text:
|Publication number
|Publication type
|Application number
|Publication date
|31 Jul 2003
|Filing date
|30 Jan 2002
|Priority date
|30 Jan 2002
|Also published as
|Publication number
|William Kauffman, Gary Sigel
|Original Assignee
|Kauffman William J., Sigel Gary A.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (5), Referenced by (14), Classifications (16), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
[0001] The present invention relates generally to composite wear layers for surface coverings. In particular, the invention relates to a composite wear layer for a surface covering, composite comprises a polyethylene terephthalate (PET) wear layer adhered to an organic/inorganic top coat layer.
[0002] The flooring industry has been working to develop wear layer systems and flooring products incorporating these systems which provide excellent gloss retention & scratch resistance. For non-residential (commercial) flooring applications such as use in schools, hospitals, stores, etc. wherein the composite wear layer must also provide excellent color stability over the lifetime of the product due to exposure to light and as well as excellent stain resistance from foot traffic conditions. Additionally, the composite wear layer must also be compatible with maintenance materials that can be applied after some wearing of the composite wear layer occurs.
[0003] U.S. Pat. No. 5,120,811, the contents of which are hereby incorporated by reference, discloses using organic/inorganic (O/I) top coat layers which provide stain and gloss protection when applied over a clear, protective layer. However, the '811 patent does not describe composites incorporating the organic/inorganic top coat layer with a composite wear layer so that it can be used in commercial flooring applications as well as residential applications.
[0004] Current compositions and methods fail to provide top coat layers, and flooring products incorporating the top coat layers, which fully satisfy the foregoing criteria. Accordingly, a need exists for such flooring.
[0005] Composite wear layers that comprise a polyethylene terephthalate wear layer adhered to an organic/inorganic top coat layer, and surface coverings and surface covering components comprising the wear layers, are disclosed. The organic/inorganic top coat layer is formed from a top coat formulation which includes a coupling agent. The coupling agent is a molecule which includes an organic polymerizable moiety such as epoxy, acrylate and the like, as well as an inorganic polymerizable moiety such as a silanol. Top coat layers formed from the top coat formulation have both organic and inorganic character. Although not limited to these thickness ranges, the wear layer is typically in the range of about 1-20 mils thickness, and the top coat layer is typically in the range of about 2 microns to about 0.5 mils thickness.
[0006] The composite wear layers can be included in surface coverings or surface covering components, such as floor and wall coverings. The surface coverings can include additional layers, for example, a substrate, a design layer, a foam layer and the like, directly or indirectly underlying the wear layer. Ideally, any layer directly underlying the polyethylene terephthalate wear layer adheres well to the wear layer.
[0007] In some embodiments, an adhesion promoter/binder is included to better adhere the polyethylene terephthalate wear layer to the organic/inorganic top coat layer. Adhesion promoters are well known to those of skill in the art, and any adhesion promoter that adequately adheres the top coat layer to the wear layer can be used. In some embodiments, hard particles, for example, aluminum oxide particles, are included in the top coat layer.
[0008] The present invention, and embodiments thereof, are described in more detail below. Although the present invention has been described with reference to certain embodiments, other embodiments may achieve similar results and advantages. Variations and modifications of the present invention will be apparent to one skilled in the art and the disclosure herein is intended to cover all such modifications and equivalents.
[0009]FIGS. 1 and 2 are cross-sectional views of two embodiments of the floor product described herein.
[0010] The present invention provides a solution to the problem of providing top coat layers and surface coverings with excellent gloss retention and scratch resistance, as well as excellent light stability and stain resistance. The solution is in the form of composite wear/top coat layers, where the wear layer is a polyethylene terephthalate (PET) film and the top coat layer is an organic/inorganic polymer, where there is adequate interlayer adhesion between the top coat and the wear layers. The composite wear/top coat layers can be included in surface coverings and surface covering components. In one embodiment, the surface covering includes a substrate, a PET wear layer and an organic/inorganic top coat layer adhered to the PET layer.
[0011] The present invention advances building and flooring materials art by providing a hard wear surface with excellent light stability, stain resistance and gloss protection which can be bonded over a PET wear layer. Since these transparent polymer/glass (organic/inorganic) compositions can be applied over clear, protective layers, there can be a wide range of applications for a wear surface which will not detract from the appearance of the support or surface being protected.
[0012] The inorganic/organic hybrids have advantages in that they can be applied as relatively thin coatings (about 0.1-0.5 mils), require modest cure energy, and exhibit outstanding performance as wear surfaces in flooring applications. Coating thicknesses of about 2-4 microns have proven to be especially outstanding in physical property tests when applied over flooring substrates. The top coat layers are typically very hard, with MOHS hardness ratings of about 1.75-4. While the hardness is typically less than that of ceramic surfaces, the hardness tends to be higher than normal "hard" polymers such as polymethyl methacrylate (PMMA), which has a MOHS hardness of 1.50. Top coat layers which are between about 13 microns and about 2 microns thick can have stain resistance and wear retention which rivals ceramic tile.
[0013] It is important that in surface coverings and surface covering components including the wear layer and a substrate layer and/or a top coat layer, there is adequate interlayer adhesion to the underlying substrate layer and/or overlying top coat layer. As used herein, the organic/inorganic top coat layer is adequately adhered to the PET wear layer when the composite 1) passes cross hatch adhesion, a standard test—ASTM D-3359, and 2) the top coat layer does not release from the wear layer when abraded, i.e., when walked upon and scratched as described in U.S. Pat. Nos. 5,843,576; 5,663,003; and 5,188,876.
[0014] Polyethylene Terephthalate (PET)
[0015] Polyethylene terephthalate is a well known polymer. When used to form the composite layers described herein, it is typically applied in the form of a film, optionally coated with an adhesion promoter to promote adhesion to a substrate and/or to the organic/inorganic top coat layer. Suitable PET films can be obtained from several sources which include Mitubishi Polyester Films LLC, and Dupont Teijin Films. Additionally, PET copolymer films can also be used, such as PETG. Copolymer films can be used as long as the majority of the film composition comprises PET units. These films can be used in thicknesses of about 1 to 20 mils and should be sufficiently transparent to see the design and color of the flooring substrate below. Suitable PET films which have been evaluated include Melinex 617/500, Melinex 725/500 and Melinex 582/400) (all from Dupont Teijin Films), where the 500 and 400 relate to different thicknesses of the PET film (5 and 4 mils respectively), and the 617, 725 and 582 relate to relate to the adhesion promoter used.
[0016] Adhesion Promoters
[0017] In some embodiments, no adhesion promoter is required to adhere the PET wear layer to the organic/inorganic top coat layer. While not wishing to be bound by a particular theory, it is believed that residual reactive functional groups on the PET wear layer form can form bonds with the organic/inorganic top coat layer as the top coat layer is cured (i.e., polymerized). However, in some embodiments, it may be advisable to use an adhesion promoter to provide adequate interlayer adhesion between the wear layer and the top coat layer.
[0018] Any adhesion promoter commonly used to adhere top coat layers and wear layers can be used. Such adhesion promoters are well known to those of skill in the art and need not be discussed in depth here. DUPONT TEIJIN FILM's 725, 582, 6445 and 617 primers are examples of acceptable primers that can be used depending upon the organic/inorganic top coating composition. Additionally, primers may also be used on the other side of the PET film to improve adhesion to the flooring substrate.
[0019] Top Coat Formulation
[0020] The top coat formulation includes at least a coupling agent as defined herein, and can include an organic polymerizable monomer and/or oligomer, an inorganic polymerizable monomer, an appropriate solvent (typically an alcoholic solvent, such as methanol, ethanol, isopropyl alcohol, propyl alcohol, and mixtures thereof.), and a polymerization initiator, for example, a photoinitiator. The formulation can also include hard particles, nanoparticles, surfactants, suspending and wetting agents, defoamers, etc., and other components typically found in top coat layers. Other polymerization initiators can be used independently or in combination with photoinitiators. These can include thermally-generated free radical initiators such as peroxides, peresters, etc., as well as cationic or anionic catalysts which can polymerize the organic moiety of the coupling agent and/or the organic polymerizable monomer. Additionally, compositions that can be cured by e-beam can be formulated without the need for initiators.
[0021] The top coat formulation can also include monomers with organic polymerizable groups, for example, reactive diluents such as (meth)acrylates, epoxy resins, vinyl ethers, and the like. When these monomers are polymerized, they become incorporated into the organic/inorganic layer along with the coupling agent.
[0022] The formulations can contain four components: (1) a poly alkyl metal oxide, e.g. tetraalkylorthosilicate (or tetraalkoxysilane), a hydrolyzed version thereof and/or a partially hydrolyzed version thereof, (2) a metal alkoxide coupling agent, a hydrolyzed version thereof and/or a partially hydrolyzed version thereof, (3) an organic functional group-containing (for example, epoxy and/or olefin-containing) polymerizable monomer and appropriate polymerization initiator, and, optionally, (4) a surfactant, for example, a nonionic surfactant such as a silicone surfactant. Poly metal oxides have the formula M(OR)n, where R is, independently, an alkyl group, and where alkyl is a straight, branched or cyclic alkyl group, typically with between 1 and 10 carbon atoms, and n is equal or greater than 3.
[0023] The top coat layer can be prepared from the formulation using virtually any thin film application method, dried and cured. The resulting hybrid film includes a chemically bonded metal oxide phase and polymer phase. Examples of compositions and methods for forming an organic/inorganic top coat layer are described, for example, in U.S. Pat. No. 5,120,811 to Glotfelter et al., the contents of which are hereby incorporated by reference in their entirety. Additionally, other examples of organic/inorganic top coat compositions include those types described in U.S. Pat. Nos. 5,679,458; 5,647,941; 5,233,006; 5399,738; 5,414,093; 5,674,964; 5,559,163; 4,644,077; 5,559,163; and 5,023,140, the contents of which are hereby incorporated by reference in their entirety.
[0024] In one embodiment, the top coat formulation includes:
[0025] (a) an acid hydrolyzed tetraalkyl orthosilicate;
[0026] (b) an acid hydrolyzed silane-containing coupling agent;
[0027] (c) a difunctional organic-functional monomer with one or more olefinic and/or epoxy groups; and
[0028] (d) a photoinitiator.
[0029] One example of a composition of this type is:
[0030] (a) about 10 to about 70% of an acid-catalyzed hydrolysis product of at least one silicate selected from tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS) and tetrapropylorthosilicate (TPOS);
[0031] (b) about 1 to about 70% acid-catalyzed epoxy/silane coupling agent;
[0032] (c) about 1 to about 70% of a difunctional, cycloaliphatic epoxy monomer having at least one cyclohexene oxide functionality;
[0033] (d) about 0.5 to about 10% of an photoinitiator capable of initiating ring-opening, cationic photopolymerization of (c); and
[0034] (e) about 0.1 to about 1% of a surfactant, for example, a poly(dimethylsiloxane) surfactant.
[0035] The individual components of the top coat formulation are discussed in more detail below.
[0036] Coupling Agent
[0037] The coupling agent includes one or more organic polymerizable moieties and one or more inorganic polymerizable moieties. The coupling agent can include, for example, two metal alkoxide moieties (upon acid hydrolysis) and two organic moieties. Additionally, the coupling agent can include three metal alkoxide moieties and one organic moiety. The hydrolysis product of the metal alkoxides polymerize to provide the top coat layer with inorganic character, and the organic polymerizable moieties can be polymerized to provide the top coat layer with organic character. Examples of metal alkoxide moieties include aluminum alkoxide, zirconium alkoxide, silicon alkoxide and titanium alkoxide moieties. The coupling agents can be dialkoxysilanes, trialkoxysilanes, and the like (and hydrolyzed or partially hydrolyzed versions thereof), provided they also include the organic polymerizable moieties.
[0038] The coupling agents can be derived from a number of readily available multi-functional organic compounds (i.e., compounds with functional groups, such as hydroxy, thiol, amine, carboxy, isocyanato, epoxy, (meth)acrylate, and the like). It is important that these functional groups can either polymerize/react with each other or polymerize/react with the polymerizable organic monomer which may be present in the formulation.
[0039] There are a number of commercially available silane coupling agents with polymerizable functional groups. Examples include acrylates, methacrylates and epoxides which contain silanes. Examples of epoxy groups include glycidyl ether and cycloaliphatic oxides. One example of an epoxy silane coupling agent is 3-glycidoxypropyltrimethoxy silane.
[0040] Inorganic Polymerizable Monomer
[0041] The inorganic polymerizable monomer is any inorganic moiety which can be polymerized to form an inorganic polymer. As used herein, an inorganic polymerizable moiety is a polymerizable group which, when polymerized, forms an inorganic polymer such as a glass. When present on the coupling agent, the moiety incorporates the coupling agent into a glass layer and/or forms a glass layer.
[0042] Silanols are an example of a metal oxide inorganic polymerizable moiety. Other metal alkoxides can be incorporated into glass layers and are also considered to be inorganic polymerizable moieties. Examples include tetraalkylsiloxanes, which can be partially and/or totally hydrolyzed, and mixtures of tetraalkylsiloxanes and partially and/or totally hydrolyzed versions thereof. Examples of suitable tetraalkoxy silanes include tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS) and tetrapropylorthosilicate (TPOS), which, upon acid hydrolysis, become incorporated into the organic/inorganic layer along with the coupling agent.
[0043] Triethylborate (TEB) or boric acid may be substituted for the TMOS, TEOS or TPOS in amounts from 0.25 to 1.5% by weight of TMOS, TEOS or TPOS in order to increase the useful lifetime of the coating solution. Other metal alkoxides can be used to vary the properties of the wear surface protective coating as long as they are compatible with the sol-gel process.
[0044] Basically, an alkyl-O-silane group is converted to an Si—O—H group by acid or base hydrolysis, and the Si—O—H groups polymerize to form Si—O—Si linkages. Each silicon atom in the polymer includes at least one oxygen bond, and can include two, three or four oxygen bonds. Various metal alkoxides can also react with and become incorporated in the inorganic polymer. The coupling agents can cross link into the polymer if they include at least two such groups and can be incorporated into the polymer network if they include at least one such group.
[0045] Additionally, colloidal metal oxide sols such as silica sols can be used in combination with coupling agents to make organic/inorganic top coatings. Examples include those described in U.S. Pat. Nos. 4,644,077 and 5,559,163, the contents of which are hereby incorporated by reference in their entirety.
[0046] Organic Polymerizable Monomer/Oligomer
[0047] Organic polymerizable monomers are well known to those of skill in the art, and include an organic polymerizable moiety, for example, an olefinic group, an epoxy group, and the like. When the polymerizable moieties are polymerized, they form an organic polymer. Similar moieties in the coupling agent incorporate the coupling agent into and/or form an organic polymer layer. Olefinic groups include vinyl ethers, vinyl, allyl, (meth)acrylate, acetylenic, etc.
[0048] As used herein, the distinction between monomers and oligomers is that oligomers tend to include a plurality, typically more than about 2 and less than about 100, repeating units.
[0049] In one embodiment, the organic polymerizable monomer and/or oligomer includes one or more reactive functional groups which polymerize under similar polymerization conditions as the polymerizable organic groups on the coupling agent. In this embodiment, the monomer and/or oligomer can react with the coupling agent while the organic portion of the organic/inorganic top coat layer is being formed. However, in another embodiment, the organic reactive functional groups in the coupling agent and the monomer and/or oligomer can polymerize under different reaction conditions. An example of this is where an epoxy group is present in the coupling agent and the monomer includes (meth)acrylate groups.
[0050] Examples of suitable epoxy monomers include ERL-4221 (Union Carbide), also known as CY-179 (Ciba-Geigy), 3,4-epoxycyclohexyl-3,4-epoxycyclohexane carboxylate, ERL-4299 (Union Carbide), also known as CY-178 (Ciba Geigy)-Bis(3,4-epoxy-6-methyl cyclohexyl) adipate, ERL-4201 (Union Carbide)-3,4-epoxy-6-methyl cyclohexanmethyl-3,4-epoxy-6-methylcyclohexane carboxylate, ERL-4206 (Union Carbide), also known as RD-4 (Ciba Geigy)-vinylcyclohexenedioxide, and DECO (Aldrich)-1,2,5,6-diepoxycyclooctane. A particularly useful epoxide is ERL-4221 available from Union Carbide.
[0051] Vinyl monomers such as triethylene glycol divinyl ether can also provide excellent gloss protection and stain resistance equivalent to the epoxy monomers. Acrylate or vinyl monomers such as described in U.S. Pat. Nos. 2,760,863; 2,791,504; 2,927,022; 3,261,686; or 3,380,831, the contents of which are hereby incorporated by reference, can be used solely or in combination with epoxy monomers depending on the degree of hardness desired for the protective coating.
[0052] Initiators
[0053] Photoinitiators
[0054] Mixtures of monomers may necessitate having mixtures of photoinitiators for both cationic and free radical types of polymerization. Free radical photoinitiators such as benzoin ethers, benzophenone and the like are well known to those of skill in the art. For cationic polymerization of epoxy and other such groups there are commercially available photoinitiators which produce an acid catalyst capable of initiating epoxy polymerization based on aryliodonium, arylsulfonium or aryldiazonium compounds. These include diphenyliodonium hexafluorophosphate and bissulfide-bis-hexafluorophosphate.
[0055] Others
[0056] Other initiators can be employed to react the organic moieties of the coupling agent and organic monomer materials. These can include well known thermal initiators that initiate free radical polymerization, or other catalysts for cationic or anionic polymerization/reaction of the coupling agent moiety with the organic monomer, or the polymerization of the coupling agent and organic monomer. If the organic moieties are cross-linked via e-beam radiation, then no initiator may be required. The important factor is that the coupling agent is chemically reacted into both organic and inorganic polymer networks.
[0057] Surfactants
[0058] A surfactant can be conveniently employed in the coating composition. Suitable surfactants include: Triton� X-100 from Rohm and Haas, Surfynol 104-E from Air Products, Aerosol OT from American Cyanamid, FC-120 from 3M, and Tergitol NP-27 from Union Carbide. Examples include silicone oil surfactants such as poly(dimethylsiloxane), which can provide the top coat layer with superior stain and gloss protection.
[0059] Substrates
[0060] Substrates for flooring are well known in the art and include a solid, filled or unfilled polymeric layer or composite, a solid layer composite comprising a fibrous web saturated with polymeric binder, and porous fibrous layers such as beater saturated felts, and non-woven fabric materials.
[0061] In one embodiment, the substrate comprises a PVC plastisol. In another embodiment, the substrate is a porous material. In an additional embodiment, the substrate is a felt.
[0062] Flooring Structures
[0063] Flooring structures are also well known in the art and can include single or multiple layers in the form of tile or sheet. They can also include solid and foam layers. They can be made from melt processing techniques, and in the case of PVC plastisols, wet coating processing techniques. Flooring structures also mean any single or multiple layer typically used in flooring products. The flooring structures can include one or more of a calendered polyvinyl chloride (PVC) layer, a foamable PVC plastisol layer and a design layer.
[0064] In one embodiment, the floor product includes a substrate of porous felt material, a PET wear layer, an adhesion promoter overlying the PET wear layer (i.e., a "primed" PET wear layer), and an organic/inorganic top coat layer overlying the primed PET wear layer. The product can also include a flooring structure in contact with the felt layer, the flooring structure including a calendered PVC basecoat in direct contact with the felt layer, a foamable PVC plastisol in contact with the basecoat, and a design layer in contact with the foamable PVC plastisol layer.
[0065] In another embodiment, the floor product comprises a melt processed, filled resilient tile flooring structure, a PET wear layer, an adhesion promoter on one surface of the PET wear layer in contact with the tile flooring structure, and additional adhesion promoter on the second surface of the PET wear layer, and an organic/inorganic top coat layer overlying the second surface of the PET wear layer. The floor product can be in the form of a tile or sheet material.
[0066] Sol Gel Transformation
[0067] The term polymerization is often used in sol-gel processing to describe the transformation of the sol phase to the gel/glass phase, since glass is a polymer. However, it is probably more correct to think of the gel-to-glass conversion as an aggregation step during which discrete oxide particles of small size (typically in the range of 4 nm for acid catalyzed silicon alkoxides) form and are chemically bonded to one another. This contrasts with the molecular polymerization concept where each functional group is reacted to form either a linear or three dimensional network.
[0068] Glasses prepared from acid-catalyzed sol-gel processes form clear, hard films due to the extremely small sizes of the aggregated oxide particles. Sol-gel derived glasses can rival the performance of traditional glasses. Silicon alkoxides are by far the easiest alkoxides from which such glasses can be formed. Tetraalkoxysilanes such as tetraethylorthosilicate (TEOS) and tetramethylorthosilicate (TMOS) are readily hydrolyzed at a pH of around 2 and condense upon evaporation of solvent to give approximately 90% yield of pure silica as determined by IR (powder dried 2 hrs. at 150 C.). If the hydrolysis product is left in solution and the solution sufficiently concentrated, a gel will form in 24-72 hours. Optionally, glasses can also be obtained by basic catalysis of silicon alkoxides. The sol gel chemistry described herein applies whether a coupling agent alone is used to prepare the sol gel glass, or whether other inorganic polymerizable moieties are present.
[0069] The alkoxysilanes in the coupling agent present in the top coat formulation can be hydrolyzed by adding water and an acid catalyst. The amount of water added determines the degree of hydrolysis in the final product. The coupling agent can include a certain degree of hydrolyzed siloxanes (i.e., siloxide groups).
[0070] The sol-gel processing conditions can be controlled to optimize various physical properties of the resulting glass. For example, one can control the particle size in the gels, which can optimize the optical clarity. The toughness of the glass can be varied, for example, by using appropriate combinations of borosilicate, zirconia/silica and other metal alkoxides. The organic monomers can be selected to provide hybrid inorganic/organic materials with desired properties.
[0071] Generally, any of the metal alkoxides based upon Al, Zr, Si, or Ti will readily form oxides after hydrolysis and solvent removal. Typically, the acid hydrolysis/condensation reactions of metal alkoxides are run using a stoichiometric amount of water and at a pH of about 2. This procedure works well for the silicon and aluminum alkoxides but other alkoxides such as zirconium and titanium can require a very low pH or slow hydrolysis reactions to maintain a reasonable stability.
[0072] Methods of Forming the Top Coat Layer
[0073] The general scheme for producing a polymer/glass hybrid is: (1) optionally preparing a hydrolyzed metal alkoxide in solution, (2) preparing a hydrolyzed coupling agent (i.e. bifunctional or polyfunctional including at least one trialkoxysilane functionality and at least one polymerizable organic functionality) in solution, and after mixing the above, (3) optionally including a polymerizable monomer, (4) including an appropriate initiator, (5) including a surfactant if desired, (6) coating on a clear, protective layer (7) drying, and polymerizing the organic and inorganic networks. In one embodiment the polymerization of the organic network is achieved by exposing the dried top coat layer to a source of actinic radiation, for example, ultraviolet or e-beam energy.
[0074] In those embodiments where the top coat layer includes inorganic metal oxide polymerizable moieties such as tetraalkoxysilanes and organic polymerizable moieties in addition to the coupling agent, the top coat layer can be formed by:
[0075] (a) producing a hydrolyzed solution comprising:
[0076] (i) a metal alkoxide;
[0077] (ii) a coupling agent having at least one reactive organic substituent;
[0078] (b) adding an organic monomer to the hydrolyzed solution, along with a suitable polymerization initiator;
[0079] (c) applying the composition in a dry thickness ranging between about 1 and about 13 microns over a clear, polyethylene terephthalate wear layer;
[0080] (d) drying the composition to remove solvent; and
[0081] (e) curing the composition.
[0082] The coating may be cured by any suitable means including heat or ultraviolet light irradiation that is compatible with the reactive groups in the top coat formulation and/or the polymerization initiator.
[0083] In another embodiment the inorganic portion of the organic/inorganic composition results from only the presence of the coupling agent.
[0084] In one embodiment the PET wear layer overlies a substrate such as a tile, sheet flooring, table top, panel, or similar article of manufacturer before step c above is carried out. In another embodiment, the PET inorganic/organic composite film is laminated to a substrate after it has been formed.
[0085] In some embodiments, the inorganic polymerizable and/or organic polymerizable monomers can be absent from the coating composition. In these embodiments, the above steps can take place, without the presence of these components.
[0086] In one embodiment, the organic/inorganic layer is formed by applying a top coat formulation including the acid-catalyzed hydrolysis product of at least one silicate (i.e., tetramethylorthosilicate, tetraethylorthosilicate or tetrapropylorthosilicate), the acid-catalyzed hydrolysis product of an epoxy/silane coupling agent; and a suitable organic monomer, to the PET wear layer. The inorganic portion of the organic/inorganic layer is cured by removing the solvent and heating the top coat layer. The organic portion of the organic/inorganic layer is cured by polymerizing the organic monomer. If the organic monomer is an olefin-containing material, the polymerization can involve exposure to actinic radiation, optionally in the presence of a photoinitiator. If the organic monomer is an epoxy group, polymerization can be effected using any conventional initiator known to initiate polymerization of epoxy groups, including initiators including thiol and/or hydroxy groups, as well as cationic catalysis which can include cationic photoinititators.
[0087] Ideally, the organic functionality of the coupling agent and the organic functionality of the monomer are reactively compatible.
[0088] Methods for Improving Interlayer Adhesion
[0089] To function as a flooring material, the PET/(organic/inorganic) composite material must adhere to the substrate. Also, the PET wear layer must adhere to the organic/inorganic top coat layer. Various adhesion primers and surface treatments can be used to gain adhesion, if required, and are selected based upon the substrate and flooring material. These can include multilayer extruded or laminated PET films, or PET films with adhesion primer coating layers. PET film with adhesion promoters are well known and commercially available. One preferred PET supplier is DuPont Teijin Films who offer a wide variety of adhesion promoters.
[0090] Methods of Applying the Composite Wear/Top Coat Layers
[0091] The wear/top coat layer can be applied by laminating a PET film to floor covering component (including, for example, a substrate, foam layer and design layer). The top coat formulation can be subsequently applied by any convention means of application, the solvent evaporated to effect the inorganic polymerization, and then the organic component subjected to appropriate polymerization conditions, for example, UV cure.
[0092] In another embodiment, the method involves moving a substrate using rolls adapted to carry the substrate, moving a PET film using rolls adapted to carry the PET film, wherein the substrate and the PET film are heated and laminated together. The temperature, dwell time, and the pressure applied to the substrate/PET film composite are adjusted to provide adhesion between the two layers after cooling. The interlayer adhesion can be improved, if necessary by applying an adhesion promoter to the substrate or the PET film before the PET film is applied.
[0093] An adhesion promoter can be applied to the PET film layer, if necessary, to promote adhesion to the organic/inorganic layer. Then, the top coat formulation can be applied and cured.
[0094] The substrate and the PET barrier layer film can be pre-heated before contacting each other, for example, using a radiator disposed adjacent to the path the substrate travels before it contacts the PET film. The PET film itself can also be preheated using a radiator disposed adjacent to a path the PET film travels before it initially contacts the substrate.
[0095] In one embodiment, a PET wear layer film is laminated to a flooring structure or substrate, the top coat layer applied over the PET wear layer to form a floor covering component, or a completed flooring covering. It is important is that the PET film layer have adequate adhesion to both the flooring structure/substrate and the top coat layer.
[0096] In another embodiment, the PET film is coated with the inorganic/organic top coat layer and the composite film laminated to a flooring structure or substrate.
[0097] Referring to now to FIG. 1, showing a schematic drawing of a particular embodiment of the floor covering described herein, a typical flooring structure 102 is illustrated that includes a felt substrate 104, a calendered PVC basecoat 106, a foamable PVC plastisol 108, an optional clear PVC layer 109, a polyethylene terephthalate (PET) wear layer 110, and an organic/inorganic layer 112 adhered to the PET wear layer. The PET wear layer 110 can include and an adhesion promoter on one or both surfaces.
[0098] Referring to FIG. 2, showing a schematic drawing of a particular tile embodiment of the floor covering described herein, a typical tile structure is illustrated which includes a melt processed, calendared filled polymer tile layer such as Armstrong's Excellon Tile (100), a polyethylene terephthalate (PET) wear layer 110, and an organic/inorganic layer 112 adhered to the PET wear layer. The PET wear layer can include an adhesion promoter on one or both surfaces.
[0099] The following examples are intended to illustrate the invention and it is thought variations will occur to those skilled in the art. Accordingly, it is intended that the scope of the invention should be limited only by the appended claims.
[0100] An organically modified sol-gel formulation (O/I) as prepared in a similar fashion to that described in Example 1 of U.S. Pat. No. 5,120,811 was sprayed onto Dupont Teijin film (identified as Melinex 617/500) that was pretreated with a proprietary acrylic polymer and taped to a tile blank. The treated film taped to a tile carrier was passed through an infrared oven (Glenro) to remove solvent. The exit surface temperature of the coated film/carrier was 137� F. This structure was subsequently UV cured at a dose of 1.1 Joules/cm2 to give good cure. Coating thickness is estimated to be between 2-6 μms based on co-weights.
[0101] Using the flat bed press Wabash, the top platumin was heat to 310� F. and bottom left at 90� F. A sandwich was prepared in which the PET-organic/inorganic coated film sample was placed on a tile blank. A smooth chrome plate placed on top of the coated film/tile and silicon pad on top of chrome plate. This structure was placed on top silicon belt piece on top of a steel plate. The entire sandwich was placed in the Wabash press and pressed at 20 tons for 3 to 5 minutes. The press was opened and the sample allowed to cool prior to removal.
[0102] Table 1 contains comparative results for stain and gloss protection for the invention versus uncoated tile.
TABLE 1 30 Min. % gloss 60 Min. % gloss 90 Min. % gloss Test Sample retained retained retained Control 46 27 17 Melinex 617/500 Invention 98 85 63
[0103] Coatings were prepared as in Example 1 except that pretreated double side Melinex 582/400 film was used.
30 Min. % gloss 60 Min. % gloss 90 Min. % gloss Test Sample retained retained retained Melinex 99 94 86 582/400 invention
[0104] Further benefit of this invention can be realized by the addition of micron size aluminum oxide to the thin hard coating. Coatings were prepared as in Example 1 except that aluminum oxide having an average size of 0.2-0.4 microns (Bawkowski E600) was added (10 gms/Qt Example 1) and Melinex 725/500 was used. Tile samples were prepared in an identical fashion to that described in Example 1.
[0105] Table 3 contains comparative results for stain and gloss protection for the invention versus uncoated tile.
TABLE 3 30 Min. % gloss 60 Min. % gloss 90 Min. % gloss Test Sample retained retained retained Control 51 31 21 Melinex 725/500 Invention 98 90 77 Example 2
[0106] Samples of O/I (organic/inorganic) coated and uncoated Melinex films on tile were prepared as per Example 1, and subjected to Light Stability testing using ASTM F1515-98. Data was obtained after 400 hours of exposure and is listed in Table 1.
TABLE 1 Xenon Test ASTM F1515-98 Delta b Cool White Fluorescent T-626457 Tile Sample Xenon exposure (hours) 400 1 Melinex 617/500 Coated 1.262 5 Melinex 617/500/ 1.134 2 Melinex 582/400 Coated 0.704 6 Melinex 582/400 1.311 3 Melinex 725/500 Coated 1.925 7 Melinex 725/500 1.276 4 Melinex 6445/500 Coated 2.915 8 Melinex 6445/500 2.754
[0107] All samples showed little discoloration with Delta b values below 3 units.
[0108] While specific embodiments have been set forth as illustrated and described above, it is recognized that variations may be made with respect to disclosed embodiments. Therefore, while the invention has been disclosed in various forms only, it will be obvious to those skilled in the art that many additions, deletions and modifications can be made without departing from the spirit and scope and no undue limits should be imposed except as set forth in the following claims.
|Cited Patent
|Filing date
|Publication date
|4 May 1936
|28 Mar 1939
|American Box Board Co
|Title not available
|Title not available
|Title not available
|Title not available
|Citing Patent
|Filing date
|Publication date
|7 Jan 2003
|18 Oct 2005
|Aps Laboratory
|Metal oxide sols as nanoscale additives for polymers
|7 Jul 2004
|26 Dec 2006
|Aps Laboratory
|Metal oxide sols as nanoscale additives for polymers
|11 Aug 2005
|7 Aug 2007
|Aps Laboratory
|Tractable silica sols and nanocomposites therefrom
|22 Dec 2004
|4 Sep 2007
|Aps Laboratory
|Preparation of metal chalcogenide nanoparticles and nanocomposites therefrom
|2 Mar 2005
|12 Aug 2008
|Aps Laboratory
|Metal phosphate sols, metal nanoparticles, metal-chalcogenide nanoparticles, and nanocomposites made therefrom
|12 Apr 2006
|12 Jan 2010
|Aps Laboratory
|Tractable metal oxide sols and nanocomposites therefrom
|30 Jun 2005
|30 Mar 2010
|Solutia Inc.
|Methods of making polymer interlayers comprising poly(cyclohexanedimethylene terephthalate-co-ethylene terephthalate) copolyester
|25 Jun 2008
|8 Mar 2011
|Solutia Inc.
|Polymer interlayers comprising blends of plasticized poly(vinyl butyral) and poly(cyclohexanedimethylene terephthalate-co-ethylene terephthalate) copolyester
|7 Jan 2003
|19 Aug 2004
|Hong-Son Ryang
|Metal oxide sols as nanoscale additives for polymers
|7 Jul 2004
|2 Dec 2004
|Hong-Son Ryang
|Metal oxide sols as nanoscale additives for polymers
|6 Nov 2003
|12 May 2005
|Parker Richard H.
|Textile products and silicone-based copolymeric coating compositions for textile products
|22 Dec 2004
|22 Jun 2006
|Aps Laboratory
|Preparation of metal chalcogenide nanoparticles and nanocomposites therefrom
|2 Mar 2005
|7 Sep 2006
|Aps Laboratory
|Metal phosphate sols, metal nanoparticles, metal-chalcogenide nanoparticles, and nanocomposites made therefrom
|7 Jan 2004
|29 Jul 2004
|Aps Lab
|Metal oxide sols as nanoscale additives for polymers
|U.S. Classification
|International Classification
|Cooperative Classification
|European Classification
|2 May 2002
Owner name: ARMSTRONG WORLD INDUSTRIES, PENNSYLVANIA
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WIMS, TEXAS. Wims was probably located thirteen miles northeast of Mount Vernon in northeastern Franklin County. In 1896 the community had a one-teacher, one-room school that served forty-two white children. A Wims post office was operated for a few months in 1901.
The following, adapted from the Chicago Manual of Style, 15th edition, is the preferred citation for this article.Cecil Harper, Jr., "WIMS, TX," Handbook of Texas Online (http://www.tshaonline.org/handbook/online/articles/hvw89), accessed October 09, 2015. Uploaded on June 15, 2010. Published by the Texas State Historical Association.
For more information about towns and counties including physical features, statistics, weather, maps and much more, visit the Town Database on TexasAlmanac.com!

subset: commoncrawl


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RIO DE JANEIRO - England's last World Cup hopes were dashed with Costa's Rica's 1-0 victory over Italy in Recife Friday.
The win puts Costa Rica into the last 16 from Group D and means Roy Hodgson's side will soon be leaving Brazil for home, exiting in the group stage for the first time in 56 years.
England travel to play Costa Rica in Belo Horizonte on Tuesday with nothing more at stake.
After 2-1 defeats to both Italy and Uruguay, England had been hoping for an Italy win to give themselves a glimmer of hope.
An Italy win over both Costa Rica and Uruguay - plus an England victory over Costa Rica - would have been needed.
But that ended with a header by Bryan Ruiz in off the underside of the bar for Costa Rica in the 44th minute.
"What have the Romans ever done for us?" joked former England international Gary Lineker on Twitter.
It is the first England have been eliminated at the group stage of the World Cup since 1958. The other group-stage exit came in 1950 - the previous time the tournament was held in Brazil.
Hodgson has meanwhile received the backing of Football Association chairman Greg Dyke who says there is no "great value" in changing the manager.
"We were not humiliated or anything like that, they were narrow defeats but it's for the football people not for me to identify why we didn't win," he said before the Costa Rica victory.
"He came to do a four year cycle leading up to the Europeans and we want him to stay and continue with that.
"It's disappointing to lose both games narrowly to both sides but there are some positives, there are a lot of young players who got blooded here who got into tournament football here."
Hodgson, 66, whose contract runs until the end of Euro 2016, said after Thursday's defeat to Uruguay that he did not feel the need to resign.
"I'm bitterly disappointed, of course, but I don't feel I need to resign, no, " he said.
"On the other hand, and if the FA think I'm not the right man to do the job, that will be their decision, and not mine.
"I've been really happy with the way the players have responded to the work we've tried to do."


text:
For several years now, the All-Star break has felt long and tedious, making us all rather anxious. When would the real games start up again in Arlington? A pennant race was just around the corner.
There's a different feeling in these parts in 2014. In fact, there's no rush at all to get on with things. The Rangers own the worst record in Major League Baseball. The All-Star break, coming on the heels of an 0-7 homestand in which the Rangers never came within two runs of winning a game, felt like the end of something.
Instead, it was more like the intermission for Les Miz. They're just now building the barricade, and there's lots of carnage to go.
So here we go again. And here are 15 reasons to keep watching the Rangers play their remaining 67 games in a lost season.
1. When they visit Toronto this weekend or New York next week, you just never know when this team might collect its second win in July.
2. Adrian Beltre is still playing his tail off, and he deserves our attention.
3. When the team comes home July 25, it's to play Oakland. This is a good chance to see the team that — not so long ago — we thought was lucky to finish ahead of Texas. The A's are 21 games ahead of the Rangers now and own the best record in baseball. That Oakland series also represents the Rangers' next chance to win their first home game in July. You don't want to see this club take an 0 for the month.
4. Yu Darvish is still Yu Darvish. No one has more 10-strikeout games in MLB the last three years. No one has a more entertaining variety of pitches. He struggled going into the break, but don't expect that to last.
5. On Aug. 11, Tampa Bay shows up. Assuming the Rays haven't dealt David Price, go see the American League strikeout leader, and remember when we used to think he could be had for the price of Martin Perez and Jurickson Profar. Where are they again?
6. You never know who might be playing first base. So far we've seen Prince Fielder, Mitch Moreland, Brad Snyder, Donnie Murphy and Carlos Pena take their shots. Apparently failed catcher J.P. Arencibia is next in line. But it's only July. Stay tuned.
7. On Aug. 15, the Angels come back to Arlington. Go there and cheer for Josh Hamilton. The booing thing isn't working. He went 8 for 17 at Globe Life Park last week. He said the boos motivate him. It's time to stop unless you just want to see him drilling pitches off the wall.
8. Two words: Jake Smolinski.
9. On Sept. 12-14, the Atlanta Braves make a rare visit to Arlington. Go see how a team that sustains winning better than any team in MLB gets it done.
10. You never know when Phil Irwin might come back.
11. There is a prize at the end of all this, just in case the losing doesn't stop. His name is Daz Cameron, a 6-1, 5-tool high school outfielder in Georgia. The first pick in the 2015 amateur draft wasn't the Rangers' target when this season began but, hey, it's out there.
12. A late summer weekend road trip to Houston isn't a bad idea. You have two choices because, in a weird bit of scheduling, the Rangers play seven games there in August. See if there's anything the Rangers can do to avoid losing their grip on the Silver Boot. Also see what it's like to have a nice, new ballpark built on the edge of downtown in a major city.
13. Assuming he doesn't get shut down because of his ankle injury, Shin-Soo Choo is worth the price of admission. I say that in part because anyone with a seven-year, $130 million contract should be worth the price of admission, but also because if he is healthy, his play and numbers should improve down the stretch. They have to, right?
14. You never know when manager Ron Washington just might blow up.
15. You never know when the next great thing, Joey Gallo, just might show up.
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Pensacola Web Design & SEO
There are 100s of graphics and website designers in Pensacola. What separates TekNek from the others? The answer is simple: marketing.
Having a website designed without marketing it, is like building a gas station in the middle of a field, WITH NO ROADS LEADING TO IT!
It is a fact that more and more people are using search engines like Google, Yahoo, and Bing instead of the old fashioned phonebook, to find what they need.


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The U.S. Travel Association today welcomed the immigration standards released by U.S. House Republicans and urged forward movement on reform.
"The House Republican immigration standards are an encouraging signal that both parties in both chambers, as well as the Administration, are ready to move forward on fixing America's broken immigration system," said Roger Dow, President and CEO of the U.S. Travel Association. "Immigration reform would strengthen U.S. security and boost economic growth, particularly in the travel sector, which supports one out of every eight American jobs and generates the third-largest trade surplus of any U.S. industry. The Senate has already passed good legislation on this issue, and we take the announcement of these principles as a sign that the House will move toward doing the same."
Dow reiterated that America's travel community strongly supports the Jobs Originated through Launching Travel (JOLT) Act, provisions of which were included in the Senate-passed immigration bill and has garnered more than 120 bipartisan supporters in the House. The Act would:
One provision alone in the JOLT Act—expanding the Visa Waiver Program—could, if extended to Argentina, Brazil, Bulgaria, Chile, Croatia, Israel, Panama, Poland, Romania and Uruguay:
The U.S. Travel Association is the national, non-profit organization representing all components of the travel industry that generates $2.0 trillion in economic output and supports 14.6 million jobs. U.S. Travel's mission is to increase travel to and within the United States.
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Pizza, Ice Cream & Games Night
Calling all grandparents & grandchildren (ages 3 - 14) – come out to the Rotino Center for an evening of fun, including pizza, ice cream and games! Cost is $7/person. Pre-registration is required.
Occurs once: Jun 27, 2014 (5:00 PM to 7:00 PM)
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Tony Rotino Center
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Ticket Price: $7
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Danny Pudi: (on showing his mother around the Community set) I could finally be like, 'See, Mom, all that stuff has paid off.' Especially because she still shows up with medical school applications.
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Dr. Feinburg is a great surgeon. Took out my sons tonsils,fixed his nose, put tube in his ear. Very proffessional & knows his business. Dr. Feinburg is quick with the visits, doesn't like to chit chat,gets down to business & gets out but he DOES know his stuff. Staff is not so great, they seem like they don't care & aren't very courteous. Wait times are long. Overall though he is a really good doctor & will fix you up right.
Was this rating useful? 0 [[ userState['ratings'][2168940].votes_count ]]
very good and useful pulled out my tonsles and is my new M.D
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Great doctor! I've been going to him for six years and I wouldn't trade him for anyone.
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Cordero, Alonso, Francisco for Kerry Wood, Chris Perez, and Chin-Soo Choo.
Trading Points:
1. Wood is making $10.5M this year and becomes a FA. Cordero has another year of making approximately $12.2M. Trade-off this year, but Cleveland has to eat another year of Cordero's contract, although it does give them a closer for the rest of this year and next. Their team payroll is currently in the $61M range, so they can handle another $2M.
2. The benefit and enticement to Cleveland is to pick up 2 good Reds prospects in Alonso and Francisco, for their rebuilding project. Both are position blocked with the Reds. Also, Yonder is guaranteed $1M next season in salary, part of his draft deal. Gives Cleveland a first baseman since they just traded for Russell Branyan, who will be a FA after the season or they can move him to third base, a position he has played in his career. They can use Francisco at 3B or try him in the OF. Or try Alonso in the OF also.
3. Wood had a terrible May racking up an ERA of 11.05 by the end of it. In June, he had 11 outings pitching 10.1 innings, giving up 4 earned runs, all on 2 HR's in 2 different games. Struck out 10 and only walked 2 in the month of June. He had 2 blown saves, 1 loss, 1 win, and 6 saves in June. He has only pitched twice in July, going 2 innings, giving up 1 hit, 2 walks, 1 K with no decisions or saves. With Cleveland being so bad, he doesn't get many opportunities. Overall, he has pitched 20 innings, given up 19 hits, 10 walks, and 18 K's for a 5.95 ERA. Since compiling a 11.05 ERA in May, he has compiled a 2.91 ERA in June and early July combined.
4. Chris Perez has an overall ERA of 2.70. In his last 15 outings (totals for June/July), he has pitched 15 innings, given up 7 hits, 3 earned runs, 1 HR, 6 walks, and 9 K's. He's a 25 year old righty. In that stretch he faced the White Sox, Nationals, Mets, Phillies, Reds, Blue Jays, Rays, Rangers, and Red Sox. Not bad teams to have success against. He's compiled a 1.80 ERA in those last 15 outings. He pitched 2 seasons for St. Louis and is in his second year with Cleveland posting a career ERA of 3.61 and a career WHIP of 1.25. Opponents are batting just .205 against him for his career. Makes the minimum and is eligible for arbitration after the season.
5. Chin-Soo Choo might be a rental as he has a Korean Military Obligation before age 30 that he might have to forego baseball for 2 years. Risky move. But he would give us that on base guy at the front of the batting order. He currently makes the minimum but is eligible for arbitration after the season. Currently batting .286 with an OBP of .390, 12 SB's (4 caught), 13 HR's, 43 RBI's, and 48 runs scored for a lousy offensive team. He just turned 28. He's a lefty. He usually bats in the 2-hole.
So Reds unload Cordero, gain a rental OFer with a good OBP and decent batting average in Choo, and replace their closer with potentially a better one who is a FA at the end of the season, freeing up $$$ on the payroll, and finally bolster the setup man part of the bullpen with Perez, who is still young and reasonably cheap.
Indians acquire 2 good prospects that give them a future first baseman, and third baseman or outfielder, a closer, but additional high salary in Cordero for one more year. They might actually want more which means you might have to give them a reliever too, to replace Perez. Doubt they'd take Masset, but I'd be willing in a heartbeat to give him up. Sick of him too. Call it a "change of scenery" move.
New Batting order:
2B Phillips
LF Choo
1B Votto
3B Rolen
RF Bruce
CF Stubbs/Heisey
SS Cabrera
C Hanigan/Hernandez


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Melbourne Central YHA is an exciting backpackers hostel in Melbourne's vibrant CBD. The hostel has an energetic backpackers bar on the ground floor and some very special private rooms with ornate balconies overlooking Flinders Street.
Hostel facilities include a tour desk for local tours, plus a high-speed YHA Connect Internet Cafe with Skype and Wi-Fi throughout the hostel, flat-screen TVs and electronic door locks.
There's free hostel activities for all guests, including walking tours of Melbourne, pub excursions and BBQs. Ask reception for more details when you check in.
The hostel has an eclectic bar (Bertha Brown) which serves tasty affordable meals, with 2-4-1 specials for YHA guests, plus coffees, cocktails and a range of local and international beers.
There is a free city circle tram that operates in the CBD with a stop directly in front of the hostel - now that's convenience!
What travellers think
Ein (Notfall) Telefon in den Privatzimmern auf dem Dach.
Fri 17 Apr 2015
I was put in a room next door to a public balcony that opened early and I was woken up several mornings by the noise. The gaps around the window frame were sufficient to blow the curtains several inches. The staff were fine, but undermanned. The public space was dark and not conducive to socialising.
Thu 19 Mar 2015


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Packers Mentor-Protégé Program Celebration
By Katie Kozak. CREATED May 28, 2013
LAMBEAU FIELD -- The Packers marked the end of the second session in their Mentor-Protégé Program today.
They held an award ceremony to recognize those involved and celebrate the program which matches new minority or female-owned businesses with mentors from well established companies in the area. Those in the program say, it gives them hope for a bright future.
"We have some exciting plans for 2013 and 14 going forward. We hope to expans several divisions that are just infants in our business," says Carol Trimberger with Door County Interior Designs.
The program is currently in its third session.
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Brett Mitchell talks with Dacia Clay.
In this episode, former Houston Symphony assistant conductor Brett Mitchell talks about just what makes John Williams' music for the Star Wars movies so special.
April 24th, 2013 11:46 AM
Brett Mitchell talks with Dacia Clay.
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drakes aim to give an experience of intimacy and welcome completely unlike any other Brighton boutique hotel. the interior mixes orientalism into a double fronted Georgian townhouse with a splash of Indochine French colonialism and a touch of decadence. the aesthetic is mirrored in the philosophy of drakes: the highest service standards combined with the comfort, subtlety and discretion today's luxury traveller expects, all delivered in a laid-back & relaxed style.
drakes has 20 bespoke designed rooms, most with superb sea-views, both to the east Brighton marina round to the west Brighton pier. all rooms are en-suite, fully air conditioned and finished to the highest standards with flat screen televisions, satellite T.V with full sky package incl sports/movies and wireless broadband connection.
smoking is not permitted anywhere in drakes or the restaurant at drakes.
the hotel is unsuitable for dogs and other pets.


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« TMS Reagents: Handle With Care! |
| But You Can't Make Them Take It? »
Posted by Derek
I've heard that Pfizer is doing something unusual with its proprietary compound collection: they're offering to let other people screen it.
Now, that's quite a step. Most companies guard their compounds pretty closely, considering them to be key assets. But I'm told that Pfizer has been meeting with several other (mostly smaller) companies, offering their (entire?) compound library as a screening resource. As I understand it, you need to come to them with a reasonably formatted HTS assay, and there's a fee in the high hundreds of thousands to run the screen.
That doesn't seem like much of a moneymaker, to be honest. The whole thing appears to me to be a way for Pfizer to strike deals with a number of other companies, since the compounds that come out of the screen will (likely as not) be covered by Pfizer's own patents. I haven't heard of how the IP issues are to be worked out in these deals, but that's the first thing that occurs to me. Anyone have more details?
Comments (17)
+ TrackBacks (0) | Category: Drug Assays
1. CMCguy on May 19, 2009 2:47 PM writes...
Harkin's back to the glory (or gory?) days of combinatorial chemistry with a twist that instead of small companies creating libraries of compounds to sell to those with HTS assays (i.e Pfizer and other big Pharma mostly) this situation is run in reverse. I do not think intent would be to make money, except perhaps to pay for some overhead required to run. Might be of value for spawning some innovation because of the constant bridging required to get (bio)assays and compounds together to produce leads but correct on IP as sure would like to see the contract in terms of ownership and other rights. Bioinformatics and Price barriers would have to be dealt with as many small companies who might have a viable assay may not be able to handle from both data and costs view although Pfizer may be selecting potential "collaborators" according to those factors. Wonder if could be a graduated system where payouts are tied to milestones (hits, candidates, tox clearance, clinical initiation etc...) as that would be a reversal of how biotech-pharma deals have been conducted.
2. You're Pfizered on May 19, 2009 3:38 PM writes...
It's brilliant, actually. You make others pay you to find new indications for your compounds.
I'd be interested to see what the contract stipulates about ownership of compounds and the data that is generated by the screens. Does Pfizer get a look-see and right of first refusal on anything that looks promising? Very interesting.
3. JC on May 19, 2009 3:49 PM writes...
Who knows maybe some of that purified garbage from the DPI collaboration will eventually find a use.
4. eurochemist on May 19, 2009 4:27 PM writes...
There are a some other (IP/confidentiality)issues with this:
1. It is hard to believe the whole of Pfizer's compound file will be screened each time owing to costs - so who does the selection of a target-focused library? Hard to imagine Pf letting its compound database out for analysis by external comp chemists .....?
2. Presumably, Pf would only release the structures of hits leaving the smaller company in the dark about negative SAR. Or does it become a 20 questions game? (did the compound library contain a pyridoquinazoline etc etc?).
It will be interesting to see how this runs.
5. milkshake on May 19, 2009 6:11 PM writes...
I think Pfizer is primarily interested in new targets and assays. And takeovers.
6. partial agonist on May 19, 2009 9:35 PM writes...
Milkshake may be on to something- you bring Pfizer a good screen, they give you a subset of their library to screen at your place, maybe with shared rights, then...
THEY set up your screen on your target with the rest (and the best?) of their compounds IN THEIR SHOP, not sharing ANYTHING!
7. viledonkey on May 20, 2009 1:18 AM writes...
I met a Pfizer person at a conference a few months ago & they did mentioned that they were thinking of doing this! They also said that they were considering offering follow-up med chem 'support' (consultancy ?).........for a fee of course!
8. Anonymous on May 20, 2009 1:49 AM writes...
Nano-dispensing technology makes that the compounds can be screened, but there isnt enough material to determine the structure, so the biotech has to go back to PFE with the screening results.
Presumably other pharmas is working on similar ideas
9. MikeyMedChem on May 20, 2009 6:20 AM writes...
My expectation would be they make a standard diverse subset available (designed by Pfizer comp chemists), maybe structure-blinded until confirmed hits are identified, and retain IP rights of the compounds themselves and anything developed via optimization, with the understanding of co-development. I suspect in certain cases, they may license compounds that hit in collaborator assays, but restrict it to specific therapeutic approaches, thereby leaving the IP field open for Pfizer for other indications. I doubt very much that they'd expect payment for the compounds, and expect that they would do internal med chem with an external collaborator if there was mutual interest in the indication. It's a brilliant idea, really - it opens the field to new approaches but makes it more likely that the chemical matter identified by these external people would be attractive for pursuit for Pfizer. It will also be a powerful enabler for the small company to (1) access a proprietary and drug-like screening set so they're not screening their target against commercial, non-proprietary libraries and (2) make inroads into a company that might provide a higher liklihood of success (read: getting to the clinic) than going it alone. I think it might also be an indication of Pfizer's realization that they don't have all the answers for fruitful drug discovery, and that more can be achieved by reaching out to others rather than playing everything so close to the vest.
10. Anonymous on May 20, 2009 6:45 AM writes...
Mikey - I completely agree. Shame they didn't do it a few years back
11. Anonymous on May 20, 2009 7:52 AM writes...
So I'm curious to know how the acquisition of Wyeth plays into this novel concept. Wyeth has a decent pipeline and a decent screening facility...does PF layoff the entire Wyeth site or do they keep portions of it??
12. Don B. on May 20, 2009 8:42 AM writes...
I would suspect that it would not take much compound to determine the ~ structure. But agree that acquistion would happen with anything that pfizer thinks is really good.
With Wyeth, I expect the med. chem. to go, the vaccines to stay, and the veternary health being up for a "decision". Of course, the Feds may force disposal of the latter overlap.
13. Joerg Kurt Wegner on May 20, 2009 3:38 PM writes...
I am curious to see any announcements on this. For now I share the IP concerns.
14. ex-Pfizerite on May 20, 2009 9:25 PM writes...
You need to remember that Pfizer has abandoned the patent rights to a large number of compounds that either washed out of the clinic or never made it into the clinic. Additionally, a screening hit is just the first step in finding an active, drug able compound for the clinic.
15. Jose on May 20, 2009 11:46 PM writes...
Presumably the structures will be blind, or covered by layers of previous patents. PFE gets nuggets of interesting biology and assays, and only has to give away the structure of a garbage wholly un-optimizable "lead" and then will be free to screen real compounds from related focused libraries. All for the dangling carrot of the riches in PFEs library and hopes of becoming a takeover target if the biology is novel enough. Many cash strapped biotech would sell their souls for that opportunity. Slick.
16. JJL on May 21, 2009 3:44 AM writes...
There have been two mentionings on conferences - SBS 2009 in Lille (25.th April) and Compound Management & Integrity in London (20.th May). The bits below are in the public domain.
"Pfizer currently works on a pilot project to allow external customers access to our file for screening their targets"
17. SP on May 24, 2009 9:01 AM writes...
Here's how structure disclosure works- you do get to screen the whole deck (~3M) if you can afford it. You only get to see the structures of hit compounds, and that assumes a reasonable hit rate- no saying, "hey, my hit rate is 99%, show me the whole deck." However, if one of those structures is part of an active development series on another Pfizer project, it stays hidden.
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text:
Columbia, SC (WLTX) --- Senior catcher Shelby Gonzalez made her final game at Carolina Stadium a memorable one. Trailing 1-0 in the fourth inning, Gonzalez hit a two-run home run that would give South Carolina a 2-1 lead and eventual win over the second ranked Florida Gators.
The homer kept the SEC tournament hopes alive for the Gamecocks. Katie Marks earned the win with her work in relief.
South Carolina's win snaps a 28-game losing streak to Florida that dated back to the 2003. It's the first win over a top-two foe since May 19, 2003, when the Gamecocks forced an if-necessary game against No. 1 UCLA in NCAA Regional play at Beckham Field.
They'll find out the playoff fate at the conclusion of SEC play Sunday.


text:
> TV Series DVD Boxset
> Burn Notice Season 6 DVD Boxset
Burn Notice Seasons 6 DVD Box Set
Cast and Crew
Creator: John T. Kretchmer,Tim Matheson,Jeremiah S. Chechik,Paul Holahan,Dennie Gordon
Leading Role: Jeffrey Donovan,Gabrielle Anwar,Bruce Campbell,Sharon Gless,Paul Tei,Paul Tei,Seth Peterson,Marc Macaulay,Brandon Morris
Summary of Burn Notice Seasons 6 DVD Box Set
A sixth season, consisting of 16 to 18 episodes, was ordered by USA Network on April 16, 2010. This announcement came just over a month after the third season had completed airing. The season is expected to begin in summer 2012. John C. McGinley will appear in multiple episodes as Tom Card, Michael's original CIA trainer. Taryn Manning will appear in one episode as one of Fiona's fellow prisoners. Jere Burns and Kristanna Loken will return to the series for multiple episodes as Anson Fullerton and Rebecca Anderson, respectively.Lauren Stamile will also return to the series as Kim Pearce. Faran Tahir will appear in the third episode as Ahmed, a ruthless Lebanese agent.


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Red Hat has announced the availability of Red Hat Enterprise Linux 7.0 for all customers and partners, marking the beginning of a new branch for one of the most used Linux operating systems in the world.
Red Hat Enterprise Linux 7.0 is based on Fedora 19, which is actually an interesting move from Red Hat. The 6.x version had quite an old-looking desktop, but the new one is more modern and actually much closer to what is being used today.
"Red Hat Enterprise Linux 7 not only lays the foundation for the open hybrid cloud and serves enterprise workloads across converged infrastructures, but it also pushes the operating system beyond today's position as a commodity platform. Built to meet modern datacenter demands along with next-generation IT requirements, Red Hat Enterprise Linux 7 powers the spectrum of enterprise IT, from application containers to cloud services."
"Bare metal servers, virtual machines, Infrastructure-as-a-Service (IaaS) and Platform-as-a-Service (PaaS) are converging to form a robust, powerful datacenter environment to meet constantly changing business needs," reads the official announcement.
The developers have explained that Red Hat Enterprise Linux 7.0 is now using XFS as the default filesystem, which allows scaling up to 500 TB. Users will have access to Linux Containers, including Docker, across physical, virtual, and cloud deployments, and Cross-realm trust will ensure better secure access for Microsoft Active Directory users across Microsoft Windows and Red Hat Enterprise Linux domains.
Choosing a newer version of Fedora for Red Hat Enterprise Linux 7.0 was a very good decision for the company and it looks like it has been quite well received. The only problem is the rate of adoption and it remains to be seen how fast users will switch to the new system.
Red Hat has also said that the new operating system will be supported, as it was to be expected, by hands-on training and certification programs. This will ensure a smooth transition from one version to another.
We can only hope that Red Hat will not keep this branch in existence for the same amount of time and that the company will make the upgrade to the next release a little bit faster.
The complete release notes can be found in the official announcement. You can also review and purchase the Red Hat Enterprise Linux 7.0 distribution from Softpedia. Please keep in mind that this is not a free operating system.


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Green space keeps you from feeling blue
The more green space a neighborhood has, the happier the people are, a new study has revealed.
Dr. Kristen Malecki, assistant professor of population health sciences at the University of Wisconsin School of Medicine and Public Health said that the results are striking across neighborhoods of Wisconsin, from the North Woods to the cities, and higher levels of green space were associated with lower symptoms of anxiety, depression and stress.
The study, which combines mental-health data from the Survey of the Health of Wisconsin (SHOW) and Landsat 5 satellite data from July 2009 that analyzed how much vegetation was present in each of the SHOW census blocks.
About 2,500 Wisconsin residents from 229 neighborhoods answered an assessment that asked them to rate their symptoms of depression, anxiety and stress, and it was found that across all strata of society, people who lived in a neighborhood with less than 10 percent tree canopy were much more likely to report symptoms of depression, stress and anxiety.
The greening of neighborhoods could be a simple solution to reducing stress, and going outside will make one feel better, said Malecki.
The study was published recently in the International Journal of Environmental Research and Public Health.
(Posted on 14-04-2014)
Free Yearly Horoscope: Select your zodiac sign
Pisces | Aquarius | Capricorn | Sagittarius | Scorpio | Libra | Virgo | Leo | Cancer | Gemini | Taurus | Aries


text:
The Garden Wing Houston House Kirk Road Houston Renfrewshire PA6 7AR
Office 01505 615571 Mobile 07799 643630 Fax 01505 615571
12 The Crescent Impington Cambridge CB4 9NY Mobile 07799 643630
individuals need advice well before a move. Too often the employer
cannot provide timely guidance, or simply offers a financial package to
deal with all the move issues. The key point is that the more help
employees and their families receive, the easier it will be for them to
accept and adjust to what will be a fundamental and sometimes traumatic
change in their lifestyles.
This help must be uppermost in HR directors' minds, once the
decision to move candidates has been taken.
Artemis Relocation has offices in Scotland and Cambridge UK
Keywords:moving, house, hunting, talent, schooling, advice, new-job,
removals, live in Scotland, work, property, fresh movers, helping to
©Artemis Relocation 2002-2007 Website development by www.web-genetics.co.uk


text:
University of Oklahoma Sooners BBQ Grilling Tools Travel Set
Our Price: $58.95
Ships Within 1-5 Business Days.
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- Officially Licensed Oklahoma Sooners BBQ Grilling Tools Travel Set College BBQ grill set. The Sooners BBQ tote stands out among other portable barbecue tool sets. It's a 3-piece BBQ tool set with silicone handles in an attractive black polyester zip-up case with an adjustable shoulder strap to match the handles of the tools inside. It includes three stainless steel tools: 1 large spatula featuring a built-in bottle opener, grill scraper, and serrated edge for cutting (17.5") , 1 BBQ fork (17"), and 1 pair of tongs (16.5"). All three tools have long handles to keep your hands away from the flames and metal loops at their ends to hang them on your barbecue. Great gift for the master griller and tailgater!747-03-100-454-0 099967233835


text:
Ultimate Software Schedules Conference Call for First Quarter 2013 Financial Results
WESTON, Fla.--(BUSINESS WIRE)-- Ultimate Software (Nasdaq: ULTI ) , a leading cloud provider of people management solutions, will be hosting a conference call on Tuesday, April 30, at 5:00 p.m. Eastern time to discuss its financial results for the first quarter of 2013.
Forward-looking information about future company performance may be discussed during the teleconference call. This call is open to the public and will be hosted by Scott Scherr, CEO, president, and founder, and Mitchell Dauerman, CFO, executive vice president, and treasurer. The call will be audiocast live via Vcall at www.investorcalendar.com/ic/cepage.asp?id=170358.
We recommend you access this site 10 minutes before the start of the call. Windows Media Player software is required to listen to the call and can be downloaded from the site. The call will be available for replay at the same Web address at 9:00 p.m. Eastern time on the day of the call.
Ultimate's press release for its 2013 first quarter financial results will be available after 4:00 p.m. Eastern time on April 30, 2013, on the company's Web site at news.ultimatesoftware.com/investors.
About Ultimate Software
Ultimate Software is a leading cloud provider of people management solutions, with more than 10 million people records in the cloud. Built on the belief that people are the most important ingredient of any business, Ultimate's award-winning UltiPro delivers HR, payroll, and talent management solutions that seamlessly connect people with the information and resources they need to work more effectively. Founded in 1990, the company is headquartered in Weston, Florida, and has more than 1,600 professionals focused on developing the highest quality solutions and services. In 2013, Ultimate was ranked #9 on FORTUNE'S list of the "100 Best Companies to Work For." Ultimate has more than 2,500 customers with employees in 144 countries, including Adobe Systems Incorporated, Culligan International, Major League Baseball, The New York Yankees Baseball Team, Pep Boys, and Texas Roadhouse. More information on Ultimate's products and services for people management can be found at www.ultimatesoftware.com.
UltiPro is a registered trademark of The Ultimate Software Group, Inc. All other trademarks referenced are the property of their respective owners.
Ultimate Software
Mitchell K. Dauerman, 954-331-7369
Chief Financial Officer and Investor Relations
KEYWORDS: United States North America Florida


text:
I picked up a box of Liqumins Electrolyte Stamina Power Pak (Orange Blast) at Vitamin Shoppe. The product claims: "feel the difference or your money back". I thought, why not try it. Typically after exerting myself in the heat, I usually drank a whole lotta water to the point of feeling nauseous. If I didn't then I'd get cramps. I'd about electrolyte supplements, but had not tried them.With a heat wave here in the East there was no better time to test it. I took a fast paced five mile walk Sunday morning. Afterwards I drank one glass of water with one packet. Tasted bad. Then "I" had not planned for it, but I mowed and did other yard work for about 1 1/2 hours - yes, wife initiated :). Then I drank one more glass with one packet. The drink after the walk had an amazing effect on me and so did the 2nd one. Good stuff.I'm pretty sure that I've been needing electrolytes rather than drinking more water. Nice to stumble upon something like this. The box has 32 packets (6.5 g each) [9 g on my scale]. I'm going to take enough for 3x per day on my hikes coming up this summer.
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Wednesday, September 25, 2013
Midweek Madness - Marland Yarde recovers from cramp to score a try
London Irish flyer Marland Yarde has been in great form so far this season, with many touting him to be an England regular in the not too distant future. He's scored some good tries in the past few weeks, and one that has to be seen to be believed.
Yarde, who hails from the Caribbean, is a genuine Test rugby prospect and has his eyes set on the 2015 Rugby World Cup. He hopes to become the first St Lucia born player to represent England.
Having moved to the UK aged nine with his family, he recently spoke of how the 2003 World Cup Final in Australia inspired him to take up rugby, despite not knowing much about it.
"To be honest I didn't even know who Jonny Wilkinson was, or any of the players. It was just the sport, enjoying the whole atmosphere and how the sport was played. I found it was really exciting. That really sparked my vision to want to be part of this sport and play," Yarde said.
Having made his international debut against Argentina earlier this year, the 21-year-old hopes to add to the two tries he scored in their 51-26 second Test win. "Having just tasted international rugby I'm really hungry for more," he says. "I know the World Cup is going to be massive and being in the squad is definitely something I'd love to achieve.
"In no way do I feel like the finished article but Stuart Lancaster has made a point that age doesn't really matter. I want to do whatever I can for London Irish to put myself in the best position towards that World Cup."
If that means running in tries when suffering from injury, so be it. We saw exactly that a few weeks ago in the Aviva Premiership, as Yarde was down getting treatment for cramp but spotted an opportunity, so promptly hopped up and got into a great position in support.
It's not the first time we've seen this type of thing happen. Both Brian O'Driscoll and Kurtley Beale have done similar, which naturally brings up the question of legality, as while it's funny to see, it probably a little unfair, especially when the doctor or physio is already on the field.
Do you have any thoughts on whether a law should be in place to prevent this type of thing from happening, or is it just a freak occurence that shouldn't really be taken very seriously? Also, do you think Yarde should be an England regular by the time the Six Nations rolls around?
Posted by Rugbydump at 12:03 pm | View Comments (43)
Posted in See it to Believe it
Viewing 43 comments
Muzz September 25, 2013 4:12 pm
VOS September 25, 2013 4:14 pm
Deanoe September 25, 2013 4:40 pm
DrG September 25, 2013 10:54 pm
AkaRed September 25, 2013 4:42 pm
Ottawa Rugger September 25, 2013 4:44 pm
Skid986 September 26, 2013 8:48 am
I_bleed_green_and_gold September 25, 2013 4:59 pm
I think it can become a problem when injuries are used as strategic moves to gain advantage (this happens to some extent to stop the clock or take a breather).
Hypothetical event:
One can imagine leaving a player injured in the opposition half (close to say the 10m mark) getting "treated". Both teams are scattered around the mid field mark since there is some back and forth kicking for territory and lets say the ball is kicked out around the 5m mark. If the one team wants to take a quick line out counter attack the injured player (who never retreated but is put onside by the ball going out) could theoretically get up, tackle the player and contest the ball. That would nullify the counter attack?
Gonzoman September 25, 2013 6:32 pm
Now assuming that none of the above actions has occurred, the off-side player must be mindful of Law 11.9 (Loitering); essentially he or she can't hang about in an offside position. Any player who loiters cannot be put onside by the action of an opposing player.
In the case of a kick to touch presented above, the injured player is off-side and loitering in a technical sense. If he or she then gets up and prevents a quick throw-in, or participates in play following a quick throw-in without being put onside by a team-mate, he or she is liable to be penalized. If a team-mate has run ahead of the injured player, then the point is moot since the injured player is then onside.
Russ September 25, 2013 5:12 pm
Matheus September 25, 2013 5:25 pm
He received the ball after the ball carrier passed him. He was in legal position.
Nice try.
paimoe Top Comment | September 25, 2013 5:51 pm
45678 September 25, 2013 5:33 pm
Reecey September 25, 2013 5:53 pm
However, in this instance, Yarde does not interfere with play until the teammate has passed him, and there is therefore nothing wrong with it.
This isn't offside, and is similar to a 9 passing the ball out to his backs, then tracking across field (ahead of the ball) to take the most direct route to the next breakdown. If a break is then made - he is free to support even though he was ahead of play seconds before. The presence of the ruck doesn't make a difference - you can't be offside from a ruck when in possession (unless you interfere with play by crossing/obstructing).
Full Back September 26, 2013 8:50 am
DrG September 26, 2013 11:59 am
Matt September 26, 2013 12:01 pm
Doesn't happen that often, but not all that rare either. Mostly it occurs when a team is receiving a kick: the catcher knocks on, and one of his team-mates, who was standing in front of him, picks the ball up. Seen it a few times in an international match.
Often seems like quite a harsh penalty, since it's very difficult to resist your instinct telling you to play the ball when it's right next to you.
Full Back September 27, 2013 1:03 pm
Matt September 27, 2013 1:59 pm
What you say does have some relevance, in that, in order to be penalised under this law, the person playing the ball needs to have "prevented an opponent from gaining an advantage". But, it's still definitely a penalty for offside, and not some other offence.
45678 September 26, 2013 7:12 pm
Skid986 September 25, 2013 6:02 pm
Gonzoman September 25, 2013 6:39 pm
Admittedly, he was loitering; however, this only means that he cannot be put onside through the actions of an opposing player (run 5m, pass/kick, intentionally touch the ball). Yarde can still be put onside by teammates, in this case by having the ball carrier run ahead of him.
It can be a little confusing, because he WAS off-side at the ruck and he WAS loitering. Once the ball leaves the ruck he is still off-side and still loitering, but he can be put onside by the action of a teammate.
Apart from the laws, you could argue that it isn't fair because he's already in a prime position to support the ball carrier. Of course, you could also argue that if he wasn't receiving treatment he would be running in support anyways.
Fair play to Yarde for identifying an opportunity and sucking it up enough to get up and continue.
cliff September 25, 2013 5:42 pm
Canadian content September 26, 2013 4:25 am
Full Back September 26, 2013 8:55 am
If a player needs treatment he should get off the pitch unless it's a serious injury in which case play should be stopped.
JD September 26, 2013 10:14 am
db September 26, 2013 2:03 pm
Moom September 26, 2013 2:04 pm
mike September 26, 2013 5:31 pm
The player is officially onside once his teammate runs past him and puts him onside.
The player was not affecting play while in an offside position and only rejoined once he was onside.
As soon as the ruck is over (balls out) the offside line is a moving line.
DrG September 26, 2013 7:57 pm
katman September 26, 2013 8:05 pm
Adman September 26, 2013 9:07 pm
I recon he was receiving some council from the coach through the team physio..."fake" cramp...info gets passed on...common place in professional rugby.
Juggernauter September 27, 2013 3:16 pm
Canadian content September 27, 2013 12:05 am
I really don't get this argument, as has been cited by many of u before, many phases start with support players in an "offside" position. Forwards are almost always ahead of the backs in set piece, aside from restarts. So are they offside? Yes if he they keep advancing forward to chase a kick or receive a pass or pick up a knockon. But no, not of they are passed by the ball carrier. Fellas this happens about a 100 times a game?
In regards to the medic, play didn't stop to attend to yarde, a la soccer, and require him to leave the pitch. It continued. There is no law currently precluding what yarde did and I do not see it as not in the spirit of the game. In fact I see the opposite. He saw an opportunity to score, which is rare, sucked it up and took it. What coach wouldn't want that?
Maybe we need a soccer like rule. But then we will require unlimited substitutions because surely a prop who is temporarily injured does not have to permanently leave the game because a medic tends to him?
If this becomes a trend, deal with it. Otherwise....
tRY TIme!
Canadian content September 27, 2013 12:05 am
I really don't get this argument, as has been cited by many of u before, many phases start with support players in an "offside" position. Forwards are almost always ahead of the backs in set piece, aside from restarts. So are they offside? Yes if he they keep advancing forward to chase a kick or receive a pass or pick up a knockon. But no, not of they are passed by the ball carrier. Fellas this happens about a 100 times a game?
In regards to the medic, play didn't stop to attend to yarde, a la soccer, and require him to leave the pitch. It continued. There is no law currently precluding what yarde did and I do not see it as not in the spirit of the game. In fact I see the opposite. He saw an opportunity to score, which is rare, sucked it up and took it. What coach wouldn't want that?
Maybe we need a soccer like rule. But then we will require unlimited substitutions because surely a prop who is temporarily injured does not have to permanently leave the game because a medic tends to him?
If this becomes a trend, deal with it. Otherwise....
tRY TIme!
DrG September 27, 2013 4:07 pm
Colombes September 27, 2013 10:04 am
maybe the physio presnece on the pitch shouldn't allow players involved to get up and play the following action
be assured u will see it again in the following weeks
mrjmmlc September 27, 2013 2:37 pm
Juggernauter September 27, 2013 3:21 pm
cheyanqui September 27, 2013 3:37 pm
As much as I am not a fan of England, I'd love to see those guys getting the ball at pace and with just a little room -- too often, they get junk ball.
Bish Bash Bosh September 28, 2013 2:41 pm
This makes it sound like he's yet to represent England, when obviously he's capped and scored two tries on debut. But yeah, him & Wade should be the regular England wings by the time the Six Nations rolls around...
Chazzle September 30, 2013 12:46 pm
Referee let it go, good try and a piece of flair play? However, physio and player were in the way as soon as play came towards them. Ref might, quite correctly, have stopped play at this point. It happens in a blur and refs at this level get used to not stopping for treatment if possible, with physio on playing area. We can understand then that once ref let play go on the rest is history.
As an offside player Marlon can rejoin play and in the circumstances looks like he did so correctly.
A brave ref to let it go and then bring play back because of the outcome!
browner October 09, 2013 1:18 pm
"When a ruck, maul, scrum or lineout forms, a player who is offside and is retiring as required by Law remains offside even when the opposing team wins possession and the ruck, maul, scrum or lineout has ended. The player is put onside by retiring behind the applicable offside line. No other action of the offside player and no action of that player's team mates can put the offside player onside.
So there it is chaps, he CAN become onside again, BUT ONLY once he's retired behind the previous ruck offside line, and the key words are in the final sentence NO OTHER ACTION. He didn't retire, so it's goes down as a Bad 'Critical' decision.


text:
Nesingwary Will KnowWarn the hunters at Nesingwary's Expedition in Northern Stranglethorn Vale.
|Head to Nesingwary's Expedition.
DescriptionGreat, just what we need, the Gurubashi on the rampage using serpents to lead the charge. Well at least we know that much.
It's probably a safe bet that the hunters at Nesingwary's Expedition have some insight into this. If they don't they at least know how to fight the serpents.
Head there and let them know what you saw here. Let them know that the trolls are using serpents as their weapon.
We know all about the serpents, <name>. But there is something else out there lurking... The jungle has come to life, <class>!
RewardsYou will receive: 9 40
GainsUpon completion of this quest you will gain:
- 12,870 experience


text: Katy Perry closed out the VMAs with a fun, boxing-themed performance of her new single, "Roar," under New York City's iconic Brooklyn Bridge. (Us Weekly broke news of the unique locale the morning of the big show.) Wearing a tiger-print sports bra and silk boxing shorts adorned with shiny red flames, the pop superstar channeled her inner Rocky and had the crowd roaring with approval.


text:
5Q: Wigglebutt Inn
The Wigglebutt Inn specializes in cageless daycare and boutique boarding for dogs. The Wigglebutt Inn's cageless daycare provides dogs with fun with other dogs of similar size and temperament followed by nap time from noon to 1 p.m. with calming music, aromatherapy and snacks. After 1 p.m., dogs can play until pick-up. Boutique boarding in the inn's dens includes spacious, white picket-fence dens with open tops and see-through picket gates. The inn's suites feature larger private dens, a shared flat-screen TV, bottled water and stylish rugs and bowls. In addition to care and boarding, The Wigglebutt Inn offers pick-up and drop-off services, hydrotherapy, dog baths, a quiet area for older dogs and a selection of pet accessories. The inn also can also host dog parties in their upstairs lounge that include air conditioned space, water, toys and treats.
George and Karen Paul, owners
The Wigglebutt Inn
2021 Pine Ridge Rd.
Naples, FL 34109
Phone: (239) 592-9663
Website: www.wigglebuttinn.com
Open: Mon.-Fri. 7 a.m.-6 p.m.
Saturday 9 a.m.-4 p.m.
Sunday noon-4 p.m.
1. What does your business offer that's unique compared to businesses like yours?
The main things that set The Wigglebutt Inn apart from other dog boarding and daycare facilities are extremely high cleanliness standards; an overnight caretaker who lives on site, which means the dogs are not left alone at night and they get an extra bathroom break between 9 p.m. and 10 p.m.; a state-of-the-art fire sprinkler system for added peace of mind; a hydrotherapy tub to pamper your dog; five luxury suites with HD TVs; a wonderful, park-like outdoor area; and a boutique boarding experience second-to-none.
2. What is the most important part of your job on a day-to-day basis?
By far, our most important job is to ensure that each and every dog in our care has a fun and safe experience and that we exceed our clients' expectations. In order to achieve this, we follow important safety and cleaning protocols and are fortunate to have excellent employees who love dogs and care about their work.
3. What are your keys to success?
The key to our success is that we care for each and every dog as though it were our own. If a dog is shy and not eating regularly, we will sit and hand feed that dog. We make sure that our employees are happy in their jobs, that they love dogs as much as we do and that they understand the importance of a clean, safe environment for our canine clients.
4. What surprises you most about your job?
How many dogs there are in Naples! There are so many wonderful dogs that come to The Wigglebutt Inn—every shape and size, both big and small—and they are all so fun and have such unique personalities. We are also always humbled by the loyalty of our great customers! We thank them for their support!
5. If there was one thing you would want people to know about your business, what would it be?
Our 10,000 sq. ft., newly renovated space on Pine Ridge Road has allowed us to have more customers experience The Wigglebutt Inn, and we will continue to strive to make that experience a great one. We are happy when the dogs run through our doors with their tails wiggling! That is how we gauge our success! We strive to be a great community partner and support many local charities. Our long-term affiliation with The Humane Society Naples since 2009 is something we are very proud of.