FLOCKED PRODUCTS HAVING A SILICONE ADHESIVE COMPOSITION AND METHODS OF MAKING AND USING THE SAME
20180171192 · 2018-06-21
Inventors
Cpc classification
C08G77/20
CHEMISTRY; METALLURGY
C09J2301/208
CHEMISTRY; METALLURGY
B05D1/286
PERFORMING OPERATIONS; TRANSPORTING
C08K5/56
CHEMISTRY; METALLURGY
C08L83/00
CHEMISTRY; METALLURGY
B05D2518/12
PERFORMING OPERATIONS; TRANSPORTING
C08L83/00
CHEMISTRY; METALLURGY
C08K5/56
CHEMISTRY; METALLURGY
B05D1/32
PERFORMING OPERATIONS; TRANSPORTING
C09J5/00
CHEMISTRY; METALLURGY
International classification
B05D1/32
PERFORMING OPERATIONS; TRANSPORTING
C09J5/00
CHEMISTRY; METALLURGY
Abstract
This invention relates generally to flocked articles and methods for making the same, more particularly to flocked products having a silicone adhesive and methods for making and using the same.
Claims
1. A flocked product, comprising: 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, wherein the silicone adhesive layer comprises: (a) a catalyst; (b) a siloxane; (c) a vinyl siloxane; and (c) a rheology modifier.
2. The flocked product of claim 1, wherein the catalyst comprises platinum.
3. The flocked product of claim 1, wherein the thermo-adhesive layer comprises one of a thermoplastic adhesive, a thermoset adhesive, or combination of a thermoplastic and thermoset adhesives.
4. The flocked product of claim 1, wherein the vinyl siloxane comprises one or more of vinyl functionality, 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.
5. The flocked product of claim 1, where the siloxane comprises one or more a polysiloxane, a 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.
6. The flocked product of claim 1, wherein the rheology modifier comprises fumed silica.
7. The flocked product of claim 1, wherein the silicone adhesive layer further comprises a coupling agent, and wherein the coupling agent comprises one or more of an organosilicone coupling agent, organotitanium coupling agent, or a combination of oranganosilicone and organotitanium coupling agents, wherein the orangosilicone coupling has the general structure of YRSi(X).sub.3, wherein the organotitanium coupling agent has the general structure of the YRTi(X).sub.3, wherein Y denotes a functional group selected from the group consisting essentially of vinyl and epoxy, amino group, and wherein X is selected from the group consisting essentially of chlorine, alkoxy, and acetoxy group.
8. A method of making the flock product of claim 1, comprising: providing the thermo-adhesive layer; contacting a silicone adhesive with the thermo-adhesive layer, wherein the contacting comprises screen printing the silicone adhesive layer on 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.
9. A flocked product, comprising: a silicone adhesive layer having: (a) a catalyst; (b) a siloxane; (c) a vinyl siloxane; and (c) a rheology modifier; a flock layer having a plurality of flock fibers; and a release sheet, wherein the silicone adhesive layer is positioned between the flock layer and release sheet, and wherein the silicone adhesive is adhered to the release sheet and flock layer.
10. The flocked product of claim 9, where the flock layer comprises a plurality of fibers having opposing first and second ends, wherein the second ends of flock fibers are adhered to silicone adhesive layer.
11. The flocked product of claim 9, where the carrier sheet has a pressure sensitive adhesive, where the pressure sensitive adhesive is positioned between the carrier sheet and the flock layer, and wherein the first ends of the flock fibers are adhered to the pressure sensitive adhesive.
12. The flocked product of claim 9, wherein the vinyl siloxane comprises one or more of vinyl functionality, 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, and wherein the the siloxane comprises one or more a poly siloxane, a poly alkyl 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.
13. The flocked product of claim 9, wherein the rheology modifier comprises fumed silica, and wherein the silicone adhesive layer further comprises a coupling agent, and wherein the coupling agent comprises one or more of an organosilicone coupling agent, organotitanium coupling agent, or a combination of oranganosilicone and organotitanium coupling agents, wherein the orangosilicone coupling has the general structure of YRSi(X).sub.3, wherein the organotitanium coupling agent has the general structure of the YRTi(X).sub.3, wherein Y denotes a functional group selected from the group consisting essentially of vinyl and epoxy, amino group, and wherein X is selected from the group consisting essentially of chlorine, alkoxy, and acetoxy group.
14. The flocked product of claim 9, further comprising: a thermo-adhesive layer comprising one or more of a thermoset adhesive, or combination of a thermoplastic and thermoset adhesives, and wherein the first ends of flock fibers are adhered to the thermo-adhesive layer.
15. A method of making the flock product of claim 9, comprising: providing the release sheet; contacting a silicone adhesive with the release sheet, wherein the contacting comprises screen printing the silicone adhesive layer on the release sheet; 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.
16. A flock transfer, comprising: a thermo-adhesive layer; a flock layer; a silicone adhesive layer positioned between the thermo-adhesive layer and the flock layer, wherein the silicone adhesive layer comprises: (a) a catalyst; (b) a siloxane; (c) a vinyl siloxane; and (c) a rheology modifier; and a carrier sheet, wherein the flock layer is positioned between the carrier sheet and the silicone adhesive layer.
17. The flock transfer of claim 16, wherein the thermo-adhesive layer comprising one or more of a thermoset adhesive, or combination of a thermoplastic and thermoset adhesives, and wherein the first ends of flock fibers are adhered to the thermo-adhesive layer.
18. The flock transfer of claim 16, where the flock layer comprises a plurality of fibers having opposing first and second ends, wherein the first ends of the flock fibers are adhered to the carrier sheet, and wherein the second ends of flock fibers are adhered to silicone adhesive layer.
19. The flock transfer of claim 16, further comprising a pressure sensitive adhesive positioned between the flock layer and the carrier sheet, wherein the first fiber ends are in contact with and adhered to the pressure sensitive adhesive.
20. The flock transfer of claim 16, wherein the rheology modifier comprises fumed silica, and wherein the silicone adhesive layer further comprises a coupling agent, and wherein the coupling agent comprises one or more of an organosilicone coupling agent, organotitanium coupling agent, or a combination of oranganosilicone and organotitanium coupling agents, wherein the orangosilicone coupling has the general structure of YRSi(X).sub.3, wherein the organotitanium coupling agent has the general structure of the YRTi(X).sub.3, wherein Y denotes a functional group selected from the group consisting essentially of vinyl and epoxy, amino group, and wherein X is selected from the group consisting essentially of chlorine, alkoxy, and acetoxy group.
21. The flock transfer of claim 16, wherein the vinyl siloxane comprises one or more of vinyl functionality, 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, and wherein the the siloxane comprises one or more a polysiloxane, a poly alkyl 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.
22. A method of making the flock product of claim 16, comprising: providing the release sheet; contacting the flock fibers the release sheet, wherein the contacting adheres the flock fibers to the release sheet; contacting a silicone adhesive with the flock fibers; and contacting a thermo-adhesive with the free surface of the silicone adhesive.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0060] Any drawings in the attached are incorporated into and form a part of the specification to illustrate several examples of the present invention(s). These drawings, together with the description, explain the principles of the invention(s). The drawings simply illustrate preferred and alternative examples of how the invention(s) can be made and used and are not to be construed as limiting the invention(s) to only the illustrated and described examples. Further features and advantages will become apparent from the following, more detailed, description of the various embodiments of the invention(s), as illustrated by the drawings referenced below.
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DETAILED DESCRIPTION
[0074] 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.
[0075] 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.
[0076] 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.
[0077] 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 polyalkyl and/or polyaryl siloxanes are generally silyl terminated.
[0078] Typically, the vinyl polyalkyl siloxane and polyaryl siloxane can comprise one or more of vinyl functionality, methylvinylsiloxane, methylvinylsiloxane, vinylsiloxane, (dimethylvinyl-terminated) dimethyl siloxane, (vinyldimethyl-terminated) siloxane, octamethylcyclotetrasilocane, (vinylphenylmethyl-terminated) dimethyl siloxane, (divinylmethyl-terminated) dimethyl siloxane, vinyldimethyl siloxane, (cyclicvinylemethyl) dimethyl siloxane, vinylmethylcyclosiloxane, trifluoropropylmethylcyclosiloxane, methyhyrdrocyclosiloxane, hexamethyldisiloxane, divinyltetramethylsiloxane, and tetramethyldisiloxane.
[0079] 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 -[SiR.sub.2O]- 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):
##STR00001##
[0080] 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 polysiloxane, 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.
[0081] 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 -[SiR.sub.2O]- are typically form about 10 to about 850. A non-limiting example of a polyalkyl siloxane is trimethylsilyl terminated poly(dimethylsioxane-co-methylhydrosiloxane), (II):
##STR00002##
[0082] 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, hydrosilicone, 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.
[0083] 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.
[0084] The silicone adhesive layer 230 can comprise one or more of a homopolymer, a copolymer, and a polymeric alloy. Generally, the silicone adhesive layer 230 comprises one or more of a siloxane and vinyl siloxane. More generally, the silicone adhesive layer 230 comprises 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 layer 230 comprises one or more of a siloxane and vinyl 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.
[0085] In some embodiments, the silicone adhesive layer 230 comprises one or more of a siloxane and vinyl siloxane polymerized and/or alloyed with one or more of acrylonitrile butadiene styrene, acrylic (PMMA), celluloid, cellulose acetate, cyclo-olefin copolymer, ethylene-vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), fluoroplastic (PTFE, FEP, PFA, CTFE, ECTFE, and/or ETFE), ionomer, liquid crystal polymer (LCP), polyacetal (POM and/or acetal), polyacrylate (acrylic), polyacrylonitrile (PAN or acrylonitrile), polyamide (PA or nylon), polyamide-imide (PAI), polyaryletherketone (PAEK and/or ketone), polybutadiene (PBD), polybutylene (PB), polybutylene terphthalate (PBT), polycaprolactone (PCL), polychlorotrifluoroethylene (PCTFE), polyethylene terephthalate (PET), polycycloheylene dimethylene terephthalate (PCT), polycarbonate (PC), polyhydroxylalkanoate (PHA), polyketone (PK), polyester, polyethylene(PE), polyetherketoneketone (PEKK), polyetherimide (PEI), polyethersulfone (PES), polysulfone, polyethlenechloriate (PEC), polyimide, polyacetic acid (PLA), polymethylpentene (PMP), polyphenylene oxide (PPO), polyphylene sulfide (PPS), polyphthalamide (PPA), polypropylen (PP), polystyrene (PS), polsulfone (PSU), polytrimethylen terphthalate (PTT), polyurethane (PU), polyvinyl acetate (PVA), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and styrene-acrylonitrile (SAN).
[0086] In some embodiments, the silicone adhesive layer 230 comprises one or more of a siloxane and vinyl siloxane polymerized and/or alloyed with one or more of acrylonitrile butadiene styrene, acrylic (PMMA), celluloid, cellulose acetate, cyclo-olefin copolymer, ethylene-vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), fluoroplastic (PTFE, FEP, PFA, CTFE, ECTFE, and/or ETFE), ionomer, liquid crystal polymer (LCP), polyacetal (POM and/or acetal), polyacrylate (acrylic), polyaryletherketone (PAEK and/or ketone), polybutadiene (PBD), polybutylene (PB), polybutylene terphthalate (PBT), polycaprolactone (PCL), polychlorotrifluoroethylene (PCTFE), polyethylene terephthalate (PET), polycycloheylene dimethylene terephthalate (PCT), polycarbonate (PC), polyhydroxylalkanoate (PHA), polyketone (PK), polyester, polyethylene(PE), polyetherketoneketone (PEKK), polyethlenechloriate (PEC), polyacetic acid (PLA), polymethylpentene (PMP), polyphenylene oxide (PPO), polystyrene (PS), polytrimethylen terphthalate (PTT), polyvinyl acetate (PVA), polyvinyl chloride (PVC), and polyvinylidene chloride (PVDC).
[0087] 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:
YRSi(X).sub.3; or
YRTi(X).sub.3.
Where Y denotes a functional group that links with organic materials, e.g. vinyl, epoxy, amino group and so on. X includes chlorine, alkoxy, and acetoxy group. It is believed that the Y functional group can link with one or more of the flock fibers, a thermoplastic adhesive, a thermoset adhesive, a hot melt adhesive, a substrate, and such. It is further believed that the X group reacts, when catalyzed by one or more of the platinum and peroxide catalyst, with one or more of silicone adhesive and silicone base. In other words, it is believed that the coupling agent further promotes and/or assists in the adhesion of the silicone adhesive layer to one or more of flock fibers, a thermoplastic adhesive, a thermoset adhesive, a hot melt adhesive, a substrate, and such. Non-limiting examples of silicone-containing coupling agents are: 3-(trimethoxysilyl) propyl acrylate, 3-[diethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl) propyl methacrylate, 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate, 3-[dimethoxy(methyl) silyl]propyl methacrylate, 3-(methoxydimethylsilyl)propyl acrylate, 3-(triethoxysilyl)propyl methacrylate, 3-(triallylsilyl)propyl acrylate, 3-(triallylsilyl)propyl methacrylate, amyltrichlorosilane, butyltrichlorosilane, tert-butyldimethylchlorosilane, butylchlorodimethylsilane, 1,2-bis(triethoxysilyl)ethane, chlorotrimethylsilane, cyclohexyltrichlorosilane, chloro(decyl)dimethylsilane, chloro(dodecyl) dimethylsilane, cyclohexyltrimethoxysilane, chloro(hexyl)dimethylsilane, dimethylethylchlorosilane, decyltrichlorosilane, dodecyltrichlorosilane, dodecyltriethoxysilane, dimethyloctadecylchlorosilane, chlorodimethylpropylsilane, dimethylisopropylchlorosilane, dimethyl-n-octylchlorosilane, chlorodiethylisopropylsilane, dodecyltrimethoxysilane, decyltriethoxysilane, ethyltrichlorosilane, triethoxyethylsilane, ethyltrimethoxysilane, trichlorohexylsilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexadecyltrimethoxysilane, 1,1,1,3,5,5,5-heptamethyl-3-[(trimethylsilyl)oxy] trisiloxane)], isobutyltrichlorosilane, trichloro(methyl)silane, triethoxymethylsilane, trimethoxy(methyl)silane, methoxy(dimethyl) octadecylsilane, trichlorooctadecylsilane, octadecyltriethoxysilane, n-octyltrichlorosilane, triethoxy-n-octylsilane, octadecyltrimethoxysilane, trichloro(propyl)silane, chlorotriethylsilane, trichlorotetradecylsilane, triisopropylsilyl chloride, trimethoxy(propyl)silane, chloro(dimethyl) thexylsilane, hexyltrichlorosilane, triethoxy(propyl)silane, trimethoxy-n-octylsilane, benzylchlorodimethylsilane, benzyltriethoxysilane, chlorodimethyl(3-phenylpropyl)silane, chlorodimethylphenylsilane, dimethoxymethylphenylsilane, diethoxy(methyl)phenylsilane, methoxy(dimethyl)octadecylsilane, phenyltrichlorosilane, triethoxyphenylsilane, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, trichloro(phenylethyl)silane, trichloro(3-phenylpropyl)silane, trichloro(6-phenylhexyl)silane, trimethoxy(2-phenylethyl)silane, trimethoxy(4-vinylphenyl)silane, 1-(trimethoxysilyl)naphthalene, trimethoxy(phenylethyl)silane (mixture of 1-phenylethyl- and 2-phenylethyl-), chlorodimethy 1(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-n-octyl)silane, chlorodimethyl[3-(2,3,4,5,6-pentafluorophenyl)propyl]silane, dichloro(methyl)(3,3,3-trifluoropropyl)silane, dimethoxy(methyl)(3,3,3trifluoropropyl) silane, pentafluorophenyldimethylchlorosilane, pentafluorophenylethoxydimethylsilane, triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane, trichloro(1H,1H,2H,2H-tridecafluoro-n-octyl)silane, trichloro(1H,1H,2H,2H-heptadecafluorodecyl)silane, trimethoxy(3,3,3-trifluoropropyl)silane, triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, triethoxy-1H,1H,2H,2H-heptadecafluorodecylsilane, trimethoxy(1H,1H,2H,2H-heptadecafluorodecyl)silane, trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, trichloro[3-(pentafluorophenyl)propyl]silane, triethoxy(pentafluorophenyl)silane, triethoxy[5,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl) heptyl]silane, trimethoxy (pentafluorophenyl)silane, trichloro(3,3,3-trifluoropropyl)silane, trimethoxy(1H,1H,2H,2H-tridecafluoro-n-octyl)silane, diethoxy(3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, [8-(glycidyloxy)-n-octyl]trimethoxysilane, triethoxy(3-glycidyloxypropyl)silane, allyltriethoxysilane, allylchlorodimethylsilane, allyltrimethoxysilane, [bicyclo[2.2.1]hept-5-en-2-yl]triethoxysilane, chlorodimethylvinylsilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, 1,1,1,5,5,5-hexamethyl-3-[(trimethylsilyl)oxy]-3-vinyltrisiloxane, trichlorovinylsilane, tinyltrimethoxysilane, triethoxyvinylsilane, dimethylethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, (11-azidoundecyl)trimethoxysilane, (bromomethyl) chlorodimethylsilane, chloro(chloromethyl) dimethylsilane, 3-trimethoxysilylpropyl chloride, 3-chloropropyltrichlorosilane, 3-chloropropyldimethoxymethylsilane, (3-cyanopropyl) dimethylchlorosilane, 2-cyanoethyltriethoxysilane, (chloromethyl)triethoxysilane, (chloromethyl) trimethoxysilane, (3-chloropropyl)diethoxy(methyl)silane, chloro(3-chloropropyl)dimethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl] isocyanurate, (3-mercaptopropyl)trimethoxysilane, 3-mercaptopropyl (dimethoxy)methylsilane, (3-mercaptopropyl)triethoxysilane, 2-propynyl [3-(triethoxysilyl) propyl]carbamate, 3-chloropropyltriethoxysilane, 3-isocyanatopropyl) trimethoxysilane, 1-[3-(triethoxysilyl)propyl]urea, N-[2-(N-vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane hydrochloride, and titanium analogues thereof. In some embodiments the coupling agent is glycidoxypropyl trimethoxysilane. In some embodiments, the silicone base includes glycidoxypropyl trimethoxysilane.
[0088] 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.
[0089] 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.
[0090] Typically, the silica comprises fumed silica. The fumed silica can comprise microscopic droplets of amorphous silica (SiO.sub.2). 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 m.sup.2/g. Typically, the fumed silica has a density from about 0.15 to about 0.2 g/cm.sup.3. 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 SiO.sub.2 and one or more of aluminum and titanium oxides, generally Al.sub.2O.sub.3 and TiO.sub.2. In some embodiments, the fumed silica can be fumed Al.sub.2O.sub.3. In some embodiments, the fumed silica can be fumed TiO.sub.2. In some embodiments, the fumed silica can comprise spherical particles with an average size of about 30 micrometers (or 30 millionths of a meter).
[0091] 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.
[0092] 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.
[0093] 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.
[0094] 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.
[0095] 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.
[0096] 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.
[0097] 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.
[0098]
[0099]
[0100]
[0101]
[0102]
[0103] The flock product 200 of
[0104]
[0105] The flock product 400 of
[0106]
[0107] The flock transfer 600 of
[0108] An advantage of the flocked products of present disclosure having a silicone adhesive layer 230 and a thermo-adhesive 220 is their ability to retain their plush flock layer 240 when applied to a substrate 290 with an iron. The flock products of prior art, such as those of
[0109] It can be appreciated that one or more voids can be created in anyone of the direct flocked product 90, flocked product 200, flocked product 400 or flock transfer product 600. 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 transfer 10 or flocked product 20 for 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.
[0110] In accordance with some embodiments, less of the fiber length is adhered to the silicone adhesive layer 230 than to one or more of the latex adhesive 270 and hot melt adhesive 222; Generally, flock adhered to a silicone adhesive 230 where less of the flock fiber length is adhered to the silicone adhesive 230, is generally dramatically softer than flock adhered to one or more of a latex adhesive 270 and hot-melt adhesive 222 where more of the flock fiber is adhered to the adhesive.
[0111] In some embodiments, substantially less flock fibers are matted down in the silicone adhesive 230 compared to one or both of latex adhesive 270 and hot-melt adhesive 222.
[0112] In some embodiments, the flock layer edges for flock fibers 240 adhered to silicone adhesive layer 230 are clearer and sharper than the flock edges of the prior art where the flock fibers 240 are adhered to one or more a latex adhesive layer 270 and a hot-melt adhesive layer 222.
[0113] In some embodiments, the processes described herein using a silicone adhesive 230 compared to the prior art process that use one or more of a latex adhesive 270 and hot-melt adhesive 222 are generally faster. The processes using a silicone adhesive 230 typically do not require an air-drying step to remove water from an aqueous latex. The silicone adhesive 230 usually polymerizes than one or more of latex adhesive 270 and/or thermally sets more quickly than the hot-melt adhesive 222. Hence, the processes using the silicone adhesive 230 are usually faster than those using a latex adhesive 270 and/or hot-melt adhesive 222.
[0114] In some embodiments, the silicone adhesive 230 has less shrinkage than the one or more of latex adhesive 270 and the hot-melt adhesive 222. The latex adhesives 270 of the prior art shrink to about 40% of its printed wet thickness. It is believed that the thicker latex adhesive films 270 cause flock layer 240 to be less plush than those of the thinner silicone adhesive 230 layers described herein.
[0115] In some embodiments, the silicone adhesive layer 230 can be electrically conductive. While not wanting to be limited by example, the silicone adhesive layer 230 can 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 layer 230 can aid in the deposition and/or contacting of the flock fibers 240 with the silicone adhesive layer 230.
[0116] It is believed that when the silicone adhesive layer 230 can lack in some embodiments sufficient electric conductivity. That is, the electric potential between the flock fiber 230 and silicone adhesive layer 230 can be insufficient to substantially deposit and/or contact some of the flock fibers 240 with the silicone adhesive layer 230. Moreover, when the silicone adhesive layer 230 lacks sufficient electrical conductivity, some of the flock fibers 240 are insufficiently deposited and/or contacted with the silicone adhesive layer 230 such that they do not stand proud. That is, some the flock fibers 240 that are insufficiently deposited and/or adhered to the silicone adhesive layer 230 and are oriented, relative to the silicone adhesive layer 230, at an angle from about 35 to about 85 degrees.
[0117] Some embodiments can include a step of providing a carrier sheet with a release adhesive. The release adhesive can be a silicone-release adhesive.
[0118] Some embodiments can include a step of printing a silicone adhesive 230 onto a release adhesive.
[0119] Some embodiments can include a step of applying a thermo-adhesive 220. The thermo-adhesive 220 can be applied to the printed silicone adhesive layer 230. The thermo-adhesive 220 can be provided as a powder. The powdered thermo-adhesive 220 typically 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 adhesive 220 has a particle size from about 200 to about 300 microns. It can be appreciated that the particle size of the powdered hot-melt adhesive 220 can refer to any one or more of the P.sub.90, P.sub.85, P.sub.80, P.sub.75, P.sub.70 and P.sub.50 particle size.
[0120] 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.
[0121] Some embodiments can include a step of applying thermal energy to one or more of anyone of the direct flocked product 90, flocked product 200, flocked product 400 or flock transfer product 600 to cure the silicon adhesive 230 and adhesively bond the flock fibers 240 to the silicone adhesive 230. In some embodiments, the applied thermal energy can adhesively bond the flock fibers 240 to the thermo-adhesive 220. In some embodiments, the applied thermal energy can adhesively bond the thermo-adhesive 220 and silicone adhesive 230 together.
[0122] Some embodiments can include a step of vacuuming the one or more of anyone of the direct flocked product 90, flocked product 200, flocked product 400 or flock transfer product 600 to remove any free flock fibers not adhered to the silicone adhesive 230. The step of vacuuming the one or more of anyone of the direct flocked product 90, flocked product 200, flocked product 400 or flock transfer product 600 can also remover any free powered thermo-adhesive 220.
[0123] Some embodiments can include a step of cutting the one or more of anyone of the direct flocked product 90, flocked product 200, flocked product 400 or flock transfer product 600. The cutting can be one of laser cutting, mechanical cutting, hot-wire cutting, or radio frequency cutting.
[0124] Commonly, the printed silicone adhesive layer 230 can 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 layer 230.
[0125] In some embodiments, the silicone adhesive layer 230 commonly 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).
[0126] In some embodiments, the printed silicone adhesive layer 230 typically has a thickness of at least about 0.0010 inches, more typically the silicone adhesive layer 230 has a thickness of at least than about 0.0025 inches, even more typically the silicone adhesive layer 230 has a thickness of at least about 0.0050 inches, and yet even more typically the silicone adhesive layer 230 has a thickness of at least about 0.0075 inches, and still yet even more typically the silicone adhesive layer 230 has 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 layer 230 usually has a thickness of at least about 15 m, more usually the silicone adhesive layer 230 has a thickness of at least than about 20 m, even more usually the silicone adhesive layer 230 has a thickness of at least about 50 m, and yet even more usually the silicone adhesive layer 230 has a thickness of at least about 80 m, still yet even more usually the silicone adhesive layer 230 has a thickness of at least about 100 m, still yet even more typically the silicone adhesive layer 230 has a thickness of at least about 150 m, or still yet even more usually the silicone adhesive layer 230 has a minimum thickness of at least about 200 m. Commonly the printed silicone adhesive layer 230 has a thickness of no more than about 210 m, even more commonly a film thickness of no more than about 200 m, even more commonly a film thickness of no more than about 150 m, and even more commonly a film thickness of no more than about 105 m. Generally, the printed silicone adhesive layer 230 has a thickness of no more than about 210 m, even more generally a film thickness of no more than about 200 m, even more generally a film thickness of no more than about 150 m, and even more generally a film thickness of no more than about 105 m and a thickness of more than about at least about 20 m, more generally a thickness of more than 50 m, even more generally a thickness of more than about 80 m, and yet even more generally a thickness of more than about 150 m, and still yet even more generally a thickness of more than about 100 m.
[0127] Generally, the printed film thickness of the silicone adhesive layer 230 is 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 fibers 240 with the silicone adhesive 230 is 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.
[0128] Generally, no more than about 0.1% of the flock fiber length is adhesively bonded to silicone adhesive layer 230, 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 layer 230.
[0129] The second fiber ends of the flock fibers 240 can be in contact with the silicone adhesive layer 230. At least some of the flock fiber length can be embedded in the silicone adhesive layer 230. In some embodiments, typically no more than about 3% of the flock fiber length can be embedded in the silicone adhesive layer 230, more typically no more than about 2% of the flock fiber length can be embedded in the silicone adhesive layer 230, even more typically no more than about 1.5% of the flock fiber length can be embedded in the silicone adhesive layer 230, yet even more typically no more than about 1% of the flock fiber length can be embedded in the silicone adhesive layer 230, still yet even more typically no more than about 0.5% of the flock fiber length can be embedded in the silicone adhesive layer 230, still yet even more typically no more than about 0.25% of the flock fiber length can be embedded in the silicone adhesive layer 230, or yet still even more typically no more than about 0.1% of the flock fiber length can be embedded in the silicone adhesive layer 230. Commonly, the total surface area of the flock fiber adhered to the silicone adhesive layer 230 comprises more than about 80% of one of the circular faces of the flock fiber 240 and 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.
[0130] Typically, the second fiber ends of the flock fibers 240 are embedded in the silicone adhesive layer 230 to 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 adhesive 230 to 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 layer 230 to 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 layer 230 to 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 layer 230 to 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 layer 230 to 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 layer 230 to 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 layer 230 to 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 layer 230 to a depth of no more than about 0.25% of the silicone adhesive layer thickness.
[0131] It can be appreciated that the flock fiber 240 length in contact with the silicone adhesive layer 230 can depend on one or both pressure and temperature applied when contacting the flock fibers 240 with the silicone adhesive layer 230 and the physical properties of the silicone adhesive layer 230 during the embedding process.
[0132] The flock layer 240 comprises a plurality of interstitial voids between the flock fibers 204, the plurality of interstitial voids has an interstitial void volume. Generally, substantially some of the silicone adhesive layer 230 flows into at least some the interstitial void volume. More generally, substantially little, if any, of the silicone adhesive layer 230 flows into at least some the interstitial void volume. Even more generally, substantially none the silicone adhesive layer 230 flows 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 layer 230. Still yet more generally, the interstitial void volume is substantially free the silicone adhesive layer 230.
[0133] In some embodiments, the silicone adhesive 105 generally 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).
[0134] In some embodiments, the cured silicone adhesive layer 230 typically has a thickness of at least about 0.0010 inches, more typically the silicone adhesive layer 230 has a thickness of at least than about 0.0025 inches, even more typically the silicone adhesive layer 230 has a thickness of at least about 0.0050 inches, and yet even more typically the silicone adhesive layer 230 has a thickness of at least about 0.0075 inches, and still yet even more typically the silicone adhesive layer 230 has 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 layer 230 usually has a minimum thickness of at least about 15 m, more usually the silicone adhesive layer 230 has a thickness of at least than about 20 m, even more usually the silicone adhesive layer 230 has a thickness of at least about 50 m, and yet even more usually the silicone adhesive layer 230 has a thickness of at least about 80 m, still yet even more usually the silicone adhesive layer 230 has a thickness of at least about 100 m, still yet even more typically the silicone adhesive layer 230 has a thickness of at least about 150 m, or still yet even more usually the silicone adhesive layer 230 has a thickness of at least about 200 m. Commonly the cured silicone adhesive layer 230 has a thickness of no more than about 210 m, even more commonly a film thickness of no more than about 200 m, even more commonly a film thickness of no more than about 150 m, and even more commonly a film thickness of no more than about 105 m. Generally, the cured silicone adhesive layer 230 has a thickness of no more than about 210 m, even more generally a film thickness of no more than about 200 m, even more generally a film thickness of no more than about 150 m, and even more generally a film thickness of no more than about 105 m and a thickness of more than about at least about 20 m, more generally a thickness of more than 50 m, even more generally a thickness of more than about 80 m, and yet even more generally a thickness of more than about 150 m, and still yet even more generally a thickness of more than about 100 m.
[0135] Generally, no more than about 0.1% of the flock fiber length is adhesively bonded to silicone adhesive layer 230, 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 layer 230.
[0136] Some embodiments of the present disclosure include a molding process. In some embodiments, the appliqu 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 layer 230 can 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 adhesive 230 while forming the appliqu and/or transfer into a geometric shape. The metalized polymeric film appliqu 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 layer 230 is 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 U.S. Pat. Nos. 7,799,164 and 9,193,214, both to Abrams, U.S. Pat. Nos. 8,110,059; 5,589,022; 5,677,037; 5,599,416; 5,520,988; and 5,143,672, all of which are incorporated in their entirety herein by this reference.
[0137] Further embodiments can include a cured silicone adhesive layer 230 having 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.
[0138] 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.
[0139] The pressure sensitive adhesive 250 can be selected such that the bonding force between the pressure sensitive adhesive 250 and the plurality of flock fibers 240 is less than the bonding force between the silicone adhesive layer 230 and the plurality of flock fibers 240. The pressure sensitive adhesive 250 can be any adhesive that adheres more strongly to the release sheet 210 than the plurality of flock fibers 240 but adheres to both enough to hold them together. For example, the pressure sensitive adhesive 250 may 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 adhesive 250 can be a water-based adhesive, that is the pressure sensitive adhesive 250 is one or more of dispersed, dissolved, suspended or emulsified within water.
[0140] It is believed that after removing the release sheet 210 from flock transfer 600 a residual amount of the pressure sensitive adhesive 250 remains on the flock fiber 240. It is further believed that the residual amount of the pressure sensitive adhesive 250 remaining on the flock fiber negatively effects the ability of the flock fibers 240 to adhere to an adhesive. The direct flock products of the present invention overall this limitation.
[0141] The plurality of flock fibers 240 may 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 fibers 240. The conductive coating can permit the flock fibers 102 to retain an electrical charge.
[0142] The flock fibers 240 can be pre-colored (yarn-dyed, by a dye sublimation process, or spun dyed) before contacting one or more of the pressure sensitive adhesive 250 or the silicone adhesive layer 230 or after the release sheet 210 is removed.
[0143] At least most, or commonly at least about 75%, and more commonly all, of the flock fibers 240 can 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 fibers 240 generally have a denier from about 1.5 to about 3.5. Commonly, the flock fibers 240 can have a titre ranging from about 0.5 to about 20 Dtex (from about 0.5 to about 2010.sup.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 fibers 240 is 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 fibers 240 have a length ranging from about 0.3 to about 3.5 mm. The flock fiber 240 placement 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/in.sup.2, more generally at least about 60% fibers/in.sup.2, and even more generally at least about 70% fibers/in.sup.2 of the flocked surface area.
[0144] Three silicone adhesive formulations 230A-230F were evaluated. The first silicone adhesive 230A had excellent integrity; however, when screen printed it was stringy. The stringy nature of the first silicone adhesive 230A rendered it unsuitable for screen printing. The second silicone adhesive 230B was more screen printable but it had less adhesive integrity than the first silicone adhesive 230A. Furthermore, the second silicone adhesive 230B had low tensile strength and was too soft. The third silicone adhesive 230C 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 formulations 230D, 230E and 230F were evaluated. Each of formulations 230D, 230E and 230F 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 formulations 230E and 230F further include, respectively, an ultra-high molecular weight additive and silica powder thickener, the silicone adhesive formulation 230D did not have either of the ultra-high molecular weight additive and silica powder thickener. The silicone adhesive 230D is a suitable base product. However, silicone adhesive 230D 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.
[0145] Some formulations of the silicone adhesive 230 can a rheology modifier comprising one or more of silicone dioxide (SiO.sub.2), titanium dioxide (TiO.sub.2), and aluminum oxide (Al.sub.2O.sub.3). In some embodiments, the silicone adhesive 230 can 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.
[0146] 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.
[0147] The plurality of flock fibers 240 in anyone of the direct flocked product 90, flocked product 200, flocked product 400 or flock transfer product 600 can be adhered to a substrate 290 by the silicone adhesive layer 230. That is, substrate 290 can be in contact with and adhered to one or more of the silicone adhesive layer 230 and thermo-adhesive 220. The substrate 290 can comprise any material. Non-limiting examples of suitable substrates 290 materials can comprise metallic materials, synthetic or natural polymeric materials, glass-based materials, ceramic materials, leather-based materials and combinations thereof. Furthermore, the substrate 290 may or may not be stretchable and/or have elastic properties.
[0148] Generally, the substrate 290 is a textile material. The textile material can be woven, nonwoven, or knit. More generally, the substrate 290 can be a stretchable and/or elastomeric textile material, such as stretchable and/or elastomeric fabric and/or apparel item. Even more generally, the substrate 290 can 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 product 90, flocked product 200, flocked product 400 or flock transfer product 600 is adhered to a textile material by one or more of the silicone adhesive 230 and thermo-adhesive 220, the adhesive bond between the flock fibers 240 and substrate 290 is substantially strong to withstand industrial wash testing. Generally, the adhesive bond between the flock fibers 240 and substrate 290 can 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.
[0149] Non-limiting examples of elastomeric polymeric materials comprise one or more of rubbers, polyisoprenes, polybutadinenes, styrene-butadienes, chloroprenes, ethylene propylene rubbers, ethylene-vinyl acetates, ethylene propylene diene rubbers, polyacrylic rubbers, epichlorohydrin rubbers, fluorosilicones, fluoroelasters, silicones, perfluoroelastomers, polyether block amides, chlorosulfonated polyethylenes and combinations thereof). Non-limiting examples of stretchable-knits/stretchable-weaves are sprang weaves, mesh-weaves, open weaves, warp knits, and two-way knits. While not wanting to be limited by an example, suitable stretchable-knits/stretchable-weave textile materials are LYCRA (a trademark of Invista), an elastane containing material, Spandex, 4-, 3-, 2-, or 1-way stretch fleece fabrics, and stretch cotton weaves (such as, stretch rayon jersey knit and/or cotton/LYRCA combinations).
[0150] 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%.
[0151] In some embodiments, the substrate 290 can comprise an item of apparel, preferably a stretchable and/or elastomeric item of apparel. Non-limiting examples of stretchable items of apparel are jerseys, leotards, pants, shirts, blouses, leggings, socks, shoes, swim and/or beach wear, athletic apparel, medical, under garments, jackets, rain gear, sweaters, and accessories. Accessories can include, without limitation, hair-bands, wrist bands, head bands, finger bands, ankle bands, rain gear, finger bands, toe-bands, arm bands, and shoe-laces.
[0152] In some embodiments, the substrate 290 can comprise non-apparel items, such as, but not limited to: dog leases, pet clothing, towels, bedding, upholstery (for home, automobile, office, garden, and beach), luggage (hard and soft), ladies' handbags, recreational and sporting items, packing, totes and carpeting.
[0153] The substrate 290 can have a single surface or a plurality of surfaces. Non-limiting examples of a single-surfaced substrate 290 are 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.
[0154] In some embodiments, the substrate 290 can 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 product 90, flocked product 200, flocked product 400 or flock transfer product 600.
[0155] Typically, the direct flocked product 90, flocked product 200, flocked product 400 and/or flock transfer product 600 adhered to a substrate 290 by a substantially flexible and/or elastic silicone adhesive layer 230 is 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 substrate 290. More typically, more typically the direct flocked product 90, flocked appliqu 200, flocked appliqu 400 or flock transfer product 600 adhered to a substrate 290 by a substantially flexible and/or elastic silicone adhesive layer 230 is substantially free of one or more of splitting, delamination and distortion after repeatability applying an elongation and/or angular stresses to the substrate 290 at 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 substrate 290 at 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 substrate 290 at 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 substrate 290 at 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 substrate 290 at least 100,000 times.
[0156] In some embodiments, the cured silicone adhesive layer 230 has elastomeric properties. Generally, the cured silicone adhesive layer 230 can 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 layer 230 can 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.
[0157] Generally, the silicone adhesive layer 230 is contact with and adhered to the substrate 290. The silicone adhesive layer 230 generally one of penetrates and/or contacts at least some of the substrate 290. By way of a non-limiting example, the substrate 290 can have a pile thickness T.sub.pile. Typically, the silicone second adhesive layer 230 in contact with the substrate 290 has an adhesive thickness of about equal to T.sub.adh, more typically the adhesive in contact with the substrate has a thickness of no more than about one-half of T.sub.adh, even more typically the adhesive in contact with the substrate has a thickness of no more than about one-quarter of T.sub.adh, yet even more typically the adhesive in contact with the substrate has a thickness of no more than about one-eighth of T.sub.adh, still yet even more typically the adhesive in contact with the substrate has a thickness of no more than about one-sixteenth of T.sub.adh, still yet even more typically the adhesive in contact with the substrate has a thickness of no more than about one-thirty-second of T.sub.adh, still yet even more typically the adhesive in contact with the substrate has a thickness of no more than about one-sixty-fourth of T.sub.adh, 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 T.sub.adh.
[0158] 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.
[0159] A plurality of film thickness values measured over the areal extent 2800 for the silicone adhesive layer 230 can be represented by a Gaussian distribution, the Gaussian distribution typically has a t value (
[0160] 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.
[0161] The phrase substantially continuous means that a film or layer substantially covers and/or coats the entire areal interface 2800 of 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.
[0162] Any of the direct flocked product 90, flocked product 200, flocked product 400 or flock transfer product 600 can 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.
[0163] 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%.
[0164] The metalized polymeric film can comprise any polymeric material. The polymeric can material comprise one or more of a homopolymer, copolymer, polymer alloy or a combination thereof, and wherein the polymeric material comprises one or more of vinyl esters, epoxies, polyolefins, polystyrenes, polyvinyls, polyacrylics, polyhalo-olefins, polydienes, polyoxides, polyesthers, polyacetals, polysulfides, polythioesters, polyamides, polythioamides, polyurethanes, polythiourethanes, polyureas, polythioureas, polyimides, polythioimides, polyanhydrides, polythianhydrides, polycarbonates, polythiocarbonates, polyimines, polysiloxanes, polysilanes, polyphosphazenes, polyketones, polythioketones, polysulfones, polysulfoxides, polysulfonates, polysulfoamides, polyphylenes, and combinations and/or mixtures thereof.
[0165] 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.
[0166] Generally, any of the direct flocked product 90, flocked product 200, flocked product 400 or flock transfer product 600 having a metalized polymer film can be substantially resistant to one or both of splitting and delamination of the flock fibers 240. More specifically, the metalized polymeric film substantially reduces splitting and/or delamination of the flock fibers 240 from a substantially elastomeric and/or stretchable substrate 290. The metalized polymeric film can reduce stresses imparted to the flock fibers 240 when stress is applied to a substantially elastomeric and/or stretchable substrate 290. More specifically, when a stress is applied to the elastomeric and/or stretchable substrate 290, the applied stress can affect the adherence of the flock fibers 240 to the substrate 290. Furthermore, the a substantially flexible and/or elastic silicone adhesive layer 230 can reduce distortion of the direct flocked product 90, flocked product 200, flocked product 400 and/or flock transfer product 600 when a stress is applied to the substrate 290. The reduced distortion of the direct flocked product 90, flocked product 200, flocked product 400 and/or flock transfer product 600 can be advantageous in retaining its, more specifically the artistic integrity and value of the direct flocked product 90, flocked product 200, flocked product 400 and/or flock transfer product 600.
[0167]
[0168] A number of variations and modifications of the disclosure can be used. It would be possible to provide for some features of the disclosure without providing others.
[0169] The foregoing discussion of the invention has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the invention are grouped together in one or more embodiments, configurations, or aspects for the purpose of streamlining the disclosure. The features of the embodiments, configurations, or aspects of the invention may be combined in alternate embodiments, configurations, or aspects other than those discussed above. This method of disclosure is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment, configuration, or aspect. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the invention.
[0170] Moreover, though the description of the invention has included description of one or more embodiments, configurations, or aspects and certain variations and modifications, other variations, combinations, and modifications are within the scope of the invention, e.g., as may be within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative embodiments, configurations, or aspects to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter.