WO2007016342A2 - Flocked articles having noncompatible insert and porous film - Google Patents
Flocked articles having noncompatible insert and porous film Download PDFInfo
- Publication number
- WO2007016342A2 WO2007016342A2 PCT/US2006/029410 US2006029410W WO2007016342A2 WO 2007016342 A2 WO2007016342 A2 WO 2007016342A2 US 2006029410 W US2006029410 W US 2006029410W WO 2007016342 A2 WO2007016342 A2 WO 2007016342A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- insert
- adhesive
- flock
- porous film
- substrate
- Prior art date
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
- B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/12—Applying particulate materials
- B05D1/14—Flocking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/16—Flocking otherwise than by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1704—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
- B44C1/1716—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06Q—DECORATING TEXTILES
- D06Q1/00—Decorating textiles
- D06Q1/10—Decorating textiles by treatment with, or fixation of, a particulate material, e.g. mica, glass beads
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06Q—DECORATING TEXTILES
- D06Q1/00—Decorating textiles
- D06Q1/12—Decorating textiles by transferring a chemical agent or a metallic or non-metallic material in particulate or other form, from a solid temporary carrier to the textile
- D06Q1/14—Decorating textiles by transferring a chemical agent or a metallic or non-metallic material in particulate or other form, from a solid temporary carrier to the textile by transferring fibres, or adhesives for fibres, to the textile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2252/00—Sheets
- B05D2252/02—Sheets of indefinite length
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/308—Heat stability
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2451/00—Decorative or ornamental articles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
- Y10T156/1056—Perforating lamina
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
- Y10T156/1062—Prior to assembly
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/14—Layer or component removable to expose adhesive
- Y10T428/1476—Release layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/14—Layer or component removable to expose adhesive
- Y10T428/1486—Ornamental, decorative, pattern, or indicia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/22—Nonparticulate element embedded or inlaid in substrate and visible
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/23907—Pile or nap type surface or component
- Y10T428/23921—With particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/23929—Edge feature or configured or discontinuous surface
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
- Y10T428/24322—Composite web or sheet
- Y10T428/24331—Composite web or sheet including nonapertured component
Definitions
- the invention relates generally to flocked articles and particularly to flocked graphics.
- Flocked articles are used in a wide variety of applications. Flocked articles are being used for textile decoration as well as molded articles. Flock is a short precision cut or pulverized natural or synthetic fiber used to produce a velvet like coating on cloth, rubber, film, or paper. Flock generally has a length between about 0.010 to 0.250 inches (0.25mm to 6.25mm).
- the present invention is directed to flocked articles and graphics comprising a compatible and/or noncompatible (or incompatible) material, such as a metallized film.
- a metallized film refers to any material, whether metal or a nonmetal, having a metal-like appearance (e.g., metal-like sheen or luster).
- a metallized film is used to provide a number of highly attractive colors, sheens and matte finishes, hi one configuration, the metallized film is metallic in appearance. In one configuration, it contains a metal layer vapor deposited on a first polymeric film with a second polymeric film being located on the opposing side of the metal layer. The metal layer is sandwiched between the first and second polymeric layers by means of a laminate adhesive.
- the polymeric layers can be UV-resistant, water resistant, thermally stable, and otherwise designed to resist wear and deterioration.
- the polymeric layers are a polycarbonate.
- water discoloration of the insert is typically not a problem. This can obviate the need to apply additional protective layers to the insert to protect any metal from oxidation.
- the metallized film can have a highly desirable mirror-like metallic look from the metallized layer, a high abrasion resistance of the sandwiching polymeric films to protect the metal and laminate adhesive from fading, discoloration, and/or corrosion, and a high ability to accept and adhere to a wide variety of hot melt thermoplastic or thermoset adhesives, whether in the form of a liquid, power, or preformed film.
- the flocked article can include a porous film to act as a binder or tie material for the otherwise incompatible or weakly compatible materials, namely the flock and the metallized film.
- the porous film can bond well to a number of otherwise compatible and noncompatible materials on opposite sides, thus serving well as a so-called "tie coat" layer.
- the film bonds to a variety of adhesives as noted above.
- the adhesives can be applied as a thermoplastic powder, a self-supporting heat-activated film, or as a liquid coating.
- the film may be readily laminated to pre-formed, self-supporting films of thermoset and/or thermoplastic adhesive(s)s, including hot melt adhesive(s).
- the porous film though having modest tensile strength when taken alone, can experience substantial improvements in tensile strength when combined with one or more other materials.
- the film by itself, lacks the strength of conventional paper carriers and therefore would at first blush appear to be a poor candidate for use in a machine (web) based-process and in products that need to be durable.
- the release adhesives when coated with water or solvent-based release adhesives the release adhesives not only provide an adhesive surface to capture and hold flock fibers but also provides a substantial improvement in film strength after the adhesive is dried and cured. While not wishing to be bound by any theory, it is believed that the release adhesive is carried into the film matrix by the combined effects of the film's porosity and permeability and, after drying, substantially fills the pores in the film to provide the desired strength enhancement.
- the synergistic effect of the release adhesive and the porosity/permeability of the film makes the porous film strong enough to withstand the forces applied during subsequent processing stages , such as web-type tensile forces, vacuum cleaning, mechanical brushing, baking, and heat transfer application processes (e.g., heat pressing, cooling, pulling the carrier, and releasing the fibers). Additional support film(s) may nonetheless be added to the side of the porous film opposite the side containing the flock to provide further support.
- each of the expressions “at least one of A, B and C”, “at least one of A, B, or C”, “one or more of A, B, and C", “one or more of A, B, or C" and "A, B, and/or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B and C together.
- Fig. 1 is a cross section of a three dimensional design according to an embodiment of the present invention
- Fig.2 is a block diagram of a process embodiment to make an intermediate flocked article for use in the three dimensional design
- Fig. 3 is a cross section of an intermediate flocked article
- Fig. 4 is a block diagram of a process embodiment to make an insert assembly for use in the three dimensional design
- Fig. 5 is a cross section of an insert assembly
- Fig. 6 is a block diagram of a process embodiment to make the three dimensional design
- Fig. 7 is a block diagram of a process embodiment to make a three dimensional design according to another embodiment
- Fig. 8 is a cross section of the three dimensional design
- Fig. 9 is an exemplary decorative media according to an embodiment of the present invention
- Fig. 10 is a cross section of another embodiment of a three dimensional design in accordance with the present invention.
- Fig. 11 is a block diagram of a process to make the three dimensional design of Fig. 10;
- Fig. 12 is a side view of a decorative media in a first step of a production process according to an embodiment of the present invention;
- Fig. 13 is a side view of the decorative media in a second step of the production process
- Figs. 1 and 9 show a three-dimensional design according to an embodiment of the present invention.
- the design 100 includes (multi-colored or sublimation printed) flocked areas 104 surrounding a plurality of compatible or noncompatible inserts 112.
- the inserts 112 are adhered to a porous film 116 by a first adhesive 120.
- the porous film 116 is adhered to the flock areas 104 by a flock (second) adhesive 124.
- the design 100 is adhered to a desired substrate, such as a textile, by a permanent (third) adhesive 128.
- the inserts 112 can be any design media, such as glass beads.
- the inserts 112 are formed from one or more polymeric light diffusing films, such as polycarbonate and/or polyester light diffusion films sold under the tradenames MakrofolTM and/or BayfolTM.
- the films are preferably metal-containing and have a first and/or second surface gloss (60° angle with black inked second surface) of at least about 50 gloss units, more preferably of at least about 75 gloss units, and even more preferably of at least about 75 gloss units, first and/or second surface roughnesses (R3Z) of no more than about 20 microns, more preferably of no more than about 3 microns, and even more preferably of no more than about 1 micron, and a luminous transmittance of no more than about 50%, more preferably no more than about 5%, and even more preferably no more than about 1%.
- first and/or second surface gloss 60° angle with black inked second surface
- the insert 112 preferably has a metallic or nonmetallic sheen and a gloss/fine matte and a thickness of no more than about 0.5 inches, more preferably of no more than about 0.25 inches, and even more preferably of no more than about 0.20 inches.
- a particularly preferred insert is MakrofolTM DPF 5072TM.
- the porous film 116 is preferably a microporous material that includes a matrix of substantially water insoluble thermoplastic organic polymer, finely divided substantially water-insoluble filler particles and a network of interconnected pores communicating substantially throughout the microporous material.
- the filler particles are distributed throughout the matrix and constitute from about 40 to about 90 percent by weight of the microporous material.
- the filler particles are a metal oxide, such as alumina, silica, and titania with silica being preferred.
- at least 50 percent by weight of the particles are amorphous precipitated silica particles.
- the particles have a preferred maximum dimension of less than about 5 micrometers, more preferably no more than about 1 micrometer, even more preferably no more than about 0.1 micrometers, and even more preferably no more than about 0.05 micrometers and a preferred average pore size of less than f4 "3 Ut l ,/ ⁇ ' ir! y if - "
- the matrix of the microporous material includes a water-insoluble thermoplastic organic polymer.
- suitable polymers include polyolefms, poly(halo-substituted olefins), polyesters, polyethylenes, polyamides, polyurethanes, polyureas, polyvinyl halides), poly(vinylidene halides), polystyrenes, polyvinyl esters), polycarbonates, polyethers, polysulfides, polyimides, polysilanes, polysiloxanes, polycaprolactones, polyacrylates, and polymethylacrylates, with polyvinyl chloride), copolymers of vinyl chloride, and mixtures thereof being preferred.
- the material may further include plasticizers, lubricants, and antioxidants.
- the microporous material is preferably coated with a substantially nonporous coating composition including a volatile liquid medium (e.g., water and/or a nonaqueous solvent) and binder dissolved or dispersed in the medium.
- a volatile liquid medium e.g., water and/or a nonaqueous solvent
- binder dissolved or dispersed in the medium.
- the binder includes a film-forming organic polymer, preferably including (a) water-soluble poly(ethylene oxide) having a preferred weight average molecular weight in the range of from about 100,000 to 3,000,000 and (b) water-soluble or water-dispersible crosslinkable urethane-acrylate hybrid polymer.
- the organic polymer may further include additional organic polymers such as water-soluble cellulosic organic polymers, water-soluble noncellulosic organic polymers, and/or water dispersible polymers such as poly(ethylene-co- acrylic acid), poly(ethylene),and polyethylene oxide).
- the poly(ethylene oxide) includes copolymers of ethylene oxide with lower alkylene oxide and homopolymers of ethylene oxide.
- the organic polymer component of the coating includes from about 20 to about 80% by weight of the urethane-acrylate hybrid polymer.
- the coating may further include surfactants and adjuvant materials. After drying and crosslinking, the peel strength between the coating and microporous material substrate is high.
- the film has a preferred puncture strength of greater than about 300g/25.4 ⁇ m, a preferred tensile strength of less than about 2% at 1000 psi, and a preferred thermal ability of less than about 5% shrinkage after 160 minutes at 90°C.
- a preferred porous film is further discussed in U.S. 6,025,068, which is incorporated herein by this reference.
- a particularly preferred porous film is sold by PPG Industries Inc. under the tradename TeslinTM.
- Battery separator membranes can also be used. Examples include Daramic Industrial CLTM sold by Daramic, Inc., and the battery separator membranesnch ⁇ ⁇ ' y ::;;:i ⁇ u «3 / ' c: 1 sold by Celgard, or by Daramic, Inc. under the tradename ArtisynTM. ArtisynTM is an uncoated, mono-layer, highly filled polyolefm sheet.
- the flock fibers in the flock layer 1104 can be any desirable material, whether natural or synthetic.
- the flock is composed of polyester (such as poly(ethylene terephthalate) and poly(cyclohexylene-dimethylene terephthalate)), vinyl, nylon, rayon, and the like.
- the various permanent adhesives 1108, 1116, and 1120 can be any suitable adhesive, with water- and solvent-based adhesives and preformed film adhesives being preferred.
- Preferred permanent adhesives include thermoset and hot melt thermoplastic adhesives, whether as a liquid, powder, or (pre-formed) self-supporting film.
- thermoset adhesives solidify, activate and/or set irreversibly when heated above a certain temperature. This property is usually associated with a cross-linking reaction of the molecular constituents induced by heat or radiation.
- Thermoset adhesives can include curing agents such as organic peroxides, isocyanates, or sulfur.
- examples of thermoplastic and thermosetting adhesives include polyethylene, phenolics, alkyds, acrylics, amino resins, polyesters, epoxides, polyurethanes, polyamides, and silicones.
- the adhesives 1108, 1116, and 1200 may contain additives, such as fillers, catalysts, colorants (dyes or pigments) and optical blocking/reflective/absorbtive materials.
- the preferred porous film namely TeslinTM and ArtisynTM, can be highly sensitive to Ultraviolet (UV) radiation and can degrade rapidly when exposed to direct sunlight.
- the adhesives may contain light blocking, absorbing, and/or reflecting materials to decrease substantially the optical transmissivity of the adhesive.
- the adhesive when on the light contacting side of the porous film, blocks at least about 75%, more preferably at least about 85%, and even more preferably at least about 95% of the UV radiation spectrum.
- Such optical blocking/reflecting/absorbing materials are known to those of skill in the art.
- a carrier sheet 204 is flocked with flock fibers 208 in the reverse order of the desired pattern.
- the carrier sheet can be any substrate that is dimensionally stable under the conditions of temperature and pressure encountered during the process.
- the carrier sheet 204 is preferably a porous film, such as the porous film 116 described above, coated with a release adhesive 212, which is preferably water-based.
- the carrier is a discontinuous sheet as opposed to a continuous sheet on a running web line.
- the release adhesive 212 can be any adhesive that adheres more strongly to the carrier sheet than the flock fibers but adheres to both enough to hold them together.
- the release adhesive 212 can be any temporary adhesive, such as a resin or a copolymer, e.g., a polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral, acrylic resin, polyurethane, polyester, polyamides, cellulose derivatives, rubber derivatives, starch, casein, dextrin, gum arabic, carboxymethyl cellulose, rosin, silicone, or compositions containing two or more of these ingredients.
- 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, ros
- the release adhesive may be applied in the form of a solution or emulsion.
- the release adhesive may be applied on the carrier in the perimeter shape of the desired design or without regard to the overall design desired.
- the ' release adhesive may be applied by any suitable technique such as, for example, by applying i the release adhesive with rollers or spraying the release adhesive.
- the exposed ends 224 of the flocked surface are sublimation printed to provide the desired design on the flock. Sublimation printing is described in copending U.S.
- sublimation ink direct printing includes inkjet or screen sublimation ink printing and sublimation transfer printing using devices such as an inkjet dye sub printer, a ribbon-based dye sub printer, a hybrid sublimation printer, and a small dye sub ribbon-based printer.
- a special heat sensitive dye is used in a computer-controlled printer, such as an HP 550TM, or Mimaki JV4TM to sublimation print the ink onto the flock fibers through vapor phase transportation of the ink from the printer to the flock fibers.
- the transferred dye is then heat and pressure thermofixed and thereby enters the amorphous areas of the fiber matrix.
- vacuuming of the flock can be conducted preferably before or after sublimation ink printing. Commonly, the color must go all the way down the fiber.
- step 220 the free ends 224 of the flock are coated with a binder adhesive 228.
- a binder adhesive 228 is a water based acrylic which binds the flock together as a unit.
- the binder adhesive 228 adhesive may contain a hot melt adhesive.
- the permanent (second) adhesive 124 is contacted with the free ends 224 of the flock 208 (or with the binder adhesive 228 depending on the process configuration employed), hi one configuration, the second adhesive 124 is a thermoplastic or thermoset adhesive and is heated to a temperature sufficient to adhere the adhesive 124 to the flock 208.
- the temperature is below the temperature at which the adhesive cross-links and is no longer reversible.
- step 236 areas of the assembly are removed to form voids 240 to receive the inserts 112.
- the sizes of the areas removed are approximately the same size as the size of the corresponding insert 112.
- the void 240 passes completely through the assembly. In other words, the void 240 is free of adhesives 120, 224, and 212, the carrier sheet 204, and flock 208.
- step 400 the first permanent adhesive 120 is contacted with the noncompatible insert 112.
- step 404 the upper surface of the porous film 116 (of which the lower surface has previously been contacted with the third permanent adhesive 128) is contacted with the first permanent adhesive 120.
- step 408 the insert 112 and first permanent adhesive 120 are cut to the size and shape of the void 240 in the intermediate flocked article 300. Cutting may be made by known techniques, such as a laser or a mechanical cutting device.
- step 412 the first (and third) permanent adhesives 120 and 128 are heat sealed. Heat sealing preferably occurs at a temperature within the thermoplastic behavior regime.
- the adhesive following step 412 is not thermoset.
- steps 404, 408, and 412 may be performed in any order.
- step 408 may be performed before step 404.
- steps 400, 404, and 412 can be performed simultaneously, such as by lamination.
- step 416 the porous film, which was not cut in step 408, is cut to a size slightly larger than the void 240. This oversize relative to the void size is shown in Fig. 1. The overlapping edge of the porous film is used to secure the insert to the intermediate flocked article.
- a tack adhesive 504 is applied to the overlapping edge of the porous film to provide the insert assembly 500 depicted in Fig. 5.
- Fig. 6 depicts the final steps of the process to form the three dimensional design 100.
- step 600 the insert 112 is positioned in the void 240 as shown in Fig. 1.
- the tack adhesive 504 temporarily holds the insert assembly 500 in position.
- step 604 the consolidated assembly formed from the insert assembly 500 and intermediate flocked article 300 is heat sealed to thermoplastically (and reversibly) set the second adhesive 124 and permanently adhere the porous film 116 to the flocked article 300.
- the final three dimensional design 100 is shown in Fig. 1.
- the design 800 includes the flock 208, insert 112, porous film 116, and first and third adhesives 120 and 128.
- the porous film 116 is contacted with the first (and optionally third) permanent adhesives 120 and 128.
- step 704 the incompatible insert 112 is positioned on the first permanent adhesive 120.
- the exposed portions of the first permanent adhesive 120 are direct flocked by known techniques.
- direct flocking is performed electrostatically by imparting a charge to the flock fibers and using an electric field to deposit the flock fibers on the oppositely charged substrate.
- the insert 112 acts as a mask and prevents flock fibers from being deposited in the area(s) to be occupied by inserts 112.
- step 712 the third permanent adhesive 128, if not already applied to the reverse side of the porous film 116, is now contacted with that side.
- step 716 the assembly is heated sealed to thermoplastically set the first and third adhesives.
- the adhesive layers which is typically r r consider ⁇ ' i ⁇ ,,, ⁇ .,,. ⁇ iui n;:: ⁇ ,/ ⁇ ::;:; Is " " " .,. performed using radiation (e.g., heat or light)
- the flocked surface can be vacuumed to remove loose flock fibers.
- the final three dimensional design 800 is depicted in Fig. 8.
- the design 1300 includes the flock 208, insert 112, and first and second permanent adhesives 124 and 128.
- the first permanent adhesive 124 is preferably a thermoset adhesive
- the second permanent adhesive 128 is a thermoplastic hot melt adhesive.
- the insert 112 components are also shown in Fig. 10.
- the insert 112 comprises first 0 and second polymer films 1304 and 1308 (which are preferably polycarbonate films) sandwiching a metal film 1312 and laminate adhesive 1316.
- the insert 112 is formed by depositing the metal film 1312, such as by vapor deposition techniques, on the first polymer film 1304, followed by contacting the metal film or second polymer film 1308 with the laminate adhesive 1316, and finally laminating the first and second polymer films, metal film, 5 and laminate adhesive together.
- the first or second polymer film can be colored, using suitable dyes or pigments or other colorants. Metal shades can be thus produced, such as brass,) copper, and the like.
- the insert is able to withstand exposure to temperature extremes and water, including washing and heat pressing.
- Other metallized films 0 and/or laminates will let the metal layer begin to corrode (e.g., from the combined effects of water and detergent) from the outside edges where it is exposed and the corrosion progresses into the laminate, which delaminates the two films at the metal layer.
- the first permanent adhesive is a composite of a thermoset adhesive contacting the flock and a thermoplastic adhesive contacting the insert.
- the 5 thermoplastic adhesive is preferably a hot melt adhesive
- Fig. 11 shows the process to manufacture the product of Fig. 10.
- a flocked transfer comprising a porous film, water-based release adhesive, and flock, is formed by electrostatic flocking techniques.
- step 1404 the free ends of the flock in the flock transfer are contacted with the first 0 permanent adhesive and insert.
- the first permanent adhesive is heated to adhere to the flock.
- the first permanent adhesive is thermoset in this step.
- This step may be performed by any technique, with lamination techniques being preferred. A preferred technique is discussed in copending U.S. Application Serial Nos. 09/621,830, filed July 24, 2000; 10/455,541, filed June 4, 2003; and 10/670,091, filed September 23, 2003.
- step 1408 the flock transfer/first permanent adhesive/insert assembly is contacted with the second permanent adhesive to form the three dimensional design 1412.
- This step may be performed using any technique, with lamination techniques being preferred. A preferred technique is discussed in copending U.S. Application Serial Nos. 09/735,721, filed December 13, 2000, and 10/455,575, filed June 4, 2003.
- the process to produce the media commences by bringing together, such as by lamination techniques, a flocked release sheet, pressure sensitive adhesive 1500, and the insert 112.
- the flocked release sheet includes flocked areas 104 embedded in the release adhesive 212, which is applied to the carrier sheet 204.
- the pressure sensitive adhesive 1500 is backed by a paper backing 1504.
- the flocked areas 104 are discontinuous being separated by a space 1508 sized to receive the insert 112.
- the pressure sensitive adhesive 1500 is applied to a surface of the insert 112.
- the paper backing 1504 is then removed and the pressure sensitive adhesive 1500 adhered to the release adhesive 212.
- the release adhesive 212 may be omitted from the space 1508, which is to be free of flock. The omission of the release adhesive from this area may be done using screen printing techniques.
- the tack adhesive 1500 is omitted and the release adhesive 212 included in the space 1508 to adhere the insert temporarily to the carrier sheet 204.
- a layer of a hot melt adhesive 1600 is applied to the free surfaces of the flock and the insert 112.
- the hot melt adhesive 1600 is applied as a compatible hot melt powder having a grind size of preferably no more than about 250 microns, even more preferably of no more than about 225 microns and even more preferably ranging from about 40 to about 200 microns.
- the hot melt powder is preferably in the form of a polyester.
- the free surfaces of the flock and insert 112 are screen printed with a permanent latex fiber adhesive, which is coated with the hot melt powder. The coated hot melt powder is then dried, vacuum brushed, and cured to prepare it for application to a substrate, such as a textile.
- Fig. 14 shows the assembly being applied to a substrate 1700.
- the adhesive layer 1600 is applied to the substrate in the presence of heat, such as applied by an iron, to soften the hot melt adhesive and cause it to adhere to the substrate.
- the hot melt adhesive readily adheres the flock and insert 112 to the substrate 1700.
- the carrier sheet 204, release adhesive 112, and pressure sensitive adhesive 1500 are peeled away from the media.
- the flocked areas 104 and insert 112 remain permanently affixed to the substrate 1700.
- the insert can include other design media in addition to or in lieu of the metal film.
- the design media include, for example, glass particles (e.g., sequins), ceramic particles, textiles, and the like.
- the insert 112 can be bonded directly to the porous film 116 in the absence of an intervening adhesive.
- the porous film 116 can be formulated to * have adhesive properties.
- the present invention in various embodiments, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various embodiments, subcombinations, and subsets thereof. Those of skill in the art will understand how to make and use the present invention after understanding the present disclosure.
- the present invention in various embodiments, includes providing devices and processes in the absence of items not depicted and/or described herein or in various embodiments hereof, including in the absence of such items as may have been used in previous devices or processes, e.g., for improving performance, achieving ease and ⁇ or reducing cost of implementation.
Abstract
The present invention is directed to flocked articles comprising a metallized film and methods of manufacturing such articles.
Description
FLOCKED ARTICLES HAVING NONCOMPATIBLE INSERT
AND POROUS FILM
FIELD
The invention relates generally to flocked articles and particularly to flocked graphics.
BACKGROUND
Flocked articles are used in a wide variety of applications. Flocked articles are being used for textile decoration as well as molded articles. Flock is a short precision cut or pulverized natural or synthetic fiber used to produce a velvet like coating on cloth, rubber, film, or paper. Flock generally has a length between about 0.010 to 0.250 inches (0.25mm to 6.25mm).
In these applications, it has been highly desired to have multi-media flocked articles including a material having a metallic sheen or luster. Metal noncompatible inserts have been used in the prior art but the metal inserts have rapidly faded due to ultraviolet light exposure, wear, and/or the effects of repeated washings. It is therefore desirable to have a multi-media flocked article having a noncompatible insert that resists fading.
SUMMARY
These and other needs are addressed by the various embodiments and configurations of the present invention. The present invention is directed to flocked articles and graphics comprising a compatible and/or noncompatible (or incompatible) material, such as a metallized film. As used herein, a "metallized film" refers to any material, whether metal or a nonmetal, having a metal-like appearance (e.g., metal-like sheen or luster).
In one embodiment of the present invention, a metallized film is used to provide a number of highly attractive colors, sheens and matte finishes, hi one configuration, the metallized film is metallic in appearance. In one configuration, it contains a metal layer vapor deposited on a first polymeric film with a second polymeric film being located on the opposing side of the metal layer. The metal layer is sandwiched between the first and second polymeric layers by means of a laminate adhesive. The polymeric layers can be UV-resistant, water resistant, thermally stable, and otherwise designed to resist wear and deterioration. Preferably, the polymeric layers are a polycarbonate. Thus, unlike conventional metal-containing noncompatible inserts water discoloration of the insert is typically not a problem. This can obviate the need to apply additional protective layers to the insert to protect any metal from oxidation.
The metallized film can have a highly desirable mirror-like metallic look from the metallized layer, a high abrasion resistance of the sandwiching polymeric films to protect the metal and laminate adhesive from fading, discoloration, and/or corrosion, and a high ability to
accept and adhere to a wide variety of hot melt thermoplastic or thermoset adhesives, whether in the form of a liquid, power, or preformed film.
The flocked article can include a porous film to act as a binder or tie material for the otherwise incompatible or weakly compatible materials, namely the flock and the metallized film. The porous film can bond well to a number of otherwise compatible and noncompatible materials on opposite sides, thus serving well as a so-called "tie coat" layer. For example, the film bonds to a variety of adhesives as noted above. The adhesives can be applied as a thermoplastic powder, a self-supporting heat-activated film, or as a liquid coating. In particular, the film may be readily laminated to pre-formed, self-supporting films of thermoset and/or thermoplastic adhesive(s)s, including hot melt adhesive(s).
The porous film, though having modest tensile strength when taken alone, can experience substantial improvements in tensile strength when combined with one or more other materials. For example, the film, by itself, lacks the strength of conventional paper carriers and therefore would at first blush appear to be a poor candidate for use in a machine (web) based-process and in products that need to be durable. However, when coated with water or solvent-based release adhesives the release adhesives not only provide an adhesive surface to capture and hold flock fibers but also provides a substantial improvement in film strength after the adhesive is dried and cured. While not wishing to be bound by any theory, it is believed that the release adhesive is carried into the film matrix by the combined effects of the film's porosity and permeability and, after drying, substantially fills the pores in the film to provide the desired strength enhancement.
The synergistic effect of the release adhesive and the porosity/permeability of the film makes the porous film strong enough to withstand the forces applied during subsequent processing stages , such as web-type tensile forces, vacuum cleaning, mechanical brushing, baking, and heat transfer application processes (e.g., heat pressing, cooling, pulling the carrier, and releasing the fibers). Additional support film(s) may nonetheless be added to the side of the porous film opposite the side containing the flock to provide further support.
These and other advantages will be apparent from the disclosure of the invention(s) contained herein.
The above-described embodiments and configurations are neither complete nor exhaustive. As will be appreciated, other embodiments of the invention are possible utilizing, alone or in combination, one or more of the features set forth above or described in detail below.
. ..
As used herein, "at least one", "one or more", and "and/or" are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions "at least one of A, B and C", "at least one of A, B, or C", "one or more of A, B, and C", "one or more of A, B, or C" and "A, B, and/or C" means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B and C together.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a cross section of a three dimensional design according to an embodiment of the present invention; Fig.2 is a block diagram of a process embodiment to make an intermediate flocked article for use in the three dimensional design;
Fig. 3 is a cross section of an intermediate flocked article;
Fig. 4 is a block diagram of a process embodiment to make an insert assembly for use in the three dimensional design; Fig. 5 is a cross section of an insert assembly;
Fig. 6 is a block diagram of a process embodiment to make the three dimensional design; Fig. 7 is a block diagram of a process embodiment to make a three dimensional design according to another embodiment;
Fig. 8 is a cross section of the three dimensional design; Fig. 9 is an exemplary decorative media according to an embodiment of the present invention;
Fig. 10 is a cross section of another embodiment of a three dimensional design in accordance with the present invention;
Fig. 11 is a block diagram of a process to make the three dimensional design of Fig. 10; Fig. 12 is a side view of a decorative media in a first step of a production process according to an embodiment of the present invention;
Fig. 13 is a side view of the decorative media in a second step of the production process;
Fig. 14 is a side view of the decorative media in a third step of the production process; and Fig. 15 is a side view of the decorative media after application to a substrate.
/ .»:=,U t./ DETA^ED DESCRJPTΪON
Figs. 1 and 9 show a three-dimensional design according to an embodiment of the present invention. The design 100 includes (multi-colored or sublimation printed) flocked areas 104 surrounding a plurality of compatible or noncompatible inserts 112. The inserts 112 are adhered to a porous film 116 by a first adhesive 120. Additionally, the porous film 116 is adhered to the flock areas 104 by a flock (second) adhesive 124. Finally, the design 100 is adhered to a desired substrate, such as a textile, by a permanent (third) adhesive 128.
The inserts 112 can be any design media, such as glass beads. In a preferred embodiment, the inserts 112 are formed from one or more polymeric light diffusing films, such as polycarbonate and/or polyester light diffusion films sold under the tradenames Makrofol™ and/or Bayfol™. The films are preferably metal-containing and have a first and/or second surface gloss (60° angle with black inked second surface) of at least about 50 gloss units, more preferably of at least about 75 gloss units, and even more preferably of at least about 75 gloss units, first and/or second surface roughnesses (R3Z) of no more than about 20 microns, more preferably of no more than about 3 microns, and even more preferably of no more than about 1 micron, and a luminous transmittance of no more than about 50%, more preferably no more than about 5%, and even more preferably no more than about 1%. The insert 112 preferably has a metallic or nonmetallic sheen and a gloss/fine matte and a thickness of no more than about 0.5 inches, more preferably of no more than about 0.25 inches, and even more preferably of no more than about 0.20 inches. A particularly preferred insert is Makrofol™ DPF 5072™.
The porous film 116 is preferably a microporous material that includes a matrix of substantially water insoluble thermoplastic organic polymer, finely divided substantially water-insoluble filler particles and a network of interconnected pores communicating substantially throughout the microporous material. The filler particles are distributed throughout the matrix and constitute from about 40 to about 90 percent by weight of the microporous material. The filler particles are a metal oxide, such as alumina, silica, and titania with silica being preferred. Preferably, at least 50 percent by weight of the particles are amorphous precipitated silica particles. The particles have a preferred maximum dimension of less than about 5 micrometers, more preferably no more than about 1 micrometer, even more preferably no more than about 0.1 micrometers, and even more preferably no more than about 0.05 micrometers and a preferred average pore size of less than
f4 "3 Ut l ,/■' ir!y if - "
1 micrometer and more" preferably of no more than about 0.1 micrometer. The pores preferably constitute from about 35 to about 95 percent by volume of the microporous material. The matrix of the microporous material includes a water-insoluble thermoplastic organic polymer. Examples of suitable polymers include polyolefms, poly(halo-substituted olefins), polyesters, polyethylenes, polyamides, polyurethanes, polyureas, polyvinyl halides), poly(vinylidene halides), polystyrenes, polyvinyl esters), polycarbonates, polyethers, polysulfides, polyimides, polysilanes, polysiloxanes, polycaprolactones, polyacrylates, and polymethylacrylates, with polyvinyl chloride), copolymers of vinyl chloride, and mixtures thereof being preferred. The material may further include plasticizers, lubricants, and antioxidants.
The microporous material is preferably coated with a substantially nonporous coating composition including a volatile liquid medium (e.g., water and/or a nonaqueous solvent) and binder dissolved or dispersed in the medium. The binder includes a film-forming organic polymer, preferably including (a) water-soluble poly(ethylene oxide) having a preferred weight average molecular weight in the range of from about 100,000 to 3,000,000 and (b) water-soluble or water-dispersible crosslinkable urethane-acrylate hybrid polymer. In addition to or in lieu of poly (ethylene oxide), the organic polymer may further include additional organic polymers such as water-soluble cellulosic organic polymers, water-soluble noncellulosic organic polymers, and/or water dispersible polymers such as poly(ethylene-co- acrylic acid), poly(ethylene),and polyethylene oxide). The poly(ethylene oxide) includes copolymers of ethylene oxide with lower alkylene oxide and homopolymers of ethylene oxide. Preferably, the organic polymer component of the coating includes from about 20 to about 80% by weight of the urethane-acrylate hybrid polymer. The coating may further include surfactants and adjuvant materials. After drying and crosslinking, the peel strength between the coating and microporous material substrate is high.
The film has a preferred puncture strength of greater than about 300g/25.4 μm, a preferred tensile strength of less than about 2% at 1000 psi, and a preferred thermal ability of less than about 5% shrinkage after 160 minutes at 90°C.
A preferred porous film is further discussed in U.S. 6,025,068, which is incorporated herein by this reference. A particularly preferred porous film is sold by PPG Industries Inc. under the tradename Teslin™. Battery separator membranes can also be used. Examples include Daramic Industrial CL™ sold by Daramic, Inc., and the battery separator membranes
„■■' y ::;;:iι u «3 /' c: 1 sold by Celgard, or by Daramic, Inc. under the tradename Artisyn™. Artisyn™ is an uncoated, mono-layer, highly filled polyolefm sheet.
The flock fibers in the flock layer 1104 can be any desirable material, whether natural or synthetic. Preferably, the flock is composed of polyester (such as poly(ethylene terephthalate) and poly(cyclohexylene-dimethylene terephthalate)), vinyl, nylon, rayon, and the like.
The various permanent adhesives 1108, 1116, and 1120 can be any suitable adhesive, with water- and solvent-based adhesives and preformed film adhesives being preferred. Preferred permanent adhesives include thermoset and hot melt thermoplastic adhesives, whether as a liquid, powder, or (pre-formed) self-supporting film. As will be appreciated, thermoset adhesives solidify, activate and/or set irreversibly when heated above a certain temperature. This property is usually associated with a cross-linking reaction of the molecular constituents induced by heat or radiation. Thermoset adhesives can include curing agents such as organic peroxides, isocyanates, or sulfur. Examples of thermoplastic and thermosetting adhesives include polyethylene, phenolics, alkyds, acrylics, amino resins, polyesters, epoxides, polyurethanes, polyamides, and silicones.
The adhesives 1108, 1116, and 1200 may contain additives, such as fillers, catalysts, colorants (dyes or pigments) and optical blocking/reflective/absorbtive materials. The preferred porous film, namely Teslin™ and Artisyn™, can be highly sensitive to Ultraviolet (UV) radiation and can degrade rapidly when exposed to direct sunlight. Accordingly, the adhesives may contain light blocking, absorbing, and/or reflecting materials to decrease substantially the optical transmissivity of the adhesive. Preferably, the adhesive, when on the light contacting side of the porous film, blocks at least about 75%, more preferably at least about 85%, and even more preferably at least about 95% of the UV radiation spectrum. Such optical blocking/reflecting/absorbing materials are known to those of skill in the art.
Referring to Figs. 1-6 and 9, a first process embodiment to manufacture the three dimensional design 100 will now be described. It is to be appreciated that those of ordinary skill in the art will envision other methods of manufacturing the design 100. Such other methods are considered to be a part of the present invention. With reference to Fig. 2, the steps to produce an intermediate flocked article 300 will now be described.
/ , ««. . - , . . , -, , -, „„„ • ,
In step 200 a carrier sheet 204 is flocked with flock fibers 208 in the reverse order of the desired pattern. The carrier sheet can be any substrate that is dimensionally stable under the conditions of temperature and pressure encountered during the process. The carrier sheet 204 is preferably a porous film, such as the porous film 116 described above, coated with a release adhesive 212, which is preferably water-based. Typically (but not always), the carrier is a discontinuous sheet as opposed to a continuous sheet on a running web line.
The release adhesive 212 can be any adhesive that adheres more strongly to the carrier sheet than the flock fibers but adheres to both enough to hold them together. For example, the release adhesive 212 can be any temporary adhesive, such as a resin or a copolymer, e.g., a polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral, acrylic resin, polyurethane, polyester, polyamides, cellulose derivatives, rubber derivatives, starch, casein, dextrin, gum arabic, carboxymethyl cellulose, rosin, silicone, or compositions containing two or more of these ingredients.
It is desired that, when the flock fibers are removed from the release adhesive, the fibers are substantially free of release adhesive. The release adhesive may be applied in the form of a solution or emulsion. The release adhesive may be applied on the carrier in the perimeter shape of the desired design or without regard to the overall design desired. The ' release adhesive may be applied by any suitable technique such as, for example, by applying i the release adhesive with rollers or spraying the release adhesive. In optional step 216, the exposed ends 224 of the flocked surface are sublimation printed to provide the desired design on the flock. Sublimation printing is described in copending U.S. Applications 10/614,340, filed July 3, 2003; 11/139,439, filed May 26, 2005; and 11/036,887, filed January 14, 2005, to Abrams, each of which is incorporated herein by this reference. As will be appreciated, common ways of performing sublimation ink direct printing include inkjet or screen sublimation ink printing and sublimation transfer printing using devices such as an inkjet dye sub printer, a ribbon-based dye sub printer, a hybrid sublimation printer, and a small dye sub ribbon-based printer. In inkjet (direct) sublimation ink printing, a special heat sensitive dye is used in a computer-controlled printer, such as an HP 550™, or Mimaki JV4™ to sublimation print the ink onto the flock fibers through vapor phase transportation of the ink from the printer to the flock fibers. The transferred dye is then heat and pressure thermofixed and thereby enters the amorphous areas of the fiber matrix. As
noted, vacuuming of the flock can be conducted preferably before or after sublimation ink printing. Commonly, the color must go all the way down the fiber.
In optional step 220, the free ends 224 of the flock are coated with a binder adhesive 228. This process is discussed in U.S. Patents 4,810,549; 5,207,851; 5,597,637; 5,858,156; 6,010,764; 6,083,332; and 6,110,560, which are incorporated herein by this reference. A suitable binder adhesive is a water based acrylic which binds the flock together as a unit. The binder adhesive 228 adhesive may contain a hot melt adhesive. hi step 232, the permanent (second) adhesive 124 is contacted with the free ends 224 of the flock 208 (or with the binder adhesive 228 depending on the process configuration employed), hi one configuration, the second adhesive 124 is a thermoplastic or thermoset adhesive and is heated to a temperature sufficient to adhere the adhesive 124 to the flock 208. For a thermoset adhesive, the temperature is below the temperature at which the adhesive cross-links and is no longer reversible.
In step 236, areas of the assembly are removed to form voids 240 to receive the inserts 112. will be appreciated, the sizes of the areas removed are approximately the same size as the size of the corresponding insert 112. The void 240 passes completely through the assembly. In other words, the void 240 is free of adhesives 120, 224, and 212, the carrier sheet 204, and flock 208.
The process yields the intermediate flocked article 300 shown in Fig. 3. With reference to Fig. 4, the steps to produce the insert 112 will now be described. hi step 400, the first permanent adhesive 120 is contacted with the noncompatible insert 112.
In step 404, the upper surface of the porous film 116 (of which the lower surface has previously been contacted with the third permanent adhesive 128) is contacted with the first permanent adhesive 120. hi step 408, the insert 112 and first permanent adhesive 120 are cut to the size and shape of the void 240 in the intermediate flocked article 300. Cutting may be made by known techniques, such as a laser or a mechanical cutting device. hi step 412, the first (and third) permanent adhesives 120 and 128 are heat sealed. Heat sealing preferably occurs at a temperature within the thermoplastic behavior regime.
Thus, when the permanent adhesive is a thermoset adhesive, the adhesive following step 412 is not thermoset.
u&ub / e 1 t 1 j Δ ΛnΛ Λna Λ Λ Λ ^
As will be appreciated, steps 404, 408, and 412 may be performed in any order. For example, step 408 may be performed before step 404. Steps 400, 404, and 412 can be performed simultaneously, such as by lamination.
In step 416, the porous film, which was not cut in step 408, is cut to a size slightly larger than the void 240. This oversize relative to the void size is shown in Fig. 1. The overlapping edge of the porous film is used to secure the insert to the intermediate flocked article.
In step 420, a tack adhesive 504 is applied to the overlapping edge of the porous film to provide the insert assembly 500 depicted in Fig. 5. Fig. 6 depicts the final steps of the process to form the three dimensional design 100.
In step 600, the insert 112 is positioned in the void 240 as shown in Fig. 1. The tack adhesive 504 temporarily holds the insert assembly 500 in position.
In step 604, the consolidated assembly formed from the insert assembly 500 and intermediate flocked article 300 is heat sealed to thermoplastically (and reversibly) set the second adhesive 124 and permanently adhere the porous film 116 to the flocked article 300.
The final three dimensional design 100 is shown in Fig. 1.
Another process embodiment to form a three dimensional design is depicted in Figs. 7 and 8. The design 800 includes the flock 208, insert 112, porous film 116, and first and third adhesives 120 and 128. In step 700, the porous film 116 is contacted with the first (and optionally third) permanent adhesives 120 and 128.
In step 704, the incompatible insert 112 is positioned on the first permanent adhesive 120.
In step 708, the exposed portions of the first permanent adhesive 120 are direct flocked by known techniques. Preferably, direct flocking is performed electrostatically by imparting a charge to the flock fibers and using an electric field to deposit the flock fibers on the oppositely charged substrate. The insert 112 acts as a mask and prevents flock fibers from being deposited in the area(s) to be occupied by inserts 112.
In optional step 712, the third permanent adhesive 128, if not already applied to the reverse side of the porous film 116, is now contacted with that side.
In step 716, the assembly is heated sealed to thermoplastically set the first and third adhesives. Following heat sealing or curing of the adhesive layers, which is typically
r r „■' iι,,,μ .,,.ιι iui n;::ιι ,/ ιι::;:; Is " " .,. performed using radiation (e.g., heat or light), the flocked surface can be vacuumed to remove loose flock fibers.
The final three dimensional design 800 is depicted in Fig. 8.
Another process embodiment to form a three dimensional design is depicted in Figs. 5 10 and 11. The design 1300 includes the flock 208, insert 112, and first and second permanent adhesives 124 and 128. The first permanent adhesive 124 is preferably a thermoset adhesive, and the second permanent adhesive 128 is a thermoplastic hot melt adhesive.
The insert 112 components are also shown in Fig. 10. The insert 112 comprises first 0 and second polymer films 1304 and 1308 (which are preferably polycarbonate films) sandwiching a metal film 1312 and laminate adhesive 1316. The insert 112 is formed by depositing the metal film 1312, such as by vapor deposition techniques, on the first polymer film 1304, followed by contacting the metal film or second polymer film 1308 with the laminate adhesive 1316, and finally laminating the first and second polymer films, metal film, 5 and laminate adhesive together. To created desired metal appearances, the first or second polymer film can be colored, using suitable dyes or pigments or other colorants. Metal shades can be thus produced, such as brass,) copper, and the like.
As a result of the properties of the adhesive, the insert is able to withstand exposure to temperature extremes and water, including washing and heat pressing. Other metallized films 0 and/or laminates will let the metal layer begin to corrode (e.g., from the combined effects of water and detergent) from the outside edges where it is exposed and the corrosion progresses into the laminate, which delaminates the two films at the metal layer.
In other configurations, the first permanent adhesive is a composite of a thermoset adhesive contacting the flock and a thermoplastic adhesive contacting the insert. The 5 thermoplastic adhesive is preferably a hot melt adhesive
Fig. 11 shows the process to manufacture the product of Fig. 10. In step 1400, a flocked transfer, comprising a porous film, water-based release adhesive, and flock, is formed by electrostatic flocking techniques.
In step 1404, the free ends of the flock in the flock transfer are contacted with the first 0 permanent adhesive and insert. The first permanent adhesive is heated to adhere to the flock.
Preferably, the first permanent adhesive is thermoset in this step. This step may be performed by any technique, with lamination techniques being preferred. A preferred technique is
discussed in copending U.S. Application Serial Nos. 09/621,830, filed July 24, 2000; 10/455,541, filed June 4, 2003; and 10/670,091, filed September 23, 2003.
In step 1408, the flock transfer/first permanent adhesive/insert assembly is contacted with the second permanent adhesive to form the three dimensional design 1412. This step may be performed using any technique, with lamination techniques being preferred. A preferred technique is discussed in copending U.S. Application Serial Nos. 09/735,721, filed December 13, 2000, and 10/455,575, filed June 4, 2003.
Yet another embodiment of the composite media will be described with reference to Figs. 12-15. The media is based on the processes described in U.S. Patents 6,010,764 and 6, 110,560, each of which is incorporated herein by this reference.
With reference to Fig. 12, the process to produce the media commences by bringing together, such as by lamination techniques, a flocked release sheet, pressure sensitive adhesive 1500, and the insert 112. The flocked release sheet includes flocked areas 104 embedded in the release adhesive 212, which is applied to the carrier sheet 204. The pressure sensitive adhesive 1500 is backed by a paper backing 1504. The flocked areas 104 are discontinuous being separated by a space 1508 sized to receive the insert 112. The pressure sensitive adhesive 1500 is applied to a surface of the insert 112. The paper backing 1504 is then removed and the pressure sensitive adhesive 1500 adhered to the release adhesive 212. For better adhesion, the release adhesive 212 may be omitted from the space 1508, which is to be free of flock. The omission of the release adhesive from this area may be done using screen printing techniques. In another configuration, the tack adhesive 1500 is omitted and the release adhesive 212 included in the space 1508 to adhere the insert temporarily to the carrier sheet 204.
With reference to Fig. 13, a layer of a hot melt adhesive 1600, whether applied as a preformed self-supporting layer, powder, or liquid, is applied to the free surfaces of the flock and the insert 112. Preferably, the hot melt adhesive 1600 is applied as a compatible hot melt powder having a grind size of preferably no more than about 250 microns, even more preferably of no more than about 225 microns and even more preferably ranging from about 40 to about 200 microns. The hot melt powder is preferably in the form of a polyester. In one configuration, the free surfaces of the flock and insert 112 are screen printed with a permanent latex fiber adhesive, which is coated with the hot melt powder. The coated hot
melt powder is then dried, vacuum brushed, and cured to prepare it for application to a substrate, such as a textile.
Fig. 14 shows the assembly being applied to a substrate 1700. The adhesive layer 1600 is applied to the substrate in the presence of heat, such as applied by an iron, to soften the hot melt adhesive and cause it to adhere to the substrate. The hot melt adhesive readily adheres the flock and insert 112 to the substrate 1700.
Referring to Fig. 14, after adherence to the substrate 1700 the carrier sheet 204, release adhesive 112, and pressure sensitive adhesive 1500 are peeled away from the media. Thus, only the flocked areas 104 and insert 112 remain permanently affixed to the substrate 1700.
A number of variations and modifications of the invention can be used. It would be possible to provide for some features of the invention without providing others.
For example, the insert can include other design media in addition to or in lieu of the metal film. The design media include, for example, glass particles (e.g., sequins), ceramic particles, textiles, and the like.
By way of further illustration, the insert 112 can be bonded directly to the porous film 116 in the absence of an intervening adhesive. The porous film 116 can be formulated to * have adhesive properties.
The present invention, in various embodiments, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various embodiments, subcombinations, and subsets thereof. Those of skill in the art will understand how to make and use the present invention after understanding the present disclosure. The present invention, in various embodiments, includes providing devices and processes in the absence of items not depicted and/or described herein or in various embodiments hereof, including in the absence of such items as may have been used in previous devices or processes, e.g., for improving performance, achieving ease and\or reducing cost of implementation.
The foregoing discussion of the invention has been presented for purposes of illustration and description. The foregoing is not intended to limit the invention to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the invention are grouped together in one or more embodiments for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an
, , intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the invention.
Moreover, though the description of the invention has included description of one or more embodiments and certain variations and modifications, other variations and modifications are within the scope of the invention, e.g., as maybe within the skill and knowledge of those in the art, after understanding the present disclosure. It is intended to obtain rights which include alternative embodiments to the extent permitted, including alternate, interchangeable and/or equivalent structures, functions, ranges or steps to those claimed, whether or not such alternate, interchangeable and/or equivalent structures, functions, ranges or steps are disclosed herein, and without intending to publicly dedicate any patentable subject matter.
Claims
1. An article, comprising:
(a) an insert comprising a design media other than flock;
(b) a flock layer; and (c) a porous film, the flock layer and insert being located on a common side of the porous film.
2. The article of claim 1, wherein the insert comprises first and second polymeric layers sandwiching a metal layer and a lamination adhesive.
3. The article of claim 1, wherein the insert is noncompatible and wherein the insert comprises one or more of glitter, glass particles, ceramic particles, and a textile
4. The article of claim 1, wherein the insert is adhered directly to the porous film in the absence of an adhesive.
5. An article, comprising:
(a) an insert comprising first and second polymeric layers sandwiching a design media and a lamination adhesive;
(b) a flock layer; and
(c) a substrate common to the insert and flock layer.
6. The article of claim 5, wherein the design media is a metal layer.
7. The article of claim 5, wherein the substrate is a porous film and wherein the insert and flock layer are adhered to the substrate by a permanent adhesive.
8. A method, comprising:
(a) providing a flock transfer, the flock transfer comprising a carrier sheet, a release adhesive, and a flock layer, a first surface of the flock layer being adhered to the carrier sheet by the release adhesive; (b) applying a permanent adhesive to a second surface of the flock layer to form a transfer assembly, the first and second surfaces being in an opposing relationship with one another;
(c) removing a selected portion of the flock layer from at least one of the transfer and transfer assembly to form a void; (d) positioning the transfer assembly and insert on a common substrate, the insert being positioned in the void; and ,, ,.
(e) adhering the transfer assembly and insert to a first surface of the common substrate.
9. The method of claim 8, wherein the common substrate is a porous film.
10. The method of claim 8, wherein the insert comprises first and second polymeric films sandwiching a design media and a lamination adhesive.
11. The method of claim 8, wherein the insert is adhered to the common substrate before the transfer assembly.
12. The method of claim 12, wherein the common substrate is larger than the insert providing an overlapping edge and wherein step (d) comprises the sub-step of applying an adhesive to the overlapping edge, wherein the overlapping edge contacts the second surface of the flock.
13. The method of claim 12, further comprising:
(f) applying a permanent adhesive to the second surface of the flock and to a second surface of the substrate, wherein the first and second surfaces of the substrate are in an opposing relationship.
14. The method of claim 12, wherein a first permanent adhesive applied to the overlapping edge is a thermoset adhesive and a second permanent adhesive applied to the second surface of the flock is a thermoset adhesive.
15. A method, comprising: (a) applying a permanent adhesive to a first surface of a substrate;
(b) adhering an insert to the permanent adhesive, the insert comprising a design media, wherein, after step (b), a first portion of the adhesive comprises the insert and a second portion of the adhesive is a free surface; and
(c) adhering flock to the free surface of permanent adhesive.
16. The method of claim 14, wherein, in step (c), the flock is electrostatically applied to the permanent adhesive and wherein, during electrostatic flock application, the insert blocks flock from adhering to the first portion of the adhesive.
17. A method, comprising:
(a) adhering flock in at least a first area but not a second area on a release adhesive coated carrier, the release adhesive being omitted from the second area;
(b) positioning an insert in the second area; and (c) substantially simultaneously applying a permanent adhesive to an exposed surface of the flock and insert.
18. The method of claim 17, wherein the carrier is a porous film.
19. The method of claim 17, wherein a tack adhesive is applied to the insert to adhere temporarily the insert to the carrier.
20. The method of claim 17, wherein the insert comprises first and second polymer films sandwiching a metal layer and a lamination adhesive.
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US60/703,925 | 2005-07-28 | ||
US70468105P | 2005-08-01 | 2005-08-01 | |
US60/704,681 | 2005-08-01 | ||
US70757705P | 2005-08-11 | 2005-08-11 | |
US60/707,577 | 2005-08-11 | ||
US71036805P | 2005-08-22 | 2005-08-22 | |
US60/710,368 | 2005-08-22 | ||
US71686905P | 2005-09-13 | 2005-09-13 | |
US60/716,869 | 2005-09-13 | ||
US71946905P | 2005-09-21 | 2005-09-21 | |
US60/719,469 | 2005-09-21 | ||
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US60/779,317 | 2006-03-03 | ||
US78652806P | 2006-03-27 | 2006-03-27 | |
US60/786,528 | 2006-03-27 |
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PCT/US2006/029409 WO2007016341A2 (en) | 2005-07-28 | 2006-07-27 | Flocked articles incorporating a porous film |
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- 2006-07-27 WO PCT/US2006/029410 patent/WO2007016342A2/en active Application Filing
- 2006-07-27 AU AU2006275682A patent/AU2006275682A1/en not_active Abandoned
- 2006-07-27 EP EP20060788789 patent/EP1917137A2/en not_active Withdrawn
- 2006-07-27 US US11/460,493 patent/US20080102239A1/en not_active Abandoned
- 2006-07-27 US US11/460,519 patent/US7799164B2/en not_active Ceased
- 2006-07-27 KR KR1020087004705A patent/KR20080034486A/en not_active Application Discontinuation
- 2006-07-27 WO PCT/US2006/029409 patent/WO2007016341A2/en active Application Filing
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2012
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AU2006275682A1 (en) | 2007-02-08 |
AU2006275682A2 (en) | 2008-03-20 |
USRE45802E1 (en) | 2015-11-17 |
US7799164B2 (en) | 2010-09-21 |
US20070026189A1 (en) | 2007-02-01 |
KR20080034486A (en) | 2008-04-21 |
JP2009502485A (en) | 2009-01-29 |
WO2007016342A3 (en) | 2008-01-17 |
WO2007016341A2 (en) | 2007-02-08 |
US20080102239A1 (en) | 2008-05-01 |
EP1917137A2 (en) | 2008-05-07 |
WO2007016341A3 (en) | 2007-11-29 |
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