WO2023198743A1 - Revêtement dur de polysiloxane multicouche flexible - Google Patents

Revêtement dur de polysiloxane multicouche flexible Download PDF

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WO2023198743A1
WO2023198743A1 PCT/EP2023/059505 EP2023059505W WO2023198743A1 WO 2023198743 A1 WO2023198743 A1 WO 2023198743A1 EP 2023059505 W EP2023059505 W EP 2023059505W WO 2023198743 A1 WO2023198743 A1 WO 2023198743A1
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coating layer
siloxane polymer
added
composition
ipa
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PCT/EP2023/059505
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English (en)
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Tiina ALAHAIVALA
Rakib KABIR
Ari KÄRKKÄINEN
Sacha Legrand
Tiina LEPPÄJÄRVI
Kaisa MALO
Matti Pesonen
Mia VIRKKUNEN
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Optitune Oy
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Publication of WO2023198743A1 publication Critical patent/WO2023198743A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

Definitions

  • the present invention relates to a layered structure comprising a flexible or bendable substrate layer (A), a first polysiloxane based coating layer (B) and a second coating layer (C) comprising a fluoropolyether compound, a method for preparing said layered structure and the use of said layered structure for flexible electronics applications.
  • Transparent plastics have been widely used as a core material in optical and transparent display industries.
  • transparent plastics such as PET (polyethylene terephthalate), PI (polyimide), PC (polycarbonate) or PMMA (polymethyl methacrylate) have been applied in flexible electronics applications, including displays, optical lens, transparent boards, and automotive industries as a lightweight alternative to glass owing to the properties of high light transmittance and suitable refractive index.
  • PET polyethylene terephthalate
  • PI polyimide
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • these plastics have the disadvantage of low abrasion resistance, because they have lower surface hardness than glass.
  • Suitable flexible hard coatings are for instance polysiloxane based flexible hard coatings as e.g. disclosed in WO 2019/193258.
  • WO 2006/082701 Al discloses a two-layer coating on a transparent plastic film substrate with a first hard coating layer from a material which contains a (meth)acrylate group containing curable compound and a (meth)acrylate group- containing reactive silicone and a second antireflection (low refractive) coating layer from a material which contains a siloxane component containing compound.
  • Such multilayer approaches have the drawback of reduced scratch resistance and a mismatch of refractive indices, which results in a heavy rainbow pattern as discussed e.g. in as discussed in CN 206270519 U.
  • the hard coating layer for improving scratch resistance is usually the inner layer in direct contact with the plastic substrate and the adhesion to the low refractive outer layer is rather weak.
  • the coating shows good scratch resistance and lower rainbow pattern but does not address the problem of high reflectance.
  • a multilayer coating which shows such an improved balance of properties.
  • Said multilayer coating comprises a polysiloxane based coating layer and a coating layer comprising a fluoropolyether compound, whereas the inner layer is a polysiloxane based flexible hard coating layer and the second layer is an anti reflective layer.
  • the present invention relates to a layered structure comprising
  • Providing a first composition comprising at least two different silane monomers, wherein at least one of the silane monomers includes an active group capable of achieving cross-linking to adjacent siloxane polymer;
  • the invention relates to a method for producing a layered structure as described above or below comprising the following steps:
  • Providing a first composition comprising at least two different silane monomers, wherein at least one of the silane monomers includes an active group capable of achieving cross-linking to adjacent siloxane polymer;
  • the present technology provides for layered structures wherein a substrate layer (A) is provided with at least two layers comprising siloxane polymers.
  • the layered structure is “bendable” in the sense that it is capable of being bent about a mandrel, having a radius of curvature, without breaking.
  • the properties of bendability can be tested using a test involving infolding or outfolding of the layered structure about a mandrel as described in WO 2019/193258.
  • the substrate layer (A) can be any kind of substrates such as glass, quartz, silicon, silicon nitride, polymers, metals and plastics or mixtures thereof. Furthermore, the substrate layer (A) can also include number of different surfaces such as different oxides, doped oxides, semimetals and the like or mixture thereof.
  • Especially preferred polymers are polymethylmethacrylate (PMMA), polyethyleneterephtalate (PET) and colorless polyimide (CPI).
  • PMMA polymethylmethacrylate
  • PET polyethyleneterephtalate
  • CPI colorless polyimide
  • the substrate layer (A) preferably has a thickness of 10 to 500 pm, more preferably 20 to 400 pm.
  • the substrate layer (A) is flexible, bendable or both, such that it is capable of being bent about a mandrel having a first minimum radius of curvature without breaking.
  • a layered structure of the present kind is in particular capable of being bent about a mandrel having a second minimum radius of curvature without breaking, said first minimum radius being smaller or equal to the second minimum radius of curvature.
  • the at least one surface of the substrate layer (A) can be modified before depositing the first composition onto at least one surface of the substrate to form a first coating layer (B).
  • the at least one surface is preferably activated to promote adhesion between the substrate layer (A) and the first coating layer (B).
  • an optional coating composition is deposited onto the at least one surface of the substrate layer (A) as such that an optional additional coating layer is formed onto the at least one surface of the substrate layer (A). Said optional additional coating layer is then on one side in adherent contact with the at least one surface of the substrate layer (A) and on the other side in adherent contact with the first coating layer (B).
  • “Adherent contact” in this regard means that there is no further coating layer or adhesive layer between the at least one surface of the substrate layer (A) and the optional additional coating layer and the optional additional coating layer and the first coating layer (B).
  • Said optional additional coating layer can have a thickness of 5 to 300 nm or a thickness of 300 nm to 5 pm.
  • Said optional additional coating layer is usually applied in specific cases such as promoting the adhesion between the substrate layer (A) and the first coating layer (B), wetting of the first coating layer (B), promoting the optical performance of the layered structure or promoting the mechanical performance of the layered structure. It is, however, preferred that no optional additional coating layer is applied between the substrate layer and the first coating layer (B).
  • the first coating layer (B) is in adherent contact with at least one surface of the substrate layer (A).
  • the first coating layer (B) usually is the inner layer of the multi-layer coating with adherent contact with at least one surface of the substrate layer (A).
  • adherent contact in this regard means that there is no further coating layer or adhesive layer between the at least one surface of the substrate layer (A) and the first coating layer (B).
  • the first coating layer (B) preferably has a thickness of 1 to 50 pm, preferably of 2 to 20 pm, more preferably 3 to 10 pm.
  • the first siloxane polymer (B-l) comprises monomer units selected from at least two different silane monomers, wherein at least one of the silane monomers includes an active group capable of achieving cross-linking to adjacent siloxane polymer chains, and wherein the adjacent siloxane polymer chains are crosslinked by means of said an active groups.
  • the first siloxane polymer (B-l) can comprise monomer units selected from 2 to 10, such as from 2 to 6, preferably from 2 to 4 different silane monomers. “Different” in this connection means that the silane monomers differ in at least one chemical moiety.
  • Active groups are preferably epoxy, alicyclic epoxy groups (e.g. glycidyl), vinyl, allyl, acrylate, methacrylate and silane groups and combinations thereof.
  • the epoxy, alicyclic epoxy groups e.g. glycidyl
  • vinyl, allyl, acrylate, methacrylate groups are capable of achieving cross-linking to adjacent siloxane polymer chains upon a thermal or radiation initiation, preferably in the presence of a suitable initiator such as a thermal or radical initiator.
  • Suitable thermal or radical initiators are preferably selected from tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'- azobis(cyclohexanecarbonitrile), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, l,l-bis(tert-butylperoxy)cyclohexane, 2,2'-azobisisobutyronitrile (AIBN), 2,5- bis(tert-butylperoxy)-Z,S-dimethylhexane, 2,5-bis(tert-Butylperoxy)- 2,5 -dimethyl-3 -hexyne, bis(l -(tert-butylperoxy)- 1 -methylethyl)benzene, 1 , 1 -bis(tert- butylperoxy)-3,3,5- trimethylcyclohexane, tert-butyl hydroperoxide, ter
  • the silane group is capable of achieving cross-linking to a carbon-carbon double bond, such as a vinyl or allyl group) of an adjacent siloxane polymer chains upon hydrosilylation, preferably in the presence of a suitable catalyst, such as a platinum (Pt)-based catalyst such as the Speier catalyst (EEPtCle.EEO), Karstedt’s catalyst (Pt(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex solution) or a rhodium (Rh)-based catalyst such as Tris(triphenylphosphine)rhodium (I) chloride.
  • a suitable catalyst such as a platinum (Pt)-based catalyst such as the Speier catalyst (EEPtCle.EEO), Karstedt’s catalyst (Pt(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex solution) or a rhodium (Rh)-based catalyst
  • the components containing the second active group also be selected from acrylate and metacrylate containing compounds other than silane monomers, such as tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylo Ipropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate and combinations thereof.
  • silane monomers such as tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylo Ipropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate and combinations thereof.
  • Suitable silane monomers are preferably represented by formula (I) RJaSiX ⁇ a (I) wherein
  • R 1 is selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alk)acrylate, epoxy, allyl, vinyl and alkoxy and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted;
  • the hydrolysable group is in particular an alkoxy group (cf. formula II).
  • the alkoxy groups of R 1 and/or the hydrolysable group X can be identical or different and preferably selected from the group of radicals having the formula -O-R 2 (II) wherein R 2 stands for a linear or branched alkyl group having 1 to 10, preferably 1 to 6 carbon atoms, and optionally exhibiting one or two substituents selected from the group of halogen, hydroxyl, vinyl, epoxy and allyl. Most preferred are methoxy and ethoxy groups.
  • di-, tri- or tetraalkoxysilanes comprising alkoxy groups according to formula (II).
  • Particularly suitable silane monomers are selected from the group of tetraethoxysilane (TEOS), tetramethoxysilane (TMS), methyltri ethoxy si lane (MTEOS), methyltrimethoxysilane (MTMS), dimethyldiethoxysilane (DMDEOS), dimethyldimethoxy silane (DMDMS), diphenyldimethoxy silane (DPDMS), 3- (Trimethoxysilyl)propylmethacrylate (MEMO), 3- (Triethoxysilyl)propylmethacrylate, 5-(Bicycloheptenyl)triethoxysilane (BCHTEOS), (3-Glycidoxypropyl)triethoxysilane, (3- Glycidoxypropyl)trimethoxy silane (GPTMS), (Heptadecafluoro- 1 , 1 ,2,2- tetrahydrodecyl)trimethoxy silane (F 17), (H
  • Perfluoropentyltrimethoxysilane 1H,1H,2H,2H-Perfluorotetradecyltriethoxysilane, 1H,1H,2H,2H-Perfluorotetradecyltrimethoxysilane, allyltrimethoxysilane (allylTMS), allyltriethoxysilane (allylTEOS), vinyltrimethoxysilane, vinyltriethoxysilane, (3-Glycidopropyl)dimethoxymethylsilane (Me-GPTMS), methacryloxypropylmethyldimethoxysilane (Me-MEMO), phenylmethyldimethoxysilane (PMDMS), Bis[(2,2,3,3,4,4- hexafluorobutyl)propanoic ester]-3-aminopropyltrimethoxysilane or mixtures thereof.
  • allyltrimethoxysilane allylTMS
  • silane monomers are selected from the group of phenylmethyl dimethoxysilane (PMDMS), 3-(Trimethoxysilyl)propylmethacrylate (MEMO) and (3-Glycidoxypropyl)trimethoxysilane (GPTMS).
  • PMDMS phenylmethyl dimethoxysilane
  • MEMO 3-(Trimethoxysilyl)propylmethacrylate
  • GTMS (3-Glycidoxypropyl)trimethoxysilane
  • R 3 and R 4 are independently selected from hydrogen and a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alk)acrylate, epoxy, allyl, vinyl, alkoxy and aryl having 1 to 6 rings, and wherein the group is substituted or unsub stitued; and
  • alkyl residue stands for 1 to 10, preferably 1 to 8, or 1 to 6 or even 1 to 4 carbon atoms, examples include ethylene and methylene and propylene.
  • “Arylene” stands for an aromatic bivalent group containing typically 1 to 3 aromatic rings, and 6 to 18 carbon atoms. Such groups are exemplified by phenylene (e.g. 1,4- phenylene and 1,3-phenylene groups) and biphenylene groups as well as naphthylene or anthracenylene groups.
  • alkylene and arylene groups can optionally be substituted with 1 to 5 substituents selected from hydroxy, halo, vinyl, epoxy and allyl groups as well as alkyl, aryl and aralkyl groups.
  • Preferred alkoxy groups contain 1 to 4 carbon atoms. Examples are methoxy and ethoxy.
  • phenyl includes substituted phenyls such as phenyltrialkoxy, in particular phenyltrimethoxy or tri ethoxy, and perfluorophenyl.
  • phenyltrialkoxy in particular phenyltrimethoxy or tri ethoxy
  • perfluorophenyl perfluorophenyl.
  • the phenyl as well as other aromatic or alicyclic groups can be coupled directly to a silicon atom, or they can be coupled to a silicon atom via a methylene or ethylene bridge.
  • the bi-silane present in the siloxane polymer in a molar amount of 0 to 50 mol%, preferably of 1 to 50 mol%, still more preferably of 3 to 35 mol%.
  • the at least two silane monomers are selected from mixture of two or more of the group of 1,2-Bis(tri ethoxy silyl)ethane (BTESE), phenylmethyl dimethoxysilane (PMDMS), 3-(Trimethoxysilyl)propylmethacrylate (MEMO) and (3-Glycidoxypropyl)trimethoxysilane (GPTMS).
  • BTESE 1,2-Bis(tri ethoxy silyl)ethane
  • PMDMS phenylmethyl dimethoxysilane
  • MEMO 3-(Trimethoxysilyl)propylmethacrylate
  • GTPMS (3-Glycidoxypropyl)trimethoxysilane
  • the first composition comprising a siloxane polymer (B-l) is preferably formed by a method comprising the steps of • Admixing the at least two different silane monomers, preferably as described above or below, in a first solvent to form a mixture;
  • the first solvent is preferably selected from the group of acetone, tetrahydrofuran (THF), toluene, 1 -propanol, 2-propanol, methanol, ethanol, water (H2O), cyclopentanone, acetonitrile, propylene glycol propyl ether, methyl -tert-butyl ether (MTBE), propylene glycol monomethylether acetate (PGMEA), methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethylether (PGME) and propylene glycol propyl ether (PnP).
  • the at least two different silane monomers can be admixed in the first solvent at any suitable temperature for solving the silane monomers. Usually, room temperature suffices.
  • the mixture is subjected to an at least partial hydrolysis in the presence of a catalyst.
  • Suitable catalysts are acidic catalysts, basic catalysts or other catalysts.
  • Acidic catalysts are preferably selected from nitric acid (HNO3), sulfuric acid (H2SO4), formic acid (HCOOH), hydrochloric acid (HC1), sulfonic acid, hydrogen fluoride (HF), acetic acid (CH3COOH), trifluoromethanesulfonic acid or -toluene sulfonic acid.
  • nitric acid (HNO3) sulfuric acid (H2SO4)
  • formic acid HCOOH
  • HC1 hydrochloric acid
  • sulfonic acid hydrogen fluoride
  • HF hydrogen fluoride
  • CH3COOH acetic acid
  • trifluoromethanesulfonic acid or -toluene sulfonic acid nitric acid (HNO3) hydrochloric acid (HC1) and formic acid (HCOOH).
  • Basic catalysts are preferably selected from triethylamine (TEA), ammonium hydroxide (NH4OH), tetraethylammonium hydroxide (TEAH), tetramethylammonium hydroxide (TMEA), l,4-diazabicyclo[2.2.2]octane, imidazole and diethylenetriamine.
  • TAA triethylamine
  • NH4OH ammonium hydroxide
  • TEAH tetraethylammonium hydroxide
  • TBEA tetramethylammonium hydroxide
  • l,4-diazabicyclo[2.2.2]octane imidazole and diethylenetriamine.
  • the hydrolysis step is preferably performed at a temperature of from 20 to 80°C for 1 to 24 hours, such as at room temperature overnight.
  • silane monomers are at least partially hydrolysed.
  • Said at least partially hydrolysed silane monomers then are at least partially polymerized, preferably by condensation polymerization and crosslinked to form a siloxane polymer.
  • Said polysiloxane usually has a relatively low molecular weight in range of about 500 to 2000 g/mol.
  • the subjecting the mixture to an at least partial hydrolysis includes refluxing.
  • a typical refluxing time is 2 h.
  • the first solvent can be changed to a second solvent in an optional further method step after the hydrolysis step.
  • the optional solvent change is advantageous, since it assists the removal of water and alcohols formed during hydrolysis of the silane monomers. In addition, it improves the properties of the final siloxane polymer solution when used as coating layer(s) on the substrate.
  • the second solvent is preferably selected from the group of propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), 1 -ethanol, 2-ethanol (IP A), acrylonitrile diacetone alcohol (DAA) or propylene glycol n-propyl ether (PnP).
  • PGME propylene glycol methyl ether
  • PMEA propylene glycol methyl ether acetate
  • IP A 2-ethanol
  • DAA acrylonitrile diacetone alcohol
  • PnP propylene glycol n-propyl ether
  • the term “partially crosslinked” means that the polymer is capable of further crosslinking at conditions conducive to cross-linking.
  • the polymer still contains at least some reactive, crosslinking groups after the first polymerisation step.
  • the further crosslinking which typically takes place after deposition of the partially crosslinked composition on a substrate, will be described below.
  • the siloxane polymer is preferably at least partially crosslinked by hydrosilylation, thermal or radiation initiation using catalysts as described above.
  • thermal crosslinking is preferably conducted at temperatures in the range of about 30 to 200 °C.
  • cross-linking is carried out at refluxing conditions of the solvent.
  • the siloxane polymer can be optionally partially cross-linked during polymerization, in particular during or immediately after condensation polymerization.
  • Various methods can be used for achieving cross-linking.
  • cross-linking method where two chains are joined via reactive groups not affecting any of the active groups intended for the UV photolithography can be employed.
  • hydrosilylation for example using a proton on one chain reacting with a double bond on another chain will achieve cross-linking of desired kind.
  • Another example is cross-linking through double bonds or epoxy groups.
  • the cross-linking of the siloxane polymer can be achieved with an active group having double bonds or epoxy groups or both, such as epoxy, vinyl or allyl or methacrylate group using radical initiators and photoacid generators.
  • Epoxy groups can be employed for UV-lithography and vice versa.
  • the proportion of active groups required for cross-linking is generally smaller than for UV lithography, e.g. about 0.1 to 10 mol%, based on the monomers, for cross-linking and about 5 to 50 mol%, based on the monomers, for UV lithography.
  • the amount of the initiator added to the reaction mixture/ solution is generally about 0.1 to 10 wt%, preferably about 0.5 to 5 wt%, calculated from the total weight of the siloxane polymer.
  • the molecular weight will typically be 2- to 10-folded.
  • the crosslinking will increase it above 3000, preferably to 4000 to 20000 g/mol.
  • additives typically introduced into the first composition comprising a siloxane polymer (B-l) include chemicals that can further modify the final surface properties of coated and cured film or improve wettability/adhesion properties of the coating layer (B) to the substrate layer (A) or the other coating layer (C) or improve coating drying and packing behavior during deposition and drying to reach good visual quality.
  • additives can be surfactants, defoamers, antifouling agents, wetting agents etc.
  • 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-331, BYK-333, BYK-341, BYK-345, BYK-348, BYK-370, BYK-377, BYK- 378, BYK-381, BYK-390, BYK-3700, all commercially available from BYK.
  • the additives are preferably present in an amount of 0.01-5 wt% by weight, more preferably 0.1 to 1 wt% of the total weight of the solids.
  • the excess of water is preferably removed from the material and at this stage it is possible to make a solvent exchange to another synthesis solvent if desired.
  • This other synthesis solvent may function as the final or one of the final processing solvents of the siloxane polymer.
  • the residual water and alcohols and other by-products may be removed after the further condensation step is finalized.
  • Additional processing solvent(s) may be added during the formulation 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.
  • the polymer is ready for processing in, for example, roll-to-roll film deposition or in a lithographic process.
  • the final siloxane polymer when the final siloxane polymer has a high content of hydroxyl groups remaining and a low content of alkoxy (e.g. ethoxy) groups, the final siloxane polymer can be dissolved into an alkaline-water developer solution (egg. tetra methyl ammonium hydroxide; TMAH, or potassium hydroxide; KOH).
  • an alkaline-water developer solution egg. tetra methyl ammonium hydroxide; TMAH, or potassium hydroxide; KOH.
  • the final siloxane polymer has a very low solubility in an alkaline-water developer of the above kind.
  • the OH- groups or other functional groups such as amino (NH2), thiol (SH), carboxyl, phenol or similar that result in solubility to the alkaline developer systems, can be attached directly to the silicon atoms of the siloxane polymer backbone or optionally attached to organic functionalities attached into the siloxane polymer backbone to filrther facilitate and control the alkaline developer solubility.
  • an initiator molecule compound is added to the siloxane composition after synthesis.
  • the initiator which can be optionally similar to the one added during polymerization, is used for creating a species that can initiate the polymerization of the “active” fiunctional group in the UV curing step.
  • cationic or anionic initiators can be used in case of an epoxy group.
  • radical initiators can be employed in case of a group with double bonds as “active” functional group in the synthesized material.
  • thermal initiators working according to the radical, cationic or anionic mechanism
  • the choice of a proper combination of the photoinitiators and sensitizers also depends on the used exposure source (wavelength). Furthermore, the selection of the used sensitizer depends on the selected initiator type.
  • the concentration of the thermal or radiation initiator and sensitizers in the composition is generally about 0.1 to 10 %, preferably about 0.5 to 5 %, calculated from the mass of the siloxane polymer.
  • the first composition comprising the siloxane polymer (B-l) is then deposited onto the onto at least one surface of the substrate to form a first coating layer (B).
  • Suitable deposition methods include spin-on, clip, spray, ink-jet, roll-to-roll, gravure, reverse gravure, bar coating, slot, flexo-graphic, curtain, screen printing coating methods, extrusion coating, dip coating, flow coating or slit coating.
  • the deposited first composition comprising the siloxane polymer (B-l) forms the coating layer (B) on the surface of the substrate (A).
  • the solvent is evaporated and the film coating layer (B) dried, preferably by thermal drying or optionally by vacuum and/or thermal drying combined. This step is also referred to as pre-curing.
  • the coating layer (B) is cured to final hardness by using thermal curing at elevated temperature or UV exposure followed by thermal curing at elevated temperature.
  • the method comprises the steps of
  • Exemplary epoxy -functional group containing monomers include (3- glycidoxypropyl)trimethoxy silane, l-(2-(Trimethoxysilyl)ethyl)cyclohexane-3,4- epoxide, (3-glycidoxypropyl)triethoxysilane, (3- glycidoxypropyl)tripropoxysilane, 3-glycidoxypropyltri(2-methoxyethoxy)silane, 2,3-epoxypropyltriethoxysilane, 3,4- epoxybutyltriethoxysilane, 4,5- epoxypentyltriethoxysilane, 5,6- epoxyhexyltriethoxysilane, 5,6- epoxyhexyltrimethoxysilane, 2-(3,4- epoxy cy cl ohexyl)ethyltri ethoxy silane, 2-(3,4- epoxy cy cl ohexyl)e
  • acrylate and metacrylate compounds such as tetraethylene glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, tricyclodecane dimethanol diacrylate, Tris(2- hydroxyethylisocyanurate) Di / Triacrylate and dipentaerythritol hexaacrylate and combinations thereof.
  • acrylates as commercially available e.g. as Miramer acrylates from Miwon.
  • Such compounds can be used as part of the silane compositions.
  • the method further includes curing the first composition comprising the siloxane polymer (B-l).
  • the thickness of the first coating layer (B) on the substrate (A) may range from 1 to 50 pm, preferably of 2 to 20 pm, more preferably 3 to 10 pm.
  • the coating layer (B) preferably is a flexible hard coat layer.
  • the hardness of the coating layer (B) is greater than 3H, over 4H, over 5H, over 6H or even over 7H as determined by ASTM D3363-00, Elcometer tester.
  • the coating layer (B) has an adhesion of 4B-5B, as tested by ASTM D3359-09, Crosshatch tester.
  • the coating layer (B) preferably has a scratch resistance as evidenced by no visual scratches on a Taber linear abrasion test (Using Linear Abraser from Taber Industries) carried out at up to 2000 linear cycles with BonStar steel wool #0000, at 500g weight, 2x2 cm head size, 2.0-inch stroke length, 60 cycles/min.
  • Second coating layer (C) The second coating layer (C) coated on at least one surface of the first coating layer (B) so that the second coating layer (C) is in adherent contact with at least one surface of the first coating layer (B).
  • the second coating layer (C) usually is an outer layer of the multi-layer coating with adherent contact with at least one surface of the first coating layer (B) as such that the first coating layer (B) is sandwiched between the substrate layer (A) and the second coating layer (C).
  • “Adherent contact” in this regard means that there is no further coating layer or adhesive layer between the at least one surface of the fist coating layer (B) and the second coating layer (C).
  • the second coating layer comprises a fluoropolyether compound.
  • the fluoropolyether compound can be a single fluoropolyether compound or a mixture of two or more, such as 2-10, preferably 2-4 different fluoropoly ether compounds.
  • the fluoropolyether compound not all hydrogen atoms may be replaced by fluorine. In case hydrogen atoms are present in the fluoropoly ether compound the molecular ratio fluorine/hydrogen is preferably at least 5, more preferably at least 10.
  • the fluoropolyether compound can also be a perfluoropolyether compound.
  • the fluoropolyether group of the fluoropolyether compound may be a linear or branched group, preferably is a linear group.
  • the repeating units of the fluoropolyether group are preferably Ci to Ce fluorinated dialcohols, more preferably Ci to C4 fluorinated dialcohols and most preferably Ci to C3 fluorinated dialcohols.
  • Preferable monomers of the fluoropoly ether group are perfluoro- 1,2-propylene glycol, perfluoro-l,3-propylene glycol, perfluoro- 1,2-ethylene glycol and difluoro- 1,1 -dihydroxy-methane, preferably perfluoro- 1,3 -propylene glycol, perfluoro- 1,2- ethylene glycol and difluoro-methanediol.
  • the latter monomer, difluoro- 1,1 -dihydroxy-methane, may be obtained by oxidizing poly(tetrafluoroethylene).
  • Preferred structures for a divalent perfluoropolyether group include -CF2O(CF2O)m(C2F4O)pCF2- wherein an average value for m and p is 0 to 150, with the proviso that m and p are not simultaneously zero,
  • particularly preferred structures are -CF2O(CF2O)m(C2F 4 O)pCF2 , -CF2O(C2F 4 O) P CF2-, and -CF(CF3)(OCF2(CF3)CF)pO(CF2)mO(CF(CF3)CF 2 O)pCF(CF3)-.
  • Preferred structures for a monovalent perfluoropolyether group include CF3CF2O(CF2O)m(C2F 4 O)pCF2-,
  • the fluoropolyether compound can comprise functional groups such as carboxy groups, alkyl ester groups, carboxyester groups, epoxy groups, amino groups, silane groups or mixtures thereof.
  • the fluoropolyether compound is a fluoropolyether silane, more preferably a fluoropolyether silane comprising hydrolysable groups (PFS).
  • fluoropolyether silane more preferably a fluoropolyether silane comprising hydrolysable groups (PFS).
  • R F is a fluoropolyether group
  • Q is a divalent linking group
  • R 3 is each independently selected from a Ci to Cio organyl or organoheteryl group
  • R 4 is each independently selected from a Ci to C20 organyl or organoheteryl group o is 1, 2 or 3 p is 0, 1 or 2 o+p is 3
  • R 5 is H, C X F2X+I with x being 1 to 10 or -Q-Si(OR 3 ) o R 4 P , with Q, R 3 , R 4 , o and p as defined above, whereby in each occurrence Q, R 3 , R 4 , o and p being present may be the same or different.
  • R 3 is each independently selected from a Ci to Cio organyl or organoheteryl group.
  • heteroatoms are present in the organyl group of R 3 they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.
  • Preferred groups OR 3 are alkoxy, acyloxy and aryloxy groups.
  • the heteroatom of the organoheteryl group of R 3 bound to the oxygen atom bound to M 1 is usually different from O.
  • the heteroatom(s) present in the organoheteryl group of R 3 are preferably selected from N, O, P or S, more preferably selected from N and O.
  • the total number of heteroatoms, if present, in R 3 is usually not more than five, preferably not more than three.
  • R 3 is a Ci to Cio organyl group containing not more than three heteroatoms, more preferably R 3 is a Ci to Cio hydrocarbyl group, even more preferably a Ci to Cio linear, branched, or cyclic alkyl group.
  • R 4 is each independently selected from a Ci to C20 organyl or organoheteryl group
  • heteroatoms are present in the organyl group of R 4 they are preferably selected from N, O, P, S or Si, more preferably selected from N and O.
  • the heteroatom of the organoheteryl group of R 4 bound to Si is usually different from O.
  • the heteroatom(s) present in the organoheteryl group of R 4 are preferably selected from N, O, P or S, more preferably selected from N and O.
  • R 4 The total number of heteroatoms, if present, in R 4 is usually not more than eight, preferably not more than five and most preferably not more than three.
  • R 4 is a Ci to C20 organyl group containing not more than three heteroatoms, more preferably R 4 is a Ci to C20 hydrocarbyl group, even more preferably a Ci to C20 linear, branched or cyclic alkyl group.
  • the total number of carbon atoms present in R 4 according to any one of the above variants is 1 to 15, more preferably 1 to 10 and most preferably 1 to 6.
  • o is preferably 1 to 3, more preferably 2 or 3 and most preferably 3
  • p is preferably 0 to 2, more preferably 0 or 1 and most preferably 0.
  • o + p is 3.
  • the fluoropolyether group R F may be a linear or branched group, preferably is a linear group.
  • the repeating units of the fluoropolyether group R F are preferably Ci to Ce fluorinated dialcohols, more preferably Ci to C4 fluorinated dialcohols and most preferably Ci to C3 fluorinated dialcohols.
  • Preferable monomers of the fluoropolyether group R F are perfluoro- 1,2-propylene glycol, perfluoro-l,3-propylene glycol, perfluoro- 1,2-ethylene glycol and difluoro- 1,1 -dihydroxy-methane, preferably perfluoro- 1,3 -propylene glycol, perfluoro- 1,2- ethylene glycol and difluoro-methanediol.
  • the latter monomer, difluoro- 1,1 -dihydroxy-methane, may be obtained by oxidizing poly(tetrafluoroethylene).
  • Preferred structures for a divalent perfluoropolyether group include -CF2O(CF2O)m(C2F4O)pCF2- wherein an average value for m and p is 0 to 50, with the proviso that m and p are not simultaneously zero,
  • Preferred structures for a monovalent perfluoropolyether group include
  • fluoropolyether groups R F are selected from
  • Q is usually having a molecular weight of not more than 500 g/mol, more preferably not more than 250 g/mol and most preferably not more than 150 g/mol.
  • divalent linking groups are amide-containing groups and alkylene groups.
  • Fluoropolyether compounds can be commercially available without public knowledge of their exact chemical structure.
  • Suitable commercially available fluoropolyether compounds are, for example Fluorolink S10 (CAS no. 223557-70-8, Solvay), OptoolTM DSX (Daikin Industries), Shin-Etsu SubelynTM 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).
  • the second coating layer (C) preferably further comprises one or more, such as one, two, three or four, preferably one to three, more preferably one or two, most preferably two second siloxane polymer(s) (C-l).
  • the second coating layer (C) comprises more than one second siloxane polymers (C-l) said siloxane polymers differ in at least one property.
  • Said at least one property can be e.g. differences in the silane monomers and/or differences in the molecular weight.
  • the second siloxane polymers (C-l) preferably comprise monomer units selected from one or more silane monomers.
  • the adjacent siloxane polymer chains are usually crosslinked by means of said active groups.
  • the second siloxane polymers (C-l) can comprise monomer units selected from 1 to 10, such as from 1 to 6, preferably from 1 to 4, more preferably 1 or 2 different silane monomers. “Different” in this connection means that the silane monomers differ in at least one chemical moiety.
  • Active groups are preferably epoxy, alicyclic epoxy groups (e.g. glycidyl), vinyl, allyl, acrylate, methacrylate and silane groups and combinations thereof.
  • Suitable thermal or radical initiators are preferably selected from tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'- azobis(cyclohexanecarbonitrile), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, l,l-bis(tert-butylperoxy)cyclohexane, 2,2'-azobisisobutyronitrile (AIBN), 2,5- bis(tert-butylperoxy)-Z,S-dimethylhexane, 2,5-bis(tert-Butylperoxy)- 2,5 -dimethyl-3 -hexyne, bis(l -(tert-butylperoxy)- 1 -methylethyl)benzene, 1 , 1 -bis(tert- butylperoxy)-3,3,5- trimethylcyclohexane, tert-butyl hydroperoxide, ter
  • the molar ratio between monomers containing a first active group, e.g. selected from epoxy, alicyclic epoxy groups (e. g. glycidyl), and vinyl and allyl groups, to monomers containing a second active group, e.g. selected from acrylate and methacrylate groups varies in the range of 1 : 100 to 100: 1, in particular 1 :10 to 10: 1, for example 5: 1 to 1 :2 or 3:1 to 1 : 1.
  • the components containing the second active group also be selected from acrylate and metacrylate containing compounds other than silane monomers, such as tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylo Ipropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate and combinations thereof.
  • silane monomers such as tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylo Ipropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate and combinations thereof.
  • the active group or active groups will be present in a concentration of about 1 to 35 % based on the molar portion of monomers.
  • Suitable silane monomers are preferably represented by formula (I) RJaSiX ⁇ a (I) wherein
  • X is a hydrolysable group or a hydrocarbon residue; and a is an integer 1 to 3.
  • the hydrolysable group is in particular an alkoxy group (cf. formula II).
  • the alkoxy groups of R 1 and/or the hydrolysable group X can be identical or different and preferably selected from the group of radicals having the formula -O-R 2 (II) wherein
  • R 2 stands for a linear or branched alkyl group having 1 to 10, preferably 1 to 6 carbon atoms, and optionally exhibiting one or two substituents selected from the group of halogen, hydroxyl, vinyl, epoxy and allyl. Most preferred are methoxy and ethoxy groups.
  • di-, tri- or tetraalkoxysilanes comprising alkoxy groups according to formula (II).
  • Particularly suitable silane monomers are selected from the group of tetraethoxysilane (TEOS), tetramethoxysilane (TMS), methyltri ethoxy si lane (MTEOS), methyltrimethoxysilane (MTMS), dimethyldiethoxysilane (DMDEOS), dimethyldimethoxy silane (DMDMS), diphenyldimethoxy silane (DPDMS), 3- (Trimethoxysilyl)propylmethacrylate (MEMO), 3- (Triethoxysilyl)propylmethacrylate, 5-(Bicycloheptenyl)triethoxysilane (BCHTEOS), (3-Glycidoxypropyl)triethoxysilane, (3- Glycidoxypropyl)trimethoxy silane (GPTMS), (Heptadecafluoro- 1 , 1 ,2,2- tetrahydrodecyl)trimethoxy silane, (Heptade
  • silane monomers are selected from the group of tetraethoxysilane (TEOS) and methyltrimethoxysilane (MTMS).
  • TEOS tetraethoxysilane
  • MTMS methyltrimethoxysilane
  • Said silane monomers are preferably present in the in the siloxane polymer in a molar amount of 50 to 100 mol%, preferably of 50 to 99 mol%, still more preferably of 65 to 97 mol%.
  • the at least two different silane monomers of the first siloxane polymer (B-l) comprise at least one bi-silane.
  • Suitable bi-silanes are preferably represented by formula (III) (R 3 ) 3 Si-Y-Si(R 4 ) 3 , (III) wherein
  • alkyl residue stands for 1 to 10, preferably 1 to 8, or 1 to 6 or even 1 to 4 carbon atoms, examples include ethylene and methylene and propylene.
  • “Arylene” stands for an aromatic bivalent group containing typically 1 to 3 aromatic rings, and 6 to 18 carbon atoms. Such groups are exemplified by phenylene (e.g. 1,4- phenylene and 1,3-phenylene groups) and biphenylene groups as well as naphthylene or anthracenylene groups.
  • alkylene and arylene groups can optionally be substituted with 1 to 5 substituents selected from hydroxy, halo, vinyl, epoxy and allyl groups as well as alkyl, aryl and aralkyl groups.
  • Preferred alkoxy groups contain 1 to 4 carbon atoms. Examples are methoxy and ethoxy.
  • phenyl includes substituted phenyls such as phenyltrialkoxy, in particular phenyltrimethoxy or tri ethoxy, and perfluorophenyl.
  • phenyltrialkoxy in particular phenyltrimethoxy or tri ethoxy
  • perfluorophenyl perfluorophenyl.
  • the phenyl as well as other aromatic or alicyclic groups can be coupled directly to a silicon atom, or they can be coupled to a silicon atom via a methylene or ethylene bridge.
  • the at least one silane monomers is selected from tetraethoxysilane (TEOS) and methyltrimethoxysilane (MTMS).
  • TEOS tetraethoxysilane
  • MTMS methyltrimethoxysilane
  • the second composition comprising at least one second siloxane polymer (C-l) is preferably formed by a method comprising the steps of
  • the second composition comprises more than one second siloxane polymer (C-l) the above steps are repeated for each one of the second siloxane polymer (C-l).
  • the first solvent is preferably selected from the group of acetone, tetrahydrofuran (THF), toluene, 1 -propanol, 2-propanol, methanol, ethanol, water (H2O), cyclopentanone, acetonitrile, propylene glycol propyl ether, methyl -tert-butyl ether (MTBE), propylene glycol monomethylether acetate (PGMEA), methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethylether (PGME) and propylene glycol propyl ether (PnP).
  • the at least two different silane monomers can be admixed in the first solvent at any suitable temperature for solving the silane monomers. Usually, room temperature suffices.
  • the mixture is subjected to an at least partial hydrolysis in the presence of a catalyst.
  • Basic catalysts are preferably selected from triethylamine (TEA), ammonium hydroxide (NH4OH), tetraethylammonium hydroxide (TEAH), tetramethylammonium hydroxide (TMEA), l,4-diazabicyclo[2.2.2]octane, imidazole and diethylenetriamine.
  • TAA triethylamine
  • NH4OH ammonium hydroxide
  • TEAH tetraethylammonium hydroxide
  • TBEA tetramethylammonium hydroxide
  • l,4-diazabicyclo[2.2.2]octane imidazole and diethylenetriamine.
  • catalysts are preferably selected from 2,2,3,3,4,4,5,5-octafluoropentylacrylate, poly(ethylene glycol) 200, poly(ethylene glycol) 300 and n-butylated melamine formaldehyde resin.
  • the hydrolysis step is preferably performed at a temperature of from 20 to 80°C for 1 to 24 hours, such as at room temperature overnight.
  • silane monomers are at least partially hydrolysed.
  • Said at least partially hydrolysed silane monomers then are at least partially polymerized, preferably by condensation polymerization and crosslinked to form a siloxane polymer.
  • the first solvent can be changed to a second solvent in an optional further method step after the hydrolysis step.
  • the optional solvent change is advantageous, since it assists the removal of water and alcohols formed during hydrolysis of the silane monomers. In addition, it improves the properties of the final siloxane polymer solution when used as coating layer(s) on the substrate.
  • the second solvent is preferably selected from the group of propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), 1 -ethanol, 2-ethanol (IP A), acrylonitrile diacetone alcohol (DAA) or propylene glycol n-propyl ether (PnP).
  • PGME propylene glycol methyl ether
  • PGMEA propylene glycol methyl ether acetate
  • IP A 2-ethanol
  • DAA acrylonitrile diacetone alcohol
  • PnP propylene glycol n-propyl ether
  • the mixture comprising the siloxane polymer can be further subjected to a crosslinking step after the hydrolysis step.
  • the siloxane polymer is preferably at least partially crosslinked by hydrosilylation, thermal or radiation initiation.
  • the term “partially crosslinked” means that the polymer is capable of further crosslinking at conditions conducive to cross-linking.
  • the polymer still contains at least some reactive, crosslinking groups after the first polymerisation step.
  • the further crosslinking which typically takes place after deposition of the partially crosslinked composition on a substrate, will be described below.
  • the siloxane polymer is preferably at least partially crosslinked by hydrosilylation, thermal or radiation initiation using catalysts as described above.
  • thermal crosslinking is preferably conducted at temperatures in the range of about 30 to 200 °C.
  • cross-linking is carried out at refluxing conditions of the solvent.
  • the siloxane polymer can be optionally partially cross-linked during polymerization, in particular during or immediately after condensation polymerization.
  • Various methods can be used for achieving cross-linking.
  • cross-linking method where two chains are joined via reactive groups not affecting any of the active groups intended for the UV photolithography can be employed.
  • hydrosilylation for example using a proton on one chain reacting with a double bond on another chain will achieve cross-linking of desired kind.
  • Another example is cross-linking through double bonds or epoxy groups.
  • the cross-linking of the siloxane polymer can be achieved with an active group having double bonds or epoxy groups or both, such as epoxy, vinyl or allyl or methacrylate group using radical initiators and photoacid generators.
  • Epoxy groups can be employed for UV-lithography and vice-versa.
  • the proportion of active groups required for cross-linking is generally smaller than for UV lithography, e.g. about 0.1 to 10 mol%, based on the monomers, for cross-linking and about 5 to 50 mol%, based on the monomers, for UV lithography.
  • the amount of the initiator added to the reaction mixture/ solution is generally about 0.1 to 10 wt%, preferably about 0.5 to 5 wt%, calculated from the total weight of the siloxane polymer.
  • the molecular weight will typically be 2- to 10-folded.
  • the crosslinking will increase it above 3000, preferably to 4000 to 20000 g/mol.
  • resulting free Si-OH groups present in backbone of the siloxane polymer can be protected by an end-capping.
  • the free Si-OH groups are reacted with silanes such as methyldichlorofluorosilane (CEFSiCHs, methylfluorodimethoxysilane ((MeO ⁇ SiFCH?), 3 -chloropropyltrimethoxy silane (Cl(CH2)3Si(OMe)3), ethyltrimethoxysilane (ETMS), or trimethylchlorosilane (CISiMes) in presence of a catalyst such as tri ethylaluminium (TEA) or imidazole.
  • a catalyst such as tri ethylaluminium (TEA) or imidazole.
  • the amount of catalyst varies from 1.5 to 2 wt% of total solid.
  • the reaction time varies from 40 to 45 min.
  • Other additives typically introduced into the second composition comprising the fluoropoly ether compound and the at least one second siloxane polymer (C-l) include chemicals that can further modify the final surface properties of coated and cured film or improve wettability/adhesion properties of the coating layer (B) to the substrate layer (A) or the other coating layer (C) or improve coating drying and packing behavior during deposition and drying to reach good visual quality.
  • additives can be surfactants, defoamers, antifouling agents, wetting agents etc.
  • 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-331, BYK-333, BYK-341, BYK-345, BYK-348, BYK-370, BYK-377, BYK- 378, BYK-381, BYK-390, BYK-3700.
  • the additives are preferably present in an amount of 0.01-5 wt% by weight, more preferably 0.1 to 1 wt% of the total weight of the solids.
  • the excess of water is preferably removed from the material and at this stage it is possible to make a solvent exchange to another synthesis solvent if desired.
  • This other synthesis solvent may function as the final or one of the final processing solvents of the siloxane polymer.
  • the residual water and alcohols and other by-products may be removed after the further condensation step is finalized.
  • Additional processing solvent(s) may be added during the formulation 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.
  • the polymer is ready for processing in, for example, roll-to-roll film deposition or in a lithographic process.
  • the concentration/ content of the group capable of being deprotonated e.g. an OH- group
  • any residual leaving groups from the silane precursors e.g. alkoxy groups
  • the concentration/ content of the group capable of being deprotonated e.g. an OH- group
  • any residual leaving groups from the silane precursors e.g. alkoxy groups
  • the molecular weight of the polymer greatly affects dissolution of the siloxane polymer material into the aqueous based developer solution.
  • the molecular weight of the polymer also greatly effects on the dissolution properties of the siloxane polymer into developer solutions.
  • the final siloxane polymer when the final siloxane polymer has a high content of hydroxyl groups remaining and a low content of alkoxy (e.g. ethoxy) groups, the final siloxane polymer can be dissolved into an alkaline-water developer solution (egg. tetra methyl ammonium hydroxide; TMAH, or potassium hydroxide; KOH).
  • an alkaline-water developer solution egg. tetra methyl ammonium hydroxide; TMAH, or potassium hydroxide; KOH.
  • the second siloxane polymer (C-l) can be diluted using a proper solvent or solvent combination to give a solid content which in film deposition will yield the preselected film thickness.
  • the solvent or solvent combination preferably comprises a fluorinated solvent such as methoxy-nonafluorobutane or l,l,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether.
  • a fluorinated solvent such as methoxy-nonafluorobutane or l,l,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether.
  • an initiator molecule compound is added to the siloxane composition after synthesis.
  • the initiator which can be optionally similar to the one added during polymerization, is used for creating a species that can initiate the polymerization of the “active” functional group in the UV curing step.
  • cationic or anionic initiators can be used.
  • radical initiators can be employed.
  • thermal initiators working according to the radical, cationic or anionic mechanism
  • the choice of a proper combination of the photoinitiators and sensitizers also depends on the used exposure source (wavelength). Furthermore, the selection of the used sensitizer depends on the selected initiator type.
  • the concentration of the thermal or radiation initiator and sensitizers in the composition is generally about 0.1 to 10 %, preferably about 0.5 to 5 %, calculated from the mass of the siloxane polymer.
  • the second composition does not include one or more second siloxane polymers (C-l).
  • the fluoropolyether compound is preferably solved in a solvent to form the second composition.
  • the fluoropolyether compound preferably is a fluoropolyether silane comprising hydrolysable groups (PFS).
  • the solvent preferably comprises, more preferably is a fluorinated solvent, such as methoxy-nonafluorobutane or l,l,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, preferably 1 , 1 , 2, 2-tetrafluoroethyl -2, 2, 2-tri fluoroethyl ether.
  • a fluorinated solvent such as methoxy-nonafluorobutane or l,l,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, preferably 1 , 1 , 2, 2-tetrafluoroethyl -2, 2, 2-tri fluoroethyl ether.
  • the second composition preferably consists of the fluoropolyether compound and the solvent.
  • the second composition comprising fluoropolyether compound is deposited onto the least one surface of the substrate to form the second coating layer (C) in adherent contact with the at least one surface of the first coating layer (B).
  • Suitable deposition methods include spin-on, clip, spray, ink-jet, roll-to-roll, gravure, reverse gravure, bar coating, slot, flexo-graphic, curtain, screen printing coating methods, extrusion coating, dip coating, flow coating or slit coating.
  • the deposited second composition comprising the fluoropolyether compound forms the second coating layer (C) on the surface of the first coating layer (B).
  • the solvent is evaporated and the second coating layer (C) dried, preferably by thermal drying or optionally by vacuum and/or thermal drying combined. This step is also referred to as pre-curing.
  • the second coating layer (C) is cured to final hardness by thermal curing at elevated temperature or by using UV exposure followed by thermal curing at elevated temperature.
  • the pre-curing and the final curing steps are combined by carrying out heating by using an increasing heating gradient.
  • the curing can be performed in three steps, the process comprising thermal pre-cure and UV-cure followed by final thermal cure. It is also possible to apply a two steps curing process where thermal pre-cure is followed by UV-cure. In such a case no final thermal cure is preferably applied after UV-cure).
  • the method further includes developing the deposited film.
  • developing comprises exposing (full area or selective exposure using photomask or reticule or laser direct imaging) the deposited first siloxane polymer composition to UV light.
  • the step of developing is typically carried out after any pre-curing step and before a final curing step.
  • the method comprises the steps of
  • Exemplary epoxy -functional group containing monomers include (3- glycidoxypropyl)trimethoxy silane, l-(2-(Trimethoxysilyl)ethyl)cyclohexane-3,4- epoxide, (3-glycidoxypropyl)triethoxysilane, (3- glycidoxypropyl)tripropoxysilane, 3-glycidoxypropyltri(2-methoxyethoxy)silane, 2,3-epoxypropyltriethoxysilane, 3,4- epoxybutyltriethoxysilane, 4,5- epoxypentyltriethoxysilane, 5,6- epoxyhexyltriethoxysilane, 5,6- epoxyhexyltrimethoxysilane, 2-(3,4- epoxycy cl ohexyl)ethyltri ethoxy silane, 2-(3,4- epoxy cy cl ohexyl)eth
  • acrylate and metacrylate compounds such as tetraethylene glycol diacrylate, trimethylo Ipropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate and combinations thereof.
  • tetraethylene glycol diacrylate trimethylo Ipropane triacrylate
  • pentaerythritol triacrylate ditrimethylolpropane tetraacrylate
  • dipentaerythritol pentaacrylate dipentaerythritol hexaacrylate and combinations thereof.
  • Such compounds can be used as part of the silane compositions.
  • the method further includes curing the second composition comprising fluoropolyether compound.
  • the thickness of the second coating layer (C) on the first coating layer (B) may range from 10 nm to 10 pm, preferably of 25 nm to 8 pm, more preferably 50 nm to 5 pm.
  • the second coating layer (C) preferably is an anti -reflective layer.
  • the second coating layer (C) a refractive index of not more than 1.30, such as in the range of 1.26 - 1.30.
  • the third coating layer (D) preferably has a thickness of 10 nm to 10 pm, preferably of 15 nm to 8 pm, more preferably 20 nm to 5 pm.
  • the third coating layer (D) comprises a siloxane polymer and optionally a fluoropolyether compound.
  • the third coating layer (D) comprises a third siloxane polymer (D-l) which comprises side chains comprising one or more fluorinated carbon groups.
  • the third siloxane polymer (D-l) comprises monomer units selected from at least one silane monomers.
  • the third siloxane polymer (D-l) can comprise monomer units selected from 1 to 10, such as from 1 to 6, preferably from 1 to 4 different silane monomers. “Different” in this connection means that the silane monomers differ in at least one chemical moiety.
  • At least one of the silane monomers includes an active group capable of achieving cross-linking to adjacent siloxane polymer chains, and wherein the adjacent siloxane polymer chains are crosslinked by means of said an active groups.
  • Active groups are preferably epoxy, alicyclic epoxy groups (e.g. glycidyl), vinyl, allyl, acrylate, methacrylate and silane groups and combinations thereof.
  • the epoxy, alicyclic epoxy groups e.g. glycidyl
  • vinyl, allyl, acrylate, methacrylate groups are capable of achieving cross-linking to adjacent siloxane polymer chains upon a thermal or radiation initiation, preferably in the presence of a suitable initiator such as a thermal or radical initiator.
  • Suitable thermal or radical initiators are preferably selected from tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'- azobis(cyclohexanecarbonitrile), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, l,l-bis(tert-butylperoxy)cyclohexane, 2,2'-azobisisobutyronitrile (AIBN), 2,5- bis(tert-butylperoxy)-Z,S-dimethylhexane, 2,5-bis(tert-Butylperoxy)- 2,5 -dimethyl-3 -hexyne, bis(l -(tert-butylperoxy)- 1 -methylethyl)benzene, 1 , 1 -bis(tert- butylperoxy)-3,3,5- trimethylcyclohexane, tert-butyl hydroperoxide, ter
  • the silane group is capable of achieving cross-linking to a carbon-carbon double bond, such as a vinyl or allyl group) of an adjacent siloxane polymer chains upon hydrosilylation, preferably in the presence of a suitable catalyst, such as a platinum (Pt)-based catalyst such as the Speier catalyst (EEPtCle.EEO), Karstedt’s catalyst (Pt(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex solution) or a rhodium (Rh)-based catalyst such as Tris(triphenylphosphine)rhodium (I) chloride.
  • a platinum (Pt)-based catalyst such as the Speier catalyst (EEPtCle.EEO)
  • Karstedt’s catalyst Pt(0)-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex solution
  • Rh rhodium
  • the molar ratio between monomers containing a first active group, e.g. selected from epoxy, alicyclic epoxy groups (e. g. glycidyl), and vinyl and allyl groups, to monomers containing a second active group, e.g. selected from acrylate and methacrylate groups varies in the range of 1 : 100 to 100: 1, in particular 1 :10 to 10: 1, for example 5: 1 to 1 :2 or 3:1 to 1 : 1.
  • the components containing the second active group also be selected from acrylate and metacrylate containing compounds other than silane monomers, such as tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylo Ipropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate and combinations thereof.
  • silane monomers such as tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylo Ipropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate and combinations thereof.
  • the active group or active groups will be present in a concentration of about 1 to 35 % based on the molar portion of monomers.
  • Suitable silane monomers are preferably represented by formula (I) RJaSiX ⁇ a (I) wherein
  • R 1 is selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alk)acrylate, epoxy, allyl, vinyl and alkoxy and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted;
  • X is a hydrolysable group or a hydrocarbon residue; and a is an integer 1 to 3.
  • the hydrolysable group is in particular an alkoxy group (cf. formula II).
  • alkoxy groups of R 1 and/or the hydrolysable group X can be identical or different and preferably selected from the group of radicals having the formula -O-R 2 wherein
  • R 2 stands for a linear or branched alkyl group having 1 to 10, preferably 1 to 6 carbon atoms, and optionally exhibiting one or two substituents selected from the group of halogen, hydroxyl, vinyl, epoxy and allyl. Most preferred are methoxy and ethoxy groups.
  • di-, tri- or tetraalkoxysilanes comprising alkoxy groups according to formula (II).
  • Particularly suitable silane monomers are selected from the group of tetraethoxysilane (TEOS), tetramethoxysilane (TMS), methyltri ethoxy si lane (MTEOS), methyltrimethoxysilane (MTMS), dimethyldiethoxysilane (DMDEOS), dimethyldimethoxy silane (DMDMS), diphenyldimethoxy silane (DPDMS), 3- (Trimethoxysilyl)propylmethacrylate (MEMO), 3- (Triethoxysilyl)propylmethacrylate, 5-(Bicycloheptenyl)triethoxysilane (BCHTEOS), (3-Glycidoxypropyl)triethoxysilane, (3- Glycidoxypropyl)trimethoxysilane (GPTMS), allyltrimethoxysilane (allylTMS), allyltriethoxysilane (allylTEOS), vinyltrimethoxysilane
  • silane monomers are selected from the group of tetraethoxysilane (TEOS), phenylmethyldimethoxysilane (PMDMS), 3- (Trimethoxysilyl)propylmethacrylate (MEMO), methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (VTMS) and (3-Glycidoxypropyl)trimethoxysilane (GPTMS).
  • TEOS tetraethoxysilane
  • PMDMS phenylmethyldimethoxysilane
  • MEMO Trimethoxysilylpropylmethacrylate
  • MTMS methyltrimethoxysilane
  • VTMS vinyltrimethoxysilane
  • GTPMS 3-Glycidoxypropyl)trimethoxysilane
  • Said silane monomers are preferably present in the in the siloxane polymer in a molar amount of 50 to 100 mol%, preferably of 50 to 99 mol
  • the at least one silane monomers of the third siloxane polymer (D-l) comprise at least one bi-silane.
  • Suitable bi-silanes are 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 a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alk)acrylate, epoxy, allyl, vinyl, alkoxy and aryl having 1 to 6 rings, and wherein the group is substituted or unsub stitued; and
  • alkyl residue stands for 1 to 10, preferably 1 to 8, or 1 to 6 or even 1 to 4 carbon atoms, examples include ethylene and methylene and propylene.
  • Alkylene stands for an aromatic bivalent group containing typically 1 to 3 aromatic rings, and 6 to 18 carbon atoms. Such groups are exemplified by phenylene (e.g. 1,4- phenylene and 1,3-phenylene groups) and biphenylene groups as well as naphthylene or anthracenylene groups.
  • the alkylene and arylene groups can optionally be substituted with 1 to 5 substituents selected from hydroxy, halo, vinyl, epoxy and allyl groups as well as alkyl, aryl and aralkyl groups.
  • Preferred alkoxy groups contain 1 to 4 carbon atoms. Examples are methoxy and ethoxy.
  • phenyl includes substituted phenyls such as phenyltrialkoxy, in particular phenyltrimethoxy or tri ethoxy, and perfluorophenyl.
  • phenyltrialkoxy in particular phenyltrimethoxy or tri ethoxy
  • perfluorophenyl perfluorophenyl.
  • the phenyl as well as other aromatic or alicyclic groups can be coupled directly to a silicon atom or they can be coupled to a silicon atom via a methylene or ethylene bridge.
  • bi-silanes include 1,2-Bis(triethoxysilyl)ethane (BTESE), 1,2- Bis(trimethoxysilyl)ethane (MEOS) and mixtures thereof.
  • the bi-silane present in the siloxane polymer in a molar amount of 0 to 45 mol%, preferably of 1 to 45 mol%, still more preferably of 3 to 30 mol%.
  • the third siloxane polymer comprises (D-l) at least one, such as 1 to 10, preferably 1 to 6, more preferably 1 or 2, most preferably one fluorinated monomer, which is capable of forming side chains comprising one or more fluorinated carbon groups.
  • Such fluorinated monomer can be a fluorinated silane monomer which is preferably represented by formula (I)
  • R 1 is selected from a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alk)acrylate, epoxy, allyl, vinyl and alkoxy and aryl having 1 to 6 rings, preferably a linear or branched alkyl, and wherein the group is substituted with one or more fluorine atoms;
  • X is a hydrolysable group or a hydrocarbon residue; and a is an integer 1 to 3.
  • the hydrolysable group is in particular an alkoxy group (cf. formula II).
  • silane monomers are e.g. (Heptadecafluoro-1, 1,2,2- tetrahydrodecyl)trimethoxy silane, (Heptadecafluoro- 1 , 1 ,2,2- tetrahydrodecyl)triethoxysilane (Fl 7), 1H,1H,2H,2H- Perfluorododecyltriethoxysilane, 1H,1H,2H,2H-Perfluorododecyltrimethoxysilane, 1H, 1H,2H,2H-Perfluorooctyltriethoxysilane, 1H, 1H,2H,2H-
  • Perfluorooctyltrimethoxysilane 1H,1H,2H,2H-Perfluoropentyltriethoxysilane, 1H, 1H,2H,2H-Perfluoropentyltrimethoxysilane, 1H, 1H,2H,2H- Perfluorotetradecyltriethoxysilane, or 1H,1H,2H,2H- Perfluorotetradecyltrimethoxysilane.
  • the fluorinated monomer can also be a monomer comprising a fluorinated polymer group.
  • Said monomer comprising a fluorinated polymer group is preferably selected from fluorinated polysiloxanes, modified perfluoropolyethers.
  • the modified perfluoropolyethers are preferably selected from silane modified perfluoropolyethers, carboxyester modified perfluoropolyethers, such as acrylate modified perfluoropolyethers and methacrylate modified perfluoropolyethers, epoxybased perfluoropolyethers and mixtures thereof.
  • fluorinated polysiloxanes and modified perfluoropolyethers can be commercially available from Shin-Etsu Subelyn® fluorinated anti-smudge coating components of the KY-100 Series, such as KY-1900 and KY-1901, Shin-Etsu Subelyn® fluorinated anti-smudge additives of the KY-1200 Series, such as KY- 1271, or Daikin fluorinated anti-smudge coating components of the OPTOOL Series such as OPTOOL UD-509, OPTOOL UD-120 and OPTOOL DSX.
  • Shin-Etsu Subelyn® fluorinated anti-smudge coating components of the KY-100 Series such as KY-1900 and KY-1901
  • Shin-Etsu Subelyn® fluorinated anti-smudge additives of the KY-1200 Series such as KY- 1271
  • Daikin fluorinated anti-smudge coating components of the OPTOOL Series such as OPTO
  • fluorinated polysiloxanes are for example poly(methyl-3,3,3- trifluoropropyl)siloxane having a molecular weight in the range of from 1500 to 20000 g/mol, preferably from 2000 to 15000 g/mol.
  • the monomers are selected from mixture of two or more of the group of 1,2-Bis(triethoxysilyl)ethane (BTESE), tetraethoxysilane (TEOS), phenylmethyl dimethoxysilane (PMDMS), 3-(Trimethoxysilyl)propylmethacrylate (MEMO), methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (VTMS) and (3- Glycidoxypropyl)trimethoxysilane (GPTMS) and additionally a fluorinated monomer selected from KY-1900, KY-1901 and KY-1271.
  • BTESE 1,2-Bis(triethoxysilyl)ethane
  • TEOS tetraethoxysilane
  • PMDMS phenylmethyl dimethoxysilane
  • MEMO 3-(Trimethoxysilyl)propylmethacrylate
  • MTMS methyltrimethoxysilane
  • VTMS vinyl
  • the third composition comprising a third siloxane polymer (D-l) is preferably formed by a method comprising the steps of
  • the first solvent is preferably selected from the group of acetone, tetrahydrofuran (THF), toluene, 1 -propanol, 2-propanol, methanol, ethanol, water (H2O), cyclopentanone, acetonitrile, propylene glycol propyl ether, methyl -tert-butyl ether (MTBE), propylene glycol monomethylether acetate (PGMEA), methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethylether (PGME) and propylene glycol propyl ether (PnP).
  • the monomers can be admixed in the first solvent at any suitable temperature for solving the monomers. Usually, room temperature suffices.
  • the mixture is subjected to an at least partial hydrolysis in the presence of a catalyst.
  • Suitable catalysts are acidic catalysts, basic catalysts or other catalysts.
  • catalysts are preferably selected from 2,2,3,3,4,4,5,5-octafluoropentylacrylate, poly(ethylene glycol) 200, poly(ethylene glycol) 300 and n-butylated melamine formaldehyde resin.
  • the hydrolysis step is preferably performed at a temperature of from 20 to 80°C for 1 to 24 hours, such as at room temperature overnight.
  • the monomers are at least partially hydrolysed.
  • Said at least partially hydrolysed monomers then are at least partially polymerized, preferably by condensation polymerization and crosslinked to form a siloxane polymer, which comprises side chains comprising one or more fluorinated carbon groups.
  • the subjecting the mixture to an at least partial hydrolysis includes refluxing.
  • a typical refluxing time is 2 h.
  • the first solvent can be changed to a second solvent in an optional further method step after the hydrolysis step.
  • the optional solvent change is advantageous, since it assists the removal of water and alcohols formed during hydrolysis of the monomers. In addition, it improves the properties of the final siloxane polymer solution when used as coating layer(s) on the substrate.
  • the second solvent is preferably selected from the group of propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), 1 -ethanol, 2-ethanol (IP A), acrylonitrile diacetone alcohol (DAA) or propylene glycol n-propyl ether (PnP).
  • PGME propylene glycol methyl ether
  • PGMEA propylene glycol methyl ether acetate
  • IP A 2-ethanol
  • DAA acrylonitrile diacetone alcohol
  • PnP propylene glycol n-propyl ether
  • the mixture comprising the siloxane polymer can be further subjected to a crosslinking step after the hydrolysis step.
  • the siloxane polymer is preferably at least partially crosslinked by hydrosilylation, thermal or radiation initiation.
  • the term “partially crosslinked” means that the polymer is capable of further crosslinking at conditions conducive to cross-linking.
  • the polymer still contains at least some reactive, crosslinking groups after the first polymerisation step.
  • the further crosslinking which typically takes place after deposition of the partially crosslinked composition on a substrate, will be described below.
  • cross-linking is carried out at refluxing conditions of the solvent.
  • the cross-linking of the siloxane polymer can be achieved with an active group having double bonds or epoxy groups or both, such as epoxy, vinyl or allyl or methacrylate group using radical initiators and photoacid generators.
  • Epoxy groups can be employed for UV-lithography and vice versa.
  • the proportion of active groups required for cross-linking is generally smaller than for UV lithography, e.g. about 0.1 to 10 mol%, based on the monomers, for cross-linking and about 5 to 50 mol%, based on the monomers, for UV lithography.
  • the amount of the initiator added to the reaction mixture/ solution is generally about 0.1 to 10 wt%, preferably about 0.5 to 5 wt%, calculated from the total weight of the siloxane polymer.
  • the free Si-OH groups are reacted with silanes such as methyldichlorofluorosilane (ChFSiCH?, methylfluorodimethoxysilane ((MeO ⁇ SiFCH?), 3 -chloropropyltrimethoxy silane (Cl(CH2)3Si(OMe)3), ethyltrimethoxysilane (ETMS), or trimethylchlorosilane (CISiMes) in presence of a catalyst such as tri ethylaluminium (TEA) or imidazole.
  • TSA tri ethylaluminium
  • the amount of catalyst varies from 1.5 to 2 wt% of total solid.
  • the reaction time varies from 40 to 45 min.
  • additives typically introduced into the first composition comprising the third siloxane polymer (D-l) include chemicals that can further modify the final surface properties of coated and cured film or improve wettability/adhesion properties of the coating layer (B) to the substrate layer (A) or the other coating layer (C) or improve coating drying and packing behavior during deposition and drying to reach good visual quality.
  • additives can be surfactants, defoamers, antifouling agents, wetting agents etc.
  • 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-331, BYK-333, BYK-341, BYK-345, BYK-348, BYK-377, BYK-378, BYK- 381, BYK-390, BYK-3700.
  • the additives are preferably present in an amount of 0.01-5 wt% by weight, more preferably 0.1 to 1 wt% of the total weight of the solids.
  • the excess of water is preferably removed from the material and at this stage it is possible to make a solvent exchange to another synthesis solvent if desired.
  • This other synthesis solvent may filnction as the final or one of the final processing solvents of the siloxane polymer.
  • the residual water and alcohols and other by-products may be removed after the further condensation step is finalized.
  • Additional processing solvent(s) may be added during the formulation 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.
  • the polymer is ready for processing in, for example, roll-to-roll film deposition or in a lithographic process.
  • the concentration/ content of the group capable of being deprotonated e. g. an OH- group
  • any residual leaving groups from the silane precursors e.g. alkoxy groups
  • the concentration/ content of the group capable of being deprotonated e. g. an OH- group
  • any residual leaving groups from the silane precursors e.g. alkoxy groups
  • the molecular weight of the polymer greatly affects dissolution of the siloxane polymer material into the aqueous based developer solution.
  • the molecular weight of the polymer also greatly effects on the dissolution properties of the siloxane polymer into developer solutions.
  • the final siloxane polymer when the final siloxane polymer has a high content of hydroxyl groups remaining and a low content of alkoxy (e.g. ethoxy) groups, the final siloxane polymer can be dissolved into an alkaline-water developer solution (egg. tetra methyl ammonium hydroxide; TMAH, or potassium hydroxide; KOH).
  • an alkaline-water developer solution egg. tetra methyl ammonium hydroxide; TMAH, or potassium hydroxide; KOH.
  • the final siloxane polymer has a very low solubility in an alkaline-water developer of the above kind.
  • the OH- groups or other functional groups such as amino (NH2), thiol (SH), carboxyl, phenol or similar that result in solubility to the alkaline developer systems, can be attached directly to the silicon atoms of the siloxane polymer backbone or optionally attached to organic functionalities attached into the siloxane polymer backbone to filrther facilitate and control the alkaline developer solubility.
  • the siloxane polymer composition can be diluted using a proper solvent or solvent combination to give a solid content which in film deposition will yield the pre-selected film thickness.
  • an initiator molecule compound is added to the siloxane composition after synthesis.
  • the initiator which can be optionally similar to the one added during polymerization, is used for creating a species that can initiate the polymerization of the “active” filnctional group in the UV curing step.
  • cationic or anionic initiators can be used in case of an epoxy group.
  • radical initiators can be employed in case of a group with double bonds as “active” functional group in the synthesized material.
  • thermal initiators working according to the radical, cationic or anionic mechanism
  • the choice of a proper combination of the photoinitiators and sensitizers also depends on the used exposure source (wavelength). Furthermore, the selection of the used sensitizer depends on the selected initiator type.
  • the composition as described above may comprise solid nanoparticles or other compounds in an amount of between 1 and 50 wt-% of the composition.
  • the nanoparticles (or similar nano-, or microscale rods, crystals, spheres, dots, buds etc.) are in particular selected from the group of light scattering, light absorbing, light emitting and/or conductive pigments, dyes, organic and inorganic phosphors, oxides, quantum dots, polymers or metals.
  • the third composition comprises a fourth siloxane polymer (D- 2).
  • Said fourth siloxane polymer (D-2) preferably does not comprise side chains comprising one or more fluorinated carbon groups.
  • the third composition preferably comprises a fluoropolyether compound as described for the second composition of the second coating layer (C) above or below.
  • Suitable deposition methods include spin-on, clip, spray, ink-jet, roll-to-roll, gravure, reverse gravure, bar coating, slot, flexo-graphic, curtain, screen printing coating methods, extrusion coating, dip coating, flow coating or slit coating.
  • the deposited third composition forms the third coating layer (D) on the surface of the second coating layer (C).
  • the solvent is evaporated and the third coating layer (D) is dried, preferably by thermal drying or optionally by vacuum and/or thermal drying combined. This step is also referred to as pre-curing.
  • the third coating layer (D) is cured to final hardness by using thermal curing at elevated temperature or UV exposure followed by thermal curing at elevated temperature.
  • acrylate and metacrylate compounds such as tetraethylene glycol diacrylate, trimethylo Ipropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate and combinations thereof.
  • tetraethylene glycol diacrylate trimethylo Ipropane triacrylate
  • pentaerythritol triacrylate ditrimethylolpropane tetraacrylate
  • dipentaerythritol pentaacrylate dipentaerythritol hexaacrylate and combinations thereof.
  • Such compounds can be used as part of the silane compositions.
  • the thickness of the third coating layer (D) on the second coating layer (C) may range from 10 nm to 10 pm, preferably of 15 nm to 8 pm, more preferably 20 nm to 5 pm.
  • the third coating layer (D) preferably is an easy-to-clean coating layer comprising a siloxane polymer as described in WO 2016/146895 or WO 2020/099290
  • the third coating layer (D) preferably is a flexible hard coat layer comprising a third siloxane polymer (D-l) which comprises side chains comprising one or more fluorinated carbon groups.
  • the third coating layer (D) preferably has a scratch resistance as evidenced by no visual scratches on a Taber linear abrasion test (Using Linear Abraser from Taber Industries) carried out at up to 2000 linear cycles with BonStar steel wool #0000, at 500g weight, 2x2 cm head size, 2.0 inch stroke length, 60 cycles/min.
  • the layered structure according to the present invention in one embodiment comprises the substrate layer (A), the first coating layer (B) and the second coating layer (C).
  • the second coating layer (C) is the outermost layer of the layered structure and sandwiches together with the substrate layer (A) the first coating layer (B). This means that preferably no further coatings or coating layers are applied on the at least one surface of the substrate layer (A).
  • the layered structure additionally comprises the third coating layer (D).
  • the layered structure according to the present invention comprises the substrate layer (A), the first coating layer (B), the second coating layer (C) and the third coating layer (D).
  • the layered structure preferably shows an adhesion of the first coating layer (B) to the substrate layer (A) of 4-5B.
  • the layered structure preferably shows an adhesion of the second coating layer (C) to the first coating layer (B) of 3-5B.
  • the layered structure preferably shows an initial water contact angle of at least 75°, preferably at least 90°.
  • the layered structure preferably shows a scratch resistance corresponding to a visual quality of 0 to 2 on a Taber linear abrasion test (Using Linear Abraser from Taber Industries) carried out at up to 500 linear cycles with BonStar steel wool #0000, at 500g weight, 2x2 cm head size, 2.0-inch stroke length, 60 cycles/min.
  • a Taber linear abrasion test (Using Linear Abraser from Taber Industries) carried out at up to 500 linear cycles with BonStar steel wool #0000, at 500g weight, 2x2 cm head size, 2.0-inch stroke length, 60 cycles/min.
  • the layered structure preferably shows a contact angle of at least 80° on a Taber linear abrasion test (Using Linear Abraser from Taber Industries) carried out at up to 500 linear cycles with BonStar steel wool #0000, at 500g weight, 2x2 cm head size, 2.0-inch stroke length, 60 cycles/min.
  • Taber linear abrasion test (Using Linear Abraser from Taber Industries) carried out at up to 500 linear cycles with BonStar steel wool #0000, at 500g weight, 2x2 cm head size, 2.0-inch stroke length, 60 cycles/min.
  • the layered structure preferably shows a transmittance at 550 nm of at least 93.0%, preferably at least 93.5%, when measured on a coated PMMA substrate or a transmittance at 550 nm of at least 89.5%, preferably at least 90.0%, when measured on a coated PET or CPI substrate.
  • Molecular weight the polymers were characterized by gel permeation chromatography.
  • the chromatographic system consisted of a GPC apparatus equipped with an isocratic HPLC pump and a refractive index detector.
  • the polysiloxanes (0,20 g; 50% solid content) were dissolved in THF (HPLC-grade; 2,30 g).
  • the analyte injection volume was 100 pL, the flow was 0,70 mL / min, and the column temperature was set to 40 °C.
  • Four polysterene exclusion-based columns were used.
  • the mobile phase was THF (HPLC grade).
  • Number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polymers were determined using internal standards, e.g.
  • T% and reflection (R%) A Konica Minolta spectrophotometer CM-3700A (Specta Magic NX software) was used to measure transmittance and reflectance.
  • Pencil hardness the pencil hardness was determined according to ASTM standard D3363-00 using a Elcometer pencil hardness tester.
  • the abrasion testing was carried out using Bon star steel wool #0000, 500 g load, 2 x 2 cm head, 2-inch stroke, 60 cycles / minute, 500 cycles using taber linear abraser 5750.
  • Visual quality the visual inspection can be observed with bear eyes, under microscope using a green or red-light quality lamp inspection. The visual quality can be scored between 0 (best) to 3 (worse).
  • Adhesion the adhesion was determined according to ASTM standard D3359-D9 using a Elcometer cross-hatch tester and Elcometer tape test.
  • GPTMS (3 -Glycidoxypropyl)trimethoxy silane, Sigma-Aldrich
  • MEMO 3 -(Trimethoxy silyl)propylmethacrylate, ABCR
  • TEOS tetraethoxysilane, Ultra Pure Solutions Inc.
  • DPDMS diphenyl dimethoxysilane, Sigma-Aldrich
  • PTMS phenyl trimethoxysilane
  • F13 lH,lH,2H,2H-perfluorooctyltrimethoxysilane, Sigma-Aldrich
  • PGME l-methoxy-2-propanol, Ultra Pure Solutions Inc.
  • DiPG dipropylene glycol
  • KY 1900 perfluoropoly ether with reactive silyl group, Shin-Etsu
  • KY 1901 perfluoropoly ether with reactive silyl group, Shin-Etsu
  • KY 1271 fluorinated anti-smudge additive
  • DSX OPTOOL DSX E (fluoropoly ether silane), Daikin
  • AIBN azobisisobutyronitrile
  • UVI Speed Cure 976 (sulfanediyldibenzene-4,l-diyl)bis(diphenylsulfonium),
  • BYK 333 polyether-modified polydimethyl siloxane
  • BYK 345 polyether-modified siloxane
  • BYK 370 polyester-modified, hydroxy-functional polydimethylsiloxane
  • BYK BYK 067A anti-foaming agents
  • M262 tri cyclodecane dimethanol diacrylate, Miwon
  • compositions for the first coating layer are adapted to the substrate especially in regard of the curing and baking conditions.
  • composition 30 is especially adapted as first coating layer for PMMA substrates
  • composition 31 is especially adapted as first coating layer for PET or CPI.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material), M270 (15% of solid material) and BYK 067A (1% of solid material) were added.
  • BTESE 21,15 g; 0,06 mol
  • GPTMS 9 g; 0,3875 mol
  • MEMO 37 g; 0,149 mol
  • Bis[(2,2,3,3,4,4-hexafluorobutyl)propanoic ester]-3-aminopropyltrimethoxysilane (2,76 g; 0,00043 mol) are mixed in acetone (112,4 g).
  • HNO3 (0,lM; 35,47 g) is added dropwise over 15 min and the reaction mixture is stirred at room temperature overnight.
  • PGME (90 g) is added and solvent exchange procedure from acetone to PGME was performed.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067 A (1% of solid material) were added.
  • BTESE 21,15 g; 0,06 mol
  • GPTMS 91 g; 0,3875 mol
  • MEMO 37 g; 0,149 mol
  • 4-trifluorom ethyltetrafluorophenyltriethoxysilane (0,05 g; 0,00131 mol) are mixed in acetone (112,4 g).
  • HNO3 (0,lM; 35,47 g) is added dropwise over 15 min and the reaction mixture is stirred at room temperature overnight.
  • PGME (90 g) is added and solvent exchange procedure from acetone to PGME was performed.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067 A (1% of solid material) were added.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • composition B-6 Composition B-6
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • composition B-8 Composition B-8
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • composition B-10 Composition B-10
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 30% solid content with IPA and the additives Speed Cure 976 (1.2 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067 A (1% of solid material) were added.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • composition B-15 Composition B-15
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • composition B-16 Composition B-16
  • PTMS (10,00 g; 0,050 mol), MEMO (18,79 g; 0,076 mol), GPTMS (77,47 g; 0,327 mol), BTESE (17,88 g; 0,050 mol) were mixed in acetone (93,11 g). HNO3 (0.1M; 29,98 g) was added dropwise over 15 min. After completion of the addition, the reaction mixture was stirred at room temperature overnight. Then the reaction mixture was transferred to a new IL round bottom flask and PGME (75 g) was added. Solvent exchange procedure from acetone to PGME was performed under low pressure.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • Composition B-17 In a IL round bottom flask, BTESE (31,91 g; 0,18 mol), MEMO (22,35 g; 0,18 mol), GPTMS (99,26 g; 0,84 mol) were mixed in acetone (15 g). HNO3 (0.1M; 37,26 g) was added dropwise over 15 min. After completion of the addition, the reaction mixture was stirred at room temperature overnight. Then the reaction mixture was transferred to a new IL round bottom flask and PGME (92 g) was added. Solvent exchange procedure from acetone to PGME was performed under low pressure.
  • composition B-18 Composition B-18
  • composition B-19 The product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • Speed Cure 976 1.5 % of solid material
  • BYK 333 1% of solid material
  • BYK 067A 1% of solid material
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • composition B-20 Composition B-20
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067 A (1% of solid material) were added.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067 A (1% of solid material) were added.
  • composition B-24 Composition B-24
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • 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
  • Formic acid 0.1M; 106,54 g
  • T 105 C for 2 h.
  • the reaction mixture was cooled to room temperature.
  • PGME 100 g was added and solvent exchange procedure from EtOH to PGME was performed under low pressure.
  • the final product was ready for processing.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067 A (1% of solid material) were added.
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067A (1% of solid material) were added.
  • composition B-28 Composition B-28
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material) and BYK 067 A (1% of solid material) were added.
  • composition B-30 Composition B-30
  • the product is then formulated before performance evaluation as follow: the material was further diluted to 33% solid content with IPA and the additives Speed Cure 976 (1.5 % of solid material), BYK 333 (1% of solid material), M270 (15% of solid content) and BYK 067A (1% of solid material) were added.
  • Part of the polymer (11.47 g as 5.23% solid content in PGME) was mixed with KY 1901 (0.4 % in Novec 7100; 6,25 g), Novec 7100 (17.85 g), IPA (12.83 g), EG (1.24 g) and TEOS-based polymer (0.36 g as 10% solid content in PGME).
  • HNO3 3M, 804 g
  • IPA 3771 g
  • TEOS 570 g, 2,736 mol
  • MTMS 373 g, 2,7382 mol
  • Part of the polymer (11.47 g as 5.23% solid content in PGMEA) was mixed with KY 1901 (0.4 % in Novec 7100; 6,25 g), Novec 7100 (17.85 g), IPA (12.83 g), EG (1.24 g) and TEOS-based polymer (0.36 g as 10% solid content in PGME).
  • HNO 3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg
  • solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • HNO3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg
  • solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • Part of the polymer (5.73 g as 5.23% solid content in PGMEA) was mixed with Novec 7100 (7.19 g), IPA (18.29 g), EG (1.24 g), TEOS-based polymer (as 10% solid content in PGME; 0.09 g) and BYK 333 (0.018 g).
  • HN0 3 (3M; 14,445 kg) and IPA (54,72 kg) are mixed.
  • MTMS (5,368 kg) and TEOS (8,196 kg) are added.
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg was added and solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • Part of the polymer (9.56 g as 5.23% solid content in PGMEA) was mixed with Novec 7100 (6.93 g), IPA (14.65 g), EG (1.24 g), TEOS-based polymer (as 10% solid content in PGME; 9.56 g) and BYK 333 (0.014 g).
  • HNO3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg
  • solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • Part of the polymer (4.78 g as 5.23% solid content in PGMEA) was mixed with Novec 7100 (3.35 g), IPA (3.09 g), PGME (6.11 g), TEOS-based polymer (as 10% solid content in PGME; 1.00 g) and BYK 333 (0.010 g).
  • HN0 3 (3M; 14,445 kg) and IPA (54,72 kg) are mixed.
  • MTMS (5,368 kg) and TEOS (8,196 kg) are added.
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg was added and solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • HNO3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg
  • solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • HNO3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg
  • solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • HNO3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg was added and solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IP A (31 kg).
  • HNO3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg
  • solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • HNO3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg
  • solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • Part of the polymer (7.17 g as 5.23% solid content in PGMEA) was mixed with KY1901 (0.4% in Novec 7100; 3.12 g), Novec 7100 (7.62 g), IPA (4.67 g), EG (0.62 g) and TEOS-based polymer (as 10% solid content in PGME; 1.12 g).
  • HN0 3 (3M; 14,445 kg) and IPA (54,72 kg) are mixed.
  • MTMS (5,368 kg) and TEOS (8,196 kg) are added.
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg was added and solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • HNO3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg
  • solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • HN0 3 (3M; 14,445 kg) and IPA (54,72 kg) are mixed.
  • MTMS (5,368 kg) and TEOS (8,196 kg) are added.
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg was added and solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • Part of the polymer (7.17 g as 5.23% solid content in PGMEA) was mixed with KY1901 (0.4% in Novec 7100; 6.24 g), Novec 7100 (7.62 g), IPA (4.67 g), EG (0.62 g) and TEOS-based polymer (as 10% solid content in PGME; 1.12 g).
  • HNO3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg was added and solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IP A (31 kg).
  • HNO3 3M; 14,445 kg
  • IPA 54,72 kg
  • MTMS 5,368 kg
  • TEOS 8,196 kg
  • the reaction mixture is stirred at RT for 3,5h.
  • the organic phase was washed five times with a mixture H2O / MTBE (1 :1).
  • IPA 70 kg
  • solvent exchange from H2O / IPA / EtOH / MeOH to IPA was performed under low pressure.
  • the solid content of the reaction mixture was adjusted to 4% by addition of IPA (31 kg).
  • Part of the polymer (7.17 g as 5.23% solid content in PGMEA) was mixed with KY 1901 (0.4% in Novec 7100; 3.12 g), Novec 7100 (5.26 g), IPA (4.67 g), EG (0.62 g) and TEOS-based polymer (as 10% solid content in PGME; 3.75 g).
  • AE 3000 (80 g) and KY 1900 (0.1 g) are mixed in IPA (20 g).
  • TEOS 43,436 kg
  • acetone 136 kg
  • HNO3 0.01 M; 2,978 kg
  • PGME 115 kg
  • solvent exchange from acetone / H2O / EtOH to PGME was performed under vacuum.
  • the solid content of the mixture was adjusted to 10% by addition of PGME.
  • Part of the polymer (10,874 g as 10% solid content in PGME) was mixed with DSX (0.4 % in Novec 7100; 18,125 g), Novec 7100 (54,07 g), PGME (58,74 g) and EG (3,59 g).
  • TEOS 86 g; 0,412 mol
  • KY 1271 (0,4 g) was added.
  • HNO3 0.1 M; 59.36 g was added dropwise and the resulting reaction mixture was refluxed for 2 h. Then, the reaction mixture was cooled to RT.
  • PGME 125.12 g was added and the solvent exchange procedure from acetone / EtOH / H2O to PGME was performed under vacuum. The solid content of the mixture was adjusted to 10% by addition of PGME.
  • Part of the polymer (8 g as 10% solid content in PGME) was mixed with KY1901 (0.4% in Novec 7100, 35 g), SC019 (0.4% in Novec 7100, 15 g), Novec 7100 (119,2 g), PGME (67,04 g) and EG (4,96 g).
  • TEOS 43,436 kg
  • acetone 136 kg
  • HNO3 0.01 M; 2,978 kg
  • PGME 115 kg
  • solvent exchange from acetone / H2O / EtOH to PGME was performed under vacuum.
  • the solid content of the mixture was adjusted to 10% by addition of PGME.
  • the first layer coating was performed on PMMA (375 pm) using a roll-to-roll pilot apparatus with composition 30.
  • the web speed was 5 m / min and the slot die speed was 650 rpm.
  • the thicknesses of 3 different coated rolls to rolls on 10 various spots in described in Table 1. The average thickness of the coatings is around 5 pm.
  • Table 1 thicknesses of 3 different coated rolls to rolls in pm
  • the purpose of the double layer was to reduce reflectance. Depending on the solid content of the material and the amount and nature of additives, the reflection properties varied.
  • the 2 nd layer was added to the PMMA substrate coated with the 1 st layer using the bar coating method.
  • the bar coater can be of different nature for example #1, #2, #3, #4 depending on the targeted thickness. When using bar coater #1, the coating thickness is around 1-2 pm, when using bar coater #2, the coating thickness is around 2-3 pm, when using bar coater #3 the coating thickness is around 5 pm, when using bar coater #4 the coating thickness is around 7-8 pm.
  • a plasma treatment might be needed after coating.
  • the substrate was pre-treated by plasma (6 min, 300 W) and then coated using a bar coater (#3) and composition B-31 for first layer.
  • Table 4 shows the reflectance (R%) and transmittance (T%) of the examples at a wavelength of 550 nm.
  • Table 5 shows that the optical properties vary depending on the composition of the second layer (C) and the thickness of the second layer (C) - indicated in the used bar coater (see Table 2).
  • Examples 13, 14, 15, 16, 17 and 18 show better mechanical properties compared to examples 5, 6, 9, 10, 11 and 12, especially in regard of abrasion resistance.
  • AR% decreases by about 2.13%-points for 50 pm CPI (example 38), 1.68%-points for 80 pm CPI (example 39) and 1.89%-points for PET (example 40).

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  • Health & Medical Sciences (AREA)
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Abstract

La présente invention se rapporte à une structure stratifiée comprenant une couche de substrat flexible ou pliable (A), une première couche de revêtement à base de polysiloxane (B) et une seconde couche de revêtement (C) comprenant un composé fluoropolyéther, à un procédé de préparation de ladite structure stratifiée et à l'utilisation de ladite structure stratifiée pour des applications électroniques flexibles.
PCT/EP2023/059505 2022-04-14 2023-04-12 Revêtement dur de polysiloxane multicouche flexible WO2023198743A1 (fr)

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Citations (10)

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Publication number Priority date Publication date Assignee Title
JP2001293818A (ja) 2000-04-11 2001-10-23 Oike Ind Co Ltd 反射防止性ハードコートフイルム
KR20040076422A (ko) 2003-02-25 2004-09-01 주식회사 코오롱 반사 방지 필름
WO2006082701A1 (fr) 2005-02-01 2006-08-10 Nitto Denko Corporation Antireflection hard coating film, optical device and image display
US20130216807A1 (en) * 2010-08-20 2013-08-22 Oxford Energy Technologies Limited Optical coating comprising porous silica nanoparticles
WO2016146895A2 (fr) 2015-03-17 2016-09-22 Optitune Oy Revêtements résistant aux rayures, faciles à nettoyer, leurs procédés de production et leur utilisation
CN206270519U (zh) 2016-12-05 2017-06-20 张家港康得新光电材料有限公司 一种抗反射透明光学膜
WO2019193258A1 (fr) 2018-04-06 2019-10-10 Optitune Oy Revêtement dur de siloxane photostructurable résistant à l'abrasion, souple et pliable
WO2020099290A1 (fr) 2018-11-13 2020-05-22 Basf Se Revêtement facile à nettoyer
US11046827B2 (en) 2016-03-11 2021-06-29 Lg Chem., Ltd. Anti-reflective film and preparation method of the same
KR20210095187A (ko) * 2019-02-27 2021-07-30 후지필름 가부시키가이샤 적층체, 적층체를 구비한 물품, 및 화상 표시 장치

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001293818A (ja) 2000-04-11 2001-10-23 Oike Ind Co Ltd 反射防止性ハードコートフイルム
KR20040076422A (ko) 2003-02-25 2004-09-01 주식회사 코오롱 반사 방지 필름
WO2006082701A1 (fr) 2005-02-01 2006-08-10 Nitto Denko Corporation Antireflection hard coating film, optical device and image display
US20130216807A1 (en) * 2010-08-20 2013-08-22 Oxford Energy Technologies Limited Optical coating comprising porous silica nanoparticles
WO2016146895A2 (fr) 2015-03-17 2016-09-22 Optitune Oy Revêtements résistant aux rayures, faciles à nettoyer, leurs procédés de production et leur utilisation
US11046827B2 (en) 2016-03-11 2021-06-29 Lg Chem., Ltd. Anti-reflective film and preparation method of the same
CN206270519U (zh) 2016-12-05 2017-06-20 张家港康得新光电材料有限公司 一种抗反射透明光学膜
WO2019193258A1 (fr) 2018-04-06 2019-10-10 Optitune Oy Revêtement dur de siloxane photostructurable résistant à l'abrasion, souple et pliable
WO2020099290A1 (fr) 2018-11-13 2020-05-22 Basf Se Revêtement facile à nettoyer
KR20210095187A (ko) * 2019-02-27 2021-07-30 후지필름 가부시키가이샤 적층체, 적층체를 구비한 물품, 및 화상 표시 장치

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CAS, no. 870998-78-0

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