MOLDED SILICONE ADHESIVE COMPOSITIONS AND METHODS OF MAKING AND USING THE SAME

This invention relates generally to radio frequency molded articles and methods for making the same, more particularly to radio frequency molded products having a silicone adhesive layer and methods for making and using the same.

FIELD

The invention relates generally to radio frequency molded transfers and appliqués, and particularly to radio frequency molded transfers and appliqués and methods of making and using the same.

BACKGROUND

Flock products of the prior art typically have three components: a thermoplastic or thermoset bottom component, a middle component comprising a thermoset water-based flock transfer adhesive, and a top component comprising flock. The function of the bottom component is to melt and flow into a substrate surface, cool, and solidify to form a mechanical or chemical adhesion to substrate. The function of the thermoset, water-based flock transfer adhesive is to form a durable adhesive bond with the bottom component and the flock. The thermoset, water-based flock transfer adhesive holds the product together and serves to create the shape of the product which is generally formed by printing or coating of the water-based adhesive in the desired shape and/or form. The thermoset, water-based adhesive is typically opaque. It also enhances the performance of the flock product with its integrity, adhesion, strength, and its other physical properties. The top flock component can have a single, multi-colored, or dyed flock fibers. The top flock layer can contain a visual image and/or a tactile and/or dimensionalized surface.

The middle component, the thermoset, water-based flock transfer adhesive, is generally a screen printable water-based latex adhesive. While the water-based thermoset adhesives are commercially successful, they do have some serious disadvantages and functional limitations. For example, about 60 wt. % of the printed material is water (and in some formulations can also include mineral spirits), and the remaining 40 wt. % being solids. The water is removed during processing and formation of the adhesive bond between the top flock layer and the bottom adhesive layer. The removal of the water from the printed water-based thermoset adhesive shrinks the printed adhesive layer. The removed water is not a component of the final flock product. Therefore, more than double the desired layer of adhesive thickness must be printed to achieve the desired final adhesive layer thickness. The 60 wt. % water (which cam also include mineral spirits in some formulations) increases the purchase and transportation costs of water-based, thermoset adhesives. Other disadvantages of the water-based adhesives of the prior art are that they can freeze in cold environments, they need to be heated during storage and transport during cold periods, the adhesive can dry on printing creating blockage (generally created by adhesive being retained in apertures of the printing screen) and cause product delays and rejection of product, they have a limited capacity of loading of titanium dioxide pigment to achieve opacity, they require a humid environment during printing to extend “open time” screen printing of the adhesive, they require a continuous need to wipe clean the printing screens to remove dried, blocking adhesive deposits on the screen, and they need more than an hour to allow for the water to be removed prior the final cure.

Yet another disadvantage of the printed and cured water-based, thermoset adhesives of the prior art is that they can become tacky when heat and pressure are applied to them. The tackiness can result in the flock being matted down into the adhesive layer during processing. The matting down can destroy the soft nature of flock upper layer. Moreover, in many applications, such as industrial work uniforms, require heat resistance that water-based thermoset latex adhesives fail to adequately provide. The water-based thermoset latex adhesives of the prior art also fail to qualify for in-mold applications such as during high temperature resin injection during molding.

The adhesion strength between the water-based, thermoset latex adhesives of the prior art and flock fibers is generally determined by the amount of contact between the latex adhesive and flock. For example, to obtain adequate adhesion between a flock fiber and a latex adhesive of the prior art, at least about 10% of the flock fiber length must be planted in the dried and cured latex adhesive. Another factor affecting the adhesive strength between the water-based, thermoset latex adhesive is the degree to which the hot-melt powder adhesive needs to sink into the latex adhesive. Yet another factor that affects the adhesion strength (tensile strength) of the water-based, thermoset latex adhesive is the thickness of printed latex adhesive. Each of these factors limit the ability to have thin, light-weight, streamlined flock product profiles. These factors also limit the opacity of the adhesive layer and the ability to flock over dark colored textiles, such as with white flock fibers over a dark colored textile or dark colored inserts and not have the dark color showing through the flock layer.

Yet another limitation of water-based, thermoset adhesives of the prior art is dye migration from textiles and/or flock that has been imprinted with a dye sublimation transfer ink. The dye migration typically occurs when heat and pressure are applied either during manufacture and/or application of the product to a substrate. For example, when heat and/or pressure are applied to white flock applied over red dye sublimation transfer print, the dye can migrate through the thermoset latex adhesive to flock and change the flock from white to pink. Still yet another limitation is the limited elastomeric properties of the thermoset latex adhesives, which effect the softness of the flock product and the substrates the flock can be applied to.

Furthermore, some water-based, thermoset adhesive latex chemistries are subject to environmental compliance restrictions. Such restrictions limit one or more of the methods by which the flock products can be made and markets that they can be used in.

Some prior art flock products are formed using a continuous film component for adhering flock to a substrate. A disadvantage of using continuous material is that it requires that unwanted inner “void” design areas (open spaces) be laboriously removed (“weeded”) to create the final product image. The continuous film products also have many of the above limitations.

A need exists for a better flock adhesive that is more convenient, efficient printability, and enhanced physical properties. Silicone adhesives overcome most, if not all, of the aforementioned problems and limitations of above-mentioned flock adhesives of the prior art.

SUMMARY

These and other needs are addressed by the various aspects, embodiments, and configurations of the present disclosure. This disclosure relates generally to flocked articles and methods for making them.

In various aspects, the present disclosure is related generally to decorative articles and specifically to articles comprising multiple layers of different materials.

Silicone adhesives are used for flat ink heat transfers. Their use for flock products, both direct flock and flock transfer products, have not been found to work satisfactorily commercially. Some of the product problems encountered in flocking applications are suitable silicone adhesive print viscosity. Having a suitable print viscosity generally ensures that when the silicone is printed, the silicone deposited from the screen onto to the surface of flock is supported by the flock fibers and does not substantially sink down into spaces between the flock fibers. The viscosity of silicone adhesive should be sufficiently low enough to allow the flock fibers when contacted with the printed adhesive to be wetted by and adhered to the adhesive and have sufficiently high enough viscosity to allow the flock fibers stand proud in it. Similarly, the viscosity of silicone adhesive should be sufficiently low enough to allow any powder adhesive contacted with the printed adhesive be located in and/or on the silicone adhesive. It is desirable that the silicone adhesive have a viscosity to be able to be printed as a film and that the deposited adhesive film be thinner than the water-based latexes of the prior art. It is also desirable that the silicone adhesive printed film have a shrinkage less than the water-based latexes of the prior art. The shrinkage of the printed film refers to the change of the film thickness between two or more of the film thicknesses of as printed layer, the layer after drying, and the layer after curing. Yet another desired property of the silicone adhesive is that it has a greater adhesion to the flock fibers than the water-based latex adhesives of the prior art. Still yet another desired property of the silicone adhesive is that it has a greater adhesion to the flock fibers and that the adhesion be with a lower contact profile of the flock fiber with the adhesive. That is, the contact profile of the flock fiber with the silicone adhesive is less with the silicone adhesive than with the water-based latex adhesives of the prior art and that the adhesion strength of the flock fibers is greater with the silicone adhesive than with the water-based latex adhesives of the prior art. It can also be appreciated that less of the flock fiber contacts the silicone adhesive of the present disclosure than the water-based latex adhesives of the prior art. Still yet another desired property of the silicone adhesives of the present disclosure is that less, if any, of a hot melt-melt adhesive is needed to achieve adhesion of the silicone adhesive to the flock fiber.

Other properties, particularly unique to the silicone adhesives of the present disclosure are a suitable “open time” or “pot-life” of the catalyzed silicone to meet processing needs, such sufficient periods for printability and cure times. Another desired property is sufficient opacity of the cured silicone adhesive film.

Some of the differences between the flocking process of the prior art and that of present disclosure are: the silicone adhesives cure times are typical faster than the water-based latexes of the prior art; the silicone adhesives can be cured immediately after being contacted with the flock fibers; the silicone adhesives do not contain water and, therefore, do not require a drying period for the removal of the water; and the silicone catalyst can be poisoned by various materials, such as nitrogen, sulfur, alcohol and water, that is the poison can defeat the catalyzation process.

The present disclosure is generally related to direct-flocked products. The flock products are made with a polymerizable silicone rather than the flock products of water-based thermoset latexes. When the silicone adhesive is cured with a hot-melt adhesive a unique adhesive is formed. The silicone adhesive generally binds the flock to the item being decorated with one or more of greater adhesion and elastic properties than the water-based adhesives of the prior art. The silicone adhesives of the present disclosure provide one or more of unique chemical and physical benefits over the water-based adhesives of the prior art. The silicone adhesives of the present disclosure typically comprise one or more of a catalyst for polymerization of one more silicones, an adhesion promoter (or coupling agent), a rheology modifier, one or more pigments, and one or more dispersion aids. The hot-melt adhesive can be a thermoplastic adhesive, a thermoset adhesive, or a combination of thermoplastic and thermoset adhesives. As will be appreciated, the thermoset hot melt adhesives generally solidify or set irreversibly when heated above a certain temperature. This property is usually associated with a crosslinking reaction of the molecular constituents induced by heat and/or radiation. Thermoset adhesives can include curing agents. Examples of thermosetting adhesives include polyethylene, phenolics, alkyds, amino resins, polyesters, epoxides, polyurethanes, polyamides, and combinations thereof. Changes necessary to enable suitable use of the polymerizable silicone for manufacturing of flocked products and subsequent include without limitation: elimination, or minimization of water, select of catalyst and amount thereof, and elimination of any catalyst poisons. The advantages of a silicone adhesive over the water-based latex adhesives of the prior art are at least: reduced, or elimination, of screen blockage or delays due to screen blockage, greater opacity of the printed adhesive film (particularly with a thinner printed adhesive film), and elimination, or substantial reduction, of film drying (such as a water removal) stage prior to curing of the printed adhesive film. Some of the advantages of a cured silicone adhesive layer over a water-based adhesive layer are that the final flock product can be one or more of: ironed onto a substrate with little, if any, matting-down of the flock fibers, injected molded with little, if any, matting-down of flock fibers, printed over a dark colored substrate with little, if any, of dark substrate showing through the flock fibers, and adhered to textiles that have been previously imprinted with a dye sublimation transfer ink with little, if any transfer of the dye sublimation ink to the flock fibers.

The silicone adhesives are substantially more environmentally friendly adhesives than the water-based latex adhesives of the prior art. The silicone adhesives generally are substantially 100 wt. % solids, compared to water-based adhesives which have about 40 wt. % solids. The silicone adhesives generally have one or more of a lower cost of adhesive solids purchase price and a lower transportation cost per pound than the water-based adhesives of the prior art.

It has been found that one or more of the following effects the performance of flock product: the percent of the flock fiber surface area in contact with the silicone adhesive, the amount of air entrained in the silicone adhesive when screen printing, any additive to the silicone adhesive (such as any rheology modifier) should be fully wetted before screen printing of the silicone adhesive, and the adhesion process of the silicone to the flock fiber. It has been found that if too much of flock fiber surface is planted/located too deeply in an adhesive, the plushness of the flock product is negatively impacted, the flock layer is less plush and, therefore less desired. It has also been found, that little, if any, air should be entrained in the silicone adhesive when the silicone adhesive is screen printed. Air entrained in the silicone adhesive generally increases the stringiness of the silicone adhesive during screen printing. Stringiness of the silicone effects the ability precisely and accurately screen print the adhesive. The stringier the silicone adhesive is the less precisely and/or less accurately the silicone can be screen printed. It has been found that fumed silica can be an appropriate rheology modifier of the silicone adhesive. It also been found the fumed silica should be fully wetted before the silicone adhesive is screen printed. If not, the screen printing process cannot be satisfactorily controlled. Addition of the fumed silica to the silicone to silicone adhesive can be by a dual asymmetrical centrifuge process. The dual asymmetrical centrifuge process can substantially fully wet the fumed silica when mixing the fumed silica with the silicone adhesive. Should any air be entrained in the silicone adhesive when mixing it silicone adhesive, it can be removed by a de-airing process. One suitable method of removing entrained air is to reduce the pressure above the silicone adhesive.

The adhesion strength can be affected by one or more of the silicone chemistry, the adhesion promoter (coupling agent), the amount of entrained air, any flock fiber surface treatment (such as any coating to assist in electro-deposition of the flock fiber), catalyst chemistry, and the rheology modifier to name a few. The adhesion strength is also affected when the chemistry of the flock fibers and the substrate substantially differ, such as when the flock fibers comprise nylon and the substrate comprise polyester.

One advantage of a direct flocking process is the elimination of a transfer sheeting having a release adhesive. Contacting of the flock fibers with the release adhesive can leave a residue on the flock fibers, which can reduce any subsequent adhesion of the flock fibers to a substrate. It is commonly believed as little as 0.01% of surface area of the flock fiber having release adhesive can diminish the adhesion of the flock fiber, more commonly as little as 0.05%, even more commonly as little as 0.1%, yet even more commonly as little as 0.2%, still yet even more commonly as little as 0.5%, still yet even more commonly as little as 1%, still yet even more commonly as little as 2%, still yet even more commonly as little as 5%, still yet even more commonly as little as 7.5%, or yet still even more commonly as little as 10%. Moreover, it is generally believed that that the adhesion of the flock layer can be affected when more than about 0.001% of the flock fibers comprising the flock layer contain a release adhesive residue, more generally more than about 0.005% of the flock fibers, even more generally more than about 0.01% of the flock fibers, yet even more generally more than about 0.02% of the flock fibers, still yet even more general more than about 0.05% of the flock fibers, still yet even more general more than about 0.075% of the flock fibers, still yet even more general more than about 0.1% of the flock fibers, still yet even more general more than about 0.15% of the flock fibers, still yet even more general more than about 0.2% of the flock fibers, still yet even more general more than about 0.25% of the flock fibers, still yet even more general more than about 0.5% of the flock fibers, still yet even more general more than about 0.75% of the flock fibers, still yet even more general more than about 1% of the flock fibers, still yet even more general more than about 2% of the flock fibers, still yet even more general more than about 2.5% of the flock fibers, still yet even more general more than about 5% of the flock fibers, still yet even more general more than about 7.5% of the flock fibers, or yet still even more general more than about 10% of the flock fibers.

In some embodiments, no more than about 0.01% of the surface area of one or more the flock fibers has release adhesive, more commonly no more than about 0.05% of the surface area of one or more the flock fibers has release adhesive, even more commonly no more than about 0.1% of the surface area of one or more the flock fibers has release adhesive, yet even more commonly no more than about 0.2% of the surface area of one or more the flock fibers has release adhesive, still yet even more commonly no more than about 0.5% of the surface area of one or more the flock fibers has release adhesive, still yet even more commonly no more than about 1% of the surface area of one or more the flock fibers has release adhesive, still yet even more commonly no more than about 2% of the surface area of one or more the flock fibers has release adhesive, still yet even more commonly no more than about 5% of the surface area of one or more the flock fibers has release adhesive, still yet even more commonly no more than about 7.5% of the surface area of one or more the flock fibers has release adhesive, or yet still even more commonly no more than about 10% of the surface area of one or more the flock fibers has release adhesive.

Some embodiments can include a continuous production capability. The continuous production process comprises a process time of no more than about 5 minutes from printing of silicone adhesive to full cure of the silicone adhesive with the flock fibers adhered thereto. The process may or may not include a step of brushing the flock product. Processes of prior art, from printing of water-based adhesive to its full cure, generally have a process time of about 8 hours. These long processes are due at least to the water removal process. Another process time advantage is that the silicone adhesive commonly has little, if any, screening blocking compared to the water-based adhesive.

Some embodiments can include silicone adhesive screen prints having finer details than their water-based adhesive screen prints of the prior art. The finer details are believed to be due to non-aqueous chemistry of silicone adhesive.

Some embodiments can include silicone adhesive formulations having an adhesion strength greater than the water-based adhesive formulations of the prior art. The higher adhesion strength of silicone adhesive formulations is believed to be due to greater tensile strength of the silicone formulations compared to the water-based adhesives of the prior art. It is also believed that the greater tensile strength of the silicone adhesive formulations is due to the ability to combine them with micron sized thermo-adhesive powders.

Some embodiments can include silicone adhesive formulations with greater opacity than the water-based adhesives of prior art. This is believed to be due higher loading capacity for one or more of titanium dioxide, silica, fumed silica and such of the silicone adhesive formulations than the water-based adhesives of the prior art. It is believed that the greater load capacity of titanium dioxide, silica, and fumed silica could be due to one or more of the chemical compatibility, such as chemical similarity of the silicone adhesive with silica and fumed (the adhesive, the silica and the fumed have silicon-oxygen linkages) and similarly for the silicone adhesive and titanium, with silicon and titanium belonging to the same chemical family in periodic table. It also believed that the greater loading capacity could due to the ability to bind organofunctional groups such as alkyl, aryl, alkylsilicone and arylsilicone functional group on silica, titanium dioxide and fumed silica.

Some embodiments can include printed silicone adhesive formulations having a greater tensile strength per mil of thickness of the printed adhesive film than the water-based adhesives of the prior art. Some embodiments can include a cured silicone adhesive-based flock product having a greater tensile strength per mil of thickness of the printed adhesive than a cured water-based adhesive flock product of the prior art.

Some embodiments can include cured silicone adhesive formulations having a greater adhesion strength to flock fibers than the water-based adhesive formulations of the prior art.

Some embodiments can include a greater % of the flock fiber length being free of adhesive when the flock fiber is adhered to a silicone adhesive than when the adhesive is a water-based adhesive. This is believed to be due to greater adhesion strength of silicone adhesive formulations compared to the water-based adhesive formulations of the prior art. The greater the % of the flock fiber length being free of adhesive the greater plushness of flock layer. It is further believed that with a higher percent of the flock fiber extending out of the silicone adhesive compared to the water-based adhesives of the prior art, the flock fibers are more able to move and give a greater sense of softness.

Some embodiments can include a cured silicone adhesive layer having a lower durometer value, that is a softer adhesive layer, than the cured water-based adhesive layers of the prior art. Some embodiments can include a cured silicone-based flock product having a lower durometer value, that is a softer flock product than the cured water-based adhesive flock products of the prior art.

Some embodiments can include a silicone adhesive-based flock product having a more streamlined look and feel than the water-based-based adhesive products of the prior art. This is believed to be due to due cured silicone adhesive layer having a thickness substantially less than the thickness of water-based adhesives of the prior art.

Some embodiments can include cured silicone adhesive formulations having greater elastomeric properties than the water-based adhesives of the prior art. Some embodiments can include silicone-based flock products having greater elastomeric properties than the water-based adhesive flock products of the prior art.

Some embodiments can include a cured silicone-based flock product having greater wash fastness than water-based adhesive flock products. It is believed that the greater wash fastness of the silicone-based flock product is due to one or more of the greater adhesion of the silicone to the flock and higher heat resistance of the silicone adhesive compared to the water-based flock adhesives of the prior art.

Some embodiments can include a cured silicone-based flock product that is an iron over flock product. Some embodiments can include a cured silicone-based flock product that can be used in an in-mold process where a molten resin is injected into a mold containing the fold product.

Some embodiments can include a cured silicone-based flock product that can be an anti-migration barrier to prevent sub-dye transfer inks from coming in contact with the flock fibers.

Some embodiments can include printing the silicone adhesive directly onto a substrate, followed by direct flocking of the silicone adhesive printed on the substrate. The substrate can comprise one or more of a hot melt film and a pressure sensitive adhesive.

In addition to eliminating materials and reducing processing time and/or steps, there are also aesthetic and functional advantages with the finished flocked product as well. The finished flock products having a silicone adhesive are generally softer to the touch, more abrasion resistance, more strongly adhesively bond, thinner and more elegant. The flock products of the prior are thicker, have cut edges show some of the thick white latex adhesive. The thinner printed silicone adhesive layer show less of cut edge than the more thickly printed latex adhesive edges.

Some embodiments can include a process comprising the steps of: placing thermoplastic hot melt adhesive film, with a paper carrier, onto the vacuum palette of a multicolor carousel flocking machine; screen printing a silicone adhesive onto the hot melt film; flocking each color of the image one-by-one into the silicone adhesive; applying thermal energy to catalyze (polymerize) the silicone adhesive; vacuum cleaning any excess flock fibers away; laser cutting out each images, “weeding” and discarding the unwanted pieces outside and/or within the design; and removing the pieces, packing, and shipping to customers. Customers can place the flock product directly onto the item being decorated and then heat press them directly to permanently fix in place (no need for transfer carrier film, flock will not matt down due to extremely high melt point of silicone). The silicone adhesive lends itself uniquely well to the manufacture of such products, to which heat is directly applied to fix it onto the final substrate, without risk of one or more of flock fibers matting down as normal (latex) flock adhesive becomes tacky, multi-color direct flocking and laser cutting. Moreover, the silicone adhesive process can eliminate one or more of the following from the current water-based adhesive process: the need for a carrier film, the need for a release adhesive, the need to remove water for printed adhesive layer; the need for a hot-melt powder, the need to brush and/or clean away of any excess powder; the need to bake at high temperatures and greater periods of time to cure the adhesive; and the need to cut pieces out of the transfer sheet. The silicone adhesive formulations can be more quickly polymerized, generally in matter of few seconds rather than minutes. Commonly, the process of the prior art requires an hour or even more to remove the water from the latex before baking to cure the adhesive. Moreover, the silicone-based flock product can be immediately brushed after curing to remove any excess flock.

This silicone direct flock technology lends itself to graphic designs that are one contiguous piece and/or “patches” of any shape that can be laser cut, such as without limitation contiguous and/or images (products) with separate pieces, held together by an added carrier film and/or paper media. These direct flock contiguous and/or images (products) with separate pieces are substantially different from the direct flocking of patches or appliques on garments by at least the use of continuous carrier film and/or paper media. It can also be applied to essentially any substrate that will not poison the catalyst, such as without limitation rubber, hot-melt adhesives, polyesters, polycarbonates, woven textiles, knitted textile, non-woven textiles, and mixed media substrates.

Some embodiments can include a process having the steps of: printing a silicone adhesive film onto a pressure sensitive adhesive coated carrier sheet; direct flocking of the printed silicone adhesive film to form a multicolored flock image; polymerization of printed silicone adhesive; vacuum cleaning of the flock layer; and laser cutting of flock product.

Some embodiments of the present disclosure are to a flocked product having a flock layer having a plurality of flock fibers, a thermo-adhesive layer, and a silicone adhesive layer positioned between the thermo-adhesive and the flock layer. The silicone adhesive layer can have a catalyst, a polysiloxane, polyvinyl siloxane, a rheology modifier. The catalyst can be platinum-containing catalyst. The thermo-adhesive layer can be one of a thermoplastic adhesive, a thermoset adhesive, or combination of a thermoplastic and thermoset adhesives. The polyvinyl siloxane can have one or more of vinyl functionalities. The polyvinyl siloxane can be selected from the group consisting essential of methylvinylsiloxane, methylvinylsiloxane, vinylsiloxane, (dimethylvinyl-terminated)dimethylsiloxane, (vinyldimethyl-terminated)siloxane, octamethylcyclotetrasilocane, (vinylphenylmethyl-terminated) dimethyl siloxane, (divinylmethyl-terminated) dimethyl siloxane, vinyldimethyl siloxane, (cyclicvinylemethyl) dimethyl siloxane, vinylmethylcyclosiloxane, trifluoropropylmethylcyclosiloxane, methyhyrdrocyclosiloxane, hexamethyldisiloxane, divinyltetramethylsiloxane, and tetramethyldisiloxane. The polysiloxane can be selected from the group consisting essentially of polyalkylsiloxane, polydialkylsiloxane, polydimethylsiloxane, octamethylcyclotetrasiloxane, methyloctadecyl siloxane, dimethylsiloxane, methyltetradecylsiloxane, docdecylsiloxane, tetradecylsiloxane, methylhexadecylsiloxane, hydrosiloxane, silanol-terminated dimethylsiloxane, hexamethylcycoltrisiloane, decamethylcyclopentasiloxane, octaphenylcyclotetrasiloxane, diphenylsilediol, trimethyltriphenylcyclotrisiloxane, and methyl-3,3,3-trifluoroproplysiloxane.

The rheology modifier can be fumed silica. The silicone adhesive layer can further have a coupling agent. The coupling agent can be selected from the group consisting essentially of an organosilicone coupling agent, organotitanium coupling agent, or a combination of oranganosilicone and organotitanium coupling agents. The orangosilicone coupling can have the general structure of Y—R—Si—(—X)3. The organotitanium coupling agent can have the general structure of the Y—R—Ti—(—X)3. Y generally denotes a functional group selected from the group consisting essentially of vinyl and epoxy, amino group. X can be selected from the group consisting essentially of chlorine, alkoxy, and acetoxy group.

Some embodiments of the present disclosure include a method of making the flock product having the steps of providing the thermo-adhesive layer, contacting a silicone adhesive with the thermo-adhesive layer, and contacting flock fibers with the silicone adhesive layer, wherein the contacting of the flock fibers with the silicone adhesive layer comprises an electrostatic flocking process. The step of contacting the silicone adhesive with the thermo-adhesive layer can include screen printing the silicone adhesive layer on the thermo-adhesive layer.

Some embodiments of the present disclosure include a flocked product having a silicone adhesive layer, a flock layer having a plurality of flock fibers, and a release sheet. The silicone adhesive layer can be positioned between the flock layer and release sheet. The silicone adhesive can be adhered to the release sheet and flock layer. The silicone adhesive layer can have a catalyst, a polysiloxane, polyvinyl siloxane, a rheology modifier. The flock layer can have a plurality of fibers having opposing first and second ends, wherein the second ends of flock fibers are adhered to silicone adhesive layer. The carrier sheet can have a pressure sensitive adhesive. The pressure sensitive adhesive can be positioned between the carrier sheet and the flock layer. The first ends of the flock fibers are generally adhered to the pressure sensitive adhesive. In some embodiments, the flocked can also have a thermo-adhesive layer. The first ends of flock fibers are generally adhered to the thermo-adhesive layer. The catalyst can be platinum-containing catalyst. The thermo-adhesive layer can be one of a thermoplastic adhesive, a thermoset adhesive, or combination of a thermoplastic and thermoset adhesives. The polyvinyl siloxane can have one or more of vinyl functionalities. The polyvinyl siloxane can be selected from the group consisting essential of methylvinylsiloxane, methylvinylsiloxane, vinylsiloxane, (dimethylvinyl-terminated)dimethylsiloxane, (vinyldimethyl-terminated)siloxane, octamethylcyclotetrasilocane, (vinylphenylmethyl-terminated) dimethylsiloxane, (divinylmethyl-terminated) dimethyl siloxane, vinyldimethyl siloxane, (cyclicvinylemethyl) dimethyl siloxane, vinylmethylcyclosiloxane, trifluoropropylmethylcyclosiloxane, methyhyrdrocyclosiloxane, hexamethyldisiloxane, divinyltetramethylsiloxane, and tetramethyldisiloxane. The polysiloxane can be selected from the group consisting essentially of polyalkylsiloxane, polydialkylsiloxane, polydimethylsiloxane, octamethylcyclotetrasiloxane, methyloctadecyl siloxane, dimethylsiloxane, methyltetradecylsiloxane, docdecylsiloxane, tetradecylsiloxane, methylhexadecylsiloxane, hydrosiloxane, silanol-terminated dimethylsiloxane, hexamethylcycoltrisiloane, decamethylcyclopentasiloxane, octaphenylcyclotetrasiloxane, diphenylsilediol, trimethyltriphenylcyclotrisiloxane, and methyl-3,3,3-trifluoroproplysiloxane. The rheology modifier can be fumed silica. The silicone adhesive layer can further have a coupling agent. The coupling agent can be selected from the group consisting essentially of an organgosilicone coupling agent, organotitanium coupling agent, or a combination of oranganosilicone and organotitanium coupling agents. The orangosilicone coupling can have the general structure of Y—R—Si—(—X)3. The organotitanium coupling agent can have the general structure of the Y—R—Ti—(—X)3. Y generally denotes a functional group selected from the group consisting essentially of vinyl and epoxy, amino group. X can be selected from the group consisting essentially of chlorine, alkoxy, and acetoxy group.

Some embodiments of the present disclosure include a method of making the flock product having the steps of providing a release sheet, contacting a silicone adhesive with the release sheet, and contacting flock fibers with the silicone adhesive layer. The contacting of the flock fibers with the silicone adhesive layer can be an electrostatic flocking process. The contacting of the silicone adhesive with the release sheet can be a screen printing the silicone adhesive layer on the release sheet.

Some embodiments of the present disclosure can include a flock transfer having a thermo-adhesive layer, a flock layer, a silicone adhesive layer positioned between the thermo-adhesive layer and the flock layer, and a carrier sheet. The flock layer can be positioned between the carrier sheet and the silicone adhesive layer. The flock layer can have a plurality of fibers having opposing first and second ends. The first ends of the flock fibers can be adhered to the carrier sheet. The second ends of flock fibers cam be adhered to silicone adhesive layer. The flock transfer can also include a pressure sensitive adhesive positioned between the flock layer and the carrier sheet. The first fiber ends can be in contact with and adhered to the pressure sensitive adhesive. The thermo-adhesive layer can be one of a thermoplastic adhesive, a thermoset adhesive, or combination of a thermoplastic and thermoset adhesives. The polyvinyl siloxane can have one or more of vinyl functionalities. The polyvinyl siloxane can be selected from the group consisting essential of methylvinylsiloxane, methylvinylsiloxane, vinylsiloxane, (dimethylvinyl-terminated)dimethylsiloxane, (vinyldimethyl-terminated) siloxane, octamethylcyclotetrasilocane, (vinylphenylmethyl-terminated)dimethylsiloxane, (divinylmethyl-terminated) dimethyl siloxane, vinyldimethyl siloxane, (cyclicvinylemethyl) dimethyl siloxane, vinylmethylcyclosiloxane, trifluoropropylmethylcyclosiloxane, methyhyrdrocyclosiloxane, hexamethyldisiloxane, divinyltetramethylsiloxane, and tetramethyldisiloxane. The polysiloxane can be selected from the group consisting essentially of polyalkylsiloxane, polydialkylsiloxane, polydimethylsiloxane, octamethylcyclotetrasiloxane, methyloctadecylsiloxane, dimethylsiloxane, methyltetradecylsiloxane, docdecylsiloxane, tetradecylsiloxane, methylhexadecylsiloxane, hydrosiloxane, silanol-terminated dimethylsiloxane, hexamethylcycoltrisiloane, decamethylcyclopentasiloxane, octaphenylcyclotetrasiloxane, diphenylsilediol, trimethyltriphenylcyclotrisiloxane, and methyl-3,3,3-trifluoroproplysiloxane. The rheology modifier can be fumed silica. The silicone adhesive layer can further have a coupling agent. The coupling agent can be selected from the group consisting essentially of an organosilicone coupling agent, organotitanium coupling agent, or a combination of oranganosilicone and organotitanium coupling agents. The orangosilicone coupling can have the general structure of Y—R—Si—(—X)3. The organotitanium coupling agent can have the general structure of the Y—R—Ti—(—X)3. Y generally denotes a functional group selected from the group consisting essentially of vinyl and epoxy, amino group. X can be selected from the group consisting essentially of chlorine, alkoxy, and acetoxy group.

Some embodiments of the present disclosure include a method of making a flock transfer having the steps of providing s release sheet, contacting the flock fibers the release sheet contacting a silicone adhesive with the flock fibers, and contacting a thermo-adhesive with the free surface of the silicone adhesive. The contacting of the flock fibers with the release sheet can adhere the flock fibers to the release sheet.

These and other needs are addressed by the various embodiments and configurations of the present invention. The present invention can provide a number of advantages depending on the particular configuration. These and other advantages will be apparent from the disclosure of the invention(s) contained herein.

The plurality of flock fibers may be formed from any natural or synthetic material. Synthetic material includes, without limitation, vinyl, rayons, nylons, polyamides, polyesters such as terephthalate polymers, such as poly(ethylene terephthalate) and poly(cyclohexylene-dimethylene terephthalate), and acrylic, and natural material includes cotton and wool. 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 retain an electrical charge.

The flock fibers may be pre-colored (yarn-dyed or spun dyed) or may be colored as part of the method of making described herein, such as by a dye sublimation transfer.

Preferably at least most, and even more preferably at least about 75%, and even more preferably all, of the flock fibers have a preferred denier of no more than about 60, more preferably no more than about 25, and even more preferably no more than about 5, with a range of from about 1.5 to about 3.5 being typical and have a titre ranging from about 0.5 to about 20 Dtex (from about 0.5 to about 20×10-7 Kg/m) and even more preferably from about 0.9 Dtex to about 6 Dtex. The length of at least most, and typically at least about 75%, of the flock fibers is preferably no more than about 4 mm, more preferably no more than about 2 mm, and even more preferably no more than about 1 mm, with a range of from about 0.3 to about 3.5 mm being typical. The flock fiber placement density relative to the surface area of the flocked portion (on which the flock is deposited) of the flocked product is preferably about 50% fibers/in2, even more preferably at least about 60% fibers/in2, and even more preferably at least about 70% fibers/in2 of the flocked surface area.

“Polymer”, “polymeric”, or “polymer composition” generally refers to a molecule comprising a plurality of repeating chemical groups, typically referred to as monomers. Polymers include man-made polymers, natural polymers and mixtures thereof. Polymers are often characterized by high molecular masses. Useful polymers include organic polymers and inorganic polymers both of which may be in amorphous, semi amorphous, crystalline, partially crystalline states, or combinations thereof. Polymers may comprise monomers having the same chemical composition or may comprise a plurality of monomers having different chemical compositions, such as a copolymer. Cross-linked polymers have linked monomer chains. Useful polymers include but are not limited to plastics, elastomers, thermoplastic elastomers, elastoplastics, thermosets, thermoplastics and acrylates. Exemplary polymers include but are not limited to acetal polymers, biodegradable polymers, cellulosic polymers, epoxies, fluoropolymers, polyolefins, polystyrenes, polyvinyls, polyacrylics, polyhalo-olefins, polydienes, polyoxides/esthers/acetals, polysulfides, polyesters/thioesters, polyamides/thioamides, polyurethanes/thiourethanes, polyureas/thioureas, polyimides/thioimides, polyanhydrides/thianhydrides, polycarbonates/thiocarbonates, polyimines, polysiloxanes/silanes, polyphosphazenes, polyketones/thioketones, polysulfones/sulfoxides/sulfonates/sulfoamides, polyphylenes, nylons, polyacrylonitrile polymers, polyamide, imide polymers, polyimides, polyarylates, polybenzimidazole, polybutylene, polycarbonate, polyesters, polyetherimide, polyethylene, polyethylene copolymers and modified polyethylenes, polyketones, poly(methyl methacrylate), polymethylpentene, polyphenylene oxides and polyphenylene sulfides, polyphthalamide, polypropylene, polyvinyls, polyurethanes, natural and synthetic rubber, silicones, styrenic resins, sulfone based resins, vinyl based resins and any combinations of these.

A “metalized material” generally refers to one or more of a polymeric composition containing metalized particles, a polymeric composition having a metalized coating, a polymeric composition having a metalized appearance, a metal-containing composition, and a combination and/or mixture thereof. The metalized material may comprise a molded polyurethane or silicone. Typically, the metalized material comprises molded polyurethane formed by high-frequency molding and/or shaping processes. More typically, the metalized material comprises molded metal-containing polyurethane formed by high-frequency molding and/or shaping processes. The high frequency molding process is commonly a radio frequency molding process. The molded polyurethane may have a single metallic hue. The metal may be any metal. Generally, the metal is silver, nickel, aluminum, or alloys and combinations thereof. The metal may be encapsulated and/or dispersed in the polymeric material. The metal may be coated to provide for additional and/or different hues. For example, the metal can be coated with yellow hue to provide for a gold look, or dark orange for copper look. Commonly, the metal may be encapsulated and/or dispersed in the polyurethane. While not wanting to be limited by example, the metal may be encapsulated and/or dispersed between two polymeric film layers. The metalized material may or may not include an adhesive layer. The metalized material typically has a metallic surface or metallic-like appearing surface and an opposing surface. The opposing surface may or may not include the adhesive layer. The adhesive layer can be in the form of an adhesive film layer. The metallic-appearing surface is commonly in the form of three-dimensional surface. The three-dimensional surface is formed during the high frequency molding process. Furthermore, edges of the metalized material can be formed during the molding process. That is, the edges may be formed using a combination of high frequency energy and/or heat. Furthermore, the edges may be formed during the molding process by the mold die, specifically by the edge of the mold die and the pressure applied during the molding process. The molding process may or may not include welding a textile base to metalized material. Commonly, the metalized material is provided without a textile base. However, when provided with a textile base, the textile base is part of the metalized material. That is, the textile base of the metalized material is not a decorative element as used herein, other than that of the metalized material the textile base is molded thereto. The high frequency molding cannot cut through flock fibers, such as nylon flock fibers, nor through typical textile materials such as polyester-containing textile materials. More specifically, the high frequency molding process cannot cut through polymeric materials having a melting point greater than nylon and/or polyester. Even more specifically, the textile base has a melt temperature of commonly no more than about 190 degrees Celsius, more commonly no more than about 180 degrees Celsius, even more commonly no more than about 170 degrees Celsius. The metalized material can be one or more of pliable, soft and washable. More specifically, the metalized material can be laundered with clothing. The metalized material can be fabricated to resemble a metallic badge, such as, a police officer's badge, a fire department badge, a federal agent's badge or such.

All percentages and ratios are calculated by total composition weight, unless indicated otherwise.

It should be understood that every maximum numerical limitation given throughout this disclosure is deemed to include each and every lower numerical limitation as an alternative, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this disclosure is deemed to include each and every higher numerical limitation as an alternative, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this disclosure is deemed to include each and every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein. By way of example, the phrase from about 2 to about 4 includes the whole number and/or integer ranges from about 2 to about 3, from about 3 to about 4 and each possible range based on real (e.g., irrational and/or rational) numbers, such as from about 2.1 to about 4.9, from about 2.1 to about 3.4, and so on.

DETAILED DESCRIPTION

In some embodiments, the flocking adhesive comprises a silicone adhesive. In some embodiments, the flocking adhesive is a silicone adhesive. The silicone adhesive can have a higher melt point compared to a latex adhesive. Moreover, flock fibers adhered to a silicone adhesive tend be less, or not at all, matted down due to the silicone adhesive than the latex adhesives of the prior art. As such, the flock fibers are less inclined, if not at all, to be matted down in the silicone adhesive when compared to a non-silicone adhesive, such as a hot melt adhesive and/or latex adhesive. Furthermore, the flock fibers are less inclined, if not at all, to be matted down around the edges of the adhesive film, thereby, having a cleaner more defined flocked product edge. Silicone adhesives generally heat cure and/or thermally set more quickly than the typical prior flock latex and/or hot melt adhesives. The shorter silicone adhesive cure and/or thermal set times allow for one or more of increased production and greater dimensional stability of flocked product compared to the flocked products of prior art based on latex and/or hot melt adhesive. Dimensional stability of flocked products having the silicone adhesives described herein can be due to any one or more of little or no shrinkage of the silicone adhesive during the curing process. Furthermore, greater dimensional stability of the flocked products having a silicone adhesive can also enable more precise cutting of the resulting flocked product.

It has found that silicone adhesives generally have a greater adhesion to the flock fibers than one or more of the conventional flock latex and hot melt adhesives. This greater adhesion of the flock fibers results in the need to embed less of the flock fiber into the adhesive film. Hence, a greater percent of the flock fiber extends above the silicone adhesive film. A flocked product having a greater percent of the flock fiber extends above the adhesive film can have one or more of a softer feel and a plusher feel can be obtained.

Conventional latex flock adhesives comprise an aqueous emulsion as such, the curing process for an aqueous based adhesive includes removal of most, if not essentially all, of the water prior to curing of the adhesive. The removal of the water increases production time. Inclusion of water within the cured adhesive can result in cured adhesive with a decreased adhesive strength, compared to cured adhesive substantially lacking any retained water. Furthermore, a thicker printed latex film is generally needed, compared to water-free adhesive film, for the same thickness of the cured adhesive film. In general, a printed aqueous latex film is about at least twice as thick as printed silicone adhesive film.

The silicone adhesive generally comprises a polymeric material comprising one or more of vinyl terminated polyalkylsiloxane and vinyl terminated polyarlysiloxane and one or more of a polyalkyl siloxane and polyaryl siloxane. The polyalkly and/or polyaryl siloxanes are generally silyl terminated.

The average molecular weights of the vinyl terminated polyalkylsiloxane and vinyl terminated polyarlysiloxane are commonly from about 750 daltons to about 50,000 daltons. The number of repeating alkyl/aryl units of —[—SiR2O—]— are typically from about 10 to about 850. The polyalkyl and/or polyaryl siloxanes can have one or more terminal vinyl entities. The number of vinyl entities per polyalkyl and/or polyaryl siloxane chain is usually from about 1 to about 5, more typically from about 1 to 4, even more typically from about 2 to about 4, yet even more typically from about 2 to about 3. A non-limiting example of a vinyl terminated polyalkyl siloxane is vinyl terminated poly(dimethylsioxane), (I):

Typically, the silicone adhesive formulation comprises a catalyst, one or more of vinyl terminated polyalkylsiloxane and vinyl terminated polyarlysiloxane, and one or more of a polyalkyl siloxane and polyaryl siloxane. The silicone adhesive formulation can also include a rheology modifier. Typically, the rheology modifier is premixed with the catalyst and the one or more of a polyalkyl siloxane and polyaryl siloxane. The siloxane can comprise without limitation one or more of a polysiloxne, a polyalkyl siloxane, polydialkylsiloxane, polydimethylsiloxane, octamethylcyclotetrasiloxane, methyloctadecyl siloxane, dimethylsiloxane, methyltetradecylsiloxane, docdecylsiloxane, tetradecylsiloxane, methylhexadecylsiloxane, hydrosiloxane, silanol-terminated dimethylsiloxane, hexamethylcycoltrisiloane, decamethylcyclopentasiloxane, octaphenylcyclotetrasiloxane, diphenylsilediol, trimethyltriphenylcyclotrisiloxane, and methyl-3,3,3-trifluoroproplysiloxane.

The average molecular weights of the polyalkylsiloxane and polyarlysiloxane are commonly from about 750 daltons to about 50,000 daltons. The number of repeating alkyl/aryl units of —[—SiR2O—]— are typically form about 10 to about 850. A non-limiting example of a polyalkyl siloxane is trimethylsilyl terminated poly(dimethylsioxane-co-methylhydrosiloxane), (II):

In some embodiments, the silicone adhesive prior to curing can comprise one or more of vinyl terminated polyalkylsiloxane and vinyl terminated polyarlysiloxane and one or more of a polyalkyl siloxane and polyaryl siloxane, a catalyst, and one or more of xylene, octamethylcyclotetrasiloxane, a linear silicone, cyclic silicone, hhdrosilicone, and octanol. The catalyst is generally premixed with the silicone base. It can be appreciated that in some embodiments, the silicone adhesive prior to curing can also comprise a rheology modifier.

The ratio of one or more of vinyl terminated polyalkylsiloxane and vinyl terminated polyarlysiloxane to the one or more of a polyalkyl siloxane and polyaryl siloxane in the silicone adhesive can commonly be one of about 75:1, more commonly be about 70:1, even more commonly be about 65:1, yet even more commonly be about 60:1, still yet even more commonly be about 55:1, still yet even more commonly be about 50:1, still yet even more commonly be about 45:1, still yet even more commonly be about 40:1, still yet even more commonly be about 35:1, still yet even more commonly be about 30:1, still yet even more commonly be about 25:1, still yet even more commonly be about 20:1, still yet even more commonly be about 15:1, still yet even more commonly be about 10:1, still yet even more commonly be about 7.5:1, still yet even more commonly be about 5:1, still yet even more commonly be about 2.5:1, still yet even more commonly be about 2:1, still yet even more commonly be about 1.9:1, still yet even more commonly be about 1.8:1, still yet even more commonly be about 1.7:1, still yet even more commonly be about 1.6:1, still yet even more commonly be about 1.5:1, still yet even more commonly be about 1.4:1, still yet even more commonly be about 1.3:1, still yet even more commonly be about 1.2:1, still yet even more commonly be about 1.1:1, still yet even more commonly be about 1:1, still yet even more commonly be about 1:1.1, still yet even more commonly be about 1:1.2, still yet even more commonly be about 1:1.3, still yet even more commonly be about 1:1.4, still yet even more commonly be about 1:1.5, still yet even more commonly be about 1:1.6, still yet even more commonly be about 1:1.7, still yet even more commonly be about 1:1.8, still yet even more commonly be about 1:1.9, still yet even more commonly be about 1:2, still yet even more commonly be about 1:2.5, still yet even more commonly be about 1:5, still yet even more commonly be about 1:7.5, still yet even more commonly be about 1:10, still yet even more commonly be about 1:15, still yet even more commonly be about 1:20, still yet even more commonly be about 1:25, still yet even more commonly be about 1:30, still yet even more commonly be about 1:35, still yet even more commonly be about 1:40, still yet even more commonly be about 1:45, still yet even more commonly be about 1:50, still yet even more commonly be about 1:55, still yet even more commonly be about 1:60, still yet even more commonly be about 1:65, still yet even more commonly be about 1:70, yet still even more commonly be about 1:75.

The silicone adhesive layer230can comprise one or more of a homopolymer, a copolymer, and a polymeric alloy. Generally, the silicone adhesive layer230comprises one or more of a siloxane and vinyl siloxane. More generally, the silicone adhesive layer230comprises one or more of a siloxane and vinyl siloxane polymerized and/or alloyed with one or more of a polyolefin, polystyrene, polyvinyl, polyacrylic, polyhalo-olefin, polydiene, polyoxide, polyesther, polyacetal, polysulfide, polythioester, polyamide, polythioamide, polyurethane, polythiourethane, polyurea, polythiourea, polyimide, polythioimide, polyanhydride, polythianhydride, polycarbonate, polythiocarbonate, polyimine, polyphosphazene, polyketone, polythioketone, polysulfone, polysulfoxide, polysulfonate, polysulfoamide, and polyphylene. Even more generally, the silicone adhesive layer230comprises one or more of a siloxane and vinly siloxane polymerized with, and alloyed with one or more of a polyolefin, polystyrene, polyvinyl, polyacrylic, polyhalo-olefin, polydiene, polyoxide, polyesther, polyacetal, polyanhydride, polycarbonate, polyphosphazene, polyketone, and polyphylene.

In some embodiments, the silicone adhesive can include a coupling agent. In some embodiments, the one or more of vinyl terminated polyalkylsiloxane, vinyl terminated polyarlysiloxane, polyalkyl siloxane, and polyaryl siloxane can comprise a coupling agent. The coupling agent can comprise one or more of organosilicone coupling agents, organotitanium coupling agents, or a combination of oranganosilicone and organotitanium coupling agents. A coupling agent generally has two functional groups with different reactivity. The general structure of the coupling agents is as follows:

Y—R—Si—(—X)3; or

The silicone adhesive general reacts with one or more of a coupling agent, flock fibers, a thermoplastic adhesive, a thermoset adhesive, a hot melt adhesive, and a substrate. The crosslinking reaction of the silicone base, coupling agent, flock fibers, a thermoplastic adhesive, a thermoset adhesive, a hot melt adhesive, and a substrate. The reaction of the one or more of the coupling agent, flock fibers, thermoplastic adhesive, thermoset adhesive, hot melt adhesive, and substrate with the silicone adhesive is generally one or more of an addition cure, condensation cure, peroxide cure, ultraviolet cure, electron-beam cure, and room temperature vulcanization cure. The reaction of the silicone adhesive with one or more of the coupling agent, flock fibers, thermoplastic adhesive, thermoset adhesive, hot melt adhesive, and substrate can be catalyzed by one or more of platinum catalyst, a zinc catalyst, and a peroxide catalyst.

In some embodiments, the one or more of vinyl terminated polyalkylsiloxane, vinyl terminated polyarlysiloxane, polyalkyl siloxane, and polyaryl siloxane can further comprise silica. Generally, the silica can be a rheology modifier for the one or more of vinyl terminated polyalkylsiloxane and vinyl terminated polyarlysiloxane and/or the one or more of a polyalkyl siloxane and polyaryl siloxane.

Typically, the silica comprises fumed silica. The fumed silica can comprise microscopic droplets of amorphous silica (SiO2). The droplets of amorphous silica are generally fused into one or more of branched, chainlike, three-dimensional secondary particles. The secondary particles can agglomerate into tertiary particles. The fumed silica can be in the form of powder. The fumed silica powder commonly has a low bulk density and high surface area. Commonly, the fumed silica has a primary particle size from about 5 to about 50 nm. The fumed silica typically comprises non-porous particles. The fumed silica particles generally have a surface area from about 50 to about 600 m2/g. Typically, the fumed silica has a density from about 0.15 to about 0.2 g/cm3. When fumed silica is mixed with a liquid silicone adhesive, the fumed silica can increase the viscosity of the liquid silicone adhesive. Moreover, the addition of fumed silica to a liquid silicone adhesive can one or more of thicken, be a reinforcing filler, and be a thixotropic agent for the liquid silicone adhesive. In some embodiments, the fumed silica can be a hydrophilic fumed silica. In some embodiments, the fumed silica can be a hydrophobic fumed silica. The hydrophobic fumed silicas are generally chemically treated with one or more of silanes and siloxanes. The one or more siloxanes are chemically bonded to the silica. The hydrophobic fumed silicas are typically characterized, among other things, by a low moisture adsorption, excellent dispersibility, and their ability to adjust rheological behavior. In some embodiments, the fumed silica can be positively charged. In some embodiments, the fumed silica can be negatively charged. In some embodiments, the fumed silica can comprise a mixed oxide comprising SiO2 and one or more of aluminum and titanium oxides, generally Al2O3 and TiO2. In some embodiments, the fumed silica can be fumed Al2O3. In some embodiments, the fumed silica can be fumed TiO2. In some embodiments, the fumed silica can comprise spherical particles with an average size of about 30 micrometers (or 30 millionths of a meter).

In some embodiments the silica can comprise one or more of dimethyl, methylvinyl siloxane and trimethysilyl treated silica, dimethylvinylated and trimethylated silica, dimethyl, methylvinyl siloxane and trimethylsilyl treated silica, hexamethyldisilizane treated silica, and trimethylated silica.

The silicone adhesive can commonly have one of from about 5 to about 35 wt % silica, more commonly from about 6 to about 34 wt % silica, even more commonly from about 7 to about 33 wt % silica, yet even more commonly from about 8 to about 32 wt % silica, still yet even more commonly from about 9 to about 31 wt % silica, still yet even more commonly from about 10 to about 30 wt % silica, still yet even more commonly from about 11 to about 29 wt % silica, still yet even more commonly from about 12 to about 27 wt % silica, still yet even more commonly from about 13 to about 25 wt % silica, still yet even more commonly from about 14 to about 24 wt % silica, still yet even more commonly from about 15 to about 23 wt % silica, or yet still even more commonly from about 16 to about 22 wt % silica.

The wt % silica in the silicone adhesive is believed to affect the printability of silicone adhesive. It is generally believed to affect the stinginess of silicone adhesive when the adhesive is screen printed.

Generally, the platinum catalyst is present in the silicone adhesive layer at a level from about 5 to about 300 ppm. In some embodiments, the platinum catalyst is present in the silicone adhesive layer at a level from about 5 to about 50 ppm. In some embodiments, the platinum catalyst is present in the silicone adhesive layer at a level from about 50 to about 150 ppm. In some embodiments, the platinum catalyst is present in the silicone adhesive layer at a level from about 150 to about 220 ppm.

Typically, the platinum catalyst is present in the silicone base at a level from about 5 to about 300 ppm. In some embodiments, the platinum catalyst is present in the silicone base at a level from about 5 to about 50 ppm. In some embodiments, the platinum catalyst is present in the silicone base at a level from about 50 to about 150 ppm. In some embodiments, the platinum catalyst is present in the silicone base at a level from about 150 to about 220 ppm.

Commonly, the platinum catalyst comprises a platinum vinylsiloxane complex. The platinum catalyst can be poisoned by one or more of amines, sulfur, chloride, epoxy, natural rubber, tin salts, mercaptans, amino compounds and polyvinylchloride.

In some embodiments, the catalyst can comprise a peroxide. The level of peroxide in one of the adhesive layer or in silicone base material can be from about 0.1 to about 1.5 wt %. The cure temperature when the adhesive is cured using a peroxide catalyst is typically from about 120 to about 170 degrees Celsius.

FIG. 1depicts a flocked transfer10of the prior art. Flock transfers10of the prior art comprise a carrier sheet213having a release adhesive212positioned between the flock fibers240and the carrier sheet213. The flock fibers have opposing first and second flock fiber ends. The first flock fiber ends are adhered to the carrier sheet213by the release adhesive212. The second flock fiber ends embedded in a latex adhesive270. The latex270is positioned between a hot melt adhesive220and the flock fibers240.

FIG. 2depicts a direct flocked product20of the prior art. Direct flocked products20of the prior art comprise an adhesive layer275positioned between a flock layer240and a substrate290. The adhesive layer275can be one of a hot melt adhesive220, a latex adhesive270, or a combination thereof. For example, the adhesive layer can comprise first and second layers with one of the first or second layers position on top of other of the first and second layers, with the first layer comprising the latex adhesive270and the second layer comprising the hot melt adhesive220.

FIG. 3depicts a direct flocked product80according to some embodiments of the present disclosure. Flocked product80can comprise a release adhesive212positioned between the flock fibers240and the carrier sheet213. The flock transfer can comprise a plurality of flock fibers240adhered to a silicone adhesive layer230. The flock fibers240have a flock fiber length114and opposing first103and second104fiber ends. The first flock fiber ends are adhered to the carrier sheet213by the release adhesive212. The second flock fiber ends are adhered to a silicone adhesive230. The silicone adhesive230is positioned between one of a hot-melt adhesive222and the flock fibers240.

FIG. 4depicts a direct flocked product90according to some embodiments of the present disclosure. Direct flock product90can comprise a silicone adhesive layer230positioned between flock fibers240and a substrate290. The silicon adhesive layer230can further comprise a hot melt adhesive222. In some embodiments, the hot melt adhesive220can be positioned between the flock fibers240and the silicone adhesive layer230. In some embodiments, the hot melt adhesive222can be positioned between the substrate290and the silicone adhesive layer230. In some embodiments, the silicone layer is positioned between the flock fiber layer240and the substrate290and is in contact with each of the flock fiber layer240and the substrate290.

FIGS. 5 and 6depict direct flocked product200and a method of making the same.FIG. 6depicts the method of making the directed flocked product200. The flocked product200can comprise a silicone adhesive layer230positioned between a thermo-adhesive layer220. The thermo-adhesive layer can be one of thermoplastic adhesive, a thermoset adhesive or a combination of thermoplastic and thermoset adhesives. Some embodiments can include a release sheet210in contact with the thermo-adhesive layer220. The thermo-adhesive layer220can be positioned between the release sheet210and the silicone adhesive layer230. The release sheet210can be a silicone release sheet210. The direct flocked product200can comprise a plurality of flock fibers240having a flock fiber length114and opposing first103and second104fiber ends. The second fiber ends are in contact with and adhered to the silicone adhesive layer230. The flock layer240can comprise a plurality of flock fibers in contact with and adhered to the silicone adhesive layer230. The silicone adhesive layer230is typically positioned between the flock layer240and the thermo-adhesive layer220. Moreover, the silicone adhesive layer230is in contact with both the flock layer240and the thermo-adhesive layer220. The thermo-adhesive layer220can be in some embodiments in contact with each of the silicone adhesive layer230and the release sheet210. The flock layer240can comprise a plurality of flock fibers comprising substantially the same color or a plurality of flock fibers comprising some fibers having one color and the other fibers having another color. In some embodiments, the flock layer240comprises substantially a single color. In some embodiments, the flock layer240comprises two or more colors, with each of the flock fibers having one of the two or more colors.

The flock product200ofFIG. 6can be made by process100ofFIG. 5. Process100typically includes: a step110, providing a thermo-adhesive220. The thermo-adhesive220may or may not be provided with a release sheet2100. In step120, a silicone adhesive230is applied to and/or contacting with the thermo-adhesive220. Generally, step120includes screen-printing the silicone adhesive220on the thermo-adhesive220. Typically, step130includes contacting and adhering flock fibers240to the silicone adhesive230. Step110can include providing a release sheet having a thermo-adhesive layer on one side of the release sheet210. The thermo-adhesive film layer has opposing first and second thermo-adhesive surfaces. Step120can include screen printing a silicone adhesive230onto a first surface of the thermo-adhesive layer220. In step130, flock fibers are contacted, in a direct flocking process, with the silicone adhesive layer230. The direct flocking can include an electrostatic process of contacting the flock fibers with the silicone adhesive layer230.

FIGS. 7 and 8depict a flock product400and a method of making the same.FIG. 8depicts flock product400. The flock product400can comprise a flock layer240, a silicone adhesive layer230, a pressure sensitive adhesive layer250, and a release sheet210. The release sheet210can be a silicone release sheet. The flock product400can comprise a plurality of flock fibers240having a flock fiber length114and opposing first103and second104fiber ends. The second fiber ends are in contact with and adhered to the silicone adhesive layer230. The flock layer240comprise a plurality of flock fibers in contact with and adhered to the silicone adhesive layer230. The silicone adhesive layer230can be positioned between the flock layer240and the pressure sensitive adhesive layer250. Moreover, the silicone adhesive layer230can be in contact with each of the flock layer240and the pressure sensitive adhesive layer250. The pressure sensitive adhesive layer250can be positioned between the silicone adhesive layer230and the release sheet210. The pressure sensitive adhesive layer250can be in contact with each of the silicone adhesive layer230and the release sheet210. The flock layer240can comprise a plurality of flock fibers comprising substantially the same color or a plurality of flock fibers comprising some fibers having one color and the other fibers having another color. In some embodiments, the flock layer240comprises substantially a single color. In some embodiments, the flock layer240comprises two or more colors, with each of the flock fibers having one of the two or more colors.

The flock product400ofFIG. 7can be made by the process300depicted inFIG. 6. The process300typically includes: a step310of providing a pressure sensitive adhesive250positioned on a release sheet220; a step320of contacting a silicone adhesive230with the pressure sensitive adhesive250; and step330of contacting and/or adhering flock fibers240to the silicone adhesive230. Step310can include providing a release sheet220having a pressure sensitive adhesive layer250on one side of the release sheet210. Step320can include screen printing a silicone adhesive230onto a first surface of the pressure sensitive adhesive layer250. The second pressure sensitive adhesive surface is in contact with the silicone release sheet210. The first and second surfaces of the pressure sensitive adhesive layer250being in an opposing relationship. Step330can include direct flocking of the silicone adhesive layer. In step330, flock fibers are contacted, in a direct flocking process, with the silicone adhesive layer230. The direct flocking can include an electrostatic process of contacting the flock fibers with the silicone adhesive layer230.

FIGS. 9 and 10depict flock transfer600and a method of making the same.FIG. 10depicts the flock transfer600. The flock transfer600can comprise a thermo-adhesive layer220, a silicone adhesive layer230, a flock layer240, a release adhesive layer260, and a release sheet210. The flock layer240comprise a plurality of flock fibers positioned between the silicone adhesive layer230and a release adhesive layer260. The flock transfer600can comprise a plurality of flock fibers240having a flock fiber length114and opposing first103and second104fiber ends. The second fiber ends104are in contact with and adhered to the silicone adhesive layer230. The first fiber ends103are in contact with and adhered to the release adhesive layer260. The flock fibers240are in contact with the silicone adhesive layer230and the release adhesive layer260. After curing of the silicone adhesive layer230, the flock fibers240are more strongly adhesively bound to the silicone adhesive layer230than to the release adhesive layer260. The release adhesive260is positioned between the flock layer240and the release sheet210. Moreover, the release adhesive260is in contact with both the flock layer240and the release sheet210. The silicone adhesive layer230is positioned between the thermo-adhesive layer220and the flock layer240. Furthermore, the silicone adhesive layer230is in contact with both the thermo-adhesive layer220and the flock layer240. The thermo-adhesive220can be one of a thermoplastic adhesive, a thermoset adhesive, or a combination of thermoplastic and thermoset adhesives. The flock layer240can comprise a plurality of flock fibers comprising substantially the same color or a plurality of flock fibers comprising some fibers having one color and the other fibers having another color. In some embodiments, the flock layer240comprises substantially a single color. In some embodiments, the flock layer240comprises two or more colors, with each of the flock fibers having one of the two or more colors. The first flock fiber ends in contact with and adhered to the silicone release sheet210. The second flock fiber ends are in contact with and adhered to a silicone adhesive230. The silicone adhesive230is positioned between thermo-adhesive220and the flock fibers240.

The flock transfer600ofFIG. 10can be made by process500depicted inFIG. 9. Process500typically includes: a step510of providing a release adhesive260on a release sheet210; a step130of contacting and/or adhering flock fibers240to the release adhesive260; a step520of contacting a silicone adhesive230with the flock fibers240; and step530of contacting a thermo-adhesive220on the free surface of the silicone adhesive230. Step510can include providing a silicone release sheet having a release adhesive layer260on one side of the silicone release sheet210. The release adhesive layer260can have opposing first and second release surfaces. Step120can include contacting and/or adhering the first ends of flock fibers to the release adhesive260. The second ends of the flock fibers are in an opposing relationship with the first ends of the flock fibers. In step520, a silicone adhesive contacted on the flock layer240. The contacting of the silicone adhesive, in step520, with the flock layer240can include screen-printing the silicone adhesive layer230. Step520can include contact the silicone adhesive230with the second ends of the flock fibers. More specifically, a first surface of the screen-printed silicone adhesive layer230is in contact with second ends of the flock fibers. The first surface of the silicone adhesive layer230is in an opposing relationship with a second surface of the silicone adhesive layer230. The second surface of the silicone adhesive layer230is sometimes also referred to as the free surface of the silicone adhesive layer230. Step530can include applying a thermo-adhesive220to the silicone adhesive layer230. More specifically, in step530can include applying a thermo-adhesive220to the second surface of the silicone adhesive layer230. The process500can also include a step of applying thermal energy (not depicted inFIG. 9) to the flock transfer600to cure the silicone adhesive layer230. The thermal energy can also fuse the thermo-adhesive layer220to the silicone adhesive layer230.

An advantage of the flocked products of present disclosure having a silicone adhesive layer230and a thermo-adhesive220is their ability to retain their plush flock layer240when applied to a substrate290with an iron. The flock products of prior art, such as those ofFIGS. 1 and 2, do not retain their plushness when applied with an iron. When applied with an iron, one or more of the latex adhesive275and hot melt adhesive222flow between the fibers and disrupt the plushness of the flock layer240. When applied by an iron the silicone adhesive230of the present disclosure does not substantially flow into the flock fiber layer240or disrupt the plushness of the flock fiber layer240.

It can be appreciated that one or more voids can be created in anyone of the direct flocked product90, flocked product200, flocked product400or flock transfer product600. The one or more voids can be created by laser cutting or any other cutting process know in the art. An insert textile or any other suitable design media can be laminated to the cut product/transfer such that the textile design (or other design media) fits and/or is visible within the one or more voids. This method/process is more efficient and provides for a superior product (in terms of one or more of adhesive strength, less manufacturing steps, less matting of flock fibers, cleaner cut edges, to name a few) than manufacturing process. The current process of the prior art includes the steps of: (a) provide a sheet of the textile (or other design media) to-be-inserted with a thermo-adhesive film backing; (b) print an adhesive (thermo-adhesive or silicone adhesive) on the textile (or other design media); (c) direct flock each flock color into the adhesive (thermo-adhesive or silicone adhesive); (d) dry and cure the adhesive (thermo-adhesive or silicone adhesive); (e) vacuum clean; and (f) final cut of product. The final product of step (f) is generally of lesser quality than the product made using flock one of prior art flocked transfer10or flocked product20for one or one of following: (i) heat pressing leaves the flock fibers, in the current utilized process, matted down a bit when the latex adhesive get tacky when dried and cured; (ii) edges of flock design, in the current utilized process, not clear as the heat pressed edge fibers matt down sideways; and (iii) flock, in the current utilized process, is not very soft because of the depth to which the flock fibers must be planted in the latex adhesive.

In accordance with some embodiments, less of the fiber length is adhered to the silicone adhesive layer230than to one or more of the latex adhesive270and hot melt adhesive222; Generally, flock adhered to a silicone adhesive230where less of the flock fiber length is adhered to the silicone adhesive230, is generally dramatically softer than flock adhered to one or more of a latex adhesive270and hot-melt adhesive222where more of the flock fiber is adhered to the adhesive.

In some embodiments, substantially less flock fibers are matted down in the silicone adhesive230compared to one or both of latex adhesive270and hot-melt adhesive222.

In some embodiments, the flock layer edges for flock fibers240adhered to silicone adhesive layer230are clearer and sharper than the flock edges of the prior art where the flock fibers240are adhered to one or more a latex adhesive layer270and a hot-melt adhesive layer222.

In some embodiments, the processes described herein using a silicone adhesive230compared to the prior art process that use one or more of a latex adhesive270and hot-melt adhesive222are generally faster. The processes using a silicone adhesive230typically do not require an air-drying step to remove water from an aqueous latex. The silicone adhesive230usually polymerizes than one or more of latex adhesive270and/or thermally sets more quickly than the hot-melt adhesive222. Hence, the processes using the silicone adhesive230are usually faster than those using a latex adhesive270and/or hot-melt adhesive222.

In some embodiments, the silicone adhesive230has less shrinkage than the one or more of latex adhesive270and the hot-melt adhesive222. The latex adhesives270of the prior art shrink to about 40% of its printed wet thickness. It is believed that the thicker latex adhesive films270cause flock layer240to be less plush than those of the thinner silicone adhesive230layers described herein.

In some embodiments, the silicone adhesive layer230can be electrically conductive. While not wanting to be limited by example, the silicone adhesive layer230can contain one or conductive materials such as without limitation an electrically conductive silicone, electrically conductive polymeric material, electrically conductive inorganic material, electrically conductive organic material, or an electrically conductive mixture thereof. The electrically conductive silicone can comprise one of a positively charged fumed silica, a negatively charged fumed silica, and a mixture or combination thereof. The electrical conductivity of the silicone adhesive layer230can aid in the deposition and/or contacting of the flock fibers240with the silicone adhesive layer230.

It is believed that when the silicone adhesive layer230can lack in some embodiments sufficient electric conductivity. That is, the electric potential between the flock fiber230and silicone adhesive layer230can be insufficient to substantially deposit and/or contact some of the flock fibers240with the silicone adhesive layer230. Moreover, when the silicone adhesive layer230lacks sufficient electrical conductivity, some of the flock fibers240are insufficiently deposited and/or contacted with the silicone adhesive layer230such that they do not stand proud. That is, some the flock fibers240that are insufficiently deposited and/or adhered to the silicone adhesive layer230and are oriented, relative to the silicone adhesive layer230, at an angle from about 35 to about 85 degrees.

Some embodiments can include a step of providing a carrier sheet with a release adhesive. The release adhesive can be a silicone-release adhesive.

Some embodiments can include a step of printing a silicone adhesive230onto a release adhesive.

Some embodiments can include a step of applying a thermo-adhesive220. The thermo-adhesive220can be applied to the printed silicone adhesive layer230. The thermo-adhesive220can be provided as a powder. The powdered thermo-adhesive220typically has a particle size from about 80 to about 300 microns, more typically from 80 to about 200 microns. In some embodiments, the powdered hot-melt adhesive220has a particle size from about 200 to about 300 microns. It can be appreciated that the particle size of the powdered hot-melt adhesive220can refer to any one or more of the P90, P85, P80, P75, P70 and P50 particle size.

In some embodiments, the thermo-adhesive can be a self-supporting, substantially continuous roll of a thermo-adhesive film. The self-supporting, substantially continuous roll of a thermo-adhesive film typically has first and second opposing sides. One or both of the first and second sides may or may not be in contact with a release sheet.

Some embodiments can include a step of applying thermal energy to one or more of anyone of the direct flocked product90, flocked product200, flocked product400or flock transfer product600to cure the silicon adhesive230and adhesively bond the flock fibers240to the silicone adhesive230. In some embodiments, the applied thermal energy can adhesively bond the flock fibers240to the thermo-adhesive220. In some embodiments, the applied thermal energy can adhesively bond the thermo-adhesive220and silicone adhesive230together.

Some embodiments can include a step of vacuuming the one or more of anyone of the direct flocked product90, flocked product200, flocked product400or flock transfer product600to remove any free flock fibers not adhered to the silicone adhesive230. The step of vacuuming the one or more of anyone of the direct flocked product90, flocked product200, flocked product400or flock transfer product600can also remover any free powered thermo-adhesive220.

Some embodiments can include a step of cutting the one or more of anyone of the direct flocked product90, flocked product200, flocked product400or flock transfer product600. The cutting can be one of laser cutting, mechanical cutting, hot-wire cutting, or radio frequency cutting.

Commonly, the printed silicone adhesive layer230can have a thickness of no more than about 0.1 mm, more commonly of no more than about 0.2 mm, even more commonly of no more than about 0.3 mm, yet even more commonly of no more than about 0.4 mm, still yet even more commonly of no more than about 0.5 mm, still yet even more commonly of no more than about 0.6 mm, still yet even more commonly of no more than about 0.7 mm, still yet even more commonly of no more than about 0.8 mm, still yet even more commonly of no more than about 0.9 mm, still yet even more commonly of no more than about 1.0 mm, still yet even more commonly of no more than about 1.1 mm, still yet even more commonly of no more than about 1.2 mm, still yet even more commonly of no more than about 1.4 mm, still yet even more commonly of no more than about 1.5 mm, or yet still even more commonly of no more than about 1.6 mm. The cured silicone adhesive film typically has a thickness of no more than about 110% of printed silicone adhesive film, more typically of no more than about 105%, even more typically of no more than about 100%, yet even more typically of no more than about 98%, still yet even more typically of no more than about 95%, still yet even more typically of no more than about 93%, still yet even more typically of no more than about 92%, still yet even more typically of no more than about 90%, still yet even more typically of no more than about 88%, still yet even more typically of no more than about 86%, still yet even more typically of no more than about 84%, still yet even more typically of no more than about 82%, still yet even more typically of no more than about 80%, still yet even more typically of no more than about 78%, still yet even more typically of no more than about 76%, still yet even more typically of no more than about 74%, still yet even more typically of no more than about 72%, still yet even more typically of no more than about 68%, still yet even more typically of no more than about 66%, still yet even more typically of no more than about 62%, or yet still even more typically of no more than about 60% of the thickness of printed silicone adhesive layer230.

In some embodiments, the silicone adhesive layer230commonly has an uncured thickness from about 2 to about 15 mils ( 1/1000 of an inch), more commonly from about 3 to about 7 mils ( 1/1000 of an inch).

In some embodiments, the printed silicone adhesive layer230typically has a thickness of at least about 0.0010 inches, more typically the silicone adhesive layer230has a thickness of at least than about 0.0025 inches, even more typically the silicone adhesive layer230has a thickness of at least about 0.0050 inches, and yet even more typically the silicone adhesive layer230has a thickness of at least about 0.0075 inches, and still yet even more typically the silicone adhesive layer230has a thickness of at least about 0.0100 inches and a thickness of no more than about 0.0750 inches, even more typically a thickness of no more than about 0.0500 inches, even more typically a thickness of no more than about 0.0250 inches, and even more typically a thickness of no more than about 0.0100 inches. In other embodiments, the printed silicone adhesive layer230usually has a thickness of at least about 15 μm, more usually the silicone adhesive layer230has a thickness of at least than about 20 μm, even more usually the silicone adhesive layer230has a thickness of at least about 50 μm, and yet even more usually the silicone adhesive layer230has a thickness of at least about 80 μm, still yet even more usually the silicone adhesive layer230has a thickness of at least about 100 μm, still yet even more typically the silicone adhesive layer230has a thickness of at least about 150 μm, or still yet even more usually the silicone adhesive layer230has a minimum thickness of at least about 200 μm. Commonly the printed silicone adhesive layer230has a thickness of no more than about 210 μm, even more commonly a film thickness of no more than about 200 μm, even more commonly a film thickness of no more than about 150 μm, and even more commonly a film thickness of no more than about 105 μm. Generally, the printed silicone adhesive layer230has a thickness of no more than about 210 μm, even more generally a film thickness of no more than about 200 μm, even more generally a film thickness of no more than about 150 μm, and even more generally a film thickness of no more than about 105 μm and a thickness of more than about at least about 20 μm, more generally a thickness of more than 50 μm, even more generally a thickness of more than about 80 μm, and yet even more generally a thickness of more than about 150 μm, and still yet even more generally a thickness of more than about 100 μm.

Generally, the printed film thickness of the silicone adhesive layer230is sufficiently thin that the flock fibers do not over-penetrate the silicone adhesive film to create aesthetic issues, such as, but not limited to matting, stiffness and/or lack of plushness of the flock layer. In some embodiments, the pressure applied when contacting the flock fibers240with the silicone adhesive230is commonly from about 0.01 to about 10 bars, more generally from about 0.05 to about 7 bar, even more generally from about 0.1 to about 5 bar, yet even more generally from about 0.5 to about 4 bar, and still yet even more generally from about 1 to about 3 bar.

Generally, no more than about 0.1% of the flock fiber length is adhesively bonded to silicone adhesive layer230, more generally no more than about 0.2%, even more generally no more than about 0.3%, yet even more generally no more than about 0.4%, still yet even more generally no more than about 0.5%, still yet even more generally no more than about 0.6%, still yet even more generally no more than about 0.7%, still yet even more generally no more than about 0.8%, still yet even more generally no more than about 0.9%, still yet even more generally no more than about 1.0%, still yet even more generally no more than about 1.1%, still yet even more generally no more than about 1.2%, still yet even more generally no more than about 1.3%, still yet even more generally no more than about 1.4%, still yet even more generally no more than about 1.5%, still yet even more generally no more than about 1.6%, still yet even more generally no more than about 1.7%, still yet even more generally no more than about 1.8%, still yet even more generally no more than about 1.9%, still yet even more generally no more than about 2.0%, still yet even more generally no more than about 2.1%, still yet even more generally no more than about 2.2%, still yet even more generally no more than about 2.3%, still yet even more generally no more than about 2.4%, still yet even more generally no more than about 2.5%, still yet even more generally no more than about 2.6%, still yet even more generally no more than about 2.7%, still yet even more generally no more than about 2.8%, still yet even more generally no more than about 2.9%, still yet even more generally no more than about 3.0%, still yet even more generally no more than about 3.1%, still yet even more generally no more than about 3.2%, still yet even more generally no more than about 3.3%, still yet even more generally no more than about 3.4%, or yet still even more generally no more than about 3.5% of the flock fiber length is adhesively bonded to silicone adhesive layer230.

The second fiber ends of the flock fibers240can be in contact with the silicone adhesive layer230. At least some of the flock fiber length can be embedded in the silicone adhesive layer230. In some embodiments, typically no more than about 3% of the flock fiber length can be embedded in the silicone adhesive layer230, more typically no more than about 2% of the flock fiber length can be embedded in the silicone adhesive layer230, even more typically no more than about 1.5% of the flock fiber length can be embedded in the silicone adhesive layer230, yet even more typically no more than about 1% of the flock fiber length can be embedded in the silicone adhesive layer230, still yet even more typically no more than about 0.5% of the flock fiber length can be embedded in the silicone adhesive layer230, still yet even more typically no more than about 0.25% of the flock fiber length can be embedded in the silicone adhesive layer230, or yet still even more typically no more than about 0.1% of the flock fiber length can be embedded in the silicone adhesive layer230. Commonly, the total surface area of the flock fiber adhered to the silicone adhesive layer230comprises more than about 80% of one of the circular faces of the flock fiber240and no more than about 20% of the cylindrical wall of the flock fiber, more commonly more than about 85% one of the circular faces of the flock fiber and no more than about 15% of the cylindrical wall of the flock fiber, even more commonly more than about 90% one of the circular faces of the flock fiber and no more than about 10% of the cylindrical wall of the flock fiber, yet even more commonly more than about 95% one of the circular faces of the flock fiber and no more than about 5% of the cylindrical wall of the flock fiber, still yet even more commonly more than about 98% one of the circular faces of the flock fiber and no more than about 2% of the cylindrical wall of the flock fiber, still yet even more commonly more than about 99% one of the circular faces of the flock fiber and no more than about 1% of the cylindrical wall of the flock fiber, and yet still even more commonly more than about 99.5% of one of the circular faces of the flock fiber and no more than about 0.5% of the cylindrical wall of the flock fiber.

Typically, the second fiber ends of the flock fibers240are embedded in the silicone adhesive layer230to a depth of no more than about 25% of the silicone adhesive layer thickness, more typically the second fiber ends are embedded in the silicone adhesive layer adhesive230to a depth of no more than about 15% of the silicone adhesive layer thickness, even more typically the second fiber ends are embedded in the silicone adhesive layer230to a depth of no more than about 10% of the silicone adhesive layer thickness, yet even more typically the second fiber ends are embedded in the silicone adhesive layer230to a depth of no more than about 5% of the silicone adhesive layer thickness, still yet even more typically the second fiber ends are embedded in the silicone adhesive layer230to a depth of no more than about 2.5% of the silicone adhesive layer thickness, still yet even more typically the second fiber ends are embedded in the silicone adhesive layer230to a depth of no more than about 2% of the silicone adhesive layer thickness, yet still even more typically the second fiber ends are embedded in the silicone adhesive layer230to a depth of no more than about 1% of the silicone adhesive layer thickness, still yet even more typically the second fiber ends are embedded in the silicone adhesive layer230to a depth of no more than about 0.5% of the silicone adhesive layer thickness, or still yet even more typically the second fiber ends are embedded in the silicone adhesive layer230to a depth of no more than about 0.25% of the silicone adhesive layer thickness.

It can be appreciated that the flock fiber240length in contact with the silicone adhesive layer230can depend on one or both pressure and temperature applied when contacting the flock fibers240with the silicone adhesive layer230and the physical properties of the silicone adhesive layer230during the embedding process.

The flock layer240comprises a plurality of interstitial voids between the flock fibers204, the plurality of interstitial voids has an interstitial void volume. Generally, substantially some of the silicone adhesive layer230flows into at least some the interstitial void volume. More generally, substantially little, if any, of the silicone adhesive layer230flows into at least some the interstitial void volume. Even more generally, substantially none the silicone adhesive layer230flows into most of the interstitial void volume. Yet even more generally, substantially most, or all, of the interstitial void volume is substantially free the silicone adhesive layer230. Still yet more generally, the interstitial void volume is substantially free the silicone adhesive layer230.

In some embodiments, the silicone adhesive105generally has a cured film thickness from about 2 to about 15 mils ( 1/1000 of an inch), more generally from about 3 to about 7 mils ( 1/1000 of an inch).

In some embodiments, the cured silicone adhesive layer230typically has a thickness of at least about 0.0010 inches, more typically the silicone adhesive layer230has a thickness of at least than about 0.0025 inches, even more typically the silicone adhesive layer230has a thickness of at least about 0.0050 inches, and yet even more typically the silicone adhesive layer230has a thickness of at least about 0.0075 inches, and still yet even more typically the silicone adhesive layer230has a thickness of at least about 0.0100 inches and a thickness of no more than about 0.0750 inches, even more typically a thickness of no more than about 0.0500 inches, even more typically a thickness of no more than about 0.0250 inches, and even more typically a thickness of no more than about 0.0100 inches. In other embodiments, the cured silicone adhesive layer230usually has a minimum thickness of at least about 15 μm, more usually the silicone adhesive layer230has a thickness of at least than about 20 μm, even more usually the silicone adhesive layer230has a thickness of at least about 50 μm, and yet even more usually the silicone adhesive layer230has a thickness of at least about 80 μm, still yet even more usually the silicone adhesive layer230has a thickness of at least about 100 μm, still yet even more typically the silicone adhesive layer230has a thickness of at least about 150 μm, or still yet even more usually the silicone adhesive layer230has a thickness of at least about 200 μm. Commonly the cured silicone adhesive layer230has a thickness of no more than about 210 μm, even more commonly a film thickness of no more than about 200 μm, even more commonly a film thickness of no more than about 150 μm, and even more commonly a film thickness of no more than about 105 μm. Generally, the cured silicone adhesive layer230has a thickness of no more than about 210 μm, even more generally a film thickness of no more than about 200 μm, even more generally a film thickness of no more than about 150 μm, and even more generally a film thickness of no more than about 105 μm and a thickness of more than about at least about 20 μm, more generally a thickness of more than 50 μm, even more generally a thickness of more than about 80 μm, and yet even more generally a thickness of more than about 150 μm, and still yet even more generally a thickness of more than about 100 μm.

Generally, no more than about 0.1% of the flock fiber length is adhesively bonded to silicone adhesive layer230, more generally no more than about 0.2%, even more generally no more than about 0.3%, yet even more generally no more than about 0.4%, still yet even more generally no more than about 0.5%, still yet even more generally no more than about 0.6%, still yet even more generally no more than about 0.7%, still yet even more generally no more than about 0.8%, still yet even more generally no more than about 0.9%, still yet even more generally no more than about 1.0%, still yet even more generally no more than about 1.1%, still yet even more generally no more than about 1.2%, still yet even more generally no more than about 1.3%, still yet even more generally no more than about 1.4%, still yet even more generally no more than about 1.5%, still yet even more generally no more than about 1.6%, still yet even more generally no more than about 1.7%, still yet even more generally no more than about 1.8%, still yet even more generally no more than about 1.9%, still yet even more generally no more than about 2.0%, still yet even more generally no more than about 2.1%, still yet even more generally no more than about 2.2%, still yet even more generally no more than about 2.3%, still yet even more generally no more than about 2.4%, still yet even more generally no more than about 2.5%, still yet even more generally no more than about 2.6%, still yet even more generally no more than about 2.7%, still yet even more generally no more than about 2.8%, still yet even more generally no more than about 2.9%, still yet even more generally no more than about 3.0%, still yet even more generally no more than about 3.1%, still yet even more generally no more than about 3.2%, still yet even more generally no more than about 3.3%, still yet even more generally no more than about 3.4%, or yet still even more generally no more than about 3.5% of the flock fiber length is adhesively bonded to silicone adhesive layer230.

Some embodiments of the present disclosure include a molding process. In some embodiments, the appliqué and/or transfer can comprise a metalized polymeric film. The metalized polymeric film can comprise a metallized polyurethane polymeric film. In such embodiments, a silicone adhesive layer230can be positioned adjacent to and in contact with the metallized polymeric film and placed in and against a metal mold and then orientated in a heat transfer machine to crosslink the silicone adhesive230while forming the appliqué and/or transfer into a geometric shape. The metalized polymeric film appliqué and/or transfer can further comprise flock (or other such decorative element such as woven or knitted textiles) a three-dimensional flocked (or textile) image can be formed. More specifically the metallized polymeric film and the one or more of flock and woven and/or knitted textile, can be combined and heat-cured in a mold so that the silicone adhesive layer230is formed into a shape as it is cured. It can be appreciated, that the flocked image can be dimensionally heat-formed in three-dimensions and that the three-dimensional shape. can be retained its shape. Moreover, the three-dimensional shape is not substantially affected by subsequent exposure to heat or pressure. Examples of metallized polymeric elements include without limitation European Publication No. 0587403, filed Sep. 7, 1993, European Publication No. 0724948, filed Feb. 6, 1996, European Publication No. 1813416, filed Sep. 29, 2005, European Publication No. 2556967, filed Jun. 6, 2010, U.S. Pat. No. 5,143,672, filed Dec. 20, 1988, U.S. Pat. No. 5,520,988, filed Nov. 12, 1993, U.S. Pat. No. 5,589,022, filed Jun. 5, 1995, U.S. Pat. No. 5,599,416, filed May 12, 1995, U.S. Pat. No. 5,677,037, filed Nov. 25, 1996, U.S. Pat. No. 5,834,037, filed Dec. 23, 1996, U.S. Pat. No. 6,103,390, filed Feb. 20, 1998, U.S. Pat. No. 6,309,582, filed Nov. 2, 1998, U.S. Pat. No. 7,105,072, filed Feb. 25, 2002, U.S. Pat. No. 7,976,762, filed Aug. 16, 2002, U.S. Pat. No. 7,799,164, filed Jul. 27, 2006, U.S. Pat. No. 8,110,059, filed May 11, 2007, U.S. Pat. No. 8,859,461, filed Jan. 24, 2012, U.S. Pat. No. 9,193,214, filed Oct. 14, 2013, U.S. Patent Publication No. 2013/0068376, filed Nov. 19, 2012, and U.S. Patent Publication No. 2014/0332146, filed Jun. 11, 2014, all of which are incorporated in their entirety herein by this reference.

Further embodiments can include a cured silicone adhesive layer230having an elasticity from about 300 to 1,000 percent. Some embodiments can include a flocked transfer having an elasticity from about 300 to 1,000 percent. Some embodiments can include a flocked transfer having a cured silicone adhesive and an elasticity from about 300 to 1,000 percent.

Some embodiments include a screen printable silicone adhesive that commonly has a cure time of from about 45 to about 75 seconds, more commonly of about 60 seconds.

The pressure sensitive adhesive250can be selected such that the bonding force between the pressure sensitive adhesive250and the plurality of flock fibers240is less than the bonding force between the silicone adhesive layer230and the plurality of flock fibers240. The pressure sensitive adhesive250can be any adhesive that adheres more strongly to the release sheet210than the plurality of flock fibers240but adheres to both enough to hold them together. For example, the pressure sensitive adhesive250may 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. Generally, the pressure sensitive adhesive250can be a water-based adhesive, that is the pressure sensitive adhesive250is one or more of dispersed, dissolved, suspended or emulsified within water.

It is believed that after removing the release sheet210from flock transfer600a residual amount of the pressure sensitive adhesive250remains on the flock fiber240. It is further believed that the residual amount of the pressure sensitive adhesive250remaining on the flock fiber negatively effects the ability of the flock fibers240to adhere to an adhesive. The direct flock products of the present invention overall this limitation.

The plurality of flock fibers240may be formed from any natural or synthetic material. Synthetic material can include, without limitation, one or more of vinyl, rayon, nylon, polyamide, polyester, acrylic, and a natural material. The polyester can comprise a terephthalate polymers, such as poly(ethylene terephthalate) and poly(cyclohexylene-dimethylene terephthalate). The natural material can be one or more of cotton and wool. In some embodiments, a conductive coating or finish can be applied continuously or discontinuously over the exterior surface of the flock fibers240. The conductive coating can permit the flock fibers102to retain an electrical charge.

The flock fibers240can be pre-colored (yarn-dyed, by a dye sublimation process, or spun dyed) before contacting one or more of the pressure sensitive adhesive250or the silicone adhesive layer230or after the release sheet210is removed.

At least most, or commonly at least about 75%, and more commonly all, of the flock fibers240can have a denier of typically of no more than about 60, more typically of no more than about 25, or even more typically no more than about 5. The flock fibers240generally have a denier from about 1.5 to about 3.5. Commonly, the flock fibers240can have a titre ranging from about 0.5 to about 20 Dtex (from about 0.5 to about 20×10-7 Kg/m) and more commonly from about 0.9 Dtex to about 6 Dtex. The length of at least most, and typically at least about 75%, of the flock fibers240is generally no more than about 4 mm, more generally no more than about 2 mm, and even more generally no more than about 1 mm. Usually, the flock fibers240have a length ranging from about 0.3 to about 3.5 mm. The flock fiber240placement density relative to the surface area of the flocked portion (on which the flock is deposited) of the flock product and/or flock transfer is generally about 50% fibers/in2, more generally at least about 60% fibers/in2, and even more generally at least about 70% fibers/in2 of the flocked surface area.

Three silicone adhesive formulations230A-230F were evaluated. The first silicone adhesive230A had excellent integrity; however, when screen printed it was stringy. The stringy nature of the first silicone adhesive230A rendered it unsuitable for screen printing. The second silicone adhesive230B was more screen printable but it had less adhesive integrity than the first silicone adhesive230A. Furthermore, the second silicone adhesive230B had low tensile strength and was too soft. The third silicone adhesive230C had a low viscosity, it would not sit up on top of flock fibers and sank down into the flock fiber layer. Three other silicone adhesive formulations230D,230E and230F were evaluated. Each of formulations230D,230E and230F comprised a mixture of methyltrimethoxysilane treated with aluminum oxide, methylvinyl siloxane hydroxy-terminated reaction product with glycidoxyproply trimethoxysilance and methyltrioxysilane-treated aluminum oxide. The silicone adhesive formulations230E and230F further include, respectively, an ultra-high molecular weight additive and silica powder thickener, the silicone adhesive formulation230D did not have either of the ultra-high molecular weight additive and silica powder thickener. The silicone adhesive230D is a suitable base product. However, silicone adhesive230D is soft, weak and time; it is generally printed down into the textile rather than standup on top of the textile. The addition of ultra-high molecular weight additive and silica powder thickener to the silicone adhesive formulation introduced entrained air into the silicone adhesive which caused the adhesive to have stringiness when screen-printed. As such the screen print quality poor.

Some formulations of the silicone adhesive230can a rheology modifier comprising one or more of silicone dioxide (SiO2), titanium dioxide (TiO2), and aluminum oxide (Al2O3). In some embodiments, the silicone adhesive230can include a rheology modifier comprising fumed silica. The silicone adhesive formulation can commonly have from about 0.01 to about 0.1 wt %, more commonly from about 0.1 to about 1.0 wt %; even more commonly from about 1.0 to about 5.02 wt %, yet even more commonly from about 5.0 to about 10.0 wt %, or still yet even more commonly from about 10.0 to about 25.0 wt % of the rheology modifier.

In some embodiments, the screen printable pot life of the two-component silicone adhesive after mixing of the two components is commonly from about one to about six hours, more commonly from about one and half to about five hours, even more commonly from about 2 to about four hours.

The plurality of flock fibers240in anyone of the direct flocked product90, flocked product200, flocked product400or flock transfer product600can be adhered to a substrate290by the silicone adhesive layer230. That is, substrate290can be in contact with and adhered to one or more of the silicone adhesive layer230and thermo-adhesive220. The substrate290can comprise any material. Non-limiting examples of suitable substrates290materials can comprise metallic materials, synthetic or natural polymeric materials, glass-based materials, ceramic materials, leather-based materials and combinations thereof. Furthermore, the substrate290may or may not be stretchable and/or have elastic properties.

Generally, the substrate290is a textile material. The textile material can be woven, nonwoven, or knit. More generally, the substrate290can be a stretchable and/or elastomeric textile material, such as stretchable and/or elastomeric fabric and/or apparel item. Even more generally, the substrate290can comprise one or more of an elastomeric polymeric material and a stretchable-knit and/or stretchable-woven material. It can be appreciated that when the anyone of the direct flocked product90, flocked product200, flocked product400or flock transfer product600is adhered to a textile material by one or more of the silicone adhesive230and thermo-adhesive220, the adhesive bond between the flock fibers240and substrate290is substantially strong to withstand industrial wash testing. Generally, the adhesive bond between the flock fibers240and substrate290can withstand one of more than 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 350, 400, 450, 500, 600, 700, 800, 900, or 1,000 industrial wash cycles without substantial delamination of adhesive bond.

In some embodiments, the stretchable and/or elastomeric material can be stretched to at least about 1.2 times of its original length in at least one direction, at least about 1.5 times of its original length in at least one direction, at least about 1.8 times of its original length in at least one direction or at least about 2.0 times of its original length in at least one direction. In some embodiments, the stretchable and/or elastomeric fabric post-stretched length, in the stretched direction, deviates from the pre-stretched length, in the stretched direction, commonly by no more than about 5%, more commonly by no more than about 2%, even more commonly by no more than about 1%, even more commonly by no more than about 0.5%, and even more commonly by no more than about 0.2%.

The substrate290can have a single surface or a plurality of surfaces. Non-limiting examples of a single-surfaced substrate290are substrates having one of a generally spherical, circular-donut, and elliptical-donut shapes. Non-limiting examples of substrate shapes having a plurality of substrate surfaces are substrates substantially resembling one of a cube, rectangular-box and tetrahedral shapes.

In some embodiments, the substrate290can comprise a substantially thick textile material, such as, but not limited to, a high pile, or loosely and/or bulky woven or knitted textile. Non-limiting examples of a high pile substrate are sweatbands and terrycloth items. The substantially thick textile material can provide a stable foundation and/or base for adhering any of the direct flocked product90, flocked product200, flocked product400or flock transfer product600.

Typically, the direct flocked product90, flocked product200, flocked product400and/or flock transfer product600adhered to a substrate290by a substantially flexible and/or elastic silicone adhesive layer230is substantially free of one or more of splitting, delamination and distortion after applying at least one cycle of an elongation or angular stress to the substrate290. More typically, more typically the direct flocked product90, flocked appliqué200, flocked appliqué400or flock transfer product600adhered to a substrate290by a substantially flexible and/or elastic silicone adhesive layer230is substantially free of one or more of splitting, delamination and distortion after repeatability applying an elongation and/or angular stresses to the substrate290at least 100 times, even more is substantially free of one or more of splitting, delamination and distortion after repeatability applying elongation and/or angular stresses to the substrate290at least 500 times, yet even more typically is substantially free of one or more of splitting, delamination and distortion after repeatability applying elongation and/or angular stresses to the substrate290at least 1,000 times, still yet even more typically is substantially free of one or more of splitting, delamination and distortion after repeatability applying elongation and/or angular stresses to the substrate290at least 10,000 times, or still yet even more typically is substantially free of one or more of splitting, delamination and distortion after repeatability applying elongation and/or angular stresses to the substrate290at least 100,000 times.

In some embodiments, the cured silicone adhesive layer230has elastomeric properties. Generally, the cured silicone adhesive layer230can have an elongation, without one or more of fracturing or rupture, of more than about 200%, more generally more than about 300%, even more generally of more than about 500%, yet even more generally of more than about 750%, and still yet even more commonly of more than about 1,000%. Typically, the cured silicon adhesive layer230can have a recovery after elongation of one of more than about 75%, more typically of more than about 90%, even more typically of more than about 95%, yet even more typically of more than about 98%, still yet even more typically of more than about 99%, or yet still even more typically of substantially about 100%. The elongation recovery is the percent of the film's shape retained after the film is stretched to 100% or more of its original length at a rate of 30 inches per minute and the stretched film allowed to retract freely for 1 minute.

Generally, the silicone adhesive layer230is contact with and adhered to the substrate290. The silicone adhesive layer230generally one of penetrates and/or contacts at least some of the substrate290. By way of a non-limiting example, the substrate290can have a pile thickness Tpile. Typically, the silicone second adhesive layer230in contact with the substrate290has an adhesive thickness of about equal to Tadh, more typically the adhesive in contact with the substrate has a thickness of no more than about one-half of Tadh, even more typically the adhesive in contact with the substrate has a thickness of no more than about one-quarter of Tadh, yet even more typically the adhesive in contact with the substrate has a thickness of no more than about one-eighth of Tadh, still yet even more typically the adhesive in contact with the substrate has a thickness of no more than about one-sixteenth of Tadh, still yet even more typically the adhesive in contact with the substrate has a thickness of no more than about one-thirty-second of Tadh, still yet even more typically the adhesive in contact with the substrate has a thickness of no more than about one-sixty-fourth of Tadh, or still yet more typically the adhesive in contact with the substrate has a thickness of no more than about one-one hundredth twenty-eighth of Tadh.

The silicone adhesive layer is generally substantially continuously distributed over areal the first extent. Although the first areal extent is shown as being conterminous, this is not necessarily the case. In some embodiments, the silicone adhesive layer is substantially elastic and continuous over the first areal extent. The silicone adhesive layer can have opposing upper and lower silicone adhesive surfaces and a silicone adhesive film thickness. In some embodiments, the silicone adhesive layer can be substantially free of holes and/or voids, respectively, extending through the adhesive film thickness. That is, the silicone adhesive layer is substantially continuously distributed and substantially free of holes and/or voids extending through its respective film thicknesses and throughout its areal extents. Substantially free of holes and/or voids means that on a macroscopic level (that is, not a microscopic and/or molecular level) the silicone adhesive layer thicknesses is greater than zero substantially over at least most, if not all, locations of the areal extent. Stated another way, in some embodiments, the silicone adhesive layer has fewer than about 10, even more generally, no more than about 5, and even more generally, no more than about 1, and even more generally, no holes and/or voids, visible to an un-aided eye of an ordinary human observer, per square centimeter surface area of the areal extent. In some embodiments, the silicone adhesive layer has no more than about 1 hole and/or void visible to an un-aided eye of ordinary human observer over the surface area of the areal extent 2800. In another embodiment, the upper and lower silicone adhesive surfaces are substantially free of interfacial voids and/or valleys. That is, the upper and lower silicone adhesive surfaces are substantially planar and/or flat.

A plurality of film thickness values measured over the areal extent 2800 for the silicone adhesive layer230can be represented by a Gaussian distribution, the Gaussian distribution typically has a “t” value (FIG. 11). In some embodiments, the Gaussian “t” value for the silicone adhesive layer230is typically less than about 4, more typically less than about 2, even more typically less than about 1, and even more typically less than about 0.5.

The silicone adhesive layer generally has elastomeric properties. More generally, the elastomeric properties of the silicone adhesive layer are substantially independent of any discontinuities that may exist within the adhesive layer. That is, the silicone adhesive is substantially elastomeric with or without discontinuities present within the silicone adhesive layer.

The phrase “substantially continuous” means that a film or layer substantially covers and/or coats the entire areal interface2800of a surface over which the film or layer is said to be substantially continuous. Moreover, “substantially continuous” means the film or layer is substantially free of holes and/or voids.

Any of the direct flocked product90, flocked product200, flocked product400or flock transfer product600can further comprise a metalized polymeric film. The metalized polymeric film can have opposing embossed and non-embossed surfaces. The non-embossed surface is usually substantially planar. The embossed surface is commonly substantially non-planar and dimensionalized. Generally, the embossed surface has a metallic luster and color and one or more valleys, ridges, facets, and featherings, which gives the embossed surface the appearance of being an engraved metallic surface. The embossed surface can contain one or more decorative elements. The one or more decorative elements can include simulated carved artwork having fine-line details, such as, scrolls, feathers, alpha-numeric characters, leaves, and such. Furthermore, the metalized polymeric film is commonly free of any cellulosic polymeric materials. Typically, the metalized polymeric film contains a thermoplastic synthetic resin film. More typically, the thermoplastic synthetic resin film is one of vinyl chloride, polyurethane or mixture thereof. The thermoplastic synthetic resin film has opposing upper and lower surfaces. A metal layer can be position on the lower surface. Generally, the metal layer is deposited by known metal vacuum evaporation methods. The metal layer can comprise aluminum, chromium, or titanium. When the metalized polymeric layer is to have the appearance of gold, the metal layer can comprise aluminum, and a gold-color ink layer can be placed on the aluminum metal layer. A transparent vinyl chloride film can be laminated on the gold-color ink layer.

In some embodiments, the metalized polymeric film can be one or more of substantially non-rigid, elastic and flexible. In such embodiments, the metalized polymeric film commonly has an elongation value in at least one direction from about 105% to about 1,000%, more commonly from about 110% to about 500%, even more commonly from about 120% to about 200%, yet even more from about 130% to about 190%, still yet even more commonly from about 150% to about 200%.

In some embodiments, the metalized polymeric film can be one or more of substantially rigid, inflexible, and inelastic. More specifically, the metalized polymeric film can be substantially rigid, inflexible, and inelastic. In some embodiments, the metalized polymeric film can comprise a metallic film. Generally, the one or more of the metalized polymeric film can comprise a metallic film and a polymeric material, more preferably a metallic film supported by the polymeric material. A non-limiting example of the metalized polymeric film comprises polyethylene terphthalate having a metallic film on at least one side of polymeric film.

Generally, any of the direct flocked product90, flocked product200, flocked product400or flock transfer product600having a metalized polymer film can be substantially resistant to one or both of splitting and delamination of the flock fibers240. More specifically, the metalized polymeric film substantially reduces splitting and/or delamination of the flock fibers240from a substantially elastomeric and/or stretchable substrate290. The metalized polymeric film can reduce stresses imparted to the flock fibers240when stress is applied to a substantially elastomeric and/or stretchable substrate290. More specifically, when a stress is applied to the elastomeric and/or stretchable substrate290, the applied stress can affect the adherence of the flock fibers240to the substrate290. Furthermore, the a substantially flexible and/or elastic silicone adhesive layer230can reduce distortion of the direct flocked product90, flocked product200, flocked product400and/or flock transfer product600when a stress is applied to the substrate290. The reduced distortion of the direct flocked product90, flocked product200, flocked product400and/or flock transfer product600can be advantageous in retaining its, more specifically the artistic integrity and value of the direct flocked product90, flocked product200, flocked product400and/or flock transfer product600.

FIG. 12depicts system1200for making some of flock products of the present disclosure. The system includes a device (not depicted) for translating a continuous thermo-set sheet1210from one the various units comprising the system. The continuous thermo-set sheet1210can comprise one of a thermoplastic adhesive, a thermoset adhesive or combination of thermoplastic and thermoset adhesives. The process1200can include an adhesive contacting unit1230for applying a silicone adhesive with the continuous thermo-set sheet1210. The adhesive contacting unit1230can be one of a screen printing unit, a curtain unit, a blade applicator, a spray coater, a kiss roller, a brush applicator, or other liquid applicators know to those of skill in the art. Typically, the adhesive contacting unit1230comprises a screen printing unit. The process1200can include one or more flocking units1240. Generally, each flocking unit1240contacts a different colored flock with to the silicone adhesive printed on the thermo-set sheet1210. The process1200can include a free flock removal unit1260. The free flock removal unit1260removes any flock not adhered to the silicone adhesive. The free flock removal unit1260commonly comprises one or more of vacuum unit and vibrator units. The vibrator unit typically shakes and/or beats the continuous thermo-set sheet1210. The one or more flocking units1240are usually positioned between the free flock removal unit1250and the adhesive contacting unit1230. The vacuum unit commonly removes the free flock by a suction and/or reduced pressure. The process1200can include a curing unit1260. The free flock removal unit1260is typically located between the curing unit1260and the one or more flocking units1240. The curing unit1260generally applies sufficient thermal energy to silicone adhesive to cure it. The process1200can include a laser cutting unit1270. The curing1260is generally positioned between the laser cutting unit1270and the free flock removal unit1250. The laser cutting unit1270generally forms the flock adhered to the thermo-set sheet by the silicone adhesive film into a flocked product that can assembled into configuration that can be configured into an automated appliqué application process line. For example, the laser cutting unit1270can form and configure the flock flocks into container that can be configure into an automated appliqué application process line.

FIG. 13depicts a process for making a flock product1300. InFIG. 13, the flock product is a silicone flock product. In various embodiments, the silicone can be used in place of one or more of the thermoplastic components (including any one or more of the polyurethane components) described herein. The flock process1300can comprise a hot-melt adhesive298, a silicone adhesive layer296, and a metalized layer (e.g., a metal layer294between two polyurethane layers292) that form a molded shape257. The molded shape257may be any shape and/or size, and is not limited by the present disclosure.

To form the molded shape257, the layers (e.g., the hot-melt adhesive298, the silicone adhesive layer296, and the metalized layer294/292) may be placed into a mold255that is heated (e.g., by a heat press, which may include a high-frequency heat source such as a radio-frequency machine253) source to cause the layers to be molded. The amount of heat applied (including a temperature and a length of time, for example) can vary, and may be any amount that causes one or more of the layers to solidify. For example, the heat may be at about 163° C. (325° F.) for about 3 minutes.

For example, the heat may have a temperature of typically about 150° C. to about 180° C., more typically about 155° C. to about 175° C., more typically about 160° C. to about 170° C., and more typically about 162° C. to about 165° C., and more typically about 163° C. Also, the heat may be applied for typically about 150 seconds to about 210 seconds, more typically about 160 seconds to about 200 seconds, more typically about 170 seconds to about 190 seconds, and more typically about 175 seconds to about 185 seconds, and more typically about 180 seconds.

In various embodiments, the hot-melt adhesive298may be positioned first, with the silicone adhesive layer296above it, and the metalized layer294/292above the silicone adhesive layer296. The metalized layer294/292may be a top layer, and the hot-melt adhesive298may be a bottom layer. The silicone adhesive layer296may be positioned between the hot-melt adhesive298and the metalized layer294/292.

The hot-melt adhesive298may correspond to any one or more of the hot-melt adhesives described herein. In certain aspects, the hot-melt adhesive298can be in contact with the silicone adhesive layer296. In other aspects, the hot-melt adhesive298can be in contact with both of the silicone adhesive layer296and the metalized layer294/292.

The silicone adhesive layer296may correspond to any one or more of the silicone adhesive layers as described herein. In addition, the silicone adhesive layer296may be substituted for any one or more of the polyurethane layer(s) described herein. The silicone adhesive layer296may be a wet film that is in contact with (e.g., spread over or coated onto) the hot-melt adhesive298prior to laying down a layer of the metalized layer294-292. In certain aspects, the silicone adhesive layer296can be in contact with the hot-melt adhesive298. In further aspects, the silicone adhesive layer296can be in contact with both of the hot-melt adhesive298and the metalized layer294/292. In still further aspects, the silicone adhesive layer296can be in contact with the metalized layer294/292.

The metalized layer294/292may be one or more layers, and any of the one or more layers can correspond to the metalized polymeric film (and metalized polymer film) as described herein. For example, the metalized layer294/292may include only one metal layer294or multiple metal layers294, and only one polyurethane layer292or multiple polyurethane layers292, in any configuration. In addition, the one or more layers of the metalized polymeric film can include any of the layers of the metallic film and the polymeric material, and does not have to have any, some or all of the polymeric material and/or layers as described herein. In some aspects, the metalized polymeric film can include only a metallic film, or only a metallic film and a single polymeric material, or one or more metallic films together with one or more polymeric materials. In certain aspects, the metalized layer294/292can be in contact with the silicone adhesive layer296. In other aspects, the metalized layer294/292can be in contact with both of the silicone adhesive layer296and the hot-melt adhesive298. In further aspects, the metalized layer294/292can be in contact with the hot-melt adhesive298.

Various configurations of the layers are possible to make the molded shape257. For example, the silicone adhesive layer296may be in contact with and adhered to the hot-melt adhesive298. The hot-melt adhesive298and the metalized layer294/292(and any one or more of the layers thereof) may have any thickness. The silicone second adhesive layer230in contact with the hot-melt adhesive298may have any thickness. For example, the silicon adhesive layer296may have a thickness of about equal to Tadh, more typically the silicon adhesive layer296has a thickness of no more than about one-half of Tadh, even more typically the silicon adhesive layer296has a thickness of no more than about one-quarter of Tadh, yet even more typically the silicon adhesive layer296has a thickness of no more than about one-eighth of Tadh, still yet even more typically the silicon adhesive layer296has a thickness of no more than about one-sixteenth of Tadh, still yet even more typically the silicon adhesive layer296has a thickness of no more than about one-thirty-second of Tadh, still yet even more typically the silicon adhesive layer296has a thickness of no more than about one-sixty-fourth of Tadh, or still yet more typically the silicon adhesive layer296has a thickness of no more than about one-one hundredth twenty-eighth of Tadh.

The silicone adhesive layer296may be generally substantially continuously distributed over the hot-melt adhesive298. The silicone adhesive layer296may be in contact with and adhered to the hot-melt adhesive298. The silicone adhesive layer296may be in contact with and adhered to the metalized layer294/292. The silicone adhesive layer296may be generally substantially continuously distributed over the hot-melt adhesive298. The metalized layer294/292may be generally substantially continuously distributed over the silicone adhesive layer296.

In some embodiments, one or more of the layers (e.g., the hot-melt adhesive298, the silicone adhesive layer296, and the metalized layer294/292) may be in liquid form prior to being heated, and then in solid form after at least some heat is applied. The heat applied may cause one or more of the layers to expand and push the silicone into the molded shape257. Although the layers may be liquid prior to having heat applied, one or more of the layers (and/or materials in the layers) can begin to solidify to hold the molded shape257. For example, the silicone adhesive layer296may solidify in the form of the molded shape257. In various aspects, the chemical changes of one or more of the layers include catalyzation that causes the phase change of the layers. In certain embodiments, additional heat may be applied to the molded shape257after the molded shape257is formed. For example, the molded shape257may be removed from the initial heat (e.g., removed from the radio-frequency machine253) and placed into subsequent heat, e.g., placed into a conveyor oven. The additional application of heat may finish the catalyzation of the one or more of the layers and solidify the molded shape257.

The heat generally accelerates the cure of the silicone adhesive layer and commonly cures at least about 50% or more of the silicone adhesive layer, more commonly at least about 60% or more of silicone adhesive layer, even more commonly at least about 70% or more of the silicone adhesive layer, yet even more commonly at least about 80% or more of the silicone adhesive layer, still yet even more commonly at least about 90% or more of the silicone adhesive layer, and yet still even more commonly at least about 99.9% or more of the silicone adhesive layer.

In various embodiments, the mold255may be a metal mold and/or die made of any suitable material, including metals such as brass or any other suitable material. The mold may include a shape256used to form the molded shape257, including various edges to cut or crimp one or more of the materials, such as a fuse edge258and a cut edge259. The high frequency molding process is commonly a radio frequency molding process as described herein.

In various embodiments, the catalyzation solidifies the molded shape257enough to be able to remove the molded shape257from the radio-frequency machine253while the molded shape257maintains its form. In some aspects, properties of any one or more of the metal layer(s)294and the polyurethane layer(s)292may assist with the molded shape257maintaining its form. The catalyzation may take additional time to complete after being heated (e.g., by the radio-frequency machine253and/or any other heating method) for the properties to finalize; for example, for the form of the molded shape257to become permanent, and/or for the adhesion of the molded shape257to become permanent. It can be appreciated that the cured silicone adhesive is substantially a thermoset adhesive with substantially little, if any, thermoplastic properties. The thermoset properties of the silicone adhesive allow the formed articles to be applied to a substrate with heat and pressure and not be substantially deformed by either the heat or pressure. Also, the silicone adhesive substantially eliminates any air bubbles within the thermoformed article. Moreover, thermoformed articles having a silicone adhesive, compared to radio frequency formed articles lacking a silicone adhesive, are substantially free of fine rigids needed to provide structural integrity of article. The fine rigids are generally required because of the bubble formation within the article arising from the radio frequency molding. It is believed that radio frequency molded articles having silicone adhesive lack such bubbles and, therefore, do not require, or require substantially less, structural rigids.

The catalyzation that occurs to the one or more of the layers may form adhesion bonds with improved strength. For example, the silicone adhesive layer296may form strong adhesion bonds with each of the hot-melt adhesive298and the metalized layer294/292. Alternatively, the silicone adhesive layer296may form strong adhesion bonds with one of the hot-melt adhesive298and/or the metalized layer294/292. In various embodiments, the silicone adhesive layer296is placed into contact with layers/materials to which a bond is desired prior to heating and/or catalyzation. Such methods may enable adhesion bonds with improved strength; however, after the silicone has been catalyzed, it may not adhere to other materials. Such features may be advantageous because, for example, the final molded form (e.g., after catalyzation) may be applied to materials by the use of heat without deforming the shape/form of the final molded form, and also the molded form may be used in industrial environments, including on industrial work uniforms.

While the figures herein have been discussed and illustrated in relation to a particular arrangement of components and/or a particular sequence of events, it should be appreciated that changes, additions, and omissions to the components and sequences can occur without materially affecting the operation of the disclosed embodiments, configuration, and aspects. For example, inFIG. 13, the positions of the hot-melt adhesive298and the silicone adhesive layer296may be changed such that the silicone adhesive layer296is under the hot-melt adhesive298and the hot-melt adhesive298is in contact with one or more components of the metalized layer294/292. Further, various materials, layers, and processes are optional.

The use of the silicone adhesive layer296as described inFIG. 13may have several advantages. For example, it may provide: a suitable print viscosity, a desirable shrinkage, a desirable adhesion, a desirable amount of hot-melt adhesive that may be used, a desirable “open time” or “pot-life”, a desirable opacity, a desirable cure time, and a desirable heat-resistivity (including no need to use a special pressure foam to heat press the molded form).

These and other advantages will be apparent from the disclosure of the disclosure contained herein.