Embodiments of the present invention are directed toward coated fabrics wherein the coating includes expandable graphite. The coated fabrics are particularly useful as construction materials.
Coated fabrics are commonly used in the construction industry. These fabrics, which may also be referred to as webbed sheets, coated mats, or coated facers, generally include a fabric, a binder, and a filler. The binder generally serves to adhere the filler particles to the fabric surface.
Coated fabrics have been used as underlayment under roofing or siding, or as facers for various construction materials such as foamed insulation boards.
For example, U.S. Pat. No. 5,112,678 teaches webbed mats coated with an aqueous mixture of mineral pigment, a polymer latex adhesive, and an inorganic binder. The coating yields a liquid impermeable mat that is useful as an underlayment or as a facer in a foam board laminating process.
U.S. Pat. No. 5,614,256 teaches a coating composition for producing water-tight, vapor-permeable, and flame-retardant articles formed by applying the coating composition to a woven, knitted, or non-woven support material. The coating composition includes an aqueous dispersion of a vinyl chloride copolymer, a flame-proofing agent, a crosslinker, and a thickener. The coated textile support materials are useful in building protection such as underlayments for roof tiles or exterior walls.
Embodiments of the present invention provide a coated fabric comprising a fabric substrate and a coating on said substrate, the coating comprising a binder and expandable graphite dispersed throughout the binder.
Embodiments of the present invention are based, at least in part, on the discovery of a coated fabric wherein the coating includes expandable graphite. Accordingly, coated fabrics of this invention exhibit fire resistivity and/or resistance to flame spread. As a result, the coated fabrics are advantageously useful in preparing construction materials that are characterized by improved flame resistance and/or resistance to flame spread.
In one or more embodiments, coated fabrics include a coating that includes a polymeric binder, expandable graphite, and optionally additional binders and/or fillers. In one or more embodiments, the coating compositions may include other conventional ingredients typically added to fabric coating compositions. In one or more embodiments, the coating is formed by applying a coating composition to a fabric substrate. The coating composition may be an aqueous or solvent-borne composition wherein the constituents of the coating (e.g., binders, fillers, and expandable graphite) are dissolved or dispersed within the compositions.
The fabric that is coated according to one or more embodiments of the present invention may include a woven, knitted, or non-woven fabric. An exemplary woven fabric is shown in
In particular embodiments, the fabric is a fiberglass mat such as a non-woven fiberglass mat. The fiber may include one or more substrate coatings in addition to the coatings applied according to the present invention. In other embodiments, the fabric is a polymeric fabric such as a non-woven polyester and/or polypropylene fabric. In particular embodiments, the fabric is a non-woven fiberglass mat characterized by a weight of from about 0.05 to about 0.15 kg/m2, or in other embodiments from about 0.08 to about 0.12 kg/m2. In particular embodiments, the fabric is a non-woven polyester mat characterized by a weight of from about 0.11 to about 0.24 kg/m2, or in other embodiments from about 0.15 to about 0.20 kg/m2. In other embodiments, the fabric is a polymeric fleece such as a polyester or polyolefin fleece.
In one or more embodiments, the fabric is a cellulosic fabric. In particular embodiments, the cellulosic fabric is kraft paper. In particular embodiments, the kraft paper may be reinforced with fiberglass.
In one or more embodiments, the non-woven fiberglass mat may be wet-formed using known techniques such as a Fourdrinier machine.
Exemplary fabrics that may be used in the practice of this invention are disclosed in U.S. Pat. Nos. 7,429,544, 7,338,702, 7,300,892, 7,833,638, 7,473,440, 7,321,010, 4,284,470, 4,539,254, 4,871,605, 5,112,678, and 5,614,256, which are incorporated herein by reference and U.S. Publication Nos 2008/0160301, 2009/0163097, and 2006/0275561, which are incorporated herein by reference.
Examples of polymer latex binders useful in the practice of one or more embodiments of this invention include, but are not limited to, styrene-butadiene-rubber (SBR), styrene-butadiene-styrene (SBS), ethylene-vinyl-chloride (EVCl), poly-vinylidene-chloride (PVdC), modified poly-vinyl-chloride (PVC), poly-vinyl-alcohol (PVOH), ethylene-vinyl-actate (EVA), and poly-vinyl-acetate (PVA). In one or more embodiments, the binder may include an asphalt. In other embodiments, the binder is devoid of asphalt. In still other embodiments, the binder may include acrylic or epoxy binders or resins, which are known in the art. Generally, acrylic binders or resins include latex polymers that derive from the polymerization of acrylates, acrylic acids, methacrylates, methacrylic acids, acrylonitrile, and/or acrylamide monomer. In other embodiments, the binder may include a polyurethane.
Examples of inorganic binders that may be used with the latex binders include, but are not limited to, calcium oxide, calcium silicate, calcium sulfate, magnesium oxychloride, magnesium oxysulfate, and other complexes of some Group IIA elements (alkaline earth metals), as well as aluminum hydroxide.
In one or more embodiments, a complex inorganic binder such as portland cement, which is a mixture of various calcium-aluminum silicates, may be used. In other embodiments, the oxychloride or oxysulfate of aluminum hydroxide and/or calcium silicate may also be used. In yet other embodiments, quicklime, which does not hydrate in a coating mix, but cures by slowly converting to limestone by adding carbon dioxide from the air, may be used.
Expandable graphite may also be referred to as expandable flake graphite, intumescent flake graphite, or expandable flake; and, for the purposes herein, these terms may be used interchangeably.
In one or more embodiments, expandable graphite includes intercalated graphite in which an intercallant material is included between the graphite layers of graphite crystal or particle. Examples of intercallant materials include halogens, alkali metals, sulfates, nitrates, various organic acids, aluminum chlorides, ferric chlorides, other metal halides, arsenic sulfides, and thallium sulfides. In certain embodiments of the present invention, the expandable graphite includes non-halogenated intercallant materials. In certain embodiments, the expandable graphite includes sulfate intercallants, also referred to as graphite bisulfate. As is known in the art, bisulfate intercalation is achieved by treating highly crystalline natural flake graphite with a mixture of sulfuric acid and other oxidizing agents which act to catalyze the sulfate intercalation.
Commercially available examples of expandable graphite include HPMS Expandable Graphite (HP Materials Solutions, Inc., Woodland Hills, Calif.) and Expandable Graphite Grades 1721 (Asbury Carbons, Asbury, N.J.). Other commercial grades contemplated as useful in the present invention include 1722, 3393, 3577, 3626, and 1722 HT (Asbury Carbons, Asbury, N.J.).
In one or more embodiments, the expandable graphite may be characterized as having a mean or average size in the range from about 30 μm to about 1.5 mm, in other embodiments from about 50 μm to about 1.0 mm, and in other embodiments from about 180 to about 850 μm. In certain embodiments, the expandable graphite may be characterized as having a mean or average size of at least 30 μm, in other embodiments at least 44 μm, in other embodiments at least 180 μm, and in other embodiments at least 300 μm. In one or more embodiments, expandable graphite may be characterized as having a mean or average size of at most 1.5 mm, in other embodiments at most 1.0 mm, in other embodiments at most 850 μm, in other embodiments at most 600 μm, in yet other embodiments at most 500 μm, and in still other embodiments at most 400 μm. Useful expandable graphite includes Graphite Grade #1721 (Asbury Carbons), which has a nominal size of greater than 300 μm.
In one or more embodiments of the present invention, the expandable graphite may be characterized as having a nominal particle size of 20×50 (US sieve). US sieve 20 has an opening equivalent to 0.841 mm and US sieve 50 has an opening equivalent to 0.297 mm. Therefore, a nominal particle size of 20×50 indicates the graphite particles are at least 0.297 mm and at most 0.841 mm.
In one or more embodiments, the expandable graphite may be characterized as having a carbon content in the range from about 70% to about 99%. In certain embodiments, the expandable graphite may be characterized as having a carbon content of at least 80%, in other embodiments at least 85%, in other embodiments at least 90%, in yet other embodiments at least 95%, in other embodiments at least 98%, and in still other embodiments at least 99% carbon.
In one or more embodiments, the expandable graphite may be characterized as having a sulfur content in the range from about 0% to about 8%, in other embodiments from about 2.6% to about 5.0%, and in other embodiments from about 3.0% to about 3.5%. In certain embodiments, the expandable graphite may be characterized as having a sulfur content of at least 0%, in other embodiments at least 2.6%, in other embodiments at least 2.9%, in other embodiments at least 3.2%, and in other embodiments 3.5%. In certain embodiments, the expandable graphite may be characterized as having a sulfur content of at most 8%, in other embodiments at most 5%, in other embodiments at most 3.5%.
In one or more embodiments, the expandable graphite may be characterized as having an expansion ratio (cc/g) in the range from about 10:1 to about 500:1, in other embodiments at least 20:1 to about 450:1, in other embodiments at least 30:1 to about 400:1, in other embodiments from about 50:1 to about 350:1. In certain embodiments, the expandable graphite may be characterized as having an expansion ratio (cc/g) of at least 10:1, in other embodiments at least 20:1, in other embodiments at least 30:1, in other embodiments at least 40:1, in other embodiments at least 50:1, in other embodiments at least 60:1, in other embodiments at least 90:1, in other embodiments at least 160:1, in other embodiments at least 210:1, in other embodiments at least 220:1, in other embodiments at least 230:1, in other embodiments at least 270:1, in other embodiments at least 290:1, and in yet other embodiments at least 300:1. In certain embodiments, the expandable graphite may be characterized as having an expansion ratio (cc/g) of at most 350:1, and in yet other embodiments at most 300:1.
In one or more embodiments, the expandable graphite, as it exists with the asphaltic component of the asphaltic sheet of the present invention, is partially expanded. In one or more embodiments, the expandable graphite is not expanded, however, to a deleterious degree, which includes that amount or more of expansion that will deleteriously the ability to form the sheet product and the ability of the graphite to serve as flame retardant at desirable levels, which include those levels that allow proper formation of the sheet. In one or more embodiments, the expandable graphite is expanded to at most 100%, in other embodiments at most 50%, in other embodiments at most 40%, in other embodiments at most 30%, in other embodiments at most 20%, and in other embodiments at most 10% beyond its original unexpanded size.
In one or more embodiments, the expandable graphite may be characterized as having a pH in the range from about 1 to about 10; in other embodiments from about 1 to about 6; and in yet other embodiments from about 5 to about 10. In certain embodiments, the expandable graphite may be characterized as having a pH in the range from about 4 to about 7. In one or more embodiments, the expandable graphite may be characterized as having a pH of at least 1, in other embodiments at least 4, and in other embodiments at least 5. In certain embodiments, the expandable graphite may be characterized as having a pH of at most 10, in other embodiments at most 7, in other embodiments at most 6.5, in other embodiments at most 6, and in other embodiments at most 5.
In one or more embodiments, the expandable graphite may be characterized by an onset temperature ranging from about 100° C. to about 280° C.; in other embodiments from about 160° C. to about 225° C.; and in other embodiments from about 180° C. to about 200° C. In one or more embodiments, the expandable graphite may be characterized by an onset temperature of at least 100° C., in other embodiments at least 130° C., in other embodiments at least 160° C., in other embodiments at least 170° C., in other embodiments at least 180° C., in other embodiments at least 190° C., and in other embodiments at least 200° C. In one or more embodiments, the expandable graphite may be characterized by an onset temperature of at most 250° C., in other embodiments at most 225° C., and in other embodiments at most 200° C. Onset temperature may also be interchangeably referred to as expansion temperature; it may also be referred to as the temperature at which expansion of the graphite starts.
In one or more embodiments, useful fillers include, but are not limited to, ground limestone (calcium carbonate), clay, sand, mica, talc, gypsum (calcium sulfate), aluminum trihydrate (ATH), antimony oxide, or a combination of any two or more of these substances. In one or more embodiments, the filler is characterized by a particle size such that at least 95% of the filler passes a 325 mesh wire screen.
In one or more embodiments, the coating compositions may include other constituents such as flow and leveling agents, defoaming agents, stabilizers, preservatives, thickeners, dispersants, waxes, processing agents, surfactants, pH buffers or adjusters, and the like.
In one or more embodiments, the coating composition employed to coat the fabrics according to the present invention include at least 10% by wt., in other embodiments at least 20% by wt., and in other embodiments at least 30% by wt. solids based on the total weight of the coating composition. In these or other embodiments, the coating compositions include at most 80% by wt., in other embodiments at most 70% by wt., and in other embodiments at most 60% by wt., solids based on the entire weight of the coating composition. In one or more embodiments, the coating compositions include from about 10 to about 80, in other embodiments from about 20 to about 70, and in other embodiments from about 30 to about 60% by wt. solids based on the entire weight of the coating composition.
In one or more embodiments, the coating compositions include at least 5% by wt., in other embodiments at least 10% by wt., and in other embodiments at least 15% by wt. polymeric binder (solids) based on the total weight of the coating composition. In these or other embodiments, the coating compositions include at most 75% by wt., in other embodiments at most 65% by wt., and in other embodiments at most 55% by wt., polymeric binder (solids) based on the entire weight of the coating composition. In one or more embodiments, the coating compositions include from about 5 to about 75, in other embodiments from about 10 to about 65, and in other embodiments from about 15 to about 55% by wt. polymeric binder based on the entire weight of the coating composition.
In one or more embodiments, the coating compositions include at least 1% by weight, in other embodiments at least 2% by wt., in other embodiments at least 5% by wt., and in other embodiments at least 7% by wt. expandable graphite based on the total weight of the solids component of the coating composition. In these or other embodiments, the coating compositions include at most 50% by wt., in other embodiments at most 40% by wt., and in other embodiments at most 30% by wt., expandable graphite based on the total weight of the solids component of the coating composition. In one or more embodiments, the coating compositions include from about 2 to about 50, in other embodiments from about 5 to about 40, and in other embodiments from about 7 to about 30% by wt. expandable graphite based on the total weight of the solids component of the coating composition.
In one or more embodiments, the coating compositions include at least 1% by wt., in other embodiments at least 3% by wt., and in other embodiments at least 5% by wt. inorganic binder based on the total weight of the solids component of the coating composition. In these or other embodiments, the coating compositions include at most 20% by wt., in other embodiments at most 15% by wt., and in other embodiments at most 10% by wt., inorganic binder based on the total weight of the solids component of the coating composition. In one or more embodiments, the coating compositions include from about 0 to about 20, in other embodiments from about 1 to about 15, and in other embodiments from about 3 to about 10% by wt. inorganic binder based on the total weight of the solids component of the coating composition. In particular embodiments, the coating composition is devoid of inorganic binder.
In one or more embodiments, the coating compositions include at least 1% by wt., in other embodiments at least 3% by wt., and in other embodiments at least 5% by wt. filler based on the total weight of the solids component of the coating composition. In these or other embodiments, the coating compositions include at most 90% by wt., in other embodiments at most 70% by wt., in other embodiments at most 50% by wt., and in other embodiments at most 30% by wt., filler based on the total weight of the solids component of the coating composition. In one or more embodiments, the coating compositions include from about 0 to about 70, in other embodiments from about 3 to about 50, and in other embodiments from about 5 to about 30% by wt. filler based on the total weight of the solids component of the coating composition. In particular embodiments, the coating composition is devoid of fillers other than expandable graphite.
In one or more embodiments, conventional methods for coating fabrics may be employed in the practice of this invention. As an example, U.S. Pat. No. 5,112,678 is incorporated herein by reference. A raw glass mat (e.g., the “substrate”) enters a coating station at a level lower than a top of an applicator roll. The direction of travel of the glass mat is parallel to a “machine direction” (M.D.) of a facer produced by the machine, while a dimension perpendicular to the machine direction is understood to be the “cross machine direction” (C.M.D.) of a resultant facer similarly oriented. The applicator roll is driven to rotate about its axis (either clockwise or counterclockwise). A coating pan is filled with a coating mix up to a level that is sufficient for the applicator roll to pull an adequate amount of coating to the top of the applicator roll. The speed of rotation of applicator roll is used to get adequate amounts of coating mix up into the glass mat as the glass mat is conveyed. In its path of conveyance, the glass mat extends around applicator roll in a wrap-arc. A scraper blade is placed so that the excess coating scraped off returns into the coating pan. After the excess is scraped off, the coated mat proceeds into a dryer section where the coated glass mat facer is dried and wrapped into rolls.
In one or more embodiments, the coated fabrics of the present invention can be used as reinforcements in various membranes. For example, the coated fabric can be used as reinforcement in roofing membranes such as asphaltic membranes, thermoplastic membranes (e.g., PVC and TPO membranes), and rubber membranes (EPDM membranes). An exemplary membrane is shown in
In one or more embodiments, the coated fabrics of the present invention can be used as facers for various construction boards including, but not limited to, polyisocyanurate and polyurethane insulation boards, cover boards, and gypsum boards. An exemplary insulation board is shown in
In still other embodiments, the coated fabrics of the present invention may be used as backing or surface treatments for various construction materials. For example, the fabrics may be used as fleece backing for roofing membranes. An exemplary membrane carrying a fleece backing is shown in
In yet other embodiments, the coated fabrics of the present invention can be used as underlayments in various construction situations such as roofing underlayment and floor underlayment. For example, roofing underlayment may be used in conjunction with shingles or metal roof systems. Also, as is known in the art, floor underlayment may be used in conjunction with tile flooring. An exemplary underlayment is shown in
In yet other embodiments, the coated fabrics of the present invention may be used as barrier fabrics in various construction situations. For example, the coated fabrics can be used as fire barriers, vapor barriers, and moisture barriers in walls.
Various modifications and alterations that do not depart from the scope and spirit of this invention will become apparent to those skilled in the art. This invention is not to be duly limited to the illustrative embodiments set forth herein.
This application is a divisional application of U.S. Non-Provisional Ser. No. 15/292,925 filed Oct. 13, 2016 and now patented as No. U.S. Pat. No. 10,273,693, which is a continuation application of Abandoned U.S. Non-Provisional Ser. No. 13/798,413 filed Mar. 13, 2013, which claims the benefit of U.S. Provisional Application Ser. No. 61/755,666, filed on Jan. 23, 2013, which are incorporated herein by reference.
Number | Name | Date | Kind |
---|---|---|---|
4284470 | Bondoc | Aug 1981 | A |
4491617 | O'Connor et al. | Jan 1985 | A |
4539254 | O'Connor et al. | Sep 1985 | A |
4615934 | Ellison | Oct 1986 | A |
4780350 | O'Connor et al. | Oct 1988 | A |
4871605 | Pagen | Oct 1989 | A |
4996812 | Venable | Mar 1991 | A |
5112678 | Gay | May 1992 | A |
5226392 | Breuer et al. | Jul 1993 | A |
5314556 | Woiceshyn | May 1994 | A |
5422179 | Dietschi et al. | Jun 1995 | A |
5504136 | Davis et al. | Apr 1996 | A |
5516817 | Slusher et al. | May 1996 | A |
5523357 | Peterson | Jun 1996 | A |
5614256 | Wierer | Mar 1997 | A |
5757592 | Arai et al. | May 1998 | A |
5981030 | Haupt et al. | Nov 1999 | A |
6055786 | Hubbard et al. | May 2000 | A |
6084008 | Liu | Jul 2000 | A |
6207085 | Ackerman | Mar 2001 | B1 |
6451897 | Niyogi | Sep 2002 | B1 |
6502360 | Carr, III et al. | Jan 2003 | B2 |
6506842 | Heck et al. | Jan 2003 | B1 |
6544596 | Clemens et al. | Apr 2003 | B2 |
6706793 | Abu-Isa et al. | Mar 2004 | B2 |
6849338 | Clemens et al. | Feb 2005 | B2 |
7070844 | Bartek | Jul 2006 | B2 |
7300892 | Porter | Nov 2007 | B2 |
7321010 | Shooshtari | Jan 2008 | B2 |
7338702 | Swales | Mar 2008 | B2 |
7429544 | Grove | Sep 2008 | B2 |
7473440 | Kajander | Jan 2009 | B2 |
7605188 | Loh et al. | Oct 2009 | B2 |
7632763 | Newton et al. | Dec 2009 | B2 |
7677009 | Bowman | Mar 2010 | B2 |
7749924 | Peng et al. | Jul 2010 | B2 |
7803723 | Herbert et al. | Sep 2010 | B2 |
7833575 | Gupta | Nov 2010 | B2 |
7833638 | Zheng | Nov 2010 | B2 |
7878301 | Gross et al. | Feb 2011 | B2 |
8178449 | La Vietes et al. | May 2012 | B2 |
8968853 | Zhou et al. | Mar 2015 | B2 |
9045904 | Hubbard et al. | Jun 2015 | B2 |
20020003026 | Hubbard et al. | Jan 2002 | A1 |
20030181597 | Glogovsky et al. | Sep 2003 | A1 |
20040020585 | Hubbard et al. | Feb 2004 | A1 |
20040121152 | Toas | Jun 2004 | A1 |
20050072114 | Shiao et al. | Apr 2005 | A1 |
20050139126 | Khan et al. | Jun 2005 | A1 |
20050145139 | Khan et al. | Jul 2005 | A1 |
20050183831 | Schwetz et al. | Aug 2005 | A1 |
20050257875 | Khan et al. | Nov 2005 | A1 |
20060144012 | Manning et al. | Jul 2006 | A1 |
20060160978 | Gupta et al. | Jul 2006 | A1 |
20060217451 | Bonapersona | Sep 2006 | A1 |
20060240224 | Khan et al. | Oct 2006 | A1 |
20060273290 | Khan et al. | Dec 2006 | A1 |
20060275561 | Agrawal | Dec 2006 | A1 |
20070186505 | Hubbard et al. | Aug 2007 | A1 |
20070193167 | Bruce et al. | Aug 2007 | A1 |
20070194482 | Douglas et al. | Aug 2007 | A1 |
20070208139 | Raulie et al. | Sep 2007 | A1 |
20070277450 | Raulie | Dec 2007 | A1 |
20080102243 | Gupta | May 2008 | A1 |
20080160301 | Nandi | Jul 2008 | A1 |
20080184651 | Bowman | Aug 2008 | A1 |
20080188590 | Gupta | Aug 2008 | A1 |
20080241472 | Shiao et al. | Oct 2008 | A1 |
20090137168 | Peng | May 2009 | A1 |
20090163097 | Kajander | Jun 2009 | A1 |
20090181216 | Peng | Jul 2009 | A1 |
20090309077 | Gupta et al. | Dec 2009 | A1 |
20090326117 | Benussi et al. | Dec 2009 | A1 |
20100130080 | Coninx et al. | May 2010 | A1 |
20100167013 | Cruz et al. | Jul 2010 | A1 |
20100326598 | Atwater | Dec 2010 | A1 |
20110011021 | La Vietes et al. | Jan 2011 | A1 |
20110073239 | Manning et al. | Mar 2011 | A1 |
20110135882 | Stanley | Jun 2011 | A1 |
20110155321 | Yang et al. | Jun 2011 | A1 |
20110173924 | Ambrose, Jr. et al. | Jul 2011 | A1 |
20110185656 | Klein | Aug 2011 | A1 |
20110313084 | Furar et al. | Dec 2011 | A1 |
20120009407 | Peeler et al. | Jan 2012 | A1 |
20120022176 | Stahl et al. | Jan 2012 | A1 |
20120045623 | Delaney et al. | Feb 2012 | A1 |
20120100289 | Egan et al. | Apr 2012 | A1 |
20120174508 | Brooks et al. | Jul 2012 | A1 |
20120189838 | Pellacani et al. | Jul 2012 | A1 |
20120244340 | Peng et al. | Sep 2012 | A1 |
20120266553 | Shiao et al. | Oct 2012 | A1 |
20130036714 | Bolton et al. | Feb 2013 | A1 |
20140013693 | Zhou et al. | Jan 2014 | A1 |
20140127443 | Zhou et al. | May 2014 | A1 |
20140141672 | Hubbard et al. | May 2014 | A1 |
20140205789 | Zhou et al. | Jul 2014 | A1 |
20140215937 | Zhou et al. | Aug 2014 | A1 |
20150038629 | Ultsch | Feb 2015 | A1 |
20150306850 | Hubbard et al. | Oct 2015 | A1 |
Number | Date | Country |
---|---|---|
101550729 | Oct 2009 | CN |
19718876 | Nov 1998 | DE |
0752458 | Jan 1997 | EP |
1541338 | Jun 2005 | EP |
2532515 | Dec 2012 | EP |
H11172860 | Jun 1999 | JP |
2011029151 | Mar 2011 | WO |
2012015538 | Feb 2012 | WO |
2013102208 | Jul 2013 | WO |
2015013176 | Jan 2015 | WO |
Entry |
---|
International Search Report for Appl. No. PCT/US2014/012732 dated Jul. 4, 2014. |
International Search Report, dated Jul. 4, 2014, International Application PCT/US2014/012683, pp. 1-10. |
First Examination Report for related Indian Patent Application No. 5516/DELNP/2015 dated Oct. 14, 2019. |
Number | Date | Country | |
---|---|---|---|
20190226213 A1 | Jul 2019 | US |
Number | Date | Country | |
---|---|---|---|
61755666 | Jan 2013 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 15292925 | Oct 2016 | US |
Child | 16375945 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13798413 | Mar 2013 | US |
Child | 15292925 | US |