WO2006130880A1 - Kit contenant un materiau de transfert d'image sans support - Google Patents

Kit contenant un materiau de transfert d'image sans support Download PDF

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Publication number
WO2006130880A1
WO2006130880A1 PCT/US2006/021668 US2006021668W WO2006130880A1 WO 2006130880 A1 WO2006130880 A1 WO 2006130880A1 US 2006021668 W US2006021668 W US 2006021668W WO 2006130880 A1 WO2006130880 A1 WO 2006130880A1
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WO
WIPO (PCT)
Prior art keywords
layer
image
melt transfer
melt
receiving layer
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Application number
PCT/US2006/021668
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English (en)
Inventor
Donald Hare
Original Assignee
Foto-Wear, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Foto-Wear, Inc. filed Critical Foto-Wear, Inc.
Publication of WO2006130880A1 publication Critical patent/WO2006130880A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
    • B41M5/0256—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet the transferable ink pattern being obtained by means of a computer driven printer, e.g. an ink jet or laser printer, or by electrographic means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
    • B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
    • B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
    • B41M5/0355—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic characterised by the macromolecular coating or impregnation used to obtain dye receptive properties

Definitions

  • the present invention relates to kits containing an optional tack free [non-stick] sheet, and an image transfer material, which does not have a support.
  • Textiles such as shirts (e.g., tee shirts) having a variety of designs thereon have become very popular in recent years. Many shirts are sold with pre-printed designs to suit the tastes of consumers. In addition, many customized tee shirt stores are now in the business of permitting customers to select designs or decals of their choice. Processes have also been proposed which permit customers to create their own designs on transfer sheets for application to tee shirts by use of a conventional hand iron, such as described in U.S. Patent No. 4,244,358. Furthermore, U.S. Patent No. 4,773,953, is directed to a method for utilizing a personal computer, a video camera or the like to create graphics, images, or creative designs on a fabric. These designs may then be transferred to the fabric by way of an ink jet printer, a laser printer, or the like.
  • U.S. Patent 5,798,179 is directed to a printable heat transfer material using a thermoplastic polymer such as a hard acrylic polymer or poly (vinyl acetate) as a barrier layer, and has a separate film-forming binder layer.
  • U.S. Patent 5,271,990 relates to an image-receptive heat transfer paper which includes an image-receptive melt-transfer film layer comprising a thermoplastic polymer overlaying the top surface of a base sheet.
  • U.S. Patent 5,502,902 relates to a printable material comprising a thermoplastic polymer and a film-forming binder.
  • U.S. Patent 5,614,345 relates to a paper for thermal image transfer to flat porous surfaces, which contains an ethylene copolymer or a ethylene copolymer mixture and a dye-receiving layer.
  • heat transfer materials are disclosed by, for example, U.S. Patent 6,410,200 which relates to a polymeric composition comprising an acrylic dispersion, an elastomeric emulsion, a plasticizer, and a water repellant .
  • U.S. Patent 6,358,660 relates to a barrier layer.
  • the barrier layer of 6,358,660 provides for "cold peel,” “warm peel” and “hot peel” applications and comprises thermosetting and/or ultraviolet (UV) curable polymers.
  • U.S. Patent 6,849,312 relates to a transferable material having a transfer blocking overcoat and to a process of using the heat transferable material having a transfer blocking overcoat .
  • the image that is placed on the imaging material may be transferred directly to the receptor element without need of an inverted or reversed image, such as disclosed in U.S. Patent No. 6,383,710 B2.
  • Traditional transfer materials required images to be added to the material in an inverted or reversed orientation so that the image, when placed face down on the receptor element, would appear in the correct orientation in the final product .
  • kits comprising an improved transfer sheet and optionally a non-stick sheet.
  • kits containing an image transfer material without a support and/or opaque layer comprising a tack free sheet, and an image transfer material which does not have a support and which does not have an opaque layer, wherein the image transfer material comprises at least one melt transfer layer and optionally at least one image-receiving layer if the melt transfer layer is not receptive to imaging.
  • the kit comprises an optional tack free sheet, and an image transfer material which does not a support and which does not have an opaque layer, wherein the image transfer material comprises at least one melt transfer layer and at least one image-receiving layer.
  • the melt transfer layer and the image-receiving layer optionally contains an opaque material within the melt transfer and/or image-receiving layer.
  • the kit comprises an optional tack free sheet, and an image transfer material which does not have a support, wherein the image transfer material comprises at least one melt transfer layer, at least one opaque layer, and at least one image- receiving layer.
  • the image transfer material also does not require a barrier layer since no support is present, thereby rendering the presence of a barrier layer unnecessary.
  • the image transfer material is thick enough such that the image-transfer material passes through a printer.
  • the top surface of the image-receiving layer is receptive to images, for instance, ink jet images, photocopy images, images by magic marker etc.
  • the melt transfer layer is itself image-receptive, the separate image receptive layer is optional.
  • the optional opaque material within the melt transfer layer or image receiving layer adds opacity.
  • the opaque material may be white for use when the receptor is dark or the opaque material may be dark when the receptor is light, to enhance visibility of the image when placed thereon.
  • the support-free imaging material of the invention which comprises at least one melt transfer layer and/or an image receiving layer may be optionally imaged, placed melt transfer layer side down on a receptor element, optionally imaged and then adhered to the receptor element using a heat source.
  • a tack free e.g. non-stick sheet
  • the image transfer material sticks to the heat source such as an iron.
  • the melt transfer layer and optional image receiving layer are placed, preferably image side up, on top of a receptor element, such as cotton or cotton/polyester blend fabrics or the like.
  • a tack free sheet is then optionally placed over the imaged material and heat, for instance, from a source such as a hand iron, or heat press is applied to the top of the optional tack free sheet. If a heat source such as an oven is used, a tack free sheet is unnecessary. A tack free sheet is also not necessary if the material does not stick to the heat source, such as a stick- free hand iron or stick-free heat press.
  • the melt transfer layer and optionally the image receiving layer then melts and adheres the image to the receptor element . After heat application, the optional non-stick sheet is removed if present and the image remains attached to the receptor element.
  • the melt transfer layer itself is of sufficient thickness so as to pass through a printer.
  • the combination of melt transfer layer and image receiving layer is of sufficient thickness so as to pass through a printer.
  • the thickness of the entire transfer material is of sufficient thickness so as to pass through a printer.
  • a suitable thickness of the at least one melt transfer layer when used without an image receiving layer so that it may pass through a printer may be readily determined by one of ordinary skill in the art depending on the specific type of melt transfer layer and printer used.
  • a suitable combined thickness of the at least one melt transfer layer and at least one image receiving layer may be readily determined so that it may pass through a printer by one of ordinary skill in the art depending on the specific type of melt transfer layer (s) used in combination with the specific types of image receiving layer (s) that are used.
  • a suitable combined thickness of the at least one melt transfer layer, at least one opaque layer, and at least one image receiving layer may be readily determined so that it may pass through a printer by one of ordinary skill in the art depending on the specific type of melt transfer layer (s) used in combination with the specific types of opaque and image receiving layer (s) that are used.
  • a suitable total thickness for the image receiving material is that thickness which allows the material to pass through a printer, and may be at least 3 mils thick, optionally at least 4 mils thick, still more optionally at least 5 mils thick, and still more optionally 6 mils thick.
  • the upper thickness limit of the image receiving material is simply that which is physically capable of passing through a printer.
  • FIGURE 1 is a cross-sectional view of one embodiment of the transfer element of the present invention.
  • FIGURE 2 illustrates the step of ironing the transfer element of the present invention onto a tee shirt or the like.
  • kits containing an image transfer material without a support and/or opaque layer comprising a tack free sheet, and an image transfer material which does not have a support and which does not have an opaque layer, wherein the image transfer material comprises at least one melt transfer layer and optionally at least one image-receiving layer if the melt transfer layer is not receptive to imaging.
  • the kit comprises an optional tack free sheet, and an image transfer material which does not a support and which does not have an opaque layer, wherein the image transfer material comprises at least one melt transfer layer and at least one image-receiving layer.
  • the melt transfer layer and the image-receiving layer optionally contains an opaque material within the melt transfer and/or image-receiving layer.
  • the kit comprises an optional tack free sheet, and an image transfer material which does not have a support, wherein the image transfer material comprises at least one melt transfer layer, at least one opaque layer, and at least one image- receiving layer.
  • the image transfer material does not require a barrier layer since no support is present, thereby rendering the presence of a barrier layer unnecessary.
  • the image transfer material is thick enough such that the image transfer material may pass through a printer.
  • the image transfer material may be thinner if it is otherwise imaged (e.g. via magic marker or other writing/painting utensil) and then applied to a receptor.
  • the top surface of the image-receiving layer is receptive to images, for instance, ink jet images, photocopy images, etc.
  • the optional opaque material within the melt transfer layer and/or image receiving layer adds opacity, such as white or dark, to enhance visibility of the image when placed thereon.
  • the top surface of the melt transfer layer or image receiving layer is optionally imaged using any conventional imaging technique including but not limited to, ink jet printers, bubblejet printers, thermal inkjet methods, piezo inkjet methods, laser printers, crayons, and the like.
  • the melt transfer layer or the image receiving layer and melt transfer layer are optionally imaged, and then placed, preferably image side up (when imaged) on top of the receptor element and further optionally imaged.
  • heat is applied (e.g., by way of a hand iron, a heat press or an oven), to the top of the optional image.
  • heat may be applied to the back side of the receptor.
  • heat may be applied to both the top of the optional image and the back side of the receptor.
  • a tack-free sheet should be placed between the iron or press and the imaged material, unless the heating device is itself tack-free.
  • the melt transfer layer melts and adheres the optionally imaged image-receiving layer to the receptor element.
  • the image-receiving layer also melts and adheres to the receptor element. After heat application, the non-stick sheet is removed and the image remains attached to the receptor element .
  • the image-receiving layer(s), when present, is coated onto the melt transfer layer (s) or onto the optional opaque layer (s) .
  • Ways of applying the melt transfer layer and/or the image receiving layer include but are not limited to extrusion and lamination.
  • the kit containing the transfer material of the present invention and the optional tack free sheet may also contain instructions for transferring an image thereon.
  • the kit may also contain optional markers, paint, crayons, pens, tee- shirts, prep-shirts or other design aids.
  • barrier layers may include, but are not limited to, the barrier layers disclosed in U.S. Patent Nos. 6,410,200, 6,358,660, 5,501,902, 5,271,990, and 5,242,739, which are herein incorporated by reference.
  • Other suitable barrier layers include those disclosed in U.S. Patent Nos. 4,021,591, 4,555,436, 4,657,557, 4,914,079, 4,927,709, 4,935,300, 5,322,833, 5,413,841, 5,679,461, 5,741,387, 5,798,179, and 5,603,966, all of which are herein incorporated by reference .
  • suitable barrier layers include the barrier layers of U.S. Patent Nos. 4,773,953, 4,980,224, 5,620,548, 5,139,917, 5,236,801, 5,883,790, 6,245,710, 6,083,656, 5,948,586, 6,265,128, 6,033,824, 6,294,307, 6,410,200 and 6,358,660, and U.S. Application Serial Numbers 09/366,300, 6,531,216, 09/637,082, 6,786,994, 6,849,312, 6,539,652, 09/791,755, 10/089,446, and 6,869,910, and Provisional U.S. Application Serial Nos.
  • Coating weights for the barrier layer may range from one (1) gram per meter square to 20 grams per meter square, optionally from 1 g/m 2 to 15 g/m 2 , still more optionally 1 g/m 2 to 8 g/m 2 .
  • the barrier layer comprises a sufficient amount or an effective amount of silicon or silicone containing compound so that the image transfer material does not stick to the printer during operation.
  • Any melt transfer layer may be used, for instance, any of the melt transfer layers disclosed in U.S. Patent Nos. 6,410,200, 6,358,660, 5,501,902, 5,271,990, 5,242,739, 4,021,591, 4,555,436, 4,657,557, 4,914,079, 4,927,709, 4,935,300, 5,322,833, 5,413,841, 5,679,461, 5,741,387, 5,798,179, 5,603,966, 4,773,953, 4, 980,224, 5,620,548, 5,139,917, 5,236,801, 5,883,790, 6,245,710, 6,083,656, 5,948,586, 6,265,128, 6,033,824, 6,294,307, 6,410,200 and 6,358,660, and U.S.
  • the melt transfer layer (s) and optional image receiving layer has sufficient tack/thickness so as to pass through a printer.
  • the melt transfer layer (s) serves as the source of adhesion during the transfer upon the application of heat.
  • the image transfer layer when present, will also melt upon the application of heat in order to assist adhesion and to assist rendering the image resistant to water (e.g. colorfast during washing) .
  • the at least one melt transfer layer (s) is sufficiently thick when used alone or when used in combination with at least one image receiving layer and/or optional opaque layer so as to pass through a printer without need of a support.
  • the thickness of the melt transfer layer ranges from 1 to 10 mils or more, alternatively 1 to 5 mils, or alternatively about 4 mils, or about 3 mils.
  • the melt transfer layer has a dry coat of about 2 to 80 g/m 2 and a thickness of 0.05 to 4 mil.
  • a suitable dry coat weight would be 10-30 g/m 2 or about 15-25 g/m 2 .
  • the melt transfer layer is a polyurethane layer having sufficient thickness to pass through a printer and upon melting adheres to the receptor element and renders the image colorfast during washing.
  • a suitable thickness for the polyurethane layer ranges from about 1.25 mils to 7 mils, or more.
  • the thickness of the polyurethane layer may be in the same range as set in the previous paragraph.
  • Any polyester, acrylic polymer, polyolefin, polyurethane or copolymer blends may be used that exhibits a melt transition temperature in the range 50°C-250°C, or when the glass transition temperature (Tg) of the polyolefin, polyester, polyurethane, acrylic polymer or copolymer blend is less than about 25 degrees Centigrade.
  • Tg glass transition temperature
  • Non-limiting examples include polyamide (4220; Bemis Associates), polyurethane (5250; Bemis Associates; EstaneTM 5700 series, in particular EstaneTM 5703 TPU of Noveon, Inc. Cleveland OH; or Daotan polyurethanes by Surface Specialties, Inc.
  • the melt transfer layer comprises an ethylene vinyl acetate/ethylene acrylic acid copolymer blend.
  • the melt transfer layer comprises a EVA based terpolymer of ethylene-vinyl acetate and maleic anhydride terpolymer.
  • the melt transfer layer comprises polyurethane. Aspects of the polyurethane that are important include the softening temperature, softness of the polymer, color of the polymer and elasticity of the polymer. It is desirable to use a polyurethane that is as soft as possible, but has high elastic properties.
  • Polyurethane products having a Shore Hardness between 7OA and 9OA are preferred.
  • Non-yellowing of the melt transfer layer is important and therefore the polyurethane should be non-yellowing.
  • Aliphatic polyurethanes are more UV stable than other polyurethanes such as aromatic polyurethanes and therefore can possess better non-yellowing properties.
  • the melt transfer layer comprises an ethylene acrylic acid co-polymer dispersion, an elastomeric emulsion, a polyurethane dispersion, and polyethylene glycol.
  • An example of this embodiment is Melt Transfer Layer Formulation 1.
  • the acrylic dispersion is present in a sufficient amount so as to provide adhesion of the melt transfer layer and image to the receptor element upon application of heat and is preferably present in an amount of from 46 to 90 weight %, more preferably 70 to 90 weight % based on the total composition of the melt transfer layer.
  • the elastomeric emulsion provides the elastomeric properties such as mechanical stability, flexibility and stretchability, and is preferably present in an amount of from 1 to 45 weight %, more preferably 1 to 20 weight % based on the total composition of the melt transfer layer.
  • the water repellent provides water resistance and repellency, which enhances the wear resistance and washability of the image on the receptor, and is preferably present in an amount of from 1 to 7 weight %, more preferably 3 to 6 weight % based on the total composition of the melt transfer layer.
  • the plasticizer provides plasticity and antistatic properties to the transferred image, and is preferably present in an amount of from 1 to 8 weight %, more preferably 2 to 7 weight % based on the total composition of the melt transfer layer .
  • the acrylic dispersion may be an ethylene acrylic acid co-polymer dispersion that is a film-forming binder that provides the "release” or "separation" from the support.
  • the melt transfer layer of the invention may utilize the film-forming binders of the image-receptive melt-transfer film layer of U.S. Patent 5,242,739, which is herein incorporated by reference.
  • the nature of the film- forming binder is not known to be critical. That is, any film-forming binder can be employed so long as it meets the criteria specified herein. As a practical matter, water-dispersible ethylene-acrylic acid copolymers have been found to be especially effective film forming binders .
  • melts and variations thereof are used herein only in a qualitative sense and are not meant to refer to any particular test procedure. Reference herein to a melting temperature or range is meant only to indicate an approximate temperature or range at which a polymer or binder melts and flows under the conditions of a melt-transfer process to result in a substantially smooth film.
  • melt behavior of polymers or binders correlate with the melting requirements described herein. It should be noted, however, that either a true melting point or a softening point may be given, depending on the nature of the material. For example, materials such as polyolefins and waxes, being composed mainly of linear polymeric molecules, generally melt over a relatively narrow temperature range since they are somewhat crystalline below the melting point. Melting points, if not provided by the manufacturer, are readily determined by known methods such as differential scanning calorimetry. Many polymers, and especially copolymers, are amorphous because of branching in the polymer chains or the side-chain constituents. These materials begin to soften and flow more gradually as the temperature is increased. It is believed that the ring and ball softening point of such materials, as determined by ASTM E-28, is useful in predicting their behavior. Moreover, the melting points or softening points described are better indicators of performance than the chemical nature of the polymer or binder.
  • the polymer may be prepared in powder form, and then, heat is applied to form a coherent mass of the polymer.
  • This process is often referred to in the textile industry as powder sintering.
  • Any polyethylene, polyamide or blends thereof may be used in the process.
  • Vestamelt 350, 432, 730, 732 and 750 (Degussa Corp.) are examples of a polyolefin polyamide blends with a typical melt transition temperature in the range of 105-130 0 C.
  • Polyethylene powders are typically low density polyethylene (LDPE) compositions with a melt temperature in the range 50- 250 0 C, preferably 70 - 190 0 C and most preferably 80-150 0 C.
  • LDPE examples include Microthene F501 (Equistar Chemical Co.) with a melt temperature of 104 0 C, and Icotex 520-5016 (Icopolymers Co.) with a melt temperature of 100 0 C.
  • melt transfer binders e.g., acrylic dispersions
  • Binder A is Michem ® 58035, supplied by Michelman, Inc., Cincinnati, Ohio. This is a 35 percent solids dispersion of Allied Chemical's AC 580, which is approximately 10 percent acrylic acid and 90 percent ethylene. The polymer reportedly has a softening point of 102 0 C and a Brookfield viscosity of 0.65 pas (650 centipoise) at 140 0 C.
  • This binder is Michem ® Prime 4983R (Michelman, Inc., Cincinnati, Ohio) .
  • the binder is a 25 percent solids dispersion of Primacor ® 5983 made by Dow Chemical Company.
  • the polymer contains 20 percent acrylic acid and 80 percent ethylene.
  • the copolymer has a Vicat softening point of 43 0 C and a ring and ball softening point of 100 0 C.
  • the melt index of the copolymer is 500 g/10 minutes (determined in accordance with ASTM D-1238) .
  • Binder C is Michem ® 4990 (Michelman, Inc., Cincinnati, Ohio) .
  • the material is 35 percent solids dispersion of Primacor ® 5990 made by Dow Chemical Company.
  • Primacor ® 5990 is a copolymer of 20 percent acrylic acid and 80 percent ethylene. It is similar to Primacor ® 5983 (see Binder B), except that the ring and ball softening point is 93 0 C.
  • the copolymer has a melt index of 1,300 g/10 minutes and Vicat softening point of 39 0 C.
  • This binder is Michem ® 37140, a 40 percent solids dispersion of a Hoechst-Celanese high density polyethylene. The polymer is reported to have a melting point of 100 0 C. Melt Transfer Binder E
  • Michem ® 32535 which is an emulsion of Allied Chemical Company's AC-325, a high density polyethylene. The melting point of the polymer is about 138 0 C. Michem ® 32535 is supplied by Michelman, Inc., Cincinnati, Ohio. Melt Transfer Binder F
  • Binder F is Michem ® 48040, an emulsion of an Eastman Chemical Company microcrystalline wax having a melting point of 88°C.
  • the supplier is Michelman, Inc., Cincinnati, Ohio.
  • Binder G is Michem ® 73635M, an emulsion of an oxidized ethylene-based polymer.
  • the melting point of the polymer is about 96 0 C.
  • the hardness is about 4-6 Shore-D.
  • the material is supplied by Michelman Inc., Cincinnati, Ohio.
  • the second component of Melt Transfer Layer Formulation 1 is an elastomeric emulsion, preferably a latex, and is compatible with the other components, and formulated to provide durability, mechanical stability, and a degree of softness and conformability to the layers.
  • Films of this material must have moisture resistance, low tack, durability, flexibility and softness, but with relative toughness and tensile strength. Further, the material should preferably have inherent heat and light stability.
  • the latex can be heat sensitized, and the elastomer can be self-crosslinking or used with compatible cross-linking agents, or both.
  • the latex should be sprayable, or roll stable for continuous runnability on nip rollers.
  • Elastomeric latexes of the preferred type are produced from the materials and processes set forth in U.S. Patents 4,956,434 and 5,143,971, which are herein incorporated by reference.
  • This curable latex is derived from a major amount of acrylate monomers such as C 4 to C 8 alkyl acrylate, preferably n-butyl acrylate, up to about 20 parts per hundred of total monomers of a monolefinically unsaturated dicarboxylic acid, most preferably itaconic acid, a small amount of crosslinking agent, preferably N-methyl acrylamide, and optionally another monolefinic monomer.
  • the third ingredient of Melt Transfer Layer Formulation 1 is a water resistant and adhesion aid such as a polyurethane dispersion.
  • the polyurethane will be a self- crosslinking formulation incorporating crosslinking agents such as melamine. This ingredient is also a softener for the acrylic dispersion and plasticizer aid.
  • Such polyurethane product may be produced by polymerizing one or more acrylate and other ethylenic monomers in the presence of an oligourethane to prepare oligourethane acrylate copolymers.
  • the oligourethane is preferably prepared from diols and diisocyanates, the aliphatic or alicyclic based diisocyanates being preferred, with lesser amounts, if any, of aromatic diisocyanates, to avoid components which contribute to yellowing.
  • Polymerizable monomers in addition to the usual acrylate and methacrylate esters of aliphatic monoalcohols and styrene, further include monomers with carboxyl groups, such as acrylic acid or methacrylic acid, and those with other hydrophylic groups such as the hydroxyalkyl acrylates (hydroxyethyl methacrylate being exemplary) .
  • the hydrophylic groups in these monomers render the copolymer product dispersible in water with the aid of a neutralizing agent for the carboxyl groups, such as dimethylethanolamine, used in amount to at least partially neutralize the carboxyl groups after dispersion in water and vacuum distillation to remove any solvents used to prepare the urethane acrylic hybrid.
  • Further formulations may include the addition of crosslinking components such as amino resins, strained amines or blocked polyisocyanates .
  • crosslinking components such as amino resins, strained amines or blocked polyisocyanates .
  • pigments and fillers could be added to any of the coating layers, such use to uniformly tint or color the layer could be used for special effect, but would not be used where an image is desired in the absence of background coloration.
  • Urethane acrylic hybrid polymers are further described in U.S. 5,708,072, and their description in this application is incorporated by reference.
  • Self crosslinking acrylic polyurethane hybrid compositions can also be prepared by the processes and materials of U.S. 5,691,425, herein incorporated by reference. These are prepared by producing polyurethane macromonomers containing acid groups and lateral vinyl groups, optionally terminal vinyl groups, and hydroxyl, urethane, thiourethane and/or urea groups. Polymerization of these macromonomers produces acrylic polyurethane hybrids which can be dispersed in water and combined with crosslinking agents for solvent- free coating compositions.
  • Autocrosslinkable polyurethane-vinyl polymers are discussed in detail in 5,623,016 and U.S. 5,571,861, and their disclosure of these materials is incorporated by reference.
  • the products usually are polyurethane-acrylic hybrids, but with self-crosslinking functions. These may be carboxylic acid containing, neutralized with, e.g. tertiary amines such as ethanolamine, and form useful adhesions and coatings from aqueous dispersion.
  • the elastomeric emulsion and polyurethane dispersion are, generally, thermoplastic elastomers.
  • Thermoplastic elastomeric polymers are polymer blends and alloys which have both the properties of thermoplastic polymers, such as having melt flow and flow characteristics, and elastomers, which are typically polymers which cannot melt and flow due to covalent chemical crosslinking (vulcanization) or regions (blocks) of highly ordered polymeric units.
  • Thermoplastic elastomers are generally synthesized using two or more monomers that are incompatible; for example, styrene and butadiene.
  • microdomains By building long runs of polybutadiene with intermittent polystyrene runs, microdomains are established which imparts the elastomeric quality to the polymer system. However, since the microdomains are established through physical crosslinking mechanisms, they can be broken by application of added energy, such as heat from a hand iron, and caused to melt and flow; and therefore, are elastomers with thermoplastic quality.
  • Thermoplastic elastomers have been incorporated into the present invention in order to provide the image system with elastomeric quality.
  • Two thermoplastic elastomer systems have been introduced; that is, a polyacrylate terpolymer elastomer (for example, Hystretch V-29) and an aliphatic urethane acryl hybrid (for example, Daotan VTW 1265) .
  • Thermoplastic elastomers can be chosen from a group that includes, for example, ether-ester, olefinic, polyether, polyester and styrenic thermoplastic polymer systems.
  • thermoplastic elastomers such as polybutadiene, polybutadiene derivatives, polyurethane, polyurethane derivatives, styrene-butadiene, styrene- butadiene-styrene, acrylonitrile-butadiene, acrylonitrile- butadiene-styrene, acrylonitrile-ethylene-styrene, polyacrylates, polychloroprene, ethylene-vinyl acetate and poly (vinyl chloride) .
  • thermoplastic elastomers can be selected from a group having a glass transition temperature (Tg) ranging from about -50 0 C to about 25 0 C.
  • the melt transfer layer may comprises polyurethane as the main or single component.
  • the melt transfer layer as a polyurethane layer preferably has sufficient thickness that upon melting adheres to the receptor element [e.g. thickness from 1 to 10 mils, alternatively from 3 to 8 mils, alternatively from 4 to 7 mils] .
  • the fourth component of Melt Transfer Layer Formulation 1 is a plasticizer such as a polyethylene glycol dispersion which provides mechanical stability, water repellency, and allows for a uniform, crack-free film. Accordingly, a reason to add the polyethylene glycol dispersion is an aid in the coating process. Further, the polyethylene glycol dispersion acts as a softening agent .
  • a preferred fourth component is Carbowax Polyethylene Glycol 400, available from Union Carbide.
  • melt Transfer Layer Formulation 1 An optional fifth ingredient of Melt Transfer Layer Formulation 1 is a surfactant and wetting agent such as polyethylene glycol mono ( (tetramethylbutyl) phenol) ether.
  • a surfactant and wetting agent such as polyethylene glycol mono ( (tetramethylbutyl) phenol) ether.
  • the representative binders, described above that are suitable for Melt Transfer Layer Formulation 1 may be used in lieu of the above-described ethylene acrylic acid copolymer dispersion.
  • the melt transfer layer is composed of a crosslinking polymer, for example, polyurethane or polyethylene. When heat is applied to the melt transfer layer, it bonds to the receptor element. The bond created is durable to washing, dry-cleaning, and is durable under mechanical stress.
  • Optional Opaque Layer (s) and Optional Opaque Materials may optionally contain one or more opaque layers or optionally contain opaque materials within the melt transfer layer (s) or within the image receiving layer (s). For instance, suitable opaque materials from the opaque layers described in pending U.S. Patent Application Nos . 10/089,446 and 10/483,387 may be used. In one embodiment of the present invention, the optional opaque layer (s) is placed between the melt transfer layer and the image receiving layer.
  • the optional opaque layer (s) or opaque materials added to the melt transfer layer or to the image receiving layer add a rigid or stiff quality to the transfer sheet for ease of handling, as well as having opacity, especially white, to enhance visibility of the image when placed thereon. That is, the opaque materials aid in ink visibility on various colored receptors when they are compounded or mixed with the melt transfer and/or image receiving layer.
  • the one or more opaque layers in combination with the melt transfer layer and the image transfer layer may provide the necessary rigidity that would normally be supplied by the support or the melt transfer layer and image receiving layer.
  • the thickness and rigidity will vary.
  • the combination of the melt transfer layer, one or more opaque layer and image receiving layer have sufficient rigidity so as to pass through, the printer without substantial damage.
  • Exemplary thickness of an opaque layer in such an instance range from about 0.5 mils to about 2.5 mils.
  • the thickness of the opaque layer is not, by itself, sufficient to allow the image transfer material to pass through a printer without a support .
  • Opaque Layer A When one or more opaque layer (s) or materials within the melt transfer layer (s) or image transfer layer (s) are employed, the opaque layer or materials provide additional background contrast for the applied image to render it visible against, for instance a dark or a light receptor.
  • the opaque layer (s) or materials within the melt transfer layer (s) or image transfer layer (s) improve the appearance and readability of an image, such as, for instance, a bar code or a color image .
  • the opaque layer (s) or materials within the melt transfer layer (s) or image transfer layer (s) preferably will be thermoplastic and optionally thermosetting as they are applied to a porous substrate such as a fabric.
  • a thermosettable formulation is employed for the opaque layers or materials within the melt transfer layer (s) or image transfer layer (s), the image fused into the fabric will have the maximum resistance to washing or dry cleaning.
  • the first optional opaque layer adds a rigid or stiff quality to the entire heat-setting label sheet for ease of handling, as well as having a white (or colored) opacity. Any pigmented resin may be used to achieve the desired outcome.
  • An embodiment of opaque layer A, Opaque Layer formulation 1 comprises styrene-butadiene latex, thermoplastic elastomer, an elastomer and an optional pigment.
  • Opaque Layer A is about 1.5 mils (wet) .
  • a pigment such as a white pigment may be used to exhibit opacity capabilities.
  • the latex is the primary chemical imparting the rigid characteristics upon drying.
  • the thermoplastic elastomer and acrylonic copolymer impart stretchability and flexibility in the final transferred product .
  • the optional Opaque Layer B preferably contains a pigment (such as a white pigment) and provides opacity.
  • a pigment such as a white pigment
  • Opaque Layer Formulation 1 comprises a vinyl acetate-ethylene copolymer, thermoplastic elastomer, an elastomer and an optional pigment such as TiO 2 .
  • the opaque materials may be included within the melt transfer layer (s) or image receiving layer (s) .
  • the thermoplastic elastomer acrylonitrile copolymer impart stretchability and flexibility in the final transferred product. Practically any TiO 2 powder addition, present at about 25% of the total formula, will provide the desired opacity. Other powdered pigments may need to be added at varying percentages to achieve the desired opacity and color intensity.
  • Opaque Layer B is coated on the heat setting label sheet at a weight of about 1.0 to 1.5 mils (wet).
  • Any pigmented resin may be used to achieve the desired outcome.
  • any type of suitable opaque material including those materials described above, may be added to the melt transfer layer or to the image-receiving layer to provide the desired opacity.
  • An optional image receiving layer is applied over the melt transfer layer or over an optional opaque layer, which may be positioned between the melt transfer layer (s) and the image receiving layer (s) . It may be used if the melt transfer layer does not sufficiently receive an image by itself.
  • the image receiving layer formulations of the present invention should be able to retain an image such as an image dye .
  • the image receiving layer preferably retains dyes, such as ink from ink jet printers, or dyes from a waterbased marker. If an ink jet ink is utilized, the image preferably has comparable resolution to standard ink jet paper.
  • the image receiving layer may become heat activated (e.g. melt and flow) to trap or encapsulate the dye image or ink and optionally impart waterfast characteristics.
  • the image receiving layer may be applied to the melt transfer layer either by a conventional saturating process such as a "dip and squeeze” process or with a coating process such as a reverse roll, meyer rod, gravure, slot die and the like.
  • the basis weight of the image receiving layer may vary, for instance, from about 2 to 60 g/m 2 , from about 2 to about 45 g/m 2 , or from about 3 to about 20 g/m 2 .
  • the image receiving layer may be capable of heat sealing the image upon application of heat (e.g. up to 22O 0 C) .
  • Heat sealing refers to a process whereby the polymer composition melts and flows so as to effectively encapsulate the image forming colorants therein. Heat sealing imparts waterfastness and washability. A heat sealed image would have newly imparted image permanence properties such as waterfastness and rub resistance.
  • the image receiving formulation includes a self -crosslinking polymer as a binder, for instance, Binder F below. In this embodiment, although not all components of the image receiving layer will technically melt, for instance, the self-cross linking EVA polymer will not melt, the layer will still heat seal the image .
  • the image receiving layer comprises binders, such as polyvinyl alcohol (PVOH) , polyesters, polyurethanes, or co- polymer blends, various colorant retention aids, various optional crosslinking agents, an optional antioxidant, or an optional softening agent.
  • binders such as polyvinyl alcohol (PVOH) , polyesters, polyurethanes, or co- polymer blends, various colorant retention aids, various optional crosslinking agents, an optional antioxidant, or an optional softening agent.
  • the binder imparts colorant retention and mechanical stability.
  • a list of applicable binders include, but are not limited to, those listed in U.S. Patent No. 5,798,179, in addition to polyolefins, polyesters, ethylene-vinyl acetate copolymers, ethylene-methacrylate acid copolymers, and ethylene-acrylic acid copolymers.
  • the binder may also be selected from the list, mentioned herein, for use in the melt transfer layer.
  • the binder is one of a self-crosslinkable acrylic copolymer, for instance, RhoplexTM NW-1402, RhoplexTM HA-16 or RhoplexTM HA-12 from the Rohm and Haas Corporation, or a hydrolyzed polyvinyl alcohol, for instance, CelvolTM 540 or CelvolTM 125, from the Celanese Corporation, or a self- crosslinking ethylene-vinyl acetate copolymer, for instance, Dur-o-setTM Elite Plus 25-299A, from Vinamul Polymers Corp.
  • the self-crosslinkable polymer binder is preferably present in an amount, based on the dry solids content of the layer, of 15-40%, and most preferably 25-35% by weight.
  • the self-crosslinkable polymer binder is a thermosetting polymer such as a self-crosslinking ethylene vinyl acetate copolymer (for instance, Dur-o-setTM Elite Plus 25-299A, from Vinamul Polymers Corp.) .
  • a thermosetting polymer such as a self-crosslinking ethylene vinyl acetate copolymer (for instance, Dur-o-setTM Elite Plus 25-299A, from Vinamul Polymers Corp.) .
  • Representative image receiving layer binders suitable to impart color retention and mechanical stability include:
  • Image Receiving Layer Binder A is Rhoplex NW-1402, a self-crosslinkable acrylic copolymer from the Rohm and Haas Corporation. This material is a 45% solids formulation with a specific gravity of 1.0 to 1.2.
  • Image Receiving Layer Binder B is Rhoplex HA-16, a self- crosslinkable acrylic copolymer from the Rohm and Haas Corporation. This material is a 46% solids formulation with a maximum viscosity of 900 CPS.
  • Image Receiving Layer Binder C is Rhoplex HA-12, a self- crosslinkable acrylic copolymer from the Rohm and Haas Corporation. This material is a 46% solids formulation with a maximum viscosity of 750 CPS. Image Receiving Layer Binder D
  • Image Receiving Layer Binder D is Celvol 540, a partially hydrolyzed polyvinyl alcohol from the Celanese Corporation.
  • Image Receiving Layer Binder E is Celvol 125, a hydrolyzed polyvinyl alcohol from the Celanese Corporation.
  • Image Receiving Layer Binder F is Dur-o-set 25-299A, a self-crosslinking EVA copolymer from Vinamul Polymers Corp. This materials is prepared as a 50% solids emulsion with a bulk density of 8.9 lb/gal .
  • thermoplastic binders other than the self-crosslinkable polymers discussed above, may also be incorporated.
  • any of the thermoplastic binders listed above for the melt transfer layer may be incorporated.
  • thermoplastic binders, such as those listed above may be incorporated in amounts of 5-40%, preferably 10-30% by weight based on the dry solids content .
  • a polyamide copolymer for instance, a nylon copolymer may be added to the image receiving layer.
  • nylon 6-12 OrgasolTM 3501 EXDNAT 1, from Atofina
  • nylon 12 Orgasol 2002 EXDNAT 1, from Atofina
  • nylon 6 Orgasol 1002 DNATl, from Atofina
  • the formulation may also include a polyvinylpyrrolidone (PVP) polymer and copolymer blends for instance, Luvicross (BASF) , Luvicross M (BASF) , Luvicross VI (a PVP-vinyl imidazole copolymer blend (BASF) ) , and Luvitec (BASF) .
  • PVP polyvinylpyrrolidone
  • the polyamide copolymers may be incorporated in amounts of 5-40%, preferably 10-30% by weight based upon the dry solids of the formulation.
  • Silica may also be added to the image receiving layer.
  • Silica is silicon dioxide, and can generally be any preparation that has a mean diameter not larger than 100 microns. Examples include the Syloid brand of silica (such as Syloid W-500, from Grace Davidson Co.), SyIojet brand of silica (such as the Sylojet P400, Grace Davidson Co.), INEOS silica (such as the Gasil HP270 or Gasil IJ45) .
  • Silica may be added in amounts ranging from 5-60%, preferably 10-40%, most preferably 15-35% by weight based on the dry solids content.
  • antioxidants include, but are not limited to, BHA; Bis (2 , 4-di-t-butylphenyl) pentaerythritol diphosphate; 4 , 4 ' -Butylidenebis (6-t-butyl-m-cresol) , C20-40 alcohols; p- Crescol/dicyclopentadiene butylated reaction product, Di
  • Isopropyldimethacrylisoslearoyl titanate Isopropyl (dioctylphosphato) titanate; isopropyltridioctylpyrophosphato) titanate; Isopropyl tri (N ethylamino-ethylamino) titanate, Lead phthalate, basic 2 , 2-Methylenebis (6-t-butyl-4-methylphenol) , Octadecyl 3,5- di-t-butyl-4-hydroxyhydrocinnamate Phosphorus; Phosphorus trichloride, reaction prods, with 1, 1 ' -biphenyl and 2, 4 -bis (1, 1-dimethylethyl) phenol Tetra (2, diallyoxymethyl-1 butoxy titanium di (di-tridecyl) phosphite; Tetraisopropyl di (dioctylphosphito) titanate; Tetrakis [methylene (3,5-d
  • crosslinking agent can be added to each formula to crosslink the binder to improve waterfastness .
  • Crosslinkers suited for this application including, but not limited to, aziridine (ie., Ionac PFAZ-322) , aziridine derivatives, multifunctional aziridines (XAMA-7 (Sybron) ) Sancure 777 (Noveon) , and melamine (ie., Cymul 323 EvCo, Inc.), and organometallics like an organic titanate such as Tyzor LA (DuPont) .
  • the self-crosslinkable polymer binder-containing image receiving formulation may further include dye retention aids, such as a cationic polymer.
  • dye retention aids include the silica listed above, the polyamide copolymer and PVA.
  • the cationic polymer may be incorporated in amounts of 1-10% by weight, preferably 1-4% by weight based upon the dry solids content of the layer.
  • Other dye retention aids may include any salt with dissociative properties. Exemplary, but non- limitive examples include salts with Group II elements such as Mg, CA, Sr or Ba, or other elements such as Al, Zn, and Cu.
  • CaCl 2 may be utilized as a dye retention aid.
  • the salt with dissociative properties may be present in amounts of 0.25-4%, preferably 1-2% by weight based upon the dry weight of the formulation.
  • the cationic polymer may be, for example, an amide-epichlorohydrin polymer, polyacrylamides with cationic functional groups, polyethyleneimines, polydiallylamines, and the like.
  • Representative cationic polymers used as a dye retention aid include :
  • Cationic Polymer A is APC-Ml, a polydiallylmethylamine hydrochloride resin from Advanced Polymers, Inc.
  • APC-Ml is a 60% solids dispersion in water with a molecular weight of 20,000.
  • Cationic Polymer B is APC-J81, a dimethyldiallylammonium chloride/a ⁇ rylamide copolymer from Advanced Polymers, Inc.
  • APC-J81 is a 25% solids dispersion in water with a molecular weight of 200,000.
  • Cationic Polymer C is APC-Al, a dimethyldiallylammonium chloride/sulfur dioxide copolymer from Advanced Polymers, Inc.
  • APC-Al is a 24% solids dispersion in water with a molecular weight of 5,000.
  • Cationic Polymer D is CP 7091 RV, a poly (diallyldimethylammonium chloride-co-diacetone acrylamide) from ECC International.
  • a compatible binder should be selected, such as a nonionic or cationic dispersion or solution.
  • binders have anionically charged particles or polymer molecules. These materials are generally not compatible with the cationic polymer which may be used in the image receiving layer.
  • the image receiving layer may contain filler agents with the purpose of opacifying and/or modulating the surface characteristics of the present invention. The surface roughness and coefficient of friction may need to be modulated depending on such factors as desired surface gloss and the imaging device's specific paper feeding requirements.
  • the filler can be selected from a group of polymers such as, for example, polyacrylates, polyacrylics, polyethylene, polyethylene acrylic copolymers and polyethylene acrylate copolymers, vinyl acetate copolymers and polyvinyl polymer blends that have various particle dimensions and shapes. Typical particle sizes may range from 0.1 to 500 microns. Preferably, the particle sizes range from 5 to 100 microns. More preferably, the particle sizes range from 5 to 30 microns.
  • the filler may also be selected from a group of polymers such as, for example, cellulose, hydroxycellulose, starch and dextran. Silicas and mica may also be selected as a filler.
  • the filler is homogeneously dispersed in the image receiving layer in concentrations ranging from 0.1 to 50%. Preferably, the filler concentration range is 1 to 10 percent.
  • the filler may also be an inorganic pigment such as titanium dioxide .
  • the image receiving layer may also contain viscosity modifiers and anti-foaming agents.
  • a viscosity modifier is a Laponite product by Southern Clay Products, Inc., Gonzales, Texas,- or Alcogum ® L-520 (Alco Chemical) .
  • An antistatic layer may be coated on the back of the melt transfer layer. Any suitable antistatic layer known in the art may be used as the antistatic layer of the present invention.
  • the antistatic layer according to the present invention may have a solution viscosity of from 0.1 to 20 cP, preferably 1-5 cP, most preferably about 2 cP, as measured on a Brookfield DV-I+ viscometer, LVl spindle at 60 rpm at a temperature of 25°C. Additionally, the antistatic layer may be wet coated in an amount of from 1 g/m 2 to 50 g/m 2 , preferably from 10-30 g/m 2 , most preferably about 18 g/m 2 .
  • the surface tension of the antistatic layer may be from 30-110 dynes/cm, preferably from 50-90 dynes/cm, most preferably about 70 dynes/cm as measured at room temperature.
  • the antistatic agents may be present in the form of a coating on the back surface of the melt transfer layer as an additional layer.
  • Antistatic agents are generally, but not necessarily, conductive polymers that promote the flow of charge away from the image transfer material. Antistats can also be "humectants” that modulate the level of moisture in a coating that affects the build up of charge. Antistats are commonly charged tallow ammonium compounds and complexes, but also can be complexed organometallics . Antistats may also be charged polymers that have a similar charge polarity as the copier/printer drum; whereby the like charge repulsion helps prevent j amming .
  • Antistatic agents include, by way of illustration, derivatives of propylene glycol, ethylene oxide-propylene oxide block copolymers, organometallic complexes such as titanium dimethylacrylate oxyacetate, polyoxyethylene oxide- polyoxypropylene oxide copolymers and derivatives of cholic acid.
  • antistats include those listed in the Handbook of Paint and Coating Raw Materials, such as t-Butylaminoethyl methacrylate,- Capryl hydroxyethyl imidazoline; Cetethyl morpholinium ethosulfate; Cocoyl hydroxyethyl imidazoline Di (butyl, methyl pyrophosphate) ethylenetitanate di(dioctyl, hydrogen phosphite); Dicyclo (dioctyl) pyrophosphate; titanate; Di (dioctylphosphato) ethylene titanate; Dimethyl diallyl ammonium chloride; Distearyldimonium chloride; N, N' -Ethylene bis-ricinoleamide; Glyceryl mono/dioleate; Glyceryl oleate; Glyceryl stearate; Heptadecenyl hydroxyethyl imidazoline; Hexyl phosphate
  • Marklear AFL-23 or Markstat AL-14 polyethers available from Whitco Industries, are used as an antistatic agents .
  • the antistatic coating may be applied on the back surface of the melt transfer layer by, for example, spreading a solution comprising an antistatic agent (i.e., with a metering rod) onto the back surface of the melt transfer layer and then drying the melt transfer layer.
  • a solution comprising an antistatic agent i.e., with a metering rod
  • the various layers of the transfer material are formed by known coating techniques, such as by curtain coating, Meyer rod, roll, blade, air knife, cascade and gravure coating procedures.
  • Figure 1 there is generally illustrated a cross-sectional view of one embodiment of the transfer sheet of the present invention.
  • the melt transfer layer 23 On top of the optional barrier layer 22 is the melt transfer layer 23.
  • the image receiving layer 24 On top of the melt transfer layer is the image receiving layer 24.
  • the image 25 is placed over the image receiving layer 24 on the side opposite the melt transfer layer.
  • An optional anti-static 26 layer may be coated on the bottom surface of the optional barrier 22 or melt transfer layer 23.
  • the melt transfer layer may either be extrusion coated or laminated onto the optional barrier layer. These are performed by methods conventional in the art.
  • the receptor or receiving element receives the transferred image.
  • a suitable receptor includes but is not limited to textiles including cotton fabric, and cotton blend fabric.
  • the receptor element may also include glass, metal, wool, plastic, ceramic or any other suitable receptor.
  • Preferably the receptor element is a tee shirt or the like.
  • the image may be applied in any desired manner.
  • the image may be formed by a color or monochrome laser printer, laser copier, bubblejet printer, inkjet printer, and the like.
  • the image may also be applied using commercial printing methods such as sheet-fed offset, screen and gravure printing methods or with crayons or markers .
  • the image receiving material may be first imaged. Then, the imaged image receiving material (e.g. melt transfer layer (s) and image receiving layers (s) ) is removed from the kit as an individual sheet [e.g. 8.5 x 11 inches or A4] or placed in the kit as a continuous roll [e.g. similar to a roll of plastic wrap in a box] and cut, imaged, and placed preferably image side up, melt transfer layer down, against a receptor element .
  • melt transfer layer s
  • image receiving layers e.g. melt transfer layer (s) and image receiving layers (s)
  • imaging can wait until after the image receiving material is placed upon the receptor.
  • the melt transfer layer (s) is placed down on the receptor with the image facing the viewer (e.g. image up) .
  • additional imaging may occur after an imaged image receiving material is placed upon the receptor element.
  • the combination of the melt transfer layer (s), optional one or more opaque layer, and image receiving layer (s) may first be optionally imaged. Or, after an optionally imaged image receiving material containing image receiving layer (s), optional one or more opaque layers and melt transfer layer (s) are placed upon the receptor element, additional imaging may occur. After the image receiving materials (e.g.
  • the melt transfer layer (s) or the image receiving layer (s) and melt transfer layer (s) ) are placed on the receptor element, whether they are imaged or not, the next step is that a heat source, for instance a hand iron, a heat press or an oven is used to apply heat to the imaged surface (e.g. top) which in turn drives or adheres the image into the receptor.
  • a heat source for instance a hand iron, a heat press or an oven is used to apply heat to the imaged surface (e.g. top) which in turn drives or adheres the image into the receptor.
  • a hand iron or heat press is used that is not made of a tack-free material (such that the imaged material layer will stick thereto)
  • a non-stick sheet should be placed between the heat source and the imaged material.
  • the heat source be it a hand iron or heat press, is made of a tack-free material, a non-stick sheet may still be placed between the heat source and the imaged material .
  • heat may be applied to the back surface of the receptor element.
  • heat may be applied to both the imaged surface and the back of the receptor element .
  • the temperature transfer range of the hand iron is generally in the range of 110 to 220 0 C with about 190 0 C being the preferred temperature .
  • the heat press operates at a temperature transfer range of 100 to 220 0 C with about 190 0 C being the preferred temperature.
  • the temperature should be set within the range of 110 to 220 °C with about 190 0 C being the preferred temperature
  • the heat source is preferably placed over the imaged side of the image receiving material (e.g. image receiving layer (s) and melt transfer layer (s) ) .
  • the hand iron or heat press may be applied to the backside of the receptor element.
  • Pressure i.e., typical pressure applied during ironing
  • the heating device is moved.
  • Figure 2 For a 8.5 x 11 (US Letter) inch web, heat is applied for about two minutes to five minutes (with about three minutes being preferred) using a hand iron and 10 seconds to 50 seconds using a heat press (with about twenty seconds being preferred) of heat and pressure, the transfer should be complete.
  • the heating time requirement may be proportionally shorter or longer depending on the web size.
  • the optional non-stick sheet is removed either prior to cooling or after cooling. The non-stick sheet is not required if the heating device is made of a non-stick material.
  • Figure 2 illustrates how the step of heat transfer from the transfer sheet 50 to a tee shirt or fabric 62 may be performed.
  • a tee shirt 62 is laid flat, as illustrated, on an appropriate support surface, and the optionally imaged surface of the image receiving layer and/or melt transfer layer is preferably positioned up and away from the tee shirt.
  • a nonstick layer is then optionally placed on top of the imaged material.
  • An iron 64 set at its highest heat setting is run and pressed across the non-stick sheet.
  • the image is transferred to the tee shirt and the optional non-stick sheet is removed if present and discarded or saved for reuse.
  • the non-stick sheet is not required if the heating device is made of a non-stick material.
  • the non-stick sheet is any non-stick or tack-free sheet in the art including but not limited to a silicone sheet, a sheet coated with a barrier layer as is known in the art, or a conventional substrate or support sheet .
  • the melt transfer layer is an ethylene acrylic acid co-polymer.
  • An example of this embodiment is Melt Transfer Layer Formulation 1:
  • Melt Transfer Layer Formulation 1 is wax free.
  • Melt Transfer Layer Formulation 1 may be prepared as follows: five parts of the elastomer dispersion are combined with eighty-six parts of an ethylene acrylic acid co-polymers dispersion by gentle stirring to avoid cavitation. Four parts of a polyurethane dispersion are then added to the mixture. Immediately following the addition of a polyurethane dispersion, four parts of a polyethylene glycol and one part of an nonionic surfactant (e.g., Triton X-100) are added. The entire mixture is allowed to stir for approximately fifteen minutes at a moderate stir rate (up to but not exceeding a rate where cavitation occurs) .
  • Triton X-100 an nonionic surfactant
  • This example relates to another melt transfer layer formulation, Melt Transfer Layer Formulation 2.
  • Melt Transfer Layer Formulation 2 may be prepared in the following manner: the ethylene acrylic acid co-polymer dispersion and the wax dispersion are stirred (for example in a beaker with a stirring bar) .
  • This example relates to another melt transfer layer formulation, Melt Transfer Layer Formulation 3.
  • This example relates to another melt transfer layer formulation, Melt Transfer Layer Formulation 4.
  • This example relates to another melt transfer layer formulation, Melt Transfer Layer Formulation 5.
  • Polyolefin-polyamide Copolymer 100 Parts (Vestamelt 432 (Degussa Co.)
  • Melt Transfer Layer Formulation 5 may be prepared by applying the copolymer powder to the support under a sintering temperature of 200 0 C. The final dry basis weight was 20 g/m 2 .
  • This example relates to another melt transfer layer formulation, Melt Transfer Layer Formulation 6.
  • Melt Transfer Layer Formulation 6 may be prepared by applying the polyethylene powder to the support under a sintering temperature of 200 0 C. The final dry basis weight was 20 g/m 2 .
  • Example 7 This example relates to an image receiving layer formulation, Image Receiving Layer Formulation 1.
  • Image Receiving Layer Formulation 1 Components Parts
  • Image Receiving Layer Formulation 1 may be prepared by mixing 5 parts cationic polymer dispersion to 95 parts ethylene acrylic co-polymer dispersion by gentle stirring.
  • This example relates to another image receiving layer formulation, Image receiving layer Formulation 2.
  • Image Receiving Layer Formulation 2 may be prepared by mixing 8 parts cationic polymer dispersion to 92 parts ethylene acrylic co-polymer dispersion by gentle stirring.
  • This example relates to another image receiving layer formulation, Image receiving Layer Formulation 3.
  • Image Receiving Layer Formulation 3 may be prepared by mixing 3 parts cationic polymer dispersion to 60 parts ethylene acrylic co-polymer dispersion by gentle stirring. 37 parts of a polyethylene wax dispersion is then mixed into the formulation by gentle stirring.
  • This example relates to another image receiving layer formulation, Image Receiving Layer Formulation 4
  • Image Receiving Layer Formulation 4 may be prepared by mixing 3 parts cationic polymer dispersion to 60 parts ethylene acrylic co-polymer dispersion by gentle stirring. 37 parts of a polyethylene wax dispersion is then mixed into the formulation by gentle stirring.
  • Example 11 This example relates to another image receiving layer formulation, Image Receiving Layer Formulation 5.
  • Image Receiving Layer Formulation 5 Components Parts
  • Image Receiving Layer Formulation 5 may be prepared by mixing 8 parts cationic polymer dispersion to 89 parts water by gentle stirring. Two parts calcium chloride and 1 part poly (ethylene oxide) are likewise dispersed into the water solution by gentle stirring.
  • Example 12 This example relates to another image receiving layer formulation, Image Receiving Layer Formulation 6.
  • Wax Dispersion (Michem Emulsion 20 Parts
  • Image Receiving Layer Formulation 6 may be prepared by mixing
  • This example relates to another image receiving layer formulation, Image Receiving Layer Formulation 7.
  • Image Receiving Layer Formulation 7 may be prepared by mixing 8 parts cationic polymer dispersion to 83 parts water by gentle stirring. Five parts polyvinyl alcohol is then dispersed via gentle stirring and heating. Once the solution cools back to room temperature, two parts calcium chloride and 1 part poly (ethylene oxide) are likewise dispersed into the water solution by gentle stirring. One part glyoxal is then stirred into the mixture via gentle stirring.
  • This example relates to an image receiving layer formulation, Image Receiving Layer Formulation 8.
  • Multifunctional Aziridine Crosslinker 1 Part (XAMA-7, Sybron Co)
  • Image Receiving Layer Formulation 8 may be prepared by mixing 5 parts cationic polymer dispersion and 1 part aziridine crosslinker to 94 parts ethylene acrylic co-polymer dispersion by gentle stirring.
  • This example relates to an image receiving layer formulation, Image Receiving Layer Formulation 9.
  • Image Receiving Layer Formulation 9 may be prepared by mixing 3 parts cationic polymer dispersion to 60 parts ethylene acrylic co-polymer dispersion by gentle stirring. 37 parts of a polyethylene wax dispersion is then mixed into the formulation by gentle stirring.
  • This example relates to an image receiving layer formulation, Image Receiving Layer Formulation 10.
  • Image Receiving Layer Formulation 10 may be prepared by mixing 3 parts cationic polymer dispersion to 60 parts ethylene acrylic co-polymer dispersion by gentle stirring. Thirty-seven parts of water is then added under gentle stirring.
  • Example 17 This example relates to an image receiving layer formulation, Image Receiving Layer Formulation 11.
  • Nylon 6-12 (Orgasol 3501 EXDNAT 1; Atofina) 8 parts
  • Image Receiving Layer Formulation 11 is displayed in dry weights. However, some of these ingredient correspond to wet amounts added to create the formulation. These wet amounts by weight are found below:
  • Nylon 6-12 (Orgasol 3501 EXDNAT 1; Atofina) n/a EVA (Microthene FE-532; Eguistar Chem. Co) n/a
  • This example relates to an image receiving layer formulation, Image Receiving Layer Formulation 12.
  • Image Receiving Layer Formulation 12 is displayed in dry parts by weights. However, some of the above ingredients correspond to wet amounts added to create the formulation. To prepare, first two stock solutions are prepared in water. These are as follows :
  • Triton X-100 1 part Microthene FE-532 20 parts
  • This example relates is the same as Image Receiving Layer Formulation 12 of Example 18, with the exception that the parts by weight of certain components are modified, the Alcogum ® L-520 (Alco Chemical) is absent and Laponite, a defoamer and an antioxidant have been added.
  • Alcogum ® L-520 Alco Chemical
  • a transfer material according to the present invention is prepared as follows: A melt transfer layer comprising a terpolymer of ethylene-vinyl acetate and maleic anhydride is extruded. The thickness of the melt transfer layer is 6 mils. Next, an Image Receiving Layer (formulation 12) is applied via a dunk and squeeze application method. After thermal drying, an image is formed on the side of the image receiving layer opposite the melt transfer layer by an ink jet printer.
  • the transfer of the image area from the image transfer sheet is completed by placing the imaged image receiving layer and melt transfer layer, image side up, on a cotton shirt.
  • a non-stick sheet is placed on top of the imaged material and heat and pressure from a conventional iron set on its highest temperature setting is applied through the non-stick sheet for a time sufficient to transfer the image area to the shirt (e.g. 3-5 minutes) . Lastly, the non-stick sheet is removed.
  • a transfer sheet according to the present invention is prepared as follows : Example 20 is repeated except the thickness of the melt transfer layer is 8 mils. Example 22
  • Example 20 is repeated, except that the back surface of the melt transfer layer is coated, with the following antistatic layer:
  • Antistatic Layer Solution Formulation 1 Components Parts
  • Quaternary ammonium salt solution 10 parts (by weight) (Statik-Blok J-2, Amstat Industries)
  • the antistatic solution is applied in a long line across the top edge of the melt transfer layer using a #4 metering rod.
  • the coated melt transfer layer is force air dried for approximately one minute.
  • the antistatic solution of this Example has the following characteristics: the solution viscosity as measured on a Brookfield DV-I+ viscometer, LVl spindle @ 60 RPM is 2.0 (cP) at 24.5°C.
  • the coating weight (wet) was 15 g/m 2 .
  • the surface tension is 69.5 dynes/cm at 24 0 C.
  • melt transfer layer and antistatic coating are dry, the uncoated side of the melt transfer layer is coated with the image receiving layer in the same manner as described in Example 20.
  • Example 22 is repeated, except that following formulation is used as the antistatic layer:
  • a transfer sheet according to the present invention is prepared as follows : Melt Transfer Layer Formulation 4 is prepared having a thickness of 7 mil. Next, an Image Receiving Layer (formulation 13) is applied via a dunk, and squeeze application method .
  • an image is formed on the side of the image receiving layer opposite the melt transfer layer by a magic marker.
  • the transfer of the image area from the imaged image transfer sheet is completed by placing image material containing melt transfer material and image receiving layer, image side up, on a cotton shirt. Next a non-stick sheet is placed on top of the imaged peeled material and heat and pressure from a conventional iron set on its highest temperature setting is applied through the non-stick sheet for a time sufficient to transfer the image area to the shirt (e.g. 3-5 minutes) . Lastly, the non-stick sheet is removed.
  • This example relates to a Barrier Layer Formulation 1 :
  • An example of optional Opaque Layer A is as follows:
  • An example of optional Opaque Layer B is as follows:
  • a transfer sheet according to the present invention is prepared as follows:
  • a melt transfer layer comprising polyurethane, for instance, Melt Transfer Layer Formulation 4 is prepared having a thickness of 9 mil.
  • an Image Receiving Layer (formulation 13) is applied via a dunk and squeeze application method . After thermal drying, an image is then formed on the image receiving layer.
  • the image transfer sheet is placed, image side up, on a cotton shirt.
  • a non-stick sheet is placed on top of the imaged material and heat and pressure from a conventional iron set on its highest temperature setting is applied through the non-stick sheet for a time sufficient to transfer the image area to the shirt (e.g. 3-5 minutes) .
  • the non-stick sheet is removed.

Abstract

L'invention concerne un kit qui comprend une feuille non collante, et un matériau de transfert d'image sans support et sans couche opaque, le matériau de transfert d'image comprenant au moins une couche de transfert thermique (MTL) et éventuellement au moins une couche de réception d'image (IRL) si la couche de transfert thermique n'est pas réceptive à l'imagerie. L'invention concerne également un autre kit qui comprend une feuille non collante facultative, et un matériau de transfert d'image sans support et sans couche opaque, le matériau de transfert d'image comprenant au moins une couche MTL et au moins une couche IRL. Dans les deux kits, les couches MTL et/ou IRL contiennent éventuellement un matériau opaque. L'invention concerne en outre un autre kit qui comprend une feuille non collante facultative, et un matériau de transfert d'image sans support, le matériau de transfert d'image comprenant au moins une couche MTL, au moins une couche opaque, et au moins une couche IRL.
PCT/US2006/021668 2005-06-02 2006-06-02 Kit contenant un materiau de transfert d'image sans support WO2006130880A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US68641805P 2005-06-02 2005-06-02
US60/686,418 2005-06-02
US70341905P 2005-07-29 2005-07-29
US60/703,419 2005-07-29

Publications (1)

Publication Number Publication Date
WO2006130880A1 true WO2006130880A1 (fr) 2006-12-07

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Application Number Title Priority Date Filing Date
PCT/US2006/021668 WO2006130880A1 (fr) 2005-06-02 2006-06-02 Kit contenant un materiau de transfert d'image sans support

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108139515A (zh) * 2015-07-07 2018-06-08 3M创新有限公司 用于光定向制品的聚氨酯层

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5525375A (en) * 1995-06-05 1996-06-11 Moore Business Forms, Inc. Process for producing hot melt release coating

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5525375A (en) * 1995-06-05 1996-06-11 Moore Business Forms, Inc. Process for producing hot melt release coating

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108139515A (zh) * 2015-07-07 2018-06-08 3M创新有限公司 用于光定向制品的聚氨酯层

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