Patent Grant
8206800
The invention relates generally to flocked articles and particularly to flocked decorative articles having a multi-component adhesive film. More specifically the invention relates to flocked decorative articles having non-compatible heat sealed materials.
Flocked decorative articles are used in a wide variety of applications. For example, flocked articles are used as patches, transfers, coated molded objects, and the like. Flock applied to a decorative article can enhance the texture and perceived value of the decorative article. To maintain a high level of plushness of the decorative flocked article, it is important to not only to permanently anchor the flock fibers in a substantially perpendicular orientation of the flocks fibers relative to the substrate and it is also important to provide space between the fibers so that fibers can move freely to create a feeling of plushness.
One technique for accomplishing these objectives, permanently adhering the flock in a substantially perpendicular orientation to the substrate and providing substantially free movement of the flock fibers, is embedding the flock fibers in pre-formed, self-supporting (A- or B-staged) thermosetting adhesive film and fully activating (that is, cross-linking or C-staging) the thermosetting adhesive to permanently adhere the flock fibers to the thermoset adhesive. Once fully cross-linked, the thermoset adhesive is no longer capable of being adhered to another material. A problem thus exists in the need of a downstream user to adhere the fully cross-linked thermoset adhesive to a substrate.
These and other needs are addressed by the various embodiments and configurations of the present invention. The present invention is directed generally to an article having adjacent thermosetting and thermoplastic adhesive layers arranged so that the thermosetting adhesive layer is between the flock and thermoplastic adhesive layer. The thermoplastic adhesive layer is a laminate or co-extruded film having multiple, typically incompatible, components. In one application, a first part or layer of the thermoplastic adhesive has, as its primary component, a first polymer, which is typically polar, and a second part or layer of the thermoplastic layer has, as its primary component, a second polymer, which is different from the first polymer and is typically non-polar. As used herein, “compatibility” refers to physical or chemical incompatibility; that is, two materials are considered to be incompatible if they will not typically adhere directly to one another unless formed and/or processed in intimate association or in conjunction with one another. For example, polyesters and polyolefins are generally chemically incompatible, as for example due to differing polarities; however, they can be adhered to or associated with one another by suitable processing techniques, such as co-extrusion or lamination.
The first and second parts can be formulated to have one or more differing properties. By way of example, the first and second parts may have one or more differing melting temperatures, softening points, viscosities, surface energies, solubility parameters, degree of crystallinity, hydrogen bonding properties, morphologies, chemical properties, physical properties, structural properties, and bond strengths. The first and second parts are preferably selected such that the first and second parts are capable of being adhered to or associated with one another by co-extrusion, lamination, or other processing techniques, and that the first part is capable of being adhered to or associated with a first material, such as a polar substrate, and the second part is capable of being adhered to or associated with a second material, such as a non-polar substrate. Preferably, the first and second parts do not flow together when the co-extruded film is softened or melted.
While not wishing to be bound by any theory, the inability of thermosetting adhesives to bond to certain types of substrates is believed to be due to chemical and/or physical differences between the thermosetting adhesive and substrate, which provide for poor adhesion of the thermosetting adhesive to the substrate. As for example, it is hard to realize an adhesive joining of the materials when materials, such as polar and non-polar substrates, have little, if any, affinity for one another.
In one embodiment, the thermosetting adhesive layer is contacted with the flock fibers and fully thermoset before contact with the thermoplastic adhesive layer. It has been discovered that, when the two adhesive layers are applied simultaneously or substantially simultaneously to the flock layer both adhesive layers can set irreversibly, even when one of the adhesive layers is a thermoplastic adhesive layer. While not wishing to be bound by any theory, the irreversible setting of the two adhesive layers is believed to be due to thermosetting curing agents migrating into the thermoplastic adhesive layer causing it to cross-link in same manner as the thermosetting adhesive layer. It has been found that applying and laminating the adhesive layers separately at differing times can solve this problem, for example, by completely curing (C-staging) the thermosetting adhesive layer before applying the thermoplastic layer immobilizes (and/or consumes) the curing agents in thermosetting adhesive layer thereby, preventing migration of the cross-linking agents into the thermoplastic adhesive layer. The fully cross-linked thermoset adhesive also can provide a barrier to inhibit flow of another adhesive, used to adhere the flock to a substrate, flowing between and/or up the longitudinal axis of the flock fibers.
In another embodiment, the thermoplastic adhesive layer is softened or at least partially liquefied and applied to the fully activated (or cross-linked) thermosetting adhesive layer firmly adhered to the flock fibers. The fully cross-linked thermosetting adhesive inhibits the flow of the softened or liquefied thermoplastic adhesive, during bonding application of the thermoplastic adhesive, into and between the flock fibers, thereby maintaining a high degree of plushness in the flock layer without compromising the bond strength between the fibers and thermosetting adhesive layer.
Yet another embodiment of the present invention includes the use of a multi-component adhesive film to adhesively bond normally incompatible surfaces, such as polar and non-polar surfaces. The ability to adhesively join non-compatible materials can permit the manufacturing of a wide variety of flocked articles, such as for example adhesively joining flock labels to natural rubber Harmony™ yoga mats from Jade Industries, or adhesively joining a flock transfer to natural rubber MOUSE RUG™ manufactured by Fiberlok® Inc. Multi-component adhesive films permit several steps to be performed simultaneously, e.g., gluing and finishing in a single step. Because the multi-component film can be in the form a pre-formed and self-supporting film prior to use, the film can be easy to handle, and the manufacturing process can be clean and environmentally friendly, as opposed to liquid adhesives. The thermoplastic adhesive film can also be three-dimensionally deep-drawn and thermoformed.
These and other advantages will be apparent from the disclosure of the invention(s) contained herein.
As used herein, “at least one”, “one or more”, and “and/or” are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions “at least one of A, B and C”, “at least one of A, B, or C”, “one or more of A, B, and C”, “one or more of A, B, or C” and “A, B, and/or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B and C together.
The above-described embodiments and configurations are neither complete nor exhaustive. As will be appreciated, other embodiments of the invention, are possible utilizing, alone or in combination, one or more of the features set forth above or described in detail below.
The release or carrier sheet 104 can be any material that is dimensionally stable under the temperatures and pressures encountered during the manufacturing process. The carrier 104 can be any low-cost, dimensionally stable substrate, such as paper, plastic film, and the like, preferably in the form of a discontinuous sheet or a running web line material (such as described in U.S. Pat. No. 6,025,068 and copending U.S. Provisional Application Ser. Nos. 60/628,836, filed Nov. 16, 2005, 60/676,124, filed Apr. 28, 2005, 60/703,925, filed Jul. 28, 2005, 60/704,681, filed Aug. 1, 2005, 60/707,577, filed Aug. 11, 2005, 60/710,368, filed Aug. 22, 2005, 60/716,869, filed Sep. 13, 2005, 60/719,469, filed Sep. 21, 2005, and 60/719,098, filed Sep. 20, 2005, to Abrams), and other known carriers. The carrier sheet 104 is preferably a porous film, such as a porous film coated with release adhesive 108, which is preferably a water-based release adhesive. A preferred porous film is discussed by Pekala in U.S. Pat. No. 6,025,068. A particularly preferred porous film is sold by PPG Industries Inc. under the trade name TESLIN™. Battery separator membranes can also be used. Examples include Daramic Industrial CL™ sold by Daramic, Inc., and the uncoated, nono-layer, highly filled polyolefin sheet battery separator membranes sold by Celgard or by Daramic, Inc. under the trade name Artisyn™. Typically, but not always, the carrier is a discontinuous as opposed to a continuous sheet on a running web line.
The release adhesive 108 can be any adhesive that adheres more strongly to the carrier sheet than the flock fibers but adheres to both enough to hold them together. For example, the release adhesive 108 can be any temporary adhesive, such as a resin or a copolymer, e.g., a polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral, acrylic resin, polyurethane, polyester, polyamides, cellulose derivatives, rubber derivatives, starch, casein, dextrin, gum arabic, carboxymethyl cellulose, rosin, silicone, or compositions containing two or more of these ingredients. The release adhesive is preferably a water-based release adhesive.
The flock 112 used in any of the processes discussed herein can be any electrostatically chargeable fiber, such as fibers made from rayon, nylon, cotton, acrylic, and polyester. The flock preferably is resilient under and has a melting and/or softening point that is greater than the temperatures and pressures experienced in design, manufacturing, and later application processes to resist softening, deformation, and melting. Due to its low melt point, acrylic flock is undesirable in many applications. Resilient flock, such as rayon, nylon, and terephthalate (e.g., poly(cyclohexylene-dimethylene terephthalate) polymer flock, is particularly preferred. In most applications, the flock orientation is at least substantially orthogonal (perpendicular) to release sheet 104 and the flock fibers are at least substantially parallel to one another. In one configuration, a conductive coating or finish is applied continuously or discontinuously over the exterior surface of the flock fibers to permit the flock fibers to hold an electrical charge. The flock fibers 112 may be pre-colored (yarn-dyed or spun dyed) before application to the release adhesive 108 or after the carrier 104 is removed, such as by sublimation dye transfer printed.
The adhesive 116 can be any suitable water- or solvent-based adhesive. The adhesive is preferably a high temperature permanent adhesive, such as polybenzimidazoles and silica-boric acid mixtures or cements, hot-melt adhesives, thermosetting adhesives, thermoplastic adhesives, polyurethane, polyester, and combinations and blends thereof. “Hot-melt adhesives” generally refer to a solid material that forms an adhesive bond upon heating and subsequent cooling, “thermosetting adhesives” generally refer to a polymer that solidifies or “sets” irreversibly when heated, and “thermoplastic” generally refers to a polymer that can be repeatedly softened when heated and hardened (re-solidified) when cooled. The irreversible setting of a thermosetting adhesive is commonly affected by cross-linking of at least most, if not all, of the cross-linking reactive entities contained in the adhesive polymer.
More preferably, adhesive 116 is an activatable, permanent thermosetting adhesive in the form of a pre-formed self-supporting film before contact with the flock. Adhesive 116 is preferably activated fully when it is heated above an activation temperature for a sufficient period of time. As will be appreciated, thermosetting adhesives solidify, activate, and/or set irreversibly (that is, become infusible and relatively insoluble in solvents) when chemical entities comprising the thermosetting adhesive chemically react (that is, cross-link) to form covalent bonds at least mostly between the reactive chemical entities comprising the thermosetting adhesive. The chemical, cross-linking reaction is typically initiated and/or maintained by a chemical initiator, thermal energy or radiation (such as, an electron beam or electromagnetic energy). The thermosetting adhesive 116 can be any high polymer that solidifies or sets irreversibly (e.g., B- or C-staged) when heated above a specific temperature (typically its softening temperature). In other words, the adhesive is commonly non-tacky and thermoplastic (or A-staged) in nature as prepared and, upon heating to a suitable temperature, fuses and becomes thermoset (e.g. B- or C-staged) or substantially infusible and insoluble. The thermoset state is usually associated with a cross-linking reaction of the molecular constituents induced by heat or radiation. Curing agents, such as organic peroxides and sulfur (in the case of rubber), may be incorporated in the adhesive 116 to facilitate or catalyze the cross-linking reaction. For example, linear polyethylene can be cross-linked to a thermosetting material either by radiation or by chemical reaction. Examples of thermosetting adhesives include acrylics, polyethylene, polyamides, epoxides, polyurethanes, phenolics, alkyds, amino resins, polyesters, epoxides, rubbers, and silicones.
In one formulation, the thermosetting adhesive 116, when in the thermoplastic state, includes a compound containing three or more isocyanate groups per molecule (such as triphenylmethane, triisocyanate, benzene triisocyanate, tolylene triisocyanate, silicon triisocyanate, ethylene tetraisocyanate, and diphenyl triisocyanate) in which a number of the isocyanate groups are blocked or masked with an isocyanate splitter-type material (such as a phenols and malonic ester), and a polyester containing three or four hydroxyl groups (such as glycerin, trimethylol propane, pentaerythritol, various polyesters with excess hydroxyl groups, and phenol formaldehyde resins). To convert the adhesive to the thermoset state, the adhesive is heated to a higher temperature, for example about 125 degrees Celsius or higher, for a short period of time to free the isocyanate groups from the masking or blocking material and permit their reaction with the hydroxyl groups of the polyester. To accelerate the decomposition reaction or the splitting off of the splitter-type material, a small amount of an accelerator such as a tertiary amine compound, tributyl amine, and tris-(dimethyl aminomethyl) phenol, may be added.
The preformed, self-supporting adhesive film can include fine particles of polymers or copolymers, as well as one or more of plasticizer(s), stabilizer(s), curing agent(s) (such as an isocyanate), pigment(s), etc. The pigment, if any, determines the color and opacity of the adhesive film. The stabilizer, used when pigment is added, prevents discoloration of the resin film.
During manufacture flocked intermediate assembly 134 may be adhered to substrate 124. In one embodiment, when thermosetting adhesive layer 116 and substrate 124 are compatible; that is, are capable of forming a substantially strong, permanent adhesive bond, thermosetting the adhesive 116 and the substrate 124 are contacted and heat and pressure applied to the carrier sheet 104. In another embodiment, when the thermosetting adhesive layer 116 and substrate 124 are substantially non-compatible, that is, are not capable of forming a substantially strong, permanent adhesive bond, or it is desirable to adhesively bond flocked intermediate assembly 134 to the substrate 124 by an adhesive other than the thermosetting adhesive 116, adhesive layer 120 is interposed between the adhesive layer 116 and the substrate 124, and heat and pressure are applied to the carrier sheet 104.
To understand the need for positioning adhesive layer 120 between thermosetting adhesive layer 116 and substrate, one should understand polymer blends and the theories behind adhesion. While not wishing to be bound by any theory, several theories have been proposed to explain polymer blends and adhesion.
A polymer blend or alloy is the polymeric material that results from mixing two or more polymers of differing chemical compositions. Polymer blends are affected by at least the following: the equilibrium phase behavior and morphology of the mixture; the interfacial properties of the mixture; the type and magnitude of the physical and chemical interactions between the components comprising the mixture; and the rheological properties of mixture. For example, depending on the free energy of mixing, two amorphous polymers can form a single miscible phase when the polymeric components are intimately mixed or the two components can form two distinct phases comprised primarily of the individual polymeric components. In general, for two or more polymers of differing chemical compositions to be miscibility ΔGmix<0 and (∂2ΔGmix/∂Φi2)T,P>0, where:
ΔGmix=ΔHmix−TΔSmix (1)
(∂2ΔGmix/∂Φi2)T,P=(∂2G/∂Φi2)V+(∂2V/∂p)T,Φi(∂2G/∂Φi∂V)2 (2)
and where ΔH and ΔS represent, respectively the enthalpic and entropic parts, T the temperature, P the pressure, V the volume, and Φi the volume fraction of component i. The thermodynamic principles of mixing can be combined with the Flory-Huggins Theory to further understand how polymeric properties, such as molecular weight, dispersive interactions, solubility parameters, hydrogen bonding, can affect polymer miscibility (or mixing).
The two most common techniques for preparing polymer blends are solution casting and melt mixing, such as by blow, sheet or co-extrusion. The mixing (or miscibility) can be complete, where polymeric materials A and B are combined to form a polymer blend AB, wherein polymers A and B are combined to produce polymer AB. Or, the mixing can be localized to a contact zone, for example a heated polymeric film (or softened or melt) of polymer A and the heated polymeric film (or softened or melt) of polymer B are contacted, such that within the contacting zone polymers A and B combine to form polymer AB, while outside of the contacting zone polymer film polymer A remains substantially polymer A and polymer B remains substantially polymer B.
It is important to note that the above only briefly outlines the general principles encompassing polymer-polymer interactions. Further more those skilled in the art recognize that there is not a method to a priori predict polymer-polymer interactions and resulting equilibrium-phase behavior.
While not wishing to be bound by any theory, several theories have been proposed to explain adhesion, the five most commonly accepted theories being: 1) mechanical interlock, 2) dispersive, 3) chemisorption, 4) electrostatic, and 5) diffusion. No one theory explains completely adhesion or the adhesion process. However, one should understand the five theories and how they impact the adhesion of materials being attached. The five theories are summarized below.
The mechanical interlocking theory postulates good adhesion when an adhesive penetrates a roughen adherent surface having crevices, pores, and/or holes, and is cured within the crevices, pores and/or pores of the adherent, thereby mechanically interlocking the cured adhesive with the adherent. Optimal mechanical interlocking of the adhesive to the adherent occurs when the adhesive wets and/or penetrates the roughened adherent surface. Maximum bond strength is typically the mechanical strength of the adhesive.
Dispersive theory involves intermolecular Van der Waals dispersive forces between closely adjoining surfaces due to Keesom and/or London forces between the adherent and adhesive. Keesom and London forces are due to dipole-dipole attractive forces. Optimal adhesion occurs when the adhesive and the adherent are in intermolecular contact, optimal intermolecular contact is achieved when the adhesive has a lower surface energy than the adherent and is able to wet and spread on the substrate surface. The strength of a Van der Waals dispersive force is typically about 0.1-40 KJ/mole and varies by 1/r6 power, where r is the distance separating the dipoles.
In the chemisorption theory an ionic or covalent bond is formed between the adhesive and the adherent, typically bond formation is across the adhesive adherent interface, either directly across the interface or through a chemical coupling agent. In some instances the adherent surface is chemically modified or derivatized to facilitate the formation of chemical bonds. The adhesive strength of a covalent bond is typically in the range of about 60-700 KJ/mole.
In the electrostatic theory the adhesive force is attributed to dipole-dipole attractive forces across the boundary separating the adhesive and adherent, the dipoles can be permanent or induced. The attractive force is typically the order of 4-20 KJ/mole and varies by 1/r3, where r is the distance separating the dipoles.
The diffusion theory is typically associated with polymer-polymer adhesion where the polymeric adhesive and adherent inter-penetrate. Optimal interpenetration typically occurs when the adhesive and adherent are mutually compatible and miscible and where the movement and entanglement of the long polymeric chains comprising the adhesive and adherent occurs. Diffusion is affected by contact time, temperature, and molecular properties, such as but not limited to: molecular weight (e.g., number average, weight average or polydispersity average); physical form (i.e., liquid or solid); and physical properties, such as for example, crystallinity, degree of cross-linking, and solubility parameters.
Returning to the adherence of flocked assembly 134 to substrate 124, one embodiment adheres the thermosetting adhesive layer 116 and substrate 124 to form a substantially strong, permanent adhesive bond. While not wanting to be bound by theory, it can be appreciated, that the thermosetting adhesive 116 is capable of adhesively bonding to substrate 124 in response to the application of heat and pressure during the cross-linking process by one or more of the following: a) the flow of the adhesive into roughened surface areas of substrate 124 that when cross-linked mechanically interlocks the adhesive 116 with the substrate 124; b) dispersive interactions (dispersive interactions typically improve adherence when the adhesive 116 has a lower surface energy than the substrate 124); c) the formation of covalent (or ionic) bonds when the substrate 124 contains chemical entries capable of chemically reacting with the adhesive 116; d) the use of electrostatic interactions, as in the case of dispersive interactions, electrostatic interactions typically improve when the adhesive 116 has a lower surface energy than substrate 124; and e) the use of diffusional interactions are less restrained prior to the adhesive 116 being fully cross-linked, wherein the polymer chains comprising adhesive 116 become covalently interconnected and substantially prevented from any diffusional movement. It can be appreciated that conditions can be such that thermosetting adhesive 116 is not capable of forming a sufficiently strong permanent bond with substrate 124 as for example, but not limited to, the adhesive 116 having a higher surface energy than substrate 124, the adhesive 116 and substrate 124 are not miscible and cannot form a strong diffusional bond, or the polarities of adhesive 116 and substrate 124 are such that dipole-dipole interactions do not favor adhesion.
In the instance where thermosetting adhesive layer 116 and substrate 124 are not substantially compatible, that is, are not capable of forming a substantially strong, permanent adhesive bond, or it is desirable to adhesively bond flocked intermediate assembly 134 to substrate 124 by an adhesive other than a thermosetting adhesive 116, adhesive layer 120 is interposed between the layer adhesive 116 and substrate 124, and heat and pressure are applied to the carrier sheet 104. In such a case the adhesive layer 120 is preferably comprised of at least a first part 128 and a second part 132, more preferably the first and second parts having at least one differing chemical or physical property. As for example, the first and second parts can differ in one or more of polarity, chemical property, physical property, and any combination thereof. In an even more preferred embodiment, the first part 128 of adhesive layer 120 is positioned adjacent to the thermosetting adhesive 116, and the first part 128 comprises one or more of a chemical property, physical property and any combination thereof that provides for enhanced adhesion of the adhesive layer 120 to the adhesive layer 116 compared to the adhesion of the adhesive layer 116 to the substrate 124. Similarly, in another even more preferred embodiment, the second part 132 of adhesive layer 120 is positioned adjacent to the substrate 124, with the second part 132 including one or more of a chemical property, physical property, and any combination thereof that provides for enhanced adhesion of the adhesive layer 120 to the substrate 124 compared to the adhesion of the adhesive layer 116 to the substrate 124. It is also to be appreciated that the interaction of the first part 128 with the adhesive layer 120 is preferably substantially strong and substantially permanent to sufficiently maintain a strong, permanent adhesive bond of the flocked assembly 134 to the substrate 124. Likewise, it is to be appreciated that the interaction of the second part 132 with the adhesive layer 120 is substantially strong and substantially permanent to sufficiently maintain a strong, permanent adhesive bond of the flocked assembly 134 to the substrate 124.
The first part 128 and the second part 132 can or cannot be chemically compatible. For example, the chemically incompatible first and second parts can be separated in adhesive layer 120 by at least one or more other parts (not depicted in
The thickness of the film 120 ranges from about 5 to about 2,500 mu and more preferably from about 10 to about 1,000 mu.
Preferably the first and second parts 128 and 132 have differing compositions, more preferably compositions that differ physically and/or chemically from one another. Even more preferably, the first part 128 and the second part 132 compositions differ in at least one chemical and/or physical adhesion property. Or stated another way, one or more chemical and/or physical adhesive properties of the first part 128 and the second part 132 differ, such that, the adhesive interaction of the first part 128 with the adhesive layer 116 differs from the adhesive interaction of the first part 128 with the substrate 124, and the adhesive interaction of the second part 132 with the adhesive layer 116 differs from the adhesive interaction of the part 132 with the substrate 124. Or stated yet another way, the adhesive interaction of the second part 132 with the substrate 124 is greater, that is, forms a stronger, more permanent bond, than the adhesive interaction of the substrate 124 with previously fully cured, thermoset adhesive layer 116; and the adhesive interaction of the part 128 with previously fully cured, thermoset adhesive layer 116 is greater, that is, forms a stronger, more permanent bond, than the adhesive interaction of substrate 124 with previously fully cured, thermoset adhesive layer 116. Stated another way, the first part 128 forms a stronger adhesive bond with the adhesive layer 116 than the second part 132, and the second part 132 a stronger adhesive bond with the substrate 124 than the first part 128.
By way of example, a first part of the layer has, as the primary component, a first polymer, which has a first adhesive property (such as polarity), and the second part of the layer has, as the primary component, a second polymer, which differs from the first polymer and typically has a second adhesive property (such as a polarity) that differs from the first adhesive property. Preferably, the first and second parts are formulated and joined together to form adhesive layer 120 so that they do not weaken and/or degrade their respective adhesive interactions within the adhesive layer 120 when heated, such as for example, when first and second parts flow together to form an adhesively weak phase when melted. While not wanting to be bound by theory, it can be appreciated that, when the first and second parts are substantially immiscible it is preferred that the first and second parts do not flow together when melted to substantially adhesively weaken the adhesive layer 120.
The first polymer can be the same as the primary polymer of the thermosetting adhesive layer 116. The second polymer may be the same as the primary polymer of the adjacent surface of the substrate 124. Potential first or second polymers for the first or second parts include rubber, polyesters, polyurethanes, polyolefins, polyvinyl chloride, nylon, polyamides, fluorocarbon, linear polyethylene, polystyrene, polypropylene, and cellulosic and acrylic resins and mixtures and co- and terpolymers thereof. For example, the first polymer, which is preferably non-polar, can be, for example, a polyester, polyolefin, and the like, and the second polymer, which is preferably polar, can be rubber, a polyurethane, a copolyolefin, polystyrene, polyvinyl chloride, polyethylene, copolyesters such as polyethylene terephthalate, and the like. Particularly preferred multi-component films are the multi-layered films manufactured by Collano Xiro.
The thermoplastic adhesive layer 120 can be any high polymer, or mixture or combination of high polymers, capable of being repeatedly softened when heated and hardened when cooled. In other words, the post-heated state of adhesive layer 120 is preferably substantially reversible while that of thermosetting adhesive 116 is not. The cross-linking process irreversibly hardens the thermosetting adhesive layer 116. In one configuration, the thermoplastic adhesive layer 120 is a dual laminated or co-extruded, solid, and self-supporting film. In another embodiment the thermosetting adhesive layer 116 and the thermoplastic adhesive layer 120 are pre-cut or configured, prior to contacting the substrate 124 and/or flocked assembly 134.
The first and second parts 128 and 132 may also be formulated to have one or more differing properties. By way of example, the first and second parts may have one or more of differing melting temperatures, softening points, viscosities, surface tensions, adhesion properties (such as, permanent or induced dipole moments, surface roughness properties, chemical entities, or such) and bond strengths. In one configuration, the first and second parts have differing adhesive properties, wherein the adhesive properties of the part 128 are such that a strong, permanent adhesive bond is formed with the thermosetting adhesive layer 116, and wherein the adhesive properties of the part 132 are such that a strong, permanent adhesive bond is formed with the substrate 124. For example, the adhesive part 128 can provide for a surface tension of the surface of the adhesive layer 120 in contact with the adhesive layer 116 to be about less than or about equal to the surface tension of the adhesive layer 116, thereby providing for enhanced adhesion. Similarly, the adhesive part 132 can provide for a surface tension of the surface of the adhesive layer 120 in contact with the substrate 124 to be about less than or about equal to the surface tension of the substrate 124, thereby providing for enhanced adhesion. It is to be appreciated that the surface tensions of the adhesive layer 116 and the substrate 124 are preferably substantially different, and that, for the adhesive layer 120 to substantially, respectively, wet the adhesive layer 116 and the substrate 124 the respective surfaces of the adhesive layer 120 should have differing surface tensions.
In one configuration, the first part 128 has a different (preferably lower) melting point than the second part 132. In one configuration, the first part 128 has a different (preferably lower) viscosity, at a given temperature, than the viscosity of the second part 132. In one configuration, the first part 128 has a different (preferably lower) softening point than the softening point of the second part 132.
The adhesive layers 116 and 120 may be in the form of a liquid or solid film, with solid being preferred, and may be manufactured by any suitable techniques. For example, the films may be solvent cast onto a backing material and, after solidification, be self-supporting, pre-formed, solid films. The first and second parts of the adhesive layer 120 are bonded together to form a film by known techniques. The adhesive film 120 can have an optional backing material. The optional backing material 220 can be any sacrificial material, including those identified above for the carrier sheet 104. In a preferred embodiment the adhesive film 120 does not have the optional backing material 220.
The system and process for manufacturing the article 100 will now be discussed with reference to
In step 300, a flocked carrier sheet 126 (depicted in
In step 304, the flocked carrier sheet 126, while on a moving web 202, is contacted with a pre-formed, self-supporting thermosetting adhesive film 316 which is a combination of the thermosetting adhesive layer 116 in the thermoplastic state, that is the thermosetting adhesive 116 is substantially in the A- and/or B-stage, and a sacrificial backing material 118 to form a second intermediate flocked assembly 138 as shown in
While in contact, the flocked carrier sheet 126 and adhesive film 316 enter into a first lamination station 208, wherein the second intermediate flocked assembly is heated and subjected to pressure. In the station 208, the film 316 is preferably heated to a temperature of at least about 300 degrees F. and more preferably from about 310 to about 450 degrees F. (or preferably above the softening point of the adhesive layer 116) while pressure (which depends on the density of the flock fibers), preferably of at least about 1 psi and more preferably ranging from about 5 to about 25 psi, is applied to the backing material 118. Preferably the applied pressure is at least sufficiently enough to cause the flock fibers to penetrate the surface of the adhesive layer 116 and be at least sufficiently permanently embedded in the adhesive layer 116. The heat and pressure are applied for at least about 0.5 minutes, more preferably at least about 1 minute. As will be appreciated, the orientation of flocked carrier sheet 126 and adhesive film 316 can be reversed, such that the carrier sheet 104 is on top and the backing material 118 on bottom, while still maintaining the contacting of the free ends of flock 112 with adhesive 116. When the orientations of flocked carrier sheet 126 and adhesive film 316 are reversed the lamination pressure is applied to the carrier sheet 104.
In step 308, the intermediate flocked assembly 138 is heated for a sufficient time (typically from about 15 seconds to about 5 minutes) for the adhesive layer 116 to reach at least a temperature to thermoset, cross-link, or substantially completely C-stage adhesive layer 116. To C-stage a thermosetting adhesive means to achieve the final stage in the reaction of a thermosetting resin in which the material is relatively insoluble and infusible. In this thermoset state the adhesive layer 116 will, as noted below, form a blocking layer to inhibit, in subsequent lamination stages, the thermoplastic adhesive layer 120 from flowing into and between the flock fibers and thereby compromising the degree of plushness of the flock fibers.
The intermediate flocked assembly 138 is allowed to cool to a temperature below the maximum temperature experienced in the first laminating station 208.
In step 312, the backing material 118 is removed from the substantially fully activated thermosetting adhesive layer 116. This can be done by any suitable technique known to those of ordinary skill in the art.
In step 316, the fully activated thermosetting adhesive layer 116 (that is, adhesive layer 116 is substantially fully cross-linked or C-staged) is contacted with the thermoplastic adhesive film 216, which is a combination of the thermoplastic adhesive layer 120 and the optional backing material 220,
While in contact, the intermediate flocked assembly 134 and film 216 enter into a second lamination station 232, where heat and pressure are applied to the third intermediate assembly 228. In the station 232, the film 216 is preferably heated to a temperature of at least about 150 degrees F. and more preferably from about 175 to about 375 degrees F. (or preferably above the softening point of the adhesive layer 120) while pressure (which depends on the density of the flock fibers), preferably of at least about 1 psi and more preferably ranging from about 5 to about 25 psi, is applied to the backing material 220 to cause the first part 128 of the thermoplastic adhesive layer 120 to firmly contact and adhere to the thermosetting adhesive layer 116. As will be appreciated, the orientation can be reversed, with the adhesive layer 116 in contact with the adhesive layer 120, such that the carrier sheet 104 is on top and the backing material 220 on bottom. In the latter, pressure is applied to the carrier sheet 104. In this step, the adhesive layer 120 is heated for a time typically ranging from about 1 to about 60 seconds. In either orientation the thermosetting adhesive layer 116 forms a blocking layer to inhibit the thermoplastic adhesive layer 120 from flowing into and between the flock fibers.
The adhesive layers 116 and 120 have differing properties. As will be appreciated, the C-staged, thermosetting adhesive layer 116, when heated, is more viscous (and therefore more resistant to flow) than the thermoplastic adhesive layer 120, which softens and flows when heated to a temperature at least about equal to or above its softening and/or melt temperature(s). While not wishing to be bound by any theory, the highly viscous, infusible state of the C-staged, thermosetting adhesive 116 is due to the cross-linking reactions when adhesive layer 116 was laminated to flocked assembly 126 in step 308. This highly viscous, infusible state substantially limits the ability of the C-staged, thermosetting adhesive layer 116 to flow between the flock fibers and/or limits the ability of the softened and/or liquefied thermoplastic adhesive layer 120 to penetrate and diffuse through the C-staged thermosetting adhesive 116 into flock layer 112 and thereby penetrate between the flock fibers comprising the flock layer. The fully activated adhesive layer 116 thus maintains the plushness of the flock layer 112. Typically, the temperature at which the C-staged, thermosetting adhesive layer 116 softens, if at all, in step 308 is greater than the temperature at which the thermoplastic adhesive layer 120 softens in step 318.
The final product 328 comprises adhesively joined assembly 228. The adhesively joined assembly 228 can also be cut to form a decorative flocked transfer assembly 328.
The optional backing material 220 may be then removed from the thermoplastic layer 120, to form a fourth intermediate assembly 226.
In optional step 320, the free surface of the thermoplastic layer 120 of the fourth intermediate assembly 226 is contacted with an optional substrate 124 to form an optional assembly 238. Optional substrate 124 is provided by optional fourth roll 236. In optional step 324, the optional assembly 238 is passed through an optional third laminating station 240 where heat and pressure are applied to the assembly 238 to form a final product 328. In the optional station 240, the film 120 is preferably heated to a temperature of at least about 150 degrees F. and more preferably from about 175 to about 375 degrees F. (or preferably above the softening point of the adhesive layer 120) while pressure (which depends on the density of the flock fibers), preferably of at least about 1 psi and more preferably ranging from about 5 to about 25 psi, is applied to the optional substrate 124 to cause the adhesive layer 120 containing the second part 132 to firmly contact and adhere to the substrate. As will be appreciated, the orientation can be reversed, while the contact of the free surface of the adhesive layer 120 with the substrate is still maintained, such that the carrier sheet 104 is on top and the optional substrate 124 on bottom in which case pressure is applied to the carrier sheet 104. In optional 240 laminating station, the adhesive layer 120 is heated for a time typically ranging from about 1 to about 60 seconds to where adhesive layer 120 is adhesively adhered to substrate 124 in flocked assembly 238 to from flocked decorative article 328. It can be appreciated that flocked assembly 238 can be cut to form decorative flocked product 328 prior to or after laminating station 240. It can also be appreciated that substrate 124 can be pre-cut prior to contacting 320.
In another embodiment, in step 326 (
The design medium 174 can be any design media including metallic or synthetic or natural polymeric design media, and can be woven or non-woven design media. Examples of design medium materials include reflective materials (such as those having a metallic sheen or luster), textiles (such as a woven nylon or polyester material textile and twill), a material containing a hologram or print image, and the like. In one configuration, the design medium 174 is an extremely durable, woven nylon textile that strongly resembles embroidery. In another configuration, the design medium 174 is a twill material. Another particularly preferred design medium is an embossed or molded article, preferably containing a permanently raised three-dimensional surface or pattern in the textile material, such as but not limited to appliqués or transfers. In another preferred embodiment the design medium 174 is a woven textile product sold under the trade name ObiTex™ by Fiberlok®, having an enhanced surface texture and luster that provides an embroidered or hand-stitched embroidered appearance. A preferred woven textile design medium can be a loosely, woven polyester with increased surface dimensionality or character, with or without a printed image, such as a sublimation dye printed image. Exemplary heat transfers that can be modified by the present invention are Lextra 3D™ with Tackle Twill and Lextra 3D NX™, both sold by Fiberlok®. In one configuration, the design medium 174 is formed from one or more polymeric light diffusing films, such as polycarbonate and/or polyester light diffusion films sold under the trade names Makrofol™ and/or Bayfol™. An exemplary heat transfer that may be modified by the present invention is Lextra 3D™ with metallic textile design medium sold by Fiberlok®.
The opposing side 176 of the insert 175 can be the same as the design medium side 174 or it can differ, as for example the opposing side 176 can be any adhesive material, polymeric material, or other material adhered to or fabricated to the design medium side 174.
When the insert 175 is positioned in registration with the cavity 173 it is contacted the thermosetting adhesive 116 while the thermosetting adhesive 116 is in a substantially thermoplastic (that is A-staged) condition. While not wanting to be bound by theory, the A-staged thermosetting adhesive 116 is tacky and capable of substantially holding the insert in registration with the cavity to form a second insert intermediate (not depicted). The second insert intermediate is contacted with the thermoplastic adhesive film 216 in step 316. In step 322 the thermosetting adhesive is bonded to the flock fibers and to the insert 175 as described above in step 312 and the adhesive layer 120 is bonded to the thermosetting adhesive layer 116 and to the insert 175 as described above in step 318. It can be appreciated that the surface 174 of the insert 175 is substantially compatible with and capable of forming a substantially strong, permanent adhesive bond both with the thermosetting adhesive 116. It can also be appreciated that the first part 128 of the thermoplastic adhesive layer 120 is compatible with and capable of forming a substantially strong, permanent adhesive bond both with the surface 176 of the insert 175 and the cross-linked thermosetting adhesive 116. Stated another way, the lower surface 176 of the insert 175 and adhesive 116 can have substantially the same or different, compatible, surface properties.
It can be appreciated, that step 312 can optionally occur within step 326. For example, step 312 can occur after a portion of intermediate 138 is removed to create the cavity 173 but prior to the second insert intermediate contacting the thermoplastic adhesive layer 216.
The thermal bonding processes of the thermosetting adhesive 116 and the adhesive layer 120 in step 322 occur in a fourth lamination station 242 to produce a flocked decorative article 177 with the insert 175 surrounded by flock. Optionally the flocked decorative article 177 can be attached to a substrate 124 in steps 320 and 324 to form the flocked decorative article 177 adhered to the substrate 124.
A number of variations and modifications of the invention can be used. It would be possible to provide for some features of the invention without providing others.
In another alternative embodiment, the thermosetting and/or thermoplastic adhesive layers are applied in liquid form rather than solid form.
In yet another alternative embodiment flocked assembly 134 can be the flock transfer assembly comprising a carrier sheet 104, release adhesive 108, flock layer 112 and a binder adhesive as disclosed by Abrams in U.S. Pat. No. 4,810,549.
In yet another alternative embodiment, the flock is applied directly to the thermosetting layer 116 with or without an intermediate adhesive on the surface of the film 316 to hold the flock in position until the flock is pressed into the softened thermosetting layer 116 in a lamination station. In one configuration, the thermosetting adhesive layer is heated to the point of being tacky (while still in the thermoplastic state) and the flock fibers electrostatically flocked into the tacky adhesive layer. The adhesive layer may then be heated to a higher temperature to soften further and cross-link the adhesive to the thermoset state while the flock fibers are pushed into the softened adhesive. In this embodiment, steps 304, 308, 312, 316, 320, 326, and 324 remain the same, and the intermediate assembly does not have the carrier sheet 104 and release adhesive 108 positioned on top of the flock layer 112.
The present invention, in various embodiments, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various embodiments, subcombinations, and subsets thereof. Those of skill in the art will understand how to make and use the present invention after understanding the present disclosure. The present invention, in various embodiments, includes providing devices and processes in the absence of items not depicted and/or described herein or in various embodiments hereof, including in the absence of such items as may have been used in previous devices or processes, e.g., for improving performance, achieving ease and\or reducing cost of implementation.
The foregoing discussion of the invention has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the invention are grouped together in one or more embodiments for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the invention.
Moreover, though the description of the invention has included description of one or more embodiments and certain variations and modifications, other variations and modifications are within the scope of the invention, e.g., as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative embodiments to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter.
The presented application claims benefit of U.S. Provisional Patent Application Ser. No. 60/864,107, filed Nov. 2, 2006, to Abrams and is incorporated fully herein by this reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 1580717 | Flick | Apr 1926 | A |
| 1975542 | Forsdale | Oct 1934 | A |
| 1992676 | Schwarz | Feb 1935 | A |
| 2047978 | MacLaurin | Jul 1936 | A |
| 2230654 | Plunkett | Feb 1941 | A |
| 2275617 | Duerr et al. | Mar 1942 | A |
| 2278227 | Thackeray et al. | Mar 1942 | A |
| 2477912 | Vallandigham | Aug 1949 | A |
| 2592602 | Saks | Apr 1952 | A |
| 2636837 | Summers | Apr 1953 | A |
| 2835576 | Ensink | May 1958 | A |
| 2916403 | Calderwood | Dec 1959 | A |
| 2981588 | Hyman | Apr 1961 | A |
| 2999763 | Sommer | Sep 1961 | A |
| 3099514 | Haber | Jul 1963 | A |
| 3215584 | McConnell et al. | Nov 1965 | A |
| 3351479 | Fairchild | Nov 1967 | A |
| 3377232 | Mencock et al. | Apr 1968 | A |
| 3411156 | Feher | Nov 1968 | A |
| 3432446 | Coppeta | Mar 1969 | A |
| 3459579 | Newman | Aug 1969 | A |
| 3496054 | Baigas | Feb 1970 | A |
| 3529986 | Kappas et al. | Sep 1970 | A |
| 3565742 | Stephens et al. | Feb 1971 | A |
| 3591401 | Snyder et al. | Jul 1971 | A |
| 3639149 | Spalding | Feb 1972 | A |
| 3644267 | Jackson, Jr. et al. | Feb 1972 | A |
| 3660200 | Anderson et al. | May 1972 | A |
| 3674611 | Petry et al. | Jul 1972 | A |
| 3772132 | Dulin, Jr. | Nov 1973 | A |
| 3775205 | Hermann et al. | Nov 1973 | A |
| 3793050 | Mumpower, Jr. | Feb 1974 | A |
| 3887737 | Baxter et al. | Jun 1975 | A |
| 3903331 | Klein | Sep 1975 | A |
| 3917883 | Jepson | Nov 1975 | A |
| 3918895 | Mizuno | Nov 1975 | A |
| 3928706 | Gibbons | Dec 1975 | A |
| 3936554 | Squier | Feb 1976 | A |
| 3953566 | Gore | Apr 1976 | A |
| 3956552 | Geary | May 1976 | A |
| 3961116 | Klein | Jun 1976 | A |
| 3979538 | Gilman et al. | Sep 1976 | A |
| 4018956 | Casey | Apr 1977 | A |
| 4025678 | Frank | May 1977 | A |
| 4031281 | Keeling | Jun 1977 | A |
| 4034134 | Gregorian et al. | Jul 1977 | A |
| 4035532 | Gregorian et al. | Jul 1977 | A |
| 4062992 | Power et al. | Dec 1977 | A |
| 4088708 | Riew | May 1978 | A |
| 4142929 | Otomine et al. | Mar 1979 | A |
| 4201810 | Higashiguchi | May 1980 | A |
| 4218501 | Kameya et al. | Aug 1980 | A |
| 4238190 | Rejto | Dec 1980 | A |
| 4251427 | Recker et al. | Feb 1981 | A |
| 4263373 | Mccaskey et al. | Apr 1981 | A |
| 4269885 | Mahn | May 1981 | A |
| 4273817 | Matsuo et al. | Jun 1981 | A |
| 4282278 | Higashiguchi | Aug 1981 | A |
| 4292100 | Higashiguchi | Sep 1981 | A |
| 4294577 | Bernard | Oct 1981 | A |
| 4308296 | Chitouras | Dec 1981 | A |
| 4314813 | Masaki | Feb 1982 | A |
| 4319942 | Brenner | Mar 1982 | A |
| 4340632 | Wells et al. | Jul 1982 | A |
| 4362773 | Shikinami | Dec 1982 | A |
| 4368231 | Egert et al. | Jan 1983 | A |
| 4370374 | Raabe et al. | Jan 1983 | A |
| 4385093 | Hubis | May 1983 | A |
| 4385588 | Bennetot | May 1983 | A |
| 4390387 | Mahn | Jun 1983 | A |
| 4396662 | Higashiguchi | Aug 1983 | A |
| 4413019 | Brenner | Nov 1983 | A |
| 4418106 | Landler et al. | Nov 1983 | A |
| 4430372 | Knoke et al. | Feb 1984 | A |
| 4438533 | Hefele | Mar 1984 | A |
| 4465723 | Knoke et al. | Aug 1984 | A |
| 4574018 | Masuda et al. | Mar 1986 | A |
| 4588629 | Taylor | May 1986 | A |
| 4610904 | Mahn, Sr. et al. | Sep 1986 | A |
| 4652478 | Maii | Mar 1987 | A |
| 4668323 | Lenards et al. | May 1987 | A |
| 4681791 | Shibahashi et al. | Jul 1987 | A |
| 4687527 | Higashiguchi | Aug 1987 | A |
| 4693771 | Payet et al. | Sep 1987 | A |
| 4741791 | Howard et al. | May 1988 | A |
| 4810549 | Abrams et al. | Mar 1989 | A |
| 4895748 | Squires | Jan 1990 | A |
| 4923848 | Akada et al. | May 1990 | A |
| 4931125 | Volkmann et al. | Jun 1990 | A |
| 4937115 | Leatherman | Jun 1990 | A |
| 4961896 | Constantino | Oct 1990 | A |
| 4966801 | Becker et al. | Oct 1990 | A |
| 4980216 | Rompp | Dec 1990 | A |
| 4985296 | Mortimer, Jr. | Jan 1991 | A |
| 5008130 | Lenards | Apr 1991 | A |
| 5009943 | Stahl | Apr 1991 | A |
| 5009950 | Wagner et al. | Apr 1991 | A |
| 5041104 | Seal | Aug 1991 | A |
| 5047103 | Abrams et al. | Sep 1991 | A |
| 5110670 | Janocha et al. | May 1992 | A |
| 5112423 | Liebe, Jr. | May 1992 | A |
| 5115104 | Bunyan | May 1992 | A |
| 5126182 | Lumb et al. | Jun 1992 | A |
| 5155163 | Abeywardena et al. | Oct 1992 | A |
| 5198277 | Hamilton et al. | Mar 1993 | A |
| 5207851 | Abrams | May 1993 | A |
| 5248536 | Du Katz | Sep 1993 | A |
| 5298031 | Gabay et al. | Mar 1994 | A |
| 5312576 | Swei et al. | May 1994 | A |
| 5338603 | Mahn et al. | Aug 1994 | A |
| 5346746 | Abrams | Sep 1994 | A |
| 5383996 | Dressler | Jan 1995 | A |
| 5385694 | Wu et al. | Jan 1995 | A |
| 5403884 | Perlinski | Apr 1995 | A |
| 5411783 | Mahn, Jr. | May 1995 | A |
| 5413841 | Mahn et al. | May 1995 | A |
| 5480506 | Mahn, Sr. et al. | Jan 1996 | A |
| 5529650 | Bowers et al. | Jun 1996 | A |
| 5543195 | Squires et al. | Aug 1996 | A |
| 5597633 | Mecke et al. | Jan 1997 | A |
| 5597637 | Abrams et al. | Jan 1997 | A |
| 5658630 | Shizukuda et al. | Aug 1997 | A |
| 5665458 | Mahn, Jr. | Sep 1997 | A |
| 5681420 | Yamane | Oct 1997 | A |
| 5685223 | Vermuelen et al. | Nov 1997 | A |
| D391572 | Lee | Mar 1998 | S |
| 5756180 | Squires et al. | May 1998 | A |
| 5766397 | Jones | Jun 1998 | A |
| 5851617 | Keiser | Dec 1998 | A |
| 5858156 | Abrams et al. | Jan 1999 | A |
| 5863633 | Squires et al. | Jan 1999 | A |
| 5866248 | Dressler | Feb 1999 | A |
| 5914176 | Myers | Jun 1999 | A |
| 5981021 | McCulloch | Nov 1999 | A |
| 6010764 | Abrams | Jan 2000 | A |
| 6025068 | Pekala | Feb 2000 | A |
| 6083332 | Abrams | Jul 2000 | A |
| 6110560 | Abrams | Aug 2000 | A |
| 6178680 | Sloot | Jan 2001 | B1 |
| 6224707 | Lion | May 2001 | B1 |
| 6247215 | Van Alboom et al. | Jun 2001 | B1 |
| 6264775 | Holeschovsky et al. | Jul 2001 | B1 |
| 6361855 | Mahn, Jr. et al. | Mar 2002 | B2 |
| 6436506 | Pinter et al. | Aug 2002 | B1 |
| 6555648 | Hinds | Apr 2003 | B1 |
| 6569538 | Kaschel | May 2003 | B1 |
| 6676796 | Pinter et al. | Jan 2004 | B2 |
| 6774067 | Demott et al. | Aug 2004 | B2 |
| 6841240 | Gorny et al. | Jan 2005 | B2 |
| 6924000 | Tallmadge | Aug 2005 | B2 |
| 6929771 | Abrams | Aug 2005 | B1 |
| 6977023 | Abrams | Dec 2005 | B2 |
| 7135518 | Bandou et al. | Nov 2006 | B2 |
| 7191720 | Thomas | Mar 2007 | B2 |
| 7229680 | Crompton | Jun 2007 | B1 |
| 7393516 | Seo et al. | Jul 2008 | B2 |
| 7410932 | Figueroa | Aug 2008 | B2 |
| 7461444 | Deaett et al. | Dec 2008 | B2 |
| 7465485 | Abrams | Dec 2008 | B2 |
| 20010008672 | Norvell et al. | Jul 2001 | A1 |
| 20020009571 | Abrams | Jan 2002 | A1 |
| 20020098329 | Abrams | Jul 2002 | A1 |
| 20030129353 | Abrams | Jul 2003 | A1 |
| 20030186019 | Abrams | Oct 2003 | A1 |
| 20030207072 | Abrams | Nov 2003 | A1 |
| 20030211279 | Abrams | Nov 2003 | A1 |
| 20040010093 | Wefringhaus et al. | Jan 2004 | A1 |
| 20040033334 | Merovitz | Feb 2004 | A1 |
| 20040050482 | Abrams | Mar 2004 | A1 |
| 20040053001 | Abrams | Mar 2004 | A1 |
| 20040055692 | Abrams | Mar 2004 | A1 |
| 20040058120 | Abrams | Mar 2004 | A1 |
| 20040081791 | Abrams | Apr 2004 | A1 |
| 20040170799 | Carr et al. | Sep 2004 | A1 |
| 20040180592 | Ray | Sep 2004 | A1 |
| 20050081985 | Abrams | Apr 2005 | A1 |
| 20050158508 | Abrams | Jul 2005 | A1 |
| 20050188447 | Gray | Sep 2005 | A1 |
| 20050260378 | Bernabeu | Nov 2005 | A1 |
| 20050266204 | Abrams | Dec 2005 | A1 |
| 20050268407 | Abrams | Dec 2005 | A1 |
| 20060026778 | Lion | Feb 2006 | A1 |
| 20060029767 | Lion | Feb 2006 | A1 |
| 20060142405 | Kijima | Jun 2006 | A1 |
| 20060150300 | Hassan et al. | Jul 2006 | A1 |
| 20060160943 | Weir | Jul 2006 | A1 |
| 20060251852 | Abrams | Nov 2006 | A1 |
| 20060257618 | Pascual Bernabeu | Nov 2006 | A1 |
| 20070022548 | Abrams | Feb 2007 | A1 |
| 20070026189 | Abrams | Feb 2007 | A1 |
| 20070102093 | Abrams | May 2007 | A1 |
| 20070110949 | Abrams | May 2007 | A1 |
| 20070148397 | Abrams | Jun 2007 | A1 |
| 20070219073 | Mannschedel | Sep 2007 | A1 |
| 20080003394 | Eke | Jan 2008 | A1 |
| 20080113144 | Abrams | May 2008 | A1 |
| 20080187706 | Lion et al. | Aug 2008 | A1 |
| 20080299397 | Kenens et al. | Dec 2008 | A1 |
| 20090280290 | Weedlun | Nov 2009 | A1 |
| 20100178445 | Shen et al. | Jul 2010 | A1 |
| Number | Date | Country |
|---|---|---|
| 606651 | Feb 1991 | AU |
| 653994 | Oct 1994 | AU |
| 757595 | Apr 1967 | CA |
| 2010076 | Aug 1990 | CA |
| 1306411 | Aug 1992 | CA |
| 2064300 | Sep 1992 | CA |
| 3004560 | Aug 1981 | DE |
| 202835 | Oct 1983 | DE |
| 19707381 | Aug 1998 | DE |
| 19734316 | Feb 1999 | DE |
| 0122656 | Oct 1984 | EP |
| 0210304 | Feb 1987 | EP |
| 0280296 | Aug 1988 | EP |
| 0351079 | Jan 1990 | EP |
| 0506601 | Sep 1992 | EP |
| 0685014 | Dec 1995 | EP |
| 0913271 | Oct 1998 | EP |
| 0989227 | Mar 2000 | EP |
| 1072712 | Jan 2001 | EP |
| 1557206 | Jul 2005 | EP |
| 1598463 | Nov 2005 | EP |
| 2442721 | Aug 1980 | FR |
| 2543984 | Oct 1984 | FR |
| 2659094 | Sep 1991 | FR |
| 2846202 | Apr 2004 | FR |
| 2881149 | Jul 2006 | FR |
| 1171296 | Nov 1969 | GB |
| 1466271 | Mar 1977 | GB |
| 2065031 | Jun 1981 | GB |
| 2101932 | Jan 1983 | GB |
| 2126951 | Apr 1984 | GB |
| 2214869 | Sep 1989 | GB |
| 0506601 | Sep 1992 | GB |
| 55104 | Oct 1984 | IE |
| 71007184 | Jun 1965 | JP |
| 55079143 | Jun 1980 | JP |
| 55-147171 | Nov 1980 | JP |
| 56058824 | May 1981 | JP |
| 56107080 | Aug 1981 | JP |
| 56108565 | Aug 1981 | JP |
| 56141877 | Nov 1981 | JP |
| 58062027 | Apr 1983 | JP |
| S61-146368 | Jul 1986 | JP |
| 62-033576 | Feb 1987 | JP |
| 62-144911 | Jun 1987 | JP |
| 63118544 | May 1988 | JP |
| 64-014021 | Jan 1989 | JP |
| S64-068582 | Mar 1989 | JP |
| 01192538 | Aug 1989 | JP |
| 01-266284 | Oct 1989 | JP |
| 01-310947 | Dec 1989 | JP |
| 02048076 | Feb 1990 | JP |
| 04-126221 | Apr 1992 | JP |
| 04-169297 | Jun 1992 | JP |
| 05255021 | Oct 1993 | JP |
| 06-171048 | Jun 1994 | JP |
| 08-267625 | Oct 1996 | JP |
| 10059790 | Mar 1998 | JP |
| 10-202691 | Aug 1998 | JP |
| 11-042749 | Feb 1999 | JP |
| 11256484 | Sep 1999 | JP |
| 11277662 | Oct 1999 | JP |
| 11348159 | Dec 1999 | JP |
| 2000084977 | Mar 2000 | JP |
| 3076851 | Aug 2000 | JP |
| 2000263673 | Sep 2000 | JP |
| 2001-226885 | Aug 2001 | JP |
| 2001270019 | Oct 2001 | JP |
| 2003063833 | Jul 2003 | KR |
| WO 8901829 | Mar 1989 | WO |
| WO 9009289 | Aug 1990 | WO |
| WO 9204502 | Mar 1992 | WO |
| WO 9312283 | Jun 1993 | WO |
| WO 9419530 | Sep 1994 | WO |
| WO 9734507 | Sep 1997 | WO |
| WO 0207959 | Jan 2002 | WO |
| WO 0209925 | Feb 2002 | WO |
| WO 02058854 | Aug 2002 | WO |
| WO 03031083 | Apr 2003 | WO |
| WO 2004005023 | Jan 2004 | WO |
| WO 2004005600 | Jan 2004 | WO |
| WO 2005035235 | Apr 2005 | WO |
| WO 2005118948 | Dec 2005 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20080124503 A1 | May 2008 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60864107 | Nov 2006 | US |
