text:
|Publication number
|Publication type
|Application number
|Publication date
|Dec 7, 1993
|Filing date
|Oct 25, 1991
|Priority date
|Aug 31, 1989
|Fee status
|Publication number
|Mary A. Krenceski, Richard W. Wheeler, Robert P. Bouvy
|Original Assignee
|Eastman Kodak Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (20), Non-Patent Citations (6), Referenced by (55), Classifications (35), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a continuation of application Ser. No. 07/401,388 filed Aug. 31, 1989, now abandoned.
This invention relates to paint-coated film having a basecoat-clearcoat appearance and, more particularly, to such a film having improved resistance to marring. It also relates to a method for making such films.
As an improvement over the spray painting of articles such as automobile bodies, boats and household appliances, a new kind of paint-coated sheet material or film has been developed to provide protective and decorative finishes. The new material comprises a flexible, stretchable, thermoplastic support sheet, also known as a carrier film, which has on one side a paint layer, also called a basecoat, of uniform thickness and appearance and, optionally, on the other side an adhesive layer. It can also have other layers such as a tie or bonding layer between the paint layer and the carrier film. In a preferred embodiment a transparent topcoat, also called a clearcoat, covers the paint layer. This combination provides an attractive basecoat-clearcoat or clear-over-color appearance.
Using known thermoforming procedures such as vacuum forming and in-mold bonding, preferred types of the paint-coated sheet material can be stretched and bonded to automobile body panels or other articles to provide a basecoat-clearcoat finish. Advantages over obtaining such finishes by spray painting include economy in the use of paint and improved control of evaporating solvents, which reduces air pollution. Furthermore, the new material has a remarkably smoother and more attractive appearance than spray painted finishes.
The new type of thermoformable sheet material and a process for its manufacture are described in the U.S. patent application of G. G. Reafler Ser. No. 116,426, filed Nov. 3, 1987 now abandoned. The process involves applying the paint composition to the surface of the thermoplastic carrier film by laminar flow coating, followed by drying and then coating and drying each additional layer in sequence to obtain a paint-coated film of excellent gloss and smoothness.
Preferred basecoat and clearcoat compositions for the paint-coated films are polyurethanes. They are especially preferred because of their flexibility and good weather resistance. A problem, however, is that these flexible polyurethane coatings are more susceptible to marring than are harder, rigid thermoset polymers which can be used as clearcoats when flexibility is not required. Marring is an injury to the coating which, though related, is different from scratching. The latter involves cutting into the polymer surface, often times all the way to the substrate. The polyurethanes are resistant to this kind of injury within reasonable limits. Marring on the other hand is the forming of a depression in the polymer surface by contact with a blunt object under conditions not severe enough to cause a scratch. Since basecoat-clearcoat finishes on automobiles, boats and the like are subject to such contacts, improvement in the mar-resistance of flexible paint-coated films of the basecoat-clearcoat type to be used for such purposes is desirable. Furthermore, it is desirable that the mar-resistance be persistent or permanent and not be lost when the finish contacts solvents commonly encountered by automobile finishes.
It is also desirable, while improving mar resistance, to preserve the capability of laminar flow coating, inasmuch as this method of coating is responsible for many of the valuable properties of the new paint-coated films, such as gloss, distinctness of image (DOI) and geometric metamerism (commonly called "flop").
The present invention provides novel paint-coated films having flexible basecoat-clearcoat finishes which have improved resistance to marring and which can be formed by laminar flow coating. The resulting products, hence, have outstanding qualities of gloss, DOI and flop plus improved mar resistance. The layers of the films have good adhesion to each other and the clear layers are free of undesirable haze. Preferred embodiments of the films are thermoformable. They can be stretched up to 100 percent in area and bonded to the contours of three-dimensional substrates by thermoforming without tearing and while retaining gloss and DOI in the stretched areas.
The protective and decorative sheet material of the invention comprises:
a flexible and, preferably, thermoformable carrier film;
a flexible paint layer coated on the carrier film;
a polyurethane clearcoat layer coated on the paint layer; and
a mar-resistant polyurethane clear topcoat layer coated on the clearcoat, the mar-resistant topcoat
a) being thinner than said clearcoat layer, and
b) being the reaction product of a mixture comprising a polyisocyanate and a reactive poly(dialkylsiloxane) having at least one reactive group, and
c) having a persistently low friction coefficient.
The method of the invention for making a mar-resistant flexible sheet material having a basecoat-clearcoat appearance comprises forming a basecoat layer on a flexible polymeric carrier film by laminar flow coating; mixing a polyol component and a polyisocyanate component of a clearcoat composition as a solution and promptly thereafter coating the resulting mixture by laminar flow coating as a clearcoat over the basecoat layer,
mixing a polyisocyanate component with a reactive silicone component as a solution and coating the resulting solution by laminar flow coating as a topcoat over the clearcoat promptly after mixing the components, the topcoat being thinner than the clearcoat, and
the reactive silicone component being a poly(dialkylsiloxane) having at least one group that is reactive with the polyisocyanate.
The invention will be further described by reference to the drawings, of which:
FIGS. 1-2 are diagrammatic cross-sections, not to scale, of protective and decorative sheet materials of the invention.
FIG. 3 is a diagrammatic representation of coating and drying apparatus with which sheet material of the invention can be manufactured.
FIG. 1 is a cross-section of one embodiment of a thermoformable sheet material 10 of the invention. Layer 11 is a flexible and stretchable, thermoplastic polymeric carrier film. Coated on the carrier film 11 is a protective and decorative paint layer 13, as used in automotive finishes.
Although not essential with all combinations of carrier films and paint compositions, a thin tie layer 12 can be coated and dried on the carrier film before the paint layer is coated in order to improve the bonding of the paint layer to the carrier film.
Coated on the upper surface of the paint layer is a flexible, thermoformable, polyurethane clearcoat layer 14. Compositions for the clearcoat layer include crosslinkable clearcoat compositions employed in automotive surface finishing. They are transparent and comprise (a) as one component, a crosslinkable polymeric polyol such as a polyester polyol, a polyurethane polyol, or an acrylic polyol and (b) as a second component, a polyisocyanate curing or crosslinking agent. These components are mixed and dissolved in a volatile organic solvent such as acetone or toluene. For example, a polyurethane polyol is diluted to 58% solids with toluene and a polyisocyanate is diluted to 85% solids with acetone. Promptly after mixing, the reactive mixture is coated over the paint layer. It is dried and cured by heating to form a crosslinked polyurethane clearcoat.
An example of such a composition is the solvent-based system comprising a polyurethane polyol as one component and an aliphatic polyisocyanate as the other, as disclosed in the patent to Porter, U.S. Pat. No. 4,719,132. Especially preferred is a two-component composition disclosed in this patent, of which one component comprises a crosslinkable poly (esterurethane) polyol and the other comprises an aliphatic polyisocyanate crosslinking agent such as a polyfunctional isocyanurate of 1,6-hexamethylene diisocyanate.
Other useful clearcoat compositions include those described in the patents to Ambrose et al, U.S. Pat. No. 4,699,814; Simpson et al, U.S. Pat. No. 4,650,718; Singer et al, U.S. Pat. No. 4,681,811; Singer et al, U.S. Pat. No. 4,703,101; and Backhouse, U.S. Pat. No. 4,220,679 and U.S. Pat. No. 4,403,003. All of these and the other patents cited herein are incorporated by reference.
In accordance with the present invention, a transparent polyurethane-siloxane topcoat 15 is coated over the clearcoat. The topcoat is also coated from a reactive mixture. The reactive components of this mixture comprise an aliphatic polyisocyanate and a reactive poly(dialkylsiloxane) and, preferably, consist essentially of (a) a polymeric polyol, (b) an aliphatic polyisocyanate and (c) a reactive poly(dialkylsiloxane). Preferably the composition also includes a small amount of a catalyst, such as dibutyl tin dilaurate to promote the desired reactions of the polyol, isocyanate and reactive siloxane. As with the clearcoat, the topcoat is formed by mixing the reactive components (and catalyst) in solution and coating the solution promptly after mixing. Inert organic solvents are used such as toluene and acetone. The polymeric polyol and the reactive siloxane can be in one solution and the polyisocyanate in another, the two being mixed just before coating.
FIG. 3 illustrates diagrammatically a preferred coating and drying apparatus which can be used to manufacture the sheet material of the invention by the preferred procedures of laminar flow coating and plural stage drying. Coating hopper 31 is an extrusion coating hopper such as the type disclosed by Beguin, U.S. Pat. No. 2,681,294. The coating hopper extrudes in laminar flow through a narrow slot a horizontally extending bead of the coating liquid in contact with the continuously moving carrier film web 30. The coating composition is thus coated as a uniform layer onto the surface of the web. The first layer coated on the web can be tie-layer 12 or paint layer 13, as shown in FIG. 1. In either case, the carrier film web supplied by roll 29, whether or not previously coated, passes in close proximity to the narrow extrusion slot 31' of the coating hopper 31. As the web passes the hopper, a laminar flow of the coating composition is extruded on the web, the entire thickness of the coating for that particular pass being applied simultaneously across the width of the web. Promptly after being coated, the web having the wet layer on its surface is drawn through the drying apparatus.
The coated web 32 is pulled or drawn by take-up rollers not shown in the drawing through successive stages of the drying apparatus. These include initial drying stages 33, 34, 35 and final curing stage 48. Preferably the stages are at successively higher temperatures, the temperatures of the initial stages of the drying zone being mild. This is especially desirable when drying an aqueous paint which contains water and organic solvents. The final stage or stages, however, can be at high temperatures to remove residual liquids and/or to cure the crosslinkable clearcoat or topcoat. For example, heated air can be introduced at 27° C., 43° C. and 66° C. via lines 37 at stages 33, 34 and 35, respectively. Baffles 41 divert the air flow away from the top of the film and cause it to flow to lower regions of the drying chamber. Sensing controls 45 and 46 aid in maintaining the appropriate air temperature and humidity by feedback mechanisms not shown in the drawing. The speed of the web is such that the coating is subjected to elevated temperature for a substantial time, e.g., for 3 to 6 minutes, in the final stage 48 where the air is admitted via line 40 at about 80° C.
Preferably, the moving web is also heated from its underside by contact with metal rollers 36 and 43 and other rollers in the several drying stages. These metal rollers of high conductivity are heated by the warm air and they transfer heat to the underside of the web, thus further increasing its temperature. In the final stage 48, the web is heated to its highest temperature as it travels through a vertical path in a floating loop section, being guided by rollers 50 and air reversers of the plenums 49 to keep the coated side of the film out of contact with rollers 51. The dried film leaving stage 48 is wound on a take-up roll not shown in the drawing.
In the preferred method of applying the transparent clearcoat and topcoat over the paint layer, the paint layer is coated and dried and thereafter the clearcoat and topcoat are applied by the same laminar flow coating method as used for applying the tie-layer and paint layer. In this method, the film having on its surface the dried paint layer and clearcoat is again passed in close proximity to the narrow extrusion slot of an extrusion coating hopper 31, as shown in FIG. 3, from which the topcoat composition is extruded in laminar flow. Again, as with the paint and clearcoat layers, the entire thickness of topcoat to be applied in the particular pass is applied simultaneously across the width of the dried paint layer. Promptly thereafter the web having the wet topcoat layer on its surface is drawn through the drying apparatus.
Since the clearcoat for the preferred sheet material of the invention is thick, it is preferred to coat such layers in two or more passes in order to dry them adequately. For example, if the clearcoat dry thickness is to be 0.12 mm, a first pass can coat and dry a layer of 0.06 mm dry thickness and a second pass can coat and dry a second layer to raise the total dry thickness to 0.12 mm. For greater thickness, additional coating and drying passes can be carried out.
For optimum quality the stepwise increase in drying temperatures and other procedures such as humidity control, of the Fronheiser et al. drying process described in U.S. patent application Ser. No. 166,083, are also preferred for drying the clearcoat and topcoat layers.
If the drying conditions are carefully controlled, e.g., by providing small temperature increases from stage to stage and having a lengthy residence time in each stage, the entire thickness of the clearcoat can be coated and dried in a single pass. However, since the clearcoat is extremely thick in the preferred sheet materials of the invention, i.e., greater than 0.1 mm when dry, the best quality is obtained when the clearcoat is coated and dried in two or more passes. The topcoat, being much thinner, can be dried in a single pass.
It is also possible to coat the topcoat simultaneously with the clearcoat layer. This wet-on-wet method of coating can be carried out with laminar flow coating hoppers suitable for simultaneous coating of multiple layers. Examples of such coating hoppers include U.S. Pat. Nos. 2,761,419; 2,761,791 and 3,005,440. Although these simultaneous multilayer coating techniques can be used, best results are obtained when the paint layer is coated and dried separately and then successive layers of the clearcoat and topcoat are coated and dried in two or more separate passes using an extrusion hopper as in U.S. Pat. No. 2,681,294 and drying each layer after it is coated.
As has already been discussed, the reactive components of the clearcoat and of the topcoat are mixed just before they are coated over the previous layer on the carrier film. A preferred way of mixing these components is disclosed in the patent to Hayward et al., U.S. Pat. No. 4,832,991, which describes the use of an in-line static mixer placed just before the coating apparatus. In the method of the present invention, such a mixer can be placed in the inlet line, not shown in the drawing, for hopper 31 of FIG. 3.
Another preferred mixing procedure is disclosed in the patent to Fronheiser, U.S. Pat. No. 4,835,021. In this embodiment the hopper 31 is a slotted dual extrusion coating hopper of the type disclosed in the patent to Miller et al., U.S. Pat. No. 3,206,323. The reactive components of the clearcoat or topcoat are fed separately to the hopper chambers and converge at the orifice of the coating hopper. Hence, mixing is delayed until the streams converge at the orifice where they mix to initiate crosslinking. In this procedure both mixing and laminar flow coating are carried out by the coating hopper.
Certain advantages of the invention are obtained to some degree even when the polyol and the polyisocyanate of the clearcoat and of the topcoat are not identical. The fact that in both coatings the reaction product is a polyurethane means that the coatings have substantial compatibility and thus, adhere well to each other. In the preferred embodiment of the invention, however, the polyol and the polyisocyanate for the clearcoat and the topcoat are chemically the same and the coatings differ chemically only in that the topcoat contains a third component, i.e., the reactive poly(dialkylsiloxane). Consequently, the two layers adhere to each other extremely well. In addition they have compatible stretching properties.
A thick clearcoat is desirable. This provides the best "wet" look and optical depth. Thickness of the clearcoat also gives a benefit when the film is stretched during application to a substrate (as in thermoforming). If the clearcoat is thin, the gloss decreases in stretched areas, especially when the basecoat contains metallic flakes. By using a thick clearcoat, this loss of gloss is eliminated or reduced. On the other hand, if a thick, urethane-siloxane clearcoat is formed by the use of a preferred laminar flow extrusion coating hopper, e.g., as in the patent to Beguin, U.S. Pat. No. 2,681,294, serious coating difficulties arise.
The difficulties include the formation of repellencies or craters in the coated layer. This can be corrected to some extent by diluting the urethane-siloxane composition to a low solids content. This, however, excessively increases the drying costs for the process and creates problems in solvent recovery.
Another potential problem in coating a urethane-siloxane clearcoat composition directly on a basecoat, especially a non-urethane basecoat, is poor adhesion.
The present invention solves or reduces both of these problems. By coating the normal urethane clearcoat directly on the basecoat and then coating the urethane-siloxane topcoat over the clearcoat, adhesion problems are reduced.
Most importantly, however, the method of the invention permits the use of laminar flow extrusion coating hoppers without serious coating difficulties such as repellencies or craters. The reason for this desirable result is that the relatively thick urethane clearcoat can be coated at a high solids content in the laminar flow process. This economizes in the drying process and in solvent recovery. On the other hand, the thin layer of urethane-siloxane composition, which is difficult to coat by laminar flow extrusion at high solids concentration, can be coated at such a low solids content or high dilution that coating difficulties are avoided. Yet, since the layer is thin, i.e., the quantity of urethane-siloxane solution coated per unit area is so small, the drying costs and solvent recovery costs are not excessive.
As already stated, the silicone component of the polyurethane-siloxane topcoat composition is a low molecular weight poly(dialkylsiloxane) which has at least one reactive group. By "reactive group" is meant groups that react with the polyisocyanate component to bond the siloxane moiety to the polyurethane chain. The alkyl groups of the silicone are lower alkyl groups, e.g., of 1 to 4 carbon atoms. Dimethylsiloxane is preferred.
The preferred reactive siloxane component is a poly(dialkylsiloxane) which has at least two active hydrogen-containing groups selected from the group consisting of hydroxyl, mercapto, primary amino and secondary amino. Such groups are highly reactive with the polyisocyanate component of the coating composition.
Commercially available examples of useful reactive siloxane polymers include:
(a) Hydroxyl-functional:
(1) Dow Corning® 1248 Fluid, a graft copolymer of the type ##STR1## wherein R is an organic spacer, x is approximately 30 and y is approximately 3. Significant features of this low molecular weight silicone polymer (˜6000 m.w.) are that the hydroxyl groups are secondary and the alcohol moiety is attached to the silicone chain via a non-hydrolyzable Si--C bond. This product is available from Dow Corning Corporation, Midland, Mich. 48640.
(2) TEGO® OF-1010 and TEGO® OF-1025 α-ω-hydroxy organo functional poly(dimethylsiloxanes) of the structure ##STR2## wherein n=approximately 9 for TEGO® OF-1010 or approximately 24 for TEGO® OF-1025. This and the other TEGO® products are available from Goldschmidt Chemical Corporation, Hopewell, Va. 23860.
(3) TEGO® Glide 410 polysiloxane polyether copolymer of the formula ##STR3## wherein x≈70 mol %, y≈15 mol % and z≈15 mol %
(b) Amino-functional:
(1) TEGO® OF-2010 and TEGO® OF-2025 α-ω-amino organo functional polydimethylsiloxanes of the structure ##STR4## wherein n=approximately 9 for TEGO® OF-2010 and approximately 24 for TEGO® OF-2025.
(2) PS513 aminopropyl terminated poly(dimethylsiloxane) of the formula ##STR5## wherein the molecular weight is approximately 27,000. This product is available from Petrarch Systems, Bristol, Pa. 19007.
The dried urethane-siloxane topcoat is thinner and, preferably, is much thinner than the clearcoat. Thus, the dry clearcoat 14 can range in thickness from about 0.025 mm (1 mil) to 0.25 mm (10 mils) or even higher. The dry thickness of the siloxane-containing topcoat 15 preferably is the range from about 0.0005 to 0.005 mm (0.02 to 0.2 mils).
It has been found, as disclosed in copending U.S. patent application Ser. No. 287,417 of Gerald G. Reafler, filed Dec. 20, 1988, that a clearcoat thickness greater than 0.1 mm (4 mils) improves the retention of gloss in stretched areas when a sheet material having a metallic flake basecoat is thermoformed. Hence, in the preferred sheet materials of the present invention the clearcoat is thick. In such preferred sheet materials the total dry thickness of the clearcoat and the topcoat is at least 0.1 mm and most preferably is at least 0.25 mm. It is also preferred that the silicone-containing topcoat be relatively thin. Of the total thickness of the two layers, the clearcoat is the major part. Preferably, its thickness is from 10 to 100 times greater than that of the topcoat.
As a consequence of coating such a thin silicone-containing topcoat over the clearcoat, the stretchability, the adhesion to the paint layer and the retention of gloss when stretched are influenced mainly by the thicker clearcoat. Nevertheless, as the applicants have found, the topcoat, although thin, markedly improves the mar-resistance of the sheet material. Furthermore, this useful property is persistent. That is to say, it is not lost when the sheet material is scrubbed with a solvent such as isopropanol to which automobile finishes often are subjected as a result of its use in windshield washer liquids.
FIG. 2 shows one form of a sheet material of the invention having coated on the side of the carrier film opposite to the paint layer, a pressure-sensitive adhesive back layer 16. This provides a means for securely bonding the sheet material to a substrate such as an automobile panel. Following the application of the adhesive layer 16, the sheet material is interwound with a thin release sheet 17 of, e.g., polyester film to permit tack-free winding of the finished sheet material on a core. An optional silicone release coating 18 can be on the release sheet 17 to aid in stripping it from the adhesive back layer prior to thermoforming the sheet material to a substrate.
The carrier film for the sheet material is an essentially planar, self-supporting, stretchable, flexible, thermoplastic polymeric film which can be transparent, translucent or opaque. It has a substantially uniform thickness, preferably, in the range from about 0.05 to 0.50 millimeter (2-20 mils). A preferred thickness is in the range from about 0.16 to 0.32 millimeters (6-13 mils).
The carrier film has heat softening and tensile elongation properties suitable for the thermoforming process. Preferred polymers for the film are those known to be useful in thermoforming and/or vacuum-forming techniques, such as polyvinyl chloride, polyvinyl acetate, ABS (acrylonitrile-butadiene-styrene) resins, polyethylene and polypropylene. Useful carrier film compositions include the polyacrylate blends with copolyesters described in U.S. Pat. No. 4,246,381, and the copolyesters derived from aromatic polyesters and glycol polyesters described in U.S. Pat. No. 4,287,325. Blends of rubber-modified styrene-maleic anhydrides with polycarbonates and/or polyesters are also useful, as are blends of poly(ether-esters) and polyesters. Particularly preferred carrier film polymers exhibit a tensile elongation at break of at least about 40 percent when measured in accordance with ASTM D-638. A highly preferred carrier film composition is a blend of copolyesters based on poly(1,4-cyclohexanedimethylene terephthalate) and rubber-modified styrene-maleic anhydride copolymers as described in U.S. Pat. No. 4,582,876. A specific example of a polymer blend of this kind which can be extruded as a carrier film consists of a blend of 55:45% by weight of a copolyester and "Dylark 600" styrene copolymer. The latter is a rubber-modified styrene-maleic anhydride copolymer available from ARCO Chemical Company, a division of Atlantic Richfield Company. The copolyester is derived from terephthalic acid, 19 mole % ethylene glycol and 81 mole % 1,4-cyclohexanedimethanol.
Other examples of stretchable carrier films include the highly flexible and stretchable films which are made by the extrusion of blends of a flexible poly(ether-ester) with a more rigid polyester as described in the copending application of Seymour, Ser. No. 151,727, filed Feb. 7, 1988 now U.S. Pat. No. 4,904,748. The carrier film can include fillers, UV absorbers, plasticizers, colorants, antioxidants, etc., known to be useful in polymeric films.
Paint or basecoat layers for the sheet materials have a colorant and/or light reflective flakes incorporated in the film-forming binder. Conventional colorants for paint compositions can be employed, including inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate, carbon black, silica, talc, china clay, metallic oxides, silicates, chromates, etc., and organic pigments, such as phthalocyanine blue, phthalocyanine green, carbazole violet, anthrapyrimidine yellow, flavanthrone yellow, isoindoline yellow, indanthrone blue, quinacridone violet, perylene reds, diazo red and others known to those skilled in the art.
Any light-reflective flakes conventionally employed in paints, particularly those employed in automotive finish paints can be used. Suitable reflective flakes include metallic flakes such as aluminum flake, copper flake, bronze flake, copper bronze flake, nickel flake, zinc flake, magnesium flake, silver flake, gold flake, platinum flake and other platelets such a mica, glass, stainless steel, coated mica, coated glass, and aluminum coated polyester film fragments. Mixtures of two or more types can be use.
The film-forming binder for the basecoat preferably is a polyurethane but other flexible film-forming resins conventionally used as binders in basecoat compositions can be used, such as acrylic polymers and polyesters, including alkyds. Examples of such binders are described in U.S. Pat. Nos. 4,681,811; 4,403,003 and 4,220,679.
Most of the polymers described in the above references are organic solvent-based polymers, although acrylic polymers can be prepared via aqueous emulsion polymerization techniques and used as aqueous-based basecoat compositions. Water-based basecoats in color-plus-clear compositions are disclosed in U.S. Pat. No. 4,403,003, and the resinous compositions used in preparing these basecoats can be used in the practice of this invention. Water-based polyurethanes such as those described in U.S. Pat. Nos. 4,719,132 and 4,147,679 are examples of preferred binders for the paint layer.
The dried paint layer preferably has a mean thickness in the range of from about 0.012 and 0.080 millimeters (0.5-3 mils). A particularly preferred mean thickness is in the range of from about 0.020 to 0.060 millimeters (0.8-2.4 mils). The paint layer preferably is applied by forming a laminar flow of the paint composition, and directing the flow into contact with the moving carrier film web to form a paint layer.
The preferred method for coating the layers in the method of the invention is laminar flow coating, using an extrusion coating hopper as disclosed, for example, in the patent to Beguin, U.S. Pat. No. 2,681,294. It is also within the scope of the invention to coat multiple layers simultaneously, using a slide coating hopper as in the patent to Mercier et al, U.S. Pat. No. 2,761,419 or the patent to Padday, U.S. Pat. No. 3,005,440 or, preferably, using an extrusion-slide hopper of the type disclosed in the patent to Russell et al, U.S. Pat. No. 2,761,417 or the patent to Jackson et al, U.S. Pat. No. 3,996,885. Also useful are multiple layer extrusion hoppers as in the patent to Russell, U.S. Pat. No. 2,761,418 and the patent to Mercier, U.S. Pat. No. 3,627,564, and other laminar flow coating methods described in Reafler patent application, Ser. No. 116,426 now abandoned cited above.
While laminar flow coating is greatly preferred, since it produces layers of the best uniformity, smoothness and gloss, it is also possible to make products within the scope of the invention by other coating methods. Other such methods include spray coating as disclosed, for example, in Research Disclosure 24,403 of July 1984; the patent to Short et al, U.S. Pat. No. 4,769,100 and European Patent Application 266 109 published May 4, 1988 (U.S. Pat. No. 4,810,540 of Rexham Corporation); bar coating as disclosed in European Patent Application 230 364 published Jul. 29, 1987 (Minnesota Mining and Manufacturing Company); and reverse roll coating as disclosured in European Patent Application 285 071 published Oct. 5, 1988 (Avery International Corporation). Even when using these other coating methods, certain advantages of the invention are obtained, such as improved resistance to marring and good adhesion of layers.
The paint layer can be coated on a support having an adhesion promoting tie-layer. Tie-layers can be formed from compositions comprising an adhesion promoting species and optionally a solvent. Useful adhesion promoting species include polymers derived from acrylonitrile, vinylidene chloride, and acrylic acid; polymers derived from methylacrylate, vinylidene chloride and itaconic acid; cellulose nitrate, and a variety of commercially available adhesion promoting species, for example, those known under the trade designations FORMVAR 7/95, FORMVAR 15/95, BUTVAR B-98 and BUTVAR B-72, sold by Monsanto, MOBAY N-50 sold by Mobay, VINAC B15sold by Air Products, ELVACITE sold by DuPont, and LEXAN sold by General Electric. Suitable solvents include methylethyl ketone, methylene chloride, tetrahydrofuran, toluene, methyl cellosolve, methanol, ethanol, propanol, butanol, mixtures thereof and the like. The tie-layer preferably has a thickness not greater than about 0.0025 millimeter and preferably is much thinner than the decorative and protective layer.
The optional adhesive back layer 16 in FIG. 2 preferably comprises a pressure-sensitive adhesive although heat activated and other adhesives can be used.
A pressure-sensitive adhesive layer can provide a tenacious bond between the substrate and the thermoformable sheet material. Preferred adhesives of this type are acrylic adhesives. Examples include acrylic copolymers of a higher alkyl acrylate such as 2-ethylhexyl acrylate copolymerized with a polar comonomer such as acrylic acid, acrylamide or maleic anhydride. The adhesive is coated from a solution with water or an organic solvent which also can contain additives such as a tackifier resin. Further examples of useful acrylic pressure-sensitive adhesives are described in the patent to Traynor et al, U.S. Pat. No. 4,726,982 of Feb. 23, 1988.
The adhesive layer preferably is applied to the carrier film by laminar flow coating as described in U.S. patent application Ser. No. 116,426 now abandoned at a dry thickness of about 0.04 to 0.12 (1.5-5 mils) millimeters.
In sheet material of the invention the carrier film, the paint layer, the clearcoat and the bonded transparent topcoat have heat softening and tensile elongation properties which render the sheet material suitable in the thermoforming process. These properties of the different layers are mutually compatible so as to permit substantial elongation by the stretching forces of thermoforming without crazing or delamination. The carrier film, paint layer, clearcoat and topcoat are of sufficiently uniform character that the sheet material exhibits substantially the same uniformity of appearance before and after the thermoforming process.
Preferably, both the topcoat and the clearcoat are clear. If desired, however, they can contain organic or inorganic colorants (i.e., pigments or dyes) provided that the concentration is sufficiently low that the layers remain transparent. Furthermore, although a smooth glossy topcoat is preferred for many purposes, it can, if desired, have a textured surface.
The glossy embodiments of the sheet material of the invention have a 20 degree gloss, as measured by ASTM Test D-2427, of at least 80. Preferred embodiments have a 20 degree gloss of at least 85 and, most preferably, at least 90. An outstanding advantage of the new sheet materials is that when heated and stretched during thermoforming from the unstressed relaxed state to an extended state having an extended area at least 50% greater than the relaxed area, the sheet material loses little or no gloss. Also the DOI and, for materials having metallic-flake-containing paint layers, the flop, remain high in the extended areas. Tests have shown that, even when stretched more than 100%, the 20 degree gloss in preferred materials remains above 80, and even above 90 for non-metallic basecoats, in the extended or stretched area.
The sheet material of the invention can be applied to a three-dimensional substrate by thermoforming with vacuum. The material is softened by heating, e.g., to a typical temperature of 115°-150° C., and plastically stretched during thermoforming to conform to the shape of the substrate. Portions of the sheet material may be stretched to an area which is up to 100% or even 150% greater than its original unstretched area. The material is thus brought into conforming contact with the substrate and is securely bonded to the substrate to form a smooth and wrinkle-free protective and decorative surface.
Alternatively, the sheet material can be applied to a substrate by the "in-mold" method. This involves molding a shaped article and simultaneously bonding it to the protective and decorative sheet material. The method comprises the steps of (1) positioning the sheet material over the molding surface of a mold, the topcoat being between the surface of the mold and the carrier film; (2) injecting into the mold a plastic composition which hardens to form the molded article and bonds to the carrier film; and (3) removing from the mold a molded substrate article having the sheet material bonded thereto. In this method the sheet material normally requires no adhesive on the back side of the carrier film since the carrier film bonds to the molded article by fusion. The term thermoforming includes the vacuum forming method and the in-mold method, both of which involve heating and stretching the sheet materials.
If desired, the sheet material can be vacuum thermoformed into a predetermined shape as described in European Patent Application 285 071 A2, published Oct. 5, 1988 (Avery International Corp.) before it is fused to a plastic substrate by the in-mold method.
Still another way of using the decorative sheet material of the invention is as a free film or toning and styling film. In this usage an ornamental strip of the sheet material is adhesively bonded to a substrate such as an automobile body or a boat hull. The film need not be thermoformable although flexibility and moderate stretchability are desirable. It is simply stretched along the length of the automobile body for example, and pressed by hand into adhesive contact with automobile. The film can be mildly heated to aid in conformance to moderate contours. Even in this usage, which does not require extensive stretching, the gloss, DOI, flop and mar-resistance of the sheet materials of the invention provide important advantages.
The invention is further illustrated by the following examples which provide a comparison between sheet materials according to the invention (having reactive silicone-containing topcoats) and other sheet materials.
Part A
A carrier film was prepared from a blend described in U.S. Pat. No. 4,582,876 as follows:
A mixture of 55:45% by weight of copolyester resin and Dylark® Styrene Copolymer 600 was compounded by extrusion. The copolyester was derived from terephthalic acid, 19 mole % ethylene glycol and 81 mole % 1,4-cyclohexanedimethanol. Dylark® Styrene Copolymer 600 is a rubber modified styrene-maleic anhydride copolymer available from ARCO Chemical Company, a division of Atlantic Richfield Company.
The blend was heated to 260°-290° C. and extruded through a die into a nip comprising two temperature-controlled chrome plated stainless steel rollers. The extruded web was then cooled on a chilled roller. The thermoplastic film has a mean thickness of about 0.20 mm (7.5 mils) and a maximum thickness deviation of less than 0.02 mm.
The carrier film prepared as described was coated with a thin layer of an aqueous tie coat composition as described in Table I. After drying, the thickness of the tie layer was approximately 0.0005 mm (0.02 mils).
TABLE I______________________________________Tie Coat Composition Approx.Ingredients % Wt.______________________________________Ethylene Glycol Monohexyl Ether <1Deionized Water 75N, N-Dimethyl Ethanolamine <1N-Methylpyrrolidone 1Diethylene Glycol Monobutyl Ether 1Acrylic Resin* 10Urethane Resin** 10diluted with water to a total solids content of3.0% by weight.______________________________________ *Styrene butyl acrylatebutyl methacrylate terpolymer **Reaction product of methylene dicyclohexyl diisocyanate and an aliphati diol
The black paint composition of Table II below was metered from a nitrogen gas pressurized vessel through a coating hopper extrusion slot having a width of 0.25 millimeter onto the carrier film moving at a speed of 8 m/min. The coating method and apparatus were substantially as described in U.S. Pat. No. 2,681,294 and included means for maintaining a pressure differential across opposite surfaces of the coating ribbon. The coating was dried at 40°-90° C. to a thickness of 0.04 mm (1.5 mil) in a plural-stage, continuous flat bed drying apparatus supplied with low velocity, warm air streams as described in the copending patent application of Fronheiser et al, Ser. No. 166,083 filed Mar. 9, 1988, now U.S. Pat. No. 4,872,270.
TABLE II______________________________________Paint Composition Approx.Ingredients % Wt.______________________________________Melamine Formaldehyde Resin 1Carbon Black 1Ethylene Glycol Monohexyl Ether 5Toluene 1N, N-Dimethyl Ethanolamine 1N-Methylpyrrolidone 5Deionized Water 60Normal Butyl Alcohol <1Diethylene Glycol Monobutyl Ether 5Urethane Resin 20______________________________________
The resulting black paint layer of the paint-coated film was thereafter coated with the following two-component clearcoat composition.
TABLE III______________________________________Clearcoat CompositionIngredient Approx. % Weight______________________________________A* Polyol:Urethane Polyol Resin 65Toluene 35Benzotriazole Absorber 1B** Polyisocyanate: 100Polyfunctional aliphaticisocyanurate resin based on1,6-hexamethylene diisocyanate______________________________________ *Available as TKUS1002 from PPG Industries, Inc. The urethane polyol resi is a derivative of neopentyl glycol, isophorone diisocyanate and 1,4cyclohexane-demethanol and has a number average molecular weight of about 2000 and a weight average molecular weight of about 6000. **Available as Desmodur N3300 from Mobay Corporation Coatings Division
Component A diluted with toluene and Component B diluted with acetone were mixed and then immediately coated onto the paint layer and dried to form a clear layer having a thickness of 0.06 millimeters.
The paint-coated film having a polyurethane clearcoat as described above was used to prepare a series of films having a thin urethane-siloxane topcoat over the polyurethane clearcoat. The topcoat composition was formed by adding a reactive poly(dialkylsiloxane) to the polyol (Component A in Table III above) and then mixing that mixture with the polyisocyanate (Component B in Table III) immediately before feeding the mixture into the extrusion coating hopper.
In each of these preparations the amount of polydialkylsiloxane in mg/ft2 was varied for different preparations in order to observe the effect of siloxane concentration. Three different siloxanes were used, namely, Dow Corning® 1248 fluid, PS513 amine-terminated poly(dimethylsiloxane) and TEGO® Glide 410 polysiloxane polyether copolymer, all of which have been described more fully above. In Table IV below they are identified, respectively, as DC1248, PS513 and TEGO 410.
Mar-resistance is difficult to quantify. However, a good correlation exists between mar-resistance and friction coefficient, which can be measured. Therefore, strips of the resulting films were subjected to friction coefficient measurements according to American National Standard IT9.4-1988 (American National Standards Institute, Inc., New York, N.Y.). One strip of each film was tested with no further treatment. A second strip, before testing, was scrubbed with a cloth soaked in isopropyl alcohol. This provided an indication of the permanence of any effect by the siloxane component on the friction coefficient. The results of the testing of these films and of a control film which had only a clearcoat and no urethane-siloxane topcoat are listed in Table IV for Films 1 (the control) through 13. The test results for another film (14) are also listed. Film 14 had no clearcoat, the urethane-siloxane topcoat being formed directly on the black paint layer. Otherwise, this film was the same as Film 13.
TABLE IV__________________________________________________________________________ Poly(diakylsiloxane) Coverage Friction CoefficientFilm Silicone (Mg/ft 2) Not Scrubbed Scrubbed w/i-PrOH__________________________________________________________________________ 1 (Control) -- None 0.55 0.55 2 DC1248 0.05 0.53 0.6+ 3 " 0.1 0.3 0.6 4 " 0.5 0.2 0.25 5 " 1.0 0.12 0.2 6 PS513 0.05 0.3 0.57 7 " 0.1 0.24 0.57 8 " 0.5 0.11 0.18 9 " 1.0 0.12 0.1410 TEGO 410 0.05 0.43 0.5611 " 0.1 0.35 0.6+12 " 0.5 0.16 0.3113 " 1.0 0.2 0.2314 (No clearcoat) " 0.5 0.16 0.6+__________________________________________________________________________
The test results in Table IV show that the control, Film 1 which had no urethane-silicone topcoat, had a high friction coefficient (0.55) both before and after being scrubbed with isopropanol. The film had a correspondingly low mar-resistance.
Film 2, which had only 0.05 mg/ft2 Poly(diakylsiloxane), had a high friction coefficient before scrubbing and it increased after scrubbing. Films 6 and 10 show similar results with the other reactive silicone components.
Films 3, 7, and 11, which before scrubbing had friction coefficients lower than the control, increased markedly in friction coefficient after scrubbing with alcohol. This suggests that the urethane-silicone topcoat at the low Poly(diakylsiloxane) coverage of 0.1 mg/ft2 probably had a small amount of unreacted silicone which was removed by scrubbing.
As shown by Films 4, 5, 8, 9, 12 and 13, when the Poly(diakylsiloxane) coverage was 0.5 mg/ft2 or higher the initial friction coefficient was low and it remained low after scrubbing.
Film 14 shows the importance of having a clearcoat under the thin urethane-silicone topcoat. In this film which had only a topcoat the initial low friction coefficient increased markedly after the film was scrubbed with alcohol.
Basecoat-clearcoat films of the invention have also been compared for friction coefficient with films which are otherwise of the same composition but in which the clearcoat contains a non-reactive silicone compound and no urethane-silicone topcoat is formed over the clearcoat. For these comparative films the clearcoat was formed from the two-component urethane composition of Table III but mixing with the composition a non-reactive poly (dimethyl siloxane) known as DC200, the latter being a product of Dow Corning Corporation. In one formulation the amount of the silicone additive was 0.1 weight percent and in the other it was 0.5 weight percent, based on the solids content of the urethane composition.
Initially, the friction coefficients of the films containing the non-reactive silicone in their clearcoats were low, e.g., of the order of 0.18 and 0.15, as compared with 0.55 for the control film of Table IV which had no silicone in its surface layer. However, this low friction coefficient was not persistent. When the films were scrubbed with isopropanol and tested again the friction coefficients had risen to 0.53 for each film.
The paint-coated films of the invention are especially useful for bonding to three-dimensional substrates such as automobile panels by vacuum thermoforming or in-mold thermoforming. In these procedures the films not only have good mar resistance but they have good retention of surface qualities when stretched during thermoforming. This is especially important when the film is coated with a paint that contains metallic flakes. Such films when stretched show a tendency to lose gloss, DOI and flop in stretched areas. Furthermore, in films that are coated with certain mar-resistant compositions this loss of surface quality is pronounced. In films of the present invention, however, mar resistance is improved while the appearance qualities in the stretched areas are also retained.
The fact that the topcoat layer in the film of the present invention is thin permits the use of low viscosity topcoat compositions which can be coated successfully by extrusion hopper coating. However, this is not the only advantage resulting from the thinness of that layer. Another is the reduction in haziness of the clear layers. The reactive silicone components having a tendency to create haze in the coating composition. If the entire clearcoat contains a sufficient amount of the silicone component to improve the friction coefficient, this degree of haze becomes unacceptable. However, the present invention, by including the silicone component only in the thin topcoat layer, achieves mar resistance without excessive haze.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
|Cited Patent
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|Apr 19, 1967
|Aug 26, 1969
|American Standard Inc
|Polyurethane-polysiloxane graft copolymers
|Oct 22, 1968
|Dec 29, 1970
|Du Pont
|Glossy microporous sheet material
|May 3, 1978
|Feb 26, 1980
|Sumitomo Chemical Company, Limited
|Method for the improvement of surface hardness of article by coating
|Feb 15, 1983
|Feb 12, 1985
|M&T Chemicals Inc.
|Siloxane-containing polymers
|Oct 16, 1984
|Jul 9, 1985
|Dow Corning Corporation
|Method for surface treatment of polyorganosiloxane gel-filled containers to prevent bubble migration into said gel
|Apr 21, 1983
|Oct 29, 1985
|Beiersdorf Aktiengesellschaft
|Gravel-resistant selfadhesive decorative film
|Mar 7, 1986
|Jul 21, 1987
|Ppg Industries, Inc.
|Color plus clear coatings employing polyepoxides and polyacid curing agents in the clear coat
|Apr 29, 1987
|Jan 12, 1988
|Ppg Industries, Inc.
|Process for the preparation of multi-layered coatings and coated articles derived therefrom
|Jul 19, 1985
|Mar 1, 1988
|Minnesota Mining And Manufacturing Company
|Polysiloxane-grafted copolymer release coating sheets and adhesive tapes
|Mar 5, 1986
|Mar 29, 1988
|Hoechst Aktiengesellschaft
|Biaxially oriented polyolefin multi-layer film
|Nov 5, 1986
|Mar 29, 1988
|Hoechst Aktiengesellschaft
|Multilayer packaging film having superior scratch resistance
|Nov 24, 1986
|Oct 11, 1988
|Raychem Corporation
|Curable organopolysiloxane composition
|Apr 15, 1987
|Dec 13, 1988
|Basf Corporation, Inmont Division
|Polyurethane resins in water-dilutable basecoats having low flash and quick-drying characteristics
|Feb 16, 1988
|Jul 4, 1989
|Becton, Dickinson And Company
|Method for preparing lubricated surfaces and product
|Nov 7, 1988
|Jul 11, 1989
|Cogent Limited
|Compositions and processes producing scratch resistant polysiloxane coatings
|Jun 29, 1989
|Apr 3, 1990
|The Dow Chemical Company
|Process for preparing polyurethane-backed substrate
|Feb 17, 1989
|Jun 12, 1990
|Eastman Kodak Company
|Paint coated sheet material with adhesion promoting composition
|Feb 25, 1988
|Oct 9, 1990
|Konica Corporation
|Thermal transfer recording medium
|Apr 27, 1988
|Nov 30, 1988
|Lord Corporation
|Reaction products of reactive silicone, polyol, and isocyanate, urethane-siloxane copolymers and coating compositions, methods of coating, coated articles, and prepolymer solutions thereof
|Title not available
|"Information about Organofunctional Silicone Fluids", Dow Corning® 1248 Fluid, Form No. 22-713A-82.
|"Information about Silicone Fluids" Dow Corning® Fluid, Bulletin 22-069 Oct. 1971.
|"Organofunctional Silicone Fluids-Silicone Polycarbinols-", Dow Corning New Product Information.
|Information about Organofunctional Silicone Fluids , Dow Corning 1248 Fluid, Form No. 22 713A 82.
|Information about Silicone Fluids Dow Corning Fluid, Bulletin 22 069 Oct. 1971.
|Organofunctional Silicone Fluids Silicone Polycarbinols , Dow Corning New Product Information.
|Citing Patent
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|Dec 16, 1993
|Mar 7, 1995
|Wolff Walsrode Ag
|Multilayered polyurethane film and the use thereof as packaging material for photosensitive material
|Aug 25, 1994
|Jul 11, 1995
|Poly Circuits, Inc.
|Conductive adhesive for use in a circuit board
|Sep 29, 1997
|Jul 21, 1998
|Maynard; Robert G.
|Paint applicator method
|Aug 18, 1997
|Oct 19, 1999
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|Paint film assembly with masking film and method of making same
|Mar 28, 1996
|Nov 16, 1999
|Rexam Industries Corp.
|Flexible composite surfacing film and method for producing same
|Jun 24, 1998
|Nov 16, 1999
|E.I. Du Pont De Nemours And Company
|Coating containing hydroxy containing acrylosilane polymer to improve mar and acid etch resistance
|May 9, 1996
|Mar 14, 2000
|Basf Coatings Ag
|Films for coating shaped-part blanks and the use thereof in automobile manufacturing
|Jul 4, 1995
|May 16, 2000
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|Substrates coated with two or more coats and process for producing these substrates
|Aug 4, 1999
|Jul 4, 2000
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|May 9, 1996
|Oct 17, 2000
|Basf Coatings Ag
|Films provided with several coating layers and the use thereof in automobile manufacturing
|Apr 15, 1997
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|Polymer Ventures, L.L.C.
|Corrosion resistant barriers
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|Chrome coated article
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|Gloss-adjusting mask layer with particulate filler
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|Decorative sheet and sheet-decorated molding containing (meth) acrylate polymers
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|Decorative system composite and method
|Jul 19, 2006
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|Method of producing a paint film part
|Nov 18, 2005
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|Jun 4, 2010
|Nov 20, 2012
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|Polymer mixture
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|Oct 1, 2013
|Entrotech Composites, Llc
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|Articles comprising protective sheets and related methods
|Jun 30, 2006
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|3M Innovative Properties Company
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|Sep 16, 2014
|Dec 29, 2015
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|Method of applying adhesive coated film
|Jun 3, 2014
|May 17, 2016
|3M Innovative Properties Company
|Adhering graphic films on irregular substrates
|Jul 11, 2001
|Aug 15, 2002
|Sellepack David M.
|Polymeric watercraft and manufacture method thereof
|Jul 11, 2001
|Aug 15, 2002
|Sellepack David M.
|Polymeric watercraft and manufacture method thereof
|Jul 31, 2003
|Feb 12, 2004
|Ohrbom Walter H.
|Gamma hydroxy carbamate compounds and method of making and using the same
|Oct 15, 2003
|Jul 1, 2004
|Daimlerchrysler Ag
|Dry-paint film for application to a component
|Jan 27, 2004
|Dec 9, 2004
|Robert Lafave
|Decorative system composite and method
|Aug 25, 2004
|Jan 27, 2005
|Bsh Bosch Und Siemens Hausgerate Gmbh
|Housing for a household appliance
|Mar 4, 2005
|Sep 22, 2005
|Miller Joseph E
|High energy curable coatings comprising thermoplastic polymers
|Dec 2, 2005
|Jun 8, 2006
|Lafave Robert J
|Method of producing a paint film part
|Jul 19, 2006
|Nov 16, 2006
|Robert Lafave
|Decorative system composite and method
|Jun 30, 2006
|Jan 4, 2007
|3M Innovative Properties Company
|Method of applying adhesive coated film
|Nov 18, 2005
|May 24, 2007
|Solaint Llc
|Decorative Paint film laminate
|Dec 5, 2005
|Jun 7, 2007
|Lear Corporation
|Method of making and inspecting an in mold coated article
|Jan 14, 2008
|May 15, 2008
|Robert Lafave
|Decorative System Composite and Method
|Sep 2, 2008
|Mar 4, 2010
|Ppg Industries Ohio, Inc.
|Coating compositions comprising the reaction product of a biomass derived polyol and a lactide
|Jun 4, 2010
|Oct 21, 2010
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|Polymer mixture
|Nov 9, 2010
|Apr 28, 2011
|Soliant Llc
|Decorative paint film laminate
|Feb 12, 2003
|May 5, 2010
|Housing for a household appliance
|Dec 7, 2007
|Jun 10, 2009
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|Oct 18, 1999
|Apr 19, 2000
|Premark RWP Holdings, Inc.
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|Jul 4, 1995
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|Basf Lacke + Farben Ag
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|May 9, 1996
|Nov 14, 1996
|Basf Lacke Und Farben Aktiengesellschaft
|Films provided with several coating layers and the use thereof in automobile manufacturing
|May 9, 1996
|Nov 14, 1996
|Basf Lacke Und Farben Aktiengesellschaft
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|May 9, 1996
|Nov 14, 1996
|Basf Lacke Und Farben Aktiengesellschaft
|Films for coating shaped-part blanks and the use thereof in automobile manufacturing
|Aug 11, 1999
|Mar 16, 2000
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|Feb 8, 2002
|Aug 22, 2002
|Leisure Life Limited
|Polymeric watercraft and manufacture method thereof
|Feb 8, 2002
|Feb 27, 2003
|Leisure Life Ltd
|Polymeric watercraft and manufacture method thereof
|Feb 12, 2003
|Aug 28, 2003
|BSH Bosch und Siemens Hausgeräte GmbH
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|Nov 15, 2006
|May 24, 2007
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|Decorative paint film laminate
|Dec 22, 2011
|Jul 5, 2012
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|Decorative article
|U.S. Classification
|428/213, 428/447, 428/215, 428/423.3, 428/332
|International Classification
|Cooperative Classification
|European Classification
|Oct 22, 1996
Owner name: AVERY DENNISON CORPORATION, CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:EASTMAN KODAK COMPANY;REEL/FRAME:008194/0242
Effective date: 19951113
|Jun 6, 1997
|Fee payment
Year of fee payment: 4
|Jun 6, 2001
|Fee payment
Year of fee payment: 8
|Jun 7, 2005
|Fee payment
Year of fee payment: 12


text:
2007-08-12 - E-2D ErstflugE-2D makes maiden flight
Erstflug für neues Frühwarnflugzeug der US Navy<br /> The first E-2D Advanced Hawkeye development aircraft, known as Delta One, built for the U.S. Navy by prime contractor Northrop Grumman Corporation, completed its first flight on August 3. Northrop Grumman Flight Test Pilot Tom Boutin and U.S. Navy Flight Test Pilot Lt. Drew Ballinger along with Northrop Grumman Flight Test Lead Weapon Systems Operator Zyad Hajo lifted off shortly before 11 a.m. and flew for approximately 1.3 hours.
While the external appearance of the E-2D is similar to the E-2C, the systems are completely redesigned and the capabilities are vastly expanded. At the heart of the aircraft is the new radar, the APY-9, which can "see" smaller targets and more of them at a greater range. The new rotodome contains an electronically scanned array that provides critically important, continuous, 360-degree scanning. This capability allows flight operators to focus the radar on select areas of interest.
Inside the aircraft, Advanced Hawkeye operators will have new radar system workstations, integrated satellite communications capabilities and other cutting-edge tools to better manage the battlespace. An additional new feature of the E-2D Advanced Hawkeye is the state-of-the-art glass cockpit that replaces prior-generation displays and avionics systems. In addition, an advancement introduced in this version allows for one of the two pilots to serve as an additional operator when necessary.

subset: commoncrawl


text:
New Ways to Discover Croatia – Olivari
Our GPN member for Croatia – Olivari d.o.o. is specialised in incoming to Croatia and South East Europe where they offer complete tourist service.
Their programmes are carefully created and developed, and personally tested to the smallest details. They put a lot of effort and attention into bringing new ideas and inovative programmes to life.
This spring they have developed new programmes which will enable you to discover Croatia in a new way.
For instance, Olivari's first suggestion is to sail into an adventure with sailing boats Ocean 1, Ocean 2 and Ocean 3 Cruising with motor ships along the magnificent Dalmatian coastline & islands is the perfect way to relax completely while on vacation, but at the same time you can get to know their cultural heritage, enjoy our beautiful nature, and cuisine.
Discover fragances, tastes, nature, culture and dive into the croatian coast.
Other suggestion done by our GPN member in Croatia – Olivari, is to revive your childhood memories on the paths of the Winnetou and mix the culture, city and country in a travel in the footsteps of UNESCO heritage of Dalmatian region.
Get to know urban heritage and enjoy a picnic in the country side on the canyon of river Zrmanja where Winnetou movies were filmed.
Visit their website www.olivari-travel.com or contact them directly for more information.


text:
Dila Nubiles - Early Morning Pleasure
Description:Frail brunette dolly woke up feeling raunchy and horny. She grabs her trusty red dildo and uses it to tease her nipples before ramming it deep down her sweet shaved pussy.
Category:+18 only (Adult)
Added:3 years ago
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text:
In an unfortunate series of events, Moschino and Jeremy Scott are under fire for plagiarizing... graffiti.
Does this look familiar at all to you? It should... because this is the image on Katy Perry's China: Through The Looking Glass dress.
Is artist Rime right to bring Jeremy Scott and Moschino to court? http://t.co/0AHQ3vr6rz pic.twitter.com/szjT6UwI9O
— VOGUE.CO.UK (@BritishVogue) August 5, 2015
According to E!, Jeremy Scott is being sued by Joseph Tierney, Street Name "Rime," based on the "iconic" and "memorable" dress.
Not only did the dress don the design, but Scott's Suit also had the eyes on the back. Clearly Rime was not consulted before the design was created, and he is now saying just that.
E! quotes the lawsuit: "Defendants paid Ms. Perry to advertise and display the clothing at the Gala. Not only did Ms. Perry and defendant Scott advertise, wear, and display the clothing at the event, they arrived at the event in a spray painted Rolls Royce, and even carried around Moschino branded cans of fake spray paint during the event, as if defendants were responsible for the artwork."
Perry is also not the only one to wear the dress, as Gigi Hadad modeled it for Milan's Fashion Week in February:
Now, I'm no legal analyst, but let me give you a little schooling on Art Appropriation, and how potentially Moschino can get out of this. As an artist myself, I would be mega upset at someone taking my good hard work and putting it on their clothes and making millions of dollars, so by all means, personally, I'd side with Rime on this one from a "Kicking down the man" aspect. But for Jeremy Scott's case, he could throw Rime a little bone called "Art Appropriation."
RemixTheBook.com states "Appropriation art takes a (usually) recognizable object, text or image and recontextualizes it. In the new context, the associations that the reader/viewer has with the appropriated object are subverted, and he or she is forced to reexamine his/her relationship to it. Therefore appropriated art is often political, satirical and/or ironic."
A fair example of this would be Shepard Fairey's "Hope" poster from the 2008 Campaign of President Barack Obama vs. The Associated Press against a photo he used to create the image. (To read more, visit ObeyGiant, Fairey's Website)
— radioc00per (@radioc00per) August 5, 2015
A more controversial pick is Sherrie Levine's After Walker Evans (1981) V. Walker Evans' Alabama Tenant Farmer's Wife (1936), in which Sherrie Levine shot a photo of Walker Evans' photo in a gallery, and reproduced her shot, and it was still considered a Contemporary and Post-Modern art legacy. (To read more, see StudentPulse.com)
— radioc00per (@radioc00per) August 5, 2015
So the question is, if Jeremy Scott has seen this particular image prior from Rime and chose to use it as a design for his clothing, could he potentially get away with using "Art Appropriation" as an excuse? I mean, Andy Warhol's Campbell Series is all based on image appropriation of the soup labels, so would a dress be the same? Since appropriation in the legal context is based on visual images, it very well could be. Which in that case, Rime, you might be out of luck.
Amy Cooper is a writer and pop culture fact nerd, and on multiple occasions has been referred to as a "Walking iPod."


text:
Randy Gibb, PhD
Dean, Colangelo College of Business
Randy Gibb is the dean of the Colangelo College of Business at Grand Canyon University; he leads a college that offers academic programs at the graduate and undergraduate levels. Dr. Gibb is a former pilot and retired colonel, U.S. Air Force, having led two different flying squadrons, served as chair of the behavioral science and leadership department at the U.S. Air Force Academy and worked as a senior military professor at the Air Force Institute of Technology. He also was chair of the human and environmental systems department at Arizona State University. Dr. Gibb earned his BS from the USAF Academy, MSE from Arizona State University, MA from the Naval Command and Staff College and PhD from Arizona State University.
Chuck Jarrell, PhD
Faculty, Colangelo College of Business
Chuck Jarrell grew up in southern West Virginia and has undergraduate degrees in aerospace engineering and business administration, and an MBA with an emphasis in marketing from West Virginia University. He earned a PhD in business administration with an emphasis in marketing from Northcentral University.
Donna L. DeMilia, PhD, CPA, CMA
Associate Professor of Accounting, Colangelo College of Business
Donna DeMilia is a dedicated accounting educator with over 20 years of experience in the classroom. She is able to bring her background in both public and private accounting to the classroom, and enjoys helping students to understand complex accounting situations through connecting them to real-life scenarios.
Ernie Scarbrough, DBA
Associate Professor, Colangelo College of Business
Ernie Scarbrough, DBA, has been a professional pilot, cost analyst, transportation analyst, air traffic controller, copper miner, sailor, securities representative, portfolio manager, certified financial planner, certified investment management analyst and a university finance professor. His nonprofit experience includes: American Cancer Society, Sojourner Center (a domestic violence crisis shelter) and John C. Lincoln's Desert Mission Board (food bank, etc.). He is also a member of Phoenix Police Department's Administrative Review and Use of Force Board.
Read more about Ernie Scarbrough
Kelly K. Damron, CPA, MBA
Assistant Professor of Accounting, Colangelo College of Business
Kelly K. Damron, CPA, MBA, is an assistant professor of accounting at Grand Canyon University. She was the recipient of the Public Service Award from the Arizona Society of CPAs in 2010. Kelly teaches introductory financial accounting, managerial accounting and advanced level accounting courses. Kelly utilizes games and other practical activities in the classroom to help students understand the topic and connect it to real-world situations. She holds a Bachelor of Science in accounting from Colorado State University and a Master of Business Administration from the W. P. Carey School of Business. She is the co-faculty advisor for the Collegiate DECA of GCU chapter.
Kevin McClean, DPS
Faculty, Colangelo College of Business
Dr. R. Kevin McClean, professor of marketing at Grand Canyon University's (GCU) Colangelo College of Business, is in his 14th year of teaching at GCU. Dr. McClean teaches at the undergraduate and graduate levels, and he served as dean of the College of Business at GCU from 2012 to 2014.
Dr. McClean has presented to industry forums and conferences regarding energy deregulation, marketing management, project management and customer service, and was a contributor to an award-winning compendium on leadership challenges. He is the founder and editor-in-chief of the "Canyon Journal of Interdisciplinary Studies," and sponsors annual academic symposia and research colloquia. He was conferred a BA in History by King's College; an MBA by St. John's University; and a Doctor of Professional Studies by Pace University. He has been inducted into Beta Gamma Sigma, honor society of collegiate schools of business; Omicron Delta Epsilon, international honor society in economics; and Delta Mu Delta, international honor society for business.
Krystal Slivinski, MA
Assistant Professor, Colangelo College of Business
Krystal Slivinski is an assistant professor of economics at Grand Canyon University. Before teaching undergraduate and MBA economics at GCU, Krystal lobbied the Arizona Legislature to improve tax, budget and regulatory policies. She also trained K-12 teachers to teach economics in a hands-on and engaging way with the Arizona Council on Economic Education. Prior to moving to Arizona, Krystal spent nearly a decade in Washington, D.C. working in think tanks and the public policy world. One of her greatest policy achievements was to help the Virginia Legislature amend the Virginia Constitution to improve protection of private property rights against eminent domain abuse. Krystal has a bachelor's degree in economics and English from West Virginia University and a master's degree in economics from George Mason University. Krystal in Phoenix with her husband and their three sons.
Read more about Krystal Slivinski


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We love Polly Pocket. Not only are the toys fun and great for imaginative play, but they're also just plain cute. So many toys for girls are overdone and the dolls aren't realistic or are look…
An American Girl: Saige Paints the Sky Movie Review
Saige Copeland, American Girl's 2013 Girl of the Year, will come to life in her own movie this summer! Nine-year-old Saige is a talented artist who loves horses. When she learns that the art program at…
Disney Princess Cinderella's Transforming Pumpkin Carriage
Since our Disney trip Bella has really been into all the Disney Princesses, especially Snow White and Cinderella. We've read the stories and listened to their songs, played dress up and pretended to be princesses….
The My Little Pony Friendship Express Train
My Little Pony friends were one of my favorites when I was a little girl and now my own daughter loves them too. Emily has several My Little Ponies and spends hours playing with them….


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Home » Insecticide Concentrates » Dylox 420 SL Insecticide » All Reviews
Displaying 1 to 3 (of 3 reviews)
23 of 24 people found this review helpful:
Dylox 402 SL for white grubs
By Brent on 05/14/2014
Verified Purchase
We tried GrubEx, Diazinon, and most other big box store products over the past 5 years or so with no noticeable impact on our lawn's grub infestation. This product killed the grubs overnight, after watering in. Birds no longer dig out grubs to eat, they just feed on surface insects now. Our lawn is coming back nicely. I applied this in May when the grubs were quite large and the product worked perfectly. I used the label suggested rate of 6.9oz/1000sqft.
1 of 1 people found this review helpful:
By Roger on 10/16/2016
applied product 2 weeks ago and had no effect on grubs ,very disappointed in the results,I thought this product was superior then Grub X .I am very disappointed in this product .
0 of 1 people found this review helpful:
Great Experience
By Sherman on 06/29/2017
Had inventory, shipped timely and arrived in perfect condition. Will use Do My Own for the foreseeable future. Thank you


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Tent Pole Clamps for up to 3" diameter perimeter tent poles to install a single fixture.
How much are you selling them for?
TOS does not allow me to "actively" solicit sales.
I had a very productive morning today and built another 42 perimeter tent pole clamps. There's 20 in the box pictured.


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August 15, 2005 by AK
Animals: a drowsy toad
Seen a few miles outside of Moscow.
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Working as a DJ in the South Florida salsa scene, Jorge Charun watched bachata, a Dominican Republic rhythm and dance, take the place of reggaeton in dance clubs and on the radio.
"There's a huge demand for bachata music now," Charun says. "A lot of people, as they play in different venues, they realize that every time they play bachata, everybody is on the dance floor."
That's why he created the first South Florida event dedicated to bachata. The South Florida Bachata Freaks Affair will be held Saturday at VK Dance Studio in North Miami Beach. It will feature professional bachata performers, workshops and an open dance floor before and after the shows. Salsa dancing will also take place.
Although bachata often uses turns and spins that are similar to salsa, it's a slower and more sensual dance, in which the partners move so close to each other that their hips touch and their legs intertwine. The basic step is from side to side, instead of back and forth.
"I like bachata because it's very sexy. It's really easy to connect when you're dancing bachata," Charun says.
Charun likes it so much that he often leaves his post as DJ and joins the dance floor, going back to his station right before the song ends.
South Florida Bachata Freaks Affair will begin 9 p.m. Saturday at 3363 NE 163rd St., Suite 101, in North Miami Beach. Admission is $20. Go to Miami.VKdance.com.
email@example.com, @babicorb or 954-356-4710


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Pawn by Aimee Carter (The Blackcoat Rebellion #1)
(Available December 2013)
You can be a VII - if you give up everything. For Kitty Doe, it seems like an easy choice. She can either spend her life as a III in misery, looked down upon by the higher ranks and forced to leave the people she loves, or she can become a VII and join the most powerful family in the country.
If she says yes, Kitty will be Masked—surgically transformed into Lila Hart, the Prime Minister's niece, who died under mysterious circumstances. As a member of the Hart family, she will be famous. She will be adored. And for the first time, she will matter.
There's only one catch. She must also stop the rebellion that Lila secretly fostered, the same one that got her killed …and one Kitty believes in. Faced with threats, conspiracies and a life that's not her own, she must decide which path to choose—and learn how to become more than a pawn in a twisted game she's only beginning to understand.
The ideas behind Pawn are the same ones behind almost every dystopian book out there, and it hasn't got much to make it stick out. The ranking system and government is neatly explained and pretty simple, which is a point in the book's favor, but its plot circles around itself constantly. It's very predictable, but it doesn't entirely lack excitement. The Harts are the perfect dastardly villains, without a shred of good in some of them. Carter succeeded in making me hate them and keeping me guessing at their true intentions. However, most of the excitement leads to a standoff almost identical to one a chapter ago. Kitty's reaction is always the same, and always centered around her love for her boyfriend and her fear of death; she doesn't change at all through the course of the book.
The premise of the book, while similar to a lot of others, wasn't disappointing. The point of dystopia is to point out flaws in our own world by exaggerating them into a fictional one, and Carter hit the nail on the head there. The idea of false equality for everyone in society and the promise that hard work would lead to the life everyone deserves mirrors some of the ideas in our society, and that aspect of the book was fairly interesting.
The symbolism of the ranking system wasn't enough to earn the book more than two stars, however. There are a lot of books with similar ideas behind them (the most similar would be Starters by Lissa Price) that are much better written, and I'd be more likely to recommend one of those.
Ex Libris, Veritas
Welcome to Verity Reviews, a book blog to promote, review, and critique YA books of all genres.
Currently Reading
As Simple as Snow
March 2017


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pittsburghpirates wrote:jetsfan1 wrote:beantheshadow wrote:
Hey no expert but responding here because I had the same situation, although my takes were 2.5 years apart. For the T6, I only sent an addendum to Y but got in everywhere, so to be honest I don't think it made much of a difference at all. If you PM me I'll send you the addendum (it was much more concise then what you seem to be thinking). Obviously not to copy, but just to get a sense of what "worked" - and I put worked in quotes because I really don't think it made a difference. The time speaks for itself.
Regardless, good luck with your retake!
Also not an expert, but to add onto what jets said I was in the virtually exact same situation as you were. I wrote an addendum for the LSAT and submitted it to everywhere I applied and my cycle has gone as well as I could have hoped. Feel free to PM me, I'm also happy to share more details and my addendum provided I can dig it up!
Not an expert either, but I jumped 12 points (scores were 2 years apart) and sent an addendum to every school I applied to. I think I had just about as good a cycle as I could have realistically hoped for, but I don't necessarily think that the addendum positively or negatively affected my outcomes. Like jets, I also kept my addendum very short. Maybe 5 sentences? Also willing to share my addendum if you'd like.


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RADHE RADHE: Rites of Holi Trailer (2014)
06 November 2014 35 mins
Bhargava and Iyer were inspired by the centennial of the Stravinsky-Nijinsky The Rite of Spring to explore another of rite of spring: the Hindu festival of Holi, famous for its revelry of color in celebration of the love between the divine Krishna and mortal-born Radha. In northern India, Bhargava filmed the ravishing images of an eight-day Holi festival held in the city of Mathura, mythic birthplace of Krishna. Iyer – who released his ECM debut, Mutations, earlier this year – then composed his score as the musical complement to Bhargava's beautiful visual ballet, drawing at times on the rhythms and chants of the Holi festival; the result is one of Iyer's warmest, most colorful creations to date, as rich melodically as it is texturally. RADHE RADHE: Rites of Holi is a kaleidoscopic experience.
Watch the official RADHE RADHE: Rites of Holi 2014 trailer in HD below or find more RADHE RADHE: Rites of Holi videos on Vidimovie.


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Family's joy as liver transplant hailed a success
A seriously ill liver-failure patient is likely to be out of hospital in three weeks after a lifesaving transplant operation hailed by doctors and his family as a success.
Ricky Cheng Kin-kwong (pictured) was last night in a stable condition in the intensive care unit at Queen Mary Hospital after the day-long transplant operation ended at 9pm on Friday.
The donor, a distant female relative aged in her 40s who passed a series of biological and psychological tests before the operation, left hospital yesterday.
Cheng's family had been desperately seeking a donor after the hepatitis B sufferer's liver function dropped to just 10 per cent of normal last Saturday. Without a transplant, he was given only a 10 per cent chance of surviving more than three months.
His siblings, who also have hereditary hepatitis B, were ruled out as potential donors, as were other relatives whose blood types did not match.
Cheng's wife, Emily Tsui Yee-wan, said she was grateful for the relative's decision to undergo the transplant and to the strangers who had stepped forward as potential donors after the family's requests for help on the internet.
'I'm looking forward to his full recovery,' she said.
Cheng's niece Angel Lam Ho-kwan, who had helped take care of him every day during the past week, said: 'We can finally relax. We're grateful for the relative's help, and also to the more than 10 strangers who actually came and had their livers tested, even though none turned out to be suitable.'
Professor Lo Chung-mau, head of the University of Hong Kong liver transplant team at Queen Mary Hospital, said the operation went well. 'The liver was donated by a distant relative and the operation went smoothly. It ended at 9pm on Friday,' he said.
He added that the key to the success of the operation was the relative's willingness to donate part of her liver. 'The most important thing was not whether the livers matched, but whether the person had the determination to do it,' he said.
Lo said Cheng's condition was stable, and it was highly likely he would be ready to leave hospital in three weeks. 'When he came his condition was not very good, so I think he will need a bit more time than usual to be fully recovered,' he said.
Cheng had been placed at the top of the waiting list for a liver from a dead donor, but it is rare to find a suitable and functional one from such a source.
Crystal Ku Wing-yin, another of Cheng's nieces, said some relatives had flown from Australia to see if they were suitable donors. More than 40 strangers had also offered to help after an appeal by Cheng's wife on Facebook which received wide media attention. None of them were deemed suitable as potential donors.
Cheng has needed drugs to control his condition since he was young. Two weeks ago, he experienced acute heartburn and was rushed to the Caritas Medical Centre in Sham Shui Po. He was prescribed drugs but the situation worsened, and he was transferred to Queen Mary Hospital.
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Climategate Scientist Jones Admits His Data Is Disorganized/
GreenTracker| Global citizens concerned about climate change and the degree to which humans can and should change the course of climate history — because it suits the interests of humans to do so — will be disappointed to learn that Professor Phil Jones, the man at the center of 'Climategate' has admitted that he has trouble 'keeping track' of critical information.
While environmental data has been collected at multiple research stations around the globe, the University of East Anglia's Climatic Research Unit, now the subject of an independent inquiry led by Britain's top scientists, exists at the center of the science storm, demanding that world governments retool economies before it is too late.
These latest admissions from Professor Jones that he cannot find the critical data for the 'hockey stick graph' and other key 'evidence' of climate change science, leave informed people on every continent speechless.
We will develop this story, based on its reporting and analysis in major media and environmental action media. Our interest is in how the 'green press' reports this latest story to readers.
Read on: 'Climategate' expert Jones says data not well organized BBC News


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Guides for Helping Adults Recover from Eating Disorders
These are written based on my experience on my own recovery and that of those whom I have worked with since. These guides are by no means intended to be used as an alternative to professional treatment. Any person in recovery from an eating disorder needs a "team" for best chances of full recovery.
In my opinion, such a team consists of:
- An ED savvy dietician who fully understands the extent to which a person recovering from an eating disorder needs to eat foods high in fat and calories and also understands that restriction is never an option at any bodyweight.
- A doctor who can monitor bloods and other vital signs during recovery
- A support person (this is the EDCP in the guides)
- An eating disorder coach. This is someone who understands eating disorders, the complications involved, and a person who manages the team by coordinating efforts and helping the EDCP when needed. This is the sort of thing I do.
You may additionally need to coordinate working with other therapists if there are co-morbid disorders present. Everyone has to work together as a team and communication is key!
All the recovery guides, podcasts, and blogs that are on this site are free. If you would like to make a donation you can do so here:
All donations go to AEDRA Meal Support Service to provide a person in need with meal support. Thank you
Eating Disorder Recovery Kit for Adults
This is designed for adults who are in recovery from an eating disorder and are actively trying to get better.
Eating Disorder Recovery Guide for Adults Helping an Adult with an Eating Disorder
This is a guide for adults who are helping another adult recover from an eating disorder. While written for partners of adult sufferers it is also relevant for parents and friends of adult sufferers.
Guides to Give to Extended Family and Friends
Eating Disorder Quick Guide for Extended Family and Friends
This quick guide is a pdf that you can send to extended family and friends so that they have a reference that will teach them the fundamentals of understanding what an eating disorder is, and how they can assist and support.
Guides for Getting Though Holidays and Special Events
Thanksgiving Holiday Contract and Survival Tips
The downloads in this post provide structure for managing Thanksgiving with a person with an eating disorder.
Eating Disorder Quick Guide for Thanksgiving
Quick guide to give to families and friends for Thanksgiving so that they know how to support and how not to unintentionally sabotage.
Download the Quick Guide Here
Eating Disorder Quick Guide for Christmas
Quick guide to give to families and friends for Christmas so that they know how to support and how not to unintentionally sabotage.
Download the Quick Guide Here
Christmas Day Contract and Survival Tips
The downloads in this post provide structure for managing Thanksgiving with a person with an eating disorder.
Additional Support:
Please visit the blog archives for in-depth information on varies eating-disorder specific topics.
Adults in recovery there is a peer-support forum for you –> info on that here.
Partners/parents of adults in recovery there is a peer support forum for here –> email me if you want an invite.
I provide coaching for adults in recovery and caregivers/partners/parents of adults in recovery. More info on this here.


text: The Butterfly Wrap is coolest skirt you'll ever own! It can be worn as many ways as you can think up! The Wrap is reversible and can be worn as a skirt, a dress or a shirt. I've come up with ten looks, how many different looks can you find?? This skirt is easy to sew. You do not need a serger for this pattern. It can be made with a regular sewing machine. The e-book is 39 pages with 16 color pictures to guide you through the step by step instructions. It prints on standard 8 1/2 x 11 paper and the sheets are taped together to create the full size pattern. This pattern is professionally CAD drawn. Specific Materials: Fabric suggestions: Cotton, Cotton Blends, Silk Types, Lightweight Satins, Lightweight Linen, Knits 3/4 to 1 7/8 yard for Print fabric. (Fabric yardage varies with skirt size and length) 3/4 to 1 7/8 yard for Solid fabric. (Fabric yardage varies with skirt size and length) Matching thread Copyright info: My patterns, tutorials, all imagery and photography are property of Butterfly Tree and are copyrighted. Any portion of this pattern, tutorial or photographs may NOT be copied, shared, or resold, whole or in part without express written permission. Handmade garments created by the purchaser using my patterns may be sold. U.S. and international copyright laws apply. CREDIT FOR THE PATTERN DESIGN AND A LINK BACK TO MY STORE IN YOUR SALES LISTING ARE REQUIRED. Thank you for your honesty and for respecting my hard work. SIZING / FINISHED MEASUREMENTS 12mo - 18mo, 2-3yr, 4-5yr, 6-7yr. Both knee length and mid calf length are included for each size


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A Novel QoS Aware RWA With Dedicated Path Protection Consideration for All Optical Networks
In all optical networks, signals has to travel over long distances and Physical Layer Impairments (PLI) accumulate as regeneration capability is not available. During transmission, Quality of Service (QoS) of signals as measured by their Bit Error Rates (BER) is degraded due to propagation in the fibers, amplifier noise, and crosstalk between channels arising from the switches and de-multiplexers which cannot be removed at the physical layer. It is possible to mitigate physical layer effects at the network layer using appropriate QoS aware Routing and Wavelength Assignment (RWA) algorithms.
Provided by: WSDOT Topic: Mobility Date Added: Jul 2012 Format: PDF


text: Cranio Care Bears was there for me for support and they sent my family a wonderful care package. It was a difficult time and when a mother is told your child will have to have surgery for crainiosynostosis- the world around you stops. After that I went on the web to research what I could to better understand what was about to happen to my little baby girl and how will this impact my family. Cranio Care Bears was teh first web site I came across and then i was forwarded to others. This is the most caring organization and I dont think they will ever know how they helped me.


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Ted Cruz explains Trump endorsement at Fort Worth event
Texas Sen. Ted Cruz spoke publicly for the first time Wednesday since his endorsement of Donald Trump and said he did it to prevent Hillary Clinton from winning.
"Although I have long had significant concerns with Donald, by any measure, Hillary Clinton would be an absolute disaster as president," Cruz said during a visit to Tarrant County Republican headquarters.
Cruz was widely booed and dropped in favorability ratings after not endorsing Donald Trump during his speech at the Republican National Convention. During the primary battle, Trump made disparaging comments about wife Heidi Cruz and Cruz's father – accusing him of involvement in the JFK assassination.
"I am not in the habit of supporting people who attack my wife and attack my father," Cruz said at a Texas GOP delegation breakfast back in July.
Cruz said he prayed and spoke with members of his family before deciding to endorse Trump last week.
"A year ago, I stood on stage and promised to support the Republican nominee, whoever that was, and I am honoring my word," Cruz said on Wednesday.
SMU political scientist Cal Jillson said Cruz was likely pressured to get on the Trump train.
"Major donors, but also other officials in Texas politics -- most clearly Lieutenant Governor Dan Patrick -- called on him to get back in line," Jillson said.
Cruz is up for re-election as Texas senator in 2018.


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Sassy Water: A Flat Tummy Weight loss program regime Staple
Sassy Water ~ Flat Tummy Weight loss program regime, Purely pure Detox. A approach to assist you drop some added kilos near your midsection by taking away a buildup of contaminants, fats, and further water body weight. Cucumber is pure diuretic, and permits your entire physique launch saved further wa


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What ballot measures are on the November 2016 ballot in San Francisco?
San Francisco voters will vote on 25 different ballot measures in the November 2016 general election. You can learn more about the ballot measures below, or at the San Francisco Department of Elections website.
San Francisco School Propositions
A – School Bonds
B – City College Parcel Tax
San Francisco Bond Measures
C – Loans to Finance Acquisition and Rehabilitation of Affordable Housing
San Francisco Charter Amendments
D – Vacancy Appointments
E – Responsibility for Maintaining Street Trees
F – Youth Voting in Local Elections
G – Police Oversity
H – Public Advocate
I – Funding for Seniors and Adults with Disabilities
J – Funding for Homelessness and Transportation
K – General Sales Tax
L – MTA Appointments and Budget
M – Housing and Development Commission
N – Non-Citizen Voting in School Board Elections
San Francisco Ordinances
O – Office Development in Candlestick Point and Hunters Point
P – Competitive Bidding for Affordable Housing Projects on City-Owned Property
Q – Prohibiting Tents on Public Sidewalks
R – Neighborhood Crime Unit
S – Allocation of Hotel Tax Funds
T – Restricting Gifts and Campaign Contributions from Lobbyists
U – Affordable Housing Requirements for Market-Rate Development Projects
V – Tax on Distributing Sugar-Sweetened Beverages
W – Real Estate Transfer Tax on Properties Over $5 Million
X – Preserving Space for Neighborhood Arts, Small Businesses and Community Services in Certain Neighborhoods
District Propositions
RR – BART Safety, Reliability and Traffic Relief


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Fox Men's Brigader Sasquatch Fleece Zip Hoodie - Grey/Army Green
Rug up and beat the chill in supreme comfort with this zip fleece hoodie. It features a plush faux fur lining to keep you toasty and multiple pockets for safe storage, while contrast army green panelling brings a modern update to any get-up.
Available in men's sizing - see size chart for correct fit!
- Fox apparel
- For men
- Style: Brigader Sasquatch Fleece Zip Hoodie
- Colour: Grey/Army Green
- Fit: Regular
- Drawstring hood
- Full length zipper & snap button closure
- Hand & chest patch pockets
- Plush faux fur lining
- Contrast panelling
- Ribbed hem & cuffs
- Materials:
- Shell: 80% cotton, 20% polyester
- Lining: 100% acrylic
- Sleeve lining/fill: 100% polyester
- Machine washable
- Our model wears a size M and is 186cm tall
Sold in over 50 countries and loved well beyond circles of dirt track enthusiasts, Fox is the most recognised and bestselling brand of motocross lifestyle apparel in the world! This handpicked tee is just what you need when you're looking for casual wear that gives you an edge. But for this price you've gotta start your engine now!


text: Does anyone have experience with that product? Spending more time with the MacBook that I bought and so far have found only one thing that annoys me. The active window does not expand to completely fill the monitor display. Add to that the Leopard does not have tabbed windows availability. Or perhaps I am simply ignorant of how to do what I want to do. I did find a reference to a product called "Sticky Window" that is interesting but did not see with a quick glance if I can "maximize" the windows as I would like.


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