TW202402542A - 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 polysiloxane based coating layer (C), a method for preparing said layered structure and the use of said layered structure for flexible electronics applications.

Description

Flexible multi-layer polysiloxane hard coating

The present invention relates to a layered structure comprising a flexible or bendable substrate layer (A), a first polysiloxane-based coating (B) and a second polysiloxane-based coating (C), with respect to 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 high light transmittance due to their high light transmittance. The properties and properties of suitable refractive index have been used in flexible electronic applications, including displays, optical lenses, transparent plates and the automotive industry as a lightweight alternative to glass. However, these plastics have the disadvantage of low wear resistance because they have a lower surface hardness than glass.

To increase wear resistance and photopatternability, flexible and bendable hardcoat films have been suggested. Suitable flexible hard coatings are, for example, polysiloxane-based flexible hard coatings as disclosed in WO 2019/193258.

Hard coats have the disadvantage of reducing the visibility of displays, for example, due to increased light reflection. To reduce light reflection, anti-reflective coatings have been proposed as an additional layer on top of the hard coat in a multi-layer approach.

For example, WO 2006/082701A1 discloses a two-layer coating on a transparent plastic film substrate having a curable compound containing (meth)acrylate groups and a reactive polysilica containing (meth)acrylate groups. A first hard coat of material from oxygen, and a second anti-reflective (low refractive) coating from a material containing a compound containing a siloxane component.

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

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

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

When applying a low refractive layer as the inner layer and a hard coat as the outer layer as discussed in TW 2009-16818 A, the coating exhibits good scratch resistance and lower rainbow patterns, but does not solve the high reflectivity problem.

Therefore, there is a need in this technology 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 use with To reduce light reflection.

In the present invention, a multilayer coating is proposed which exhibits such an improved balance of properties. The multi-layer coating consists of two polysiloxane-based coatings, with the inner layer being a polysiloxane-based flexible hard coat and the second layer being an anti-reflective layer.

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

Furthermore, the invention relates to a method for producing a layered structure as described above or below, comprising the following steps: ● Provide a first composition comprising at least two different silane monomers, wherein at least one of the silane monomers includes a reactive group capable of achieving cross-linking with adjacent siloxane polymers; ● Subjecting the first composition to at least partial hydrolysis of the monomers to form a composition comprising the first siloxane polymer (B-1); ● Provide a second composition containing at least one silane monomer; ● Subjecting the second composition to at least partial hydrolysis of the monomers to form a composition comprising one or more second siloxane polymers (C-1); ● Provide flexible or bendable substrates or both; ● Deposit the first composition onto at least one surface of the substrate to form a first coating (B); ● Cross-linking the siloxane polymer chains of the first coating (B) so as to obtain a first coating (B) comprising a cross-linked siloxane polymer in adhesive contact with the at least one surface of the substrate; ● Deposit the second composition onto the first coating (B) to form a second coating (C) in adhesive contact with the first coating (B); ● Cross-linking the siloxane polymer chains of the second coating (C) to obtain a second coating comprising one or more cross-linked siloxane polymers in adhesive contact with the first coating (B) Layer (C).

The multilayer coatings of the present invention exhibit good interlayer adhesion, resulting in an improved balance of properties in terms of mechanical properties (especially scratch resistance) and optical properties (especially low refractive index).

In one specific embodiment, an additional third coating is applied to the second coating, which further improves the mechanical properties of the multilayer coating.

In this specific example, the invention relates to a layered structure comprising: (A) Substrate layer; and (B) a first coating coated on at least one surface of the substrate layer (A), (C) a second coating coated on at least one surface of the first coating (B) such that the second coating (C) is in adhesive contact with at least one surface of the first coating (B), and (D) The third coating (D) coated on at least one surface of the second coating (C) such that the third coating (D) and at least one surface of the second coating (C) adhesive contact, in The first coating (B) includes a first siloxane polymer (B-1); The second coating (C) includes one or more second siloxane polymers (C-1); and The substrate layer (A) is flexible, bendable or both.

Furthermore, in this particular embodiment, the invention relates to a method for manufacturing a layered structure as described above or below, comprising the steps of: ● Provide a first composition comprising at least two different silane monomers, wherein at least one of the silane monomers includes a reactive group capable of achieving cross-linking with adjacent siloxane polymers; ● Subjecting the first composition to at least partial hydrolysis of the monomers to form a composition comprising the first siloxane polymer (B-1); ● Provide a second composition containing at least one silane monomer; ● Subjecting the second composition to at least partial hydrolysis of the monomers to form a composition comprising one or more second siloxane polymers (C-1); ● Provide a third composition containing at least one silane monomer and at least one monomer containing a fluorocarbon group; ● Subjecting the third composition to at least partial hydrolysis of the monomers to form a composition comprising a siloxane polymer comprising side chains comprising one or more fluorocarbon groups ; ● Provide flexible or bendable substrates or both; ● Deposit the first composition onto at least one surface of the substrate to form a first coating (B); ● Cross-linking the siloxane polymer chains of the first coating (B) so as to obtain a first coating (B) comprising a cross-linked siloxane polymer in adhesive contact with the at least one surface of the substrate; ● Deposit the second composition onto the first coating (B) to form a second coating (C) in adhesive contact with the first coating (B); ● Cross-linking the siloxane polymer chains of the second coating (C) to obtain a second coating comprising one or more cross-linked siloxane polymers in adhesive contact with the first coating (B) Layer (C); ● Deposit the third composition onto the second coating (C) to form a third coating (D) in adhesive contact with the second coating (C); ● Cross-linking the siloxane polymer chains of the third coating (D) to obtain a third coating comprising one or more cross-linked siloxane polymers in adhesive contact with the second coating (C) Layer (D).

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

Various illustrative and non-limiting embodiments of construction and methods of operation, along 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 "include" and "include" are used in this document as open limitations, which neither exclude nor require the presence of unstated characteristics. The features described in the subparagraphs may be freely combined with each other unless expressly stated otherwise.

The present technology provides a layered structure in which substrate layer (A) has at least two layers comprising a siloxane polymer. The layered structure is "bendable," meaning that it can bend around a mandrel with a radius of curvature without breaking.

As described in WO 2019/193258, bending properties can be tested using a test involving folding in or out of a layered structure about a mandrel.

Substrate layer (A) The substrate layer (A) can be any kind of substrate, such as glass, quartz, silicon, silicon nitride, polymer, metal, 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 design polymers.

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

Substrate layer (A) may be the outermost layer of the device or an inner layer of a single stack. The substrate layer (A) can be coated on one 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 such that it can be bent about a mandrel having a first minimum radius of curvature without breaking. The layered structure of the present invention is particularly capable of bending without breakage about a mandrel having a second minimum radius of curvature, 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 prior to depositing the first composition on at least one surface of the substrate to form the first coating (B).

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

Suitable for physical modification to plasma treatment or 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 (B).

In one embodiment, the optional coating composition is deposited on at least one surface of the substrate layer (A), and thus 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 with the first coating (B) on the other side.

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

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

In certain cases, optional additional coatings are usually applied, such as promoting adhesion between the substrate layer (A) and the first coating (B), wetting the first coating (B), promoting delamination The optical performance of the structure may enhance the mechanical performance of the layered structure.

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

First coat (B) The first coating (B) is coated on at least one surface of the substrate layer (A) to form the first coating (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 (B) is typically an inner layer of a multi-layer coating having adhesive contact with at least one surface of the substrate layer (A). In this context, "adhesive contact" means that there is no other coating or adhesive layer between the substrate layer (A) and at least one surface of the first coating (B).

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

The first coating layer (B) contains the 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 is capable of achieving cross-linking with adjacent siloxane polymer chains. reactive groups, and adjacent siloxane polymer chains are cross-linked by means of these reactive groups.

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 groups are preferably epoxy, alicyclic epoxy (such as glycidyl), vinyl, allyl, acrylate, methacrylate and silane groups and combinations thereof.

Thus, epoxy, alicyclic epoxy (such as glycidyl), vinyl, allyl, acrylate, methacrylate groups are preferably used in thermal or radiation initiation with suitable initiators such as Cross-linking with adjacent siloxane polymer chains can be achieved in the presence of thermal or free radical initiators).

Suitable thermal or free radical initiators are preferably selected from tertiary amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanemethane) nitrile), benzyl peroxide, 2,2-bis(tertiary butylperoxy)butane, 1,1-bis(tertiary butylperoxy)cyclohexane, 2,2'-azobis Isobutyronitrile (AIBN), 2,5-bis(tertiary butylperoxy)-Z,S-dimethylhexane, 2,5-bis(tertiary butylperoxy)-2,5-dimethylhexane Methyl-3-hexyne, bis(1-(tertiary butylperoxy)-1-methylethyl)benzene, 1,1-bis(tertiary butylperoxy)-3,3,5- Trimethylcyclohexane, tertiary butyl hydroperoxide, tertiary butyl peracetate, tertiary butyl peroxide, tertiary butyl peroxybenzoate, tertiary butyl peroxyisopropyl carbonate, Cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauryl peroxide, 2,4-pentanedione peroxide, peracetic acid or potassium persulfate. Particularly preferred is 2,2'-azobisisobutyronitrile (AIBN).

The silane group can be used in the hydrosilylation, preferably in the presence of suitable catalysts such as those based on platinum (Pt), such as Speier catalysts (H ₂ PtCl ₆ .H ₂ O), Karstedt catalysts (Pt(0)-1,3- divinyl-1,1,3,3-tetramethyldisiloxane complex solution) or a rhodium (Rh)-based catalyst such as tris(triphenylphosphine)rhodium(I) chloride) Achieve cross-linking with carbon-carbon double bonds (such as vinyl or allyl) of adjacent siloxane polymer chains.

In a specific example, a monomer containing a first reactive group, such as a monomer selected from epoxy, alicyclic epoxy (such as glycidyl), vinyl and allyl, and a second reactive group, For example, the molar ratio between monomers selected from acrylate groups and methacrylate groups is 1:100 to 100:1, specifically 1:10 to 10:1, such as 5:1 to 1:2 or Varies within the range of 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, trimethylolpropane triacrylate, etc. Acrylates, neopenterythritol triacrylate, bistrimethylpropane tetraacrylate, dipenterythritol pentaacrylate and dipenterythritol hexaacrylate, and combinations thereof.

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

The suitable silane monomer is preferably represented by formula (I) R ¹ _a SiX _4-a (I) wherein R ¹ is selected from hydrogen and includes linear and branched chain alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, ( Alkyl) acrylate, epoxy, allyl, vinyl and alkoxy groups and aryl groups having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X is hydrolyzable group or hydrocarbon residue; and a is an integer from 1 to 3.

The hydrolyzable groups are especially alkoxy groups (see formula II).

The alkoxy groups ^of R ¹ and/or ^the hydrolyzable group A straight or branched chain alkyl group of 6 carbon atoms, optionally presenting one or two substituents selected from the group consisting of halogen, hydroxyl, vinyl, epoxy and allyl. Most preferred are methoxy and ethoxy.

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

Particularly suitable silane monosystems are selected from the group consisting of: tetraethoxysilane (TEOS), tetramethoxysilane (TMS), methyltriethoxysilane (MTEOS), methyltrimethoxysilane (MTMS) ), dimethyldiethoxysilane (DMDEOS), dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPDMS), 3-(trimethoxysilyl)propylmethyl acrylate (MEMO), 3-(triethoxysilyl)propyl methacrylate, 5-(bicycloheptenyl)triethoxysilane (BCHTEOS), (3-glycidoxypropyl )Triethoxysilane, (3-glycidoxypropyl)trimethoxysilane (GPTMS), (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane (F17) , (Heptafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, 1H,1H,2H , 2H-Perfluorododecyltrimethoxysilane, 1H,1H,2H,2H-Perfluorooctyltriethoxysilane, 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane (F13 ), 1H,1H,2H,2H-Perfluoropentyltriethoxysilane, 1H,1H,2H,2H-Perfluoropentyltrimethoxysilane, 1H,1H,2H,2H-Perfluorotetradecane Triethoxysilane, 1H,1H,2H,2H-perfluorotetradecyltrimethoxysilane, allyltrimethoxysilane (allylTMS), allyltriethoxysilane (allylTEOS), ethylene Trimethoxysilane, vinyltriethoxysilane, (3-glycidyloxypropyl)dimethoxymethylsilane (Me-GPTMS), methacryloxypropylmethyldimethoxysilane silane (Me-MEMO), phenylmethyldimethoxysilane (PMDMS), bis[(2,2,3,3,4,4-hexafluorobutyl)propionate]-3-amino Propyltrimethoxysilane or mixtures thereof.

The silane monomer is preferably selected from phenylmethyldimethoxysilane (PMDMS), 3-(trimethoxysilyl)propyl methacrylate (MEMO) and (3-glycidoxypropyl) Trimethoxysilane (GPTMS) group.

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 a specific example, at least two different silane monomers of the first siloxane polymer (B-1) include at least one disilane.

A suitable bissilane is preferably represented by formula (III) (R ³ ) ₃ Si-Y-Si(R ⁴ ) ₃ , (III) wherein R ³ and R ⁴ are independently selected from hydrogen and straight or branched chain alkane. Groups consisting of alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl, alkoxy and aryl groups with 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, aryl, -O -Alkylene-O-; -O-arylene-O-; Alkylene-O-alkylene, aryl-O-arylene; Alkylene- ^{Z 1} C(=O)Z ² -Alkylene, aryl-Z ¹ C(=O)Z ² -Aryl and -O-alkylene-Z ¹ C(=O)Z ² -phenylene-O-;-O -arylene-Z ¹ C(=O)Z ² -arylene-O-, where Z ¹ and Z ² are each selected from direct bonds or -O-.

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

"Aryl" represents an aromatic divalent group typically containing 1 to 3 aromatic rings and 6 to 18 carbon atoms. Such groups are exemplified by phenylene groups (eg 1,4-phenylene and 1,3-phenylene groups) and biphenylene groups as well as naphthylene or anthracenyl groups.

Alkylene and aryl groups are optionally substituted by 1 to 5 substituents selected from hydroxyl, halo, vinyl, epoxy and allyl and alkyl, aryl and aralkyl.

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

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

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

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

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

The first composition including siloxane polymer (B-1) is preferably formed by a method including the following steps: ● Mix at least two different silane monomers, preferably as described above or below, in the 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 at least partial polymerization and cross-linking of the hydrolyzable monomers; ● Replace the first solvent with the second solvent as appropriate; ● Further cross-linking of the mixture may be initiated by hydrosilation, heat or radiation, as appropriate.

The first solvent is preferably selected from the following group: acetone, tetrahydrofuran (THF), toluene, 1-propanol, 2-propanol, methanol, ethanol, water (H ₂ O), 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 can be mixed in the first solvent at any suitable temperature to dissolve the silane monomers. Normally, room temperature is sufficient.

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

Suitable catalysts are acidic catalysts, basic 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 basic 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 at room temperature overnight.

During the hydrolysis step, the silane monomer is at least partially hydrolyzed. The at least partially hydrolyzed silane monomer is then at least partially polymerized, preferably by condensation polymerization, and cross-linked to form a siloxane polymer.

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

According to a preferred embodiment, the mixture is subjected to at least partial hydrolysis including reflux. Typical reflow time is 2 hours.

After the hydrolysis step, in an optional further method step, the first solvent can be exchanged for a second solvent. Optional solvent exchange is advantageous as it helps remove water and alcohol formed during hydrolysis of the silane monomer. Additionally, when used as a coating on a substrate, it improves the properties of the final siloxane polymer solution.

The second solvent is preferably selected from 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) group.

The mixture containing the siloxane polymer may further undergo a crosslinking step after the hydrolysis step. Thus, the siloxane polymer is preferably at least partially cross-linked by hydrosilylation, heat or radiation.

In this context, the term "partially cross-linked" means that the polymer is capable of further cross-linking under conditions conducive to cross-linking. In practice, the polymer still contains at least some reactive crosslinking groups after the first polymerization step. Further cross-linking that typically occurs after the partially cross-linked composition is deposited on the substrate is described below.

The siloxane polymer is preferably at least partially cross-linked by hydrogenation, heat or radiation using a catalyst as described above.

Therefore, thermal cross-linking is preferably performed at a temperature in the range of about 30°C to 200°C.

Typically cross-linking is carried out under reflux conditions of the solvent.

In order to improve the resolution of the material when used in photolithography, the siloxane polymer may optionally be partially cross-linked during polymerization, in particular during condensation polymerization or immediately after condensation polymerization. Various methods can be used to achieve cross-linking. For example, a cross-linking method may be used in which the two chains are joined via reactive groups that do not interfere with any reactive groups intended for UV photolithography. For example, hydrosilylation, such as using protons on one chain to react with double bonds on another chain, will achieve the desired kind of cross-linking. Another example is cross-linking via double bonds or epoxy groups.

Different reactive groups are preferred for cross-linking and for photolithography. Thus, siloxane polymers can be cross-linked using free radical initiators and photoacid generators with reactive groups having double bonds or epoxy groups or both, such as epoxy, vinyl or allyl groups. or methacrylate group).

Epoxies can be used for UV photolithography and vice versa. The proportion of reactive groups required for cross-linking is usually smaller than that required for UV photolithography, for example about 0.1 to 10 mol % based on monomer for cross-linking and about 5 to 50 mol % based on monomer. For use in UV photolithography.

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 cross-linking, the molecular weight will typically be 2 to 10 times greater. Therefore, cross-linking will increase it to more than 3000 g/mol, preferably to 4000 to 20000 g/mol, based on molecular weights in the range of about 500 to 2000 g/mol.

Optionally, the resulting free Si-OH groups present in the backbone of the siloxane polymer can be protected by end-capping. For capping, the free Si-OH groups are combined with silane (such as methyldichlorofluorosilane (Cl ₂ FSiCH _{3 )} , methylfluorodimethoxysilane ((MeO) ₂ SiFCH ₃ ), 3-chloropropyltrimethyl Oxysilane (Cl(CH ₂ ) ₃ Si(OMe) ₃ ), ethyltrimethoxysilane (ETMS) or trimethylchlorosilane (ClSiMe ₃ )) in a catalyst such as triethylaluminum (TEA) or imidazole The amount of catalyst varied from 1.5 to 2 wt% of total solids. The reaction time varied from 40 to 45 min.

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

These additives can be surfactants, defoaming agents, 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 solids.

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

By adjusting the hydrolysis and condensation conditions, the groups capable of deprotonation (e.g., OH-groups) and any residual leaving groups (e.g., alkoxy groups) from the silane precursor of the siloxane polymer composition can be controlled. concentration/content, and also controls the final molecular weight of the siloxane polymer. 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 developing solution.

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

On the other hand, if the final siloxane polymer has a high residual alkoxy-group content and it contains hardly any OH-groups, then the final siloxane polymer will show better performance in the above types of alkali-water developers. Has very low solubility in. OH-groups or other functional groups such as amine (NH ₂ ), thiol (SH), carboxyl, phenol or similar functional groups that create solubility in alkaline developer systems can be attached directly to the siloxane polymer Silicon atoms in the polymer backbone or optionally organic functional groups attached to the siloxane polymer backbone are attached to further promote and control alkaline developer solubility.

After 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, another amount of initiator molecular compound is added to the siloxane composition after synthesis. The initiator may optionally be similar to the initiator added during polymerization to produce a substance that can initiate polymerization of the "active" functional groups in the UV curing step. Therefore, in the case of epoxy groups, cationic or anionic initiators can be used. Free radical initiators can be used in the case of groups in synthetic materials that have double bonds as "reactive" functional groups. In addition, thermal initiators (working according to free radical, cationic or anionic mechanisms) can be used to promote cross-linking of "reactive" functional groups. The selection 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 thermal or radiation initiator and sensitizer in the composition is generally about 0.1 to 10%, preferably about 0.5 to 5%, calculated based on the mass of the siloxane polymer.

Compositions as described above may include solid nanoparticles or other compounds in an amount between 1 wt% and 50 wt% of the composition. Nanoparticles (or similar nano- or microscale rods, crystals, spheres, dots, buds, etc.) are especially selected from the group consisting of light-scattering, light-absorbing, light-emitting and/or conductive pigments, dyes, organic and inorganic phosphors, oxides, Quantum dots, polymers or groups of metals.

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

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

Suitable deposition methods include spin coating, pinch coating, spray, inkjet, roll-to-roll, gravure printing, reverse gravure printing, bar coating, slot coating, flexographic printing, curtain coating, screen printing coating Distribution method, extrusion coating, dip coating, flow coating or slot coating.

The deposited first composition including siloxane polymer (B-1) forms coating (B) on the surface of 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 optionally by combined vacuum and/or thermal drying. This step is also called pre-curing.

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

In one specific example, the pre-curing and final curing steps are combined by heating using an increasing heating gradient. Curing can be performed in three steps, in addition to a thermal-only cure process that includes thermal pre-cure and UV cure, followed by final thermal cure. A two-step curing process can also be applied, with thermal pre-curing followed by UV curing. In this case, it is preferred not to apply final thermal curing after UV curing.

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

Therefore, in a specific example, the method consists of the following steps - Pre-curing or drying of the first coating (B) deposited on the substrate (A); - Exposure to this coating (B) as appropriate; - Optionally develop the coating (B) thus obtained; and - Cured coating (B).

Exemplary epoxy functional group-containing monomers include (3-glycidoxypropyl)trimethoxysilane, 1-(2-(trimethoxysilyl)ethyl)cyclohexane-3,4-cyclo Oxide, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)tripropoxysilane, 3-glycidoxypropyltris(2-methoxy Ethoxy)silane, 2,3-epoxypropyltriethoxysilane, 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, trimethylolpropane triacrylate, neopentylerythritol triacrylate, bis(trimethylolpropane) Tetraacrylate, dipenterythritol pentaacrylate, tricyclodecane dimethanol diacrylate, tris(2-hydroxyethylisocyanurate) di/triacrylate and dineopenterythritol hexaacrylate and combinations thereof. Such acrylates are commercially available, for example Miramer acrylate from Miwon. Such compounds can be used as part of the silane composition.

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

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

Coating (B) is preferably a flexible hard coating.

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

In addition, coating (B) was superior to scratch resistance as evidenced by the absence of visual scratches in the Taber Linear Abrasion Test (using a linear abrasion machine from Taber Industries) using BonStar Steel Wool #0000, in 500 g weight, 2×2 cm head size, 2.0-inch stroke length, up to 2000 linear cycles at 60 cycles/min.

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

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

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

The following discussion may apply to each of the second siloxane polymers (C-1):

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

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

Adjacent siloxane polymer chains are then cross-linked, usually by means of 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.

Reactive groups, if present, are preferably epoxy, cycloaliphatic epoxy (eg glycidyl), vinyl, allyl, acrylate, methacrylate and silane groups and combinations thereof.

Thus, epoxy, alicyclic epoxy (such as glycidyl), vinyl, allyl, acrylate, methacrylate groups are preferably used in thermal or radiation initiation with suitable initiators such as Cross-linking with adjacent siloxane polymer chains can be achieved in the presence of thermal or free radical initiators).

Suitable thermal or free radical initiators are preferably selected from tertiary amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanemethane) nitrile), benzyl peroxide, 2,2-bis(tertiary butylperoxy)butane, 1,1-bis(tertiary butylperoxy)cyclohexane, 2,2'-azobis Isobutyronitrile (AIBN), 2,5-bis(tertiary butylperoxy)-Z,S-dimethylhexane, 2,5-bis(tertiary butylperoxy)-2,5-dimethylhexane Methyl-3-hexyne, bis(1-(tertiary butylperoxy)-1-methylethyl)benzene, 1,1-bis(tertiary butylperoxy)-3,3,5- Trimethylcyclohexane, tertiary butyl hydroperoxide, tertiary butyl peracetate, tertiary butyl peroxide, tertiary butyl peroxybenzoate, tertiary butyl peroxyisopropyl carbonate, Cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauryl peroxide, 2,4-pentanedione peroxide, peracetic acid or potassium persulfate. Particularly preferred is 2,2'-azobisisobutyronitrile (AIBN).

The silane group can be used in the hydrosilylation, preferably in the presence of suitable catalysts such as those based on platinum (Pt), such as Speier catalysts (H ₂ PtCl ₆ .H ₂ O), Karstedt catalysts (Pt(0)-1,3- divinyl-1,1,3,3-tetramethyldisiloxane complex solution) or a rhodium (Rh)-based catalyst such as tris(triphenylphosphine)rhodium(I) chloride) Achieve cross-linking with carbon-carbon double bonds (such as vinyl or allyl) of adjacent siloxane polymer chains.

In a specific example, a monomer containing a first reactive group, such as a monomer selected from epoxy, alicyclic epoxy (such as glycidyl), vinyl and allyl, and a second reactive group, For example, the molar ratio between monomers selected from acrylate groups and methacrylate groups is 1:100 to 100:1, specifically 1:10 to 10:1, such as 5:1 to 1:2 or Varies within the range of 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, trimethylolpropane triacrylate, etc. Acrylates, neopenterythritol triacrylate, bistrimethylpropane tetraacrylate, dipenterythritol pentaacrylate and dipenterythritol hexaacrylate, and combinations thereof.

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

The suitable silane monomer is preferably represented by formula (I) R ¹ _a SiX _4-a (I) wherein R ¹ is selected from hydrogen and includes linear and branched chain alkyl, cycloalkyl, alkenyl, alkynyl, ( Alkyl) acrylate, epoxy, allyl, vinyl and alkoxy groups and aryl groups having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X is hydrolyzable group or hydrocarbon residue; and a is an integer from 1 to 3.

The hydrolyzable groups are especially alkoxy groups (see formula II).

The alkoxy groups ^of R ¹ and/or ^the hydrolyzable group A straight or branched chain alkyl group of 6 carbon atoms, optionally presenting one or two substituents selected from the group consisting of halogen, hydroxyl, vinyl, epoxy and allyl. Most preferred are methoxy and ethoxy.

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

Particularly suitable silane monosystems are selected from the group consisting of: tetraethoxysilane (TEOS), tetramethoxysilane (TMS), methyltriethoxysilane (MTEOS), methyltrimethoxysilane (MTMS) ), dimethyldiethoxysilane (DMDEOS), dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPDMS), 3-(trimethoxysilyl)propylmethyl acrylate (MEMO), 3-(triethoxysilyl)propyl methacrylate, 5-(bicycloheptenyl)triethoxysilane (BCHTEOS), (3-glycidoxypropyl )Triethoxysilane, (3-glycidoxypropyl)trimethoxysilane (GPTMS), (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane, (deca Heptafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane (F17), 1H,1H,2H,2H-perfluorodecyltriethoxysilane, 1H,1H,2H ,2H-Perfluorooctyltrimethoxysilane, 1H,1H,2H,2H-Perfluorooctyltriethoxysilane, 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane, 1H ,1H,2H,2H-Perfluoropentyltriethoxysilane, 1H,1H,2H,2H-Perfluoropentyltrimethoxysilane, 1H,1H,2H,2H-Perfluorotetradecyltriethyl Oxysilane, 1H,1H,2H,2H-perfluorotetradecyltrimethoxysilane, allyltrimethoxysilane (allylTMS), allyltriethoxysilane (allylTEOS), vinyltrimethoxysilane silane, vinyltriethoxysilane, (3-glycidyloxypropyl)dimethoxymethylsilane (Me-GPTMS), methacryloxypropylmethyldimethoxysilane ( Me-MEMO), phenylmethyldimethoxysilane (PMDMS), bis[(2,2,3,3,4,4-hexafluorobutyl)propionate]-3-aminopropyltrimethyl Oxysilane or mixtures thereof.

The silane monomer is preferably selected from the group 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 a specific example, at least two different silane monomers of the first siloxane polymer (B-1) include at least one disilane.

A suitable bissilane is preferably represented by formula (III) (R ³ ) ₃ Si-Y-Si(R ⁴ ) ₃ , (III) wherein R ³ and R ⁴ are independently selected from hydrogen and straight or branched chain alkane. Groups consisting of alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl, alkoxy and aryl groups with 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, aryl, -O -Alkylene-O-; -O-arylene-O-; Alkylene-O-alkylene, aryl-O-arylene; Alkylene- ^{Z 1} C(=O)Z ² -Alkylene, aryl-Z ¹ C(=O)Z ² -Aryl and -O-alkylene-Z ¹ C(=O)Z ² -phenylene-O-;-O -arylene-Z ¹ C(=O)Z ² -arylene-O-, where Z ¹ and Z ² are each selected from direct bonds or -O-.

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

"Aryl" represents an aromatic divalent group typically containing 1 to 3 aromatic rings and 6 to 18 carbon atoms. Such groups are exemplified by phenylene groups (eg 1,4-phenylene and 1,3-phenylene groups) and biphenylene groups as well as naphthylene or anthracenyl groups.

Alkylene and aryl groups are optionally substituted by 1 to 5 substituents selected from hydroxyl, halo, vinyl, epoxy and allyl and alkyl, aryl and aralkyl.

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

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

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

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

Particularly preferably, at least one silane monosystem is selected from the group 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: ● Mix at least two different silane monomers, preferably as described above or below, in the 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 at least partial polymerization and cross-linking of the hydrolyzable monomers; ● Replace the first solvent with the second solvent as appropriate; ● Further cross-linking of the mixture may be initiated by hydrosilation, heat or radiation, as appropriate.

In the case where the second composition includes 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 following group: acetone, tetrahydrofuran (THF), toluene, 1-propanol, 2-propanol, methanol, ethanol, water (H ₂ O), 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 can be mixed in the first solvent at any suitable temperature to dissolve the silane monomers. Normally, room temperature is sufficient.

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

Suitable catalysts are acidic catalysts, basic 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 basic 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 diethylene triamine.

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 at room temperature overnight.

During the hydrolysis step, the silane monomer is at least partially hydrolyzed. The at least partially hydrolyzed silane monomer is then at least partially polymerized, preferably by condensation polymerization, and cross-linked to form a siloxane polymer.

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

According to a preferred embodiment, the mixture is subjected to at least partial hydrolysis including reflux. Typical reflow time is 2 hours.

After the hydrolysis step, in an optional further method step, the first solvent can be exchanged for a second solvent. Optional solvent exchange is advantageous as it helps remove water and alcohol formed during hydrolysis of the silane monomer. Additionally, when used as a coating on a substrate, it improves the properties of the final siloxane polymer solution.

The second solvent is preferably selected from 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) group.

The mixture containing the siloxane polymer may further undergo a crosslinking step after the hydrolysis step. Thus, the siloxane polymer is preferably at least partially cross-linked by hydrosilylation, heat or radiation.

In this context, the term "partially cross-linked" means that the polymer is capable of further cross-linking under conditions conducive to cross-linking. In practice, the polymer still contains at least some reactive crosslinking groups after the first polymerization step. Further cross-linking that typically occurs after the partially cross-linked composition is deposited on the substrate is described below.

The siloxane polymer is preferably at least partially cross-linked by hydrogenation, heat or radiation using a catalyst as described above.

Therefore, thermal cross-linking is preferably performed at a temperature in the range of about 30°C to 200°C.

Typically cross-linking is carried out under reflux conditions of the solvent.

In order to improve the resolution of the material when used in photolithography, the siloxane polymer may optionally be partially cross-linked during polymerization, in particular during condensation polymerization or immediately after condensation polymerization. Various methods can be used to achieve cross-linking. For example, a cross-linking method may be used in which the two chains are joined via reactive groups that do not interfere with any reactive groups intended for UV photolithography. For example, hydrosilylation, such as using protons on one chain to react with double bonds on another chain, will achieve the desired kind of cross-linking. Another example is cross-linking via double bonds or epoxy groups.

Different reactive groups are preferred for cross-linking and for photolithography. Thus, siloxane polymers can be cross-linked using free radical initiators and photoacid generators with reactive groups having double bonds or epoxy groups or both, such as epoxy, vinyl or allyl groups. or methacrylate group).

Epoxies can be used for UV photolithography and vice versa. The proportion of reactive groups required for cross-linking is usually smaller than that required for UV photolithography, for example about 0.1 to 10 mol % based on monomer for cross-linking and about 5 to 50 mol % based on monomer. For use in UV photolithography.

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 cross-linking, the molecular weight will typically be 2 to 10 times greater. Therefore, cross-linking will increase it to more than 3000 g/mol, preferably to 4000 to 20000 g/mol, based on molecular weights in the range of about 500 to 2000 g/mol.

Optionally, the resulting free Si-OH groups present in the backbone of the siloxane polymer can be protected by end-capping. For capping, the free Si-OH groups are combined with silane (such as methyldichlorofluorosilane (Cl ₂ FSiCH _{3 )} , methylfluorodimethoxysilane ((MeO) ₂ SiFCH ₃ ), 3-chloropropyltrimethyl Oxysilane (Cl(CH ₂ ) ₃ Si(OMe) ₃ ), ethyltrimethoxysilane (ETMS) or trimethylchlorosilane (ClSiMe ₃ )) in a catalyst such as triethylaluminum (TEA) or imidazole The amount of catalyst varied from 1.5 to 2 wt% of total solids. The reaction time varied from 40 to 45 min.

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

These additives can be surfactants, defoaming agents, 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.

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 solids.

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

By adjusting the hydrolysis and condensation conditions, the groups capable of deprotonation (e.g., OH-groups) and any residual leaving groups (e.g., alkoxy groups) from the silane precursor of the siloxane polymer composition can be controlled. concentration/content, and also controls the final molecular weight of the siloxane polymer. 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 developing solution.

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

On the other hand, if the final siloxane polymer has a high residual alkoxy-group content and it contains hardly any OH-groups, then the final siloxane polymer will show better performance in the above types of alkali-water developers. Has very low solubility in. OH-groups or other functional groups such as amine (NH ₂ ), thiol (SH), carboxyl, phenol or similar functional groups that create solubility in alkaline developer systems can be attached directly to the siloxane polymer Silicon atoms in the polymer backbone or optionally organic functional groups attached to the siloxane polymer backbone are attached to further promote and control 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 achieve a solids content that will produce a preselected film thickness during film deposition.

The solvent or combination of solvents may include fluorinated solvents such as methoxy-nonafluorobutane or 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether.

Typically, another amount of initiator molecular compound is added to the siloxane composition after synthesis. The initiator may optionally be similar to the initiator added during polymerization to produce a substance that can initiate polymerization of the "active" functional groups in the UV curing step. Therefore, in the case of epoxy groups, cationic or anionic initiators can be used. Free radical initiators can be used in the case of groups in synthetic materials that have double bonds as "reactive" functional groups. In addition, thermal initiators (working according to free radical, cationic or anionic mechanisms) can be used to promote cross-linking of "reactive" functional groups. The selection 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 selected.

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

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

Suitable deposition methods include spin coating, pinch coating, spray, inkjet, roll-to-roll, gravure printing, reverse gravure printing, bar coating, slot coating, flexographic printing, curtain coating, screen printing coating Distribution method, extrusion coating, dip coating, flow coating or slot coating.

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

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

In one specific example, the pre-curing and final curing steps are combined by heating using an increasing heating gradient. Curing can be performed in three steps, in addition to a thermal-only cure process that includes thermal pre-cure and UV cure, followed by final thermal cure. A two-step curing process can also be applied, with thermal pre-curing followed by UV curing. In this case, it is preferred not to apply final thermal curing after UV curing.

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

Therefore, in a specific example, the method consists of the following steps - Pre-curing or drying of the second coating (C) deposited on the first coating (A); - Exposure to obtain a second coating (C) depending on the situation; - Optionally develop the second coating (C) thus obtained; and - Cure the second coat (C).

Exemplary epoxy functional group-containing monomers include (3-glycidoxypropyl)trimethoxysilane, 1-(2-(trimethoxysilyl)ethyl)cyclohexane-3,4-cyclo Oxide, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)tripropoxysilane, 3-glycidoxypropyltris(2-methoxy Ethoxy)silane, 2,3-epoxypropyltriethoxysilane, 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, trimethylolpropane triacrylate, neopentylerythritol triacrylate, bis(trimethylolpropane) Tetraacrylate, dipenterythritol pentaacrylate and dipenterythritol hexaacrylate and combinations thereof. Such compounds can be used as part of the silane composition.

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

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

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

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

The third coating (D) is optional depending on the situation. In some embodiments, the layered structure may include an additional third coating (D) coated on at least one surface of the second coating (C) such that the third coating (D) is consistent with the second coating (C). C) At least one surface is in adhesive contact. In this context, "adhesive contact" means that there is no other coating or adhesive layer between the third substrate layer (D) and at least one surface of the second coating (C).

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

Preferably, the third coating layer (D) includes a siloxane polymer and optionally a fluoropolyether compound.

In a 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 the two documents are attached to this article by full text citation.

In another specific example, the third coating (D) includes a third siloxane polymer (D-1) including side chains including one or more fluorinated carbon groups.

The third siloxane polymer (D-1) contains 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 a specific example, at least one of the silane monomers includes reactive groups capable of achieving cross-linking with adjacent siloxane polymer chains, and wherein the adjacent siloxane polymer chains are assisted by the reactive groups Cross-linking.

The reactive groups are preferably epoxy, alicyclic epoxy (such as glycidyl), vinyl, allyl, acrylate, methacrylate and silane groups and combinations thereof.

Thus, epoxy, alicyclic epoxy (such as glycidyl), vinyl, allyl, acrylate, methacrylate groups are preferably used in thermal or radiation initiation with suitable initiators such as Cross-linking with adjacent siloxane polymer chains can be achieved in the presence of thermal or free radical initiators).

Suitable thermal or free radical initiators are preferably selected from tertiary amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanemethane) nitrile), benzyl peroxide, 2,2-bis(tertiary butylperoxy)butane, 1,1-bis(tertiary butylperoxy)cyclohexane, 2,2'-azobis Isobutyronitrile (AIBN), 2,5-bis(tertiary butylperoxy)-Z,S-dimethylhexane, 2,5-bis(tertiary butylperoxy)-2,5-dimethylhexane Methyl-3-hexyne, bis(1-(tertiary butylperoxy)-1-methylethyl)benzene, 1,1-bis(tertiary butylperoxy)-3,3,5- Trimethylcyclohexane, tertiary butyl hydroperoxide, tertiary butyl peracetate, tertiary butyl peroxide, tertiary butyl peroxybenzoate, tertiary butyl peroxyisopropyl carbonate, Cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauryl peroxide, 2,4-pentanedione peroxide, peracetic acid or potassium persulfate. Particularly preferred is 2,2'-azobisisobutyronitrile (AIBN).

The silane group can be used in the hydrosilylation, preferably in the presence of suitable catalysts such as those based on platinum (Pt), such as Speier catalysts (H ₂ PtCl ₆ .H ₂ O), Karstedt catalysts (Pt(0)-1,3- divinyl-1,1,3,3-tetramethyldisiloxane complex solution) or a rhodium (Rh)-based catalyst such as tris(triphenylphosphine)rhodium(I) chloride) Achieve cross-linking with carbon-carbon double bonds (such as vinyl or allyl) of adjacent siloxane polymer chains.

In a specific example, a monomer containing a first reactive group, such as a monomer selected from epoxy, alicyclic epoxy (such as glycidyl), vinyl and allyl, and a second reactive group, For example, the molar ratio between monomers selected from acrylate groups and methacrylate groups is 1:100 to 100:1, specifically 1:10 to 10:1, such as 5:1 to 1:2 or Varies within the range of 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, trimethylolpropane triacrylate, etc. Acrylates, neopenterythritol triacrylate, bistrimethylpropane tetraacrylate, dipenterythritol pentaacrylate and dipenterythritol hexaacrylate, and combinations thereof.

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

The suitable silane monomer is preferably represented by formula (I) R ¹ _a SiX _4-a (I) wherein R ¹ is selected from hydrogen and includes linear and branched chain alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, ( Alkyl) acrylate, epoxy, allyl, vinyl and alkoxy groups and aryl groups having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X is hydrolyzable group or hydrocarbon residue; and a is an integer from 1 to 3.

The hydrolyzable groups are especially alkoxy groups (see formula II).

The alkoxy groups ^of R ¹ and/or ^the hydrolyzable group A straight or branched chain alkyl group of 6 carbon atoms, optionally presenting one or two substituents selected from the group consisting of halogen, hydroxyl, vinyl, epoxy and allyl. Most preferred are methoxy and ethoxy.

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

Particularly suitable silane monosystems are selected from the group consisting of: tetraethoxysilane (TEOS), tetramethoxysilane (TMS), methyltriethoxysilane (MTEOS), methyltrimethoxysilane (MTMS) ), dimethyldiethoxysilane (DMDEOS), dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPDMS), 3-(trimethoxysilyl)propylmethyl acrylate (MEMO), 3-(triethoxysilyl)propyl methacrylate, 5-(bicycloheptenyl)triethoxysilane (BCHTEOS), (3-glycidoxypropyl )Triethoxysilane, (3-glycidoxypropyl)trimethoxysilane (GPTMS), allyltrimethoxysilane (allylTMS), allyltriethoxysilane (allylTEOS), vinyl Trimethoxysilane (VTMS), vinyltriethoxysilane, (3-glycidoxypropyl)dimethoxymethylsilane (Me-GPTMS), methacryloxypropylmethyldimethylsilane Methoxysilane (Me-MEMO), phenylmethyldimethoxysilane (PMDMS), bis[(2,2,3,3,4,4-hexafluorobutyl)propionate]-3- Aminopropyltrimethoxysilane or mixtures thereof.

The silane monomer is preferably selected from the following group: tetraethoxysilane (TEOS), phenylmethyldimethoxysilane (PMDMS), 3-(trimethoxysilyl)propyl methacrylate ( MEMO), methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (VTMS) and (3-glycidoxypropyl)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 a specific example, the at least one different silane monomer of the third siloxane polymer (D-1) includes at least one disilane.

A suitable bissilane is preferably represented by formula (III) (R ³ ) ₃ Si-Y-Si(R ⁴ ) ₃ , (III) wherein R ³ and R ⁴ are independently selected from hydrogen and straight or branched chain alkane. Groups consisting of alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl, alkoxy and aryl groups with 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, aryl, -O -Alkylene-O-; -O-arylene-O-; Alkylene-O-alkylene, aryl-O-arylene; Alkylene- ^{Z 1} C(=O)Z ² -Alkylene, aryl-Z ¹ C(=O)Z ² -Aryl and -O-alkylene-Z ¹ C(=O)Z ² -phenylene-O-;-O -arylene-Z ¹ C(=O)Z ² -arylene-O-, where Z ¹ and Z ² are each selected from direct bonds or -O-.

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

"Aryl" represents an aromatic divalent group typically containing 1 to 3 aromatic rings and 6 to 18 carbon atoms. Such groups are exemplified by phenylene groups (eg 1,4-phenylene and 1,3-phenylene groups) and biphenylene groups as well as naphthylene or anthracenyl groups.

Alkylene and aryl groups are optionally substituted by 1 to 5 substituents selected from hydroxyl, halo, vinyl, epoxy and allyl and alkyl, aryl and aralkyl.

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

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

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

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

In addition, the third siloxane polymer (D-1) contains at least one type, such as 1 to 10 types, preferably 1 to 6 types, more preferably 1 type, capable of forming side chains including one or more fluorinated carbon groups. Or 2 types, preferably one fluorinated monomer.

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 selected from a group consisting of straight chain and Branched chain alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and alkoxy and aryl groups with 1 to 6 rings, preferably straight chain or branched chain alkyl, and wherein the group is substituted by one or more fluorine atoms; X is a hydrolyzable group or hydrocarbon residue; and a is an integer from 1 to 3.

The hydrolyzable groups are especially alkoxy groups (see formula II).

Examples of such silane monomers are, for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) Triethoxysilane (F17), 1H,1H,2H,2H-perfluorodecyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 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-Perfluorotetradecyl Alkyltrimethoxysilane.

Fluorinated monomers can also be monomers containing fluorinated polymer groups. The monomer containing fluorinated polymer groups 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. Polyethers, epoxy-based perfluoropolyethers and mixtures thereof.

Such fluorinated polysiloxanes and modified perfluoropolyethers are commercially available from Shin-Etsu Subelyn®'s KY-100 series of fluorinated antifouling coating components, such as KY-1900 and KY-1901, Shin -Etsu Subelyn®'s 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 with a molecular weight in the range of 1500 to 20000 g/mol, preferably 2000 to 15000 g/mol. .

At least one fluorinated monomer is preferably present in the siloxane polymer in an amount by weight of 0.1 to 45 wt%, preferably 0.5 to 45 wt%, still more preferably 1 to 40 wt%.

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

The third composition including the third siloxane polymer (D-1) is preferably formed by a method including the following steps: ● In the first solvent, mix at least one silane monomer and at least one fluorinated monomer (preferably as described above or below) to form a mixture; ● Subjecting the mixture to at least partial hydrolysis of the monomers in the presence of a catalyst, thereby causing at least partial polymerization and cross-linking of the hydrolyzable monomers; ● Replace the first solvent with the second solvent as appropriate; ● Further cross-linking of the mixture may be initiated by hydrosilation, heat or radiation, as appropriate.

The first solvent is preferably selected from the following group: acetone, tetrahydrofuran (THF), toluene, 1-propanol, 2-propanol, methanol, ethanol, water (H ₂ O), 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 can be mixed in the first solvent at any suitable temperature to dissolve the monomers. Normally, room temperature is sufficient.

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

Suitable catalysts are acidic catalysts, basic 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 basic 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 diethylene triamine.

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 at room temperature overnight.

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

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

According to a preferred embodiment, the mixture is subjected to at least partial hydrolysis including reflux. Typical reflow time is 2 hours.

After the hydrolysis step, in an optional further method step, the first solvent can be exchanged for a second solvent. Optional solvent exchange is advantageous as it helps to remove water and alcohol formed during hydrolysis of the monomers. Additionally, when used as a coating on a substrate, it improves the properties of the final siloxane polymer solution.

The second solvent is preferably selected from 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) group.

The mixture containing the siloxane polymer may further undergo a crosslinking step after the hydrolysis step. Thus, the siloxane polymer is preferably at least partially cross-linked by hydrosilylation, heat or radiation.

In this context, the term "partially cross-linked" means that the polymer is capable of further cross-linking under conditions conducive to cross-linking. In practice, the polymer still contains at least some reactive crosslinking groups after the first polymerization step. Further cross-linking that typically occurs after the partially cross-linked composition is deposited on the substrate is described below.

The siloxane polymer is preferably at least partially cross-linked by hydrogenation, heat or radiation using a catalyst as described above.

Therefore, thermal cross-linking is preferably performed at a temperature in the range of about 30°C to 200°C.

Typically cross-linking is carried out under reflux conditions of the solvent.

In order to improve the resolution of the material when used in photolithography, the siloxane polymer may optionally be partially cross-linked during polymerization, in particular during condensation polymerization or immediately after condensation polymerization. Various methods can be used to achieve cross-linking. For example, a cross-linking method may be used in which the two chains are joined via reactive groups that do not interfere with any reactive groups intended for UV photolithography. For example, hydrosilylation, such as using protons on one chain to react with double bonds on another chain, will achieve the desired kind of cross-linking. Another example is cross-linking via double bonds or epoxy groups.

Different reactive groups are preferred for cross-linking and for photolithography. Thus, siloxane polymers can be cross-linked using free radical initiators and photoacid generators with reactive groups having double bonds or epoxy groups or both, such as epoxy, vinyl or allyl groups. or methacrylate group).

Epoxies can be used for UV photolithography and vice versa. The proportion of reactive groups required for cross-linking is usually smaller than that required for UV photolithography, for example about 0.1 to 10 mol % based on monomer for cross-linking and about 5 to 50 mol % based on monomer. For use in UV photolithography.

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 cross-linking, the molecular weight will typically be 2 to 10 times greater. Therefore, cross-linking will increase it to more than 3000 g/mol, preferably to 4000 to 20000 g/mol, based on molecular weights in the range of about 500 to 2000 g/mol.

Optionally, the resulting free Si-OH groups present in the backbone of the siloxane polymer can be protected by end-capping. For capping, the free Si-OH groups are combined with silane (such as methyldichlorofluorosilane (Cl ₂ FSiCH _{3 )} , methylfluorodimethoxysilane ((MeO) ₂ SiFCH ₃ ), 3-chloropropyltrimethyl Oxysilane (Cl(CH ₂ ) ₃ Si(OMe) ₃ ), ethyltrimethoxysilane (ETMS) or trimethylchlorosilane (ClSiMe ₃ )) in a catalyst such as triethylaluminum (TEA) or imidazole The amount of catalyst varied from 1.5 to 2 wt% of total solids. The reaction time varied from 40 to 45 min.

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

These additives can be surfactants, defoaming agents, 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 -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 solids.

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

By adjusting the hydrolysis and condensation conditions, the groups capable of deprotonation (e.g., OH-groups) and any residual leaving groups (e.g., alkoxy groups) from the silane precursor of the siloxane polymer composition can be controlled. concentration/content, and also controls the final molecular weight of the siloxane polymer. 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 developing solution.

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

On the other hand, if the final siloxane polymer has a high residual alkoxy-group content and it contains hardly any OH-groups, then the final siloxane polymer will show better performance in the above types of alkali-water developers. Has very low solubility in. OH-groups or other functional groups such as amine (NH ₂ ), thiol (SH), carboxyl, phenol or similar functional groups that create solubility in alkaline developer systems can be attached directly to the siloxane polymer Silicon atoms in the polymer backbone or optionally organic functional groups attached to the siloxane polymer backbone are attached to further promote and control alkaline developer solubility.

After 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.

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

Typically, another amount of initiator molecular compound is added to the siloxane composition after synthesis. The initiator may optionally be similar to the initiator added during polymerization to produce a substance that can initiate polymerization of the "active" functional groups in the UV curing step. Therefore, in the case of epoxy groups, cationic or anionic initiators can be used. Free radical initiators can be used in the case of groups in synthetic materials that have double bonds as "reactive" functional groups. In addition, thermal initiators (working according to free radical, cationic or anionic mechanisms) can be used to promote cross-linking of "reactive" functional groups. The selection 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 selected.

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

Compositions as described above may include solid nanoparticles or other compounds in an amount between 1 wt% and 50 wt% of the composition. Nanoparticles (or similar nano- or microscale rods, crystals, spheres, dots, buds, etc.) are especially selected from the group consisting of light-scattering, light-absorbing, light-emitting and/or conductive pigments, dyes, organic and inorganic phosphors, oxides, Quantum dots, polymers or groups of metals.

In a third specific example, the third composition includes 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) contains monomer units selected from at least one silane monomer.

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

The following procedure applies to all specific instances of tertiary coating (D):

The third composition preferably contains 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.

Fluoropolyether compounds generally have 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 fluoropolyether compounds, not all hydrogen atoms can be replaced by fluorine. If hydrogen atoms are present in the fluoropolyether compound, the fluorine/hydrogen molecular ratio 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 can be a linear or branched chain group, preferably a linear group.

The repeating units of the fluoropolyether group are preferably C ₁ to C ₆ fluorinated diols, more preferably C ₁ to C ₄ fluorinated diols, and most preferably C ₁ to C ₃ fluorinated diols.

Preferred monomers for fluoropolyether groups are perfluoro-1,2-propanediol, perfluoro-1,3-propanediol, perfluoro-1,2-ethylene glycol and difluoro-1,1-dihydroxy- Methane, preferably perfluoro-1,3-propanediol, perfluoro-1,2-ethylene glycol and difluoro-methanediol.

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

The preferred structure of the divalent perfluoropolyether group includes -CF ₂ O(CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ -, where the average value of m and p is 0 to 150, and the limiting conditions are If m and p are not zero at the same time, -CF(CF ₃ )O(CF(CF ₃ )CF ₂ O) _p CF(CF ₃ )-, -CF ₂ O(C ₂ F ₄ O) _p CF ₂ -, and -(CF ₂ ) ₃ O(C ₄ F ₈ O) _p (CF ₂ ) ₃ -, where the average value of p is from 3 to 150.

Among them, particularly preferred structures are -CF ₂ O(CF ₂ O) _m (C ₂ F ₄ O) _p CF _2- , -CF ₂ O(C ₂ F ₄ O) _p CF ₂ -, and -CF(CF ₃ )(OCF ₂ (CF ₃ )CF) _p O(CF ₂ ) _m O(CF(CF ₃ )CF ₂ O) _p CF(CF ₃ )-.

Preferred structures of monovalent perfluoropolyether groups include CF ₃ CF ₂ O(CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ -, CF ₃ CF ₂ O(C ₂ F ₄ O) pCF ₂ - , CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O) _p CF(CF ₃ )-, or a combination thereof, where the average value of m and p is 0 to 150 and m and p are not independently 0 .

Fluoropolyether compounds may contain functional groups such as carboxyl groups, alkyl ester groups, carboxyl ester groups, epoxy groups, amine groups, silanyl groups, or mixtures thereof.

In a specific example, the fluoropolyether compound is a fluoropolyethersilane, more preferably a fluoropolyethersilane (PFS) containing hydrolyzable groups.

The fluoropolyethersilane (PFS) containing hydrolyzable groups is preferably selected from compounds R ^{5 -RF} -Q-Si(OR ³ ) _o R ⁴ _p (IV) according to the following formula (IV) wherein ^RF is fluorine Polyether group; Q is a divalent linking group; R ³ is each independently selected from C ₁ to C ₁₀ organic groups or organic heteroatom groups; R ⁴ is each independently selected from C ₁ to C ₂₀ organic groups or organic heteroatoms base; o is 1, 2 or 3 p is 0, 1 or 2 o+p is 3 R ⁵ is H, C _x F _2x+1 , where x is 1 to 10 or -Q-Si(OR ³ ) _o R ⁴ _p , where Q, R ³ , R ⁴ , o and p are as defined above, where Q, R ³ , R ⁴ , o and p may be the same or different on each occurrence.

R ³ is each independently selected from C ₁ to C ₁₀ organic groups or organic heteroatom groups.

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 from N and O.

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

The heteroatom of the organic heteroatom group of ^R3 attached to the oxygen atom bound to ^M1 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 in ^R3 (if present) 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 hydrocarbon group, even better, a C ₁ to C ₁₀ straight chain or branched chain. chain or cyclic alkyl.

Preferably, the total number of carbon atoms present in ^R3 according to any of the above variants is from 1 to 6, more preferably from 1 to 4.

R ⁴ is each independently selected from C ₁ to C ₂₀ organic groups or organic heteroatom groups.

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 from N and O.

The heteroatom of the organic heteroatom group attached to ^R4 of 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 in R ⁴ (if present) 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 hydrocarbon group, even better, a C ₁ to C ₂₀ straight chain or branched chain. chain or cyclic alkyl.

Preferably, the total number of carbon atoms present in ^R4 according to any of the above variants is from 1 to 15, more preferably from 1 to 10, and most preferably from 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 generally has a molecular weight of 150 to 10,000 g/mol, preferably 250 to 5,000 g/mol and most preferably 350 to 2,500 g/mol.

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

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

The repeating units of the fluoropolyether group ^RF are preferably C ₁ to C ₆ fluorinated diols, more preferably C ₁ to C ₄ fluorinated diols, and most preferably C ₁ to C ₃ fluorinated diols.

The preferred monomers for the fluoropolyether group R ^F are perfluoro-1,2-propanediol, perfluoro-1,3-propanediol, perfluoro-1,2-ethylene glycol and difluoro-1,1-diol. Hydroxy-methane, preferably perfluoro-1,3-propanediol, perfluoro-1,2-ethylene glycol and difluoro-methane glycol.

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

The preferred structure of the divalent perfluoropolyether group includes -CF ₂ O(CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ -, where the average value of m and p is 0 to 50, with the restriction If m and p are not zero at the same time, -CF(CF ₃ )O(CF(CF ₃ )CF ₂ O) _p CF(CF ₃ )-, -CF ₂ O(C ₂ F ₄ O) _p CF ₂ -, and -(CF ₂ ) ₃ O(C ₄ F ₈ O) _p (CF ₂ ) ₃ -, where the average value of p is from 3 to 50.

Among them, particularly preferred structures are -CF ₂ O(CF ₂ O) _m (C ₂ F ₄ O) _p CF _2- , -CF ₂ O(C ₂ F ₄ O) _p CF ₂ -, and -CF(CF ₃ )(OCF ₂ (CF ₃ )CF) _p O(CF ₂ ) _m O(CF(CF ₃ )CF ₂ O) _p CF(CF ₃ )-.

Preferred structures of monovalent perfluoropolyether groups include CF ₃ CF ₂ O(CF ₂ O) _m (C ₂ F ₄ O) _p CF ₂ -, CF ₃ CF ₂ O(C ₂ F ₄ O)pCF ₂ - , CF ₃ CF ₂ CF ₂ O(CF(CF ₃ )CF ₂ O) _p CF(CF ₃ )-, or a combination thereof, where the average value of m and p is 0 to 50 and m and p are not independently 0 .

Particularly preferred are fluoropolyether groups R ^F selected from -CF ₂ O-[C ₂ F ₄ O] _m -[CF ₂ O] _n -, where 1 < n < 8 and 3 < m < 10 R- [C ₃ F ₆ O] _n -, where n = 2 to 10 and R is a straight chain or branched chain, preferably a straight chain perfluoro C ₂ or C ₃ alcohol, preferably a C ₃ 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, 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-containing 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).

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

Suitable deposition methods include spin coating, pinch coating, spray, inkjet, roll-to-roll, gravure printing, reverse gravure printing, bar coating, slot coating, flexographic printing, curtain coating, screen printing coating Distribution method, extrusion coating, dip coating, flow coating or slot coating.

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

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

In one specific example, the pre-curing and final curing steps are combined by heating using an increasing heating gradient. Curing can be performed in three steps, in addition to a thermal-only cure process that includes thermal pre-cure and UV cure, followed by final thermal cure. A two-step curing process can also be applied, with thermal pre-curing followed by UV curing. In this case, it is preferred not to apply final thermal curing after UV curing.

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

Therefore, in a specific example, the method consists of the following steps - Pre-curing or drying of the third coating (D) deposited on the second coating (C); - Depending on the situation, the third coating (D) is obtained by exposure; - Optionally develop the third coating (D) thus obtained; and - Cure the third coat (D).

Exemplary epoxy functional group-containing monomers include (3-glycidoxypropyl)trimethoxysilane, l-(2-(trimethoxysilyl)ethyl)cyclohexane-3,4-cyclo Oxide, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)tripropoxysilane, 3-glycidoxypropyltris(2-methoxy Ethoxy)silane, 2,3-epoxypropyltriethoxysilane, 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, trimethylolpropane triacrylate, neopentylerythritol triacrylate, bis(trimethylolpropane) Tetraacrylate, dipenterythritol pentaacrylate and dipenterythritol hexaacrylate and combinations thereof. Such compounds can be used as part of the silane composition.

According to a specific embodiment, the method further includes curing the third composition.

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

In a 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 specific example, the third coating (D) is preferably a flexible hard coating, which includes a third siloxane polymer (D-1), which includes one or more fluorocarbon groups. The side chain.

In yet another specific example, the third coating layer (D) is preferably a flexible hard coating layer including the fourth siloxane polymer (D-2).

Preferably, the hardness of the third coating (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 and Elcometer tester.

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

Additionally, the third coating (D) was superior to scratch resistance as evidenced by the absence of visual scratches in the Taber Linear Abrasion Test (using a linear abrasion machine from Taber Industries) using BonStar Steel Wool #0000 , perform up to 2000 linear cycles at 500 g weight, 2×2 cm head size, 2.0-inch stroke length, 60 cycles/min.

Hierarchical 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 this specific example, the second coating (C) is the outermost layer of the layered structure and is sandwiched with the first coating (B) and the substrate layer (A). This means that preferably no other coating or coatings are applied to at least one surface of the substrate layer (A).

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

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

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

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

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

Additionally, the layered structure preferably exhibits 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) using BonStar Steel Wool #0000 at 500 g Weight, 2×2 cm head size, 2.0-inch stroke length, up to 500 linear cycles at 60 cycles/min.

Additionally, the layered structure preferably exhibits a contact angle of at least 70° in the Taber Linear Abrasion Test (using a linear abrasion machine from Taber Industries) using BonStar Steel Wool #0000 at 500 g weight, 2 × 2 cm Head size, 2.0-inch stroke length, and up to 500 linear cycles at 60 cycles/minute.

Furthermore, the layered structure preferably exhibits a reflectance of no more than 4.0%, preferably no more than 3.5%, at 550 nm when measured on a coated PMMA substrate.

Additionally, the layered structure preferably exhibits a transmittance of at least 93.0%, preferably at least 93.5%, at 550 nm when measured on a coated PMMA 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 replacement for glass.

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

Example 1. Determination method Molecular weight : Polymers were characterized by gel permeation chromatography. The chromatography system consists of GPC equipment equipped with an isocratic HPLC pump and a refractive index detector. Polysiloxane (0.20 g; 50% solids 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 is THF (HPLC grade). Use internal standards to determine the number average molecular weight ( M _n ) and weight average molecular weight ( M _w ) of the polymer, for example, two series of polystyrenes (Series A: 5 types of polystyrene, where M _w = 120.000 g/mol , 42.400 g/mol, 10.700 g/mol, 2.640 g/mol, 474 g/mol and series B: 4 polymers, where M _w = 193.000 g/mol, 16.700 g/mol, 6.540 g/mol, 890 g /mol).

Solid content : The solid content of the polymer was determined using a Mettler Toledo HB43 instrument. Samples were weighed on aluminum pans/cups and measurements were performed using approximately 1 g of material.

Viscosity : The tool used is Grabner Instrument Viscometer MINIVIS-II. The method used is "falling ball viscosity measurement". The samples were measured at T=20°C by using steel balls with a diameter of 3.175 mm.

Film thickness and refractive index ( RI ): Use ellipsometer UVISEL-VASE Horiba Jobin-Yvon to measure film thickness and refractive index. Use Gorilla Glass 4 or silicon wafer (Diameter: 150 mm, Type/Dopant: 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; rear surface: etched; Flat 1 SEMI standard) or other suitable substrate for measurement. It can be used before using the spray tool (typical spray method: scanning speed: 300 mm/s; spacing: 50 mm; gap: 100 mm; flow rate: 5-6 ml/min; atomization air pressure: 5 kg/cm ² ) A film of the material is prepared on a treated (plasma) glass substrate, followed by thermal curing, for example, at T=150°C for 60 min.

Transmittance ( T% ) and reflection ( R% ) : Use Konica Minolta spectrophotometer CM-3700A (Specta Magic NX software) to measure transmittance and reflectance.

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

Pencil Hardness ( PEHA ): Pencil hardness is measured using an Elcometer pencil hardness tester in accordance with ASTM standard D3363-00.

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

Abrasion: For layer 2 and layer 3, use Bon Star Steel Wool #0000, 500 g load, 2 x 2 cm head, 2 inch stroke, 60 cycles/min, 500 cycles, use Taber Linear Abraser 5750 Conduct an abrasion test.

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

Adhesion: Adhesion is measured according to ASTM standard D3359-D9 using Elcometer cross-hatch tester and Elcometer tape test.

2. List of components used in the examples: a) Silane monomer: GPTMS = (3-glycidoxypropyl)trimethoxysilane, Sigma-Aldrich PMDMS = phenylmethyldimethoxysilane , Sigma-Aldrich MEMO = 3-(trimethoxysilyl)propyl methacrylate ABCR BTESE = 1,2-bis(triethoxysilyl)ethane, Momentive Performance Materials MTMS = methyltrimethoxy Silanes, ABCR TEOS = Tetraethoxysilane, Ultra Pure Solutions Inc. DPDMS = Diphenyldimethoxysilane, Sigma-Aldrich PTMS = Phenyltrimethoxysilane, Sigma-Aldrich Me-GPTMS = (3-GPTMS Glyceroxypropyl)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-Perfluoro Decyltrimethoxysilane, VWR labscan 1H,1H,2H,2H-Perfluorodecyltriethoxysilane, Sigma-Aldrich (Heptadecafluoro-1,1,2,2-tetrahydrodecyl) Triethoxysilane, Sigma-Aldrich Fluorine-free hexyl triethoxysilane, Sigma-Aldrich Bis[(2,2,3,3,4,4-hexafluorobutyl)propionate]-3-amino Propyltrimethoxysilane. It is prepared by the reaction between aminopropyltrimethoxysilane (APTMES, Sigma-Aldrich) and 2,2,3,3,4,4-hexafluorobutylacrylate (OFPA, Sigma-Aldrich). 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 (eluent: cyclohexane/EtOAc=3/1). Excess OFPA is removed under low pressure.

b) Polysiloxane poly(methyl-3,3,3-trifluoropropylsiloxane), Mw = 2500 D, ABCR poly(methyl-3,3,3-trifluoropropylsiloxane) ), Mw 14000 D, ABCR TEOS-based polymer/100%-TEOS polymer: In a 500 mL round bottom flask, combine TEOS (43.46 g) and acetone (136.08 g). _HNO3 (0.1 M; 29.98 g) was added dropwise over 10-15 minutes. The reaction mixture was refluxed for 2 hours. After cooling to room temperature, PGME (115 g) was added. The solvent exchange procedure from EtOH/ _H2O /acetone to PGME was performed under vacuum. The final solids content of the mixture was adjusted to 10% by adding more PGME.

c) Solvent: 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 Tertiary 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 silicone group, Shin-Etsu KY 1901 = Perfluoropolyether with reactive silicone group, Shin-Etsu KY 1271 = Fluorinated antifouling additive, Shin-Etsu DSX = OPTOOL DSX E (Fluoropolyethersilane), Daikin SC 019 = Fluoropolyether compound, Shin-Etsu SC 011 = Fluoropolyether compound, Shin-Etsu Novec 7100 = Methoxy-nonafluorobutane isomer mixture, 3M AE 3000 = 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, Daikin

f) Other chemical substances: AIBN = azobisisobutyronitrile, Sigma Aldrich UVI Speed Cure 976 = (diphenyl-4,1-diyl sulfide) bis(diphenylsulfonium), Lambson BYK 333 = polyether modified of polydimethylsiloxane, BYK BYK 345 = polyether-modified siloxane, BYK BYK 370 = polyester-modified, hydroxyl-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 Examples of First Coating ( B ) The composition used for the first coating is adapted to the substrate in particular in terms of curing and baking conditions. Therefore, the composition 30 is particularly suitable as the first coating of the PMMA substrate, and the composition 31 is particularly suitable as the first coating of PET or CPI.

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

Composition B-2 In a 500 mL round-bottomed flask, combine 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) was mixed with acetone (112,4 g) in. _HNO3 (0,1 M; 35,47 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure was performed from acetone to PGME. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-3 In a 500 mL round-bottomed flask, combine BTESE (21,15 g; 0,06 mol), GPTMS (91 g; 0,3875 mol), MEMO (37 g; 0,149 mol) and 4-Tri Fluoromethyl-tetrafluorophenyltriethoxysilane (0,05 g; 0,00131 mol) was mixed in acetone (112,4 g). _HNO3 (0,1 M; 35,47 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure was performed from acetone to PGME. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-4 In a 500 mL round-bottomed flask, combine 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) was mixed in acetone (112,4 g). _HNO3 (0,1 M; 35,47 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure was performed from acetone to PGME. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-5 In a 500 mL round-bottomed flask, combine BTESE (21,15 g; 0,06 mol), GPTMS (91 g; 0,3875 mol), MEMO (37 g; 0,149 mol) and poly(formaldehyde) (3,3,3-Trifluoropropylsiloxane) (2 g; Mw=2500 D) was mixed in acetone (112,4 g). _HNO3 (0,1 M; 35,47 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure was performed from acetone to PGME. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-6 In a 500 mL round-bottomed flask, combine BTESE (21,15 g; 0,06 mol), GPTMS (91 g; 0,3875 mol), MEMO (37 g; 0,149 mol) and poly(formaldehyde) (3,3,3-Trifluoropropylsiloxane) (2,3 g; Mw=14000 D) was mixed in acetone (112,4 g). _HNO3 (0,1 M; 35,47 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure was performed from acetone to PGME. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-7 In a 500 mL round-bottomed flask, combine BTESE (21,15 g; 0,06 mol), GPTMS (91 g; 0,3875 mol), MEMO (37 g; 0,149 mol) and 1H,1H ,2H,2H-Perfluorodecyltriethoxysilane (0,73 g) was mixed in acetone (112,4 g). _HNO3 (0,1 M; 35,47 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure was performed from acetone to PGME. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-8 In a 500 mL round bottom flask, combine BTESE (21,15 g; 0,06 mol), GPTMS (91 g; 0,3875 mol), MEMO (37 g; 0,149 mol) and (17 Fluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane (0,5 g) was mixed in acetone (112,4 g). _HNO3 (0,1 M; 35,47 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure was performed from acetone to PGME. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-9 In a 500 mL round-bottomed flask, combine BTESE (21,15 g; 0,06 mol), GPTMS (91 g; 0,3875 mol), MEMO (37 g; 0,149 mol) and fluorine-free hexyl Triethoxysilane (2 g) was mixed in acetone (112,4 g). _HNO3 (0,1 M; 35,47 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure was performed from acetone to PGME. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-10 In a 500 mL round-bottomed flask, mix BTESE (21,15 g; 0,06 mol), GPTMS (91 g; 0,3875 mol), and MEMO (37 g; 0,149 mol) with acetone ( 112,4 g). _HNO3 (0,1 M; 35,47 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure was performed from acetone to PGME. Additional PGME was added to give a polymer with 41.85% solids content. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 30% solids and the additives Speed Cure 976 (1.2% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-11 In a 1 L round bottom flask, mix MTMS (78,46 g; 0,576 mol), TEOS (20 g; 0,096 mol), GPTMS (22,69 g; 0,096 mol) with EtOH (121, 15g). 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 at low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-12 In a 1 L round bottom flask, combine BTESE (63,83 g; 0,18 mol), MEMO (14,90 g; 0,06 mol), GPTMS (226,9 g; 0,96 mol) in acetone (229,21 g). _HNO3 (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 at low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-13 In a 1 L round-bottomed flask, combine BTESE (63,83 g; 0,18 mol), MEMO (14,90 g; 0,06 mol), and GPTMS (218,38 g; 0,924 mol) , F17 (20,46 g; 0,036 mol) mixed in acetone (238,18 g). _HNO3 (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 at low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-14 In a 1 L round-bottomed flask, combine BTESE (63,83 g; 0,18 mol), MEMO (14,90 g; 0,06 mol), and GPTMS (218,38 g; 0,924 mol) , F13 (18,36 g; 0,036 mol) mixed in acetone (238,60 g). _HNO3 (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 at low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-15 In a 1 L round-bottomed flask, combine BTESE (14.51 g; 0,0409 mol), MEMO (20.33 g; 0,0818 mol), and GPTMS (62.87 g; 0,266 mol) , DPDMS (5,06 g; 0,020 mol) were mixed in acetone (77,03 g). _HNO3 (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 at low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-16 In a 1 L round bottom flask, add 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) in acetone (93,11 g). _HNO3 (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 at low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-17 In a 1 L round bottom flask, combine BTESE (31,91 g; 0,18 mol), MEMO (22,35 g; 0,18 mol), GPTMS (99,26 g; 0,84 mol) in acetone (15 g). _HNO3 (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. The solvent exchange procedure from acetone to PGME was performed at low pressure. A portion of the previous solution (50 g, 50% solids in PGME) was mixed with AIBN (0.1 g) and the reaction mixture was stirred at T = 105 °C for 5 min. After cooling to room temperature, the final product is ready for processing. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-18 In a 1 L round bottom flask, combine 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) mixed in acetone (88,23 g). _HNO3 (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 at low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-19 In a 1 L round bottom flask, mix MEMO (35,02 g; 0,141 mol), GPTMS (86,85 g; 0,366 mol), and BTESE (20,00 g; 0,056 mol) with IPA ( 106,25 g). _HNO3 (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. Perform the solvent exchange procedure from IPA to IPA under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-20 In a 500 mL round-bottomed flask, mix MTMS (90,00 g; 0,660 mol) and GPTMS (22,31 g; 0,094 mol) in EtOH (112,31 g). Formic acid (0.1 M; 122,32 g) was added dropwise over 15 min. 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 at low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-21 In a 250 mL round-bottom flask, combine 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) mixed. HCl (0.1 M; 4,88 g) was added dropwise over 15 min. 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. The solvent exchange procedure of EtOH/MeOH/H ₂ O to IPA was carried out under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-22 In a 250 mL round bottom flask, combine 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) mixed. Formic acid (0.1 M; 7,26 g) was added dropwise over 15 min. 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. The solvent exchange procedure of EtOH/MeOH/H ₂ O to IPA was carried out under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-23 In a 1 L round bottom flask, combine BTESE (31,91 g; 0,18 mol), GPTMS (99,26 g; 0,84 mol), MEMO (22,25 g; 0,18 mol) in acetone (115 g). _HNO3 (0,1 M; 36,26 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (92 g) was added and acetone to PGME solvent exchange procedure was performed at low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-24 In a 1 L round bottom flask, add 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) mixed in EtOH (103,09 g). Formic acid (0.1 M; 71,04 g) was added dropwise and the reaction mixture was refluxed at T=105°C for 2 h. Cool the reaction mixture to room temperature. PGME (90 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 with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-25 In a 1 L round bottom flask, add 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) mixed in EtOH (154,86 g). Formic acid (0.1 M; 106,54 g) was added dropwise and the reaction mixture was refluxed at T=105°C for 2 h. Cool the reaction mixture to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was carried out under low pressure. AIBN (1.11 g) was then added at room temperature and the reaction mixture was stirred at T = 95 °C for 5 min. After cooling to room temperature, the final product is ready for processing. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-27 In a 1 L round-bottomed flask, mix GPTMS (450 g; 1,902 mol), MEMO (150,00 g; 0,54 mol), and PMDMS (49,53 g; 0,27 mol). _HNO3 (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 of MeOH/H ₂ O to DAA was performed under low pressure. The solids content of the final formulation was still 50%. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-28 In a 500 ml round-bottomed flask, mix MTMS (40 g; 0,2936 mol), TEOS (61,17 g; 0,29364 mol), and EtOH (101.17 g; 2,2075 mol). Formic acid (0.1 M; 74 g) was added dropwise and the reaction mixture was refluxed at T=105°C for 2 h. Cool the reaction mixture to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was carried out 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 with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-29 In a 500 ml round-bottomed flask, mix MTMS (40 g; 0,2936 mol), TEOS (61,17 g; 0,29364 mol), and EtOH (101.17 g; 2,2075 mol). Formic acid (0.1 M; 33 g) was added dropwise and the reaction mixture was refluxed at T=105°C for 2 h. Cool the reaction mixture to room temperature. PGME (33 g) was added and a solvent exchange procedure from EtOH to PGME was carried out 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 h. Cool the reaction mixture to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was carried out under low pressure. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids) and BYK 067A (1% solids) were added Material).

Composition B-30 In a 1 L round bottom flask, mix GPTMS (900 g), MEMO (301,32 g), and PMDMS (99,09 g). _HNO3 (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 solvent exchange of MeOH/ _H2O to DAA was performed under vacuum. The final solids content of the reaction mixture was adjusted to 50% by adding DAA. The product was then formulated as follows for subsequent performance evaluation: the material was further diluted with IPA to 33% solids and the additives Speed Cure 976 (1.5% solids), BYK 333 (1% solids), M270 (15% solids) were added ) and BYK 067A (1% solid material).

Composition B-31 In a 500 mL round-bottomed flask, mix BTESE (21,15 g; 0,06 mol), GPTMS (91 g; 0,3875 mol), and MEMO (37 g; 0,149 mol) with acetone ( 112,4 g). _HNO3 (0,1 M; 35,47 g) was added dropwise over 15 min and the reaction mixture was stirred at room temperature overnight. PGME (90 g) was added and a solvent exchange procedure was performed from acetone to PGME. Additional PGME was added to give a polymer with 41.85% solids content. The product was then formulated for subsequent performance evaluation as follows: the material was further diluted to 30% solids with IPA and the additives Speed Cure 976 (1.2% solids), BYK 370 (1% solids) and BYK 067A (1% solids) were added Material).

b) Preparation Example of Second Coating ( C ) Composition C-1 In a 500 ml round-bottom flask, add MTMS (10,5 g; 0,0771 mol), TEOS (30,0 g; 0,1440 mol), EtOH (163 g; 3,52 mol). HCl (1,0 M; 33,9 g) was added dropwise and the reaction mixture was stirred at room temperature for 3,5 h. The organic phase was washed 5 times with the mixture H ₂ O/MTBE (0,9:1,05). EtOH (183.43 g) was added and the solvent exchange procedure to EtOH was carried out under vacuum. The solids content of the reaction mixture was adjusted to 4% by adding EtOH (25.44 g). TEA (0,130 g) was then added at room temperature and the reaction mixture was stirred at T=70 °C for 45 min. After cooling to room temperature, the organic phase was washed 5 times with a H ₂ O/MTBE mixture (0,9:1,05). The organic phase was collected, EtOH (89.04 g) and PGME (190 g) were added and solvent exchange to PGME was performed under vacuum. ClSiMe ₃ (0,041 g) was added at room temperature and the reaction mixture was stirred at T=105 °C for 30 min. Part of the polymer (11.47 g, 5.23% solids in PGME) 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) were mixed.

Composition C-2 In a 10 L round-bottomed flask, mix HNO ₃ (3 M, 804 g) and IPA (3771 g), and then use a separatory funnel to mix TEOS (570 g, 2,736 mol) and MTMS ( 373 g, 2,7382 mol). After the addition, the reaction mixture was stirred at room temperature for 3,5 hours. Several washing steps were carried out with a mixture of H ₂ O/MTBE (0,9:1,05) for 4 days. Part of the polymer (11.47 g, 5.23% solids in PGMEA) 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) were mixed.

Composition C-3 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. Part of the polymer (11.47 g, 5.23% solids in PGMEA) 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) were mixed.

Composition C-4 In a 250 L reactor, TEOS (43,436 g) was mixed with acetone (136 g). _HNO3 (0.01 M; 2,978 g) was added slowly 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/ _H2O /EtOH to PGME was performed under vacuum. The solids content of the mixture was adjusted to 10% by adding more PGME. Part of the polymer (6 g, 10% solids in PGME) with DSX (0.4% in AE 3000; 18,75 g), AE 3000 (56,125 g), PGME (65,68 g) and DiPG (3 ,72 g) mixed.

Composition C-5 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. A portion of the polymer (30.59 g, 5.23% solids in PGMEA) was mixed with IPA (69.40 g) and BYK 333 (0.064 g).

Composition C-6 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. A portion of the polymer (5.73 g, 5.23% solids in PGMEA) 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) mixed.

Composition C-7 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. A portion of the polymer (9.56 g, 5.23% solids in PGMEA) 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) mixed.

Composition C-8 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. A portion of the polymer (4.78 g, 5.23% solids in PGMEA) with Novec 7100 (3.35 g), IPA (3.09 g), PGME (6.11 g), TEOS-based polymer (10% solids in PGME; 1.00 g) and BYK 333 (0.010 g) mixed.

Composition C-9 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. A portion of the polymer (11.47 g, 5.23% solids in PGMEA) was mixed with IPA (69.40 g) and BYK 333 (0.064 g).

Composition C-10 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. A portion of the polymer (22.94 g, 5.23% solids in PGMEA) was mixed with IPA (69.40 g) and BYK 333 (0.064 g).

Composition C-11 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. A portion of the polymer (19.12 g, 5.23% solids in PGMEA) was mixed with IPA (69.40 g) and BYK 333 (0.064 g).

Composition C-12 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. A portion of the polymer (17.20 g, 5.23% solids in PGMEA) was mixed with IPA (69.40 g) and BYK 333 (0.064 g).

Composition C-13 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. Part of the polymer (5.73 g, 5.23% solids in PGMEA) 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% solid content in PGME, 3 g) were mixed.

Composition C-14 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids 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 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. A portion of the polymer (7.17 g, 5.23% solids in PGMEA) with KY1901 (0.4% in Novec 7100; 3.12 g), Novec 7100 (7.62 g), IPA (4.67 g), EG (0.62 g) and based TEOS polymer (10% solids in PGME; 1.12 g) was mixed.

Composition C-16 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. Part of the polymer (7.17 g, 5.23% solids in PGMEA) 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) was mixed.

Composition C-17 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. Part of the polymer (7.17 g, 5.23% solids in PGMEA) 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) was mixed.

Composition C-18 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. A portion of the polymer (7.17 g, 5.23% solids in PGMEA) with KY1901 (0.4% in Novec 7100; 6.24 g), Novec 7100 (7.62 g), IPA (4.67 g), EG (0.62 g) and based TEOS polymer (10% solids in PGME; 1.12 g) was mixed.

Composition C-19 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. Part of the polymer (7.17 g, 5.23% solids in PGMEA) 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) was mixed.

Composition C-20 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. Part of the polymer (7.17 g, 5.23% solids in PGMEA) 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) was mixed.

Composition C-21 was mixed with HNO ₃ (3 M; 14,445 kg) and IPA (54,72 kg) in a 250 L reactor. Add MTMS (5,368 kg) and TEOS (8,196 kg). The reaction mixture was stirred at room temperature for 3,5 hours. The organic phase was washed five times with H ₂ O/MTBE mixture (1:1). IPA (70 kg) was added and solvent exchange of _H2O /IPA/EtOH/MeOH to IPA was performed at low pressure. The solids 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 stirred for a further 36 minutes at T=60°C. After cooling to room temperature, the organic layer was washed 6 times with _H2O /MTBE mixture. PGMEA (87 kg) was added and solvent exchange from IPA/MTBE to PGMEA was performed at low pressure. The solids content of the reaction mixture was adjusted to 4% by adding PGMEA (20 kg). ClSiMe ₃ (0,041 g) was added to the reaction mixture, which was further stirred at T=105 °C for 1,5 h. After cooling to room temperature, approximately 21 kg of solvent was removed by distillation, yielding a final solids content of 5.23%. Part of the polymer (7.17 g, 5.23% solids in PGMEA) 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) was mixed.

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

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

c) Preparation Example of the Third Coating ( D ) Composition D-1 In a 250 L reactor, TEOS (43,436 g) and acetone (136 g) were mixed. _HNO3 (0.01 M; 2,978 g) was added slowly 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/ _H2O /EtOH to PGME was performed under vacuum. The solids 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) was mixed with acetone (136 g). _HNO3 (0.01 M; 2,978 g) was added slowly 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/ _H2O /EtOH to PGME was performed under vacuum. The solids content of the mixture was adjusted to 10% by adding more PGME. Part of the polymer (10,874 g, 10% solids in PGME) with DSX (0.4% in Novec 7100; 18,125 g), Novec 7100 (54,07 g), PGME (58,74 g) and EG (3 ,59 g) mixed.

Composition D-3 In a 1 L round bottom flask, dissolve TEOS (86 g; 0,412 mol) in acetone (272 g). Add KY 1271 (0.4 g). _HNO3 (0.1 M; 59.36 g) was added dropwise and the resulting reaction mixture was refluxed for 2 h. 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 solids content of the mixture was adjusted to 10% by adding more PGME. Part of the polymer (8 g, 10% solids in PGME) 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) were mixed.

Composition D-4 In a 250 L reactor, TEOS (43,436 g) was mixed with acetone (136 g). _HNO3 (0.01 M; 2,978 g) was added slowly 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/ _H2O /EtOH to PGME was performed under vacuum. The solids content of the mixture was adjusted to 10% by adding more PGME. Part of the polymer (6 g, 10% solid content in PGME) and KY 1901 (0,675 g) and SC 019 (0,525 g), PGME (65,68 g) dissolved in Novec 7100 (32,55 g) , EG (3,72 g) and additional Novec 7100 (41,01 g) blended.

Composition D-5 In a 500 ml round-bottomed flask, mix MTMS (40 g; 0,2936 mol), TEOS (61,17 g; 0,29364 mol), and EtOH (101.17 g; 2,2075 mol). Formic acid (0.1 M; 74 g) was added dropwise and the reaction mixture was refluxed at T=105°C for 2 h. Cool the reaction mixture to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was carried out under low pressure. The solid content was adjusted to 41.85% by adding PGME. A portion of the aforementioned material was then formulated for subsequent potency evaluation as follows: the material was further diluted (0.47 g) 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-bottomed flask, mix MTMS (40 g; 0,2936 mol), TEOS (61,17 g; 0,29364 mol), and EtOH (101.17 g; 2,2075 mol). Formic acid (0.1 M; 74 g) was added dropwise and the reaction mixture was refluxed at T=105°C for 2 h. Cool the reaction mixture to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was carried out under low pressure. The solid content was adjusted to 41.85% by adding PGME. A portion of the aforementioned material was then formulated as follows for subsequent potency evaluation: the material 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) (0.955 g).

Composition D-7 In a 500 ml round-bottomed flask, mix MTMS (40 g; 0,2936 mol), TEOS (61,17 g; 0,29364 mol), and EtOH (101.17 g; 2,2075 mol). Formic acid (0.1 M; 74 g) was added dropwise and the reaction mixture was refluxed at T=105°C for 2 h. Cool the reaction mixture to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was carried out under low pressure. The solid content was adjusted to 41.85% by adding PGME. A portion of the aforementioned material was then formulated as follows for subsequent potency evaluation: the material 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) (1.79 g).

Composition D-8 In a 500 ml round-bottomed flask, mix MTMS (60 g; 0.44 mol), TEOS (91,76 g; 0,44 mol), and EtOH (151.76 g). Formic acid (0.1 M; 110.99 g) was added dropwise and the reaction mixture was refluxed at T=105°C for 2 h. Cool the reaction mixture to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was carried out under low pressure. The solid content was adjusted to 41.85% by adding PGME. A portion of the aforementioned material was then formulated as follows for subsequent potency evaluation: 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) to further dilute the material (0.89 g).

Composition D-9 In a 500 ml round-bottomed flask, mix MTMS (60 g; 0.44 mol), TEOS (91,76 g; 0,44 mol), and EtOH (151.76 g). Formic acid (0.1 M; 110.99 g) was added dropwise and the reaction mixture was refluxed at T=105°C for 2 h. Cool the reaction mixture to room temperature. PGME (100 g) was added and a solvent exchange procedure from EtOH to PGME was carried out under low pressure. The solid content was adjusted to 41.85% by adding PGME. A portion of the aforementioned material was then formulated for subsequent potency evaluation as follows: the material 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) (2.69 g).

4. Preparation and characteristics of coatings a) The first layer of two-layer coating or three-layer coating on PMMA substrate ( B ) The first layer is coated using a roll-to-roll pilot equipment with composition 30 on PMMA (375 μm ) on. The web speed is 5 m/min and the slot die speed is 650 rpm. The coating was cured by pre-bake at T=75°C for 3 minutes, followed by UV exposure at 1000 W for 30 seconds, and then final bake at T=75°C as stated.

Three different coated roll-to-roll thicknesses at 10 different points as described in Table 1. The average coating thickness is approximately 5 µm. Table 1 : Thickness in µm for 3 different coated roll-to-roll rolls Point 1 Point 2 Point 3 Point 4 Point 5 Point 6 Point 7 Point 8 Point 9 Point 10 PMMA coating roll to roll 1 5,4 5,3 5,6 5,3 5,7 5,5 5,6 5,6 5,1 5,3 PMMA coating roll to roll 2 5,3 5,6 5,6 5,8 5,6 5,6 5,6 5,5 5,8 5,3 PMMA coating roll to roll 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 reflectivity. Reflective properties vary depending on the solids content of the material and the amount and nature of additives. Layer 2 was added to the PMMA substrate that was coated with Layer 1 using the doctor bar coating method. Depending on the target thickness, the bar coater can have different properties, such as #1, #2, #3, #4. When using the #1 bar coater, the coating thickness is approximately 1-2 µm; when using the #2 bar coater, the coating thickness is approximately 2-3 µm; when using the #3 bar coater When using the #4 bar coater, the coating thickness is approximately 5 µm; when using the #4 bar coater, the coating thickness is approximately 7-8 µm. Plasma treatment may be required after coating. Cure the coating in an oven at T=80°C for 1 hour.

The third layer ( D ) The purpose of the third layer is to improve the mechanical properties. The spatula coating method is also used. Cure the coating in an oven at T=80°C for 1 hour.

The PMMA substrate was coated with the following coatings of two layers listed in Table 2 and three layers listed in Table 3 respectively. Table 2 : Two-layer coating on PMMA substrate Example Composition layer (B) Composition layer (C) Blade coater 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 Table 3 : Three-layer coating on PMMA substrate Example Composition layer (B) plasma treatment Composition layer (C) Blade coater plasma treatment Composition layer (D) Blade coater 19 B-30 C-5 2 D-9 2 20 B-30 without C-5 2 1 minute D-4 2 twenty one B-30 C-9 3 D-2 2 twenty two B-30 C-10 1 D-1 2 twenty three B-30 C-11 1 D-2 2 twenty four B-30 C-12 1 D-3 3 25 B-30 C-12 1 D-1 2 26 B-30 1 minute C-5 2 1 minute D-7 2 27 B-30 without C-5 2 1 minute D-7 2 28 B-30 without C-5 2 6 minutes D-7 2 29 B-30 without C-5 2 1 minute D-2 2 30 B-30 without C-5 2 6 minutes D-6 2 31 B-30 without C-5 2 6 minutes D-2 1 32 B-30 without C-5 2 6 minutes D-1 2 33 B-30 without C-5 4 6 minutes D-7 1 34 B-30 without C-5 2 6 minutes D-6 1

5. Characteristics of the Examples a) Optical properties of the two-layer coating on the PMMA substrate. Measure the reflectance and transmittance of Examples 1, 2, 3, 4, 5, 7 and 8.

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

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

Table 4 shows the reflectance (R%) and transmittance (T%) of the embodiment at a wavelength of 550 nm. Table 4 : Reflectance (R%) and transmittance (T%) of two layers of coating on PMMA at 550 nm wavelength Example 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 4 shows that the optical properties vary 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 exhibits a transmittance of 92.98%.

Therefore, all embodiments exhibit improved optical properties. Example 5 achieves the best optical properties. It can be seen from Examples 1 and 2 that increasing the thickness of the second layer (C) improves the optical properties.

b) Mechanical properties of two-layer coatings on PMMA substrate The mechanical properties of Examples 5, 6, 9, 10, 11, 12, 13, 14, 15, 16, 17 and 18 were measured and are listed in Table 5 . Table 5 : Mechanical properties of two-layer coatings on PMMA Wear test 500 cycles, 500 g Example Membrane VQ WCA VQ CA adhesion 5 84 all disappear 0B 6 82 all disappear 0B 9 83 almost disappear 0B 10 The membrane can 103 3 (all disappear) 11 The membrane can 81 almost disappear 0B 12 76 almost disappear 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 Membrane is OK but cloudy at edges 103 3 83 17 Turbid 108 3 82 18 Quite cloudy 101 1-2 83

Compared to Examples 5, 6, 9, 10, 11 and 12, Examples 13, 14, 15, 16, 17 and 18 exhibit better mechanical properties, especially with regard to wear resistance.

c) Optical properties of three-layer coatings on PMMA substrate. Measure the reflectance and transmittance of Examples 19, 20, 21, 22, 23 and 24.

The reflectance of the three-layer coatings of Examples 20, 21, 22, 23 and 24 in the wavelength range from 360 nm to 740 nm is shown in Figure 3.

The transmittance of the three-layer coatings of Examples 20, 21, 22, 23 and 24 in the wavelength range from 360 nm to 740 nm is shown in Figure 4.

In Figures 5 and 6, the reflectance (Figure 5) and transmittance (Figure 6) of the three-layer coating of Example 19 in the wavelength range from 360 nm to 740 nm are the same as the reflection of the two-layer coating of Example 5. rate and transmittance. It can be seen that the optical properties of the three-layer coating are only slightly weakened compared to the two-layer coating.

Table 6 shows the reflectance (R%) and transmittance (T%) of the embodiment at a wavelength of 550 nm. Table 6 : Reflectance (R%) and transmittance (T%) of the three-layer coating on PMMA at a wavelength of 550 nm Example R% (at 550 nm) T% (at 550 nm) 20 2.99 94.19 twenty one 3.05 94.04 twenty two 2.76 94.28 twenty three 2.99 94.11 twenty four 2.80 94.17

Bare PMMA exhibits a transmittance of 92.98%.

Therefore, all embodiments exhibit improved optical properties.

d) Mechanical properties of three-layer coatings on PMMA substrate The mechanical properties of Examples 20, 26, 27, 28, 29, 30, 31, 32, 33 and 34 were measured and listed in Table 7. Table 7 : Mechanical properties of two-layer coatings on PMMA Wear test 500 cycles, 500 g Example Membrane VQ WCA VQ CA 20 Bad cloudiness, bad leveling issues 115 2-3 108 26 Can 115 0 112 27 Leveling problem 118 3 110 28 Very minor leveling issues 61 0-1 102 29 Bad cloudiness, bad leveling issues 113 1 105 30 Yes, almost no turbidity 96 0 85 31 Can 104 1 64 32 Can 117 3 96 33 Can 109 2 87 34 Can 108 3 71

The three-layer coatings of Examples 20 and 26 to 34 exhibit improved mechanical properties compared to the two-layer coating 5 with the same second coating. Therefore, the mechanical properties of a two-layer coating with good optical properties but poor mechanical properties can be improved by applying a third coating that does not significantly impair the optical properties but significantly improves them, if required for consistent application. mechanical properties.

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 3 layers with different formulations. [Figure 4] Shows the transmittance of 3 layers with different formulations. [Figure 5] Shows the reflectivity of 2-layer and 3-layer coatings on PMMA. [Figure 6] shows the transmittance of 2-layer and 3-layer coatings on PMMA.

Claims (15)

A hierarchical structure that contains (A) Substrate layer; (B) a first coating coated on at least one surface of the substrate layer (A), and (C) a second coating coated on at least one surface of the first coating (B) such that the second coating (C) is in adhesive contact with at least one surface of the first coating (B), in The first coating (B) includes a first siloxane polymer (B-1); The second coating (C) includes one or more second siloxane polymers (C-1); and The substrate layer (A) is flexible, bendable or both. The layered structure of claim 1, wherein the first siloxane polymer (B-1) includes monomer units selected from at least two different silane monomers, wherein at least one of the silane monomers includes Reactive groups capable of achieving crosslinking with adjacent siloxane polymer chains, and wherein the adjacent siloxane polymer chains are crosslinked by means of the reactive group. The layered structure of any one of the preceding claims, wherein the one or more second siloxane polymers (C-1) independently comprise monomer units selected from at least one silane monomer. The layered structure of any one of the preceding claims, wherein the first coating (B) has a thickness of 1 to 50 µm, preferably 2 to 20 µm, more preferably 3 to 10 µm, and/or the second coating The coating (C) has a thickness of 10 nm to 10 µm, preferably 25 nm to 8 µm, more preferably 50 nm to 5 µm. The layered structure of any one of the preceding claims, wherein the material of the substrate layer (A) is selected from the group consisting of glass, quartz, silicon, silicon nitride, polymers, metals and plastics, and combinations thereof. The layered structure of claim 5, wherein the plastics are selected from thermoplastic polymers such as polyolefins, polyesters, polyamides, polyimides, acrylic polymers such as poly(methyl methacrylate) and Custom designed polymers. The layered structure of any one of the preceding claims, wherein the thickness of the substrate layer (A) is 10 to 500 µm, preferably 20 to 400 µm. The layered structure of any one of the preceding claims, further comprising a third coating (D) coated on at least one surface of the second coating (C), such that the third coating (D) ) is in adhesive contact with at least one surface of the second coating (C). The layered structure of claim 8, wherein the third coating (D) includes a siloxane polymer and optionally a fluoropolyether compound. The layered structure of claim 8 or 9, wherein the third coating (D) has a thickness of 10 nm to 10 µm, preferably 15 nm to 8 µm, and more preferably 20 nm to 5 µm. A method for producing a hierarchical structure as in any of the preceding claims, comprising the following steps: providing a first composition comprising at least two different silane monomers, wherein at least one of the silane monomers includes a reactive group capable of achieving cross-linking with an adjacent siloxane polymer; subjecting the first composition to at least partial hydrolysis of the monomers to form a composition comprising the first siloxane polymer (B-1); providing a second composition comprising at least one silane monomer; subjecting the second composition to at least partial hydrolysis of the monomers to form a composition comprising one or more second siloxane polymers (C-1); Provide substrates that are flexible or bendable or both; Depositing the first composition onto at least one surface of the substrate to form a first coating (B); cross-linking the siloxane polymer chains of the first coating (B) so as to obtain a first coating (B) comprising a cross-linked siloxane polymer in adhesive contact with the at least one surface of the substrate; Depositing the second composition onto the first coating (B) to form a second coating (C) in adhesive contact with the first coating (B); Cross-linking the siloxane polymer chains of the second coating (C) to obtain a second coating comprising one or more cross-linked siloxane polymers in adhesive contact with the first coating (B) (C). The method of claim 11, wherein the first composition including the siloxane polymer (B-1) is formed by a method including the following steps: mixing the at least two different silane monomers in the first solvent to form a mixture; subjecting the mixture to at least partial hydrolysis of the monomers in the presence of a catalyst, thereby at least partially polymerizing and crosslinking the hydrolyzable monomers; Replace the first solvent with a second solvent as appropriate; The mixture is further crosslinked by hydrosilylation, thermal or radiation initiation, as appropriate, and/or the second composition including one or more siloxane polymers is formed by: mixing the at least one silane monomer in the first solvent to form a mixture; subjecting the mixture to at least partial hydrolysis of the monomers in the presence of a catalyst, thereby at least partially polymerizing and crosslinking the hydrolyzable monomers; If necessary, replace the first solvent with a second solvent. The method of claim 11 or 12, wherein the first composition and/or the second composition is produced by spin coating, pinch coating, spraying, inkjet, roll-to-roll, gravure printing, reverse gravure printing Deposition is carried out by printing, bar coating, slot coating, flexographic printing, curtain coating, screen printing coating method, extrusion coating, dip coating, shower coating or slot coating. The method of claim 11 to 13 further includes the following steps providing a third composition comprising at least one silane monomer and at least one monomer containing a fluorinated carbon group; subjecting the third composition to at least partial hydrolysis of the monomers to form a composition comprising a siloxane polymer comprising side chains comprising one or more fluorocarbon groups; Depositing the third composition onto the second coating (C) to form a third coating (D) in adhesive contact with the second coating (C); Cross-linking the siloxane polymer chains of the third coating (D) to obtain a third coating comprising one or more cross-linked siloxane polymers in adhesive contact with the second coating (C) (D). Use of a layered structure according to any one of the preceding claims in flexible electronic applications including displays, optical lenses, transparent panels and the automotive industry, especially as a lightweight alternative to glass.