MXPA99008983A - Two-layer printable material - Google Patents

Abstract

A printable material which includes a flexible first layer having first and second surfaces and a second layer. The first layer may be a film or a cellulosic nonwoven web. The second layer overlays and is bonded to the first surface of the first layer and includes a nonwoven web. The first layer has a basis weight of from about 20 to about 140 grams per square meter. The thermoplastic polymer has a melting point of from about 90°C to about 250°C and the second layer has a basis weight of at least about 10 grams per square meter. The first layer may be a cellulosic nonwoven web, such as a latex-impregnated paper. The second layer may be thermally bonded to the first layer or bonded by an adhesive. A release layer may be present between the first layer and the heat-activated adhesive. The second layer may contain from about 0.1 to about 20 percent by weight, based on the weight of the second layer, of a materiel which increases the viscosity of an ink jet ink when printed on the second layer. The second layer also may contain from about 0.1 to about 5 percent by weight, based on the weight of the second layer, of a cationic polymer. When the second layer is prepared from a thermoplastic polymer, the ink jet printale material may be used as a heat transfer material. Methods of preparing the printable material also are described.

Description

PRINTING MATERIAL OF TWO LAYERS Background of the Invention The present invention relates to a printable material such as an ink jet printable material. In certain embodiments, the present invention relates to a heat transfer material. t The popularity in recent years of personal computers in homes and businesses has simulated the development of several types of printers. The initials, relatively inexpensive printers were impact or dot matrix printers which used a ribbon and a plurality of pins to place a desired image on a substrate which was typically paper. Even though the best dot matrix printers are capable of almost giving an impression of letter quality, they are typically both slow and noisy. Laser printers are quiet, produce high quality images, and can print an excess of four pages per minute. Such printers, however, tend to be very expensive for common use in homes and even in some small businesses. This is especially true of color laser printers. Inkjet printers fill the gap between dot matrix printers and laser printers, both with respect to magen cost and quality.

The advent of relatively low cost and improved color printers has helped the development of a significant industry which involves the application of selected designs to the order, messages, illustrations, and the like (hereinafter referred to collectively as "selected graphics by the customer ") on items of clothing such as shirts, sweatshirts and the like. These graphs selected by the customer are typically commercially available products made for that specific end use and printed on a release transfer paper. These are applied to the article of clothing by means of heat and pressure, after which the transfer or release paper is removed.

Some effort has been directed to allow customers the opportunity to prepare their own graphics for application to a clothing item. The preparation of such graphics may involve the use of colored crayons made of heat transfer material. Such crayons have been made available in a case, which also includes a transfer sheet with unspecified heat having a pattern delineated thereon. In a variation of the case, the transferable pattern is created from a multiple of a heat transfer sheet and a copy sheet of the lifting or reversing type having a transferable coating with pressure of the transferable material with heat on it. By generating the pattern or art work on the reverse side of the transfer sheet with the pressure of a drawing instrument, an identical heat transferible image pattern is created on the back surface of the transfer sheet by transfer with pressure d the copy sheet. The identical transferable image with heat can then be applied to a t-shirt or other article by heat transfer.

The creation of designs or creative images perzonalizados on a fabric such as a shirt or similar through the use of a personal computer system has been described. The method involves electronically generating an image, electronically transferring the image to a printer, printing the image with the aid of the printer on a reverse surface of a transfer sheet which has a final or top coating consisting essentially of Singapore Dammar resin, Place the reverse side of the transfer sheet against the fabric, and apply energy to the back part of the transfer sheet to transfer the image to the fabric. The transfer sheet can be any commercially available transfer sheet, the heat transferible coating which has been coated with a Singapore Dammar resin coating. The use of abrasive particles in the Singapore Dammar resin coating has also been described. The abrasive particles serve to improve the receptivity of the transfer sheet to various wax-based inks and crayons.

Additionally, improved heat transfer papers have an increased receptivity for images made with wax-based crayons, thermal printer ribbons, and impact ribbon or dot matrix printers have been described. For example, a cellulosic base sheet has an image receptor coating that contains from about 15 to about 80 percent of a film-forming binder and from about 85 to about 20 percent by weight of a polymer in powder consisting of particles having diameters of from about 2 to about 50 microns. The binder is typically a latex. Alternatively, a cellulosic base sheet has an image receptor coating which is typically formed by melt extrusion or by laminating a film to the base sheet. The surface to the coating or the film is then altered by, for example, passing the coated base sheet through a recording roller.

Some effort has been directed to generally improve the transfer of a laminate by supporting an image to a substrate. For example, an improved release has been described, in which with the transfer the release is divided from a carrier and forms a protective coating on the transferred image. The release is applied as a solution and contains a montan wax, a rosin ester or a hydrocarbon resin, a solvent and an ethylene-vinyl acetate copolymer having a low vinyl acetate content.

An additional effort has been directed to improve the adhesion of the transferred laminate to the porous, semi-porous, or non-porous materials, and to the development of a conformable transfer layer which allows the melted transfer fabric to be used to transfer uneven surfaces images.

It is well known to those of ordinary skill in the art that current ink jet inks are water based systems. That is, the dyes used in such inks are soluble in water. Therefore, substrates printed with dye jet inks have a pronounced propensity to squeeze or even lose an image in the presence of moisture or water. In addition, the graphics selected by the client produced by publication programs above the desktop and printed by inkjet printers result in graphics in which they are generally not satisfactorily transferred by means of known heat transfer papers. This is particularly true when the transfer is attempted with a plate held in the hand. Consequently, there is an opportunity for an improved heat transfer paper which has been developed specifically for graphics printed with an ink jet printer, for example an ink jet printable heat transfer paper. There is also an opportunity for a transfer paper with improved heat, which has an improved durability especially in the presence of water, and which results in a softer image and more folded transfer. More generally, there is an opportunity for an improved material which has been developed specifically for printed graphics with an ink jet printer, where the printed graphics will have an improved durability, especially in the presence of water.

Synthesis of the Invention The present invention relates to some of the difficulties and problems discussed above by providing a printable material which includes a first flexible layer having the first and second surfaces and a second layer. The first layer can be a film or a fibrous sheet type material. For example, the fibrous sheet type material can be a nonwoven cellulosic fabric. As another example, the first layer may be a latex impregnated paper.

The second layer covers and is attached to the first surface of the first layer and includes a nonwoven fabric formed of synthetic natural polymer. Natural polymers include hydrocarbons such as rubber and gutta percha (polyisoprene). A synthetic polymer can generally be a thermoplastic or thermosetting polymer. The first layer can have a basis weight of from about 20 to about 140 grams per square meter (gsm). The second layer can have a basis weight of at least about 10 grams per square meter. For example, the second layer can have a basis weight of from about 10 grams per square meter to about 115 grams per square meter. As another example, the second layer can have a basis weight of from about 17 grams per square meter to about 115 grams per square meter.

The second layer is generally attached to the first layer by any means known to those of ordinary skill in the art. For example, the second layer may be attached to the first surface of the first layer by means of an adhesive. As an example, the adhesive can be a heat activated adhesive, such as a copolymer of acrylic acid-ethylene. If desired, a release layer may be present between the first layer and the adhesive. Other adhesives such as wet adhesives, setting adhesives and the like can be employed.

Alternatively, the second layer may be thermally bonded to the first surface of the first layer. This can be achieved by placing a fusible fabric between the two layers and heating them in a press at a temperature sufficient to at least partially soften or melt the meltable fabric. The meltable fabric will typically be prepared from a thermoplastic polymer having a melting point of adequately low softening. The use of such fabrics is well known to those of ordinary skill in the art. When the second layer has been prepared from a thermoplastic polymer, a separate meltable fabric is typically not required; The first and second layers can be heated in a press at a temperature sufficient to soften or partially melt at least a portion of the second layer which is adjacent to the first layer.

The present invention also provides an ink jet printable material which includes a first flexible layer having the first and second surfaces and a second layer. The first layer can be a film or a fibrous sheet type material as described above. The second layer covers and is attached to the first surface of the first layer as described above, and includes a nonwoven fabric formed of a natural or synthetic polymer, again as described above. The second layer contains from about 0.1 to about 20 weight percent, based on the weight of the polymer of which the second layer is composed, of a material which increases the viscosity of an inkjet ink when printed on the second layer. Such material may be, by way of illustration only, a polyvinyl alcohol or a polyoxyethylene. The second layer may also contain from about 0.1 to about 5 weight percent, again based on the weight of the polymer of which the second layer of a cationic polymer is composed.

The present invention further provides an ink jet printable heat transfer material which includes a first flexible layer having the first and second surfaces and a second layer as already described. The first layer can be a film or a fibrous sheet type material. For example, the fibrous type sheet material can be a cellulosic nonwoven fabric. As another example, the first layer may be a paper impregnated with latex.

The second layer covers and is attached to the first surface of the first layer and includes a nonwoven fabric formed of a thermoplastic polymer. For example, the second layer may be a melt blown fabric formed of, by way of example only, a polyamide. The first layer can have a basis weight of from about 20 to about 140 grams per square meter. The thermoplastic polymer can have a melting point of from about 90 degrees centigrade to about 250 degrees centigrade and the second layer can have a basis weight of at least about 10 grams per square meter. For example, the second layer can have a basis weight of from about 10 grams per square meter to about 115 grams per square meter. As another example, the second layer can have a basis weight of from about 17 grams per square meter to about 115 grams per square meter.

The second layer is generally joined to the first layer by means known to those of ordinary skill in the art. For example, the second layer may be attached to the first surface of the first layer by means of an adhesive. As an example, the adhesive may be a heat activated adhesive, such as an acrylic acid-ethylene copolymer If desired, a release layer may be present between the first layer and the adhesive Other adhesives such as adhesives wet, setting adhesives, and the like can be employed.

Alternatively, the second layer can be thermally bonded to the first surface of the first layer. This was easily achieved by heating the first and second layers in a press at a temperature sufficient to soften or partially melt a part of the second layer which is on one side of the first layer. The second layer contains from about 0.1 to about 20 weight percent, based on the weight of the polymer of which the second layer is composed, of a material which increases the viscosity of an inkjet ink printed on the second layer. cap. Such material may be, by way of example only, a polyvinyl alcohol or a polyoxyethylene. The second layer may also contain from about 0.1 to about 5 weight percent, based on the weight of the polymer of which the second layer is composed, of a cationic polymer. For example, the cationic polymer can be a polyamide with cationic functional groups, an amide-epichlorohydrin resin, a polyethylene imine, a polyacrylamide with cationic functional groups, or a urea-formadehyde resin. In addition, the second layer may contain in amounts of from about 0.1 to about 80 percent by weight of the polymer mass being transferred, a binder which functions as a meltable polymer adhesive (referred to as such herein). forward) which becomes part of the pledge. For example, the meltable polymer adhesive may be a copolymer of acrylic acid-ethylene, a copolymer of acrylic acid-vinyl chloride, a polyacrylate or a phenoxy resin.

The present invention further provides a method for preparing a printable material which involves providing a first flexible layer having the first and second surfaces, the first flexible layer is a film or a nonwoven cellulosic fabric; providing a second layer which includes a nonwoven fabric formed of a natural or synthetic polymer; covering the second layer on the first surface of the first layer; and joining the second layer to the first surface of the first layer. If the material is to be printed with an inkjet printer, the method can also include treating the second layer with a composition which includes water and a material which increases the viscosity of an inkjet ink when it is printed on the second layer. Such material may be, by way of illustration only, a polyvinyl alcohol or a polyoxyethylene. The treatment is carried out under conditions sufficient to provide a quantity of the material in the second layer of from about 0.1 to about 20 weight percent, on a dry weight basis, based on the weight of the second layer before the treatment (for example based on the weight of the polymer of which the second layer is composed). The second layer can also be treated with a cationic polymer solution under conditions sufficient to provide an amount of cationic polymer in the second layer of from about 0.1 to about 5 weight percent, again based on the weight of the second layer. layer before treatment. The second layer can be treated sequentially with two different compositions containing the material that increases the viscosity of the ink from the ink jet and the cationic polymer, respectively, or with a unique composition that both contain the material that increases the viscosity of the ink of the ink jet and the cationic polymer. The first and second layers are as defined.

The present invention also provides a method for preparing a printable material which involves providing a first flexible layer having the first and second surfaces, the first flexible layer being a film or a nonwoven cellulosic fabric; providing a second layer which includes a nonwoven fabric formed of a natural or synthetic polymer; coating the first surface of the first layer with an adhesive; and overlaying the second layer on the adhesive coating to join the second layer to the first layer. As with the above method, if the material is to be printed with an ink jet printer, the method may also include treating the second layer with a composition which includes water and a material which increases the viscosity of the ink. Ink jet when printed on the second layer. Again, such material can be, by way of illustration only, a polyvinyl alcohol or a polyoxyethylene and the treatment is carried out under conditions sufficient to provide a quantity of the material in the second layer from about 0.1 to about 20 percent by weight, on a dry weight basis based on the weight of the second layer before treatment. The second layer can also be treated with a cationic polymer solution under conditions sufficient to provide an amount of cationic polymer in the second layer of from about 0.1 to about 5 weight percent based on the weight of the second layer before treatment. The second layer can be treated sequentially with two different compositions containing the viscosity increase material of the ink jet ink and the cationic polymer, respectively, or with a unique composition containing both the viscosity increase material of the ink. of the ink jet and the cationic polymer. The first and second layers are as defined.

In any of the above methods, the use of a second prepared layer of a thermoplastic polymer allows the resulting material to be used as a heat transfer material. This is particularly true where the thermoplastic polymer has a melting point of from about 90 degrees centigrade to about 250 degrees centigrade. Where the resulting material is to be used as a heat transfer material, any of the above methods may further include treating the second layer with an aqueous dispersion of a meltable polymer adhesive which becomes part of the garment. Such treatment is carried out under conditions sufficient to provide an amount of the meltable polymer adhesive in the second layer which is from about 0.1 to about 80 weight percent of the polymer mass that is being transferred. The treatment may be separate or simultaneous with any or all other treatments required by any given method. For example, where treatments with a material which increases the viscosity of an inkjet ink when printed on the second layer, a cationic polymer, and a meltable polymer adhesive are required, three solutions or compositions can be employed. of different treatment. As another example, two can be used. solutions or treatment compositions with any of two of the three materials that are present in the same treatment solution composition. As yet another example, all three materials may be present in a single treatment composition. Any given treatment solution or composition can be applied by any method known to those of ordinary skill in the art, including those methods already indicated. In addition, the same method can be employed for each treatment solution or composition, or as many different methods as different solutions or treatment compositions can be used.

The present invention further provides a method for preparing a material having a durable graphic printed thereon which involves providing a first flexible layer having the first and second surfaces, the first flexible layer being a film or a nonwoven cellulosic fabric.; providing a second layer which includes a nonwoven fabric formed of a thermoplastic polymer; covering the second layer on the first surface of the first layer; joined the second layer to the first surface of the first layer; print an image of the second treated layer; and melt the second layer. The first and second layers are as defined. If the material is to be printed with an inkjet printer, the method may also include treating the second layer with a composition which includes water and or material which increases the viscosity of an inkjet ink when printed on the second layer.

As used herein, the term "merge" means that the second layer is heated under conditions which are sufficient to at least partially melt at least that part of the second layer on which a graphic image has been printed. The heating can be carried out by any means known to those of ordinary skill in the art. Such methods include, by way of illustration only, passing the material between a heated pressure point, infrared heaters, furnaces, hot air and the like. The heating may involve the entire outer surface of the second layer or only selected parts thereof, such as the part on which the graphic image has been printed.

The present invention further provides a method for preparing a material having durable graphs thereon which involves providing a printed material having a first layer and a second layer; the printable material includes a first flexible layer having the first and second surfaces, the first flexible layer is a film or a nonwoven cellulosic fabric and has a basis weight d from about 20 to about 140 grams per square meter; and a second layer which comprises a non-woven fabric formed of a thermoplastic polymer, the second layer of which is attached to the first surface of the first layer, and has a melting point of from about 90 degrees centigrade to about 250 degrees centigrade. , and has a base weight of at least about 10 grams per square meter. The second layer may include from about 0.1 to about 20 weight percent, on a dry weight basis, based on the weight of the second layer, of a material which increases the viscosity of an inkjet ink when it is printed on the second layer. The method may also include transferring the second melted layer to a cloth under the influence of heat and pressure.

Detailed description of the invention As used herein, the term "fibrous sheet type material" is intended to include any fibrous material which is typically prepared by placing by air or wetting relatively short fibers to form a sheet or non-woven fabric. Thus, the term includes non-woven fabrics prepared from a supply for making paper. Such a supply may include, by way of illustration, only cellulose fibers, a combination of cellulosic fibers and non-cellulosic fibers, or only non-cellulosic fibers. When the supply contains only cellulosic fibers or a mixture of cellulosic fibers and non-cellulosic fibers, the resulting fabric is referred to herein as a "cellulosic nonwoven fabric". Non-cellulosic fibers include, by way of illustration only, fibers and glass wool prepared from thermosetting and thermoplastic polymers, as is well known to those of ordinary skill in the art. Of course, the non-woven cellulosic fabric may also contain additives and other materials such as fillers, for example, clay and titanium dioxide, as is well known in the art for making paper.

In general, the term "cellulosic fibers" is intended to include cellulosic fibers from any source. Sources of cellulosic fibers include, by way of illustration only, woods, such as softwoods and hardwoods; straw and grass, such as rice, esparto, wheat, rye and sabai; bamboo; jute, linen, soft rush, hemp, linen, abaca, henequen and cotton and cotton lint. Softwoods and hardwoods are the most commonly used sources of cellulosic fibers. In addition, the cellulosic fibers can be obtained by any of the commonly used pulping processes, such as the mechanical, chemistry and semi-chemical and chemical processes. For example, soft wood and hardwood kraft pulps are desirable for their firmness and tear resistance, but other pulps, such as recycled fibers, sulfite pulp and the like, may also be used depending on the application.

As used herein, the term "thermosetting polymer" means a crosslinked polymer which does not flow when heated; once set at a critical temperature for a given material, a thermosetting polymer may not be resurfaced or reworked. Examples of the thermosetting polymers include, by way of illustration only, the alkyd resins, such as the anhydride-glycerol-italic resins, the glyceryl-maleic acid resins, the glycerol-adipic acid resins and the pentaerythritol-anhydride resins phthalic allylic resins, in which such monomers as diallyl phthalate, diallyl isophthalate diallyl maleate and diallyl chloroendate serve as non-volatile crosslinking agents in polyester compounds; amino resins such as aniline-formaldehyde resins, ethylene urea-formaldehyde resins, dicyandiamine-formaldehyde resins, melamine-formaldehyde resins, sulfonamide-formaldehyde resins and urea-formaldehyde resins; epoxy resins, such as the bisphenol A-epichlorohydrin resins crosslinked; phenolic resins such as phenol-formaldehyde resins, including Novolacs and resols; and thermosetting polyesters, silicones and urethanes.

The term "thermoplastic polymer" is used herein to mean any polymer which softens and flows when heated; such a polymer can be heated and smoothed a number of times without undergoing any basic alteration in the characteristics, provided that the heating is below the decomposition temperature of the polymer. Examples of the thermoplastic polymers include, by way of illustration only, end-cap polyacetals, such as poly (oxymethylene) or polyformaldehyde, poly (trichloroacetaldehyde), p 1 i (n_v aleraldehyde), poly. { acetaldehyde), and poly (propionaldehyde); acrylic polymers, such as polyacrylamide, poly (aryl acid), poly (methacrylic acid), poly (ethylacrylate), and poly (methyl methacrylate); fluorocarbon polymers, such as poly (tetrafluoroethylenes), perfluorinated ethylene-propylene copolymers, ethylene-tetrafluoroethylene copolymers, poly (chloro-trifluoroethylene), ethylene-chlorotrifluoroethylene copolymers, poly (vinylidene fluoride), and poly (vinyl fluoride) ); polyamides, such as poly (6-aminocaproic acid) or poly (e-caprolactam), poly (hexamethylene adipamide), poly (hexamethylene sebacamide), and poly (11-aminoundecanoic acid); polyarylamides, such as poly (imino-1,3-phenyleneimino-phthaloyl) or poly (m-phenylene isophthalamide); parylenes, such as poly-p-xylylene and poly (chloro-p-xylynene); polyaryl ethers, such as poly (oxy-2, β-dimethyl-1, 4-phenylene) or poly (p_-phenylene oxide); polyaryl sulfones, such as poly (oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenylene-isopropylidene-1,4-phenylene) and poly (sulphonyl-1,4-phenyleneoxy-1) 4-phenylenesulfonyl-4,4'-biphenylene); polycarbonates, such as poly (bisphenol A) opol (carbonyldioxy-1,4-phenyleneisopropylidene-1,4-phenylene), polyesters, such as poly (ethylene terephthalate), poly (tetramethylene terephthalate), and poly (cyclohexylene-1) , 4-dimethylene terephthalate) or poly (oxymethylene-1,4-cyclohexylenomethylene-oxytetraephthaloyl); polyaryl sulfides, such as poly (p_-phenylene sulfide) or poly (thio-l, 4-phenylene); polyimides, such as poly (pyromellimid-1,4-phenylene); polyolefins such as polyethylene, polypropylene, poly (l-butene), poly (2-1, 4-phenylene); polyolefins such as polyethylene, polypropylene, poly (l-butene), poly (2-butene), poly (1-pentene), poly (2-pentene), poly (3-methyl-l-pentene) and poly (4-) methyl-1-pentene); vinyl polymers, such as poly (vinyl acetate), poly (vinylidene chloride), and poly (vinyl chloride); diene polymers, such as 1,2-poly-1,3-butadiene, 1,4-poly-1,3-butadiene, polyisoprene, and polychloroprene; polystyrenes; copolymers of the above such as acrylonitrile-butadiene-styrene copolymers (ABS); and similar.

As used herein, the term "polymer" generally includes, but is not limited to homopolymers; copolymers, such as, for example, block, graft, random and alternating copolymers; and the terpolymers; and the mixtures and modifications thereof. In addition, unless specifically limited otherwise, the term "polymer" will include all possible geometric configurations of the material. These configurations include but are not limited to isotactic, syndiotactic and random symmetries.

The term "cationic polymer" is intended to include any water-soluble polymer containing cationic functional groups. For example, the cationic polymer can be an amide-epichlorohydrin polymer, a polyacrylamide with cationic functional groups, polyethylene imine, polydialkylamine, a quaternary polycationic synthetic organic polymer, a polyacrylamide with cationic functional groups or the like.

The term "non-woven fabric" is used herein to mean a fabric of fibers in which the fibers are placed in a random manner. Therefore, a non-woven fabric can be formed by such processes such as wet laying, dry laying, melt blowing, coformming, spun bonding and carding and bonding.

The term "meltblown fabric" means a nonwoven fabric prepared by known meltblown processes. By way of illustration only, such processes are exemplified by the following references, each of which is incorporated herein by this mention: (a) references to blow molding include, by way of example, U.S. Patents 3,016,599 issued to RW Perry, Jr., 3,704,198 issued to JS Prentice, 3,755,527 issued to JP Keller et al., 3,849,241 granted to RR Butin and others, 3,978,185 granted to RR Butin and others, and 4,663,220 granted to TJ isneski and others. See also the work of V. A. Wente, "Superfine Thermoplastic Fibers", Industrial Chemistry and Engineering, volume 48, number 8, pages 1342-1346 (1956); VA Wente et al., "Manufacture of Superfine Organic Fibers", Naval Research Laboratory, Washington DC, report of the Naval Research Laboratory 4364 (111437), dated May 2, 1954, Department of Commerce of the United States of America, Technical Services Office; and the work of Robert R. Butin and Dwight T. Lohkamp, "Blowing with Fusion - A One-Step Tissue Process for New Non-Woven Products", Journal of the Pulp and Paper Industry Technical Association, volume 56 , number 4, pages 74-77 (1973); Y (b) coformation references (for example references describing a meltblowing process in which the fibers or particles are mixed with the melt blown fibers as they are formed) and which include the patents of the United States of America numbers 4,100,324 granted to RA Anderson and others and 4,118,531 granted to ER Hauser.

Spunbond non-woven fabrics are made of fibers which are formed by extruding a melted thermoplastic material as filaments from a plurality of thin, usually circular, capillary vessels in a spinner with the diameter of the extruded filaments then being rapidly reduced , for example, by means of pulling eductive or non-eductive fluid or by means of other well-known splicing mechanisms. The production of non-woven fabrics bonded with yarn is illustrated in such patents as those of the United States of America Nos. 3,276,944 issued to Levy; 3,338,992 and 3,341,394 granted to Kinney; 3,502,538 issued to Peterson; 3,502,763 granted to Hartman; 3,542,615 issued to Dobo and others; 3,655,862 issued to Dorschner and others; 3,692,618 issued to Dorschner et al .; 3,705,068 granted to Dobo and others; 3,802,817 granted Matsuki et al .; 3,853,651 granted to Porte; 4,064,605 issued to Akiyama and others; 4,091,140 granted to Harmon; 4,100,319 issued to Schwartz; 4,340,563 granted to Appel and Morman; 4,405,297 issued to Appel and Morman; 4,434,204 granted to Hartman and others; 4,627,811 issued to Greiser and Wagner; and 4,644,045 granted to Fowells; and Canadian Patent No. 803,714 issued to Harmon.

The term "material which increases the viscosity in an inkjet ink when printed on the second layer" is intended to include any material which acts as a viscosity modifier of the inkjet ink as described herein. . For example, such a material may be, by way of illustration only, a polyvinyl alcohol or a polyoxyethylene, or a polyethylene glycol. When a poly (ethylene glycol) is employed, it will desirably be a poly (ethylene glycol) having a weight average molecular weight of from about 100,000 to about 2,000,000. The poly (ethylene glycol) desirably will have a weight average molecular weight from about 100,000 to about 600,000.

As noted above, the ink-jet printable material of the present invention includes a first flexible layer having the first and second surfaces and a second layer. The first layer can be a film or a fibrous sheet type material. For example, the first layer may be a cellulosic nonwoven fabric. As another example, the first layer may be a paper impregnated with latex.

The second layer covers and is attached to the first surface of the first layer and includes a non-woven fabric formed of a natural or synthetic polymer. Natural polymers include hydrocarbons, such as rubber and gutta perch (polyisoprene). A synthetic polymer can generally be a thermosetting polymer or a thermoplastic polymer. The first layer can have a basis weight of from about 20 to about 140 grams per square meter (gsm). The second layer can have a basis weight of at least about 10 grams per square meter. For example, the second layer can have a basis weight of from about 10 grams per square meter to about 115 grams per square meter. As another example, the second layer can have a basis weight of from about 17 grams per square meter to about 115 grams per square meter.

The second layer is generally joined to the first layer by any means known to those of ordinary skill in the art. For example, the second layer can be attached to the first surface of the first layer by means of an adhesive. As an example, the adhesive can be a heat activated adhesive, such as an acrylic acid-ethylene copolymer. Other adhesives, such as wet adhesives, setting adhesives, and the like, may be employed. If desired, a release layer may be present between the first layer and the adhesive. For example, the release layer may be composed of a silicone or an ethylene or polyethylene copolymer film.

Alternatively, the second layer may be thermally bonded to the first surface of the first layer. This can be achieved by placing a fusible fabric between the two layers and heating them in a press at a sufficient temperature to soften or partially melt the meltable telephone. The meltable fabric will typically be prepared from a thermoplastic polymer having a melting point or softening adequately low. The use of such fabrics is known by those who have an ordinary skill in the art. When the second layer has been prepared from a thermoplastic polymer, the first and second layers can be heated in a press at a temperature sufficient to soften to partially melt a part of the second layer which is adjacent to the first layer.

The second layer may contain from about 0.1 to about 20 weight percent based on the weight of the second layer, of a material which increases the viscosity of an ink jet ink when printed on the second layer. Such material may be, by way of illustration only, a polyvinyl alcohol or a polyoxyethylene. Such material may be by way of illustration only, or poly (vinyl alcohol) or polyoxyethylene. This can be applied by any convenient means to the second layer. For example, the material can be dissolved in a suitable solvent, such as water, and applied to the second layer by means of a Meyer rod, a doctor blade, by spraying, embedding, etching or other known methods.

The second layer may also contain from about 0.1 to about 5 weight percent, based on the weight of the second layer of a cationic polymer. Examples of the cationic polymers include, by way of illustration only, polyamides, amide-epichlorohydrin resins, polyethylene imines, polyacrylamides and urea-formaldehyde resins. As with the viscosity reducing material of the ink, the cationic polymer can be dissolved in a suitable solvent such as water, and applied in a similar manner. If desired, both the ink viscosity reducing material and the cationic polymer can be present in the same solution.

The present invention further provides a printable inkjet heat transfer material that includes a first flexible layer having the first and second surfaces and a second layer. The first layer can be a film or a fibrous sheet type material. For example, the fibrous sheet type material can be a cellulosic nonwoven fabric. As another example, the first layer may be a paper impregnated with latex.

The second layer covers and is attached to the first surface of the first layer and includes a nonwoven fabric formed of a thermoplastic polymer. For example, the second layer may be a melt blown fabric, formed of, by way of example only, a polyamide. The first layer can have a basis weight of from about 20 to about 140 grams per square meter. The thermoplastic polymer can have a melting point of from about 90 degrees centigrade to about 250 degrees centigrade and the second layer can have a basis weight of at least about 10 grams per square meter. For example, the second layer can have a basis weight of from about 10 grams per square meter to about 115 grams per square meter. As another example, the second layer can have a basis weight of from about 17 grams per square meter to about 115 grams per square meter.

The second layer is generally joined to the first layer by any means known to those of ordinary skill in the art. For example, the second layer may be attached to the first surface of the first layer by means of an adhesive. As an example, the adhesive can be a heat activated adhesive, such as an acrylic acid-ethylene copolymer. If desired, a release layer may be present between the first layer and the adhesive. Other adhesives, such as wet adhesives, curable adhesives and the like can be employed.

Alternatively, the second layer may be thermally bonded to the first surface of the first layer. This is easily achieved by heating the first and second layers in a press at a temperature sufficient to partially soften or melt a part of the second layer 1 which is on one side of the first layer.

The second layer can contain from about 0.1 to about 20 percent by weight based on the weight of the second layer, of a material which increases the viscosity of an inkjet ink when printed on the second layer. For example, the second layer may contain from about 0.1 to about 5 percent by weight of the material that increases the viscosity of the ink. Such material may be, by way of illustration only, a polyvinyl alcohol or a polyoxyethylene. This can be applied for any convenient means to the second layer. For example, the material can be dissolved in a suitable solvent, such as water, and applied to the second layer by means of a Meyer rod, a doctor blade, sprayed, embedded and pressurized, gravure printing, or other method known. The second layer may also contain from about 0.1 to about 5 weight percent, based on the weight of the second layer of a cationic polymer. The cationic polymer can be applied as a solution in a similar manner.

The second layer may additionally contain latex binders or meltable polymer adhesives, fillers and pigments, and / or thermoplastic polymer particles, as desired. In general, any latex binder typically employed to prepare a saturated paper can be used as the meltable polymer adhesive. Examples of such binders are shown in the Table given below. In the Table, the terms "acrylic" and "acrylates" include "methacrylic" and "methacrylate", respectively.

TABLE A Examples of Suitable Binder Networks for the Second Cap As noted above, the meltable polymer adhesive is typically present in the second cap at a level of from about 0.1 to about 80 per cent by weight of the polymer mass what is being transferred. For example, the meltable polymer adhesive may be present at a level of from about 0.1 to about 40 per cent by weight.

In general, any of the pigment fillers typically present in the paper furnish may be included with the meltable polymer adhesive. Examples of such fillers and pigments include, by way of illustration only clay, talc, silica, titanium dioxide; and colored pigments. The fillers and pigments may be present in the second layer at levels of from about 0.1 to about 40 weight percent, based on the amount of the meltable polymer adhesive on a dry weight basis. Where the printable material is to be used as a heat transfer material, the amount of fillers and pigments present in the second layer can vary from about 0.1 to about 5 percent by weight.

Finally, the particles of the thermoplastic polymers may also be present in the second layer. In general, the thermoplastic polymer powder can be any thermoplastic polymer which meets the criteria set forth herein. For example, the thermoplastic polymer in powder may be a polyolefin, a polyester, a polyamide, or a vinyl acetate-ethylene copolymer. Such particles may be present in the second layer at levels of from about 0.1 to about 40 percent by weight based on the amount of the meltable polymer adhesive on a dry weight basis. When the printable material is to be employed as a heat transfer material, the amount of thermoplastic particles present in the second layer can vary from about 0.1 to about 5 percent by weight.

Therefore, the heat transfer material of the present invention is a non-woven fabric laminated to a flexible substrate. A small amount of an additive, desirably from about 0.1 to about 5 percent based on the weight of the non-woven fabric, is added to prevent scattering or featheredging of the ink. This additive is the viscosity increase material already described. Also as already described, the material can be applied to the non-woven fabric, such as, for example, a water solution and then dried. Poly (vinyl alcohol) and polyoxyethylene or poly (ethylene oxide) have been shown to be very effective at low aggregates. This is probably due to its ability to provide a high viscosity to the inks very quickly before their spreading occurs.

The advantages of the ink jet printable material of the present invention include the wide availability of polymers for meltblown fabrics, the ease of construction of the absorbent and heavy coating and the ease of manufacturing a laminate. The resulting product appeared to give less print feathered and, with the selection of suitable polymer, provides a heat transfer material which imparts good cleaning of fabrics to which the images were transferred by means of the heat transfer material of the present invention. Also, it is possible to use the concept to produce durable, inkjet printable and fusible coatings. The yarns can possibly be made by cutting in slits the sewing of fabrics blown with fusion.

The printable inkjet heat transfer material of the present invention can contain amounts of from zero to about 80 weight percent of the polymer mass being transferred, a meltable polymer adhesive which becomes part of the garment. By way of illustration, the meltable polymer adhesive may be present in an amount of from about 0.1 to about 80 weight percent. For example, the meltable polymer adhesive may be a copolymer of acrylic acid-ethylene, a copolymer of acrylic acid-vinyl chloride, a polyacrylate, or a phenoxy resin. The total weight of the transferable polymer mass typically ranges from about 25 to about 70 grams per square meter. Thus far, heat transfer materials having a high proportion of meltblown polymer (e.g. relatively small amount of meltable adhesive) have been very effective. Heavier melt blown fabrics provide a more surface area for rapid ink absorption, and the presence of the polymer in higher proportions provides better ink retention (better wash of the transferred image) with inkjet inks Pigmented or with other pigmented printing methods, it is expected that the polymer types other than the polyamides used in the examples will also have an acceptable wash.

As already indicated, the heat transfer material can have a releasable layer or coating whether or not the adhesive layer is used to join the second layer to the first layer. A release layer is desirable for transferring the images by means of a plate held in the hand or if desired in cold release properties.

The present invention further provides a method for preparing a printable material which involves providing a first flexible layer having the first and second surfaces, the first flexible layer is a film or a nonwoven cellulosic fabric; providing a second layer which includes a nonwoven fabric formed of a natural or synthetic polymer; covering the second layer on the first surface of the first layer; and joining the second layer to the first surface of the first layer. If the material is to be printed with an inkjet printer, the method can also include treating the second layer with a composition which includes water and a material which increases the viscosity of an inkjet ink when printed on the second layer. Such material may be, by way of illustration only, a polyvinyl alcohol or a polyoxyethylene. The treatment is carried out under conditions sufficient to provide a quantity of the material in the second layer of from about 0.1 to about 20 weight percent, on a dry weight basis, based on the weight of the second layer before the treatment (for example, based on the weight of the polymer of which the second layer is composed). The second layer can also be treated with a solution of a cationic polymer under conditions sufficient to provide an amount of cationic polymer in the second layer of from about 0.1 to about 5 percent by weight, again based on the weight of the second layer before treatment. The second layer can be treated in sequence with two different compositions containing the viscosity-increasing material of the ink-jet ink and the cationic polymer, respectively, or with a unique composition containing both the viscosity-increasing material of the inkjet ink and cationic polymer. The first and second layers are as defined.

The present invention also provides a method for preparing a printable material which involves providing a first flexible layer having the first and second surface, the first flexible layer is a film or a nonwoven cellulosic fabric; providing a second layer which includes a nonwoven fabric formed of a synthetic natural polymer; coating the first surface of the first layer with an adhesive; and covering the second layer on the adhesive coating to join the second layer to the first layer. As with the foregoing method, if the material is to be printed with an ink jet printer, the method may also include treating the second layer with a composition which includes water and a material which increases the viscosity of an ink. Ink jet when printed on the second layer. Again, such material can be, by way of illustration only, a polyvinyl alcohol or a polyoxyethylene and the treatment is carried out under conditions sufficient to provide a quantity of the material in the second layer of from about 0.1 to about 20 percent by weight, on a dry weight basis, based on the weight of the second layer before treatment. The second layer can also be treated with a cationic polymer solution under conditions sufficient to provide an amount of cationic polymer in the second layer from about 0.1 to about 5 weight percent, based on the weight of the second layer before of the treatment. The second layer can be treated in sequence with two different compositions containing the ink viscosity increase material of the ink jet and the cationic polymer, respectively, or with a unique composition that both contain the material that increases the viscosity of the ink of the ink jet and the cationic polymer. The first and second layers are as defined.

In any of the above methods, the use of a second prepared layer of a thermoplastic polymer allows the resulting material to be used as a heat transfer material. This is particularly true when the thermoplastic polymer has a melting point of from about 90 degrees centigrade to about 250 degrees centigrade. Where the resulting material is to be used as a heat transfer material, any of the above methods may further include treating the second layer with an aqueous dispersion of a meltable polymer adhesive which becomes part of the garment. Such treatment is carried out under conditions sufficient to provide an amount of the meltable polymer adhesive in the second layer which is from about 0.1 to about 80 weight percent of the mass of polymer that is being transferred. The treatment may be separated from or simultaneous with all other treatments required by any given method. For example, where treatments with a material which increases the viscosity of an inkjet ink when printed on the second layer, a cationic polymer and a meltable polymer adhesive are required, three compositions or treatment solutions may be employed. different As another example, two compositions or treatment solutions can be used, with any two of the three materials being present in the same treatment solution composition. As yet another example, all three materials may be present in a single treatment composition. Any composition or treatment solution Fairy can be applied by any method known to those of ordinary skill in the art, including those methods already indicated. In addition, the same method can be employed for each treatment solution or composition, or as many different methods as different compositions or treatment solutions can be used.

The present invention further provides a method for preparing a material having a durable graphic printed thereon which involves providing a first flexible layer having the first and second surfaces, the first flexible layer being a film or a nonwoven cellulosic fabric; providing a second layer which includes a nonwoven fabric formed of a thermoplastic polymer; covering the second layer on the first surface of the first layer; joining the second layer to the first surface of the first layer; print an image on the second treated layer; and melt the second layer. The first and second layers are as defined. If the material is to be printed with an inkjet printer, the method can also include treating the second layer with a composition which includes water and a material which increases the viscosity of an inkjet ink when it is printed on the second layer.

As used herein, the term "merge" means that the second layer is heated under conditions which are sufficient to at least partially melt at least that portion of the second layer on which a graphic image is printed. The heating can be carried out by any means known to those of ordinary skill in the art. Such methods include, by way of illustration only, passing the material between a heated pressure point, infrared heaters, furnaces, hot air, and the like. The heating may involve the entire outer surface of the second layer or only selectable parts thereof, such as the part on which the graphic image is printed.

The present invention further provides a method for preparing a material having durable graphics thereon which involves providing a printable material having a first layer and a second layer.; print an image on the second layer; and merge the second layer. The printable material includes a first flexible layer having the first and second surfaces, the first flexible layer is a film or a cellulosic nonwoven fabric and has a basis weight of from about 20 to about 140 grams per square meter; and a second layer which comprises a nonwoven fabric formed of a thermoplastic polymer and the second layer covers and is attached to the second surface of the first layer, has a melting point of from about 90 degrees centigrade to about 250 degrees centigrade, and has a basis weight of at least about 10 grams per square meter. The second layer may include from about 0.1 to about 20 weight percent, on a dry weight basis, based on the weight of the second layer, of a material which increases the viscosity and a dull inkjet ink when it is printed on the second layer. The second method may include the transfer of the second fused layer to a fabric under the influence of heat and pressure.

The present invention is further described by the following examples. Such examples, however, should not be considered as limiting in any form of the spirit or scope of the invention.

Examples The examples all used co-melt blown fabrics prepared with a copolyamide having a melted point of 115 degrees centigrade (Platamid® H585, Elf Atoche North America, Inc., of Philadelphia, Pennsylvania). Meltblown webs having base weights of 12.5, 18, 36 and 5 grams per square meter were prepared. The meltblown copolyamide fibers were very slow to harden, resulting in a blocked roller. The material was, however, successfully wound up on the release paper. After hardening, the resulting fabrics were tightly bonded and very porous. Unlike faster hardening polymer fabric such as polypropylene, the fabrics were somewhat like film type, it was difficult to scrape the fibers from them. This surprising result gave a laminate which behaves almost like a coated paper without any need for an additional bonding of another densification. The printing tests were done with a Canon BJC 600 inkjet printer.

The first layers used in the examples were as follows: FL-A The first layer A was of a commercial class of kraft paper coated with silicone.

FL-B This first layer was a lite label base coated on the underside with 1.8 mils (0.046 mm) of a melt index 50C rtetacrylic acid-ethylene copolymer (Nucrel® 599, E. I. DuPont de Nemours et al.

Company, Inc., of Wilmington, Delaware).

FL-C The first C layer was a kraft saturating base that had a basis weight of 75 grams per square meter and was saturated to a 50 gram collection per square meter with a hard acrylic latex (Hycar® 26672 from BF Goodrich Company of Cleveland, Ohio) containing 20 parts of Ti02 per 100 parts of latex on a dry weight basis. The resulting saturated paper had a release coating consisting of a mixture of Hycar® 26672, 20 parts of calcium stearate (Nopcote® C-104, Henkle Corporation, of Ambler, Pensylvania), 20 parts of ur-poly (ethylene oxide) having a weight average molecular weight of 20,000, and 3 parts of a polyethoxylated octylphenol surfactant (Triton® X-100 Rohm &Haas Company, of San Luis MO). The weight of the coating was 16 grams per square meter. The paper had a tie layer on the release layer which consisted of an acrylic acid-ethylene copolymer dispersed in water (Michem® Prime 4983, Michelman, Inc., of Cincinnati, Ohio); the base weight of the coating was 6 grams per square meter.

FL-D This first layer was a kraft saturating base with a 30 grams per square meter saturant consisting of a mixture of Hycar® 26672 and 20 parts per weight of titanium dioxide per 100 parts of latex on a dry weight basis. The paper had a release coating of 14 grams per square meter of a mixture of 10 parts of Hycar® 26672, 20 parts of Nopcote® C-104, 10 parts of the polyethylene glycol described in relation to FL-C and 30 parts of Celite. ® 263 (from Manville Products Corporation, Denver, Colorado), or diatomaceous earth flattening agent, all parts by weight on a dry weight basis.

A variety of aqueous solutions were employed to treat the non-woven fabrics or the second layers. These solutions are summarized in Table 1 (all percentages are by weight and all parts are by weight on a dry weight basis) Table 1 Summary of Aqueous Treatment Solutions Table 1 Continuation Code Description TS-P 15 percent solids solution of 100 parts of Paphen® PKHW-35 (one phenoxy resin latex from Phenoxy Associates, Rock Hill, SC) and 25 parts of Airvol® 523. TS-Q 2.5 percent of solids solution of Polyox® N60K, a polyethylene from Union Carbide Corporation, of Danbury, CT.

The treatment weights were calculated from a wet coating weight since the treatment weights were very small compared to the weight of the total laminate. Transfers were made to a 100 percent cotton jersey material with a Hix shirt press (from Hix Corporation, Pittsburgh, KS) for 25 seconds at 177 degrees Celsius. The washing tests were done in a domestic washing machine on the warm / warm setting using Surf® detergent. The test results were compared with impressions and transfer made with a heat transfer paper type C-90642, a product which has gained acceptance in the market.

Various heat transfer materials were prepared by pressing the meltblown fabrics onto a paper substrate using the t-shirt press at 71 degrees centigrade for 25 seconds. The treatment solutions were applied to fabrics blown with melting with a Meyer No. 6 rod. The various materials are summarized in Table 2 and the results of the printing and washing test are summarized in Table 3 Table 2 Summary of Heat Transfer Materials _ "Treatment Table 2, Continuation Treatment Base weight in grams per square meter.

Table 3 Summary of Print and Wash Tests Table 3, Continuation The results demonstrate a surprisingly good impression with the material having only small amounts of polyvinyl or polyoxyethylene alcohol. The latte has very little effect but Primacor® 4983, a copolymer of acrylic acid-ethylene, seemed to help wash. The heavier-melt blown fabrics were printed better and provided a better wash.

Even when the description has been made and detail with respect to specific incorporations of the same, it will be appreciated by those skilled in the art, to achieve or understanding of the foregoing, which alterations, variations and equivalents of these additions can be easily conceived. Therefore, the scope of the present invention should be established as that of the appended claims any equivalents thereof.

Claims (36)

R E I V I N D I C A C I O N S

1. A printable material that includes: a first flexible layer having the first and second surfaces, the first flexible layer is a film or a nonwoven cellulosic fabric; Y a second covering layer and is attached to the first surface of the first layer, which second layer comprises a nonwoven fabric formed of a natural or synthetic polymer; where : the first layer has a basis weight of from about 20 to about 140 grams per square meter; Y the second layer has a basis weight of at least 10 grams per square meter.

2. The printable material as claimed in clause 1 characterized in that the first layer is a cellulosic nonwoven fabric.

3. The printable material as claimed in clause 2 characterized in that the cellulosic woven fabric is a paper impregnated wlatex.

4. The printable material as claimed in clause 1 characterized in that the second cap is attached to the first surface of the first layer by means of an adhesive.

5. The printable material as claimed in clause 1 characterized in that the second cap is thermally bonded to the first surface of the first layer.

6. A printable material wtint jet comprising: a first flexible layer having the first and second surfaces, the first flexible layer is a film or a nonwoven cellulosic fabric; Y a second covering layer and is attached to the first surface of the first layer, which second layer comprises a nonwoven fabric formed of a natural or synthetic polymer; wherein: the first layer has a basis weight of from about 20 to about 140 grams per square meter; the second layer has a basis weight of at least about 10 grams per square meter; Y the second layer contains from about 0.1 to about 20 weight percent, based on the weight of the second layer of a material which increases the viscosity of an ink jet ink when printed on the second layer.

7. The ink jet printable material as claimed in clause 6 characterized in that the first layer is a cellulosic nonwoven fabric.

8. The ink jet printable material as claimed in clause 7 characterized in that the cellulosic nonwoven fabric is a paper impregnated wlatex.

9. The ink-jet printable material as claimed in clause 6, characterized in that the second layer is attached to the first surface of the first layer by means of an adhesive.

10. The ink jet printable material as claimed in clause 9 characterized in that the adhesive is a copolymer of acrylic acid-ethylene activated by heat.

11. The printable material wtint jet as claimed in clause 6 characterized in that the second layer is thermally bonded to the first surface d of the first layer.

12. The tint jet printable material as claimed in clause 6 characterized in that the material which increases the viscosity of an ink jet ink when printed on the second layer is selected from the group consisting of polyvinyl alcohol ) and polyoxyethylene.

13. The tint jet printable material as claimed in clause 6 characterized in that the second layer contains from about 0.1 to about 5 weight percent, based on the weight of the second layer d a cationic polymer.

14. An ink jet printable transfer material comprising: a first flexible layer having the first and second surfaces, the first flexible layer is a film or a nonwoven cellulosic fabric; and a second covering layer and is attached to the first surface of the first layer, which second layer comprises a nonwoven fabric formed of a thermoplastic polymer; where : the first layer has a basis weight of from about 20 to about 140 grams per square meter; the thermoplastic polymer has a melting point of from about 90 degrees centigrade to about 250 degrees centigrade; the second layer has a basis weight of at least about 10 grams per square meter; Y the second layer contains from about 0.1 to about 20 weight percent, based on the weight of the second layer, of a material which increases the viscosity of an ink jet ink when printed on the second layer.

15. The ink-jet printable heat transfer material as claimed in clause 14 characterized in that the first layer is a cellulosic non-woven fabric.

16. The ink-jet printable transfer material as claimed in clause 15 characterized in that the cellulosic non-woven fabric is a paper impregnated with latex.

17. The ink-jettable transfer material as claimed in clause 14 characterized in that the fabric is a melt blown fabric.

18. The ink-jet printable transfer material as claimed in clause 17 characterized in that the thermoplastic polymer is a polyamide.

19. The inkjet printable heat transfer material as claimed in clause 18 characterized in that the polyamide has a melting point of from about 90 degrees centigrade to about 160 degrees centigrade.

20. The ink-jet printable heat transfer material as claimed in clause 14 characterized in that the second layer is attached to the first surface of the first layer by means of an adhesive.

21. The heat transfer material printable with ink jet as claimed in clause 20 characterized in that the adhesive is a copolymer of acrylic acid-ethylene activated by heat.

22. The heat transfer material printable with an ink jet as claimed in clause 20 characterized in that the release layer is present between the first layer and the adhesive.

23. The ink-jet printable heat transfer material as claimed in clause 14 characterized in that the second layer is thermally bonded to the first surface of the first layer.

24. The inkjet printable heat transfer material as claimed in clause 14 characterized in that the material which increases the viscosity of an ink jet ink when printed on the second layer is selected from the group consisting of polyvinyl alcohol and polyoxyethylene.

25. The inkjet printable heat transfer material as claimed in clause 14 characterized in that the second layer contains from about 0.1 to about 5 weight percent, based on the weight of the second layer of an ink jet. cationic polymer.

26. The inkjet printable heat transfer material as claimed in clause 14 characterized in that the second layer contains from about 0.1 to about 80 weight percent, based on the mass of polymer that is being transferred of a meltable polymer adhesive.

27. A method for preparing a printable material which comprises: providing a first flexible layer having the first and second surfaces, the first flexible layer is a film or a non-woven cellulosic fabric; providing a second layer which comprises a nonwoven fabric formed of a natural or synthetic polymer; covering the second layer on the first surface of the first layer; Y joining the second layer to the first surface of the first layer; where: the first layer has a base weight of about 20 to about 140 grams per square meter; the second layer has a basis weight of at least about 10 grams per square meter.

28. The method as claimed in clause 27 characterized in that it further comprises treating the second layer with a composition comprising water and a material which increases the viscosity of a tint jet ink when printed on the second layer, under condition sufficient to provide the second layer of from about 0.1 to about 20 weight percent, based on the weight of the second layer of said material.

29. A method for preparing a printable material which comprises: providing a first flexible layer having the first and second surfaces, the first flexible layer of a film or a non-woven cellulosic fabric; treat the first surface of the first cap with an adhesive; providing a second layer which comprises a nonwoven fabric formed of a natural or synthetic polymer; Y covering the second layer against the treatment adhesive on the first surface of the first layer; where : the first layer has a basis weight of from about 20 to about 140 grams per square meter; Y the second layer has a basis weight of at least about 10 grams per square meter.

30. The method as claimed in clause 29, characterized in that it also comprises treating the second layer with a composition comprising water and a material which increases the viscosity of an inkjet ink when it is printed on the second layer, under Sufficient conditions to provide in the second layer of from about 0.1 to about 20 weight percent, based on the weight of the second layer of said material.

31. A method for preparing a material having durable graphics printed thereon comprising: providing a first flexible layer having the first and second surfaces, the first flexible layer is a film or a non-woven cellulosic fabric; providing a second layer which comprises a nonwoven fabric formed of a thermoplastic polymer; covering the second layer on the first surface of the first layer; joining the second layer to the first surface of the first layer; print an image on the second layer; Y melt the second printed layer; where : the first layer has a basis weight of from about 20 to about 140 grams per square meter; Y the second layer has a basis weight of at least about 10 grams per square meter.

32. The method as claimed in clause 31, characterized in that it also comprises treating the second layer, before printing an image thereon, with a composition comprising water and a material which increases the viscosity of the jet ink. ink when printed on the second layer, under conditions sufficient to provide in the second layer of from about 0.1 about 20 weight percent, based on the weight of the second layer of said material.

33. A method for preparing a material that has durable graphic graphics on it that comprises: Provide a printable material which includes: a first flexible layer having the first and second surfaces, the first flexible layer being a film or a nonwoven cellulosic fabric, the first layer having a basis weight of from about 20 to about 140 grams per square meter; Y a second layer which comprises a knitted fabric formed of a thermoplastic polymer whose second cap covers and is attached to the first surface of the first layer, has a melting point of from about 90 degrees centigrade to about 250 degrees centigrade, and has a basis weight of at least about 10 grams per square meter; print an image on the second layer; Y merge the second layer.

34. The method as claimed in clause 33 characterized in that the second layer further comprises from about 0.1 to about 20 weight percent, based on the weight of the second layer, of a material which increases the viscosity of the second layer. an inkjet ink when printed on the second layer.

35. The method as claimed in clause 33, characterized in that it also comprises transferring the second melted layer to a cloth under the influence of heat and pressure.

36. The method as claimed in clause 34, characterized in that it also comprises transferring the second melted layer to a cloth under the influence of heat and pressure. U M E N A printable material which includes a first flexible layer having the first and second surfaces and a second layer. The first layer can be a film or a non-woven cellulose cloth. The second layer covers and is attached to the first surface of the first layer and includes a woven fabric n. The first layer has a basis weight of from about d 20 to about 140 grams per square meter. The thermoplastic polymer has a melting point of from about 90 degrees centigrade to about 250 degrees centigrade, and the second layer has a basis weight of at least about 10 grams per square meter. The first layer can be a cellulosic non-woven fabric, such as a paper impregnated with latex. The second layer can be thermally bonded to the first bonded layer by means of an adhesive. A release layer can be present between the first layer and the hot activated adhesive. The second layer may contain from about 0. to about 20 weight percent, based on the weight of the second layer, of a material which increases the viscosity of an inkjet ink when printed on the second. The second layer may also contain from about 0. to about 5 weight percent, based on the weight of the second layer, of a cationic polymer. When the second cap is prepared from a thermoplastic polymer, the ink jet imprint material can be used as a heat transfer material. Methods for preparing a printable material are also described.