the siloxane polymer can also be controlled. This greatly affects the solubility of the siloxane polymer material in aqueous-based developer solutions. In addition, the molecular weight of the polymer also greatly affects the solubility characteristics of the siloxane polymer in the developer solution.

Thus, for example, it has been found that the final siloxane polymer is soluble in an alkaline-water developer solution (e.g., tetramethylammonium hydroxide; TMAH or potassium hydroxide; KOH) when the final siloxane polymer has a high content of residual hydroxyl groups and a low content of alkoxy (e.g., ethoxy) groups.

On the other hand, if the residual alkoxy-group content of the final siloxane polymer is high and it contains almost no OH-groups, the final siloxane polymer has very low solubility in the above-mentioned types of alkaline-water developers. OH-groups or other functional groups, such as amine ( _NH2 ), thiol (SH), carboxyl, phenol or similar functional groups that impart solubility to alkaline developer systems can be directly attached to the silicon atoms of the siloxane polymer backbone or, as the case may be, to organic functional groups attached to the siloxane polymer backbone to further promote and control the alkaline developer solubility.

Following synthesis, the siloxane polymer composition can be diluted using an appropriate solvent or combination of solvents to obtain a solids content that will produce a preselected film thickness during film deposition.

Typically, a further amount of an initiator molecule compound is added to the siloxane composition after synthesis. The initiator may, as the case may be, be similar to the initiator added during the polymerization and is used to produce a substance that can initiate the polymerization of the "active" functional groups in the UV curing step. Thus, in the case of epoxy groups, cationic or anionic initiators can be used. In the case of groups with double bonds as "active" functional groups in the synthetic material, free radical initiators can be employed. Furthermore, thermal initiators (working according to a free radical, cationic or anionic mechanism) can be used to promote the crosslinking of the "active" functional groups. The choice of the appropriate combination of photoinitiators and sensitizers also depends on the exposure source (wavelength) used. Furthermore, the choice of sensitizer used depends on the type of initiator chosen.

The concentration of the thermal or radiation initiator and the sensitizer in the composition is generally about 0.1 to 10%, preferably about 0.5 to 5%, calculated on the mass of the siloxane polymer.

The composition as described above may comprise solid nanoparticles or other compounds in an amount between 1 wt% and 50 wt% of the composition. The nanoparticles (or similar nano- or micro-scale rods, crystals, balls, dots, buds, etc.) are particularly selected from the group of light scattering, light absorbing, light emitting and/or conductive pigments, dyes, organic and inorganic phosphors, oxides, quantum dots, polymers or metals.

Then, a first composition including a siloxane polymer (B-1) is deposited on at least one surface of the substrate to form a first coating layer (B).

Preferably, the first coating layer (B) is in adhesive contact with at least one surface of the substrate.

Suitable deposition methods include spin coating, nip coating, spraying, ink jetting, roll-to-roll, gravure printing, reverse gravure printing, doctor bar coating, slot coating, flexographic printing, curtain coating, screen printing coating, extrusion coating, dip coating, shower coating or slot coating.

The deposited first composition comprising the siloxane polymer (B-1) forms a coating (B) on the surface of the substrate (A). Typically, after deposition or during the deposition step, the solvent is evaporated and the film coating (B) is dried, preferably by thermal drying or, as the case may be, by combined vacuum and/or thermal drying. This step is also called pre-curing.

In a second subsequent step, the coating (B) is cured to a final hardness by thermal curing at elevated temperature or by using UV exposure followed by thermal curing at elevated temperature.

In one specific example, the pre-cure and final cure steps are combined by heating using an increasing heating gradient. In addition to a heat-only curing process, curing can be performed in three steps, the process comprising a thermal pre-cure and a UV cure followed by a final thermal cure. A two-step curing process can also be applied, wherein a thermal pre-cure is followed by a UV cure. In this case, preferably no final thermal cure is applied after the UV cure.

According to a specific embodiment, the method further comprises developing the deposited film. In one embodiment, developing comprises exposing the deposited first siloxane polymer composition (full area or selective exposure using a mask or crosshairs or laser direct imaging) to UV light. The developing step is typically performed after any pre-curing step and before the final curing step.

Thus, in a specific embodiment, the method comprises the following steps: -    pre-curing or drying a first coating layer (B) deposited on a substrate (A); -    exposing the coating layer (B) as appropriate; -    developing the coating layer (B) thus obtained as appropriate; and -    curing the coating layer (B).

Exemplary monomers containing epoxy functional groups include (3-glycidyloxypropyl)trimethoxysilane, 1-(2-(trimethoxysilyl)ethyl)cyclohexane-3,4-epoxide, (3-glycidyloxypropyl)triethoxysilane, (3-glycidyloxypropyl)tripropoxysilane, 3-glycidyloxypropyltri(2-methoxyethoxy)silane, 2,3-epoxypropyltriethyl triethoxysilane, 3,4-epoxybutyltriethoxysilane, 4,5-epoxypentyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 4-(trimethoxysilyl)butane-1,2-epoxide.

Other examples of functionalized compounds are acrylate and methacrylate compounds such as tetraethylene glycol diacrylate, trihydroxymethylpropane triacrylate, pentaerythritol triacrylate, di(trihydroxymethylpropane) tetraacrylate, dipentaerythritol pentaacrylate, tricyclodecane dimethanol diacrylate, tri(2-hydroxyethyl isocyanurate) di/triacrylate and dipentaerythritol hexaacrylate and combinations thereof. Such commercially available acrylates are, for example, Miramer acrylates from Miwon. Such compounds can be used as part of the silane composition.

According to a specific embodiment, the method further comprises curing the first composition comprising the siloxane polymer (B-1).

The thickness of the first coating layer (B) on the substrate (A) (ie, film thickness) may be in the range of 1 to 50 µm, preferably 2 to 20 µm, and more preferably 3 to 10 µm.

The coating layer (B) is preferably a flexible hard coating layer.

Preferably, the hardness of the coating (B) is greater than 3H, greater than 4H, greater than 5H, greater than 6H or even greater than 7H as measured by ASTM D3363-00, Elcometer tester.

Preferably, the adhesion of the coating (B) is 4B-5B as tested by ASTM D3359-09, Crosshatch tester.

In addition, the coating (B) was better in scratch resistance as evidenced by no visual scratches in the Taber Linear Abrasion Test (using a Linear Abrasion Machine from Taber Industries) with BonStar steel wool #0000, 500 g weight, 2×2 cm head size, 2.0 inch stroke length, 60 cycles/minute up to 2000 linear cycles.

Second coating layer (C) A second coating layer applied on at least one surface of the first coating layer (B) such that the second coating layer (C) is in adhesive contact with at least one surface of the first coating layer (B). Therefore, the second coating layer (C) is typically an outer layer of a multi-layer coating layer having adhesive contact with at least one surface of the first coating layer (B), so that the first coating layer (B) is sandwiched between the substrate layer (A) and the second coating layer (C). In this context, "adhesive contact" means that there is no other coating layer or adhesive layer between the first coating layer (B) and at least one surface of the second coating layer (C).

The second coating layer (C) preferably has a thickness of 10 nm to 10 µm, more preferably 25 nm to 8 µm, and more preferably 50 nm to 5 µm.

The second coating layer includes a fluoropolyether compound.

The fluoropolyether compound may be a single fluoropolyether compound or a mixture of two or more, such as 2 to 10, preferably 2 to 4 different fluoropolyether compounds.

The fluoropolyether compound generally has a molecular weight of 150 to 100,000 g/mol, more preferably 250 to 50,000 g/mol, and most preferably 350 to 25,000 g/mol.

In the fluoropolyether compound, not all hydrogen atoms may be replaced by fluorine. If hydrogen atoms are present in the fluoropolyether compound, the molecular ratio of fluorine/hydrogen is preferably at least 5, more preferably at least 10. The fluoropolyether compound may also be a perfluoropolyether compound.

The fluoropolyether group of the fluoropolyether compound may be a linear or branched chain group, preferably a linear chain group.

The repeating units of the fluoropolyether group are preferably _C1 to _C6 fluorinated diols, more preferably _C1 to _C4 fluorinated diols, and most preferably _C1 to _C3 fluorinated diols.

Preferred monomers of the fluoropolyether group are perfluoro-1,2-propylene glycol, perfluoro-1,3-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-methane glycol.

The latter monomer, difluoro-1,1-dihydroxy-methane, can be obtained by oxidation of poly(tetrafluoroethylene).

Preferred structures of the divalent perfluoropolyether group include _-CF2O ( _CF2O ) _m ( _C2F4O ) _pCF2- , wherein the average values of m and p are from 0 to ₁₅₀ , with the proviso that m and _p are not simultaneously zero, -CF( _CF3 )O(CF( _CF3 ) _CF2O ) _pCF ( _CF3 )-, _{-CF2O (C2F4O)pCF2-, and -(CF2)3O(C4F8O)p(CF2)3- , wherein the average value of p is from 3} to 150.

Among them, particularly preferred structures are _-CF2O ( _CF2O ) _m ( _C2F4O ) _pCF2- , _-CF2O ( _C2F4O ) _pCF2- , and -CF( _CF3 )( _OCF2 ( _CF3 )CF _{)pO ( CF2 ) mO (} CF( _CF3 ) _{CF2O ) pCF} ( _CF3 )-.

Preferred structures of the _monovalent perfluoropolyether group include _CF3CF2O (CF2O) _m ( _C2F4O ) _pCF2- , _{CF3CF2O (C2F4O ) pCF2- , CF3CF2CF2O} (CF( _CF3 )CF2O) _pCF ( _CF3 )-, or combinations thereof, wherein the average values of m and p are ₀ to ₁₅₀ and _{m and p} are not independently ₀ .

The fluoropolyether compound may contain functional groups such as carboxyl groups, alkyl ester groups, carboxyl ester groups, epoxy groups, amine groups, silane groups or mixtures thereof.

In one embodiment, the fluoropolyether compound is a fluoropolyether silane, more preferably a fluoropolyether silane (PFS) containing a hydrolyzable group.

The fluoropolyether silane (PFS) containing a hydrolyzable group is preferably selected from a compound according to the following formula (IV): ^R5 - ^RF -Q-Si( ^OR3 ) _oR4p ( _IV ) wherein ^RF is a ^{fluoropolyether} group; Q is a divalent linking group; ^R3 is independently selected from a _C1 to _C10 organic group or an organic heteroatom group; ^R4 is independently selected from a _C1 to _C20 organic group or an organic heteroatom group; o is 1, 2 or 3 p is 0, 1 or 2 o+p is 3 ^R5 is H, _{CxF2x +1} , wherein x is 1 to 10 or -Q-Si( ^OR3 ) _oR4p , ^wherein Q, ^R3 , ^R4 , o and _p are as defined above, wherein Q, ^R3 , ^R4 at each occurrence is , o and p may be the same or different.

^R3 are each independently selected from a _C1 to _C10 organic group or an organic heteroatom group.

If a heteroatom is present in the organic group of R ³ , it is 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.

The heteroatom of the organic heteroatom group of R ³ connected to the oxygen atom bonded to M ¹ is usually different from O.

The heteroatom present in the organic heteroatom group of R ³ is 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 usually does not exceed five, preferably does not exceed three.

Preferably, R ³ is a C ₁ to C ₁₀ organic group containing no more than three heteroatoms, more preferably, R ³ is a C ₁ to C ₁₀ alkyl group, and even more preferably a C ₁ to C ₁₀ linear, branched or cyclic alkyl group.

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

^R4 are each independently selected from a _C1 to _C20 organic group or an organic heteroatom group.

If a heteroatom is present in the organic group of R ⁴ , it is preferably selected from N, O, P, S or Si, more preferably selected from N and O.

The heteroatom of the organic heteroatom group of R ⁴ connected to Si is usually different from O.

The heteroatom present in the organic heteroatom group of R ⁴ is 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 usually does not exceed eight, preferably does not exceed five, and most preferably does not exceed three.

Preferably, R ⁴ is a C ₁ to C ₂₀ organic group containing no more than three heteroatoms, more preferably, R ⁴ is a C ₁ to C ₂₀ alkyl group, and even more preferably, a C ₁ to C ₂₀ linear, branched or cyclic alkyl group.

Preferably, the total number of carbon atoms present in R ⁴ according to any of the above variations is 1 to 15, more preferably 1 to 10, and most preferably 1 to 6.

o 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 fluoropolyether group ^RF typically 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 ^RF , not all hydrogen atoms may be replaced by fluorine. If hydrogen atoms are present in the fluoropolyether group ^RF , the molecular ratio of fluorine/hydrogen is preferably at least 5, more preferably at least 10. More preferably, the fluoropolyether group ^RF is a perfluoropolyether group.

The fluoropolyether group ^RF can be a linear or branched chain group, preferably a linear chain group.

The repeating units of the fluoropolyether group ^RF are preferably _C1 to _C6 fluorinated diols, more preferably _C1 to _C4 fluorinated diols, and most preferably _C1 to _C3 fluorinated diols.

Preferred monomers of the fluoropolyether group ^RF are perfluoro-1,2-propylene glycol, perfluoro-1,3-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-methane glycol.

The latter monomer, difluoro-1,1-dihydroxy-methane, can be obtained by oxidation of poly(tetrafluoroethylene).

Preferred structures of the divalent perfluoropolyether group include _-CF2O ( _CF2O ) _m ( _C2F4O ) _pCF2- , wherein the average values of m and p are from 0 to ₅₀ , with the proviso that m and _p are not simultaneously zero, -CF( _CF3 )O(CF( _CF3 ) _CF2O ) _pCF ( _CF3 )-, _{-CF2O (C2F4O)pCF2-, and -(CF2)3O(C4F8O)p(CF2)3- , wherein the average value of p is from 3} to 50.

Among them, particularly preferred structures are _-CF2O ( _CF2O ) _m ( _C2F4O ) _pCF2- , _-CF2O ( _C2F4O ) _pCF2- , and -CF( _CF3 )( _OCF2 ( _CF3 )CF _{)pO ( CF2 ) mO (} CF( _CF3 ) _{CF2O ) pCF} ( _CF3 )-.

Preferred structures of the _monovalent perfluoropolyether group include _CF3CF2O (CF2O) _m ( _C2F4O ) _pCF2- , _{CF3CF2O (C2F4O ) pCF2- , CF3CF2CF2O} (CF( _CF3 )CF2O) _pCF ( _CF3 )-, or combinations thereof, wherein the average values of m and p are ₀ to 50 and _{m and p} are not _{independently 0} .

Particularly preferred is a fluoropolyether group ^RF selected from _-CF2O- [ _C2F4O ] _m- [ _CF2O ] _n- , wherein ₁ < n _{< 8 and 3 < m < 10 R-[C3F6O ] n-} , wherein n = 2 to 10 and R is a linear or branched chain, preferably a linear perfluoro _C2 or _C3 alcohol, preferably a _C3 alcohol;

The divalent linking group Q connects the perfluoropolyether to the silicon-containing group.

Q usually has a molecular weight of no more than 500 g/mol, more preferably no more than 250 g/mol and most preferably no more than 150 g/mol. Examples of divalent linking groups are amide groups and alkylene groups.

Fluoropolyether compounds are commercially available without public knowledge of their precise chemical structures.

Suitable commercially available fluoropolyether compounds are, for example, Fluorolink S10 (CAS No. 223557-70-8, Solvay), Optool ^™ DSX (Daikin Industries), Shin-Etsu Subelyn ^™ KY-1900 and KY-1901 (Shin-Etsu Chemical), Dow ^Corning® 2634 (CAS No. 870998-78-0) and SC-011 and SC-019 (Shin-Etsu Chemical).

In the first specific example, the second coating layer (C) preferably further comprises one or more, such as one, two, three or four, preferably one to three, more preferably one or two, and most preferably two second siloxane polymers (C-1). In the case where the second coating layer (C) comprises more than one second siloxane polymer (C-1), the siloxane polymers differ in at least one property. The at least one property may be, for example, a difference in silane monomers and/or a difference in molecular weight.

The following discussion can be applied to each of the second siloxane polymer (C-1):

The second siloxane polymer (C-1) preferably comprises monomer units selected from one or more silane monomers.

Thus, at least one of the silane monomers may include a reactive group capable of achieving cross-linking to adjacent siloxane polymer chains.

Adjacent siloxane polymer chains are then usually cross-linked via these reactive groups.

The second siloxane polymer (C-1) may comprise monomer units selected from 1 to 10, such as 1 to 6, preferably 1 to 4, more preferably 1 or 2 different silane monomers. "Different" in this context means that the silane monomers differ in at least one chemical moiety.

Preferred reactive groups, if present, are epoxide, alicyclic epoxide (e.g., glycidyl), vinyl, allyl, acrylate, methacrylate, and silane, and combinations thereof.

Thus, epoxy, alicyclic epoxy (e.g., glycidyl), vinyl, allyl, acrylate, methacrylate groups are capable of crosslinking with adjacent siloxane polymer chains when initiated thermally or by radiation, preferably in the presence of a suitable initiator (e.g., a thermal or free radical initiator).

Suitable thermal or free radical initiators are preferably selected from triamyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile), benzoyl peroxide, 2,2-bis(tertiary butylperoxy)butane, 1,1-bis(tertiary butylperoxy)cyclohexane, 2,2'-azobisisobutyronitrile (AIBN), 2,5-bis(tertiary butylperoxy)-Z,S-dimethylhexane, 2,5-bis(tertiary butylperoxy)-2,5- Dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, isopropyl hydroperoxide, cyclohexanone peroxide, diisopropyl peroxide, lauryl peroxide, 2,4-pentanedione peroxide, peracetic acid or potassium persulfate. Particularly preferred is 2,2'-azobisisobutyronitrile (AIBN).

Silane groups are capable of crosslinking with carbon-carbon double bonds (such as _{vinyl or} allyl) of adjacent siloxane polymer chains during hydrosilylation, preferably in the presence of a suitable catalyst (such as platinum (Pt)-based catalysts, such as Speier's catalyst ( _H2PtCl6.H2O ), Karstedt's catalyst (Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution) or rhodium (Rh)-based catalysts, such as tris(triphenylphosphine)rhodium(I) chloride).

In a specific example, the molar ratio between the monomer containing the first reactive group, e.g., selected from epoxy, alicyclic epoxy (e.g., glycidyl), vinyl and allyl, and the monomer containing the second reactive group, e.g., selected from acrylate and methacrylate, ranges from 1:100 to 100:1, specifically 1:10 to 10:1, e.g., 5:1 to 1:2 or 3:1 to 1:1.

In some specific examples, the component containing the second reactive group is also selected from compounds containing acrylates and methacrylates other than silane monomers, such as tetraethylene glycol diacrylate, trihydroxymethylpropane triacrylate, pentaerythritol triacrylate, ditrimethylpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and combinations thereof.

In some embodiments, the reactive group or groups will be present at a concentration of about 1 to about 35% based on the molar fraction of the monomer.

Suitable silane monomers are preferably represented by formula (I): R ¹ _a SiX _4-a (I) wherein R ¹ is selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxide, allyl, vinyl and alkoxy, and an aromatic group having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X is a hydrolyzable group or a hydrocarbon residue; and a is an integer of 1 to 3.

The hydrolyzable group is especially an alkoxy group (see formula II).

^R1 and/or the alkoxy group of the hydrolyzable group X may be the same or different and are preferably selected from the group ^-OR2 (II) having the following formula: wherein ^R2 represents a linear or branched alkyl group having 1 to 10, preferably 1 to 6 carbon atoms and optionally presents one or two substituents selected from the group consisting of halogen, hydroxyl, vinyl, epoxy and allyl. The most preferred are methoxy and ethoxy.

Particularly preferred are di-, tri- or tetraalkoxysilanes containing alkoxy groups according to formula (II).

Particularly suitable silane monomers are selected from the group consisting of tetraethoxysilane (TEOS), tetramethoxysilane (TMS), methyltriethoxysilane (MTEOS), methyltrimethoxysilane (MTMS), dimethyldiethoxysilane (DMDEOS), dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPDMS), 3-(trimethoxysilyl)propylmethacrylate (MEMO), 3-(triethoxysilyl)propylmethacrylate Ester, 5-(bicycloheptenyl)triethoxysilane (BCHTEOS), (3-glycidyloxypropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane (GPTMS), (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane (F17), 1H,1H,2H,2H-perfluorododecyltriethoxysilane, 1H,1H,2H,2H-perfluoro Dodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, 1H,1H,2H,2H-perfluoropentyltriethoxysilane, 1H,1H,2H,2H-perfluoropentyltrimethoxysilane, 1H,1H,2H,2H-perfluorotetradecyltriethoxysilane, 1H,1H,2H,2H-perfluorotetradecyltrimethoxysilane, allyltrimethoxysilane (all ylTMS), allyl triethoxysilane (allylTEOS), vinyl trimethoxysilane, vinyl triethoxysilane, (3-glycidyloxypropyl) dimethoxymethyl silane (Me-GPTMS), methacryloxypropyl methyl dimethoxy silane (Me-MEMO), phenyl methyl dimethoxy silane (PMDMS), bis [(2,2,3,3,4,4-hexafluorobutyl) propionate] -3-aminopropyl trimethoxy silane or a mixture thereof.

The silane monomer is preferably selected from the group consisting of tetraethoxysilane (TEOS) and methyltrimethoxysilane (MTMS).

The silane monomers are preferably present in the siloxane polymer in a molar amount of 50 to 100 mol %, preferably 50 to 99 mol %, and more preferably 65 to 97 mol %.

In one embodiment, the at least two different silane monomers of the first siloxane polymer (B-1) include at least one bissilane.

Suitable bissilanes are preferably represented by the formula (III): (R ³ ) ₃ Si—Y—Si(R ⁴ ) ₃ , (III) wherein R ³ and R ⁴ are independently selected from hydrogen and a group consisting of a linear or branched alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an (alkyl)acrylate group, an epoxide group, an allyl group, a vinyl group, an alkoxy group and an aryl group having 1 to 6 rings, and wherein the group is substituted or unsubstituted; and Y is a linking group selected from divalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, —O-alkylene-O—; —O-arylene-O—; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z ¹ C(═O)Z ² -alkylene, arylene-Z ¹ C(═O)Z ² -arylene and -O-alkylene-Z ¹ C(═O)Z ² -phenylene-O—; -O-arylene-Z ¹ C(═O)Z ² -arylene-O—, wherein Z ¹ and Z ² are independently selected from a direct bond or —O—.

In divalent "alkylene" groups and other similar aliphatic groups, the alkyl residue (or the residue derived from the alkyl part) represents 1 to 10, preferably 1 to 8, or 1 to 6 or even 1 to 4 carbon atoms, examples include ethylene and methylene and propylene.

"Arylene" represents an aromatic divalent radical typically containing 1 to 3 aromatic rings and 6 to 18 carbon atoms. Such radicals are exemplified by phenylene (e.g., 1,4-phenylene and 1,3-phenylene) and biphenylene as well as naphthylene or anthracenylene.

The alkylene group and the arylene group may be substituted with 1 to 5 substituents selected from the group consisting of a hydroxyl group, a halogen group, a vinyl group, an epoxy group and an allyl group as well as an alkyl group, an aryl group and an aralkyl group, as the case may be.

Preferred alkoxy groups contain 1 to 4 carbon atoms. Examples are methoxy and ethoxy.

The term "phenyl" includes substituted phenyl groups, such as phenyltrialkoxy groups, especially phenyltrimethoxy or triethoxy groups, and perfluorophenyl groups. The phenyl group and other aromatic or alicyclic groups can be coupled directly to the silicon atom, or they can be coupled to the silicon atom via a methylene or ethylene bridge.

Exemplary bissilanes include 1,2-bis(triethoxysilyl)ethane (BTESE), 1,2-bis(trimethoxysilyl)ethane (MEOS), and mixtures thereof.

Preferably, the bissilane is present in the siloxane polymer in a molar amount of 0 to 50 mol %, preferably 1 to 50 mol %, and more preferably 3 to 35 mol %.

Particularly preferably, at least one silane monomer is selected from the group consisting of tetraethoxysilane (TEOS) and methyltrimethoxysilane (MTMS).

The second composition comprising at least one second siloxane polymer (C-1) is preferably formed by a method comprising the following steps: ●   Mixing at least two different silane monomers, preferably as described above or below, in a first solvent to form a mixture; ●   Subjecting the mixture to at least partial hydrolysis of the monomers in the presence of a catalyst, thereby causing the hydrolyzed monomers to at least partially polymerize and crosslink; ●   Optionally replacing the first solvent with a second solvent; ●   Optionally crosslinking the mixture by hydrosilylation, heat or radiation initiation.

In case the second composition comprises more than one second siloxane polymer (C-1), the above steps are repeated for each of the second siloxane polymers (C-1).

The first solvent is preferably selected from the group consisting of acetone, tetrahydrofuran (THF), toluene, 1-propanol, 2-propanol, methanol, ethanol, water ( _H2O ), cyclopentanone, acetonitrile, propylene glycol propyl ether, methyl tertiary butyl ether (MTBE), propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether (PGME) and propylene glycol propyl ether (PnP).

At least two different silane monomers may be mixed in a first solvent at any suitable temperature to dissolve the silane monomers. Typically, room temperature is sufficient.

In the next process step, the mixture undergoes at least partial hydrolysis in the presence of a catalyst.

Suitable catalysts are acidic catalysts, alkaline catalysts or other catalysts.

The acidic catalyst is preferably selected from nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), formic acid (HCOOH), hydrochloric acid (HCl), sulfonic acid, hydrogen fluoride (HF), acetic acid (CH ₃ COOH), trifluoromethanesulfonic acid or p-toluenesulfonic acid. Particularly preferred acidic catalysts are nitric acid (HNO ₃ ), formic acid (HCOOH) and hydrochloric acid (HCl).

The alkaline catalyst is preferably selected from triethylamine (TEA), ammonium hydroxide (NH ₄ OH), tetraethylammonium hydroxide (TEAH), tetramethylammonium hydroxide (TMEA), 1,4-diazabicyclo[2.2.2]octane, imidazole and diethylenetriamine.

Other catalysts are preferably selected from 2,2,3,3,4,4,5,5-octafluoropentyl acrylate, poly(ethylene glycol) 200, poly(ethylene glycol) 300 and n-butyl melamine formaldehyde resin.

The hydrolysis step is preferably carried out at a temperature of 20 to 80°C for 1 to 24 hours, such as overnight at room temperature.

During the hydrolysis step, the silane monomers are at least partially hydrolyzed. The at least partially hydrolyzed silane monomers are then at least partially polymerized, preferably by condensation polymerization and crosslinking to form a siloxane polymer.

The polysiloxanes typically have a relatively low molecular weight in the range of about 500 to 2000 g/mol.

According to a preferred embodiment, subjecting the mixture to at least partial hydrolysis comprises refluxing. Typical reflux time is 2 hours.

After the hydrolysis step, in an optional further process step, the first solvent may be replaced with a second solvent. The optional solvent replacement is advantageous because it helps remove water and alcohol formed during the hydrolysis of the silane monomers. In addition, it improves the properties of the final siloxane polymer solution when used as a coating on a substrate.

The second solvent is preferably selected from the group consisting of propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), 1-ethanol, 2-ethanol (IPA), acrylonitrile diacetone alcohol (DAA) or propylene glycol n-propyl ether (PnP).

The mixture comprising the siloxane polymer may be further subjected to a crosslinking step after the hydrolysis step. Thereby, the siloxane polymer is preferably at least partially crosslinked by hydrosilylation, heat or radiation.

In this context, the term "partially crosslinked" means that the polymer is capable of further crosslinking under conditions that are favorable for crosslinking. In practice, the polymer still contains at least some reactive crosslinking groups after the first polymerization step. Further crosslinking that typically occurs after the partially crosslinked composition is deposited on a substrate will be described below.

The siloxane polymers are preferably at least partially crosslinked by hydrosilylation, heat or radiation using a catalyst as described above.

Thus, thermal crosslinking is preferably performed at a temperature in the range of about 30°C to 200°C.

Typically the crosslinking is carried out under refluxing conditions of the solvent.

In order to improve the resolution of the material when used in photolithography, the siloxane polymer can be partially crosslinked during polymerization, especially during or immediately after condensation polymerization, as appropriate. Various methods can be used to achieve the crosslinking. For example, a crosslinking method can be used in which two chains are joined via reactive groups that do not affect any active groups intended for UV photolithography. For example, hydrosilylation, such as using a proton on one chain to react with a double bond on another chain, will achieve the desired type of crosslinking. Another example is crosslinking via double bonds or epoxy groups.

Different reactive groups are preferred for crosslinking and for photolithography. Thus, crosslinking of siloxane polymers can be achieved using free radical initiators and photoacid generators with reactive groups having double bonds or epoxy groups or both, such as epoxy, vinyl or allyl or methacrylate groups.

Epoxy groups can be used for UV lithography, and vice versa. The proportion of reactive groups required for crosslinking is generally less than that required for UV lithography, for example, about 0.1 to 10 mol % based on monomer for crosslinking and about 5 to 50 mol % based on monomer for UV lithography.

The amount of initiator added to the reaction mixture/solution is generally about 0.1 to 10 wt %, preferably about 0.5 to 5 wt %, based on the total weight of the siloxane polymer.

Due to partial crosslinking, the molecular weight will typically be 2 to 10 times higher. Thus, with a molecular weight in the range of about 500 to 2000 g/mol, crosslinking will increase it to more than 3000 g/mol, preferably to 4000 to 20000 g/mol.

Optionally, the resulting free Si-OH groups present in the backbone of the siloxane polymer can be protected by end-capping. For end-capping, the free Si-OH groups are reacted with silanes such as methyldichlorofluorosilane ( _Cl2FSiCH3 , methylfluorodimethoxysilane ((MeO) _2SiFCH3 ), 3 _- chloropropyltrimethoxysilane (Cl( _CH2 ) _3Si (OMe) ₃ ), ethyltrimethoxysilane (ETMS) or trimethylchlorosilane ( _ClSiMe3 ) in the presence of a catalyst such as triethylaluminum (TEA) or imidazole. The amount of catalyst varies in _the range of 1.5 to 2 wt% of the total solids. The reaction time varies in the range of 40 to 45 min.

Other additives typically introduced into the second composition comprising the fluoropolyether compound and at least one second siloxane polymer (C-1) include chemicals that can further modify the final surface properties of the coated and cured film or improve the wetting/adhesion properties of the coating (B) to the substrate layer (A) or other coatings (C) or improve the coating drying and packaging behavior during deposition and drying to achieve good visual quality.

Such additives may be surfactants, defoamers, antifouling agents, wetting agents, etc. Examples of such additives include: BYK-301, BYK-306, BYK-307, BYK-308, BYK-333, BYK-051, BYK-036, BYK-028, BYK-057A, BYK-011, BYK-055, BYK-036, BYK-067A, BYK-08 8. BYK-302, BYK-310, BYK-322, BYK-323, BYK-33l, BYK-333, BYK-341, BYK-345, BYK-348, BYK-370, BYK-377, BYK-378, BYK-381, BYK-390, BYK-3700.

The additive is preferably present in an amount of 0.01 to 5 wt %, more preferably 0.1 to 1 wt %, based on the total weight of the solids.

Before further condensation, excess water is preferably removed from the material, and it is possible at this stage to change the solvent to another synthesis solvent if necessary. This other synthesis solvent may serve as the final processing solvent or one of the final processing solvents for the siloxane polymer. Residual water and alcohol and other by-products may be removed after the further condensation steps are completed. Additional processing solvents may be added during the formulation steps to form the final processing solvent combination. Additives such as thermal initiators, radiation sensitive initiators, sensitizers, surfactants and other additives may be added before the final filtration of the siloxane polymer. After formulating the composition, the polymer is ready to be processed, for example in roll-to-roll film deposition or in a lithography process.

By adjusting the hydrolysis and condensation conditions, the concentration/content of groups capable of deprotonation (e.g., OH-groups) and any residual groups left from the silane precursor of the siloxane polymer composition (e.g., alkoxy groups) can be controlled, and the final molecular weight of the siloxane polymer can also be controlled. This greatly affects the solubility of the siloxane polymer material in aqueous-based developer solutions. In addition, the molecular weight of the polymer also greatly affects the solubility characteristics of the siloxane polymer in the developer solution.

Thus, for example, it has been found that the final siloxane polymer is soluble in an alkaline-water developer solution (e.g., tetramethylammonium hydroxide; TMAH or potassium hydroxide; KOH) when the final siloxane polymer has a high content of residual hydroxyl groups and a low content of alkoxy (e.g., ethoxy) groups.

On the other hand, if the residual alkoxy-group content of the final siloxane polymer is high and it contains almost no OH-groups, the final siloxane polymer has very low solubility in the above-mentioned types of alkaline-water developers. OH-groups or other functional groups, such as amine ( _NH2 ), thiol (SH), carboxyl, phenol or similar functional groups that impart solubility to alkaline developer systems can be directly attached to the silicon atoms of the siloxane polymer backbone or, as the case may be, to organic functional groups attached to the siloxane polymer backbone to further promote and control the alkaline developer solubility.

As mentioned above, the method of preparing the second siloxane polymer (C-1) is repeated for each of the second siloxane polymers (C-1).

The second siloxane polymer (C-1) can be diluted using an appropriate solvent or combination of solvents to obtain a solids content that will produce a preselected film thickness during film deposition.

The solvent or solvent combination preferably comprises a fluorinated solvent, such as methoxy-nonafluorobutane or 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether.

Typically, a further amount of an initiator molecule compound is added to the siloxane composition after synthesis. The initiator may, as the case may be, be similar to the initiator added during the polymerization and is used to produce a substance that can initiate the polymerization of the "active" functional groups in the UV curing step. Thus, in the case of epoxy groups, cationic or anionic initiators can be used. In the case of groups with double bonds as "active" functional groups in the synthetic material, free radical initiators can be employed. Furthermore, thermal initiators (working according to a free radical, cationic or anionic mechanism) can be used to promote the crosslinking of the "active" functional groups. The choice of the appropriate combination of photoinitiators and sensitizers also depends on the exposure source (wavelength) used. Furthermore, the choice of sensitizer used depends on the type of initiator chosen.

The concentration of the thermal or radiation initiator and the sensitizer in the composition is generally about 0.1 to 10%, preferably about 0.5 to 5%, calculated on the mass of the siloxane polymer.

In a second embodiment, the second composition does not include one or more second siloxane polymers (C-1). In the second embodiment, the fluoropolyether compound is preferably dissolved in a solvent to form the second composition.

In this embodiment, the fluoropolyether compound is preferably a fluoropolyether silane (PFS) containing a hydrolyzable group.

The solvent preferably comprises, more preferably is a fluorinated solvent, such as methoxy-nonafluorobutane or 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, preferably 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether.

In this embodiment, the second component preferably consists of a fluoropolyether compound and a solvent.

The following procedure applies to all specific instances of the second coating (C):

A second composition comprising a fluoropolyether compound is deposited on at least one surface of the substrate to form a second coating layer (C) that is in adhesive contact with at least one surface of the first coating layer (B).

Suitable deposition methods include spin coating, nip coating, spraying, ink jetting, roll-to-roll, gravure printing, reverse gravure printing, doctor bar coating, slot coating, flexographic printing, curtain coating, screen printing coating, extrusion coating, dip coating, shower coating or slot coating.

The deposited second composition comprising a fluoropolyether compound forms a second coating layer (C) on the surface of the first coating layer (B). Typically, after deposition or during the deposition step, the solvent is evaporated and the second coating layer (C) is dried, preferably by thermal drying or, as the case may be, by combined vacuum and/or thermal drying. This step is also called pre-curing.

In a second subsequent step, the second coating layer (C) is cured to a final hardness by thermal curing at elevated temperature or by using UV exposure followed by thermal curing at elevated temperature.

In one specific example, the pre-cure and final cure steps are combined by heating using an increasing heating gradient. In addition to a heat-only curing process, curing can be performed in three steps, the process comprising a thermal pre-cure and a UV cure followed by a final thermal cure. A two-step curing process can also be applied, wherein a thermal pre-cure is followed by a UV cure. In this case, preferably no final thermal cure is applied after the UV cure.

According to a specific embodiment, the method further comprises developing the deposited film. In one embodiment, developing comprises exposing the deposited first siloxane polymer composition (full area or selective exposure using a mask or crosshairs or laser direct imaging) to UV light. The developing step is typically performed after any pre-curing step and before the final curing step.

Therefore, in a specific example, the method comprises the following steps: -    pre-curing or drying the second coating layer (C) deposited on the first coating layer (A); -    exposing the second coating layer (C) obtained thereby as appropriate; -    developing the second coating layer (C) obtained thereby as appropriate; and -    curing the second coating layer (C).

Exemplary monomers containing epoxy functional groups include (3-glycidyloxypropyl)trimethoxysilane, 1-(2-(trimethoxysilyl)ethyl)cyclohexane-3,4-epoxide, (3-glycidyloxypropyl)triethoxysilane, (3-glycidyloxypropyl)tripropoxysilane, 3-glycidyloxypropyltri(2-methoxyethoxy)silane, 2,3-epoxypropyltriethyl triethoxysilane, 3,4-epoxybutyltriethoxysilane, 4,5-epoxypentyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 4-(trimethoxysilyl)butane-1,2-epoxide.

Other examples of functionalized compounds are acrylate and methacrylate compounds such as tetraethylene glycol diacrylate, trihydroxymethylpropane triacrylate, pentaerythritol triacrylate, di(trihydroxymethylpropane) tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate and combinations thereof. Such compounds can be used as part of the silane composition.

According to a specific embodiment, the method further comprises curing the second composition comprising the fluoropolyether compound.

The thickness (ie, film thickness) of the second coating layer (C) on the first coating layer (B) may be in the range of 10 nm to 10 µm, preferably 25 nm to 8 µm, and more preferably 50 nm to 5 µm.

The second coating layer (C) is preferably an anti-reflection layer.

Preferably, the refractive index of the second coating layer (C) is not greater than 1.30, such as in the range of 1.26 to 1.30.

Optionally optional third coating layer (D) In some specific examples, the layered structure may include an additional third coating layer (D) coated on at least one surface of the second coating layer (C), so that the third coating layer (D) is in adhesive contact with at least one surface of the second coating layer (C). In this regard, "adhesive contact" means that there is no other coating layer or adhesive layer between the third substrate layer (D) and at least one surface of the second coating layer (C).

The third coating layer (D) preferably has a thickness of 10 nm to 10 µm, more preferably 15 nm to 8 µm, and more preferably 20 nm to 5 µm.

Preferably, the third coating layer (D) comprises a silicone polymer and, if appropriate, a fluoropolyether compound.

In one specific example, the third coating (D) is preferably an easy-to-clean coating comprising a siloxane polymer as described in WO 2016/146895 or WO 2020/099290. The disclosures of both documents are hereby incorporated by reference in their entirety.

In another embodiment, the third coating layer (D) comprises a third siloxane polymer (D-1) comprising side chains comprising one or more fluorinated carbon groups.

The third siloxane polymer (D-1) comprises monomer units selected from at least one silane monomer.

The third siloxane polymer (D-1) may comprise monomer units selected from 1 to 10, such as 1 to 6, preferably 1 to 4 different silane monomers. "Different" in this context means that the silane monomers differ in at least one chemical moiety.

In one embodiment, at least one of the silane monomers includes a reactive group capable of achieving crosslinking with adjacent siloxane polymer chains, and wherein the adjacent siloxane polymer chains are crosslinked via the reactive group.

The reactive group is preferably an epoxy group, an alicyclic epoxy group (such as a glycidyl group), a vinyl group, an allyl group, an acrylate group, a methacrylate group, a silyl group, and a combination thereof.

Thus, epoxy, alicyclic epoxy (e.g., glycidyl), vinyl, allyl, acrylate, methacrylate groups are capable of crosslinking with adjacent siloxane polymer chains when initiated thermally or by radiation, preferably in the presence of a suitable initiator (e.g., a thermal or free radical initiator).

Suitable thermal or free radical initiators are preferably selected from triamyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile), benzoyl peroxide, 2,2-bis(tertiary butylperoxy)butane, 1,1-bis(tertiary butylperoxy)cyclohexane, 2,2'-azobisisobutyronitrile (AIBN), 2,5-bis(tertiary butylperoxy)-Z,S-dimethylhexane, 2,5-bis(tertiary butylperoxy)-2,5- Dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, isopropyl hydroperoxide, cyclohexanone peroxide, diisopropyl peroxide, lauryl peroxide, 2,4-pentanedione peroxide, peracetic acid or potassium persulfate. Particularly preferred is 2,2'-azobisisobutyronitrile (AIBN).

Silane groups are capable of crosslinking with carbon-carbon double bonds (such as _{vinyl or} allyl) of adjacent siloxane polymer chains during hydrosilylation, preferably in the presence of a suitable catalyst (such as platinum (Pt)-based catalysts, such as Speier's catalyst ( _H2PtCl6.H2O ), Karstedt's catalyst (Pt(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution) or rhodium (Rh)-based catalysts, such as tris(triphenylphosphine)rhodium(I) chloride).

In a specific example, the molar ratio between the monomer containing the first reactive group, e.g., selected from epoxy, alicyclic epoxy (e.g., glycidyl), vinyl and allyl, and the monomer containing the second reactive group, e.g., selected from acrylate and methacrylate, ranges from 1:100 to 100:1, specifically 1:10 to 10:1, e.g., 5:1 to 1:2 or 3:1 to 1:1.

In some specific examples, the component containing the second reactive group is also selected from compounds containing acrylates and methacrylates other than silane monomers, such as tetraethylene glycol diacrylate, trihydroxymethylpropane triacrylate, pentaerythritol triacrylate, ditrimethylpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and combinations thereof.

In some embodiments, the reactive group or groups will be present at a concentration of about 1 to about 35% based on the molar fraction of the monomer.

Suitable silane monomers are preferably represented by formula (I): R ¹ _a SiX _4-a （I） wherein R ¹ is selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxide, allyl, vinyl and alkoxy, and an aromatic group having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X is a hydrolyzable group or a hydrocarbon residue; and a is an integer of 1 to 3.

The hydrolyzable group is especially an alkoxy group (see formula II).

^R1 and/or the alkoxy group of the hydrolyzable group X may be the same or different and are preferably selected from the group having the following formula ^-OR2 (II) wherein ^R2 represents a linear or branched alkyl group having 1 to 10, preferably 1 to 6 carbon atoms and optionally presents one or two substituents selected from the group consisting of halogen, hydroxyl, vinyl, epoxy and allyl. The most preferred are methoxy and ethoxy.

Particularly preferred are di-, tri- or tetraalkoxysilanes containing alkoxy groups according to formula (II).

Particularly suitable silane monomers are selected from the group consisting of tetraethoxysilane (TEOS), tetramethoxysilane (TMS), methyltriethoxysilane (MTEOS), methyltrimethoxysilane (MTMS), dimethyldiethoxysilane (DMDEOS), dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPDMS), 3-(trimethoxysilyl)propyl methacrylate (MEMO), 3-(triethoxysilyl)propyl methacrylate, 5-(bicycloheptenyl)triethoxysilane (BCHTEOS), (3-glycidyloxypropyl)triethoxysilane , (3-glycidyloxypropyl)trimethoxysilane (GPTMS), allyltrimethoxysilane (allylTMS), allyltriethoxysilane (allylTEOS), vinyltrimethoxysilane (VTMS), vinyltriethoxysilane, (3-glycidyloxypropyl)dimethoxymethylsilane (Me-GPTMS), methacryloxypropylmethyldimethoxysilane (Me-MEMO), phenylmethyldimethoxysilane (PMDMS), bis[(2,2,3,3,4,4-hexafluorobutyl)propionate]-3-aminopropyltrimethoxysilane or a mixture thereof.

The silane monomer is preferably selected from the group consisting of tetraethoxysilane (TEOS), phenylmethyldimethoxysilane (PMDMS), 3-(trimethoxysilyl)propylmethacrylate (MEMO), methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (VTMS) and (3-glycidyloxypropyl)trimethoxysilane (GPTMS).

The silane monomers are preferably present in the siloxane polymer in a molar amount of 50 to 100 mol %, preferably 50 to 99 mol %, and more preferably 65 to 97 mol %.

In one embodiment, the at least one different silane monomer of the third siloxane polymer (D-1) comprises at least one bissilane.

Suitable bissilanes are preferably represented by the formula (III): (R ³ ) ₃ Si-Y-Si(R ⁴ ) ₃ , (III) wherein R ³ and R ⁴ are independently selected from hydrogen and a group consisting of a linear or branched alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an (alkyl)acrylate group, an epoxide group, an allyl group, a vinyl group, an alkoxy group and an aryl group having 1 to 6 rings, and wherein the group is substituted or unsubstituted; and Y is a linking group selected from divalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, -O-alkylene-O-; -O-arylene-O-; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z ¹ C(═O)Z ² -alkylene, arylene-Z ¹ C(=O)Z ² -arylene and -O-alkylene-Z ¹ C(=O)Z ² -phenylene-O-; -O-arylene-Z ¹ C(=O)Z ² -arylene-O-, wherein Z ¹ and Z ² are independently selected from a direct bond or -O-.

In divalent "alkylene" groups and other similar aliphatic groups, the alkyl residue (or the residue derived from the alkyl part) represents 1 to 10, preferably 1 to 8, or 1 to 6 or even 1 to 4 carbon atoms, examples include ethylene and methylene and propylene.

"Arylene" represents an aromatic divalent radical typically containing 1 to 3 aromatic rings and 6 to 18 carbon atoms. Such radicals are exemplified by phenylene (e.g., 1,4-phenylene and 1,3-phenylene) and biphenylene as well as naphthylene or anthracenylene.

The alkylene group and the arylene group may be substituted with 1 to 5 substituents selected from the group consisting of a hydroxyl group, a halogen group, a vinyl group, an epoxy group and an allyl group as well as an alkyl group, an aryl group and an aralkyl group, as the case may be.

Preferred alkoxy groups contain 1 to 4 carbon atoms. Examples are methoxy and ethoxy.

The term "phenyl" includes substituted phenyl groups, such as phenyltrialkoxy groups, especially phenyltrimethoxy or triethoxy groups, and perfluorophenyl groups. The phenyl group and other aromatic or alicyclic groups can be coupled directly to the silicon atom, or they can be coupled to the silicon atom via a methylene or ethylene bridge.

Exemplary bissilanes include 1,2-bis(triethoxysilyl)ethane (BTESE), 1,2-bis(trimethoxysilyl)ethane (MEOS), and mixtures thereof.

Preferably, the bissilane is present in the siloxane polymer in a molar amount of 0 to 45 mol %, preferably 1 to 45 mol %, and more preferably 3 to 30 mol %.

In addition, the third siloxane polymer (D-1) comprises at least one, for example 1 to 10, preferably 1 to 6, more preferably 1 or 2, and most preferably one fluorinated monomer capable of forming a side chain comprising one or more fluorinated carbon groups.

Such fluorinated monomers may be fluorinated silane monomers, which are preferably represented by formula (I): R ¹ _a SiX _4-a (I) wherein R ¹ is a group selected from the group consisting of linear and branched alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, (alkyl)acrylates, epoxide groups, allyl groups, vinyl groups and alkoxy groups and aryl groups having 1 to 6 rings, preferably linear or branched alkyl groups, and wherein the group is substituted with one or more fluorine atoms; X is a hydrolyzable group or a hydrocarbon residue; and a is an integer from 1 to 3.

The hydrolyzable group is especially an alkoxy group (see formula II).

Examples of such silane monomers are (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane (F17), 1H,1H,2H,2H-perfluorododecyltriethoxysilane, 1H,1H,2H,2H-perfluorododecyltrimethoxysilane, 1H,1H,2H,2H- Perfluorooctyltriethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, 1H,1H,2H,2H-perfluoropentyltriethoxysilane, 1H,1H,2H,2H-perfluoropentyltrimethoxysilane, 1H,1H,2H,2H-perfluorotetradecyltriethoxysilane or 1H,1H,2H,2H-perfluorotetradecyltrimethoxysilane.

The fluorinated monomer may also be a monomer containing a fluorinated polymer group. The monomer containing a fluorinated polymer group is preferably selected from fluorinated polysiloxane and modified perfluoropolyether.

The modified perfluoropolyether is preferably selected from silane-modified perfluoropolyether, carboxyl ester-modified perfluoropolyether, such as acrylate-modified perfluoropolyether and methacrylate-modified perfluoropolyether, epoxy-based perfluoropolyether and mixtures thereof.

Such fluorinated polysiloxanes and modified perfluoropolyethers are commercially available from Shin-Etsu Subelyn® in the KY-100 series of fluorinated antifouling coating components, such as KY-1900 and KY-1901, Shin-Etsu Subelyn® in the KY-1200 series of fluorinated antifouling additives, such as KY-1271, or the OPTOOL series of Daikin fluorinated antifouling coating components, OPTOOL UD-509, OPTOOL UD-120, and OPTOOL DSX.

Other suitable fluorinated polysiloxanes are, for example, poly(methyl-3,3,3-trifluoropropyl)siloxane having a molecular weight in the range of 1500 to 20000 g/mol, preferably 2000 to 15000 g/mol.

The at least one fluorinated monomer is preferably present in the siloxane polymer in an amount of 0.1 to 45 wt %, more preferably 0.5 to 45 wt %, and even more preferably 1 to 40 wt %.

Particularly preferably, the monomer is a mixture of two or more selected from the following groups: 1,2-bis(triethoxysilyl)ethane (BTESE), tetraethoxysilane (TEOS) phenylmethyldimethoxysilane (PMDMS), 3-(trimethoxysilyl)propylmethacrylate (MEMO), methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (VTMS) and (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and another fluorinated monomer selected from KY-1900, KY-1901 and KY-1271.

The third composition comprising the third siloxane polymer (D-1) is preferably formed by a method comprising the following steps: ●   In a first solvent, at least one silane monomer and at least one fluorinated monomer (preferably as described above or below) are mixed to form a mixture; ●   Subjecting the mixture to at least partial hydrolysis of the monomers in the presence of a catalyst, thereby causing the hydrolyzed monomers to at least partially polymerize and crosslink; ●   Optionally replacing the first solvent with a second solvent; ●   Optionally crosslinking the mixture by hydrosilylation, heat or radiation.

The first solvent is preferably selected from the group consisting of acetone, tetrahydrofuran (THF), toluene, 1-propanol, 2-propanol, methanol, ethanol, water ( _H2O ), cyclopentanone, acetonitrile, propylene glycol propyl ether, methyl tertiary butyl ether (MTBE), propylene glycol monomethyl ether acetate (PGMEA), methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether (PGME) and propylene glycol propyl ether (PnP).

The monomers may be mixed in the first solvent at any suitable temperature to dissolve the monomers. Typically, room temperature is sufficient.

In the next process step, the mixture undergoes at least partial hydrolysis in the presence of a catalyst.

Suitable catalysts are acidic catalysts, alkaline catalysts or other catalysts.

The acidic catalyst is preferably selected from nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), formic acid (HCOOH), hydrochloric acid (HCl), sulfonic acid, hydrogen fluoride (HF), acetic acid (CH ₃ COOH), trifluoromethanesulfonic acid or p-toluenesulfonic acid. Particularly preferred acidic catalysts are nitric acid (HNO ₃ ), formic acid (HCOOH) and hydrochloric acid (HCl).

The alkaline catalyst is preferably selected from triethylamine (TEA), ammonium hydroxide (NH ₄ OH), tetraethylammonium hydroxide (TEAH), tetramethylammonium hydroxide (TMEA), 1,4-diazabicyclo[2.2.2]octane, imidazole and diethylenetriamine.

Other catalysts are preferably selected from 2,2,3,3,4,4,5,5-octafluoropentyl acrylate, poly(ethylene glycol) 200, poly(ethylene glycol) 300 and n-butyl melamine formaldehyde resin.

The hydrolysis step is preferably carried out at a temperature of 20 to 80°C for 1 to 24 hours, such as overnight at room temperature.

During the hydrolysis step, the monomer is at least partially hydrolyzed. The at least partially hydrolyzed monomer is then at least partially polymerized, preferably by condensation polymerization and crosslinking to form a siloxane polymer comprising side chains comprising one or more fluorinated carbon groups.

The siloxane polymers typically have a relatively low molecular weight in the range of about 500 to 2000 g/mol.

According to a preferred embodiment, subjecting the mixture to at least partial hydrolysis comprises refluxing. Typical reflux time is 2 hours.

After the hydrolysis step, in an optional further process step, the first solvent may be replaced with a second solvent. Optional solvent replacement is advantageous because it helps remove water and alcohol formed during the hydrolysis of the monomers. In addition, it improves the properties of the final siloxane polymer solution when used as a coating on a substrate.

The second solvent is preferably selected from the group consisting of propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), 1-ethanol, 2-ethanol (IPA), acrylonitrile diacetone alcohol (DAA) or propylene glycol n-propyl ether (PnP).

The mixture comprising the siloxane polymer may be further subjected to a crosslinking step after the hydrolysis step. Thereby, the siloxane polymer is preferably at least partially crosslinked by hydrosilylation, heat or radiation.

In this context, the term "partially crosslinked" means that the polymer is capable of further crosslinking under conditions that are favorable for crosslinking. In practice, the polymer still contains at least some reactive crosslinking groups after the first polymerization step. Further crosslinking that typically occurs after the partially crosslinked composition is deposited on a substrate will be described below.

The siloxane polymers are preferably at least partially crosslinked by hydrosilylation, heat or radiation using a catalyst as described above.

Thus, thermal crosslinking is preferably performed at a temperature in the range of about 30°C to 200°C.

Typically the crosslinking is carried out under refluxing conditions of the solvent.

In order to improve the resolution of the material when used in photolithography, the siloxane polymer can be partially crosslinked during polymerization, especially during or immediately after condensation polymerization, as appropriate. Various methods can be used to achieve the crosslinking. For example, a crosslinking method can be used in which two chains are joined via reactive groups that do not affect any active groups intended for UV photolithography. For example, hydrosilylation, such as using a proton on one chain to react with a double bond on another chain, will achieve the desired type of crosslinking. Another example is crosslinking via double bonds or epoxy groups.

Different reactive groups are preferred for crosslinking and for photolithography. Thus, crosslinking of siloxane polymers can be achieved using free radical initiators and photoacid generators with reactive groups having double bonds or epoxy groups or both, such as epoxy, vinyl or allyl or methacrylate groups.

Epoxy groups can be used for UV lithography, and vice versa. The proportion of reactive groups required for crosslinking is generally less than that required for UV lithography, for example, about 0.1 to 10 mol % based on monomer for crosslinking and about 5 to 50 mol % based on monomer for UV lithography.

The amount of initiator added to the reaction mixture/solution is generally about 0.1 to 10 wt %, preferably about 0.5 to 5 wt %, based on the total weight of the siloxane polymer.

Due to partial crosslinking, the molecular weight will typically be 2 to 10 times higher. Thus, with a molecular weight in the range of about 500 to 2000 g/mol, crosslinking will increase it to more than 3000 g/mol, preferably to 4000 to 20000 g/mol.

Optionally, the resulting free Si-OH groups present in the backbone of the siloxane polymer can be protected by end-capping. For end-capping, the free Si-OH groups are reacted with silanes such as methyldichlorofluorosilane ( _Cl2FSiCH3 , methylfluorodimethoxysilane ((MeO) _2SiFCH3 ), 3 _- chloropropyltrimethoxysilane (Cl( _CH2 ) _3Si (OMe) ₃ ), ethyltrimethoxysilane (ETMS) or trimethylchlorosilane ( _ClSiMe3 ) in the presence of a catalyst such as triethylaluminum (TEA) or imidazole. The amount of catalyst varies in _the range of 1.5 to 2 wt% of the total solids. The reaction time varies in the range of 40 to 45 min.

Other additives typically incorporated into the first composition comprising the third siloxane polymer (D-1) include chemicals that can further modify the final surface properties of the coated and cured film or improve the wetting/adhesion properties of the coating (B) to the substrate layer (A) or other coatings (C) or improve the coating drying and packaging behavior during deposition and drying to achieve good visual quality.

Such additives may be surfactants, defoamers, antifouling agents, wetting agents, etc. Examples of such additives include: BYK-301, BYK-306, BYK-307, BYK-308, BYK-333, BYK-051, BYK-036, BYK-028, BYK-057A, BYK-011, BYK-055, BYK-036, BYK-067A, BYK-088, BYK-302, BYK-310, K-322, BYK-323, BYK-33l, BYK-333, BYK-341, BYK-345, BYK-348, BYK-377, BYK-378, BYK-381, BYK-390, BYK-3700.

The additive is preferably present in an amount of 0.01 to 5 wt %, more preferably 0.1 to 1 wt %, based on the total weight of the solid.

Before further condensation, excess water is preferably removed from the material, and it is possible at this stage to change the solvent to another synthesis solvent if necessary. This other synthesis solvent may serve as the final processing solvent or one of the final processing solvents for the siloxane polymer. Residual water and alcohol and other by-products may be removed after the further condensation steps are completed. Additional processing solvents may be added during the formulation steps to form the final processing solvent combination. Additives such as thermal initiators, radiation sensitive initiators, sensitizers, surfactants and other additives may be added before the final filtration of the siloxane polymer. After formulating the composition, the polymer is ready to be processed, for example in roll-to-roll film deposition or in a lithography process.

By adjusting the hydrolysis and condensation conditions, the concentration/content of groups capable of deprotonation (e.g., OH-groups) and any residual groups left from the silane precursor of the siloxane polymer composition (e.g., alkoxy groups) can be controlled, and the final molecular weight of the siloxane polymer can also be controlled. This greatly affects the solubility of the siloxane polymer material in aqueous-based developer solutions. In addition, the molecular weight of the polymer also greatly affects the solubility characteristics of the siloxane polymer in the developer solution.

Thus, for example, it has been found that the final siloxane polymer is soluble in an alkaline-water developer solution (e.g., tetramethylammonium hydroxide; TMAH or potassium hydroxide; KOH) when the final siloxane polymer has a high content of residual hydroxyl groups and a low content of alkoxy (e.g., ethoxy) groups.

On the other hand, if the residual alkoxy-group content of the final siloxane polymer is high and it contains almost no OH-groups, the final siloxane polymer has very low solubility in the above-mentioned types of alkaline-water developers. OH-groups or other functional groups, such as amine ( _NH2 ), thiol (SH), carboxyl, phenol or similar functional groups that impart solubility to alkaline developer systems can be directly attached to the silicon atoms of the siloxane polymer backbone or, as the case may be, to organic functional groups attached to the siloxane polymer backbone to further promote and control the alkaline developer solubility.

Following synthesis, the siloxane polymer composition can be diluted using an appropriate solvent or combination of solvents to obtain a solids content that will produce a preselected film thickness during film deposition.

Typically, a further amount of an initiator molecule compound is added to the siloxane composition after synthesis. The initiator may, as the case may be, be similar to the initiator added during the polymerization and is used to produce a substance that can initiate the polymerization of the "active" functional groups in the UV curing step. Thus, in the case of epoxy groups, cationic or anionic initiators can be used. In the case of groups with double bonds as "active" functional groups in the synthetic material, free radical initiators can be employed. Furthermore, thermal initiators (working according to a free radical, cationic or anionic mechanism) can be used to promote the crosslinking of the "active" functional groups. The choice of the appropriate combination of photoinitiators and sensitizers also depends on the exposure source (wavelength) used. Furthermore, the choice of sensitizer used depends on the type of initiator chosen.

The concentration of the thermal or radiation initiator and the sensitizer in the composition is generally about 0.1 to 10%, preferably about 0.5 to 5%, calculated on the mass of the siloxane polymer.

The composition as described above may comprise solid nanoparticles or other compounds in an amount between 1 wt% and 50 wt% of the composition. The nanoparticles (or similar nano- or micro-scale rods, crystals, balls, dots, buds, etc.) are particularly selected from the group of light scattering, light absorbing, light emitting and/or conductive pigments, dyes, organic and inorganic phosphors, oxides, quantum dots, polymers or metals.

In a third embodiment, the third composition comprises a fourth siloxane polymer (D-2).

The fourth siloxane polymer (D-2) preferably does not contain side chains containing one or more fluorinated carbon groups.

The third siloxane polymer (D-2) comprises monomer units selected from at least one silane monomer.

Preferably, the silane monomer units of the fourth siloxane polymer (D-2) and the method for preparing the fourth siloxane polymer (D-2) are as described above for the third siloxane polymer (D-1), preferably except that no fluorinated monomer as described above for the third siloxane polymer (D-1) is present in the fourth siloxane polymer (D-2).

The following procedures apply to all specific instances of the third coating (D):

The third component preferably comprises a fluoropolyether compound as described above or below with respect to the second component of the second coating layer (C).

The third composition is deposited onto at least one surface of the second coating layer (C) to form a third coating layer (D) that is in adhesive contact with at least one surface of the second coating layer (C).

Suitable deposition methods include spin coating, nip coating, spraying, ink jetting, roll-to-roll, gravure printing, reverse gravure printing, doctor bar coating, slot coating, flexographic printing, curtain coating, screen printing coating, extrusion coating, dip coating, shower coating or slot coating.

The deposited third composition forms a third coating layer (D) on the surface of the second coating layer (C). Typically, after deposition or during the deposition step, the solvent is evaporated and the third coating layer (D) is dried, preferably by thermal drying or, as the case may be, by combined vacuum and/or thermal drying. This step is also called pre-curing.

In a second subsequent step, the third coating layer (D) is cured to a final hardness by thermal curing at elevated temperature or by using UV exposure followed by thermal curing at elevated temperature.

In one specific example, the pre-cure and final cure steps are combined by heating using an increasing heating gradient. In addition to a heat-only curing process, curing can be performed in three steps, the process comprising a thermal pre-cure and a UV cure followed by a final thermal cure. A two-step curing process can also be applied, wherein a thermal pre-cure is followed by a UV cure. In this case, preferably no final thermal cure is applied after the UV cure.

According to a specific embodiment, the method further comprises developing the deposited film. In one embodiment, developing comprises exposing the deposited first siloxane polymer composition (full area or selective exposure using a mask or crosshairs or laser direct imaging) to UV light. The developing step is typically performed after any pre-curing step and before the final curing step.

Therefore, in a specific example, the method comprises the following steps: -    pre-curing or drying the third coating layer (D) deposited on the second coating layer (C); -    exposing the third coating layer (D) obtained as appropriate; -    developing the third coating layer (D) obtained as appropriate; and -    curing the third coating layer (D).

Exemplary monomers containing epoxy functional groups include (3-glycidyloxypropyl)trimethoxysilane, 1-(2-(trimethoxysilyl)ethyl)cyclohexane-3,4-epoxide, (3-glycidyloxypropyl)triethoxysilane, (3-glycidyloxypropyl)tripropoxysilane, 3-glycidyloxypropyltri(2-methoxyethoxy)silane, 2,3-epoxypropyltriethyl triethoxysilane, 3,4-epoxybutyltriethoxysilane, 4,5-epoxypentyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 4-(trimethoxysilyl)butane-1,2-epoxide.

Other examples of functionalized compounds are acrylate and methacrylate compounds such as tetraethylene glycol diacrylate, trihydroxymethylpropane triacrylate, pentaerythritol triacrylate, di(trihydroxymethylpropane) tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate and combinations thereof. Such compounds can be used as part of the silane composition.

According to a specific embodiment, the method further comprises curing the third component.

The thickness of the third coating layer (D) on the second coating layer (C) (ie, film thickness) may be in the range of 10 nm to 10 µm, preferably 15 nm to 8 µm, and more preferably 20 nm to 5 µm.

In one specific example, the third coating (D) is preferably an easy-to-clean coating comprising a siloxane polymer as described in WO 2016/146895 or WO 2020/099290.

In another embodiment, the third coating layer (D) is preferably a flexible hard coating layer, which comprises a third siloxane polymer (D-1) comprising a side chain comprising one or more fluorinated carbon groups.

In another embodiment, the third coating layer (D) is preferably a flexible hard coating layer comprising a fourth siloxane polymer (D-2).

Preferably, the hardness of the third coating layer (D) is greater than 3H, greater than 4H, greater than 5H, greater than 6H or even greater than 7H as measured by ASTM D3363-00, Elcometer tester.

Preferably, the adhesion of the third coating (D) is 4B-5B as tested by ASTM D3359-09, Cross-Hatch tester.

In addition, the third coating (D) had better scratch resistance as evidenced by no visual scratches in the Taber Linear Abrasion Test (using a Linear Abrasion Machine from Taber Industries) with BonStar steel wool #0000, 500 g weight, 2×2 cm head size, 2.0 inch stroke length, 60 cycles/minute up to 2000 linear cycles.

Layered structure In a specific example, the layered structure according to the present invention includes a substrate layer (A), a first coating layer (B) and a second coating layer (C). In the specific example, the second coating layer (C) is the outermost layer of the layered structure and is sandwiched with the first coating layer (B) and the substrate layer (A). This means that preferably no other coating layer or coating layer is coated on at least one surface of the substrate layer (A).

In another specific example, the layered structure further includes a third coating layer (D). In this specific example, the layered structure according to the present invention includes a substrate layer (A), a first coating layer (B), a second coating layer (C) and a third coating layer (D). In this specific example, the third coating layer (D) is the outermost layer of the layered structure and is sandwiched with the substrate layer (A), the second coating layer (C) and the first coating layer (B), wherein the first coating layer (B) is preferably the innermost layer that is in contact with the surface of the substrate layer. This means that preferably no other coating layer or coating layer is coated on at least one surface of the substrate layer (A).

The layered structure exhibits a good balance of properties including good adhesion of the different layers to each other, high scratch resistance and low reflectivity.

The layered structure better shows the adhesion of the first coating layer (B) to the substrate layer (A) of 4-5B.

In addition, the layered structure better shows the adhesion of the second coating layer (C) to the first coating layer (B) of 3-5B.

Furthermore, the layered structure preferably exhibits an initial water contact angle of at least 75°, preferably at least 90°.

In addition, the layered structure preferably exhibits a scratch resistance corresponding to a visual quality of 0 to 2 in the Taber Linear Abrasion Test (using a Linear Abrasion Machine from Taber Industries) with BonStar steel wool #0000, 500 g weight, 2×2 cm head size, 2.0 inch stroke length, 60 cycles/minute for up to 500 linear cycles.

In addition, the layered structure preferably exhibits a contact angle of at least 80° in the Taber Linear Abrasion Test (using a Linear Abrasion Machine from Taber Industries) with BonStar steel wool #0000, 500 g weight, 2×2 cm head size, 2.0 inch stroke length, 60 cycles/minute for up to 500 linear cycles.

Furthermore, the layered structure preferably exhibits a reflectivity at 550 nm of no more than 4.0%, preferably no more than 3.5%, when measured on a coated PMMA substrate, or a reflectivity at 550 nm of no more than 6.0%, preferably no more than 5.5%, when measured on a coated PET or CPI substrate.

Additionally, the layered structure preferably exhibits a transmittance at 550 nm of at least 93.0%, preferably at least 93.5%, when measured on a coated PMMA substrate, or a transmittance at 550 nm of at least 89.5%, preferably at least 90.0%, when measured on a coated PET or CPI substrate.

The layered structure according to the present invention is suitable for use in flexible electronic applications including displays, optical lenses, transparent panels and the automotive industry, especially as a lightweight substitute for glass.

The present invention is further characterized by the following non-limiting embodiments:

Example 1. Determination Methods Molecular weight : The polymers were characterized by gel permeation chromatography. The chromatography system consisted of a GPC apparatus equipped with an isocratic HPLC pump and a refractive index detector. Polysiloxane (0.20 g; 50% solid content) was dissolved in THF (HPLC grade; 2.30 g). The analyte injection volume was 100 µL, the flow rate was 0.70 mL/min, and the column temperature was set to 40 °C. Four polystyrene exclusion-based columns were used. The mobile phase was THF (HPLC grade). Internal standards were used to determine the number average molecular weight ( _Mn ) and weight average molecular weight ( _Mw ) of polymers, for example, two series of polystyrenes (Series A: 5 polystyrenes with _Mw = 120.000 g/mol, 42.400 g/mol, 10.700 g/mol, 2.640 g/mol, 474 g/mol and Series B: 4 polymers with _Mw = 193.000 g/mol, 16.700 g/mol, 6.540 g/mol, 890 g/mol).

Solids Content : The solids content of the polymers was determined using a Mettler Toledo HB43 instrument. The samples were weighed on an aluminum pan/cup and the measurement was performed using approximately 1 g of material.

Viscosity : The instrument used was a Grabner Instruments viscometer MINIVIS-II. The method used was "falling ball viscosity measurement". The sample was measured at T = 20°C using a steel ball with a diameter of 3.175 mm.

Film thickness and refractive index ( RI ): Film thickness and refractive index are measured using an elliptical polarizer UVISEL-VASE Horiba Jobin-Yvon. Gorilla Glass 4 or silicon wafer (diameter: 150 mm, type/doping: P/Bor, orientation: <1-0-0>, resistivity: 1-30 Ω. cm, thickness: 675+/-25 μm, TTV: <5 μm, particles: < 20 @ 0,2 μm, front surface: polished; back surface: etched; Flat 1 SEMI standard) or other suitable substrates are used for measurement. The material film can be prepared on a pre-treated (plasma) glass substrate using a spray tool (typical spraying method: scanning speed: 300 mm/s; spacing: 50 mm; gap: 100 mm; flow rate: 5-6 ml/min; atomization gas pressure: 5 kg/cm ² ) followed by thermal curing, e.g. at T=150°C for 60 min.

Transmittance ( T% ) and reflectance ( R% ) : The transmittance and reflectance were measured using a Konica Minolta spectrophotometer CM-3700A (Specta Magic NX software).

Color and turbidity measurements : L*(D 65), a*(D 65), b*(D 65) and turbidity were measured using a Konica Minolta spectrophotometer CM-3700A (Specta Magic NX software).

Pencil Hardness ( PEHA ): Pencil hardness is measured according to ASTM Standard D3363-00 using an Elcometer Pencil Hardness Tester.

Water Contact Angle ( WCA ): Static contact angle measurements were performed by an optical tensiometer using distilled water (4 µL droplet size). The average of three measurement points was recorded as the measurement result and the Young-Laplace equation was used as a numerical method to describe the droplet profile (tool: attention theta optical tensiometer).

Erosion: For the second and third layers, the erosion test was conducted using a taber linear abrader 5750 with Bon star steel wool #0000, 500 g load, 2×2 cm head, 2 inch travel, 60 cycles/min, 500 cycles.

Visual Quality ( VQ ): Visual inspection can be performed with the naked eye and under a microscope using a green or red quality light. Visual quality can be rated from 0 (best) to 3 (poor).

Adhesion: Adhesion was measured according to ASTM Standard D3359-D9 using the Elcometer cross-hatch tester and the Elcometer tape tester.

2. List of components used in the examples: a) Silane monomers: GPTMS = (3-glycidyloxypropyl)trimethoxysilane, Sigma-Aldrich PMDMS = phenylmethyldimethoxysilane, Sigma-Aldrich MEMO = 3-(trimethoxysilyl)propyl methacrylate ABCR BTESE = 1,2-bis(triethoxysilyl)ethane, Momentive Performance Materials MTMS = methyltrimethoxysilane, ABCR TEOS = tetraethoxysilane, Ultra Pure Solutions Inc. DPDMS = diphenyldimethoxysilane, Sigma-Aldrich PTMS = phenyltrimethoxysilane, Sigma-Aldrich Me-GPTMS = (3-glycidyloxypropyl)methyldimethoxysilane, ABCR trimethoxy(octyl)silane, Sigma-Aldrich 4-Trifluoromethyl-tetrafluorophenyltriethoxysilane, ABCR F13 = 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, Sigma-Aldrich 1H,1H,2H,2H-perfluorooctyltriethoxysilane, Sigma-Aldrich F17 = 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, VWR labscan 1H,1H,2H,2H-perfluorododecyltriethoxysilane, Sigma-Aldrich (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane, Sigma-Aldrich Fluoride-free hexyltriethoxysilane, Sigma-Aldrich Bis[(2,2,3,3,4,4-hexafluorobutyl)propionate]-3-aminopropyltrimethoxysilane. It is prepared by reaction between aminopropyltrimethoxysilane (APTMES, Sigma-Aldrich) and 2,2,3,3,4,4-hexafluorobutylacrylate (OFPA, Sigma-Aldrich). The preparation is described below: In a 100 mL 3-neck round-bottom flask, APTMES (10 g) was cooled to T = 0 °C. OFPA (33.51 g) was added dropwise at T = 0 °C. The reaction mixture was allowed to reach room temperature and then stirred at T = 60 °C for 18 hours. The reaction was monitored by TLC (solvent: cyclohexane/EtOAc = 3/1). Excess OFPA was removed under reduced pressure.

b) Polysiloxanes Poly(methyl-3,3,3-trifluoropropylsiloxane), Mw = 2500 D, ABCR Poly(methyl-3,3,3-trifluoropropylsiloxane), Mw 14000 D, ABCR TEOS-based polymers/100%-TEOS polymers: In a 500 mL round-bottom flask, TEOS (43.46 g) and acetone (136.08 g) were mixed. HNO ₃ (0.1 M; 29.98 g) was added dropwise over 10-15 min. The reaction mixture was refluxed for 2 h. After cooling to room temperature, PGME (115 g) was added. A solvent exchange procedure from EtOH/H ₂ O/acetone to PGME was performed under vacuum. The final solids content of the mixture was adjusted to 10% by adding more PGME.

c)   Solvents: DAA = diacetone alcohol, Merck EtOH = ethanol, Altia VWR PGME = 1-methoxy-2-propanol, Ultra Pure Solutions Inc. MeOH = methanol, Merck IPA = 2-propanol, Merck PGMEA = propylene glycol monoethyl ether acetate, Ultra Pure Solutions Inc. MTBE = methyl tert-butyl ether, Sigma-Aldrich EG = ethylene glycol, Sigma-Aldrich DiPG = dipropylene glycol, Sigma-Aldrich Acetone, Brenntag

d) Catalyst: HNO ₃ = nitric acid, Merck HCl = hydrochloric acid, Merck Formic acid, Sigma-Aldrich TEA = triethylamine, Sigma-Aldrich

e)   Fluorinated additives KY 1900 = Perfluoropolyether with reactive silyl groups, Shin-Etsu KY 1901 = Perfluoropolyether with reactive silyl groups, Shin-Etsu KY 1271 = Fluorinated antifouling additive, Shin-Etsu DSX = OPTOOL DSX E (fluoropolyether silane), Daikin SC 019 = Fluoropolyether compounds, Shin-Etsu SC 011 = Fluoropolyether compounds, Shin-Etsu Novec 7100 = Mixture of isomers of methoxy-nonafluorobutane, 3M AE 3000 = 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, Daikin

f) Other chemicals: AIBN = azobisisobutyronitrile, Sigma Aldrich UVI Speed Cure 976 = (diphenyl-4,1-diyl)bis(diphenylstennium sulfide), Lambson BYK 333 = polyether-modified polydimethylsiloxane, BYK BYK 345 = polyether-modified siloxane, BYK BYK 370 = polyester-modified, hydroxy-functional polydimethylsiloxane, BYK BYK 067A = defoamer, BYK M262 = tricyclodecane dimethanol diacrylate, Miwon M2372 = tris(2-hydroxyethyl isocyanurate) di/triacrylate, Miwon M270 = tetraethylene glycol diacrylate, Miwon ClSiMe ₃ = chlorotrimethylsilane, Sigma-Aldrich

3. Preparation Examples a) Preparation Example of the First Coating ( B ) The composition used for the first coating is particularly adapted to the substrate in terms of curing and baking conditions. Thus, composition 30 is particularly suitable for the first coating of a PMMA substrate, and composition 31 is particularly suitable for the first coating of a PET or CPI substrate.

Composition B-1 In a 2 L round bottom flask, GPTMS (900 g; 3,804 mol), PMDMS (99,06 g; 0,27 mol) and MEMO (301,32 g; 0,54 mol) were mixed. HNO ₃ (0,1 M; 212,4 g) was added dropwise over 15 minutes. The reaction mixture was then stirred at room temperature overnight. Diacetone alcohol (DAA; 600 g) was then added and a solvent exchange from MeOH/EtOH/H ₂ O to DAA was performed under low pressure. The final solid content was adjusted to 50% by adding additional DAA. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material), M270 (15% solid material) and BYK 067A (1% solid material) were added.

Composition B-2 In a 500 mL round-bottom flask, BTESE (21.15 g; 0.06 mol), GPTMS (91 g; 0.3875 mol), MEMO (37 g; 0.149 mol) and bis[(2,2,3,3,4,4-hexafluorobutyl)propionate]-3-aminopropyltrimethoxysilane (2.76 g; 0.00043 mol) were mixed in acetone (112.4 g). HNO ₃ (0.1 M; 35.47 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure from acetone to PGME was performed. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-3 In a 500 mL round-bottom flask, BTESE (21.15 g; 0.06 mol), GPTMS (91 g; 0.3875 mol), MEMO (37 g; 0.149 mol) and 4-trifluoromethyl-tetrafluorophenyltriethoxysilane (0.05 g; 0.00131 mol) were mixed in acetone (112.4 g). HNO ₃ (0.1 M; 35.47 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure from acetone to PGME was performed. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-4 In a 500 mL round-bottom flask, BTESE (21.15 g; 0.06 mol), GPTMS (91 g; 0.3875 mol), MEMO (37 g; 0.149 mol) and 1H,1H,2H,2H-perfluorooctyltriethoxysilane (2.05 g; 0.0040 mol) were mixed in acetone (112.4 g). HNO ₃ (0.1 M; 35.47 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure from acetone to PGME was performed. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-5 In a 500 mL round-bottom flask, BTESE (21.15 g; 0.06 mol), GPTMS (91 g; 0.3875 mol), MEMO (37 g; 0.149 mol) and poly(methyl-3,3,3-trifluoropropylsiloxane) (2 g; Mw=2500 D) were mixed in acetone (112.4 g). HNO ₃ (0.1 M; 35.47 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure from acetone to PGME was performed. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-6 In a 500 mL round-bottom flask, BTESE (21.15 g; 0.06 mol), GPTMS (91 g; 0.3875 mol), MEMO (37 g; 0.149 mol) and poly(methyl-3,3,3-trifluoropropylsiloxane) (2.3 g; Mw=14000 D) were mixed in acetone (112.4 g). HNO ₃ (0.1 M; 35.47 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure from acetone to PGME was performed. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-7 In a 500 mL round-bottom flask, BTESE (21.15 g; 0.06 mol), GPTMS (91 g; 0.3875 mol), MEMO (37 g; 0.149 mol) and 1H,1H,2H,2H-perfluorododecyltriethoxysilane (0.73 g) were mixed in acetone (112.4 g). HNO ₃ (0.1 M; 35.47 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure from acetone to PGME was performed. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-8 In a 500 mL round-bottom flask, BTESE (21.15 g; 0.06 mol), GPTMS (91 g; 0.3875 mol), MEMO (37 g; 0.149 mol) and (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane (0.5 g) were mixed in acetone (112.4 g). HNO ₃ (0.1 M; 35.47 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure from acetone to PGME was performed. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-9 In a 500 mL round-bottom flask, BTESE (21.15 g; 0.06 mol), GPTMS (91 g; 0.3875 mol), MEMO (37 g; 0.149 mol) and fluorine-free hexyltriethoxysilane (2 g) were mixed in acetone (112.4 g). HNO ₃ (0.1 M; 35.47 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure from acetone to PGME was performed. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-10 In a 500 mL round bottom flask, BTESE (21.15 g; 0.06 mol), GPTMS (91 g; 0.3875 mol), MEMO (37 g; 0.149 mol) were mixed in acetone (112.4 g). HNO ₃ (0.1 M; 35.47 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure from acetone to PGME was performed. Additional PGME was added to give a polymer with a solid content of 41.85%. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 30% solid content with IPA and the additives Speed Cure 976 (1.2% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-11 MTMS (78.46 g; 0.576 mol), TEOS (20 g; 0.096 mol), GPTMS (22.69 g; 0.096 mol) were mixed in EtOH (121.15 g) in a 1 L round-bottom flask. Formic acid (0.1 M; 86.40 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was refluxed for 2 hours. The reaction mixture was then cooled to room temperature and PGME (100 g) was added. The solvent exchange procedure from EtOH to PGME was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-12 In a 1 L round-bottom flask, BTESE (63.83 g; 0.18 mol), MEMO (14.90 g; 0.06 mol), GPTMS (226.9 g; 0.96 mol) were mixed in acetone (229.21 g). HNO ₃ (0.1 M; 74.59 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a 2 L round-bottom flask and PGME (150 g) was added. A solvent exchange procedure from acetone to PGME was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-13 In a 1 L round-bottom flask, BTESE (63.83 g; 0.18 mol), MEMO (14.90 g; 0.06 mol), GPTMS (218.38 g; 0.924 mol), F17 (20.46 g; 0.036 mol) were mixed in acetone (238.18 g). HNO ₃ (0.1 M; 74.59 g) was added dropwise over 15 minutes. After the addition was completed, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a 2 L round-bottom flask and PGME (150 g) was added. The solvent exchange procedure from acetone to PGME was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-14 In a 1 L round-bottom flask, BTESE (63,83 g; 0,18 mol), MEMO (14,90 g; 0,06 mol), GPTMS (218,38 g; 0,924 mol), F13 (18,36 g; 0,036 mol) were mixed in acetone (238,60 g). HNO ₃ (0.1 M; 74,59 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a 2 L round-bottom flask and PGME (150 g) was added. The solvent exchange procedure from acetone to PGME was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-15 In a 1 L round-bottom flask, BTESE (14.51 g; 0.0409 mol), MEMO (20.33 g; 0.0818 mol), GPTMS (62.87 g; 0.266 mol), DPDMS (5.06 g; 0.020 mol) were mixed in acetone (77.03 g). HNO ₃ (0.1 M; 23.96 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a new 1 L round-bottom flask and PGME (60 g) was added. The solvent exchange procedure from acetone to PGME was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-16 PTMS (10,00 g; 0,050 mol), MEMO (18,79 g; 0,076 mol), GPTMS (77,47 g; 0,327 mol), BTESE (17,88 g; 0,050 mol) were mixed in acetone (93,11 g) in a 1 L round-bottom flask. HNO ₃ (0.1 M; 29,98 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a new 1 L round-bottom flask and PGME (75 g) was added. The solvent exchange procedure from acetone to PGME was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-17 In a 1 L round-bottom flask, BTESE (31.91 g; 0.18 mol), MEMO (22.35 g; 0.18 mol), GPTMS (99.26 g; 0.84 mol) were mixed in acetone (15 g). HNO ₃ (0.1 M; 37.26 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a new 1 L round-bottom flask and PGME (92 g) was added. A solvent exchange procedure from acetone to PGME was performed under low pressure. A portion of the previous solution (50 g, 50% solid content in PGME) was mixed with AIBN (0.1 g) and the reaction mixture was stirred at T = 105 ° C for 5 minutes. After cooling to room temperature, the final product was ready for processing. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-18 In a 1 L round-bottom flask, BTESE (25,00 g; 0,070 mol), Me-GPTMS (36,25 g; 0,164 mol), GPTMS (38,88 g; 0,164 mol), MEMO (17,51 g; 0,070 mol) were mixed in acetone (88,23 g). HNO ₃ (0.1 M; 26,25 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a new 1 L round-bottom flask and PGME (70,58 g) was added. The solvent exchange procedure from acetone to PGME was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-19 In a 1 L round-bottom flask, MEMO (35.02 g; 0.141 mol), GPTMS (86.85 g; 0.366 mol), BTESE (20.00 g; 0.056 mol) were mixed in IPA (106.25 g). HNO ₃ (0.1 M; 33.53 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a new 1 L round-bottom flask and IPA (75 g) was added. The solvent exchange procedure from IPA to IPA was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-20 MTMS (90,00 g; 0,660 mol), GPTMS (22,31 g; 0,094 mol) were mixed in EtOH (112,31 g) in a 500 mL round-bottom flask. Formic acid (0.1 M; 122,32 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a new 500 mL round-bottom flask and PGMEA (100 g) was added. The solvent exchange procedure from EtOH to PGMEA was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-21 In a 250 mL round-bottom flask, TEOS (14,00 g; 0,048 mol), MTMS (1,00 g; 0,0074 mol), F17 (7,34 g; 0,0129 mol), GPTMS (1,31 g; 0,006 mol) were mixed. HCl (0.1 M; 4,88 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a new 250 mL round-bottom flask and IPA (14,3 g) was added. A solvent exchange procedure from EtOH/MeOH/H ₂ O to IPA was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-22 In a 250 mL round-bottom flask, TEOS (14,00 g; 0,067 mol), MTMS (1,91 g; 0,014 mol), F17 (11,4 g; 0,0196 mol), GPTMS (2,65 g; 0,0112 mol) were mixed. Formic acid (0.1 M; 7,26 g) was added dropwise over 15 minutes. After the addition was complete, the reaction mixture was stirred at room temperature overnight. The reaction mixture was then transferred to a new 250 mL round-bottom flask and IPA (18,48 g) was added. A solvent exchange procedure from EtOH/MeOH/H ₂ O to IPA was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-23 In a 1 L round-bottom flask, BTESE (31.91 g; 0.18 mol), GPTMS (99.26 g; 0.84 mol), MEMO (22.25 g; 0.18 mol) were mixed in acetone (115 g). HNO ₃ (0.1 M; 36.26 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (92 g) was added and a solvent exchange procedure from acetone to PGME was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-24 MTMS (58.02 g; 0.42 mol), TEOS (19.57 g; 0.090 mol), MEMO (7.00 g; 0.028 mol), GPTMS (18.50 g; 0.078 mol) were mixed in EtOH (103.09 g) in a 1 L round-bottom flask. Formic acid (0.1 M; 71.04 g) was added dropwise and the reaction mixture was refluxed at T = 105 °C for 2 hours. The reaction mixture was cooled to room temperature. PGME (90 g) was added and a solvent exchange procedure from EtOH to PGME was performed under reduced pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-25 MTMS (98,73 g; 0.724 mol), MEMO (15,00 g; 0,060 mol), TEOS (12,58 g; 0,060 mol), GPTMS (28,55 g; 0,12 mol) were mixed in EtOH (154,86 g) in a 1 L round-bottom flask. Formic acid (0.1 M; 106,54 g) was added dropwise and the reaction mixture was refluxed at T = 105 °C for 2 hours. The reaction mixture was cooled to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was performed under reduced pressure. AIBN (1.11 g) was then added at room temperature and the reaction mixture was stirred at T = 95 °C for 5 minutes. After cooling to room temperature, the final product was ready for processing. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-27 In a 1 L round bottom flask, GPTMS (450 g; 1,902 mol), MEMO (150,00 g; 0,54 mol), PMDMS (49,53 g; 0,27 mol) were mixed. HNO ₃ (0,1 M; 106,2 g) was added dropwise and the reaction mixture was stirred at room temperature overnight. DAA (300 g) was added and a solvent exchange procedure from MeOH/H ₂ O to DAA was performed under low pressure. The solid content of the final formulation was still 50%. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-28 In a 500 ml round-bottom flask, MTMS (40 g; 0,2936 mol), TEOS (61,17 g; 0,29364 mol), EtOH (101.17 g; 2,2075 mol) were mixed. Formic acid (0.1 M; 74 g) was added dropwise and the reaction mixture was refluxed at T = 105 ° C for 2 hours. The reaction mixture was cooled to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was performed under low pressure. The solid content was adjusted to 41.85% by adding PGME. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-29 In a 500 ml round-bottom flask, MTMS (40 g; 0,2936 mol), TEOS (61,17 g; 0,29364 mol), EtOH (101.17 g; 2,2075 mol) were mixed. Formic acid (0.1 M; 33 g) was added dropwise and the reaction mixture was refluxed at T = 105 ° C for 2 hours. The reaction mixture was cooled to room temperature. PGME (33 g) was added and a solvent exchange procedure from EtOH to PGME was performed under low pressure. Trimethoxy(octyl)silane (5 g, 0,0213 mol) was now added to the solution. Formic acid (0.1 M; 3,46 g) was added dropwise and the reaction mixture was refluxed at T = 105 ° C for 2 hours. The reaction mixture was cooled to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was performed under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material) and BYK 067A (1% solid material) were added.

Composition B-30 In a 1 L round bottom flask, GPTMS (900 g), MEMO (301.32 g), PMDMS (99.09 g) were mixed. HNO ₃ (0.1 M; 212.4 g) was added slowly over 10-15 minutes. The reaction mixture was then stirred at room temperature overnight. DAA (600 g) was added and a solvent exchange of MeOH/H ₂ O to DAA was performed under vacuum. The final solid content of the reaction mixture was adjusted to 50% by adding DAA. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5% solid material), BYK 333 (1% solid material), M270 (15% solid content) and BYK 067A (1% solid material) were added.

Composition B-31 In a 500 mL round bottom flask, BTESE (21.15 g; 0.06 mol), GPTMS (91 g; 0.3875 mol), MEMO (37 g; 0.149 mol) were mixed in acetone (112.4 g). HNO ₃ (0.1 M; 35.47 g) was added dropwise over 15 minutes and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure from acetone to PGME was performed. Additional PGME was added to give a polymer with a solid content of 41.85%. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 30% solid content with IPA and the additives Speed Cure 976 (1.2% solid material), BYK 370 (1% solid material) and BYK 067A (1% solid material) were added.

b) Preparation of the second coating ( C ) Example Composition C-1 In a 500 ml round-bottom flask, MTMS (10.5 g; 0.0771 mol), TEOS (30.0 g; 0.1440 mol), EtOH (163 g; 3.52 mol) were mixed. HCl (1.0 M; 33.9 g) was added dropwise and the reaction mixture was stirred at room temperature for 3.5 hours. The organic phase was washed 5 times with a mixture H ₂ O/MTBE (0.9:1.05). EtOH (183.43 g) was added and a solvent exchange procedure was carried out to EtOH under vacuum. The solid content of the reaction mixture was adjusted to 4% by adding EtOH (25.44 g). TEA (0.130 g) is then added at room temperature and the reaction mixture is stirred at T = 70 ° C for 45 minutes. After cooling to room temperature, the organic phase is washed 5 times with a H ₂ O/MTBE mixture (0.9:1.05). The organic phases are collected, EtOH (89.04 g) and PGME (190 g) are added and a solvent exchange to PGME is carried out under vacuum. ClSiMe ₃ (0.041 g) is added at room temperature and the reaction mixture is stirred at T = 105 ° C for 30 minutes. A portion of the polymer (11.47 g, 5.23% solids in PGME) was mixed with KY 1901 (0.4% in Novec 7100; 6,25 g), Novec 7100 (17.85 g), IPA (12.83 g), EG (1.24 g) and TEOS based polymer (0.36 g, 10% solids in PGME).

Composition C-2 In a 10 L round-bottom flask, HNO ₃ (3 M, 804 g) and IPA (3771 g) were mixed, followed by TEOS (570 g, 2,736 mol) and MTMS (373 g, 2,7382 mol) using a separatory funnel over 20 minutes. After addition, the reaction mixture was stirred at room temperature for 3.5 hours. Several washing steps with a mixture of H ₂ O/MTBE (0.9:1.05) were performed for 4 days. A portion of the polymer (11.47 g, 5.23% solids in PGMEA) was mixed with KY 1901 (0.4% in Novec 7100; 6,25 g), Novec 7100 (17.85 g), IPA (12.83 g), EG (1.24 g) and TEOS based polymer (0.36 g, 10% solids in PGME).

Composition C-3 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (11.47 g, 5.23% solids in PGMEA) was mixed with KY 1901 (0.4% in Novec 7100; 6,25 g), Novec 7100 (17.85 g), IPA (12.83 g), EG (1.24 g) and TEOS based polymer (0.36 g, 10% solids in PGME).

Composition C-4 In a 250 L reactor, TEOS (43,436 g) and acetone (136 g) were mixed. HNO ₃ (0.01 M; 2,978 g) was slowly added to the reaction mixture over 10-20 minutes. The reaction mixture was then refluxed for 1 hour. After cooling to room temperature, PGME (115 kg) was added and a solvent exchange of acetone/H ₂ O/EtOH to PGME was performed under vacuum. The solid content of the mixture was adjusted to 10% by adding more PGME. A portion of the polymer (6 g, 10% solid content in PGME) was mixed with DSX (0.4% in AE 3000; 18,75 g), AE 3000 (56,125 g), PGME (65,68 g) and DiPG (3,72 g).

Composition C-5 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T = 105°C for 1,5 hours. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (30.59 g, 5.23% solid content in PGMEA) is mixed with IPA (69.40 g) and BYK 333 (0.064 g).

Composition C-6 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T=60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (5.73 g, 5.23% solids in PGMEA) was mixed with Novec 7100 (7.19 g), IPA (18.29 g), EG (1.24 g), TEOS-based polymer (10% solids in PGME; 0.09 g), and BYK 333 (0.018 g).

Composition C-7 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (9.56 g, 5.23% solids in PGMEA) was mixed with Novec 7100 (6.93 g), IPA (14.65 g), EG (1.24 g), TEOS-based polymer (10% solids in PGME; 9.56 g), and BYK 333 (0.014 g).

Composition C-8 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (4.78 g, 5.23% solids in PGMEA) was mixed with Novec 7100 (3.35 g), IPA (3.09 g), PGME (6.11 g), a TEOS-based polymer (10% solids in PGME; 1.00 g), and BYK 333 (0.010 g).

Composition C-9 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T = 105°C for 1,5 hours. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (11.47 g, 5.23% solid content in PGMEA) is mixed with IPA (69.40 g) and BYK 333 (0.064 g).

Composition C-10 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T=60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T = 105°C for 1,5 hours. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (22.94 g, 5.23% solid content in PGMEA) is mixed with IPA (69.40 g) and BYK 333 (0.064 g).

Composition C-11 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T=60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T = 105°C for 1,5 hours. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (19.12 g, 5.23% solid content in PGMEA) is mixed with IPA (69.40 g) and BYK 333 (0.064 g).

Composition C-12 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T = 105°C for 1,5 hours. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (17.20 g, 5.23% solid content in PGMEA) is mixed with IPA (69.40 g) and BYK 333 (0.064 g).

Composition C-13 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T=60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (5.73 g, 5.23% solids in PGMEA) was mixed with EG (0.62 g), IPA (3,41 g), Novec 7100 (8.78 g), KY 1901 (0.4% in Novec 7100; 3.12 g) and 100%-TEOS polymer (10% solids in PGME, 3 g).

Composition C-14 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (428.3 g, 5.23% solids in PGMEA) was mixed with PGME (732.98 g), EtOH (345.8 g), M262 (4.29 g), M2372 (4.29 g), and BYK 345 (0.896 g).

Composition C-15 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (7.17 g, 5.23% solids in PGMEA) was mixed with KY1901 (0.4% in Novec 7100; 3.12 g), Novec 7100 (7.62 g), IPA (4.67 g), EG (0.62 g) and TEOS-based polymer (10% solids in PGME; 1.12 g).

Composition C-16 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (7.17 g, 5.23% solids in PGMEA) was mixed with SC 011 (0.4% in Novec 7100; 3.12 g), Novec 7100 (7.62 g), IPA (4.67 g), EG (0.62 g) and TEOS-based polymer (10% solids in PGME; 1.12 g).

Composition C-17 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T=60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (7.17 g, 5.23% solids in PGMEA) was mixed with SC 019 (0.4% in Novec 7100; 3.12 g), Novec 7100 (7.62 g), IPA (4.67 g), EG (0.62 g) and TEOS-based polymer (10% solids in PGME; 1.12 g).

Composition C-18 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (7.17 g, 5.23% solids in PGMEA) was mixed with KY1901 (0.4% in Novec 7100; 6.24 g), Novec 7100 (7.62 g), IPA (4.67 g), EG (0.62 g), and TEOS-based polymer (10% solids in PGME; 1.12 g).

Composition C-19 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T = 60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (7.17 g, 5.23% solids in PGMEA) was mixed with SC 011 (0.4% in Novec 7100; 3.12 g), Novec 7100 (5.26 g), IPA (4.67 g), EG (0.62 g) and TEOS-based polymer (10% solids in PGME; 3.75 g).

Composition C-20 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T=60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (7.17 g, 5.23% solids in PGMEA) was mixed with SC 019 (0.4% in Novec 7100; 3.12 g), Novec 7100 (5.26 g), IPA (4.67 g), EG (0.62 g) and TEOS-based polymer (10% solids in PGME; 3.75 g).

Composition C-21 In a 250 L reactor, HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) were mixed. MTMS (5,368 kg) and TEOS (8,196 kg) were added. The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with a H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and a solvent exchange of H ₂ O/IPA/EtOH/MeOH to IPA was performed under low pressure. The solid content of the reaction mixture was adjusted to 4% by adding IPA (31 kg). TEA (0.3417 kg) was added at room temperature and the reaction mixture was further stirred at T=60°C for 36 minutes. After cooling to room temperature, the organic layer is washed 6 times with a H ₂ O/MTBE mixture. PGMEA (87 kg) is added and a solvent exchange from IPA/MTBE to PGMEA is performed under reduced pressure. The solid content of the reaction mixture is adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) is added to the reaction mixture, which is further stirred at T=105° C. for 1,5 h. After cooling to room temperature, about 21 kg of solvent are removed by distillation, giving a final solid content of 5.23%. A portion of the polymer (7.17 g, 5.23% solids in PGMEA) was mixed with KY 1901 (0.4% in Novec 7100; 3.12 g), Novec 7100 (5.26 g), IPA (4.67 g), EG (0.62 g) and TEOS-based polymer (10% solids in PGME; 3.75 g).

Composition C-22 : AE 3000 (80 g) and KY 1900 (0.1 g) were mixed in IPA (20 g).

Composition C-23 : AE 3000 (80 g) and KY 1901 (0.1 g) were mixed in IPA (20 g).

c) Preparation of the third coating ( D ) Example Composition D-1 In a 250 L reactor, TEOS (43,436 g) and acetone (136 g) were mixed. HNO ₃ (0.01 M; 2,978 g) was slowly added to the reaction mixture over 10-20 minutes. The reaction mixture was then refluxed for 1 hour. After cooling to room temperature, PGME (115 kg) was added and a solvent exchange of acetone/H ₂ O/EtOH to PGME was performed under vacuum. The solid content of the mixture was adjusted to 10% by adding more PGME. A portion of the polymer (40 g, 10% solids in PGMEA) was mixed with DSX (0.4% in Novec 7100; 125 g), Novec 7100 (375.3 g), IPA (439 g) and EG (24.8 g).

Composition D-2 In a 250 L reactor, TEOS (43,436 g) and acetone (136 g) were mixed. HNO ₃ (0.01 M; 2,978 g) was slowly added to the reaction mixture over 10-20 minutes. The reaction mixture was then refluxed for 1 hour. After cooling to room temperature, PGME (115 kg) was added and a solvent exchange of acetone/H ₂ O/EtOH to PGME was performed under vacuum. The solid content of the mixture was adjusted to 10% by adding more PGME. A portion of the polymer (10,874 g, 10% solids in PGME) was mixed with DSX (0.4% in Novec 7100; 18,125 g), Novec 7100 (54,07 g), PGME (58,74 g) and EG (3,59 g).

Composition D-3 In a 1 L round-bottom flask, TEOS (86 g; 0,412 mol) was dissolved in acetone (272 g). KY 1271 (0.4 g) was added. HNO ₃ (0.1 M; 59.36 g) was added dropwise and the resulting reaction mixture was refluxed for 2 hours. The reaction mixture was then cooled to room temperature. PGME (125.12 kg) was added and a solvent exchange procedure of acetone/EtOH/H ₂ O to PGME was performed under vacuum. The solid content of the mixture was adjusted to 10% by adding more PGME. A portion of the polymer (8 g, 10% solids in PGME) was mixed with KY1901 (0.4% in Novec 7100; 35 g), SC019 (0.4% in Novec 7100; 15 g), Novec 7100 (119,2 g), PGME (67,04 g) and EG (4,96 g).

Composition D-4 In a 250 L reactor, TEOS (43,436 g) and acetone (136 g) were mixed. HNO ₃ (0.01 M; 2,978 g) was slowly added to the reaction mixture over 10-20 minutes. The reaction mixture was then refluxed for 1 hour. After cooling to room temperature, PGME (115 kg) was added and a solvent exchange of acetone/H ₂ O/EtOH to PGME was performed under vacuum. The solid content of the mixture was adjusted to 10% by adding more PGME. A portion of the polymer (6 g, 10% solids in PGME) was mixed with KY 1901 (0.675 g) and SC 019 (0.525 g), PGME (65.68 g), EG (3.72 g) and additional Novec 7100 (41.01 g) dissolved in Novec 7100 (32.55 g).

Composition D-5 In a 500 ml round-bottom flask, MTMS (40 g; 0,2936 mol), TEOS (61,17 g; 0,29364 mol), EtOH (101.17 g; 2,2075 mol) were mixed. Formic acid (0.1 M; 74 g) was added dropwise and the reaction mixture was refluxed at T = 105 ° C for 2 hours. The reaction mixture was cooled to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was performed under low pressure. The solid content was adjusted to 41.85% by adding PGME. A portion of the above material was then formulated for subsequent performance evaluation as follows: the material (0.47 g) was further diluted with IPA (34.52 g), KY 1901 (0.4% in Novec 7100, 2.5 g), and Novec 7100 (14.96 g).

Composition D-6 In a 500 ml round-bottom flask, MTMS (40 g; 0,2936 mol), TEOS (61,17 g; 0,29364 mol), EtOH (101.17 g; 2,2075 mol) were mixed. Formic acid (0.1 M; 74 g) was added dropwise and the reaction mixture was refluxed at T = 105 ° C for 2 hours. The reaction mixture was cooled to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was performed under low pressure. The solid content was adjusted to 41.85% by adding PGME. A portion of the above material was then formulated for subsequent performance evaluation as follows: the material (0.955 g) was further diluted with IPA (46.76 g), EG (2.48 g), KY 1901 (0.4% in Novec 7100, 22.5 g), and Novec 7100 (27.39 g).

Composition D-7 In a 500 ml round-bottom flask, MTMS (40 g; 0,2936 mol), TEOS (61,17 g; 0,29364 mol), EtOH (101.17 g; 2,2075 mol) were mixed. Formic acid (0.1 M; 74 g) was added dropwise and the reaction mixture was refluxed at T = 105 ° C for 2 hours. The reaction mixture was cooled to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was performed under low pressure. The solid content was adjusted to 41.85% by adding PGME. A portion of the above material was then formulated for subsequent performance evaluation as follows: the material (1.79 g) was further diluted with IPA (46.10 g), EG (2.48 g), KY 1901 (0.4% in Novec 7100, 22.5 g), and Novec 7100 (27.21 g).

Composition D-8 In a 500 ml round-bottom flask, MTMS (60 g; 0.44 mol), TEOS (91.76 g; 0.44 mol), EtOH (151.76 g) were mixed. Formic acid (0.1 M; 110.99 g) was added dropwise and the reaction mixture was refluxed at T = 105 ° C for 2 hours. The reaction mixture was cooled to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was performed under low pressure. The solid content was adjusted to 41.85% by adding PGME. A portion of the above material was then formulated for subsequent performance evaluation as follows: the material (0.89 g) was further diluted with IPA (22.86 g), EG (1.24 g), KY 1901 (0.4% in Novec 7100, 11.25 g), SC 019 (0.4% in Novec 7100, 6.25 g), and Novec 7100 (7.14 g).

Composition D-9 In a 500 ml round-bottom flask, MTMS (60 g; 0.44 mol), TEOS (91.76 g; 0.44 mol), EtOH (151.76 g) were mixed. Formic acid (0.1 M; 110.99 g) was added dropwise and the reaction mixture was refluxed at T = 105 ° C for 2 hours. The reaction mixture was cooled to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was performed under low pressure. The solid content was adjusted to 41.85% by adding PGME. A portion of the above material was then formulated for subsequent performance evaluation as follows: the material (2.69 g) was further diluted with EG (3.72 g), KY 1901 (0.4% in Novec 7100, 18.75 g), PGME (69.34 g) and Novec 7100 (55.95 g).

4. Preparation and properties of the coatings a) Two- or three-layer coatings on PMMA substrates First layer ( B ) The first layer coating was carried out on PMMA (375 μm) using a roll-to-roll pilot plant with composition 30. The web speed was 5 m/min and the slot die speed was 650 rpm. The coatings were cured by pre-baking at T=75°C for 3 minutes, followed by UV exposure at 1000 W for 30 seconds and then final baking at T=75°C as described.

Thickness of the roll-to-roll coating for 3 different coatings at 10 different points as described in Table 1. The average coating thickness is approximately 5 µm. Table 1 : Thickness of the roll-to-roll coating for 3 different coatings in µm Point 1 Point 2 Point 3 Point 4 Point 5 Point 6 Point 7 Point 8 Point 9 Point 10 PMMA coating roller to roller 1 5,4 5,3 5,6 5,3 5,7 5,5 5,6 5,6 5,1 5,3 PMMA coating roller to roller 2 5,3 5,6 5,6 5,8 5,6 5,6 5,6 5,5 5,8 5,3 PMMA coating roller to roller 3 5,1 5,5 5,6 5,8 5,6 5,7 5,7 5,7 5,6 5,6

The purpose of the second layer ( C ) double layer is to reduce the reflectivity. Depending on the solid content of the material and the amount and nature of the additives, the reflective properties vary. The second layer is added to the PMMA substrate coated with the first layer using a bar coater. Depending on the target thickness, bar coaters can have different properties, such as #1, #2, #3, #4. When using bar coater #1, the coating thickness is about 1-2 µm; when using bar coater #2, the coating thickness is about 2-3 µm; when using bar coater #3, the coating thickness is about 5 µm; when using bar coater #4, the coating thickness is about 7-8 µm. Plasma treatment may be required after coating. Cure the coating in an oven at T = 80 ° C for 1 hour.

The following coatings were applied on the PMMA substrates as listed in Table 2. Table 2 : Two-layer coatings on PMMA substrates Embodiment Composition layer (B) Composition layer (C) Scraper coating machine Plasma treatment 1 B-30 C-2 2 without 2 B-30 C-2 3 without 3 B-30 C-4 2 without 4 B-30 C-5 1 without 5 B-30 C-5 2 without 6 B-30 C-7 1 without 7 B-30 C-7 2 without 8 B-30 C-8 2 without 9 B-30 C-9 4 without 10 B-30 C-13 2 without 11 B-30 C-14 3 without 12 B-30 C-15 1 without 13 B-30 C-16 1 without 14 B-30 C-17 1 without 15 B-30 C-18 1 without 16 B-30 C-19 1 without 17 B-30 C-20 1 without 18 B-30 C-21 1 without

b) Two-layer coating on PET or CPI substrates First layer ( B ) The substrate was pre-treated by plasma (6 min, 300 W) and then coated with the first layer using a bar coater (#3) with composition B-31. The coating was pre-cured at T=120°C for 90 sec (PET) or at T=140°C for 3 min (CPI), then UV cured (30 sec, 500 W) and finally baked at T=120°C for 10 min (PET) or at T=140°C for 15 min (CPI).

Second layer ( C ) After plasma treatment (1 min, 300 W), the previous layer was applied using a bar coater (#2) and composition C-22 for the second layer. The coating was cured at T = 120 °C for 0.5 h (PET) or at T = 140 °C for 0.5 h (CIP).

The following coatings were applied on PET and CPI substrates with two layers of coating as listed in Table 3. Table 3 : Two layers of coating on PET or CPI substrates Embodiment Substrate Composition layer (B) Composition layer (C) Scraper coating machine 35 CPI 50 µm 36 CPI 80 µm 37 PET 38 CPI 50 µm B-31 C-22 2 39 CPI 80 µm B-31 C-22 2 40 PET B-31 C-22 2

5. Properties of Examples a) Optical Properties of Two Coatings on PMMA Substrates The reflectivity and transmittance of Examples 1, 2, 3, 4, 5, 7 and 8 were measured.

The reflectivity of these two coatings in the wavelength range of 360 nm to 740 nm is shown in Figure 1.

The transmittance of these two coatings in the wavelength range of 360 nm to 740 nm is shown in Figure 2.

Table 4 shows the reflectivity (R%) and transmittance (T%) of the embodiment at 550 nm. Table 4 : Reflectivity (R%) and transmittance (T%) of two coating layers on PMMA at 550 nm Embodiment R% (at 550 nm) T% (at 550 nm) 1 3.39 93.97 2 2.09 94.82 3 4.0 93.15 5 0.72 95.66 7 2.23 94.62 8 2.75 94.38

Table 5 shows the variation of the optical properties depending on the composition of the second layer (C) and the thickness of the second layer (C) (see Table 2) as indicated in the bar coater used.

Bare PMMA exhibited a transmittance of 92.98%.

Therefore, all examples show improved optical properties. Example 5 obtains the best optical properties. It can be seen from Examples 1 and 2 that the increase in the thickness of the second layer (C) improves the optical properties.

b) Mechanical properties of two coatings on PMMA substrates The mechanical properties of Examples 5, 6, 9, 10, 11, 12, 13, 14, 15, 16, 17 and 18 were measured and listed in Table 5. Table 5 : Mechanical properties of two coatings on PMMA Abrasion test 500 cycles, 500 g Embodiment Film VQ WCA VQ CA Adhesion 5 84 All gone 0B 6 82 All gone 0B 9 83 Almost disappeared 0B 10 The membrane can 103 3 (all disappeared) 11 The membrane can 81 Almost disappeared 0B 12 76 Almost disappeared 0B 13 The membrane can 93 3 83 14 The membrane can 96 (2)-3 81 15 The membrane can 97 2-(3) 84 16 The membrane is OK, but the edges are cloudy 103 3 83 17 Turbid 108 3 82 18 Quite cloudy 101 1-2 83

Compared with Examples 5, 6, 9, 10, 11 and 12, Examples 13, 14, 15, 16, 17 and 18 show better mechanical properties, especially in terms of wear resistance.

c) Optical properties of two coating layers on CPI and PET substrates. The reflectivity and transmittance of Examples 35, 36, 37, 38, 39 and 40 were measured.

The reflectivity of these two coatings in the wavelength range of 360 nm to 740 nm is shown in FIG. 3 .

Compared to the bare substrate (Examples 35 to 37), the reflectivity of all coated substrates (Examples 38 to 40) decreased. At 550 nm wavelength (i.e., the wavelength range where the human eye is most sensitive), the ΔR% of 50 μm CPI decreased by about 2.13% points (Example 38), 80 μm CPI decreased by 1.68% points (Example 39), and PET decreased by 1.89% points (Example 40).

The transmittance of these two coatings in the wavelength range of 360 nm to 740 nm is shown in FIG. 4 .

Compared to the bare substrate (Examples 35 to 37), the transmittance of all coated substrates (Examples 38 to 40) increased. At 550 nm wavelength (i.e., the wavelength range where the human eye is most sensitive), the ΔT% of 50 μm CPI increased by about 1.25% points (Example 38), 80 μm CPI increased by 1.22% points (Example 39), and PET increased by 1.04% points (Example 40).

d) Mechanical properties of two-layer coatings on CPI and PET substrates The mechanical properties of Examples 38 to 40 were measured and listed in Table 6. Table 6: Mechanical properties of two-layer coatings on CPI and PET substrates initial 400c 800c 1200c 1600c 2000c Embodiment PEHA Adhesion WCA Initial VQ CA VQ CA VQ CA VQ CA VQ CA 38 H 5B 113 0 112 0 112 0 112 0 111 0-1 110 39 3H 5B 115 0 114 0 110 0 111 0 114 0-1 113 40 3H 5B 114 0 114 0 112 0 113 0 114 0-1 111

After 2000 cycles of eraser, all coated substrates showed no signs of scratches and maintained a water contact angle of more than 100°. Therefore, the coated samples showed excellent wear resistance and excellent hydrophobicity. The bare substrate had very poor wear because it was full of scratches after hundreds of cycles of eraser, and the initial water contact angle was about 75°.

without

[Figure 1] shows the reflectivity of a 2-layer system with different materials/formulations. [Figure 2] shows the transmittance of a 2-layer system with different materials/formulations. [Figure 3] shows the reflectivity of a 2-layer coating. [Figure 4] shows the transmittance of a 2-layer coating.

Claims (15)

A layered structure comprising (A) a substrate layer; (B) a first coating layer coated on at least one surface of the substrate layer (A); and (C) a second coating layer coated on at least one surface of the first coating layer (B), so that the second coating layer (C) is in adhesive contact with at least one surface of the first coating layer (B), wherein the first coating layer (B) comprises a first siloxane polymer (B-1) and has a thickness of 1 to 50 μm; the second coating layer (C) comprises a fluoropolyether compound and has a thickness of 10 nm to 10 μm; and the substrate layer (A) is flexible, bendable, or both, and has a thickness of 10 to 500 μm. The layered structure of claim 1, wherein the first siloxane polymer (B-1) comprises monomer units selected from at least two different silane monomers, wherein at least one of the silane monomers comprises an active group capable of achieving crosslinking with adjacent siloxane polymer chains, and wherein the adjacent siloxane polymer chains are crosslinked with the aid of the active group. A layered structure as claimed in claim 1, wherein the second coating layer (C) further comprises one or more second siloxane polymers (C-1). A layered structure as claimed in claim 1, wherein the first coating layer (B) has a thickness of 2 to 20 μm, and/or the second coating layer (C) has a thickness of 25 nm to 8 μm. A layered structure as claimed in claim 1, wherein the material of the substrate layer (A) is selected from the group consisting of glass, quartz, silicon, silicon nitride, polymer, metal and plastic and combinations thereof. A layered structure as claimed in claim 5, wherein the plastics are selected from thermoplastic polymers, polyesters, polyamides, polyimides, acrylic polymers and custom designed polymers. A layered structure as claimed in claim 1, wherein the thickness of the substrate layer (A) is 20 to 400 μm. The layered structure of claim 1 further comprises a third coating layer (D) coated on at least one surface of the second coating layer (C), so that the third coating layer (D) is in adhesive contact with at least one surface of the second coating layer (C). The layered structure of claim 8, wherein the third coating layer (D) comprises a silicone polymer and a fluoropolyether compound selected as appropriate. A layered structure as claimed in claim 8, wherein the third coating layer (D) has a thickness of 10 nm to 10 μm. A method for producing a layered structure as claimed in any one of claims 1 to 10, comprising the following steps: providing a first composition comprising at least two different silane monomers, wherein at least one of the silane monomers comprises an active group capable of achieving crosslinking with an adjacent siloxane polymer; subjecting the first composition to at least partial hydrolysis of the monomers to form a composition comprising a first siloxane polymer (B-1); providing a second composition comprising a fluoropolyether compound; providing a flexible or bendable substrate or both; ; depositing the first component onto at least one surface of the substrate to form a first coating layer (B) in adhesive contact with the at least one surface of the substrate; cross-linking the siloxane polymer chains of the first coating layer (B) to obtain a first coating layer (B) comprising cross-linked siloxane polymers in adhesive contact with the at least one surface of the substrate; depositing the second component onto the first coating layer (B) to form a second coating layer (C) in adhesive contact with the first coating layer (B); curing the second component of the second coating layer (C). The method of claim 11, wherein the first component comprising a siloxane polymer (B-1) is formed by a method comprising the following steps: Mix the at least two different silane monomers in a first solvent to form a mixture; subject the mixture to at least partial hydrolysis of the monomers in the presence of a catalyst, thereby causing the hydrolyzed monomers to at least partially polymerize and crosslink; optionally replacing the first solvent with a second solvent; optionally further crosslinking the mixture by hydrosilylation, heat or radiation. The method of claim 11, wherein the first component and/or the second component is deposited by spin coating, nip coating, spraying, ink jetting, roll-to-roll, gravure printing, reverse gravure printing, doctor bar coating, slot coating, flexographic printing, curtain coating, screen printing coating, extrusion coating, dip coating, shower coating or slot coating. The method of claim 11 further comprises the steps of providing a third composition comprising a siloxane polymer and, if appropriate, a fluoropolyether compound; depositing the third composition onto the second coating layer (C) to form a third coating layer (D) in adhesive contact with the second coating layer (C); cross-linking the siloxane polymer chains of the third coating layer (D) to obtain a third coating layer (D) comprising one or more cross-linked siloxane polymers in adhesive contact with the second coating layer (C). A use of a layered structure as claimed in any one of claims 1 to 10 in flexible electronic applications selected from displays, optical lenses, transparent panels and the automotive industry.

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