Classifications

• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
  • C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • 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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • G02B1/105—
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31507—Of polycarbonate
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31511—Of epoxy ether
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
  • Y10T428/31544—Addition polymer is perhalogenated
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31547—Of polyisocyanurate
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

• Hardcoats have been used to protect the face of optical displays. These hardcoats typically contain inorganic oxide particles, e.g., silica, of nanometer dimensions dispersed in a binder precursor resin matrix, and sometimes are referred to as “ceramers”.
• inorganic oxide particles e.g., silica
• U.S. Pat. No. 6,660,389 (Liu et al.) describes information display protectors for display devices having an information display area, comprising a stack of flexible substantially transparent sheets, the sheets having on one side thereof an adhesive layer and having on the other side thereof a hardcoat layer comprising inorganic oxide particles dispersed in a binder matrix and a low surface energy fluorinated compound, the stack being cut so that the sheets will fit the information display area.
• the low surface energy fluorinated compound can be part of the hardcoat layer or can be a separate layer atop the hardcoat layer.
• the protectors have very good scratch, smudge and glare resistance.
• the stack of protectors can be stored, for example, on a personal digital assistant or its cover or case.
• WO 2005/111157 describes (Abstract) A hard coating composition for use as a stain repellent single layer on an optical display.
• the coating composition adds a monomer of a mono or multi(methyl)acrylate bearing at least one monovalent hexafluoropolypropylene oxide derivative and a free radically reactive compatibilizer consisting of either a fluoroalkyl-group containing acrylate compatibilizer or a fluoroalkylene-group containing acrylate compatibilizer to a conventional hydrocarbon-based hard coat formulation.
• the resultant coating is substantially smooth and forms a durable surface layer that has low surface energy that is stain and ink repellent.
• WO2006/102383 describes various polymerizable perfluoropolyether urethane additives and there use as hardcoats for optical displays.
• WO 03/002628 describes (Abstract) A perfluoropolyether-containing composition which has an affinity for nonfluorinated substrates and can form on the surface thereof a film firmly adherent to the surface. It is a composition containing carbon-carbon double bonds which comprises (A) a triisocyanate obtained by trimerizing a diisocyanate and (B) a combination of at least two compounds having active hydrogen, the component (B) comprising (B-1) a perfluoropolyether having at least one active hydrogen atom and (B-2) a monomer having an active hydrogen atom and a carbon-carbon double bond.
• optical substrates having a surface layer and optical displays comprising such optical substrates.
• the surface layer comprises the reaction product of a polymerizable mixture comprising at least one perfluoropolyether urethane polymeric material comprising at least two free-radically polymerizable groups and greater than 6 ethylene oxide repeat units and at least one non-fluorinated crosslinker comprising at least two free-radically polymerizable groups.
• a free-radically polymerizable composition comprising a mixture of reaction products of i) at least one polyisocyanate; ii) at least one isocyanate reactive perfluoropolyether compound; iii) at least one isocyanate reactive compound comprising greater than 6 repeat units of ethylene oxide; and iv) at least one isocyanate reactive non-fluorinated crosslinker comprising at least two free-radically polymerizable groups.
• the composition may be a coating dispersed in an alcohol-containing solvent that is particularly useful for coating optical substrates such as polycarbonate, acrylic, cellulose acetate, and cellulose triacetate.
• multifunctional perfluoropolyether urethane compositions that comprise the reaction product of a polyisocyanate with an isocyanate reactive perfluoropolyether compound, an isocyanate reactive multifunctional hydrocarbon crosslinker, and an isocyanate reactive compound having greater than 6 ethylene oxide repeat units.
• Preferred multifunctional perfluoropolyether urethane compositions are set forth in the claims.
• the perfluoropolyether urethane polymeric material comprises at least two (meth)acrylate groups such as a terminal group having at least two (meth)acrylate groups.
• the perfluoropolyether urethane may comprise a monovalent perfluoropolyether moiety such as F(CF(CF 3 )CF 2 O) a CF(CF 3 )— wherein a ranges from 4 to 15.
• At least one (e.g. non-fluorinated) hydrocarbon crosslinker that comprises at least three free-radically polymerizable groups is typically employed.
• the surface layer or polymerizable composition further comprises inorganic oxide particles.
• a hardcoat layer comprising inorganic oxide particles is disposed between the substrate and an inorganic particle free surface layer.
• optical displays including a light transmissive optical substrate.
• the surface layer of the optical substrate comprises the reaction product of a polymerizable mixture comprising at least one free-radically polymerizable perfluoropolyether urethane polymeric material having ethylene oxide repeat units.
• certain multifunctional perfluoropolyether urethane compositions are described.
• coating compositions are described that comprise a (e.g. ultraviolet) polymerizable mixture comprising the perfluoropolyether urethane polymeric material dispersed in an alcohol-containing solvent.
• a free-radically polymerizable coating composition that comprises a mixture of reaction products of
• At least one polyisocyanate i) at least one polyisocyanate, ii) at least one isocyanate reactive perfluoropolyether compound, iii) at least one isocyanate reactive compound containing greater than 6 ethylene oxide repeat units, and iv) at least one isocyanate reactive (e.g. non-fluorinated) hydrocarbon crosslinker comprising two or more free-radically polymerizable groups.
• the perfluoropolyether compound (i.e. ii) and ethylene oxide repeat unit containing compound (i.e. iii) preferably comprise a (e.g. terminal) alcohol, thiol, or amine group.
• both the perfluoropolyether compound and the ethylene oxide compound contain (e.g. terminal) reactive alcohol groups.
• the isocyanate employed is typically at least trifunctional. However, when one of more of the isocyanate reactive compounds have at least difunctional isocyanate reactivity, difunctional isocyanates can be employed.
• the hydrocarbon crosslinker typically comprises (meth)acryl groups such as (meth)acrylate groups.
• a substantial excess of hydrocarbon crosslinker (i.e. iv) is typically employed such that the perfluoropolyether urethane polymeric material as well as other reaction products of the reaction mixture comprise unreacted free-radically polymerizable groups which can be subsequently cured for example by radiation (e.g. UV) curing.
• the perfluoropolyether urethane composition is made by first reacting a polyisocyanate with a perfluoropolyether compound containing an alcohol, thiol, or amine group, followed by reaction with one or more ethylene oxide compounds containing an alcohol, thiol, or amine group.
• the perfluoropolyether urethane additive is then combined with the (e.g. non-fluorinated) isocyanate reactive multifunctional free-radically polymerizable (e.g. (meth)acrylate) crosslinker.
• these perfluoropolyether urethane additives can be formed by other reaction sequences such as by first reacting the polyisocyanate with the crosslinker, followed by the addition of the ethylene oxide containing compound.
• the additives could be made by reacting all three components concurrently.
• Alcohol based coating compositions are especially useful for coating light transmissive substrates such as polycarbonate, acrylic, cellulose acetate, and cellulose triacetate which are susceptible to swelling, cracking, or crazing by organic solvents such as ketones (e.g. MEK), aromatic solvents (e.g. toluene), and esters (e.g. acetate solvents).
• ketones e.g. MEK
• aromatic solvents e.g. toluene
• esters e.g. acetate solvents
• One or more polyisocyanate materials are employed in the preparation of the perfluoropolyether urethane.
• a variety of polyisocyanates may be utilized as component i) in the preparation of the perfluoropolyether urethane polymeric material.
• Polyisocyanate means any organic compound that has two or more reactive isocyanate (—NCO) groups in a single molecule such as diisocyanates, triisocyanates, tetraisocyanates, etc., and mixtures thereof. Cyclic and/or linear polyisocyanate molecules may usefully be employed. For improved weathering and diminished yellowing the polyisocyanate(s) of the isocyanate component is typically aliphatic.
• Useful aliphatic polyisocyanates include, for example, bis(4-isocyanatocyclohexyl)methane (H 12 MDI) such as available from Bayer Corp., Pittsburgh, Pa. under the trade designation “Desmodur W”; isophorone diisocyanate (IPDI) such as commercially available from Huels America, Piscataway, N.J.; hexamethylene diisocyanate (HDI) such as commercially available from Aldrich Chemical Co., Milwaukee, Wis.; trimethyl hexamethylene diisocyanate such as commercially available from Degussa, Corp., Dusseldorf, Germany under the trade designation “Vestanate TMDI”; and m-tetramethylxylene diisocyanate (TMXDI) such as commercially available from Aldrich Chemical Co., Milwaukee, Wis.
• H 12 MDI bis(4-isocyanatocyclohexyl)methane
• IPDI isophorone di
• aromatic isocyanates such as diphenylmethane diisocyanate (MDI) such as commercially available from Bayer Corp., Pittsburgh, Pa. under the trade designation “Mondur M”; toluene 2,4-diisocyanate (TDI) such as commercially available from Aldrich Chemical Co., Milwaukee, Wis., and 1,4-phenylene diisocyanate are also useful.
• MDI diphenylmethane diisocyanate
• TDI toluene 2,4-diisocyanate
• 1,4-phenylene diisocyanate 1,4-phenylene diisocyanate
• Preferred polyisocyanates include derivatives of the above-listed monomeric polyisocyanates. These derivatives include, but are not limited to, polyisocyanates containing biuret groups, such as the biuret adduct of hexamethylene diisocyanate (HDI) available from Bayer Corp. under the trade designation “Desmodur N-100”, polyisocyanates based on HDI containing isocyanurate groups, such as that available from Bayer Corp. under trade designation “Desmodur N-3300”, as well as polyisocyanates containing urethane groups, uretdione groups, carbodiimide groups, allophonate groups, and the like. These derivatives are preferred as they are polymeric, exhibit very low vapor pressures and are substantially free of isocyanate monomer.
• biuret groups such as the biuret adduct of hexamethylene diisocyanate (HDI) available from Bayer Corp. under the trade designation “Desmodur N-100”
• Various isocyanate reactive perfluoropolyethers materials can be utilized as component ii).
• the synthesis of various perfluoropolyether materials having (e.g. terminal) isocyanate reactive groups such as OH, SH or NHR wherein R is H of an alkyl group of 1 to 4 carbon atoms is known.
• a methyl ester material e.g. having an average molecular weight of 1,211 g/mol
• U.S. Pat. No. 3,250,808 (Moore et al.), the disclosure of which is incorporated herein by reference, with purification by fractional distillation.
• Perfluoropolyether alcohol materials can be made by a procedure similar to that described in U.S. Publication No. 2004-0077775, filed May 24, 2002.
• Perfluoropolyether alcohol materials having an SH group can be made using this same process by use of aminoethane thiol rather than aminoethanol.
• Perfluoropolyether amine materials can be synthesized as described in US 2005/0250921.
• One or more isocyanate reactive perfluoropolyether materials are employed in the preparation of the perfluoropolyether urethane.
• the perfluoropolyether urethane material is preferably prepared from an isocyanate reactive HFPO-material.
• HFPO- refers to the end group F(CF(CF 3 )CF 2 O) a CF(CF 3 )— of the methyl ester F(CF(CF 3 )CF 2 O) a CF(CF 3 )C(O)OCH 3 , wherein “a” averages 2 to 15. In some embodiments, a averages between 3 and 10 or a averages between 5 and 8.
• Such species generally exist as a distribution or mixture of oligomers with a range of values for a, so that the average value of a may be non-integer. For example, in one embodiment, “a” averages 6.2.
• the molecular weight of the HFPO-perfluoropolyether material varies depending on the number (“a”) of repeat units from about 940 g/mole to about 1600 g/mole, with 1100 g/mole to 1400 g/mole typically being preferred.
• the ethylene oxide containing isocyanate reactive compound generally comprises greater than 6 repeat units of ethylene oxide.
• the number of ethylene oxide repeat units may be at least 7, 8, or 9 repeat units.
• the isocyanate reactive ethylene oxide containing compound has at least 10 repeat units of ethylene oxide.
• the number of repeat units may be 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.
• the number of ethylene oxide repeat units does not exceed about 40 and may be for example up to 25, 30, or 35 repeat units.
• the ethylene oxide containing compounds may be represented by the following formula:
• X 1 is OH, SH or NHR, where R is H or lower alkyl of 1 to 4 carbon atoms;
• R 1 is H, —C(O)C(R 2 ) ⁇ CH 2 , where R 2 is a lower alkyl of 1 to 4 carbon atoms or H or F, or a group selected from alkyl, aryl, alkaryl, aralkyl, that can optionally be substituted with a heteroatom, a heteoratom functional groups (such as —OH —SH, and —NH 2 ), or a (meth)acryl functional group; and j ranges from 7 to 40.
• the ethylene oxide containing compound may also comprise other alkylene oxide compounds such as propylene oxide.
• alkylene oxide repeat units are typically ethylene oxide repeat units.
• Various isocyanate reactive non-fluorinated hydrocarbon crosslinkers can be employed in the synthesis of the perfluoropolyether urethane polymeric material.
• Such crosslinkers comprise at least two and preferably three free-radically polymerizable groups.
• the free-radically polymerizable groups are preferably (meth)acryl and more preferably (meth)acrylate groups.
• Suitable isocyanate reactive non-fluorinated hydrocarbon crosslinkers may be described by the formula:
• Q is a connecting group of valency at least 2;
• Q can comprise a straight chain, branched chain, or cyclic-containing connecting group.
• Q can include an alkylene, an arylene, an aralkylene, an alkarylene.
• Q can optionally include heteroatoms such as O, N, and S, and combinations thereof.
• Q can also optionally include a heteroatom-containing functional group such as carbonyl or sulfonyl, and combinations thereof.
• Exemplary isocyanate reactive crosslinkers include for example 1,3-glycerol dimethacrylate available from Echo Resin Inc. of Paris, Mo. and pentaerythritol triacrylate, available from Sartomer of Exton, Pa. under the trade designation “SR444C”.
• Additional useful isocyanate reactive (meth)acrylate crosslinkers include hydantoin moiety-containing poly(meth)acrylates, for example, as described in U.S. Pat. No. 4,262,072 (Wendling et al.).
• the total mole fraction of isocyanate reactive groups used in making the perfluoropolyether urethane material is 1.0 or greater.
• the polymerizable compositions described herein typically comprise at least 0.2 mole fraction of crosslinking agent(s), it is typically preferred to maximize the concentration of isocyanate reactive hydrocarbon crosslinker to improve the durability and compatibility with the binder of the hardcoat.
• the total amount of crosslinking agent(s) may comprise at least 0.5 mole fraction and may be at least 0.6 mole fraction, at least 0.7 mole fraction, at least 0.8 mole fraction, or at least 0.9 mole of the sum of the isocyanate reactants.
• the mole fraction of the perfluoropolyether reactant is typically at least 0.05 and no greater than 0.5.
• the mole fraction of ethylene oxide repeat unit containing reactant is also typically at least 0.05 and no greater than 0.5.
• the reaction product generally includes a distribution of various reaction products.
• the reaction product of the polyisocyanate with all three reactants ii, iii, and iv
• the reaction product of the polyisocyanate with two of the three as well as reaction products of the polyisocyanate the individual reactants are also present.
• the perfluoropolyether urethane composition is of the formula:
• Ri is a residue of a multi-isocyanate
• X and X j are each independently O, S or NR, where R is H or lower alkyl of 1 to 4 carbon atoms;
• Q is independently a connecting group of valency at least 2;
• R j is H, —C(O)C(R 2 ) ⁇ CH 2 , where R 2 is a lower alkyl of 1 to 4 carbon atoms or H or F, or a group selected from alkyl, aryl, alkaryl, aralkyl, that can optionally be substituted with a heteroatom, heteoratom functional groups (such as —OH —SH, and —NH 2 ), or a (meth)acryl functional group.
• perlfluoropolyether urethane materials can be prepared having at least one of each of the unit of this formula.
• Q in association with the Rf group is a straight chain, branched chain, or cycle-containing connecting group.
• Q can include an alkylene, an arylene, an aralkylene, an alkarylene.
• Q can optionally include heteroatoms such as O, N, and S, and combinations thereof.
• Q can also optionally include a heteroatom-containing functional group such as carbonyl or sulfonyl, and combinations thereof.
• Q When X is O, Q is typically not methylene and thus contains two or more carbon atoms. In some embodiments, X is S or NR. In some embodiments, Q is an alkylene having at least two carbon atoms. In other embodiments, Q is a straight chain, branched chain, or cycle-containing connecting group selected from arylene, aralkylene, and alkarylene. In yet other embodiments, Q contains a heteroatom such as O, N, and S and/or a heteroatom containing functional groups such as carbonyl and sulfonyl.
• Q is a branched or cycle-containing alkylene group that optionally contains heteroatoms selected from O, N, S and/or a heteroatom-containing functional group such as carbonyl and sulfonyl.
• Q contains a nitrogen containing group such an amide group such as —C(O)NHCH 2 CH 2 —, —C(O)NH(CH 2 ) 6 —, and —C(O)NH(CH 2 CH 2 O) 2 CH 2 CH 2 —.
• the perfluoropolyether urethane polymeric material described herein may be employed alone or in combination with various other fluorinated compounds having at least one moiety selected from fluoropolyether, fluoroalkyl, and fluoroalkylene linked to at least one free-radically reactive group.
• fluoropolyether fluoropolyether
• fluoroalkyl fluoroalkylene linked to at least one free-radically reactive group.
• second fluorinated compound it is typically preferred that such second fluorinated compound also comprises an HFPO-moiety.
• Various fluorinated materials that can be employed in combination with the perfluoropolyether urethane polymeric material described are also described in WO2006/102383.
• the polymerizable perfluoropolyether urethane composition is typically dispersed in a hardcoat composition in combination with a (e.g. alcohol based) solvent, applied to an optical substrate and photocured to form the easy to clean, stain and ink repellent light transmissible surface layer.
• the hardcoat is a tough, abrasion resistant layer that protects the optical substrate and the underlying display screen from damage from causes such as scratches, abrasion and solvents.
• the hardcoat is formed by coating a curable liquid ceramer composition onto the substrate and curing the composition in situ to form a hardened film.
• the surface energy can be characterized by various methods such as contact angle and ink repellency, as determined by the test methods described in the Examples.
• stain repellent refers to a surface treatment exhibiting a static contact angle with water of at least 70 degrees. More preferably, the contact angle is at least 80 degrees and most preferably at least 90 degrees. Alternatively, or in addition thereto, the advancing contact angle with hexadecane is at least 50 degrees and more preferably at least 60 degrees. Low surface energy results in anti-soiling and stain repellent properties as well as rendering the exposed surface easy to clean.
• Another indicator of low surface energy relates to the extent to which ink from a pen or marker beads up when applied to the exposed surface.
• the surface layer and articles exhibit “ink repellency” when ink from pens and markers beads up into discrete droplets and can be easily removed by wiping the exposed surface with tissues or paper towels, such as tissues available from the Kimberly Clark Corporation, Roswell, Ga. under the trade designation “SURPASS FACIAL TISSUE.”
• Durability can be defined in terms of results from a modified oscillating sand test (Method ASTM F 735-94) carried out at 250 rpm for 5 minutes as described in the Test Methods of this application.
• a durable coating exhibits an ink repellency loss value of 65 mm (75% loss) or less, more preferably 40 mm (45% loss) or less, most preferably 0 mm (no loss) of ink repellency (IR) in this test.
• the perfluoropolyether urethane polymeric material described herein can be employed as the sole fluorinated component of a one-layer hardcoat composition.
• the hardcoat composition typically further comprises (e.g. surface modified) inorganic particles.
• the thickness of the hardcoat surface layer is typically at least 0.5 microns, preferably at least 1 micron, and more preferably at least 2 microns.
• the thickness of the hardcoat layer is generally no greater than 25 microns. Preferably the thickness ranges from 3 microns to 5 microns.
• an inorganic particle free perfluoropolyether urethane polymer containing surface layer may be employed alone for uses where durability is not required.
• an inorganic particle free perfluoropolyether urethane polymer containing surface layer may be provided in combination with an inorganic particle containing hardcoat layer disposed between the substrate and the surface layer. This will be referred to as a two-layer hardcoat.
• the surface layer preferably has a thickness ranging from about 10 to 200 nanometers.
• the total of all (per)fluorinated compounds ranges from 0.01% to 10%, and more preferably from 0.1% to 1%, of the total solids of the hardcoat composition.
• the amount of perfluoropolyether urethane(s) in the coating compositions ranges from 0.01 to 50 wt-% solids, and more preferably from 1 to 25 wt-% solids.
• binder precursors that form a crosslinked polymeric matrix upon curing can be employed in the hardcoat.
• the isocyanate reactive non-fluorinated crosslinking materials previously described are suitable binder precursors.
• Di(meth)acryl binder precursors include for example 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol monoacrylate monomethacrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylate, alkoxylated cyclohexane dimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone modified neopentylglycol hydroxypivalate diacrylate, caprolactone modified neopentylglycol hydroxypivalate diacrylate, cyclohexanedimethanol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, hydroxypivalaldehyde modified tri
• Tri(meth)acryl binder precursore include for example glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylates (e.g. having 3 to 20 ethoxylate repeat), propoxylated glyceral triacrylates, trimethylolpropane triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate.
• Higher functionality (meth)acryl containing compounds include for example ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate.
• PET3A pentaerythritol triacrylate
• PET4A pentaerythritol tetraacrylate
• Oligomeric (meth)acryl such as urethane acrylates, polyester acrylates, epoxy acrylates; and polyacrylamide analogues of the foregoing can also be employed as the binder.
• the binder may comprise one or more N,N-disubstituted acrylamide and or N-substituted-N-vinyl-amide monomers as described in Bilkadi et al.
• the hardcoat may be derived from a ceramer composition containing about 20 to about 80% ethylenically unsaturated monomers and about 5 to about 40% N,N-disubstituted acrylamide monomer or N-substituted-N-vinyl-amide monomer, based on the total weight of the solids in the ceramer composition.
• polymerizable compositions described herein may further comprise at least one free-radical thermal initiator and/or photoinitiator.
• an initiator and/or photoinitiator typically, if such an initiator and/or photoinitiator are present, it comprises less than about 10 percent by weight, more typically less than about 5 percent of the polymerizable composition, based on the total weight of the polymerizable composition.
• Free-radical curing techniques are well known in the art and include, for example, thermal curing methods as well as radiation curing methods such as electron beam or ultraviolet radiation. Further details concerning free radical thermal and photopolymerization techniques may be found in, for example, U.S. Pat. No. 4,654,233 (Grant et al.); U.S. Pat. No. 4,855,184 (Klun et al.); and U.S. Pat. No. 6,224,949 (Wright et al.).
• Useful free-radical thermal initiators include, for example, azo, peroxide, persulfate, and redox initiators, and combinations thereof.
• Useful free-radical photoinitiators include, for example, those known as useful in the UV cure of acrylate polymers such as described in WO2006/102383.
• the polymerizable composition for use as the surface layer or an underlying hardcoat layer preferably contains surface modified inorganic particles that add mechanical strength and durability to the resultant coating.
• the inorganic oxide particles can consist essentially of or consist of a single oxide such as silica, or can comprise a combination of oxides, such as silica and aluminum oxide, or a core of an oxide of one type (or a core of a material other than a metal oxide) on which is deposited an oxide of another type.
• Silica is a common inorganic particle.
• the inorganic oxide particles are often provided in the form of a sol containing a colloidal dispersion of inorganic oxide particles in liquid media.
• the sol can be prepared using a variety of techniques and in a variety of forms including hydrosols (where water serves as the liquid medium), organosols (where organic liquids so serve), and mixed sols (where the liquid medium contains both water and an organic liquid), e.g., as described in U.S. Pat. No. 5,648,407 (Goetz et al.); U.S. Pat. No. 5,677,050 (Bilkadi et al.) and U.S. Pat. No. 6,299,799 (Craig et al.), the disclosure of which is incorporated by reference herein.
• Aqueous sols e.g. of amorphous silica
• Sols generally contain at least 2 wt-%, at least 10 wt-%, at least 15 wt-%, at least 25 wt-%, and often at least 35 wt-% colloidal inorganic oxide particles based on the total weight of the sol.
• the amount of colloidal inorganic oxide particle is typically no more than 50 wt-% (e.g. 45 wt-%).
• the surface of the inorganic particles can be “acrylate functionalized” as described in Bilkadi et al.
• the sols can also be matched to the pH of the binder, and can contain counter ions or water-soluble compounds (e.g., sodium aluminate), all as described in Kang et al. '798.
• Various high refractive index inorganic oxide particles can be employed such as for example zirconia (“ZrO 2 ”), titania (“TiO 2 ”), antimony oxides, alumina, tin oxides, alone or in combination. Mixed metal oxide may also be employed.
• Zirconias for use in the high refractive index layer are available from Nalco Chemical Co. under the trade designation “Nalco OOSSOO8” and from Buhler AG Uzwil, Switzerland under the trade designation “Buhler zirconia Z-WO sol”.
• Zirconia nanoparticle can also be prepared such as described in U.S. patent application Ser. No. 11/027,426 filed Dec. 30, 2004 and U.S. Pat. No. 6,376,590.
• the inorganic nanoparticles are preferably treated with a surface treatment agent.
• Surface-treating the nano-sized particles can provide a stable dispersion in the polymeric resin.
• the surface-treatment stabilizes the nanoparticles so that the particles will be well dispersed in the polymerizable resin and results in a substantially homogeneous composition.
• the nanoparticles can be modified over at least a portion of its surface with a surface treatment agent so that the stabilized particle can copolymerize or react with the polymerizable resin during curing.
• the incorporation of surface modified inorganic particles is amenable to covalent bonding of the particles to the free-radically polymerizable organic components, thereby providing a tougher and more homogeneous polymer/particle network.
• a surface treatment agent has a first end that will attach to the particle surface (covalently, ionically or through strong physisorption) and a second end that imparts compatibility of the particle with the resin and/or reacts with resin during curing.
• surface treatment agents include alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, silanes and titanates.
• the preferred type of treatment agent is determined, in part, by the chemical nature of the metal oxide surface. Silanes are preferred for silica and other for siliceous fillers. Silanes and carboxylic acids are preferred for metal oxides such as zirconia.
• the surface modification can be done either subsequent to mixing with the monomers or after mixing.
• silanes it is preferred in the case of silanes to react the silanes with the particle or nanoparticle surface before incorporation into the resin.
• the required amount of surface modifier is dependant upon several factors such as particle size, particle type, modifier molecular wt, and modifier type. In general, it is preferred that approximately a monolayer of modifier is attached to the surface of the particle. The attachment procedure or reaction conditions required also depend on the surface modifier used. For silanes it is preferred to surface treat at elevated temperatures under acidic or basic conditions for from 1-24 hr approximately. Surface treatment agents such as carboxylic acids may not require elevated temperatures or extended time.
• surface treatment agents suitable for the compositions include compounds such as, for example, isooctyl trimethoxy-silane, N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethyl carbamate, N-(3-triethoxysilylpropyl)methoxyethoxyethyl carbamate, 3-(methacryloyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-(methacryloyloxy)propylmethyldimethoxysilane, 3-(acryloyloxypropyl)methyldimethoxysilane, 3-(methacryloyloxy)propyldimethylethoxysilane, 3-(methacryloyloxy)propyldimethylethoxysilane, vinyldimethylethoxysi
• the surface modification of the particles in the colloidal dispersion can be accomplished in a variety known ways, such as described in U.S. patent application Ser. No. 11/027,426 filed Dec. 30, 2004; U.S. Pat. No. 6,376,590.
• a combination of surface modifying agents can be useful, wherein at least one of the agents has a functional group co-polymerizable with a hardenable resin. Combinations of surface modifying agent can result in lower viscosity.
• the polymerizing group can be ethylenically unsaturated or a cyclic function subject to ring opening polymerization.
• An ethylenically unsaturated polymerizing group can be, for example, an acrylate or methacrylate, or vinyl group.
• a cyclic functional group subject to ring opening polymerization generally contains a heteroatom such as oxygen, sulfur or nitrogen, and preferably a 3-membered ring containing oxygen such as an epoxide.
• a preferred combination of surface modifying agent includes at least one surface modifying agent having a functional group that is copolymerizable with the organic component of the polymerizable resin and a second amphiphilic modifying agent, such as a polyether silane, that may act as a dispersant.
• the second modifying agent is preferably a polyalkyleneoxide containing modifying agent that is optionally co-polymerizable with the organic component of the polymerizable composition.
• Non-silica containing fully condensed nanoparticles typically have a degree of crystallinity (measured as isolated metal oxide particles) greater than 55%, preferably greater than 60%, and more preferably greater than 70%.
• the degree of crystallinity can range up to about 86% or greater.
• the degree of crystallinity can be determined by X-ray diffraction techniques.
• Condensed crystalline (e.g. zirconia) nanoparticles have a high refractive index whereas amorphous nanoparticles typically have a lower refractive index.
• the inorganic particles preferably have a substantially monodisperse size distribution or a polymodal distribution obtained by blending two or more substantially monodisperse distributions.
• the inorganic particles can be introduced having a range of particle sizes obtained by grinding the particles to a desired size range.
• the inorganic oxide particles are typically non-aggregated (substantially discrete), as aggregation can result in optical scattering (haze) or precipitation of the inorganic oxide particles or gelation.
• the inorganic oxide particles are typically colloidal in size, having an average particle diameter of 5 nanometers to 100 nanometers.
• the particle size of the high index inorganic particles is preferably less than about 50 nm in order to provide sufficiently transparent high-refractive index coatings.
• the average particle size of the inorganic oxide particles can be measured using transmission electron microscopy to count the number of inorganic oxide particles of a given diameter.
• the optical film having a perfluoropolyether urethane containing surface layer as described herein may have a gloss or matte surface.
• Matte films typically have lower transmission and higher haze values than typical gloss films.
• the haze is generally at least 5%, 6%, 7%, 8%, 9%, or 10% as measured according to ASTM D1003.
• gloss surfaces typically have a gloss of at least 130 as measured according to ASTM D 2457-03 at 60°; matte surfaces have a gloss of less than 120.
• a particulate matting agent can be incorporated into the polymerizable composition in order to impart anti-glare properties to the surface layer.
• the particulate matting agent also prevents the reflectance decrease and uneven coloration caused by interference with an associated hard coat layer.
• Exemplary systems incorporating matting agents into a hard coating layer, but having a different hard coating composition, are described, for example, in U.S. Pat. No. 6,693,746, and herein incorporated by reference.
• exemplary matte films are commercially available from U.S.A. Kimoto Tech of Cedartown, Ga., under the trade designation “N4D2A.”
• the amount of particulate matting agent added is between about 0.5 and 10% of the total solids of the composition, depending upon the thickness of the layer, with a preferred amount around 2%.
• the average particle diameter of the particulate matting agent has a predefined minimum and maximum that is partially dependent upon the thickness of the layer. However, generally speaking, average particle diameters below 1.0 microns do not provide the degree of anti-glare sufficient to warrant inclusion, while average particle diameters exceeding 10.0 microns deteriorate the sharpness of the transmission image.
• the average particle size is thus preferably between about 1.0 and 10.0 microns, and more preferably between 1.7 and 3.5 microns, in terms of the number-averaged value measured by the Coulter method.
• inorganic particles or resin particles are used including, for example, amorphous silica particles, TiO 2 particles, Al 2 O 3 particles, cross-linked acrylic polymer particles such as those made of cross-linked poly(methyl methacrylate), cross-linked polystyrene particles, melamine resin particles, benzoguanamine resin particles, and cross-linked polysiloxane particles.
• resin particles are more preferred, and in particular cross-linked polystyrene particles are preferably used since resin particles have a high affinity for the binder material and a small specific gravity.
• spherical and amorphous particles can be used as for the shape of the particulate matting agent. However, to obtain a consistent anti-glare property, spherical particles are desirable. Two or more kinds of particulate materials may also be used in combination.
• silica particulate matting agent having an average particle size of 3.5 microns is commercially available from W.R. Grace and Co., Columbia, Md. under the trade designation “Syloid C803”.
• inorganic particles can also be incorporated into the hardcoat compositions.
• conducting metal oxide nanoparticles such as antimony tin oxide, fluorinated tin oxide, vanadium oxide, zinc oxide, antimony zinc oxide, and indium tin oxide. They can also be surface treated with materials such as 3-methacryloxypropyltrimethoxysilane. These particles can provide constructions with antistatic properties. This is desirable to prevent static charging and resulting contamination by adhesion of dust and other unwanted debris during handling and cleaning of the film.
• such metal oxide particles are incorporated into the top (thin) layer of the two-layer constructions of this invention, in which the fluorinated hardcoat is applied to a hydrocarbon-based hardcoat.
• conducting metal oxide nanoparticles useful in this embodiment include antimony double oxide available from Nissan Chemical under the trade designations Celnax CXZ-2101P and CXZ-2101P-F2.
• the perfluoropolyether urethane polymeric material alone or in combination with the hardcoat composition can be dispersed in a solvent to form a dilute coating composition.
• the amount of solids in the coating composition is typically at least 20 wt-% and usually no greater than about 50 wt-%.
• an alcohol based solvent including for example methanol, ethyl alcohol, isopropyl alcohol, propanol, etc. as well as glycol ethers such as propylene glycol monomethyl ether or ethylene glycol monomethyl ether, etc.
• the coating compositions may contain predominantly alcohol solvent(s).
• alcohol based solvent(s) may be combined with other (i.e. non-alcohol) solvents.
• Thin coating layers can be applied to the optical substrate using a variety of techniques, including dip coating, forward and reverse roll coating, wire wound rod coating, and die coating.
• Die coaters include knife coaters, slot coaters, slide coaters, fluid bearing coaters, slide curtain coaters, drop die curtain coaters, and extrusion coaters among others. Many types of die coaters are described in the literature such as by Edward Cohen and Edgar Gutoff, Modern Coating and Drying Technology, VCH Publishers, NY 1992, ISBN 3-527-28246-7 and Gutoff and Cohen, Coating and Drying Defects: Troubleshooting Operating Problems, Wiley Interscience, NY ISBN 0-471-59810-0.
• a die coater generally refers to an apparatus that utilizes a first die block and a second die block to form a manifold cavity and a die slot.
• the coating fluid under pressure, flows through the manifold cavity and out the coating slot to form a ribbon of coating material.
• Coatings can be applied as a single layer or as two or more superimposed layers. Although it is usually convenient for the substrate to be in the form of a continuous web, the substrate may also be a succession of discrete sheets.
• optical display can refer to any conventional optical displays, including but not limited to multi-character multi-line displays such as liquid crystal displays (“LCDs”), plasma displays, front and rear projection displays, cathode ray tubes (“CRTs”), and signage, as well as single-character or binary displays such as light emitting diodes (“LEDs”), signal lamps, and switches.
• LCDs liquid crystal displays
• CRTs cathode ray tubes
• LEDs light emitting diodes
• the exposed surface of such display panels may be referred to as a “lens.”
• the invention is particularly useful for displays having a viewing surface that is susceptible to being touched or contacted by ink pens, markers and other marking devices, wiping cloths, paper items and the like.
• the protective coatings of the invention can be employed in a variety of portable and non-portable information display articles.
• These articles include PDAs, cell phones (including combination PDA/cell phones), LCD televisions (direct lit and edge lit), touch sensitive screens, wrist watches, car navigation systems, global positioning systems, depth finders, calculators, electronic books, CD and DVD players, projection television screens, computer monitors, notebook computer displays, instrument gauges, instrument panel covers, signage such as graphic displays and the like.
• the viewing surfaces can have any conventional size and shape and can be planar or non-planar, although flat panel displays are preferred.
• the coating composition or coated film can be employed on a variety of other articles as well such as for example camera lenses, eyeglass lenses, binocular lenses, mirrors, retroreflective sheeting, automobile windows, building windows, train windows, boat windows, aircraft windows, vehicle headlamps and taillights, display cases, road pavement markers (e.g. raised) and pavement marking tapes, overhead projectors, stereo cabinet doors, stereo covers, watch covers, as well as optical and magneto-optical recording disks, and the like.
• camera lenses eyeglass lenses, binocular lenses, mirrors, retroreflective sheeting
• automobile windows building windows, train windows, boat windows, aircraft windows, vehicle headlamps and taillights
• display cases road pavement markers (e.g. raised) and pavement marking tapes
• overhead projectors stereo cabinet doors, stereo covers, watch covers, as well as optical and magneto-optical recording disks, and the like.
• Suitable substrates can be utilized in the articles of the invention.
• Suitable substrate materials include glass as well as thermosetting or thermoplastic polymers such as polycarbonate, poly(meth)acrylate (e.g., polymethyl methacrylate or “PMMA”), polyolefins (e.g., polypropylene or “PP”), polyurethane, polyesters (e.g., polyethylene terephthalate or “PET”), polyamides, polyimides, phenolic resins, cellulose diacetate, cellulose triacetate, polystyrene, styrene-acrylonitrile copolymers, epoxies, and the like.
• the substrate will be chosen based in part on the desired optical and mechanical properties for the intended use.
• Such mechanical properties typically will include flexibility, dimensional stability and impact resistance.
• the substrate thickness typically also will depend on the intended use. For most applications, a substrate thickness of less than about 0.5 mm is preferred, and is more preferably about 0.02 to about 0.2 mm.
• Self-supporting polymeric films are preferred. Films made from polyesters such as PET or polyolefins such as PP (polypropylene), PE (polyethylene) and PVC (polyvinyl chloride) are particularly preferred.
• the polymeric material can be formed into a film using conventional filmmaking techniques such as by extrusion and optional uniaxial or biaxial orientation of the extruded film.
• the substrate can be treated to improve adhesion between the substrate and the hardcoat layer, e.g., chemical treatment, corona treatment such as air or nitrogen corona, plasma, flame, or actinic radiation.
• corona treatment such as air or nitrogen corona, plasma, flame, or actinic radiation.
• an optional tie layer or primer can be applied to the substrate and/or hardcoat layer to increase the interlayer adhesion.
• Various light transmissive optical films are known including but not limited to, multilayer optical films, microstructured films such as retroreflective sheeting and brightness enhancing films, (e.g. reflective or absorbing) polarizing films, diffusive films, as well as (e.g. biaxial) retarder films and compensator films such as described in U.S. Patent Application Publication No. 2004/0184150.
• multilayer optical films provide desirable transmission and/or reflection properties at least partially by an arrangement of microlayers of differing refractive index.
• the microlayers have different refractive index characteristics so that some light is reflected at interfaces between adjacent microlayers.
• the microlayers are sufficiently thin so that light reflected at a plurality of the interfaces undergoes constructive or destructive interference in order to give the film body the desired reflective or transmissive properties.
• each microlayer For optical films designed to reflect light at ultraviolet, visible, or near-infrared wavelengths, each microlayer generally has an optical thickness (i.e., a physical thickness multiplied by refractive index) of less than about 1 ⁇ m.
• Multilayer optical film bodies can also comprise one or more thick adhesive layers to bond two or more sheets of multilayer optical film in a laminate.
• polymeric multilayer optical films and film bodies can comprise additional layers and coatings selected for their optical, mechanical, and/or chemical properties. See U.S. Pat. No. 6,368,699 (Gilbert et al.).
• the polymeric films and film bodies can also comprise inorganic layers, such as metal or metal oxide coatings or layers
• Suitable adhesive compositions include (e.g. hydrogenated) block copolymers such as those commercially available from Kraton Polymers of Westhollow, Tex. under the trade designation “Kraton G-1657”, as well as other (e.g. similar) thermoplastic rubbers.
• Other exemplary adhesives include acrylic-based, urethane-based, silicone-based, and epoxy-based adhesives.
• Preferred adhesives are of sufficient optical quality and light stability such that the adhesive does not yellow with time or upon weather exposure so as to degrade the viewing quality of the optical display.
• the adhesive can be applied using a variety of known coating techniques such as transfer coating, knife coating, spin coating, die coating and the like. Exemplary adhesives are described in U.S. Patent Application Publication No. 2003/0012936. Several of such adhesives are commercially available from 3M Company, St. Paul, Minn. under the trade designations 8141, 8142, and 8161.
• Free-radically polymerizable refers to the ability of monomers, oligomers, polymers or the like to participate in crosslinking reactions upon exposure to a suitable source of free radicals.
• (Meth)acryl refers to functional groups including acrylates, methacrylates, acrylamides, methacrylamides, alpha-fluoroacrylates, thioacrylates and thio-methacrylates.
• a preferred (meth)acryl group is acrylate.
• “Monovalent perfluoropolyether moiety” refers to a perfluoropolyether chain having one end terminated by a perfluoroalkyl group.
• HFPO- refers to the end group F(CF(CF 3 )CF 2 O)aCF(CF 3 )— of the methyl ester F(CF(CF 3 )CF 2 O)aCF(CF 3 )C(O)OCH3, wherein “a” averages 2 to 15. In some embodiments, a averages between 3 and 10 or a averages between 5 and 8. Such species generally exist as a distribution or mixture of oligomers with a range of values for a, so that the average value of a may be non-integer. In one embodiment a averages 6.2. This methyl ester has an average molecular weight of 1,211 g/mol, and can be prepared according to the method reported in U.S. Pat. No. 3,250,808 (Moore et al.), the disclosure of which is incorporated herein by reference, with purification by fractional distillation.
• spots The number of spots was determined visually in a 25 cm 2 area by counting the number of spots with the coating held against a black background. When the composition includes a particulate matting agent such as silica, the spots are white in appearance and can be more easily detected.
• the methyl ester material for preparation of the alcohol can be prepared according to the method reported in U.S. Pat. No. 3,250,808 (Moore et al.), the disclosure of which is incorporated herein by reference, with purification by fractional distillation.
• Polyisocyanate was obtained from Bayer Polymers LLC, of Pittsburgh, Pa. under the trade designation “Desmodur N100”. (“DesN100”)
• Polyisocyanate was obtained from Bayer Polymers LLC, of Pittsburgh, Pa. under the trade designation “Desmodur N3300”. (“DesN3300”)
• Pentaerythritol triacrylate (“PET3A”), under the trade designation “SR444C”, was obtained from Sartomer Company of Exton, Pa.
• BHT 2,6-di-t-butyl-4-methylphenol
• DBTDL dibutyltin dilaurate
• a 500 ml roundbottom flask equipped with magnetic stir bar was charged with 25.0 g (0.131 eq, 191 EW, 1.0 mole fraction) Des N100, 106.75 g methyl ethyl ketone (MEK), and 0.05 g BHT.
• the reaction was swirled to dissolve all the reactants, the flask was placed in a oil bath at 55 degrees Celsius, and fitted with a condenser under dry air. Sixty-five microliters of a 10% dibutyltin dilaurate solution in MEK was added to the reaction. Over 20 min, 17.59 g (0.0131 eq, 1344 EW, 0.10 mole fraction)
• the perfluoropolyether urethane multiacrylates of Preparations 2-14, C1 and C2 were made by substantially the same procedure with 1.0 mole fraction (Des N100) isocyanate, the HFPO-alcohol at 0.10 mole fraction and each of the modifying alcohols at the mole fractions indicated in column 5 of the following Table 1.
• the HFPO—C(O)NHCH 2 CH 2 OH amidol of 1344 molecular weight was used for Example numbers C1, C3, 2, 3, 4, 5; whereas the HFPO—C(O)NHCH 2 CH 2 OH amidol of 1314 molecular weight was used for C2.
• Example HFPO PET3A/Alcohol No. Mole fraction Modifying Alcohol Mole Fractions C7 0.25 None 0.8/0.0 11 0.25 C 18 H 37 (OCH 2 CH 2 ) 20 OH 0.65/0.15 Brij 78 12 0.25 C 18 H 37 (OCH 2 CH 2 ) 20 OH 0.55/0.25 Brij 78
• ceramer hardcoat base compositions (“HCB-1”, “HCB-2” and “HCB-3”) used in the examples were made as described in column 10, line 25-39 and Example 1 of U.S. Pat. No. 5,677,050 to Bilkadi, et al. with the following (wt-% solids) additions:
• Syloid C 803 is a fine silica from W.R. Grace and Co., Columbia, Md.
• Disperbyk 163 is a dispersant from Byk-Chemie USA, Wallingford, Conn.
• Irgacure 819 and 184 are photoinitiators from Ciba Specialty Chemicals, Tarrytown, N.Y.
• Sartomer SR 295, SR238, SR399 are all multifunctional acrylate monomers from Sartomer Corp., West Chester, Pa.
• ZrO 2 sols (40.8% solids in water) was prepared were prepared in accordance with the procedures described in U.S. patent application Ser. No. 11/079,832 filed Mar. 14, 2005 that claims priority to U.S. patent application Ser. No. 11/078,468 filed Mar. 11, 2005.
• the resulting ZrO 2 sols were evaluated with Photo Correlation Spectroscopy (PCS), X-Ray Diffraction and Thermal Gravimetric Analysis as described in U.S. patent application Ser. Nos. 11/079,832 and 11/078,468.
• the ZrO 2 sols used in the examples had properties in the ranges that follow:
• PCS Data Intensity Volume- (Intensity- Dispersion avg size avg size avg)/(Volume- Index (nm) (nm) avg) 1.0–2.4 23.0–37.0 8.0–18.8 1.84–2.97
• SM Zirconia Surface Modified Zirconia Nanoparticles
• the reaction mixture was heated under vacuum (24-40 torr) and the 1-methoxy-2-propanol/water azeotrope was distilled off to remove substantially all of the water, while slowly adding 70.5 lbs of additional 1-methoxy-2-propanol. 0.4 lbs of 30% ammonium hydroxide was added to the reaction mixture, then the reaction was concentrated to 59.2% solids by distilling off 1-methoxy-2-propanol.
• the surface modification reaction resulted in a mixture containing 59.2% surface modified zirconia (ZrO 2 -SM), by weight, in 1-methoxy-2-propanol.
• the final mixture was filtered through a 1 micron filter.

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