US20060216524A1 - Perfluoropolyether urethane additives having (meth)acryl groups and hard coats - Google Patents

Perfluoropolyether urethane additives having (meth)acryl groups and hard coats Download PDF

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Publication number
US20060216524A1
US20060216524A1 US11/087,413 US8741305A US2006216524A1 US 20060216524 A1 US20060216524 A1 US 20060216524A1 US 8741305 A US8741305 A US 8741305A US 2006216524 A1 US2006216524 A1 US 2006216524A1
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United States
Prior art keywords
group
groups
optionally
additive
meth
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Abandoned
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US11/087,413
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English (en)
Inventor
Thomas Klun
Naiyong Jing
Richard Pokorny
Zai-Ming Qiu
Mark Pellerite
William Coggio
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
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3M Innovative Properties Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Priority to US11/087,413 priority Critical patent/US20060216524A1/en
Assigned to 3M INNOVATIVE PROPERTIES COMPANY reassignment 3M INNOVATIVE PROPERTIES COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: COGGIO, WILLIAM D., JING, NAIYONG, KLUN, THOMAS P., PELLERITE, MARK J., POKORNY, RICHARD J., QIU, ZAI-MING
Priority to PCT/US2006/010344 priority patent/WO2006102383A1/en
Priority to KR1020077021774A priority patent/KR20070114190A/ko
Priority to CN2006800092064A priority patent/CN101146840B/zh
Priority to KR1020137013814A priority patent/KR101397831B1/ko
Priority to JP2008503117A priority patent/JP5118017B2/ja
Priority to TW95109966A priority patent/TWI412779B/zh
Priority to EP06739223.3A priority patent/EP1866355B1/en
Priority to US11/277,162 priority patent/US7718264B2/en
Publication of US20060216524A1 publication Critical patent/US20060216524A1/en
Priority to US12/718,481 priority patent/US8147966B2/en
Priority to US13/396,669 priority patent/US8476398B2/en
Priority to US13/908,102 priority patent/US8729211B2/en
Priority to US14/247,379 priority patent/US8981151B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • 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
    • 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
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    • 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
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    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • 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
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    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
    • 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
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    • 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
    • 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
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    • 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
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    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
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    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • 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
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • 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
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    • 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
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • Optical hard coats are applied to optical display surfaces to protect them from scratching and marking. Desirable product features in optical hard coats include durability to scratches and abrasions, and resistance to inks and stains.
  • Fluorinated polymers Materials that have been used to date for surface protection include fluorinated polymers, or fluoropolymers. Fluoropolymers provide advantages over conventional hydrocarbon based materials in terms of high chemical inertness (in terms of solvent, acid, and base resistance), dirt and stain resistance (due to low surface energy), low moisture absorption, and resistance to weather and solar conditions.
  • Fluoropolymers have also been investigated that are crosslinked to a hydrocarbon-based hard coating formulation that improves hardness and interfacial adhesion to a substrate.
  • a hydrocarbon-based hard coating formulation that improves hardness and interfacial adhesion to a substrate.
  • free-radically curable perfluoropolyethers provide good repellency to inks from pens and permanent markers when added to ceramer hard coat compositions, which comprise a plurality of colloidal inorganic oxide particles and a free-radically curable binder precursor, such as described in U.S. Pat. No. 6,238,798 to Kang, and assigned to 3M Innovative Properties Company of St. Paul, Minn.
  • the invention relates to fluorocarbon- and urethane-(meth)acryl-containing additives.
  • the additive comprises a perfluoropolyether urethane having a monovalent perfluoropolyether moiety and a multi-(meth)acryl terminal group and is described in the detailed description below as formula (1).
  • the additive comprises a perfluoropolyether-substituted urethane acrylate having a monovalent perfluoropolyether moiety described in the detailed description below as formula (3A) and more preferably as formula (3B).
  • the additive comprises one or more perfluoropolyether urethanes having a monovalent perfluoropolyether moiety and a multi-(meth)acryl group of the formula (4) as described further in the detailed description below.
  • the additive comprises one or more perfluoropolyether urethanes having a monovalent perfluoropolyether moiety and a multi-(meth)acryl group of the formula (5) as described below in the detailed description.
  • the additive comprises one or more perfluoropolyether urethanes with multi-(meth)acryl groups of the formula (6) as described below in the detailed description.
  • the invention realtes to a hardcoat composition
  • a hardcoat composition comprising a (e.g. small amount of a) hardcoat-compatible, monovalent perfluoropolyether moiety-containing urethane multi-(meth)acryl additive, a hydrocarbon hardocat composition; and optionally a plurality of surface modified inorganic nanoparticles.
  • the hardcoat preferably comprises one or more of the embodied additives just described.
  • the hardcoat is preferably provided as a surface layer on an optical substrate.
  • the hardcoat may be provided as a single layer disposed on an optical substrate.
  • a first (e.g. different composition) hardcoat layer may be disposed on the optical substate with a hardcoat of the invention disposed on the first hardcoat layer.
  • a particulate matting agent may be incorporate to impart anti-glare properties to the optical hard coating layer.
  • the particulate matting agent can also prevent the reflectance decrease and uneven coloration caused by interference of the hard coat layer with the underlying substrate layer.
  • the hardcoats provide any one or combination of enhanced stain and ink repellency properties, adequate smoothness, and improved durability.
  • the (e.g. optical) hard coats having these fluorocarbon additives described herein generally do not need compatibilizers to enhance the compatibility between a fluoropolymer additive and the conventional hard coat material.
  • free-radically reactive fluoroalkyl or fluoroalkylene group-containing compatibilizers can also be employed such as a perfluorobutyl-substituted acrylate or a fluoroalkyl- or fluoroalkylene-substituted thiol or polythiol.
  • FIG. 1 illustrates an article having a hard coated optical display formed in accordance with a preferred embodiment of the present invention.
  • (meth)acryl refers to functional groups including acrylates, methacrylates, acrylamides, methacrylamides, alpha-fluoroacrylates, thioacrylates and thio-methacrylates.
  • a preferred (meth)acryl group is acrylate.
  • perfluoropolyether moiety refers to a perfluoropolyether chain having one end terminated by a perfluoroalkyl group.
  • ceramer is a composition having inorganic oxide particles, e.g. silica, of nanometer dimensions dispersed in a binder matrix.
  • the phrase “ceramer composition” is meant to indicate a ceramer formulation in accordance with the present invention that has not been at least partially cured with radiation energy, and thus is a flowing, coatable liquid.
  • the phrase “ceramer composite” or “coating layer” is meant to indicate a ceramer formulation in accordance with the present invention that has been at least partially cured with radiation energy, so that it is a substantially non-flowing solid.
  • 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 curing energy.
  • polymer will be understood to include polymers, copolymers (e.g. polymers using two or more different monomers), oligomers and combinations thereof, as well as polymers, oligomers, or copolymers that can be formed in a miscible blend.
  • 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 about 6.2, and the methyl ester has an average molecular weight of 1,211 g/mol, and which 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.
  • 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.
  • a combination of low surface energy (e.g. anti-soiling, stain resistant, oil and/or water repellency) and durability (e.g. abrasion resistance) is desired for the coating layer for these displays while maintaining optical clarity.
  • the hard coating layer functions to decrease glare loss while improving durability and optical clarity.
  • 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 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 300 rpm for 15 minutes as described in Experiment 1 of this application.
  • a durable coating exhibits an ink repellency value of 65 mm or less, more preferably 40 mm or less, most preferably 0 mm in this test.
  • Coatings appropriate for use as optical hard coatings must be substantially free of visual defects.
  • Visual defects that may be observed include but are not limited to pock marks, fish eyes, mottle, lumps or substantial waviness, or other visual indicators known to one of ordinary skill in the art in the optics and coating fields.
  • a “rough” surface as described in the Experimental has one or more of these characteristics, and may be indicative of a coating material in which one or more components of the composition are incompatible with each other.
  • a substantially smooth coating characterized below as “smooth” for the purpose of the present invention, presumes to have a coating composition in which the various components, in the reacted final state, form a coating in which the components are compatible or have been modified to be compatible with one another and further has little, if any, of the characteristics of a “rough” surface.
  • the surface layer preferably exhibits an initial haze of less than 2% and/or an initial transmission of at least 90%.
  • FIG. 1 a perspective view of an article (here a computer monitor 10 ) is illustrated as having an optical display 12 coupled within a housing 14 .
  • the optical display 12 is a substantially transparent material having optically enhancing properties through which a user can view text, graphics or other displayed information.
  • the optical display 12 includes hard coating layer 18 applied to an optical substrate 16 .
  • the thickness of the hardcoat 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.
  • the hardcoat layer described herein i.e. comprising at least one fluorocarbon- and urethane-(meth)acryl-containing additive and at least one non-fluorinated crosslinking agent
  • the surface layer preferably preferably has a thickness ranging from about 10 to 200 nanometers.
  • 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.
  • the substrate layer 16 may consist of any of a wide variety of non-polymeric materials, such as glass, or polymeric materials, such as polyethylene terephthalate (PET), bisphenol A polycarbonate, cellulose triacetate, poly(methyl methacrylate), and biaxially oriented polypropylene which are commonly used in various optical devices.
  • PET polyethylene terephthalate
  • bisphenol A polycarbonate bisphenol A polycarbonate
  • cellulose triacetate cellulose triacetate
  • poly(methyl methacrylate) poly(methyl methacrylate)
  • biaxially oriented polypropylene which are commonly used in various optical devices.
  • the composition of the hard coating layer 18 prior to application and curing to the optical substrate 16 , is formed from a mixture of a conventional hydrocarbon-based, and more preferably acrylate-based, hard coat composition and a fluorocarbon- and urethane-acrylate-containing additive described in formulas (1), (3A), (4), (5) and (6) below. Methods for forming the hard coating compositions for each of the preferred embodiments are described below in the experimental section.
  • the fluorocarbon- and urethane-acrylate-containing additive is a perfluoropolyether urethane having a monovalent perfluoropolyether moiety and a multi-acrylate terminal group combined with a conventional hydrocarbon-based (more preferably acrylate-based) hard coat material.
  • the perfluoropolyether urethane having a monovalent perfluoropolyether moiety and a multi-acrylate terminal group is added at between about 0.01% and 10%, and more preferably between about 0.1% and 1%, of the total solids of the hard coat composition.
  • the additive is ofthe formula (1): R i —(NHC(O)XQR f ) m , —(NHC(O)OQ(A) p ) n (1) wherein R i is the residue of a multi-isocyanate; X is O, S or NR, where R is H or lower alkyl of 1 to 4 carbon atoms; R f is a monovalent perfluoropolyether moiety composed of groups comprising the formula: F(R fc O) x C d F 2d —, wherein each R fc independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms, each x independently represents an integer greater than or equal to 2, and wherein d is an integer from 1 to 6; Q is independently a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene, a straight or branched
  • the mole fraction of isocyanate groups is arbitrarily given a value of 1.0, then the total mole fraction of m and n units used in making materials of formula (1) is 1.0 or greater.
  • the mole fractions of m:n ranges from 0.95:0.05 to 0.05:0.95.
  • the mole fractions of m:n are from 0.50:0.50 to 0.05:0.95. More preferably, the mole fractions of m:n are from 0.25:0.75 to 0.05:0.95 and most preferably, the mole fractions of m:n are from 0.25:0.75 to 0.10:0.95.
  • the mole fractions of m:n total more than one, such as 0.15:0.90, the m unit is reacted onto the isocyanate first, and a slight excess (0.05 mole fraction) of the n units are used.
  • diisocyanates di-functional isocyanates
  • modified diisocyanate materials and higher functional isocyanates
  • R i residue of multi-isocyanate and still fall within the spirit of the present invention.
  • multifunctional materials based on hexamethylene diisocyanate (“HDI”) are utilized.
  • HDI hexamethylene diisocyanate
  • DesmodurTM N100 available from Bayer Polymers LLC of Pittsburgh, Pa.
  • R i may also be utilized as R i in the present invention.
  • diisocyanates such as toluene diisocyanate (“TDI”) or isophorone diisocyanate (“IPDI”) may also be utilized as R i in the present invention.
  • TDI toluene diisocyanate
  • IPDI isophorone diisocyanate
  • Non-limiting examples of aliphatic and aromatic isocyanate materials, for example, that may be used include DesmodurTM 3300, DesmodurTM TPLS2294, and DesmodurTM N 3600, all obtained from Bayer Polymers LLC of Pittsburgh, Pa.
  • HOQ(A) p Materials used to make the additive of formula (1) may be described by the formula: HOQ(A) p , which are exemplified by, for instance, 1,3-glycerol dimethacrylate, available from Echo Resins Inc. of York, Mo.; and pentaerythritol triacrylate, available as SR444C from Sartomer of Exton, Pa.
  • the monovalent perfluoropolyether moiety R f is a hexafluoropropylene oxide (“HFPO”) moiety of the formula: F(CF(CF 3 )CF 2 O) a CF(CF 3 )—, wherein a is between about 3 and 10.
  • HFPO hexafluoropropylene oxide
  • 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.
  • the additives of this preferred embodiment are made by first reacting the polyisocyanate with the perfluoropolyether-containing alcohol, thiol, or amine, followed by reaction with the hydroxyl functional multiacrylate, usually in a non-hydroxylic solvent and in the presence of a catalyst such as an organotin compound.
  • the additives of this preferred embodiment are made by reacting the polyisocyanate with the hydroxyl functional multiacrylate, followed by reaction with the perfluoropolyether-containing alcohol, thiol, or amine, usually in a non-hydroxylic solvent and in the presence of a catalyst such as an organotin compound.
  • the additives could be made by reacting all three components simultaneously, usually in a non-hydroxylic solvent and in the presence of a catalyst such as an organotin compound.
  • a hard coating composition may be formed by the addition of a perfluoropolyether urethane with a mono-acrylate terminal group according to the formula R i —(NHC(O)XQR f ) m , —(NHC(O)OQA) n to a hydrocarbon-based hard coating formulation.
  • the fluorocarbon- and urethane-acrylate-containing additive comprises a perfluoropolyether-substituted urethane acrylate having a monovalent perfluoropolyether moiety added at between about 0.01% and 10%, and more preferably between about 0.1% and 1%, of the total solids of the hard coat composition.
  • the additive is of the formula (3A): R f -Q-(XC(O)NHQOC(O)C(R) ⁇ CH 2 ) f (3A) where R f is a monovalent perfluoropolyether moiety composed of groups comprising the formula: F(R fc O) x C d F 2d —, wherein each R fc independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms, each x independently represents an integer greater than or equal to 2, and wherein d is an integer from 1 to 6; a is 2-15; Q is independently a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene, a straight or branched chain or cycle-containing connecting group optionally containing heteroatoms such as O, N, and S and optionally a heteroatom-containing functional group such as carbonyl or sulfonyl
  • HFPO-Q-(XC(O)NHQOC(O)C(R) ⁇ CH 2 ) f 3B) where HFPO is F(CF(CF 3 )CF 2 O) a CF(CF 3 )—; a is 2-15; Q is independently a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene, a straight or branched chain or cycle-containing connecting group optionally containing heteroatoms such as O, N, and S and optionally a heteroatom-containing functional group such as carbonyl or sulfonyl, and combinations thereof; X is independently O, S or NR, where R is H or lower alkyl of 1 to 4 carbon atoms and f is 1-5.
  • Two preferred HFPO-substituted urethane acrylates that can be utilized include: HFPO—C(O)NHC 2 H 4 OC(O)NHC 2 H 4 OC(O)C(CH 3 ) ⁇ CH 2 and HFPO—C(O)NHC(C 2 H 5 )(CH 2 OC(O)NHC 2 H 4 OC(O)C(CH 3 ) ⁇ CH 2 ) 2 .
  • the fluorocarbon- and urethane-acrylate-containing additive is formed from one or more perfluoropolyether urethanes having a monovalent perfluoropolyether moiety and multi-meth(acryl) groups added at between about 0.01% and 10%, and more preferably between about 0.1% and 1%, of the total solids of the hard coat composition.
  • the additive is of the formula (4): R i —(NHC(O)XQR f ) m , —(NHC(O)OQ(A) p ) n , —(NHC(O)XQG) o ,—(NCO) q (4) wherein R i is the residue of a multi-isocyanate; X is independently O, S or NR, where R is H or lower alkyl of 1 to 4 carbon atoms; R f is a monovalent perfluoropolyether moiety composed of groups comprising the formula: F(R fc O) x C d F 2d —, wherein each R fc independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms, each x independently represents an integer greater than or equal to 2, and wherein d is an integer from 1 to 6; Q is independently a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an al
  • the monoalcohol, monothiol or monoamine HXQG used in making materials of formula (4) may include materials such as C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 OH, H 2 NCH 2 CH 2 CH 2 (SiOCH 3 ) 3 , HSCH 2 CH 2 CH 2 Si(OCH 3 ) 3 , and HEA (“hydroxyethylacrylate”).
  • the fluorocarbon- and urethane-acrylate-containing additive is formed from one or more perfluoropolyether urethanes having a monovalent perfluoropolyether moiety and multi-meth(acryl) groups added at between about 0.01% and 10%, and more preferably between about 0.1% and 1%, of the total solids of the hard coat composition.
  • the additive is of the formula (5): (R i ) c —(NHC(O)XQR f ) m , —(NHC(O)OQ(A) p ) n , —(NHC(O)XQG) o , (R f (Q)(XC(O)NH) y ) z —, —NHC(O)XQD(QXC(O)NH) u ) s —, D 1 (QXC(O)NH) y ) zz —NHC(O)OQ(A) t Q 1 Q(A) t OC(O)NH)) v —, —(NCO) w (5) wherein R i is the residue of a multi-isocyanate; c is 1 to 50; X is independently O, S or NR, where R is H or lower alkyl; R f is a monovalent perfluoropolyether moiety composed of groups compris
  • the materials used to make the additive of formula (5) include those of the formula: R f (Q)(XH) y , which is exemplified by HFPO—C(O)NHCH 2 CH 2 CH 2 N(CH 2 CH 2 OH) 2 .
  • the materials used to make the additive of formula (5) include those of the formula: HXQDQXH, which is exemplified by hydrocarbon polyols such as HO(CH 2 ) 10 OH and fluorochemical diols such as HOCH 2 (CF 2 ) 4 CH 2 OH.
  • the materials used to make the additive of formula (5) may include those of the formula: D(QXH) y ) zz , which is exemplified by fluorochemical diols C 4 F 9 SO 2 N(CH 2 CH 2 OH) 2 .
  • the materials used to make the additive of formula (5) may also include those of the formula: HOQ(A) t Q 1 Q(A) t OH, which is exemplified by Hydantoin hexaacrylate (HHA), prepared as described in Example 1 of U.S. patent application No. 4,262,072 to Wendling et al, and CH 2 ⁇ C(CH 3 )C(O)OCH 2 CH(OH)CH 2 O(CH 2 ) 4 OCH 2 CH(OH)CH 2 OC(O)C(CH 3 ) ⁇ CH 2 .
  • HHA Hydantoin hexaacrylate
  • the fluorocarbon- and urethane-acrylate-containing additive is formed from one or more perfluoropolyether urethanes with multi-meth(acryl) groups added at between about 0.01% and 10%, and more preferably between about 0.1% and 1%, of the total solids of the hard coat composition.
  • the additive is of the formula (6): (R i ) c —(NHC(O)XQR f ) m , —(NHC(O)OQ(A) p ) n , —(NHC(O)XQG), —(NHC(O)XQR f2 (QXC(O)NH) u ) r —, —NHC(O)XQD(QXC(O)NH) u ) s —, D 1 (QXC(O)NH) y ) zz —NHC(O)OQ(A) t Q 1 Q(A) t OC(O)NH)) v —, —(NCO) w (6) wherein R i is the residue of a multi-isocyanate; c is 1 to 50; X is independently O, S or NR, where R is H or lower alkyl; R f is a monovalent perfluoropolyether moiety
  • the materials used to make the additive of formula (9) may also include those of the formula: HXQR f2 QXH, which is exemplified by (H(OCH 2 C(CH 3 )(CH 2 OCH 2 CF 3 )CH 2 ) aa OH) (Fox-Diol, having a MW about 1342 and available from Omnova Solutions Inc. of Akron, Ohio).
  • the fluorocarbon- and urethane-(meth)acryl additive(s) described herein are employed as the sole perfluoropolyether containing additive in a hardcoat composition.
  • the additive(s) described herein may be employed in combination with various other perfluoropolyether fluorocarbon(meth)acryl materials such as HFPO—C(O)NHCH 2 CH 2 OC(O)CH ⁇ CH 2 and various (per)fluoropolyether acryl compounds such as described in U.S. application Ser. No. 10/841159, filed May 7, 2004; (Docket No. 59727US002) and U.S. Provisional Application Ser. No. 60/569351, filed May 7, 2004 (Docket No.
  • Exemplary materials include compound of the structures: HFPO—C(O)N(H)C(CH 2 OC(O)CH ⁇ CH 2 ) 2 CH 2 CH 3 , and HFPO—C(O)N(H)C(CH 2 OC(O)CH ⁇ CH 2 ) 2 H.
  • the hardcoat may be provided as a single layer disposed on an optical substrate.
  • the total of all (per)fluoropolyether acryl compounds, i.e. the fluorocarbon- and urethane-(meth)acryl additive(s) of the invention and other perfluoropolyether fluorocarbon(meth)acryl materials
  • a first e.g.
  • the fluorocarbon- and urethane-(meth)acryl-containing additives described herein may be present in the surface coating at amounts ranging from 0.01 to 50 wt-% solids, and more preferably from 1 to 25 wt-% solids; whereas the various other (per)fluoropolyether acryl compounds may be present at weight percents from 1 to 20%, and preferably from 1 to 10%.
  • the ratio of fluorocarbon- and urethane-(meth)acry-containing additive to other (per)fluoropolyether acryl compounds is at least 1 to 1 and more preferably is about 3 to 1.
  • the fluorocarbon- and urethane(meth)acryl additives e.g. those of formulas (1), (3A), (4), (5) or (6)
  • various other (per)fluoropolyether(meth)acryl compounds may be combined with one or more compatibilizers.
  • Typical Q 3 groups include: —SO 2 N(R)CH 2 CH 2 —; —SO 2 N(CH 2 CH 2 ) 2 —; —(CH 2 ) m —; —CH 2 O(CH 2 ) 3 —; and —C(O)NRCH 2 CH 2 —, where R is H or lower alkyl of 1 to 4 carbon atoms and m is 1 to 6.
  • R is H or lower alkyl of 1 to 4 carbon atoms and m is 1 to 6.
  • the fluoroalkyl or fluoroalkylene group is a perfluoroalkyl or perfluoroalkylene group.
  • fluoroalkyl- or alkylene-substituted compatibilizers meeting these criteria for use in the composition of the hard coat layer 18 is the perfluorobutyl-substituted acrylate compatibilizers.
  • Exemplary, non-limiting perfluorobutyl-substituted acrylate compatibilizers meeting these criteria and useful in the present invention include one or more of C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 OC(O)CH ⁇ CH 2 , C 4 F 9 SO 2 N(CH 2 CH 2 OC(O)CH ⁇ CH 2 ) 2 , or C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 OC(O)C(CH 3 ) ⁇ CH 2 .
  • the free-radically reactive fluoroalkyl or fluoroalkylene group-containing compatibilizers described above are preferably added at between about 0.5% and 20%, and more preferably between about 1% and 10%, of the total solids of the hard coat composition.
  • a preferred fluoroalkyl-substituted compatibilizer that may be utilized in the composition of the hard coat layer 18 is: (1H,1H,2H,2H)-perfluorodecyl acrylate, available from Lancaster Synthesis of Windham, N.H. Numerous other (meth)acryl compounds with perfluoroalkyl moieties that may also be utilized in the composition of the hard coat layer are mentioned in U.S. Pat. No. 4,968,116, to Hulme-Lowe et al., and in U.S. Pat. No.
  • fluorochemical (meth)acrylates that meet these criteria and may be utilized include, for example, 2,2,3,3,4,4,5,5-octafluorohexanediol diacrylate and ⁇ -hydro 2,2,3,3,4,4,5,5-octafluoropentyl acrylate (H—C 4 F 8 —CH 2 O—C(O)—CH ⁇ CH 2 ).
  • fluorochemical (meth)acrylates that may be used alone, or as mixtures, are described in U.S. Pat. No. 6,238,798, to Kang et al., and assigned to Minnesota Mining and Manufacturing Company of St. Paul, Minn., and herein incorporated by reference.
  • compatibilizer that may be used is a fluoroalkyl- or fluoroalkylene-substituted thiol or polythiol to a ceramer hard coating composition.
  • this type of compatibilizer includes one or more of the following: C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 OC(O)CH 2 SH, C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 OC(O)CH 2 CH 2 SH, C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 SH, and C 4 F 9 SO 2 N(CH 3 )CH(OC(O)CH 2 SH)CH 2 OC(O)CH 2 SH.
  • the conventional hard coat material used as a portion of layer 18 in any of the preferred embodiments described above is a hydrocarbon-based material well known to those of ordinary skill in the optical arts. Most preferably, the hydrocarbon-based material is an acrylate-based hard coat material.
  • One preferable hard coat material for use in the present invention is based on PETA (pentaerythritol tri/tetra acrylate).
  • PETA pentaerythritol tri/tetra acrylate
  • PET3A pentaerythritol triacrylate
  • PET4C pentaerythritol triacrylate
  • PET4A pentaerythritol tetraacrylate
  • crosslinking agents include, for example, poly(meth)acryl monomers selected from the group consisting of (a) di(meth)acryl containing compounds such as 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
  • Such compounds are widely available from vendors such as, for example, Sartomer Company of Exton, Pa.; UCB Chemicals Corporation of Smyrna, Ga.; and Aldrich Chemical Company of Milwaukee, Wis.
  • Additional useful (meth)acrylate materials include hydantoin moiety-containing poly(meth)acrylates, for example, as described in U.S. Pat. No. 4,262,072 (Wendling et al.).
  • polymerizable compositions according to the present invention 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 initiators include benzophenone and its derivatives; benzoin, alpha-methylbenzoin, alpha-phenylbenzoin, alpha-allylbenzoin, alpha-benzylbenzoin; benzoin ethers such as benzil dimethyl ketal (commercially available under the trade designation “IRGACURE 651 ” from Ciba Specialty Chemicals Corporation of Tarrytown, N.Y.), benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether; acetophenone and its derivatives such as 2-hydroxy-2-methyl-1-phenyl-1-propanone (commercially available under the trade designation “DAROCUR 1173” from Ciba Specialty Chemicals Corporation) and 1-hydroxycyclohexyl phenyl ketone (commercially available under the trade designation “IRGACURE 184
  • sensitizers such as 2-isopropyl thioxanthone, commercially available from First Chemical Corporation, Pascagoula, Miss., may be used in conjunction with photoinitiator(s) such as “IRGACURE 369”.
  • composition of any of these preferred embodiments is applied to an optical substrate layer 16 of an optical display 12 and photocured to form the easy to clean, stain and ink repellent optical hard coating layer 18 .
  • the presence of the urethane functionality, in addition to the fluorocarbon component, in the additive eliminates the need for comonomers introduced to the composition to compatibilize the fluorochemical component with the hydrocarbon-based crosslinker.
  • the hard coat material forming layer 18 of any of the above-preferred embodiments further contains surface modified inorganic particles that add mechanical strength to the resultant coating.
  • surface modified inorganic particles that add mechanical strength to the resultant coating.
  • colloidal silica reacted with a methacryl silane coupling agent such as A-174 (available from Natrochem, Inc.), other dispersant aids such as N,N dimethylacrylamide and various other additives (stabilizers, initiators, etc.).
  • a particulate matting agent is incorporated into the composition of the layer 18 in order to impart anti-glare properties to the layer 18 .
  • the particulate matting agent also prevents the reflectance decrease and uneven coloration caused by interference with an associated hard coat layer.
  • the particulate matting agent should preferably be transparent, exhibiting transmission values of greater than about 90%.
  • the haze value is preferably less than about 5%, and more preferably less than about 2%, and most preferably less than about 1%.
  • 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 18, with a preferred amount around 2%.
  • the anti-glare layer 18 preferably has a thickness of 0.5 to 10 microns, more preferably 0.8 to 7 microns, which is generally in the same thickness range of gloss hard coatings.
  • 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.
  • Thin coating layers 18 of any of the preferred embodiments can be applied to the optical substrate 16 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, Modem 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.
  • sample hard coats having the given compositions were formulated and applied to PET substrates and compared to hard coat formulations having less than all the desired components.
  • the coatings were visually inspected and tested for ink repellency, durability and surface roughness. The experimental procedures and tabulated results are described below:
  • HFPO— refers to the end group F(CF(CF 3 )CF 2 O) a CF(CF 3 )— wherein a averages about 6.22, with an average molecular weight of 1,211 g/mol, 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.
  • DesmodurTM (Des) N100, DesmodurTM 3300, DesmodurTM TPLS2294, DesmodurTM N 3600, and Isophorone diisocyanate (IPDI) were obtained from Bayer Polymers LLC, of Pittsburgh, Pa.
  • PAPI Poly[(phenyl isocyanate)-co-formaldehyde]
  • MEHQ 4-methoxy phenol
  • HO(CH 2 ) 10 OH is available from Sigma Aldrich of Milwaukee, Wis.
  • FOX-diol H(OCH 2 CCH 3 (CH 2 OCH 2 CF 3 )CH 2 ) x OH) (MW about 1342), is available from Omnova Solutions Inc. of Akron, Ohio.
  • Pentaerythritol tetracrylate (“PET4A”), under the trade designation “SR295”, was obtained from Sartomer Company of Exton, Pa.
  • Pentaerythritol triacrylate (“PET3A”), under the trade designation “SR444C”, was obtained from Sartomer Company of Exton, Pa.
  • TMPTA Trimethylolpropane triacrylate
  • Hydantoin hexaacrylate was prepared as described in Example 1 of U.S. Pat. No. 4,262,072.
  • FBSEE C 4 F 9 SO 2 N(C 2 H 4 OH) 2
  • a fluorochemical diol can be prepared as described in column 5, line 31 and in FIG. 9 of U.S. Pat. No. 3,734,962 (1973).
  • MeFBSE C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 OH
  • MeFBSE C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 OH
  • FBSEA C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 OC(O)CH ⁇ CH 2
  • HFPO AEA HFPO—C(O)NHCH 2 CH 2 OC(O)CH ⁇ CH 2
  • FC-1 Monofunctional Perfluoropolyether Acrylate
  • Fomblin Zdol (HOCH 2 CF 2 (OCF 2 CF 2 ) n (OCF 2 ) m CH 2 OH ) is available from Solvay Solexis, Inc. of Italy.
  • HSA Hydroxyethyl acrylate
  • H 2 NCH 2 CH 2 CH 2 Si(OCH 3 ) 3 is available from Sigma Aldrich of Milwaukee, Wis.
  • HSCH 2 CH 2 CH 2 Si(OCH 3 ) 3 is available from Sigma Aldrich of Milwaukee, Wis.
  • IEM 2-isocyanato-ethyl-methacrylate
  • the amines, 2-amino-2-ethyl-1,3-propane diol, and 1,1-bis-(hydroxyethyl)-1,3 aminopropane were obtained from Sigma-Aldrich of Milwaukee, Wis.
  • UV photoinitiator 1-hydroxycyclohexyl phenyl ketone used was obtained from Ciba Specialty Products, Tarrytown, N.Y. and sold under the trade designation “Irgacure 184.”
  • the photoinitiator 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one used was obtained from Ciba Specialty Products, Tarrytown, N.Y. and sold under the trade designation “Irgacure 907.”
  • Methyl perfluorobutyl ether (HFE 7100) was obtained from 3M Company, St. Paul, Minn.
  • DBTDL Dibutyltin dilaurate
  • MW refers to molecular weight and “EW” refers to equivalent weight.
  • ° C.” may be used interchangeably with “degrees Celsius” and “mol” refers to moles of a particular material and “eq” refers to equivalents of a particular material.
  • Me constitutes a methyl group and may be used interchangeably with
  • HFPO— refers to the end group F(CF(CF 3 )CF 2 O) a CF(CF 3 )— wherein a has average values of about 4.41, 6.2, 6.85, and 8.07.
  • the material F(CF(CF 3 )CF 2 O) a CF(CF 3 )COOCH 3 (HFPO—C(O)OCH 3 ) 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.
  • a 500 ml roundbottom flask equipped with magnetic stir bar was charged with 25.0 g (0.131 eq, 191 EW) Des N100, 43.13 g (0.087 eq, 494.3 EW) of Sartomer SR444C, 25.3 mg of MEHQ, and 126.77 g methyl ethyl ketone (MEK).
  • the reaction was swirled to dissolve all the reactants, the flask was placed in a oil bath at 60 degrees Celsius, and fitted with a condenser under dry air. Two drops of dibutyltin dilaurate was added to the reaction.
  • a 500 ml roundbottom 2-necked flask equipped with magnetic stir bar was charged with 25.00 g (0.131 eq, 191 EW) Des N100, 26.39 g (0.0196 eq, 1344 EW) F(CF(CF 3 )CF 2 O) 6.85 CF(CF 3 )C(O)NHCH 2 CH 2 OH, and 109.62 g MEK, and was swirled to produce a homogeneous solution.
  • the flask was placed in an 80 degrees Celsius bath, charged with 2 drops of dibutyltin dilaurate catalyst, and fitted with a condenser. The reaction was cloudy at first, but cleared within two minutes.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 20 hours after sealing the bottle. A clear solution was obtained after reaction, which showed no unreacted —NCO signal in FTIR analysis.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 20 hours after sealing the bottle. A clear solution was obtained after reaction, which showed no unreacted —NCO signal in FTIR analysis.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 20 hours after sealing the bottle. A clear solution was obtained after reaction, which showed no unreacted —NCO signal in FTIR analysis.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 20 hours after sealing the bottle. A clear solution was obtained after reaction, which showed no unreacted —NCO signal in FTIR analysis.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 20 hours after sealing the bottle. A clear solution was obtained after reaction, which showed no unreacted —NCO signal in FTIR analysis.
  • a 240 ml bottle was charged with 5.79 g Des N3300 (EW about 193, about 30 milliequivalents NCO), 6.71 g HFPODO (MW about 1341, 10 milliequivalents OH), 9.89 g PET3A (EW about 494.3, about 20 milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst and 52 g MEK (about 30% solid) under nitrogen.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 10 hours after sealing the bottle. There was a small amount of precipitate formed upon standing at room temperature. FTIR analysis showed no unreacted —NCO signal.
  • a 240 ml bottle was charged with 5.79 g Des N3300 (EW about 193, about 30 milliequivalents NCO), 6.71 g HFPODO (MW about 1341, 10 milliequivalents OH), 6.72 g HFPO—C(O)NHCH 2 CH 2 OH (MW about 1344, 5 milliequivalents OH), 7.42 g PET3A (EW about 494.3, about 15 milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst, 27 g MEK and 10 g C 4 F 9 OCH 3 (about 20% solid) under nitrogen.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 10 hours after sealing the bottle. Separation into two liquid phases occurred upon standing at room temperature. Addition of more C 4 F 9 OCH 3 produced a clear homogeneous solution at about 17% solids. FTIR analysis showed no unreacted —NCO signal.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 10 hours after sealing the bottle. A clear solution was obtained at 70 degrees Celsius after reaction, but there was a small amount of precipitate formed upon standing at room temperature.
  • FTIR analysis showed no unreacted —NCO signal.
  • a 240 ml bottle was charged with 5.79 g Des N3300 (EW about 191, about 30 milliequivalents NCO), 6.71 g Fox-Diol (MW about 1341, 10 milliequivalents OH), 6.72 g HFPO—C(O)NHCH 2 CH 2 OH (MW about 1344, 5 milliequivalents OH), 7.40 g PET3A (EW about 494.3, about 15 milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst, 56 g MEK and 50 g C 4 F 9 OCH 3 (about 19% solid) under nitrogen.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 10 hours after sealing the bottle. A clear solution was obtained after reaction. FTIR analysis showed no unreacted —NCO signal.
  • a 240 ml bottle was charged with 5.79 g Des N3300 (EW about 191, about 30 milliequivalents NCO), 10.0 g Fomblin Zdol (MW about 2000, 10 milliequivalents OH), 9.89 g PET3A (EW about 494.3, about 20 milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst, 63 g MEK and 40 g C 4 F 9 OCH 3 (about 18% solid) under nitrogen.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 10 hours after sealing the bottle. A clear solution was obtained after reaction. FTIR analysis showed no unreacted —NCO signal.
  • a 240 ml bottle was charged with 5.79 g Des N3300 (EW about 191, about 30 milliequivalents NCO), 6.14 g HHA (MW about 1228, 10 milliequivalents OH), 12.29 g HFPO—C(O)NHCH 2 CH 2 OH (MW about 1229, 10 milliequivalents OH), 4.93 g PET3A (EW about 494.3, about 10 milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst, 85 g MEK and 25 g C 4 F 9 OCH 3 (about 20% solid) under nitrogen.
  • the solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 10 hours after sealing the bottle. A clear solution was obtained after reaction. FTIR analysis showed no unreacted —NCO signal.
  • a 120 ml bottle was charged with 3.75 g PAPI (EW about 134, about 28 milliequivalents NCO), 10.75 g HFPO—C(O)NHCH 2 CH 2 OH (MW about 1344, 8 milliequivalents OH), 9.88 g PET3A (EW about 494.3, about 20 milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst and 37 g MEK (about 40% solid) under nitrogen. The solution was reacted at 70 degrees Celsius in an oil bath with a magnetic stir bar for 5 hours after sealing the bottle. A clear solution was obtained after reaction. FTIR analysis showed no unreacted —NCO.
  • a 500 ml roundbottom flask equipped with stir bar was charged with 25.00 g (0.1309 eq) Des N100, 103.43 g MEK, 2 drops of DBTDL, 26.39 g (0.0196 eq) HFPO—C(O)NHCH 2 CH 2 OH, 1344 equivalent weight, and 0.05 g BHT, and placed in a 60 degrees Celsius oil bath.
  • 3.52 g (0.0196 eq) H 2 N(CH 2 ) 3 Si(OCH 3 ) 3 was added to the reaction, followed in 10 minutes by the addition of 48.52 g (0.0982 eq, 494.3 equivalent weight) SR444C.
  • the reaction showed no residual isocyanate by FTIR after a total reaction time of 5.75 hours.
  • PET3A EW about 494.3, about 20 milliequivalents OH
  • a 1-liter round-bottom flask was charged with 291.24 g (0.2405 mol) of HFPO—C(O)OCH 3 and 21.2 g (0.2405 mol) N-methyl-1,3-propanediamine, both at room temperature, resulting in a cloudy solution.
  • the flask was swirled and the temperature of the mixture rose to 45 degrees Celsius, and to give a water-white liquid, which was heated overnight at 55 degrees Celsius.
  • the product was then placed on a rotary evaporator at 75 degrees Celsius and 28 inches of Hg vacuum to remove methanol, yielding 301.88 g of a viscous slightly yellow liquid, nominal molecular weight is equal to 1267.15 g/mol.
  • the solution was heated in a oil bath at 70 degrees Celsius for 6 hours with a magnetic stirring after sealing the bottle.
  • Fourier Transform Infrared Spectroscopy (FTIR) analysis indicated no remaining isocyanate.
  • FTIR Fourier Transform Infrared Spectroscopy
  • the abrasion resistance of the cured films was tested cross-web to the coating direction by use of a mechanical device capable of oscillating cheesecloth or steel wool fastened to a stylus (by means of a rubber gasket) across the film's surface.
  • the stylus oscillated over a 10 cm wide sweep width at a rate of 3.5 wipes/second wherein a “wipe” is defined as a single travel of 10 cm.
  • the stylus had a flat, cylindrical geometry with a diameter of 1.25 inch (3.2 cm).
  • the device was equipped with a platform on which weights were placed to increase the force exerted by the stylus normal to the film's surface.
  • the cheesecloth was obtained from Summers Optical, EMS Packaging, a subdivision of EMS Acquisition Corp., Hatsfield, Pa. under the trade designation “Mil Spec CCC-c-440 Product #S12905”. The cheesecloth was folded into 12 layers. The steel wool was obtained from Rhodes-American, a division of Homax Products, Bellingham, Wash. under the trade designation “#0000-Super-Fine” and was used as received. A single sample was tested for each example, with the weight in grams applied to the stylus and the number of wipes employed during testing reported.
  • Taber Testing The Taber test was run according to ASTM D1044-99 using CS-10 wheels.
  • a smooth film for the purposes of the present invention, is deemed to be a surface layer that is substantially continuous and free of visible defects in reflected light as observed by visual observation of the coating surface at a wide variety of possible angles. Typically, visual observation is accomplished by looking at the reflection of a light source from the coating surface at an angle of about 60 degrees from perpendicular. Visual defects that may be observed include but are not limited to pock marks, fish eyes, mottle, lumps or substantial waviness, or other visual indicators known to one of ordinary skill in the art in the optics and coating fields.
  • a “rough” surface as described below has one or more of these characteristics, and may be indicative of a coating material in which one or more components of the composition are incompatible with each other.
  • a substantially smooth coating characterized below as “smooth” for the purpose of the present invention, presumes to have a coating composition in which the various components, in the reacted final state, form a coating in which the components are compatible or have been modified to be compatible with one another and further has little, if any, of the characteristics of a “rough” surface.
  • the surfaces may also be classified for dewetting as “good,” “very slight” (v.sl), “slight” (sl), “fair,” or “poor.”
  • a “good” surface meaning a substantially smooth surface having little dewetting.
  • a “very slight,” slight”, or “fair” categorization means that the surface has an increasing portion of defects but is still substantially acceptable for smoothness.
  • a “poor” surface has a substantial amount of defects, indicating a rough surface that has a substantial amount of dewetting.
  • ceramer hardcoat (“HC-1”) used in the examples was made as described in column 10, line 25-39 and Example 1 of U.S. Pat. No. 5,677,050 to Bilkadi, et al.
  • Durability was assessed using a modified Oscillating Sand Method (ASTM F 735-94).
  • An orbital shaker was used (VWR DS-500E, from VWR Bristol, Conn.).
  • a disk of diameter 85 mm was cut from the sample, placed in a 16 ounce jar lid (jar W216922 from Wheaton, Millville, N.J.), and covered with 50 grams of 20-30 mesh Ottawa sand (VWR, Bristol, Conn.).
  • the jar was capped and placed in the shaker set at 300 rpm for 15 minutes.
  • a Sharpie permanent marker was used to draw a line across the diameter of the disk surface. The portion of the ink line that did not bead up was measured.
  • Table 6 shows the results of another set of examples that was run at two levels of additives in an HC-1 hardcoat in which the sand test was run for 25 minutes at 300 rpm. The examples were run according to the same procedure as examples in Table 1 described above.
  • TABLE 6 Percentage Percentage HC-1 in Preparation Preparation Ink coating number in coating Smoothness Repellency 99.8 9 0.2 sl 20 99.0 9 1.0 sl 10 99.8 8 0.2 good 29 99.0 8 1.0 poor 25 99.8 10 0.2 good 38 99.0 10 1.0 good 30 99.8 11 0.2 good 40 99.0 11 1.0 fair 20 99.8 12 0.2 good 36 99.0 12 1.0 poor 22 99.8 19 0.2 good 20 99.0 19 1.0 sl 49 99.8 5.2 0.2 good 5
  • Table 7 shows the results of another set of examples that was run at two levels of additives in an HC-1 hardcoat in which the sand test was run for 25 minutes at 300 rpm and in a separate set for 35 minutes at 300 rpm.
  • the examples were run according to the same procedure as examples in Table 1 described above.
  • HC-1 was applied to the 5-mil Melinex 618 film with a metered, precision die coating process.
  • the hardcoat formulation with HC-1 and Des N100/0.85 PET3A/0.15 HFPO (Preparation 5.2) was diluted to 30 wt-% solids in isopropanol and coated onto the 5-mil PET backing to achieve a dry thickness of 5 microns.
  • a flow meter was used to monitor and set the flow rate of the material from a pressurized container. The flow rate was adjusted by changing the air pressure inside the sealed container which forces liquid out through a tube, through a filter, the flow meter and then through the die. The dried and cured film was wound on a take up roll.
  • the coatings were dried in a 10-foot oven at 100 degrees Celsius, and cured with a 300-watt Fusion Systems H bulb at 100, 75, 50, and 25% power.
  • the coating shown in Table 12 below was evaluated in a series of tests. The sand test was run for 15 minutes at 300 rpm. The Steel Wool Test was run checking for damage to the coating at 100, 250, 500, 750, and 1000 cycles. The results are summarized in Table 12. Contact angles were also run on selected samples before and after testing and these results are shown in Table 13. TABLE 12 (Preparation Steel Wool Taber testing Wt.
  • UV Chips Taber testing Change in haze from HC-1 in Weight % dose % Ink without % haze after initial value in % coating in coating power repellency scratches
  • 500 cycles after 500 cycles 99.27 0.73 100 0 1000 10.83 10.51 99.27 0.73 75 0 1000 8.38 8.04 99.27 0.73 50 0 1000 11.05 10.62 99.27 0.73 25 0 1000 8.35 8.04
  • the present invention provides fluorocarbon- and urethane-acrylate-containing additives that can be used in coating compositions to provide coating layers having high surface energies and smoothness.
  • fluorocarbon- and urethane-acrylate-containing additives are preferably introduced to conventional hard coating materials and cured to form optical hard coating layers having enhanced stain and ink repellency properties, adequate smoothness, and improved durability. Further, optical hard coatings having these additives do not need compatibilizers designed to enhance the compatibility between a fluoropolymer additive and the conventional hard coat material.
  • a transparent polyethylene terephthalate (PET) film obtained from e.i. duPont de Nemours and Company, Wilmington, Del. under the trade designation “Melinex 618” having a thickness of 5.0 mils and a primed surface.
  • a hardcoat composition substantially the same as Example 3 of U.S. Pat. No. 6,299,799 (S-1) was coated onto the primed surface with a metered, precision die coating process. The hardcoat was diluted in IPA to 30 wt-% solids and coated onto the 5-mil PET backing to achieve a dry thickness of 5 microns.
  • a flow meter was used to monitor and set the flow rate of the material from a pressurized container. The flow rate was adjusted by changing the air pressure inside the sealed container which forces liquid out through a tube, through a filter, the flow meter and then through the die. The dried and cured film was wound on a take up roll and used as the input backing for the coating solutions described below.
  • the hardcoat coating and drying parameters were as follows: Coating width: 6′′ (15 cm) Web Speed: 30 feet (9.1 m) per minute Solution % Solids: 30.2% Filter: 2.5 micron absolute Pressure Pot: 1.5 gallon capacity (5.7 l) Flow rate: 35 g/min Wet Coating Thickness: 24.9 microns Dry Coating Thickness: 4.9 microns Conventional Oven Temps: Zone 1 - 140° F. (60° C.) Zone 2 - 160° F. (53° C.) Zone 3 - 180° F. (82° C.) Each zone was 10 ft (3 m) in length.
  • the coating compositions of the surface layer were coated onto the hardcoat layer of either the first or the second substrate using a precision, metered die coater.
  • a syringe pump was used to meter the solution into the die.
  • the solutions were diluted with MEK to a concentration of 1% and coated onto the hardcoat layer to achieve a dry thickness of 60 nm.

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US11/087,413 US20060216524A1 (en) 2005-03-23 2005-03-23 Perfluoropolyether urethane additives having (meth)acryl groups and hard coats
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JP2008503117A JP5118017B2 (ja) 2005-03-23 2006-03-22 （メタ）アクリル基を有するパーフルオロポリエーテルウレタン添加剤およびハードコート
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US20130261280A1 (en) 2013-10-03
US8147966B2 (en) 2012-04-03
CN101146840B (zh) 2011-06-15
US7718264B2 (en) 2010-05-18
WO2006102383A1 (en) 2006-09-28
KR20070114190A (ko) 2007-11-29
EP1866355B1 (en) 2017-08-23
TW200639422A (en) 2006-11-16
US20120142883A1 (en) 2012-06-07
TWI412779B (zh) 2013-10-21
US8729211B2 (en) 2014-05-20
EP1866355A1 (en) 2007-12-19
US20100160595A1 (en) 2010-06-24
JP5118017B2 (ja) 2013-01-16
CN101146840A (zh) 2008-03-19
JP2008538195A (ja) 2008-10-16
US20060216500A1 (en) 2006-09-28
KR101397831B1 (ko) 2014-05-20
US20140221689A1 (en) 2014-08-07
KR20130063551A (ko) 2013-06-14
US8981151B2 (en) 2015-03-17
US8476398B2 (en) 2013-07-02

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