wall cladding and composite structure to support a wall cladding

专利摘要:
WALL CLADDING A wall cladding includes a composite structure that includes a first layer forming a non-image side of the composite structure and a second layer laminated to the first layer forming an image side of the composite structure. The first layer includes a textile material to facilitate airflow over the non-image side. The image side has a surface roughness less than or equal to 5 (Mi)m by the PPS method. The second layer includes a synthetic polymeric fiber in a non-woven structure and a synthetic polymeric film. The wall cladding is a Type-II wall cladding that is PVC free.
公开号:BR112015018473B1
申请号:R112015018473-1
申请日:2014-01-31
公开日:2021-05-04
发明作者:Xiaoqi Zhou；Xulong Fu；Paul C. Landrum
申请人:Hewlett-Packard Development Company, L.P.；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED ORDERS
[001] N/A. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[002] N/A. FUNDAMENTALS
[003] Large format print media are used in applications such as wallcovering, banners, and signs of many types that can be printed using a variety of printing techniques to create images with one or more symbols, text and photographs. The durability of large-format media and the image printed on them is something to consider for wallcovering. More specifically, something that is taken into account is the mechanical resistance to friction and other mechanical wear. BRIEF DESCRIPTION OF THE DRAWINGS
[004] Various features of examples in accordance with the principles described herein will be more easily understood with reference to the detailed description that follows when taken in conjunction with the accompanying drawings in which like reference numerals designate like structural elements and in which:
[005] Figure 1A illustrates a side view of a composite structure for print media for wall covering according to an example according to the principles described in this document.
[006] Figure 1B illustrates a side view of another composite structure for print media for wall covering according to an example according to the principles described in this document.
[007] Figure 2 illustrates a side view of a wall covering according to an example according to the principles described in this document.
[008] Figure 3 illustrates a flowchart of a method of manufacturing a wall covering according to an example according to the principles described in this document.
[009] Figure 4 illustrates a schematic view of a laminator used to laminate together the layers of a composite structure according to an example of the principles described in this document.
[0010] Certain examples have other features that are in addition to or in place of the features illustrated in the figures cited above. These and other features are described in detail below with reference to the figures cited above. DETAILED DESCRIPTION
[0011] Examples according to the principles described in this document are aimed at a composite structure to support fingerprint media and especially a wall covering that employs the composite structure. Wall cladding in a durability that can meet or exceed Type II commercial utility wall cladding standards or specifications by providing a durable Type II wall cladding that is also free from poly(vinyl chloride) (PVC) , which is harmful to the environment. PVC-free wallcovering according to the principles described in this document overcomes the environmental problems inherent in vinyl wallcoverings, but does so without sacrificing durability, image quality and usability, for example.
[0012] The composite structure includes laminated layers that form a non-image side and an image side of the composite structure. The non-image side or the wrong side of the composite structure is the side that would face a wall and be attached to it in a wall covering application, or even in a sign or banner application that had a single side of the image. The image side of the composite structure is the side that includes the material layers that receive support and protect an image. A first layer of the composite structure includes a textile material. The textile material has a textile structure to facilitate the flow of air over the non-image side or the wrong side of the composite structure. A second layer of the composite structure is laminated to the first layer to form the image side of the composite structure. The second layer includes a synthetic polymeric component and is configured with a surface roughness of less than approximately 5 µm by PPS method. The composite structure provides mechanical breaking strength (tensile strength) to the wall covering that exceeds 50 lbs of force (222 N) in both machine direction (MD) and cross machine direction (CMD) as specified in the specifications of superior category or Type II wall coverings.
[0013] In some examples, the synthetic polymeric component of the second layer is a synthetic polymeric film with a high molecular weight polymer. In other examples, the synthetic polymeric component of the second layer is a synthetic polymeric fiber in a fiber composition of a non-woven structure. The fiber composition of the second layer further includes natural fibers.
[0014] A wall covering that includes the composite structure further includes an image-receiving layer coated over the second layer (i.e., on the image side of the composite structure). The image-receiving layer is configured to receive an imaging material, an ink, for example, which is printed in the form of an image. In addition, the wall coating further includes an anti-mechanical wear layer on the image-receiving layer. The anti-mechanical wear layer is configured to protect the wall covering surface and any image printed on it from mechanical damage such as friction and wear. The anti-mechanical wear layer on the wall cladding facilitates a mechanical wear resistance of 300 cycles or more of abrasion as specified in the Type II or higher category wall cladding specifications. More especially, the anti-mechanical wear layer has a first structure before image printing that is porous and configured to receive an ink colorant and allows other ink components of the imaging material to penetrate through the anti-mechanical wear layer and stop inside the image-receiving layer of the wallcovering during printing. The anti-mechanical wear layer turns into a second structure after the ink colorant has been printed onto an outermost surface of the wall covering and the other ink components have penetrated into the image-receiving layer to form the image. The second structure of the mechanical anti-wear layer is a transparent, non-porous thin-film structure on the outermost surface of the wall covering, thus further protecting the image. Wall coverings comprising the composite structure and the anti-mechanical wear layer in accordance with principles described herein can have improved durability.
[0015] As used herein, the article "one, one" is intended to have its common meaning in patent art, ie, "one, one or more". “A layer”, for example, generally means one or more layers and for this reason, “the layer” means “the layer(s)” in this document. The expression “at least”, as used in this document, means that the number can be equal to or greater than the quoted number. The expression “not greater than”, as used herein, means that the number may be equal to or less than the quoted number. The term “approximately”, as used herein, means that the quoted value is within the normal tolerances of the equipment used to measure the value; or in some examples, the value may differ by plus or minus 20%, or plus or minus 15%, or plus or minus 10%, or plus or minus 5%, or plus or minus 1%, for example. Any ranges of values given in this document include values that fall within the given ranges. The term "substantially", as used herein, means most, or substantially all, or all of the amount, ranging from approximately 51% to approximately 100%, for example.
[0016] In addition, any reference in this document to "from above", "from below", "top", "bottom", "upwards", "downwards", "rear", "front", "left ” or “right” is not intended to be a limitation hereunder. The designations "first" and "second", when used in this document, are intended to distinguish between items and are not intended to imply any sequence, order, or importance of one item in relation to another or to any order of operation , unless otherwise indicated. In addition, the examples in this document are intended to be illustrative only and are presented for discussion purposes and not by way of limitation.
[0017] The term "wallcovering", as used herein, means a large-format print medium that has a length that is much greater than a width (or vice versa) on a large-format office paper small or photographic support products (such as letter, A4, legal, etc. sizes). Wallcovering can be supplied, for example, on a coil that is 1.37 meters (54 inches) wide and 27.43 meters (30 linear yards) long. In addition, the term "wall covering" means a printing medium that supports various imaging materials and applications, various types of inkjet inks and inkjet printing, for example, for imaging , including digital printing. In addition, the term “wall cladding” means a product that conforms to federal and industry standards or specifications for wall cladding including, but not limited to, CCC-W-408A and D, ASTM 793, and CFFAW-101D. In accordance with these standards, wall claddings have weight and durability requirements that depend on the category or type to which the wall cladding falls. Category 1 is for decorative wall cladding only, while Category VI is for commercial utility wall cladding. Types I, II and III wallcoverings are substantially equivalent to Categories IV, V and VI, respectively, among the standards. Wall covering according to the principles described in this document has a wear durability of Type II wall coverings, or possible of a higher category, in accordance with the standards mentioned above and may meet or exceed the established criteria for coverings. Type II wall panel in accordance with the standards mentioned above. In the present document, the term “wall covering”, “wall covering print holder” and “wall covering digital print holder” may be used interchangeably. “Wear” refers to a minimum friction standard and minimum breaking strength standard, respectively, of ASTM F793, as will be described below.
[0018] The term "composite", as used herein, means a material manufactured from at least two constituting layers having one or both of them different physical properties and chemical properties different from each other, the constituting layers remaining separate at the molecular level and distinct within the composite structure. The composite is a laminated structure. In some examples, the composite further includes an adhesive builder layer laminated between two other builder layers. A "composite structure", as used herein, is a support or substrate for the print media supporting the composite structure and the layers of wall covering material, including, but not limited to, one or more image-receiving layers, imaging, protective materials, as well as adhesive materials with which the composite structure is coated in the form of separate layers. In addition, the composite structure supports the wall cladding when applied or fixed to a surface or wall in a variety of applications and environments, such as environments with a high moisture content and a high degree of abrasion, for example.
[0019] The term "textile material" as used herein is intended to mean a textile, cloth, woven material, woven cloth, or other textile product that has a mechanical strength and permeability to air. The term “textile structure” is intended to mean a structure that has a warp and weft, which is one of woven, non-woven, knitted, tufted, crocheted, knotted, and pressed, for example. The terms "warp" and "weft" refer to weaving terms that have their meanings in the weaving technique as used herein, just as warp refers to longitudinally arranged or longitudinal yarns on a loom, whereas weft refers to the cross threads on a loom.
[0020] According to some examples of the principles described in this document, a composite structure is provided to support a wall cladding. The composite structure has an image side and a non-image side. The composite structure comprises a first layer and a second layer laminated together. The first layer forms the non-image side of the composite structure, or is adjacent to it. The non-image side is a side of the composite structure that is intended to face a wall or wall surface for attachment and may be referred to as the wrong side of the composite structure. The second layer forms the image side of the composite structure, or is adjacent to it. The image side of the composite structure serves as support for the material layers with which a surface of the second layer is coated to facilitate the formation of an image side image. For this reason, the second layer is a smooth material which can still be flat to receive the coating layers. The composite structure can be porous or non-porous and can be substantially flexible. “Flexible” is intended to mean pliable and capable of being wound and uncoiled without breaking or cracking, for example.
[0021] “Smooth” means that the surface roughness of the second layer is not more than approximately 5 µm by the PPS method (ie Parker Print Surf method). In some examples, the surface roughness by the PPS method of the second layer is not more than 4 μm, or not more than 3 μm, or not more than 2 μm, or not more than 1 micron, or not more than approximately 0.5 micron. The composite structure is a durable, flexible support. “Durable” means that the composite structure has a high tolerance to certain physical forces and forces of surface degradation. The durability of the composite structure is manifested in one or more of tear and tensile strength, surface abrasion, water and solvent resistance, fire resistance, dimensional stability, stain resistance, thermal aging, cold weather, and others described in ASTM wall cladding classification standards F793 and Federal Specification CCC-W-408D, for example, for Type II commercial utility wall claddings. The composite structure in accordance with the principles of the present invention meets these specifications or standards and may exceed them when incorporated into wall coverings.
[0022] The first layer of the composite structure includes a textile material having warp and weft to facilitate air flow on the non-image side. Airflow refers to either one or both flows through a thickness of textile material (in the x and y direction, for example). Proper airflow helps to prevent any harmful biological growths such as mold and mildew from forming. Adequate air flow can be validated by two separate methods. A first method uses fluid flow measurements by ASTM E96, which determine the relative rate of water-vapor transmission through a medium. A second method is in accordance with ASTM D6329 in combination with UL GreenGuard Test Method P040, which determines a medium's ability to create and sustain mold and mildew formations.
[0023] The textile material has a textile structure that includes, but is not limited to, a woven, non-woven, knitted and tufted; and has a textile surface which may be flat or bulging. In addition, the textile structure may have a surface roughness or texture to form channels or paths for airflow at the interface with the wall surface to which the textile material is to be attached to facilitate airflow. The textile can have either mechanical strength properties or air permeability properties, or both types of properties. In some examples, the first layer textile is a woven textile including, but not limited to, satin, poplin and crepe. In some examples, the first layer textile is a knitted textile including, but not limited to, circular knit, warp knit, and warp knit with a micro denier face.
[0024] In some examples, the textile is a woven textile in which the warp threads and the weft threads are mutually positioned at an angle of approximately 90 degrees. This woven textile includes, but is not limited to, textile with a simple stitch structure, textile with a twill stitch structure in which the twill stitch produces diagonal lines on one face of the textile, or a satin stitch. The direction of the diagonal lines of twill stitch, for example, as seen along a warp direction, can extend to the right or left forming a Z or S twill pattern. Compared to plain weave (of the same parameters fabric) twills have longer floats, fewer intersections, and a more open construction to aid airflow. Unlike the twill weave, the satin weave has a smooth fabric surface free of twill threads making the distribution of stitches interweaving between the weft and warp threads as random as possible to avoid strands of twill. twill. The term "interwoven stitches" means a number of warp yarns float over a single warp yarn, or vice versa, i.e. a number of warp yarns float over a single weft yarn. In some satin stitch examples, the interbraid stitches are repeated 5 by 5, 6 by 6, 7 by 7, or 8 by 8.
[0025] In some examples, the textile is a knitted textile with a loop structure including one or both of a warp-knit textile and a weft-knit textile. Knit-weft textile refers to the fact that the loops of a row of textile are formed from the same yarn. Warp-knit textile refers to the fact that any loop in the textile structure is formed from a separate yarn introduced mainly in a longitudinal direction of the textile. In some examples, the textile of the first layer is a non-woven product, a flexible textile, for example, which includes a multiplicity of fibers or filaments that are either linked together or interlocked with each other or both, by a chemical treatment process ( such as a solvent treatment, for example), a mechanical treatment process (such as by stamping), a heat treatment process, or by a combination of two or more of these processes.
[0026] The textile of the first layer comprises one or both of natural fibers and synthetic fibers. Natural fibers that can be used in the first layer textile include, but are not limited to, wool, cotton, silk, linen, jute, linseed, or hemp. Additional fibers that can be used, but not limited to, rayon fibers, or those of thermoplastic aliphatic polymer fibers derived from renewable sources, including, but not limited to, corn starch, tapioca products, or sugar cane. These additional fibers are also referred to herein as "natural" fibers for simplification of the discussion. In some examples, the fiber used in the first layer textile includes a combination of two or more of the natural fibers listed above, a combination of any of the natural fibers listed above with another natural fiber or synthetic fiber, a mixture of two, or more of the natural fibers listed above, or a mixture of any of them with another natural fiber or with a synthetic fiber.
[0027] The synthetic fiber that can be used in the textile of the first layer is polymeric fiber that includes, but is not limited to, non-poly(vinyl chloride) (PVC) fibers made of polyester, polyamide, polyimide, poly(acrylic acid) , polypropylene, polyethylene, polyurethane, polystyrene, polyaramid, such as, for example, KEVLAR®, polytetrafluoroethylene, such as TEFLON®, for example (both registered trademarks of EI du Pont de Nemours and Company), fiberglass, polytrimethylene, polycarbonate , poly(ethylene terephthalate) or poly(butylene terephthalate). In some examples, the fiber used in the first layer textile includes a combination of two or more of the polymeric fibers, a combination of any one of the polymeric fibers with another polymeric fiber or with a natural fiber, a mixture of two or more of the fibers polymeric fibers or a mixture of any of the polymeric fibers with another polymeric fiber or with a natural fiber. In some examples, synthetic fiber includes modified polymeric fibers. The term "modified fibers" refers to one or both of the polymeric fiber and the textile as a whole having undergone a chemical or physical process, such as, but not limited to, one or more of a copolymerization with monomers from other polymers , a chemical grafting reaction to contact a chemical functional group with one or both of both the polymeric fiber and the textile surface, a plasma treatment, a solvent treatment, an acid etching and a biological treatment, an enzymatic treatment or an antimicrobial treatment to prevent biological degradation. The term “PVC free” means that there is no poly(vinyl chloride) polymer (PVC) or vinyl chloride monomer units present in the wall cladding or composite structure.
[0028] In some examples, the textile comprises both natural fiber and synthetic polymeric fiber, synthetic fibers constituting approximately 90% of the total fiber count and natural fibers constituting approximately 10% of the total fiber count. The percentage of the total fiber count of synthetic fibers and natural fibers in the textile in these examples can range from approximately 80% synthetic fiber and approximately 20% natural fiber, or from approximately 70% synthetic fiber and approximately 30% fiber natural, or approximately 60% synthetic fiber and approximately 40% natural fiber, or approximately 50% synthetic fiber and approximately 50% natural fiber, or approximately 40% synthetic fiber and approximately 60% natural fiber , or approximately 30% synthetic fiber and approximately 70% natural fiber or approximately 20% synthetic fiber and approximately 80% natural fiber or approximately 10% synthetic fiber and approximately 90% natural fiber. In some examples, the textile of the first layer further comprises additives, including, but not limited to, one or more colorants (pigments, dyes, dyes, for example), antistatic agents, brightening agents, nucleating agents, antioxidants, stabilizers. UV, filters, flame retardants, and lubricants, for example. Additives are included to improve various properties of the textile material.
[0029] The second layer of the composite structure comprises a PVC-free synthetic polymeric component which is a synthetic polymeric fiber in a non-woven structure and a synthetic polymeric film. In some examples, the PVC-free synthetic polymeric component is synthetic polymeric fiber in a fiber composition that further includes natural fiber. Synthetic polymeric fiber includes, but is not limited to, those fibers made from polyolefins, polyamides, polyesters, polyurethanes, polycarbonates, poly(acrylic acids) a combination of two or more of the fibers or a mixture of two or more of the fibers. The synthetic polyolefin fiber may include, but is not limited to, polyethylene fiber, polyethylene copolymer fiber, polypropylene fiber, polypropylene copolymer fiber, a combination of two or more of the polyolefin fibers, a combination of any of the fibers of polyolefin with another polymeric fiber, blends of two or more of polyolefinic fibers or more of any one of the polyolefinic fibers with another polymeric fiber. In some examples, the fiber composition may include a synthetic cellulosic material including, but not limited to, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate and nitrocellulose.
[0030] The fiber composition is used to form a web of the second layer having the non-woven structure, using papermaking equipment, for example. The second layer synthetic polymeric fiber can have an average length in the range of approximately 1 millimeter (mm) to approximately 3 mm. This length is comparable to the length of natural cellulosic fibers. In some examples, the synthetic polymeric fiber has a length greater than 3 mm, as long as the synthetic polymeric fiber does not have a negative impact on the formation of the second layer using papermaking equipment, on a wire mill fabric. paper, for example. In some examples, the synthetic polymeric fiber has a diameter in the range of approximately 10 µm (µm) to approximately 40 µm with an average length in the range of approximately 2 mm and approximately 3 mm. The amount of synthetic polymeric fiber in the second layer depends on the fiber length. The use of longer synthetic fibers, for example, can allow an improvement in the dimensional stability of the composite structure with the use of lower amounts of synthetic polymeric fibers.
[0031] As indicated above, the fiber composition of the second layer of the composite structure comprises both synthetic polymeric fiber and natural fiber. Natural fiber includes natural cellulose fiber derived either from deciduous species or from deciduous and coniferous species. In some examples, the ratio of deciduous to coniferous fibers in the second layer ranges from approximately 100:0 to approximately 50:50. Natural cellulosic fiber can be processed into a variety of pulps including, but not limited to, woodless pulp, such as bleached or unbleached kraft chemical pulp and bleached or unbleached chemical sulfite pulp; wood pulp, such as one or more of ground wood pulp, thermomechanical pulp, and chemo-thermomechanical pulp; non-wood natural fiber pulp, such as one or more bamboo fiber, bagasse fiber, recycled fiber, cotton fiber; a combination of two or more pulps, or a mixture of two or more pulps.
[0032] The proportion of synthetic polymeric fiber in the fiber composition of the second layer which further includes natural fiber can be within the limits of approximately 10% to approximately 80% by weight of the total fiber. In some examples, the proportion of synthetic polymeric fiber by weight of total fibers in the second layer fiber composition is from approximately 10% to approximately 70%, or from approximately 10% to approximately 60%, or from approximately 10% to approximately 50%, or from approximately 10 to approximately 40%, or from approximately 10% to approximately 30%, or from approximately 10% to approximately 20%. In some examples, the proportion of synthetic polymeric fiber by weight of total fibers in the second layer fiber composition is from approximately 10% to approximately 80%, or from approximately 10% to approximately 80%, or from approximately 15% to approximately 80% or from approximately 20% to approximately 80%, or from approximately 25% to approximately 40%.
[0033] The fiber composition of the second layer of the composite structure may further comprise a polymeric binder. The polymeric binder can be premixed with one or both fibers, the synthetic polymeric fiber and the natural fiber, for example. Examples of polymeric binder included in the composition of the second layer include, but are not limited to, water-soluble polymers such as poly(vinyl alcohol), starch derivatives, gelatin, cellulose derivatives, acrylamide polymers; water-dispersible polymers such as acrylic polymers or copolymers, vinyl acetate latex, polyesters and styrene-butadiene or acrylonitrile-butadiene copolymer latex; a combination of two or more of the above polymeric binders; or a mixture of two or more of the above polymeric binders. The polymeric binder can have a glass transition temperature (Tg) within the range of approximately -30°C to approximately 10°C. In some examples, the Tg of the polymeric binder is within the range of -25°C to approximately 10°C, or -20°C to approximately 10°C, or -15°C to approximately 10°C or -10°C to approximately 10°C. A ratio of latex resin binder to natural cellulosic fiber in the second layer composition can range from approximately 1:20 to approximately 1:1. In some examples, the ratio of latex resin binder to natural cellulosic fiber in the second layer composition ranges from approximately 1:15 to approximately 1:1 or from approximately 1:10 to approximately 1:1, or from approximately 1: 5 to approximately 1:1. Furthermore, aqueous coupling agents can also be used in the fiber composition in an amount that improves the bond between the fibers. Representative examples of commercially available coupling agents include, but are not limited to, Dow Corning® Z 6032, Dow Corning® Z 6030, and Dow Corning® Z 6040 silanes from Dow Corning, Inc., MI, USA or Struktol® SCA 98 organosilanes , Struktol® SCA 930, and Struktol® SCA 960 from Struktol Company of America, OH, USA.
[0034] In other examples, the PVC-free synthetic polymeric component of the second layer of the composite structure is a high molecular weight synthetic polymeric film. "High molecular weight" means a weight average molecular weight (Mw) that is greater than 1 x 104 grams per mol (g/mol). The synthetic polymeric film can be comprised of a vinyl chloride-free polymer including, but not limited to, one or both, homopolymers and copolymers of polyethylene (PE), polypropylene (PP), nylon (polyamides), polystyrene, acrylonitrile butadiene styrene ( ABS), polycarbonate, a combination of two or more of them, or a mixture of two or more of them. "Vinyl chloride-free polymer" means that there is no polyvinyl chloride (PVC) present in the synthetic polymeric film, or that the synthetic polymeric film does not contain any vinyl chloride chain unit (i.e., a film free from PVC), as poly(vinyl chloride) is known to be harmful to the environment, as mentioned above.
[0035] The synthetic polymeric film of the second layer of the composite structure may have a thickness ranging from approximately 40 µm to approximately 300 µm. In some examples, the thickness of the synthetic polymeric film of the second layer is between approximately 60 μm and approximately 300 μm or approximately 80 μm and approximately 300 μm or approximately 100 μm and approximately 300 μm or approximately 125 μm and approximately 300 μm or approximately 150 μm and approximately 300 μm or approximately 200 μm and approximately 300 μm. In some examples, the thickness of the synthetic polymeric film of the second layer of the composite structure is between approximately 40 μm and approximately 250 μm, or approximately 40 μm and approximately 200, or approximately 40 μm and approximately 175 μm, or approximately 40 μm and approximately 150 μm, or approximately 40 μm and approximately 125 μm, or approximately 40 μm and approximately 100 μm.
[0036] Furthermore, the synthetic polymeric film of the second layer of the composite structure may have a density that is between approximately 0.50 grams per cubic centimeter (g/cm3) and approximately 1.2 g/cm3. In some examples, the density of the synthetic polymeric film of the second layer is between approximately 0.55 g/cm3 and approximately 1.2 g/cm3, or approximately 0.60 g/cm3 and approximately 1.2 g/cm3 or approximately 0.65 g/cm3 and approximately 1.2 g/cm3 or approximately 0.70 g/cm3 and approximately 1.2 g/cm3 or between approximately 0.75 g/cm3 and approximately 1.2 g/cm3. In some examples, the density of the synthetic polymeric film of the second layer of the composite structure is between approximately 0.50 g/cm3 and approximately 1.0 g/cm3 or approximately 0.50 g/cm3 and approximately 0.90 g/cm3 or approximately 0.50 g/cm3 and approximately 0.85 g/cm3 or approximately 0.50 g/cm3 and approximately 0.80 g/cm3 or approximately 0.50 g/cm3 and approximately 0.75 g/cm3 or approximately 0.50 g/cm3 and approximately 0.70 g/cm3.
[0037] In one example, the synthetic polymeric film is a polypropylene film having a weight average molecular weight (Mw) within a range of approximately 2.90 x 105 g/mol to approximately 3.95 x 105 g/mol, as measured by gel permeation chromatography (GPC) calibrated with a polystyrene standard. The molecular weight distribution as shown by Mw/Mn, where Mn is the number average molecular weight, ranges from approximately 2.9 to approximately 4.8 for this example. Furthermore, in this example, the polypropylene film can be either uni-oriented or biaxially oriented with a density of approximately 0.85 g/cm3 for the amorphous area and approximately 0.94 g/cm3 for the crystalline area. In addition, the polypropylene film can have a melting point that can be between approximately 140°C and approximately 185°C.
[0038] The composite structure may further comprise a bonding layer directly on the synthetic polymeric film of the second layer. The bonding layer serves to provide better adhesion between the synthetic polymeric film and a subsequent layer of material applied over the film to form a wall covering, including an image-receiving layer, as will be described in more detail below. The bonding layer can consist of a polymeric material with a surface free energy that is greater than the surface free energy of the synthetic polymeric film, a surface free energy that is greater than 30 milli-Newton per meter (mN/m), as measured at 20°C. In some examples, the polymeric material of the tie layer has a free surface energy that is greater than 35 mN/m or greater than 38 mN/m or greater than 40 mN/m.
[0039] Examples of polymeric binding layer material include, but are not limited to, various polyacrylates, various polymethylacrylates, polyethyleneoxide, poly(vinyl alcohol), poly(ethylene terephthalate), polyamide, polycarbonate, polystyrene, polychloropene, polyoxyethylene, polystyrene, poly(2-vinylpyridine), epoxy resins, a combination of two or more of these materials, or a mixture of two or more of these materials. A proportion of the binding layer material in the synthetic polymeric film of the second layer can range from approximately 0.01 grams per square meter (g/m2) to approximately 5 g/m2. In some examples, the proportion of binding layer material on the synthetic polymeric film is between approximately 0.1 g/m2 and approximately 5 g/m2 or between approximately 0.2 g/m2 and approximately 5 g/m2, or approximately 0.35 g/m2 and approximately 5 g/m2 or approximately 0.5 g/m2 and approximately 5 g/m2. In some examples, the proportion of binding layer material on the synthetic polymeric film is between approximately 0.01 g/m2 and approximately 4.5 g/m2 or approximately 0.01 g/m2 and approximately 4 g/m2. or approximately 0.01 g/m2 and approximately 3.5 g/m2 or approximately 0.01 g/m2 and approximately 3 g/m2 or approximately 0.01 g/m2 and approximately 2.5 g/m2 or approximately 0, 01 g/m2 and approximately 2 g/m2, or approximately 0.5 g/m2 and approximately 2.0 g/m2.
[0040] In some examples, the composite structure further comprises an adhesive laminated between the first layer and the second layer. The adhesive can consist of an aqueous latex adhesive that is selected from a wide variety of resin latex. The resin latex adhesive may include, but is not limited to, resins formed by the polymerization of hydrophobic addition monomers. Examples of hydrophobic addition monomers include, but are not limited to, C1-C12 alkyl acrylate and methacrylate (such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate , sec-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , sec-butyl methacrylate, tert-butyl methacrylate), aromatic monomers (such as styrene, phenyl methacrylate, o-tolyl methacrylate, m-tolyl methacrylate, p-tolyl methacrylate, benzyl methacrylate), containing monomers hydroxyl (such as hydroxyethylacrylate, hydroxyethylmethacrylate), carboxylic acid containing monomers (such as acrylic acid, methacrylic acid, for example), vinyl ester monomers (such as vinyl acetate, vinyl propionate, vinyl benzoate inyl, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate), vinyl benzene monomer, (C1-C12)alkyl acrylamide and methacrylamide (such as tert-butyl acrylamide, sec-butyl acrylamide, N,N-dimethylacrylamide), crosslinking monomers (such as divinyl benzene, ethylene glycol dimethacrylate, bis(acryloylamido)methylene), and combinations thereof. Polymers produced from one of the polymerization and copolymerization of alkyl acrylate, alkyl methacrylate, vinyl esters and styrenic derivatives can also be used. Representative examples of commercially available adhesive products include, but are not limited to, Acronal® 788 or Acronal® 866 from BASF North America; RayCril® 347 from Specialty Polimers, Inc., OR, USA; and Flexbond® 325 or Flexbond® 825 from Air Products, Inc., PA, USA.
[0041] Figure 1A illustrates a side view of an example of a composite structure according to an example of the principles described in this document. The composite structure (100) includes the first layer (110), and a second layer (120) laminated to the first layer (110). A non-image side (112) of the composite structure (100) is the wrong side of the first layer (110). One side of the image (122) of the composite structure (100) is the front of the second layer (120).
[0042] Figure 1B illustrates a side view of another example of the composite structure according to an example of the principles described in this document. The composite structure (100) includes a first layer (110), a second layer (120) laminated to the first layer (110), the second layer (120) including a synthetic polymeric film and a bonding layer (125) directly thereon. second layer (120). In some examples, the composite structure further includes an adhesive (130) laminated between the first layer (110) and the second layer (120). In Figure 1B, the image side (122) of the composite structure (100) is associated with the bond layer (125) on the front side of the second layer (120).
[0043] In some examples of the principles described in this document, a wall covering is provided. The wall coating comprises any of the above-described examples of the composite structure and further comprises an image-receiving layer coated on the image side of the composite structure and an anti-mechanical wear layer coated on the image-receiving layer. Wallcovering in accordance with the principles described in this document has a durability that can meet, or exceed, the Type II wallcovering standards or specifications identified in this document. The wall covering has a mechanical tear strength that is between at least 50 lb (222 N) and approximately 60 lb (267 N) or between approximately 55 lb (245 N) and approximately 60 lb (267 N). In some examples, the mechanical breaking strength in MD is between approximately 58 lb (258 N) and approximately 60 lb (267 N), and in CMD it is between approximately 55 lb (245 N) and approximately 58 lb (258 N). ). In addition, the wall covering has a minimum wash resistance of 300 cycles or perhaps more of linear abrasion. In this case, the minimum washout strength and the mechanical break strength can be referred to as “wear” to simplify the discussion.
[0044] The image-receiving layer comprises a pigment filler, a water-based polymeric binder, and a latex film-forming agent. The image-receiving layer may further comprise an additive which includes, but is not limited to, one or both of a processing agent and a property modifier. The pigment filler is selected from one or both of an organic filler or an inorganic filler in the form of a solid powder or in a dispersed paste, for example. Examples of inorganic pigment filler include, but are not limited to, aluminum silicate, clay, kaolin clay, a calcium carbonate, silica, alumina, boehmite, mica, talc, a combination of two or more of them, or a mixture of two or more of them. The calcium carbonate can be one or more of ground calcium carbonate (GCC), precipitated calcium carbonate (PCC), modified GCC and modified PCC. Examples of organic pigment filler include, but are not limited to, particles either existing in a dispersed paste or in the form of a powder of solids, of polystyrene and its copolymers, polymethylacrylate and its copolymers, polyacrylates and its copolymers, polyolefins and its copolymers, such as polyethylene and polypropylene, a combination of two or more of the polymers, or a mixture of two or more of the polymers.
[0045] The image-receiving layer water-based polymeric binder includes, but is not limited to, polyvinyl alcohol, styrene-butadiene emulsion, acrylonitrile-butadiene latex, a combination of two or more of the binders, a combination of one or more of binders with other aqueous binders, a mixture of two or more of the binders or a mixture of one or more of the binders with other aqueous binders. Other aqueous binders that may be included in the water-based polymeric binder include, but are not limited to, starch, one or more of oxidized starch, cationized starch, esterified starch, enzymatically denatured starch; gelatine; casein; soy protein; cellulose derivatives, for example one or both of carboxymethyl cellulose and hydroxyethyl cellulose; acrylic emulsion; vinyl acetate emulsion; polyester emulsion; and polyvinyl pyrrolidone.
[0046] The image-receiving layer includes the polymeric binder in a proportion ranging from approximately 5 parts to approximately 40 parts per 100 parts of pigment filler by dry weight. In some examples, the proportion of polymeric binder ranges from approximately 7 parts to approximately 40 parts per 100 parts of pigment filler by dry weight, or from approximately 10 parts to approximately 40 parts per 100 parts of pigment filler by dry weight or of approximately 15 parts to approximately 40 parts per 100 parts of dry weight pigment filler. In some examples, the proportion of polymeric binder in the image-receiving layer ranges from approximately 5 parts to approximately 35 parts per 100 parts of pigment filler by dry weight, or from approximately 5 parts to approximately 30 parts per 100 parts of pigment loading by dry weight, or from approximately 5 parts to approximately 25 parts per 100 parts of pigment filler by dry weight.
[0047] The latex film forming agent of the image-receiving layer is provided to facilitate the formation of a film of a latex paint (i.e. an image) which can be subsequently deposited on the wall covering as an image. The latex film forming agent can be any type of chemical agent having a water compatibility, and thermal volatility that is capable of reducing an elastic modulus of paint latex particles and providing temporary plasticization to promote chain movement of the paint. polymer to improve the formation of a latex paint film from latex paint particles. Representative examples of latex film-forming agents include, but are not limited to, citrate or sebacate compounds, ethyloxy alcohols, glycol oligomers and other low molecular weight polymers, glycol ether, glycerol acetals, surfactants that are either anionic, or cationic or non-ionic and has a main chain of more than 12 carbons, cyclic amide-like lactams such as β-lactam, Y-lactam, and δ-lactam, a combination of two or more of them, or a mixture of two or more of them. In some examples, the latex paint film-forming agent is a cyclic amide-like lactam such as β-lactam, Y-lactam, lact-lactam or a mixture thereof. In one example, the latex paint film-forming agent is a Y-lactam. Representative examples of Y-lactam include, but are not limited to, N-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidone and 2-pyrrolidone.
[0048] A ratio of an amount of pigment loading to an amount of film-forming agent can be between approximately 200:1 and approximately 10:1. In some examples, the ratio of the amount of pigment loading to the amount of film-forming agent is between approximately 150:1 and approximately 10:1 or between approximately 100:1 and approximately 10:1 or between approximately 80:1 and approximately 10:1, or between approximately 65:1 and approximately 10:1, or between approximately 50:1 and approximately 10:1 or between approximately 35:1 and approximately 10:1. In some examples, the ratio of the amount of pigment loading to the amount of film-forming agent is between approximately 200:1 and approximately 15:1 or between 200:1 and approximately 20:1, or between approximately 200:1 and approximately 25:1, or between approximately 200:1 and approximately 30:1, or between approximately 200:1 and approximately 35:1, or between approximately 200:1 and approximately 40:1. In some examples, the ratio of the amount of pigment loading to the amount of film-forming agent is between approximately 100-1 and approximately 11:1 or between approximately 50:1 and approximately 12:1, or between approximately 35:1 and approximately 13:1 or between approximately 30:1 and approximately 14:1.
[0049] The anti-mechanical wear layer coated on the image-receiving layer of the wall coating in accordance with the principles described herein is a protective layer having a first structure prior to image formation on the wall coating (using a print by jet and ink, for example). The first structure is porous and configured to receive the paint colorant and to allow the other paint components to penetrate through the mechanical anti-wear layer to the image-receiving layer of the wall covering. The first structure of the anti-mechanical wear layer transforms into a second structure to further protect an image after image formation. The transformation takes place after the ink colorant has deposited on the outermost surface of the mechanical anti-wear layer and after the other ink components have penetrated into the image-receiving layer to form the image using inkjet printing. The second structure of the mechanical anti-wear layer is non-porous and transparent and provides a thin protective film on the outermost surface of the wall covering.
[0050] The anti-mechanical wear layer having the first structure and the second structure according to the principles described in the present document can comprise three types of polymeric particles. A first type of polymeric particles has a substantially non-deformable stage and a substantially deformable stage. "Non-deformable stage" means that particles are non-deformable prior to printing an ink image on the image-receiving layer, but that they may deform or form a film (ie, "deformable stage") under temperature conditions of printing a printing process, such as inkjet printing with latex ink that forms an image on the wall covering. Thus "non-deformable" also means that the particles are rigid and can form a porous assembly or coating to protect the wall covering prior to printing an image on it, but that the particles are also able to coalesce and run to form a film localized, due at least in part to the rise in temperature during a curing step of printing an image to protect an image subsequently printed thereon. More especially, the temperature of the printing or curing process is above a glass transition temperature (Tg) of the first type of particles of the mechanical anti-wear layer to coalesce and drain.
[0051] The first type of polymeric particles (hereafter "first particles") mechanical may have a Tg that is between approximately 50°C and approximately 200°C. In some examples, the Tg of the first particles is between approximately 50°C and approximately 190°C, or between approximately 50°C and approximately 175°C, between approximately 50°C and approximately 150°C, or between approximately 50°C C and approximately 135°C, or between approximately 50°C and approximately 125°C. In some, the Tg of the first particles found between particles are rigid and compacted together in a porous layer or arrangement (on a microscopic scale) in the mechanical anti-wear layer before printing and in ambient storage conditions, but are configured to deform and coalesce into a localized, non-porous or continuous film under printing conditions and an image with an ink, such as with a latex ink, for example.
[0052] The first particles are selected from reactive polymeric particles and non-reactive polymeric particles. The term "reactive polymeric particles" means that the particles are configured to cross-link, or be capable of cross-linking, (either through self-crosslinking, within a single molecular chain, for example, or within a multiplicity of molecular chains , such as in the presence of a crosslinking agent) after exposure to heat, during printing, for example. Under such conditions, the reactive polymeric particles can coalesce, so that the reactive polymeric particles flow away from each other to form a film at least partially due to a chemical bond during the crosslinking reaction. Crosslinking of the reactive polymeric particles can form a continuous, non-porous protective film that either oozes on heat or becomes crosslinked.
[0053] The first particles can be configured, for example, to be reactive by incorporating a crosslinkable functional group to the particles. In this example, the crosslinkable functional group is configured to be activated by heat which initiates the crosslinking reaction with an increase in temperature, such as during printing or curing processes, for example. As a result, after printing an image with an ink on the wall covering that includes the mechanical anti-wear layer that includes these first particles, the dissolution of these particles and the crosslinking of the crosslinkable functional groups causes these particles to coalesce and cause the printed ink pigment becomes entrenched so that these particles physically interlock with the printed or otherwise deposited ink and protect the image.
[0054] The reactive polymeric particles included as the first particles in this case have macromolecular chains capable of a crosslinking and coalescing reaction, as described above. Examples of such reactive polymeric particles include, but are not limited to, particles of a polymer having an epoxy functional group on the polymer backbone, particles of a polymer having an epoxy functional group on a polymer side chain, particles of a polymer having acid groups fatty, particles of a polymer having alkoxysilane groups, particles of a polymer having acetoacetoxy groups, particles of a polymer having hydroxyl groups, particle of a polymer having amine groups, and particles of a polymer having carboxyl groups.
[0055] The term "non-reactive particles" means that the particles do not initiate a crosslinking reaction, but are instead configured to coalesce and flow together to form a film due to an increase in temperature above the Tg of the particles, by exposure to heat during a printing process, for example. For this reason, the mechanical anti-wear layer including non-reactive first particles on a wall coating in accordance with the principles described herein forms a continuous, non-porous protective film that remains uncrosslinked after an image is printed on the wall coating. Wall.
[0056] The first non-reactive particles can be selected from polymers formed by one or both of polymerization and copolymerization of hydrophobic addition monomers. Examples of hydrophobic addition monomers include, but are not limited to, acrylate and (C1-C12) alkyl methacrylate monomers (such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate , isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate , isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate), aromatic monomers (such as styrene, phenyl methacrylate, o-tolyl methacrylate, m-tolyl methacrylate, p-tolyl methacrylate, benzyl methacrylate ), hydroxyl-containing monomers (such as hydroxyethylacrylate, hydroxyethylmethacrylate), carboxylic acid containing monomers (such as acrylic acid, methacrylic acid), vinyl ester monomers (such as vinyl acetate, vinyl propionate, benzoate vinyl, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate), vinyl benzene monomers, (C1-C12)alkyl acrylamide and methacrylamide monomers (such as tert-butyl acrylamide, sec-butyl acrylamide, N,N- dimethylacrylamide), and olefinic monomers (such as polyethylene, polypropylene, and copolymers thereof). Non-reactive, non-deformable particles can also be selected from polytetrafluoroethylene (PTFE), silica, silicone, paraffin wax, carnauba wax, montana wax, a combination of two or more of the monomers or materials, or a mixture of two or more of monomers or materials.
[0057] The anti-mechanical wear layer further comprises a second type of polymeric particles. The second type of polymeric particles (hereafter "second particles") are manufactured from substantially soft polymeric material. By definition, in the present invention, "soft" polymeric material refers to a polymeric material that has a Tg that is not greater than the Tg of the polymeric material of the first particles. In some examples, the Tg of the second particles is at least 2 to approximately 2.5 orders of magnitude lower than the Tg of the first particles. The second particles are configured to provide some adhesive strength to the first particles and a third type of polymeric particles (described below) and to hold the first particles and third particles on a surface of the image-receiving layer. Second particles, for example, provide an adhesive coating on one or both of the first particles and third particles. In this example, the second particles can chemically bond with the surfaces of one or more of the first particles, the third particles and the image-receiving layer, or they can bond by physical force or by an interlocking action through the formation of the film between the surfaces of the particles and the image-receiving layer, or by a combination of binding mechanisms.
[0058] In some examples, the second particles have a morphology that includes one or both of spherical and similar to spherical, the second particles can be dispersed in an aqueous solution, in the form of a polymeric latex, for example. The second particles can have a particle size ranging from the sub-micron scale to no more than approximately 10 µm in diameter. “On the sub-micrometer scale” means it is less than approximately 1 µm. Examples of polymeric latex material used to produce these second latex particles include, but are not limited to, acrylic polymer or copolymer latex, vinyl acetate latex, polyester latex, styrene-butadiene latex, acrylonitrile copolymer latex -butadiene, styrene acrylic copolymer latex, styrene acrylic latex, styrene acrylonitrile latex, styrene maleic anhydride latex, vinyl acrylic latex, vinyl acetate latex, vinyl ester latex, vinyl ether latex, a combination of two or more of latexes, or a mixture of two or more latexes.
[0059] In some examples, the second particles are present in a solvent, in an aqueous solvent, for example, in the form of a molecular colloid or a colloidal suspension. In these colloidal examples, the second particles have a diameter on the nanometer scale, or on a subnanometer scale. “On the nanometer scale” means from 1 nanometer (nm) to less than 1 µm. “On the sub-nanometric scale” means less than 1 nm. Examples of polymeric materials used to produce these second colloidal particles include, but are not limited to, poly(vinyl alcohol), starch and starch derivatives, gelatin and gelatin derivatives, cellulose and cellulose derivatives, acrylamide polymers, polyethylene glycol, derivatives of polyethylene glycol, polyurethane, polyvinylpyrrolidone, maleic anhydride polymer, maleic anhydride copolymers, a combination of two or more of the materials, or mixtures of two or more of the materials. In another example, the second particles include a combination of the polymeric latex particles described above and the smaller colloidal polymeric particles described above, or a mixture thereof.
[0060] The anti-mechanical wear layer further comprises a third type of polymeric particles. The third type of polymeric particles (hereinafter "third particles") is produced from a polyalkene homopolymer, a polyalkene copolymer, a modified polyalkene, a combination of two or more of the polyalkenes, or a mixture of two or more of them, for example . By definition, a "polyalkene" in the present invention refers to a polymeric material formed by polymerizing an alkene monomer, i.e., CnH2n and its derivatives, for example, where n is between approximately 7,000 and approximately 20,000. Examples of the polymers used to make the third particles include, but are not limited to, polyethylene homopolymer, polypropylene homopolymer, polytetrafluoroethylene (PTFE), amide modified polyethylene, amide modified polypropylene, PTFE modified polyethylene, PTFE modified polypropylene, modified polyethylene by maleic anhydride, maleic anhydride modified polypropylene, oxidized polyethylene, oxidized polypropylene, chloride-functionalized polyethylene, chloride-functionalized polypropylene, a combination of two or more of the polyalkenes, or a mixture of two or more of the polyalkenes.
[0061] The third particles may have a hardness value less than approximately 2 dmm as measured by the ASTM D-5 method. In some examples, the third particles have a hardness value less than approximately 1 dmm, or less than approximately 0.5 dmm. In some examples, the third particles have a hardness value in dmm that is between approximately 0.1 and approximately 2, or between approximately 0.1 and approximately 1.5, or between approximately 0.1 and approximately 1.0, or between about 0.1 and about 0.75, between about 0.1 and about 0.5, or between about 0.1 and about 0.25. In addition, the third particles can have a melting point that is between approximately 120°C and approximately 200°C. In some examples, the melting point of the third particles is between approximately 125°C and approximately 200°C, or between approximately 130°C and approximately 200°C. In some examples, the melting point of the third particles is between approximately 120°C and approximately 190°C, or between approximately 120°C and approximately 180°C, or between approximately 120°C and approximately 170°C, or between approximately 120°C and approximately 160°C, or between approximately 130°C and approximately 170°C. Furthermore, the third particles can have a particle size that is at least approximately ten times larger than that of the first particles. In some examples, the third particles have a particle size that is at least approximately 25 times larger than the first particles, or at least approximately 50 times larger than the first particles, or at least approximately 75 times larger than that of the first particles, or at least approximately 100 times larger than that of the first particles, or approximately 125 times that of the first particles.
Representative commercially available examples of the third particles include, but are not limited to, ACumist® micronized polyolefin waxes manufactured by Honeywell, NJ, USA, SLIP-AYD® waxes by Elementis Specialties, Inc. NJ, USA, and Licowax® waxes by Clariant, Germany. In another example, the third particles are produced from a micronized polyalkene compound dispersed in an aqueous solvent. A dry weight ratio of first particles to second particles to third particles in the anti-mechanical wear layer can be between approximately 20:1:2 and approximately 10:1:0.4. In some examples, the dry weight ratio of first particles to second particles to third particles in the anti-mechanical wear layer is between approximately 20:1:2 and approximately 16:1:1.6, or between approximately 20: 1:2 and approximately 14:1:1,2, or between approximately 20:1:2 and approximately 12:1:0.8.
[0063] Figure 2 illustrates a side view of a wall covering according to an example of the principles described in this document. The wall covering includes a composite structure (201) that includes a first layer (210) laminated to a second layer (220). In some examples, the composite structure (201) is substantially equivalent to any of the examples described above for the composite structure. The wall covering further includes an image-receiving layer (240) coated over the image side of the composite structure (201), the image side being opposite an unimage side (212) (or reverse side) of the composite structure (201). The wall coating further includes a mechanical anti-wear layer (250) coated over the image-receiving layer (240) to provide an image-forming surface (202) for the wall coating (200).
[0064] A coating weight of the image-receiving layer of the wall cladding can be between approximately 5 g/m2 and approximately 30 g/m2. In some examples, the image-receiving layer coating weight is between approximately 5 g/m2 and approximately 25 g/m2, or between approximately 5 g/m2 and approximately 20 g/m2, or between approximately 5 g/m2 and approximately 15 g/m2, or between approximately 5 g/m2 and approximately 10 g/m2. In some examples, the image-receiving layer coating weight is between approximately 6 g/m2 and approximately 25 g/m2, or approximately 7 g/m2 and approximately 20 g/m2, or approximately 8 g/m2 and approximately 15 g/m2. A coating weight of the mechanical anti-wear layer of the wall covering can be between approximately 0.5 g/m2 and approximately 10 g/m2. In some examples, the coating weight of the mechanical anti-wear layer is between approximately 0.5 g/m2 and approximately 8 g/m2, or between approximately 0.5 g/m2 and approximately 6 g/m2. In some examples, the coating weight of the anti-mechanical wear layer is between approximately 0.7 g/m2 and approximately 10 g/m2, or between approximately 0.8 g/m2 and approximately 8 g/m2, or between approximately 1 g/m2 and approximately 5 g/m2.
[0065] In some examples, according to the principles described in this document, a method of manufacturing a wall covering is proposed. Figure 3 illustrates a flowchart of a method (300) of fabricating a wall covering in accordance with an example of the principles described herein. The wall cladding that is produced is substantially equivalent to any of the examples of the wall cladding, including the composite structure, described above. The method (300) comprises providing (310) a textile material of the first layer. The textile material of the first layer includes any of the textile materials and structures described above, including woven, non-woven, knitted or tufted textile structures. The textile material of the first layer is provided (310) using a textile fabrication technique, for example.
[0066] The method (300) of manufacturing a wall covering further comprises forming (320) a second layer that includes a synthetic polymeric component. The second layer includes any of the examples described above for the second layer. The second layer can be, for example, a non-woven paper composition that is formed (320) using papermaking techniques and papermaking equipment. In this example, the second layer is formed (320) using a papermaking process (wet forming process) in which the fibers are suspended in water, taken to a forming unit where the water is drained through a wire mesh or sieve in constant motion and the fibers are deposited on the wire mesh, then the fibers are lifted from the wire mesh to be dried. In order to have a targeted web or formed sheet, the fiber concentration for the nonwoven paper composition can be very low, such as on the order of less than approximately 0.5% by weight.
[0067] The synthetic polymeric fiber used in the formation (320) of the second layer may not be able to self-bond, with hydrogen bonding, for example, as is wood fiber. Therefore, a method of external bonding with the synthetic polymeric fiber is employed, such as with one or more of a variety of types of binder and application methods. A binder can be applied, for example, both before web formation and after web formation. After web formation, the binder can be applied by saturation, spraying, printing, foaming or a combination thereof. After application of the binder, the web can be dried and in some instances the binder can be activated with steam-heated cans, for example. At the end of the processing line the web is calendered to thicken, smooth and soften the non-woven paper to achieve the target density and smooth character of the second layer. A target roughness of not more than 5 µm by the PPS method is achieved, for example, with various combinations of calendering pressure within a range of approximately 35 kilograms per square centimeter (kg/cm2) to approximately 140 kg/cm2 and a temperature of calendering between approximately 25°C and approximately 300°C.
[0068] The method (300) of manufacturing a wall covering further comprises laminating (330) the first layer and the second layer together to form a composite structure. The first and second layers are laminated (330) to each other using a laminator. Figure 4 illustrates a schematic view of a laminator (400) used to laminate the layers of the composite structure together in accordance with an example of the principles described herein.
[0069] As illustrated in Figure 4, the first layer (412) provided is wound on a first roller (410) and the second formed layer (422) is wound on the second roller (420). The first layer (412) is unwound under tension from the first roller (410) and separately, the second layer (422) is unwound under tension from the second roller (420). The first layer (412) and the second layer (422) are fed together into a laminating cylinder (430) where they are laminated together to form the composite structure (401), which is dried in a dryer or dryer oven ( 435) and rolled onto a finishing cylinder (440). In some examples, the second layer (422) is unwound from the second roller (420) to be coated with an adhesive from an adhesive bath (not shown). In some of these examples, the adhesive is coated onto the second layer (422) using a gauge rod which is facilitated by a collection cylinder (also not illustrated). In other examples, the second layer (422) is introduced to the laminating roller (430) without an adhesive coating. A voltage within the range of approximately 60 Newton (N) and approximately 120 N can be applied to the second layer (422), and a voltage within the range of 80 N to approximately 160 N can be applied to the first layer (412), using the laminator (400) is used. The first layer (412) and the second layer (422) are laminated together in the lamination cylinder (430) at a speed that can vary from approximately 10 meters/minute to 30 meters/minute, and are then dried in the dryer (435) using a peak temperature that can range from approximately 50°C to approximately 150°C.
[0070] The method (300) of producing a wall coating further comprises coating (340) an image-receiving layer on an image side of the composite structure. The image side is adjacent to the second layer. The image-receiving layer may be coated onto the composite structure using an applicator, including, but not limited to, one or more of spray coater, rotary coater, slit die applicator, fountain curtain applicator, blade applicator , rod applicator, air knife applicator, or air brush applicator. The image-receiving layer is then dried using one or more of a fan, a fan, an infrared lamp and an oven. The method (300) further comprises coating (350) an anti-mechanical wear layer over the image-receiving layer. The anti-mechanical wear layer can be coated (350) onto the composite structure using any of the coaters or applicators listed above or another method of application. The anti-mechanical wear layer is then dried using one or both of thermal heating and airflow.
[0071] Although not illustrated, the method of manufacturing a wall cladding may further comprise forming an image on the image side of the wall cladding. An image can be formed on the wall covering in accordance with the principles described herein using printing techniques such as one or more of inkjet printing, digital inkjet printing and digital inkjet printing. high speed. In addition, the image can be formed using one or more of aqueous pigment inks, aqueous UV inks, aqueous latex inks. Representative examples of printers used to print onto wallcoverings include, but are not limited to, HP DesignJet printers: L25500, L26500, and L65500; HP Scitex printers: LX600, LX800, LX850, and Turbojet 8600 UV from Hewlett-Packard Company. Representative inkjet inks used by the printers listed above include, but are not limited to, HP 791, HP 792, and HP Scitex TJ210. Printers can be used in a default wallpaper profile with a production print mode or a normal print mode. The print mode can vary the ink application within the range of approximately 50% to approximately 250% of each other.
[0072] In some examples, the non-image side of the wall covering is coated or treated with an adhesive to produce adhesion to a wall or other surfaces. Examples of wall adhesion adhesives for wallcoverings include, but are not limited to, Pro-880 Premium Clear Strippable wallpaper adhesives, Pro-838 Heavy Duty Clear, Pro-543 Universal, ECO-888 Strippable with Mildew Guard, and Golden Harvest Wheat, all from Roman Decorating Products, IL, USA; wallpaper adhesives Zinsser® Sure Grip®-128 and Zinsser Sure Grip®-132, both from Rust-Oleum® Corporation, USA; wallpaper adhesives Dynamite® DEFENDER, Dynamite® 234, Dynamite® C-11, each by Gardner-Gibson, FL, USA; Polycell® Paste the Wall wallpaper adhesive from AkzoNobel Group of Companies, UK; ECOFIX adhesive from Ecofix AB, Sweden; and Metylan and Solvite wallpaper stickers from Henkel, Germany.
[0073] Specific examples and evaluations of the composite structure and wall cladding including the same are given below. EXAMPLES
[0074] All measured values are within the measurement tolerance for the equipment used, unless otherwise indicated.
[0075] Samples of wall coverings were prepared in accordance with the principles described herein for evaluation as Type II durable wall coverings under ASTM F793, "Standard Classification of Wall Covering by Use Characteristic". Wall Cladding by Usage Characteristic) (2010 version substantially followed Federal Specification CCC-W-408D), which defines the durability requirements of wall cladding from 'decorative' wall cladding (Category I) to more drastic cases of use defined as “commercial utility” wall coverings of Type I (Category IV), Type II (Category V), Type III (Category VI) and up to "Type IV". Under ASTM F793, there are approximately 15 individual tests for various criteria of wear, strength and strength that can be conducted. To claim a specific use rating, the wallcovering must pass all 15 test criteria. The higher the rank or use case, the higher the required strength standards. Table I presents two of the ASTM F793 (2010) classification criteria tests, by way of example, for Type I (Category IV), Type II (Category V) and Type III commercial utility wall coverings ( Category VI) and by way of comparison, Category III for Decorative wall cladding with a high degree of utility.
[0076] The minimum washability, referenced in Section 7.7 of ASTM F793, and the minimum breaking strength referenced in Section 7.9 of ASTM F793, were conducted on the wall coating samples in accordance with the principles described herein that were prepared in the present document for evaluation. As seen from Table I, wallcoverings according to Category III have a significantly lower minimum washability standard and no standard for breaking strength compared to Categories IVVI. Minimum washability is reported in number of cycles and minimum breaking strength is reported in lb force (N) in ASTM F793. Table I
Sample Preparation
[0077] Table 2 shows the composition of the samples of wall coatings prepared according to the principles described in this document, having a composite support structure, an image-receiving layer and an anti-mechanical wear layer, as described above . More specifically the first layer of the composite structure (Layer 1) for both Example 1 and 2 consisted of a woven textile material having 90% of the total fiber count made up of polyester fibers and 10% of the total fiber count made up of natural cotton fibers and having a thread count of 46 x 48 (identified in Table 2 as Textile A). The second layer (Layer 2) of the composite structure of Example 1 consisted of a non-woven fiber composition (identified in Table 2 as Composition A); and in Example 2, the second layer (Layer 2) consisted of a polypropylene film with a basis weight of 170 g/m2. Composition A included 12% by weight of polyethylene fibers, 8% by weight of calcium carbonate filler, 69% by weight of natural cellulose fibers and 11% by weight of other additives such as binder, coupling agent, colorant and optical brightening agent.
[0078] An adhesive was applied to Layer 2 using rod #60; a tension of 75 Newton (N) was applied to Layer 2 and a tension of 100 N was applied to Layer 1 using a rolling mill. Layers 1 and 2 were laminated together at a speed of 20 metres/minute and dried using a peak temperature of 80°C.
[0079] Two different comparative samples were included in the evaluation Comparative Sample 1 was a commercially available PVC-free HP wallpaper (Hewlett-Packard Co., USA) based on a non-woven composite material without synthetic fibers having a receptive layer of image consisting of a calcium carbonate based inorganic pigment coating with a coating weight of 15 g/m2 (decorative grade, for example). Comparative Sample 2 was a commercially available printable digital wallcovering that included a composition of polyester and natural fibers, marketed as Type II commercial strength and PVC free. Table 2

The two samples of Examples 1 and 2 were coated with a pigmented coating, Coating A, as an image-receiving layer, having a coating weight of 12 g/m2. In addition, the two samples of Examples 1 and 2 were coated with a multistructured coating, Coating B, as a mechanical anti-wear layer, having a coating weight of 5 g/m2, over pigmented coating A. A production coater equipped with a rod application station Mayer was used to coat the two coating layers with a wet-on-dry sequence. Drying was carried out in an 8 meter hot air drying channel with a total coating speed of 200 meters per minute.
[0081] The composition of the pigmented coating (Coating A) is listed in Table 3. Hydrocarb® 60 and Hydrocarb® 90 are calcium carbonate pigment fillers from Omya North America. Acronal® 866 is a styrene-acrylic binder from BASF Corporation, North America. The film forming agent was a 2-pyrrolidone, supplied by Aldrich Inc. BYK® Dynwet® 8 is a silicone-free wetting agent and BYK®-024 is a VOC-free silicone defoamer, both from BYK USA, Inc., CT. Pigmented coating A was prepared in a high shear mixer. The final solids content after mixing was 52% and the viscosity was 180 centipoise (cps) as measured by a Brookfield viscometer at 100 rpm. Table 3

[0082] The composition of the multistructured coating (Coating B) is shown in Table 4. RayCat® 061 consists of polyacrylic polymeric particles (ie, the first type of particles) and RayCat® 100 consists of shaped acrylate-based polymeric particles. of latex (ie, the second type of particles), both from Specialty Polymers, Inc., OR, USA, SLIP-AYD® SL300 consists of a high melting point polyethylene wax dispersion (ie, the third type of particles) from Elementis Specialties.
[0083] Multistructure coating B was prepared by mixing the ingredients at room temperature in a mixing tank with a medium shear speed (50-100 rpm) for 30 minutes. The mixture was filtered through a 200 mesh sieve and left for 1 for the gas to escape before use. Table 4

[0084] Image Print on Samples: Samples from Examples 1 and 2 and Comparative Samples 1 and 2 were printed using an HP DesignJet L26500 printer equipped with HP 792 Latex Inks, using a six-color process at 110° C and at a speed of 100 sq ft per hour (9.29 m2 per hour) (a 10-pass bidirectional color profile). An image was created over each Swatch with an equal percentage of each of the six ink colors. A final visual appearance of the image was a gray area in the Samples. According to ASTM F793, the image included many different colors. Minimum Washability Test
[0085] Sample Preparation for Wall Cladding Washability: In accordance with ASTM F793 section 7.7, a fragment each of Samples from Examples 1 and 2 and Comparative Samples 1 and 2 was cut into 6.5 inch specimens (16.51 cm) x 17 inches (43.18 cm) so that a longer dimension is in the cross-machine direction. As specified in ASTM F793, an area with many different printed colors was selected on each Sample.
[0086] The minimum washability test (solvent resistance) in accordance with ASTM F793 was conducted by exposing the various Samples to a nylon bristle brush and a detergent solution prepared in accordance with "Note 1" in section 7.4 of ASTM F793, in a BYK Abrasion Tester from BYK-Gardner USA, Columbus, MD with a linear back-and-forth action, attempting to erase the image side of the Samples using the target cycle number in Table 1. After testing is complete, Samples were subjectively classified as “pass” or “fail” in accordance with the guidelines listed in 7.7.2 and the visual classification criteria listed in 7.4.2 of ASTM F793, “there will be no evidence of a noticeable change in the printed surface or base.” Table 5 presents the results of the minimum washability test for the Samples. Table 5
Minimum Breaking Strength Test
[0087] Sample Preparation for the Breakage Resistance of Wall Coatings: In accordance with ASTM F793 section 7.9, samples were cut in the machine direction (MD) and the samples were cut in the cross-machine direction (CMD) of the Samples of Examples 1 and 2 and Comparative Samples 1 and 2, either printed or unprinted, in 4-inch (10.16 cm) x 6-inch (15.24 cm) copies. The average of all specimens cut and tested on MD was calculated and compared to an average of all specimens cut and tested on CMD. There were two replica specimens for each Sample.
[0088] Minimum breaking strength (tensile strength) testing in accordance with ASTM F793 was conducted at the HP Analytical Services Laboratory by exposing the Samples to a standard force gauge tester, Instron Model No. 5566, Tensile & Tear Instrument, of Instron, USA. Two clamps were used to grip the longer ends of the rectangular-shaped specimens from the respective Samples, then pulling with increasing force until breakage (ie, material separation) occurred. The Table lists the minimum breaking strength test results for the Samples (average tensile strength in pounds (lb)) The average breaking strength of the Samples from Example 1 and Example 2 was approximately twice as high in the direction of machine and approximately four times greater in the cross-machine direction than the respective average for Comparative Samples 1 and 2. Table 6

[0089] For both the minimum washability test and the minimum breaking strength test, the Samples of Examples 1 and 2, in accordance with the principles described herein, met or exceeded the values in Table 1 in ASTM F793 for Type II commercial utility wallcoverings and did so without the use of a PVC component.
[0090] Therefore, examples of a composite structure, a wall cladding employing the composite structure, and a method of producing a wall cladding that includes the composite structure have been described. It should be understood that the examples described above are simply illustrative of some of the many specific examples that represent the principles of what is claimed. Clearly those skilled in the art could easily develop numerous other arrangements without departing from the scope defined by the claims that follow.

权利要求:
Claims (11)
[0001]
1. Wall cladding, CHARACTERIZED in that it comprises: a composite structure having an image side and a non-image side, the composite structure comprising: a first layer having a textile material structure with warp and weft to facilitate the flow of air over the non-image side; and a second layer laminated to the first layer, the second layer comprising one of a synthetic polymeric fiber in a non-woven structure, the second layer having a surface roughness of less than 5 µm by the image-side PPS method; an image-receiving layer coated on the second layer to support an ink image; and an anti-mechanical wear layer coated over the image-receiving layer, the wall coating being PVC-free and having a washability and tear-resistance of Type-II wall coatings; wherein the second layer further comprises a natural fiber and the amount of synthetic polymeric fiber in the composition of the second layer is within 10% to 80% by weight of the total fibers; wherein the first layer comprises one or both of natural fibers and synthetic fibers; wherein the natural fibers of the first layer are selected from wool, cotton, silk, linen, jute, linseed, hemp, rayon, thermoplastic aliphatic polymer fibers and combinations of two or more thereof, wherein the thermoplastic aliphatic polymer fibers are derived from corn starch, tapioca and sugar cane products; wherein the synthetic fibers of the first layer are selected from poly(vinyl chloride) free fibers made from polyester, polyamide, polyimide, poly(acrylic acid), polypropylene, polyethylene, polyurethane, polystyrene, polyaramid, poly(terephthalate). ethylene), fiberglass, polycarbonate, poly(butylene terephthalate) and combinations of two or more thereof; wherein the mechanical anti-wear layer has a first porous structure without an image printed on the wall covering, and the first porous structure is transformable into a second, transparent, non-porous film structure with image printing.
[0002]
2. Wall covering, according to claim 1, CHARACTERIZED by the fact that the first layer of the composite structure is a textile material comprising one or both of natural fibers and synthetic fibers having the textile structure which is a woven, not woven, knitted and tufted, the textile structure to provide airflow channels on the non-image side.
[0003]
3. Wall covering, according to claim 1, CHARACTERIZED by the fact that the first layer of the composite structure is a textile material comprising both natural fibers and synthetic fibers in a woven structure, an amount of natural fibers being 10% of a total fiber count and an amount of synthetic fibers being 90% of the total fiber count.
[0004]
4. Wall covering, according to claim 1, CHARACTERIZED by the fact that the second layer of the composite structure further comprises natural cellulose fiber in the non-woven structure.
[0005]
5. Wall coating according to claim 1, CHARACTERIZED by the fact that the image-receiving layer comprises pigment filler, a water-based polymeric binder in a proportion within a range of 5 parts to 40 parts per 100 parts of pigment loading by dry weight, and a latex film-forming agent, at a pigment loading to latex film-forming ratio within a range of 200:1 to 10:1.
[0006]
6. Wall coating according to claim 1, CHARACTERIZED by the fact that the anti-mechanical wear layer comprises first polymeric particles that are rigid but deformable and have a glass transition temperature (Tg) within a range of 50 °C to 200 °C; second polymeric particles that are soft and that have a Tg that is no greater than the Tg of the first polymeric particles; and third polymeric particles of a polyalkene material having a melting point within a range of 120°C to 200°C, a dry weight ratio of first polymeric particles to second polymeric particles to third polymeric particles within a range of 20:1:2 to 10:1:0.4.
[0007]
7. Wall coating according to claim 6, CHARACTERIZED by the fact that the first polymeric particles are coalescible and the film-forming particles are selected from a reactive polymeric material and a non-reactive polymeric material, the second particles being a polymeric binder, and wherein the third polymeric particles have a formula CnH2n where n is within a range of 7,000 to 20,000.
[0008]
8. Wall covering according to claim 1, CHARACTERIZED by the fact that the first layer comprises natural and synthetic fibers and that the amount of synthetic polymeric fiber in the second layer is within the range of 10% to 40% by weight of total fiber.
[0009]
9. Wall covering, according to claim 8, CHARACTERIZED by the fact that it further comprises the ink image on the image side, in which the first transformable porous structure is transformed into a transparent, non-porous film structure to protect the image in ink.
[0010]
10. Composite structure to support a wall covering, CHARACTERIZED by the fact that it comprises: a first layer of textile material forming an imageless side of the composite structure, the first layer of textile material comprising one or both of natural fibers and synthetic fibers or both in a textile structure which is one of woven, non-woven, mesh and tufted material to facilitate airflow on the non-image side; and a second layer laminated to the first layer to form an image side of the composite structure, the second layer comprising a synthetic polymeric component in one of a non-woven textile structure and having a surface roughness less than or equal to 5 µm by the PPS method; where the composite structure is PVC free and has a mechanical break strength greater than 50 lb (222 N) of Type-II wallcovering standards; wherein in the non-woven fiber structure, the second layer further comprises a natural fiber and the amount of synthetic polymeric fiber is within the range of 10% to 80% by weight of the total fiber; wherein the natural fibers of the first layer are selected from wool, cotton, silk, linen, jute, linseed, hemp, rayon, thermoplastic aliphatic polymer fibers and combinations of two or more thereof, wherein the thermoplastic aliphatic polymer fibers are derived from corn starch, tapioca and sugarcane products; wherein the synthetic fibers of the first layer are selected from poly(vinyl chloride) free fibers made from polyester, polyamide, polyimide, poly(acrylic acid), polypropylene, polyethylene, polyurethane, polystyrene, polyaramid, poly(terephthalate). ethylene), fiberglass, polycarbonate, poly(butylene terephthalate) and combinations of two or more thereof.
[0011]
11. Composite structure, according to claim 10, CHARACTERIZED by the fact that the second layer further comprises a polymeric binder in the non-woven fiber structure and the natural fiber of the second layer is cellulose fiber, the synthetic polymeric component consisting of fibers polymers selected from the group consisting of polyolefins, polyamide, polyesters, polyurethanes, polycarbonates, polyacrylics, a combination of two or more of the polymeric fibers and in a mixture of two or more of them, a ratio of the polymeric binder to the cellulosic fibers being within the range from 1:20 to 1:1.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112015018473B1|2021-05-04|wall cladding and composite structure to support a wall cladding

---

US9919551B2|2018-03-20|Printable medium

---

EP3022063B1|2018-12-26|Printable medium

---

US9707790B2|2017-07-18|Printable media

---

US9777435B2|2017-10-03|Printing substrate

---

WO2018048423A1|2018-03-15|Fabric print medium

---

EP3265321B1|2019-10-09|Printable media

---

WO2018048422A1|2018-03-15|Fabric print medium

---

CN109937143B|2022-02-11|Printable media

---

US10619295B2|2020-04-14|Fabric print medium

---

WO2018048420A1|2018-03-15|Fabric print medium

---

US20200338920A1|2020-10-29|Fabric printable medium

---

US11279163B2|2022-03-22|Fabric printable medium

---

US20200407910A1|2020-12-31|Fabric printable medium

同族专利:

---

公开号 | 公开日

---

KR20150129666A|2015-11-20|

---

BR112015018473A2|2017-07-18|

---

KR102034577B1|2019-10-21|

---

EP2969562A4|2016-08-10|

---

EP2969562B1|2020-04-08|

---

WO2014158347A1|2014-10-02|

---

US8563100B1|2013-10-22|

---

CN104302478A|2015-01-21|

---

CN104302478B|2016-02-03|

---

EP2969562A1|2016-01-20|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US4296162A|1978-03-14|1981-10-20|Jean Raymond W|Wallcoverings|

---

US4489188A|1982-07-02|1984-12-18|Eastman Kodak Company|Coalescent-containing coating composition|

---

US4460643A|1983-02-07|1984-07-17|The Dexter Corporation|Nonwoven fibrous backing for vinyl wallcover|

---

US5236987A|1987-07-02|1993-08-17|Velsicol Chemical Corporation|Isodecyl benzoate coalescing agents in latex compositions|

---

US4844972A|1987-12-23|1989-07-04|Borden, Inc.|Woven-backed vinyl decorative-coverings with starchy-PVA prepaste adhesive|

---

US5441784A|1994-04-04|1995-08-15|Decora, Incorporated|Paper base wallcoverings|

---

DE19531142C2|1995-08-24|1997-09-25|Polymer Chemie Gmbh|Structural foam wallpaper|

---

US20050014431A1|1999-07-21|2005-01-20|Carmody Debra J.|Polymer coated web with good water vapor permeability|

---

JP2003504248A|1999-07-21|2003-02-04|デクスター、スペシアリティマテリアルズ、リミテッド|Polymer coated web with good water vapor permeability|

---

US6440269B1|1999-12-06|2002-08-27|Domtar, Inc.|Base sheet for wallcoverings|

---

US6547929B2|2000-04-12|2003-04-15|Rohm And Haas Company|Paper having improved print quality and method of making the same|

---

GB0025886D0|2000-10-23|2000-12-06|Murray Nicholas J|Method and apparatus for producing a transfer image and method and apparatus for transfering a coating|

---

KR100388851B1|2001-03-09|2003-06-25|주식회사 엘지화학|Non-Woven Fabric Wall Paper with High Opacity and Shaped Pattern and Method for Manufacturing thereof|

---

US20060292318A1|2003-09-03|2006-12-28|Parrinello Luciano M|Water resistant ink jet printable sheet|

---

US6689517B1|2002-08-20|2004-02-10|Eastman Kodak Company|Fabric imaging element|

---

DE10252739A1|2002-11-13|2004-10-28|Stora Enso Maxau Gmbh & Co. Kg|Wallpaper paper and process for its manufacture|

---

US6764804B2|2002-12-11|2004-07-20|Eastman Kodak Company|Adhesive imaging member with composite carrier sheet|

---

CA2456384A1|2003-10-24|2005-04-24|Dan L. Jackson|Breathable laminate|

---

US7696262B2|2003-12-19|2010-04-13|Hewlett-Packard Development Company, L.P.|Wetting agent combinations for inkjet printing|

---

JP4512381B2|2004-02-12|2010-07-28|日清紡ホールディングス株式会社|Textile products containing biodegradable plastics|

---

US8216660B2|2005-05-04|2012-07-10|Shawmut Corporation|Halogen and plasticizer free permeable laminate|

---

US20070218796A1|2006-03-17|2007-09-20|Yao Peter C|Paper composite for billboards and banners|

---

US20070275617A1|2006-05-25|2007-11-29|Wp Ip, Llc|Decorative flame barrier surface covering|

---

US20070287345A1|2006-06-09|2007-12-13|Philip Confalone|Synthetic nonwoven wallcovering with aqueous ground coating|

---

US20100167005A1|2007-02-21|2010-07-01|Johns Manville|Directly decoratable composite materials, method for their manufacture and their use|

---

US8628833B2|2007-04-23|2014-01-14|Hewlett-Packard Development Company, L.P.|Stackable ink-jet media|

---

US20090068412A1|2007-09-12|2009-03-12|Shawmut Corporation|Polyurethane upholstery|

---

US20090075070A1|2007-09-13|2009-03-19|3M Innovative Properties Company|Photographic print with an adhesive composite|

---

ES2351234T3|2007-10-20|2011-02-01|Cognis Ip Management Gmbh|USE OF ACETAL GLICEROL.|

---

US20090233056A1|2008-03-11|2009-09-17|Anderson Sr Andy W|Polypropylene Laminate Wallcovering|

---

US20100310838A1|2009-06-03|2010-12-09|Michael Ketzer|Printing of non-woven fabrics and their use in composite materials|

---

AT12513U1|2010-12-02|2012-06-15|Schaefer Philipp|COMPOSITE|US9370958B2|2013-01-30|2016-06-21|Hewlett-Packard Development Company, L.P.|Printable medium|

---

EP3022063B1|2013-07-15|2018-12-26|Hewlett-Packard Development Company, L.P.|Printable medium|

---

US9919551B2|2014-02-19|2018-03-20|Hewlett-Packard Development Company, L.P.|Printable medium|

---

US9707790B2|2014-03-17|2017-07-18|Hewlett-Packard Development Company, L.P.|Printable media|

---

EP2995741B8|2014-09-15|2018-02-21|Wed S.R.L.|Waterproof decorative sheath system for walls of moist environments, and method for making it|

---

JP2016080866A|2014-10-16|2016-05-16|富士ゼロックス株式会社|Maintenance necessity estimation device and program|

---

US11065900B2|2015-03-11|2021-07-20|Hewlett-Packard Development Company, L.P.|Transfer of latex-containing ink compositions|

---

EP3233510B1|2015-04-10|2020-09-09|Hewlett-Packard Development Company, L.P.|Fabric print medium|

---

FR3034783B1|2015-04-13|2020-05-29|Coating Developpement|PRE-SIZED WALLPAPER|

---

KR102062044B1|2015-06-10|2020-01-03|휴렛-팩커드 디벨롭먼트 컴퍼니, 엘.피.|Printable media|

---

CN105038361A|2015-07-09|2015-11-11|江门市凃派涂装科技工程有限公司|Multifunctional weather-resistant putty paint for exterior walls and preparation method therefor|

---

KR102046770B1|2015-07-09|2019-11-20|휴렛-팩커드 디벨롭먼트 컴퍼니, 엘.피.|Printable film|

---

US10040306B2|2015-07-09|2018-08-07|Hewlett-Packard Development Company, L.P.|Printable film|

---

CN108025579B|2015-09-29|2020-12-25|惠普发展公司，有限责任合伙企业|Printable media|

---

US20180326773A1|2016-01-19|2018-11-15|Hewlett-Packard Development Company, L.P.|Embossed print media|

---

CN106213925A|2016-08-25|2016-12-14|费孝锋|A kind of dining table cloth after improvement|

---

CN110691695A|2017-07-06|2020-01-14|惠普发展公司，有限责任合伙企业|Fabric print media|

---

CN111169059A|2018-11-09|2020-05-19|万喜人家健康科技有限公司|Preparation method and preparation equipment of mesh-hole high-polymer film forming material|

---

TWI706067B|2019-04-10|2020-10-01|弘裕企業股份有限公司|Manufacturing method and structure of imitation paper double wrinkle printing cloth|

---

WO2021113385A1|2019-12-02|2021-06-10|Shurtape Technologies, Llc|Roof underlayment|

---

EP3960954A1|2020-02-25|2022-03-02|Tecnografica S.pA.|Decorative panel comprising an elastic fabric for the decoration of surfaces|

---

CN111469501A|2020-04-13|2020-07-31|浙江缇慕家居用品有限公司|Composite wall cloth|

法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2020-04-07| B25G| Requested change of headquarter approved|Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P. (US) |

---

2021-04-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-05-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 31/01/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US13/830.198|2013-03-14|

---

US13/830,198|US8563100B1|2013-03-14|2013-03-14|Wall covering|

---

PCT/US2014/014319|WO2014158347A1|2013-03-14|2014-01-31|Wall covering|

---