Patent Grant
8092733
This invention relates to plastic composites formed by injection molding, particularly to plastic composites which find use as decorative appliqués for motor vehicle trim, and more particularly, to decorative appliqués having a wide variety of decorative patterns which may exhibit exceptional “depth of image” provided by a layer of relatively clear plastic forming the outer surface.
Transportation vehicles, particularly automobiles, are marketed and sold on the basis of differentiation over other competitive models. Differentiation may be by style or color, and may often be accomplished by using trim panels or appliqués on the interior or exterior of the vehicle which denote different levels of luxury, price or value. These appliqués or panels may also form protective coverings for areas that protrude from adjacent surfaces. These panels may be generally color-coordinated with the adjacent surfaces of the vehicle but may also be bright, reflective, wood grained, marbleized or metallized in appearance.
Originally, real wood appliqués and finished metal panels were used, however, their popularity suffered due to their high cost and limited durability. Subsequently, wood veneers and films with vacuum-deposited metal layers found favor, however, these solutions did not produce the look of luxury or the extended durability required in today's market.
Various proposals have been suggested and practiced for the manufacture of plastic composites for use as automotive interior trim and exterior trim panels or appliqués. One approach has been to form a metal or plastic substrate and apply multiple coatings thereon to produce a high gloss Class A-surfaced part. The substrates may be formed from steel, or any one of a wide range of known plastic materials such as ABS, PP, ABS/PC blends, PU, TPO, PET, PBT or other equivalent high strength plastic materials suitable for injection molding into a product shape. The coatings for such substrates may be selected from known coatings such a primer coat, an adhesion promoter, a base coat and a clear coat, and in the case of metals, an electrodeposition coat. Examples of such coatings are set forth in U.S. Pat. Nos. 4,681,811 and 5,320,869. The solvents used in such systems may cause undesirable environmental and emission problems.
Another approach is to form a paint film and inject polymeric material behind the paint film to produce a part with a desired colormatch on its exposed Class A surface. Examples of known paint film and injection molded plastic parts are disclosed in U.S. Pat. Nos. 5,432,666 and 5,009,821. Such systems may require the separate manufacture and handling of the film. Furthermore, the outer surface being a paint film may not exhibit an exceptional depth of image and may be readily scratched or abraded.
Still another approach to providing a colored plastic part is to provide an enamel coating that will reduce emissions while producing a crater resistant surface on the part being coated. One such system is set forth in U.S. Pat. No. 4,396,680. Such systems may require the use of expensive conventional coating systems and baking ovens to form a finish on the substrate that has the desired appearance.
Yet another approach is to provide laminating equipment in which a color layer is formed by extrusion and then connected to a substrate. U.S. Pat. No. 4,349,592 discloses the use of such a technique in the manufacture of a decorative molding exterior trim part.
Various other proposals have been suggested to produce decorative trim parts and appliqués which have unique decorative patterns, high distinctness of image (DOI) and exceptional “depth of image” which give the impression of luxury and high value. “Depth of image” is herein defined as the emphasis of a decorative pattern by a preferably clear resin layer overlying it, which provides the appearance that the pattern lies deep beneath the top surface of the clear outer layer. This is derived from wood finishing where multiple layers of wax or coatings are applied and buffed out to provide a grain pattern that appears to lie well below the top surface or has depth.
For instance, U.S. Pat. No. 5,338,592 is directed at laminating a series of wood veneers to form an overlay sheet, finishing, cutting and drying the overlay to form a shape, molding a transparent resin layer onto the front surface of the wooden shape and molding a synthetic resin core material onto the rear surface of a wooden shape. However, the effort of forming the wooden veneer overlay to the desired shape is both time consuming and costly.
Similarly, U.S. Pat. No. 5,525,179 is directed at manufacturing a lining part comprising a blank having a preformed shape and a cutout with an edge, injection molding a first plastic material to form a back surface, followed by injection molding a second plastic material to form a front surface coating which also coats the edges of the part. Again, a preformed shape is disclosed.
As disclosed in the '179 reference, German Published Application 41 24 297 describes a similar process using a preshaped blank and employing polymethyl-methacrylate (PMMA) as the outer layer. However, this reference does not disclose the use of a plastic backing layer.
U.S. Pat. No. 6,444,317 is directed at preparing a laminate film including a polyolefin film layer and a primer layer and injection molding a polyolefin resin onto the polyolefin film layer to form an outer layer.
Regarding decorative wood articles, U.S. Pat. No. 6,444,319 assigned to Erwin Behr, GmbH & Co. is directed at surface coating of an interior fitting for vehicles with a lacquer or resin layer wherein a wood veneer component is inserted into a mold and spaced from the cavity so that a liquid surface coating material having at least two mixed components may be introduced into the space between the mold and wood veneer component. United States Patent Application Publications Nos. 2003/0044598 and 2003/0162045, also to Behr, disclose the use of a liquid coating material curable by UV radiation, and the application of a coating material based on vegetable-oil-modified resin and natural vegetable oils, with the addition to the coating material of ceramic micro-particles, respectively.
Finally, United States Patent Application Publication No. 2002/0007898 is directed at a method of making a molded wood part having a wood grain pattern wherein a wood fiber substrate is formed, coated with a water impermeable substrate and a pattern transferred to the substrate using a hydrographic process. A protective top coat may be applied over the pattern. One example of a hydrographic process is disclosed in U.S. Pat. No. 4,010,057 wherein a thin film on which a pattern is printed is floated on the surface of a liquid and the pattern is transferred onto the surface of the object by submerging the surface of the object in the liquid.
While the various methods are suitable for their intended purpose, they all involve processing considerations that either produce emissions, require heavy capital investment in facilities or require unnecessary handling of one or more layers of material in the manufacture of a decorative exterior or interior trim product and do not produce an exceptional depth of image of the decorative layer.
Thus, there is a continuing need in this field of art for an article and its method of manufacture that will obviate the above problems.
In a first aspect, the present disclosure is directed at a method for manufacturing an appliqué or trim panel having a decorative layer, a backing layer and an outer layer, comprising the steps of providing a mold core and a mold cover which cooperate to form a cavity space wherein the core and cover are aligned along one or more shearing edges, providing a sheet of paper and forming the sheet to the shape of at least a portion of the cavity space, the sheet of paper having a front side and a back side and including an image printed on said top surface, placing the formed sheet of paper in the cavity space and aligning the mold core and the mold cover to form a first injection volume. This may be followed by injecting a first polymer against the backside of the formed sheet of paper to substantially conform the formed sheet of paper against the cover side of the first injection volume thereby forming a decorative paper composite comprising a backing layer at least partially formed behind the formed sheet of paper and solidifying the backing layer. This may be followed by retracting the core and the decorative paper composite from the mold cover along the one or more shear edges by an amount related to the thickness of the outer layer thereby forming a second injection volume, injecting a second polymer into the second injection volume against the front side of the decorative paper composite to form an outer layer, and solidifying the second polymer to form the molded appliqué or trim panel, wherein the second polymer is a clear plastic and wherein the sheet of paper has a basis weight in the range of 13-200 lbs. and/or a thickness in the range of 0.003-0.0225 inches and includes a printed image on the top surface.
In another aspect, the present disclosure is directed at a method for manufacturing an appliqué or trim panel having a decorative layer, a backing layer and an outer layer, comprising the steps of providing a mold core and a mold cover which cooperate to form a cavity space wherein the core and cover are aligned along one or more shearing edges, providing a sheet of paper and forming the sheet to the shape of at least a portion of said cavity space, the sheet of paper having a front side and a back side and including an image printed on the top surface and placing the formed sheet in the cavity space. This may be followed by aligning the mold core and the mold cover to form a first injection volume, injecting a first polymer against the front side of the formed sheet of paper to substantially conform the formed sheet of paper against the core side of the first injection volume, thereby forming a decorative paper composite comprising an outer layer overlying the formed sheet of paper, and solidifying the outer layer. This may be followed by retracting the core along the one or more shear edges from the mold cover and the decorative composite by an amount equal to the thickness of the backing layer, thereby forming a second injection volume, injecting a second polymer into the second injection volume against the backside of the decorative paper composite layer to form a backing layer, and solidifying the second polymer to form a molded appliqué or trim panel, wherein the first polymer is a clear plastic and wherein the sheet of paper has a basis weight in the range of 13-200 lbs. and/or a thickness in the range of 0.003-0.0225 inches.
In still another aspect, the present disclosure is directed at a method for manufacturing an appliqué having a decorative layer, a backing layer and an outer layer, comprising the steps of providing a mold core and mold cover which cooperate to form a cavity space, providing a sheet of paper and forming the sheet to the shape of at least a portion of the cavity space, the sheet of paper having a front side and a back side and including an image printed on the top surface and placing the formed sheet of paper in the cavity space. This may be followed by aligning the mold core and the mold cover to form a first injection volume, injecting a first polymer against the back side of the decorative layer to substantially conform the formed sheet of paper against the cover side of the first injection volume thereby forming a decorative paper composite comprising a backing layer at least partially formed behind the formed sheet of paper and solidifying said backing layer. This may be followed by retracting the core from the cover and removing the decorative paper composite, providing a second mold core and second mold cover which cooperate to form a second cavity space, and placing the decorative paper composite upon said second mold core. This may be followed by aligning the second mold cover and second mold core including the decorative paper composite to form a second injection volume, injecting a second polymer into the second injection volume against the front side of the decorative paper composite to form an outer layer, and solidifying the second polymer to form a molded appliqué or trim panel, wherein the second polymer is a clear plastic and wherein the sheet of paper has a basis weight in the range of 13-200 lbs. and/or a thickness in the range of 0.003-0.0225 inches.
In still another aspect, the present disclosure relates to a method for manufacturing a multi-layer composite product of injection molded plastic by providing a moveable mold part comprising at least a first mold core; providing a stationary mold part comprising at least a first mold cover including a first cavity and a second mold cover including a second mold cavity, the second cavity of greater volume than the first cavity and providing a sheet of paper and forming the sheet to the shape of at least a portion of the first cavity, the sheet of paper having a front side and a back side and including an image printed on said top surface. This may be followed by placing the formed sheet of paper into the first cavity and aligning the first mold cover with the first mold core to form a first injection volume, injecting a first polymeric material into the first injection volume behind the formed sheet of paper and solidifying the first polymeric material to form a decorative paper composite. This may be followed by sequentially moving the first mold core including the decorative paper composite with respect to the stationary mold part to selectively align the first mold core including the decorative paper composite with the second mold cover, the second mold cover and the first mold core including the decorative paper composite, forming a second injection volume. This may be followed by injecting a second polymeric material into the second injection volume formed between the decorative paper composite and the second mold cover to form an outer layer, wherein at least one of the first polymeric material and the second polymeric material comprise a clear plastic and solidifying the second polymeric material to form a composite product, wherein the sheet of paper has a basis weight in the range of 13-200 lbs. and/or a thickness in the range of 0.003-0.0225 inches.
In a still further aspect, the present disclosure relates to a method for manufacturing a multi-layer composite product of injection molded plastic by providing a moveable mold part comprising at least a first mold cover including a first cavity, providing a stationary mold part comprising at least a first mold core including a first projecting profile and a second mold core including a second projecting profile, the second profile smaller than the first profile and providing a sheet of paper and forming the sheet to the shape of at least a portion of the first mold core, the sheet of paper having a front side and a back side and including an image printed on said top surface. This may be followed by placing the formed sheet of paper into the first cavity and aligning the first mold cover with the first mold core to form a first injection volume, injecting a first polymeric material into the first injection volume between the formed sheet of paper and the first mold cover and solidifying the first polymeric material to form a decorative paper composite. This may be followed by sequentially moving the first mold cover including the decorative paper composite with respect to the stationary mold part to selectively align the first mold cover including the decorative paper composite with the second mold core, the second mold core and the first mold cover including the decorative paper composite forming a second injection volume, injecting a second polymeric material into the second injection volume formed between the decorative composite and the second mold core to form a backing layer, wherein at least one of the first polymeric material and the second polymeric material comprise a clear plastic; and solidifying the second polymeric material to form a composite product, wherein the sheet of paper has a basis weight in the range of 13-200 lbs. and/or a thickness in the range of 0.003-0.0225 inches.
In a still further aspect, the present disclosure relates to a method for manufacturing an appliqué or trim panel having a decorative layer, a backing layer and an outer layer, comprising the steps of providing a mold core and mold cover which cooperate to form a cavity space, providing a sheet of paper and forming the sheet to the shape of at least a portion of the cavity space, the sheet of paper having a front side and a back side and including an image printed on said top surface and placing the formed sheet of paper in the cavity space. This may be followed by aligning the mold core and the mold cover to form a first injection volume, injecting a first polymer against the front side of the formed sheet of paper to substantially conform the formed sheet of paper against the core side of the first injection volume thereby forming a decorative paper composite comprising an outer layer at least partially formed in front of the decorative layer and solidifying said outer layer. This may be followed by retracting the core from said cover and removing the decorative paper composite, providing a second mold core and second mold cover which cooperate to form a second cavity space, and placing the decorative paper composite upon the second mold cover. This may be followed by aligning the second mold cover and second mold core including the decorative paper composite to form a second injection volume, injecting a second polymer into the second injection volume against the back side of the decorative paper composite to form the backing layer, and solidifying the second polymer to form a molded appliqué or trim panel, wherein the first polymer comprises a clear plastic and wherein the sheet of paper has a basis weight in the range of 13-2001 lbs. and/or a thickness in the range of 0.003-0.0225 inches.
In a still further aspect, the present disclosure relates to a method for manufacturing an appliqué or trim panel having a decorative layer, a backing layer and an outer layer, comprising the steps of providing a mold core and a mold cover which cooperate to form a cavity space wherein the core and cover are aligned along one or more shearing edges, providing a sheet of paper and forming the sheet to the shape of at least a portion of the cavity space, the sheet of paper having a front side and a back side and including an image printed on the top surface and placing the formed sheet of paper against the mold cover overlying at least a portion of the cavity space. This may be followed by aligning the mold core and the mold cover to form an injection volume, injecting a first polymer against the backside of the formed sheet of paper and injecting a second polymer against the front side of the formed sheet of paper, and solidifying the first and the second polymers to form a molded appliqué or trim panel, wherein the second polymer comprises a clear plastic and wherein the sheet of paper has a basis weight in the range of 13-2001 lbs. and/or a thickness in the range of 0.003-0.0225 inches.
In a still further aspect, the present disclosure relates to a method for the in-line production of an appliqué or trim component having a decorative layer, a molded backing layer and a molded outer layer, comprising the steps of providing an inkjet printer adjacent to a plastic molding press, providing a sheet of paper having a front side and a back side to the printer, wherein the sheet of paper has a basis weight in the range of 13-2001 lbs. and/or a thickness in the range of 0.003-0.0225 inches and advancing the sheet through the printer whereby droplets of ink are deposited from one or more printheads in the printer onto the front surface of the sheet, the droplets deposited in such a pattern so as to create a printed image. This may be followed by drying said ink droplets, expelling the sheet from the printer and trimming the sheet to shape. This may be followed by providing a mold core and a mold cover which cooperate to form a cavity space wherein the core and cover are aligned along one or more shearing edges, directly forming the sheet to the shape of at least a portion of the cavity space, the sheet of paper including an image printed on the top surface and placing the formed sheet of paper in the cavity space. This may be followed by aligning the mold core and the mold cover to form a first injection volume, injecting a first polymer against the backside of the formed sheet of paper to substantially conform the formed sheet of paper against the cover side of the first injection volume thereby forming a decorative paper composite comprising a backing layer at least partially formed behind the formed sheet of paper and solidifying said backing layer. This may be followed by retracting the core and the decorative paper composite from the mold cover along the one or more shear edges by an amount related to the thickness of the outer layer thereby forming a second injection volume, injecting a second polymer into the second injection volume against the front side of the decorative paper composite to form an outer layer, and solidifying the second polymer to form the molded appliqué or trim panel.
In still another aspect, the present disclosure relates to an appliqué' or trim panel for decorating or protecting a surface, comprising a decorative paper layer including a top surface and a back surface and including a printed image printed on the top surface, an injection molded plastic backing layer on the back surface and an injection molded plastic outer layer on the top surface, wherein the outer layer comprises a clear plastic and wherein the paper layer has a basis weight in the range of 13-2001 lbs. and/or a thickness in the range of 0.003-0.0225 inches and includes a printed image on the top surface.
Other advantages of the present invention will become readily apparent to those skilled in the art from the following detailed description, wherein it is shown and described preferred embodiments of the invention. As will be realized the invention is capable of other and different embodiments, and its several details are capable of modification in various respects, without departing from the invention. Accordingly, the description is to be regarded as illustrative in nature and not as restrictive.
The features, operation and advantages of the invention may be better understood from the following detailed description of the preferred embodiments taken in conjunction with the attached drawings, in which
Decorative panels in the form of appliqués and bezels are found in many markets; automotive, appliance, marine, furniture, etc. Some of these panels also function as protective trim strips along the sides of boats and cars to prevent minor bumping damage. These panels may take on any appearance to differentiate the product which they are installed upon. Protective trim appliqués are often bright, reflective metal-appearing laminates or extrusions with a plastic outer layer. Popular inside the vehicle are “real wood” appliqués that use a preformed wood laminate which is coated with a clear plastic layer. A key to these wood-appearing products is the relatively thick outer coating which yields a luxurious, expensive-appearing image. The present invention provides a molding process for producing thin appliqués having exceptional decorative appearance and depth. An appliqué of this type is shown at 10 in
A second decorative appliqué is shown in
The construction of the appliqué or trim panel of the present invention is shown in simplified cross-sectional view in
A key to the present invention is an uncomplicated process for forming thin appliqués or trim panels. In a preferred embodiment as shown in
Turning to
Preferably, the clear plastic outer layer 5 comprises a copolymer and more particularly a cyclic olefin copolymer, such as TOPAS® 6015S-04 from Ticona, or a co-polyester alloy, such as OPTIMUM® 800 Grade from Engineered Plastics Corporation. The appliqué 10 as formed by the method of the present invention may be of any thickness suitable for the application for which the appliqué is intended, typically from about 1.0 mm. to about 5.0 mm. with a clear outer layer 5 typically of about 0.5 mm. to about 1.0 mm. in thickness, depending on the molding properties of the clear resin used for the outer layer 5.
Unique to the specific construction and method of the present invention is the ability to mold the appliqué 10 in a single mold set (core 2, cover 4) without having to exchange mold halves to accommodate the outer layer 5. Also unique is the ability to produce very thin appliqués, of about 1 mm. in thickness by a single injection mold set.
The process of a preferred embodiment of the present invention preferably comprises (see
Appliqués and trim panels, according to the present invention, may also preferably include fastening means for attachment to other surfaces, including but not limited to, hook and loop, molded bosses which interact with Palnuts, molded Xmas tree projections, and sections which snap-fit into adjacent or mounting surfaces. Alternately, the fastening features may include dielocks, undercuts and various other female features known in the art.
An alternate method of forming the appliqué of the present invention involves a 2 stage process as described in
A third method for alternatively forming an appliqué of the present invention is disclosed in U.S. Pat. No. 6,468,458, commonly assigned to the assignee of the present invention and included herein by reference. This method, as shown in
In one exemplary embodiment, the relatively thin decorative layer may comprise paper on which a pattern or decoration has been printed, preferably by screen printing, rotogravure or using an inkjet printer. The paper may sheets having a basis weight for 500 sheets of 13 to 200 lbs. More specifically, the paper may be book paper having a basis weight of 30-120 lbs. (for 500 sheets, 25 inches by 38 inches, and having a corresponding grammage of 44-178 grams per square meter, and corresponding thickness of 0.0032-0.0078 inches), bond paper having a basis weight of 13-40 lbs. (for 500 sheets, 17 inches by 22 inches, and having a corresponding grammage of 49-151 grams per square meter, and corresponding thickness of 0.0032-0.0073 inches), cover paper having a basis weight of 50-160 lbs. (for 500 sheets, 20 inches by 26 inches, and having a corresponding grammage of 135-433 grams per square meter, and corresponding thickness of 0.0068-0.0185 inches), index paper having a basis weight of 90-220 lbs. (for 500 sheets 25.5 inches by 30.5 inches and having a corresponding grammage of 163-398 grams per square meter, and corresponding thickness of 0.0074-0.0178 inches) or TAG paper having a basis weight of 100-500 lbs. (for 500 sheets 24 inches by 36 inches and having a corresponding grammage of 163-488 grams per square meter, and corresponding thickness of 0.0074-0.0225 inches). Paper may also be referred to by point, wherein a point equals 0.001 inch in thickness of the sheet, and may range from 3-22.5.
By “paper” it is understood to mean a material made primarily of cellulose pulp, which has been processed into flexible sheets or rolls by deposition from an aqueous suspension.
The decoration of the paper may include printing in the form of words, symbols, graphics, logos, icons and other markings which enhances the appearance of the paper surface.
Once decorated the paper may be formed to a shape complementing a surface of the injection mold in which it will be encapsulated with one or more polymer resins. The process for forming the paper, see
This may then be followed by placing, 508, the formed paper in the injection mold and forming a clear front side or opaque back side layer on the paper. This may then be followed by forming a clear or opaque layer on the remaining outer surface of the paper such that the paper is substantially encapsulated in plastic and forming a decorative appliqué or trim panel according to
In a still further exemplary embodiment, the printing and forming to shape of a paper substrate having a basis weight between 13-200 lbs., including all values therein in 1 lb. increments, or 3-22.5 points (thickness), including all values therein in 0.5 point increments, may be integrated directly into the forming of an interior trim component as part of a continuous in-line process flow. This may provide additional efficiencies in material and labor costs, and allow for an in-line and continuous processing wherein different product options or designs may be readily customized on the surface of the paper without having to build a significant inventory.
This in-line process may be accomplished using an inkjet printer and printing an image of a pattern, graphics, logos, icons, etc. directly onto a sheet of paper that will form a portion of the interior trim component or appliqué.
Direct inkjet printing may be accomplished directly adjacent a plastic injection molding press as described in
As described in
Once the ink has been deposited it may be dried 606 (by the application of heat or other energy (UV, RF, IR) by the polymerization (cross-linking) of the ink, or by using heated paper fed to the printer). The sheet may be expelled from the printer, trimmed to shape and exposed to a source of steam 608 for a period of about 1-10 seconds, preferably 3-5 seconds. The paper may next 610 be placed into a closed porous mold heated to about 160-200° F. and dry air forced through the mold to dry the formed paper to a moisture content of about 5%. This may be followed by any of the processes described in
A thin wood veneer from Kimpara & Co., LTD. of Japan about 0.5 mm. in thickness was placed between the core and cover of an injection mold for an instrument panel appliqué such as shown in
A first plastic material, 5135 polypropylene from Huntsman, LLC was injected behind the wood veneer layer to conform the layer to the shape of a contoured cavity area in the mold cover and fill out the cavity space to form a backing layer. After solidifying the backing layer the core portion of the mold set was retracted 1.5 mm with the backing layer and decorative layer composite remaining tightly affixed to the mold core. The resulting cavity space formed by the retraction of the core from the cover was filled with a second polymer material, V825 poly(methylmethacrylate) from the Atoglas Division of Atofina, the chemical branch of TOTAL. Upon cooling and demolding the appliqué, a wood grained molding having a luxurious appearance was obtained.
Using the same molding set up as in Example 1, a section of coarsely woven fabric, a circular knit, WF0023 from Collins and Aikman Products Co. was positioned between the mold core and mold cover. TOPAS® 6015S-04, a cyclic olefin copolymer from Ticona, was injected behind the fabric to shape it to the contoured cavity space in the mold cover and back the fabric with clear polymer. Upon cooling, the mold core was retracted along with the combined fabric and backing layer and a second layer of cyclic olefin copolymer was injected into the open space, thus forming a protective top layer on the fabric. Upon cooling and demolding, a unique appearing appliqué was formed having an open weave fabric appearance buried deep in a clear layer
Thus, a thin walled decorative appliqué which may function as a decorative or protective surface or edging may be produced using an efficient molding process whereby a thin decorative layer is shaped by injecting a first plastic material, preferably as a backing layer, behind the decorative layer, and subsequently a second plastic material, preferably a clear polymer, is injected on the opposite side, preferably the front side of the decorative layer, to form an appliqué or trim panel. Three preferred arrangements of mold alignment are disclosed, although other arrangements may be possible.
The appliqué or trim component formed by these methods is distinguished by a wide variety of relatively thin decorative materials that may comprise the decorative layer, by additives in the form of tints, pigments and flakes that may be used in the injection molded layers to emphasize the decorative layer, by the use of, preferably, a clear polymer as the outer layer of the appliqué which provides a unique depth of image which further emphasizes the appearance of the underlying decorative layer, and by the forming of the thin decorative layer by the injection of the first plastic material.
Variations and modifications are possible without departing from the scope and spirit of the present invention as defined by the appended claims.
This application is a continuation-in-part of U.S. application Ser. No. 11/428,107 filed Jun. 30, 2006, now U.S. Pat. No. 7,674,414, which is a continuation of International Application No. PCT/US2005/000170 filed Jan. 3, 2005 and published Aug. 4, 2005 as International Publication No. WO 2005/070647, designating the United States, and which claims benefit of U.S. Provisional Application No. 60/533,632 filed Dec. 31, 2003.
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| Number | Date | Country | |
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| 20100075140 A1 | Mar 2010 | US |
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| 60533632 | Dec 2003 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/US2005/000170 | Jan 2005 | US |
| Child | 11428107 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11428107 | Jun 2006 | US |
| Child | 12564028 | US |
