2. Description of the Prior Art 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 business which permit 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 iron, such as described in U.S. Patent No.

4,244,358 issued September 23, 1980. Furthermore, U.S.

Patent No. 4,773,953 issued September 27, 1988, 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.

Therefore, in order to attract the interest of consumer groups which are already captivated by the tee shirt rage described above, the present inventor provides the capability of transferring photographic images directly to a receiver element using a material capable of holding and transferring an image. A unique advantage of the invention is to enable all consumers to wear and display on apparel their favorite moments captured on film and to do so in the single most cost and time efficient means.

US Patent 5,620,548 is directed to a silver halide photographic transfer element and to a method for transferring an image from the transfer element to a receptor surface.

SUMMARY OF THE INVENTION Accordingly, the present invention is directed to a conventional silver halide photographic element (e.g. wet processing), which comprises, a support having a front and rear surface, and a transfer layer of the invention which has a melting point of at least 650C, preferably at least 1000C, and which is capable of transferring and adhering developed image and non-image areas from said front surface of said support upon the application of heat energy to the rear surface of the support, said transfer layer strips from said front surface of the support by liquefying and releasing from said support when heated, said liquefied transfer layer

providing adherence to a receptor element by flowing onto said receptor element and solidifying thereon, said adherence does not require an external adhesive layer and occurs in an area at least coextensive with the area of said silver halide grains, and at least one silver halide light sensitive emulsion layer containing light sensitive silver halide grains on said front surface of the support. The particle size of the transfer material is from 1 to 50 micrometers, preferably 2 to 50 micrometers, and more preferably 1 to 20 micrometers.

The silver halide photographic element of the invention is applicable to conventional photographic systems (e.g. wet processing) such as color paper (e.g. print and reversal), color negative film, color reversal film, black and white film or paper, instant film or the like. All types of silver halide photographic elements containing the claimed transfer layer may be transferred in accordance with the process of the invention.

The receptor surface for the image may be a textile such as a shirt (e.g. tee shirt) or the like. Other suitable receptor surfaces include canvas, paper, glass, or receptor supports used by the museum or conservatory industry.

The transfer layer of the invention does not contain silver halide emulsions and is most preferably between the support and the closest silver halide light sensitive emulsion layer to the support.

The present invention also relates to a method of applying a photographic image to a receptor element, which comprises the steps of: (a) exposing imagewise a silver halide photographic element, which comprises, a support having a front and rear surface, a transfer layer of the invention which is capable of transferring and adhering developed image and non-image areas from said front surface of said support upon the application of heat energy to the rear surface of the support, said transfer

layer strips from said front surface of the support by liquefying and releasing from said support when heated, said liquefied transfer layer providing adherence to a receptor element by flowing onto said receptor element and solidifying thereon, said adherence does not require an external adhesive layer and occurs in an area at least coextensive with the area of said silver halide grains, and at least one silver halide light sensitive emulsion layer containing light sensitive silver halide grains on said front surface of the support; (b) developing the imagewise exposed silver halide light sensitive photographic element to form a photographic image; (c) positioning the front surface of said silver halide photographic element against said receptor element; and (d) applying energy (e.g. heat) to the rear surface of the silver halide photographic element to transfer said photographic image to said receptor element.

The receptor element may be textile, leather, ceramic, wool, glass or plastic. Preferably, the receptor element is a shirt or the like. Energy applied to the rear surface of the silver halide photographic element is heat and/or pressure (e.g. via ironing).

The transfer layer of the invention is capable of transferring and adhering developed image and non-image areas from the front surface of the support upon the application of heat energy to the rear surface of the support. The transfer layer strips from said front surface of the support by liquefying and releasing from the support when heated. The liquefied transfer layer provides adherence to a receptor element by flowing onto the receptor element and solidifying thereon. The adherence does not require an external adhesive layer and occurs in an area at least coextensive with the area of the silver halide grains.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention will become more fully understood from the detailed description given hereinbelow, and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein: FIGURE 1 is a cross-sectional view of the preferred embodiment of the silver halide photographic transfer element of the present invention; and FIGURE 2 illustrates the step of ironing the silver halide photographic transfer element onto a tee shirt or the like.

DETAILED DESCRIPTION OF THE INVENTION A requirement of a suitable transfer material when it is used is that it adhere strongly to fibrous supports, polymer films (e.g. polyethylene), and optionally to glassy supports.

The transfer layer of the invention must also be capable of transfer from the photographic support and adherence to a receptor support without the requirement of a separate surface adhesive layer. Without being bound by any theory, upon back surface heating of the support, the transfer layer would undergo a solid to solution phase transition resulting in a transfer to the receiving layer. Edge to edge adhesion, to the receiving layer, would occur upon cooling of the transfer layer onto the receiving layer. Upon cooling, an image layer would be completely transferred onto the receiving layer with an excess of transfer layer providing mechanical and thermal stability, as well as washability.

Suitable transfer layers include compositions comprising materials from U.S. Patent Nos. 5,501,902, 5,271,990 and 5,242,739. The contents of U.S. Patent Nos. 5,501,902, 5,271,990 and 5,242,739 are herein

incorporated by reference. These patents are discussed in turn hereinbelow.

The transfer layer of the present invention may utilize the materials of the second layer of U.S. Patent No. 5,501,902.

The transfer layer preferably includes particles of a thermoplastic polymer having largest dimensions of less than about 50 micrometers, and preferably from about 1 to about 20 micrometers. The particles will more preferably have dimensions of from about 2 to about 10 micrometers. In general, the thermoplastic polymer can be any thermoplastic polymer which meets the criteria set forth herein. Desirably, the powdered thermoplastic polymer will be selected from the group consisting of polyolefins, polyesters, and ethylene- vinyl acetate copolymers.

The transfer layer also includes from about 10 to about 50 weight percent of a film-forming binder, based on the weight of the thermoplastic polymer. Desirably, the amount of binder will be from about 10 to about 30 weight percent. In general, any film-forming binder may be employed which meets the criteria set forth herein.

When the transfer layer includes a cationic polymer, a nonionic or cat ionic dispersion or solution may be employed as the binder. Suitable binders include polyacrylates, polyethylenes, and ethylenevinyl acetate copolymers. The latter are particularly desired because of their stability in the presence of cationic polymers.

The binder desirably will be heat softenable at temperatures of about 1200Celsius or lower.

The basis weight of the transfer layer may vary as desired, but the transfer layer is preferably present in an amount from about 5 to about 30 g/m2. Desirably, the basis weight will be from about 10 to about 20 g/m2. The transfer layer can be applied to the support, either directly or over another layer, by means well known to those having ordinary skill in the art. For example,

the transfer layer may be applied by roll, blade and air-knife coating procedures.

When the photographic material is intended to be used as a heat-transfer material, the transfer layer will have a melting point of from about 65 to about 180 degrees Celsius. The term "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.

Manufacturers' published data regarding the 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.

When the material is intended to be used as a heat- transfer layer, the transfer layer desirably also will contain from about 2 to about 20 weight percent of a cationic polymer, based on the weight of the thermoplastic polymer. The cationic polymer may be, for example, an amide-epichlorohydrin polymer, polyacrylamides with cationic functional groups, polyethyleneimines, polydiallylamines, and the like.

When a cationic polymer is present, a compatible binder should be selected. The binder desirably will be a nonionic binder, either in the form of a solution or a nonionic or cationic dispersion or emulsion. As is well known in the paper coating art, many commercially available binders have anionically charged particles or polymer molecules. These materials are generally not compatible with the cat ionic polymer which may be used in the present invention.

One or more other components may be used in the transfer layer. For example, the transfer layer may contain from about 1 to about 20 weight percent of a humectant, based on the weight of the thermoplastic polymer. Desirably, the humectant will be selected from the group consisting of ethylene glycol and poly(ethylene glycol). The poly(ethylene glycol) typically will have a weight average molecular weight of from about 100 to about 40,000. A poly(ethylene glycol) having a weight-average molecular weight of from about 200 to about 800 is particularly useful.

The transfer layer also may contain from about 0.2 to about 10 weight percent of a fluid (e.g. ink) viscosity modifier, based on the weight of the thermoplastic polymer. The viscosity modifier desirably will 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 of from about 100,000 to about 600,000.

Other components which may be present in the transfer layer include from about 0.1 to about 5 weight percent of a weak acid and from about 0.5 to about 5 weight percent of a surfactant, both based on the weight of the thermoplastic polymer. A particularly useful weak acid is citric acid. The term "weak acid" is used herein to mean an acid having a dissociation constant less than one (or a negative log of the dissociation constant greater than 1).

The surfactant may be an anionic, a nonionic, or a cationic surfactant. When a cationic polymer is present in the transfer layer, the surfactant should not be an anionic surfactant.

Desirably, the surfactant will be a nonionic or cationic surfactant. However, in the absence of the cationic polymer, an anionic surfactant may be used, if desired. Examples of anionic surfactants include, among others, linear and branched-chain sodium alkylbenzenesulfonates, linear and branched-chain alkyl sulfates, and linear and branched-chain alkyl ethoxy sulfates. Cationic surfactant include, by way of illustration, tallow trimethylammonium chloride.

Examples of nonionic surfactants, include, again by way of illustration only, alkyl polyethoxylates, polyethoxylated alkylphenols, fatty acid ethanol amides, complex polymers of ethylene oxide, propylene oxide, and alcohols, and polysiloxane polyethers. More desirably, the surfactant will be a nonionic surfactant.

For heat transfer applications, the photographic material of the invention may have a release layer or a melt-transfer layer located above the support and below the silver halide photographic layer(s). Such a melt- transfer film layer typically comprises a film forming binder, as already described, or other polymer. The layer desirably is applied by extrusion coating, but other methods also may be used. The melt-transfer film layer desirably is formed from a polyethylene or a

copolymer of ethylene with acrylic acid, methacrylic acid, vinyl acetate, or acrylic acid esters such as ethyl acrylate. The polymer desirably will have a melt flow rate of at least about 30 grams per 10 minutes (g/10 minutes), as determined in accordance with ASTM Method D-1238, although the melt flow rate may be as high as about 4,000 g/10 minutes. More desirably, the melt flow rate of the polymer will be from about 300 to about 700 g/10 minutes. The basis weight of the melt- transfer film layer desirably will be from about 10 to about 50 grams per square meter (g/m2), with a basis weight of from about 30 to about 50 being more desired.

A release layer may be included, either in place of or in addition to the melt-transfer film layer. In the former instance, the release layer will be placed above the support and below the photographic layer(s). In the preferred latter instance, the release layer will be placed between the support and the melt-transfer film layer. The release layer desirably will be a low molecular weight ethylene-acrylic acid copolymer applied from an aqueous dispersion. The melt flow rate of the ethylene-acrylic acid copolymer desirably will be at least about 200 g/10 minutes, more desirably from about 800 to about 1,200 g/10 minutes. Such dispersion also may contain a paraffin wax, which is mixed as an emulsion with the ethylene-acrylic acid copolymer dispersion. The paraffin wax emulsion can be any of those which are commercially available, such as Chemwax 40 (Chematron, Inc., Charlotte, N.C.). The ratio of paraffin wax to the copolymer may vary from 0 to about 4, with a ratio of about 1 being more desirable. The basis weight of the release layer desirably will be from about 2 to about 20 g/m2, more desirably from about 6 to about 10 g/m2. The release coating as described melts easily and provides easy release from the first layer for hand ironing of images onto a fabric; such characteristic is especially useful if heating of the

image is irregular, which is not atypical of hand- ironing techniques.

The various layers of the photographic material are formed by known coating techniques, such as by curtain coating, Meyer rod, an air knife, and gravure coating procedures. The resulting material, then is dried by means of, for example, steam-heated drums, air impingement, radiant heating, or some combination thereof, or by other methods known in the art. Some care must be exercised, however, to assure that drying temperatures are sufficiently low so that the particles of thermoplastic polymer present in the transfer layer do not melt during the drying process.

Heat transfer of an image in the photographic material of the present invention may be by any known means, such as by a hand-held iron or a heat transfer press. The transfer temperature typically will be from about 1200 to about 205° Celsius, for from about 5 seconds to about 2 minutes.

Accordingly, the transfer layer of the invention may comprise particles of a thermoplastic polymer preferably having largest dimensions of less than about 50 micrometers, preferably from about 1 to about 20 micrometers, and more preferably from about 2 to about 10 micrometers, from about 10 to about 50 weight percent of a film-forming binder, based on the weight of the thermoplastic polymer, and from about 0.2 to about 10 weight percent of a viscosity modifier, based on the weight of the thermoplastic polymer.

The transfer layer has a melting point of more than 650C, preferably more than 1000C and more preferably from about 100 to about 180 degrees Celsius. The transfer layer may also contain from about 2 to about 20 weight percent of a cat ionic polymer, based on the weight of the thermoplastic polymer. The transfer layer may also contain from about 1 to about 20 weight percent of a humectant, based on the weight of the thermoplastic

polymer. The humectant may be (1) ethylene glycol or (2) polyethylene glycol (e.g. having a weight-average molecular weight of from about 100 to about 40,000, preferably about 200 to about 800).

The viscosity modifier may be a polyethylene glycol having a weight average molecular weight of from 100,000 to about 2,000,000, preferably from about 100,000 to about 600,000. The viscosity modifier may be low or high viscosity methyl cellulose or polyvinyl alcohol.

The transfer layer may also include about 0.1 to about 5 weight percent of a weak acid, based on the weight of the thermoplastic polymer. The transfer layer may also include about 0.5 to about 5 weight percent of a surfactant (e.g. nonionic or cationic) based on the weight of the thermoplastic polymer.

A release layer is optionally interposed between the support and the photographic layer containing transfer layer of the invention.

The transfer layer may further comprise from about 1 to about 20 weight percent of a humectant, based on the weight of the thermoplastic polymer (and optionally from about 0.2 to about 10 weight percent of a fluid (e.g. ink) viscosity modifier, based on the weight of the thermoplastic polymer), and from 0.5 to about 5 weight percent of a surfactant, based on the weight of the thermoplastic polymer.

The transfer layer of the present invention may also utilize the materials of the image receptive melt- transfer film layer of U.S. Patent 5,271,990.

The transfer layer may be comprised of a thermoplastic polymer which melts at above 650C, preferably above 100"C, and more preferably in the range of from about 100 to about 180 degrees Celsius(OC). In another embodiment, the thermoplastic polymer melts in the range of from about 80"C to 1200C, preferably from 1000C to about 1200C.

The nature of the thermoplastic polymer is not known to be critical, but generally it should be photographically inert (e.g. not adversely affecting the properties relating to the photographic image). That is, any known thermoplastic polymer can employed so long as it meets the criteria specified herein. Preferably, the thermoplastic polymer is selected from the group consisting of polyolefins, polyesters, and ethylene- vinyl acetate copolymers, having a particle size of less than 50 micrometers, preferably having a particle size of less than 20, and more preferably less than 10 micrometers.

If desired, as already noted, the photographic material containing the transfer layer of the invention may optionally comprise a melt-transfer film layer and an image receptive film layer as defined in US Patent 5,271,990. In this instance, the melt-transfer film layer overlays the top surface of the base sheet and the image receptive film layer overlays the melt-transfer film layer.

In general, the melt-transfer film layer is comprised of a first thermoplastic polymer and the image receptive film layer is comprised of a second thermoplastic polymer, each of which melts above 650C, preferably above 1000C, and more preferably in the range of from about 1000C to about 1800C. Preferably, the first thermoplastic polymer is selected from the group consisting of polyolefins, polyesters, ethylene-vinyl acetate copolymers, ethylene-methacrylic acid copolymers, and ethylene-acrylic acid copolymers. In addition, the second thermoplastic polymer preferably is selected from the group consisting of polyolefins, polyesters, and ethylene-vinyl acetate copolymers.

The term "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 thermoplastic polymer melts and flows under film forming conditions to result in a substantially smooth film.

Accordingly, the transfer layer may comprise a thermoplastic polymer selected from the group consisting of polyolefins, polyesters, and ethylene-vinyl acetate copolymers and which melts above 650C, and preferably above 100"C, and more preferably in the range of from about 100 to about 180 degrees Celsius, and most preferably in the range of about 100 to about 120 degrees Celsius.

An example of the transfer layer of the invention is produced by coextrding a 25 micrometer film of Elvax 3200 and a 19 micrometer film of Surlyn 1702 as described in Example 1 of US Patent 5,271,990. Elvax 3200 is supplied by E. I. Du Pont de Nemours & Company, Inc., Polymer Products Department, Ethylene Polymers Division, Wilmington, Del. Elvax 3200 is an ethylene- vinyl acetate copolymer containing approximately 25k vinyl acetate and modified with wax. It has a melt index of 32 g/10 minutes. Surlyn 1702 also supplied by DuPont. Surlyn 1702 is an ionomer consisting of a cross- linked ethylene-methacrylic acid copolymer having a melt index of 14 g/10 minutes.

The transfer layer of the present invention may also utilize the materials of the image-receptive melt- transfer film layer of U.S. Patent 5,242,739.

The transfer layer may comprise from about 15 to about 80 percent by weight of a film-forming binder selected from the group consisting of ethylene-acrylic acid copolymers, polyolefins, and waxes and from about 85 to about 20 percent by weight of a powdered thermoplastic polymer selected from the group consisting of polyolefins, polyesters, polyamides, waxes, epoxy polymers, ethylene-acrylic acid copolymers, and ethylene-vinyl acetate copolymers, wherein each of said

film-forming binder and said powdered thermoplastic polymer melts above about 65"C, preferably above about 100, and more preferably in the range of from about 100 to about 180 degrees Celsius and said powdered thermoplastic is preferably of particles which are from about 1 to about 50 micrometers in diameter, preferably about 2 to 50, and more preferably 1 to about 20 micrometers in diameter.

Thus, the transfer layer comprises from about 15 to about 80 percent by weight of a film-forming binder and from about 85 to about 20 percent by weight of a powdered thermoplastic polymer. Each of the film- forming binders and powdered thermoplastic polymers melt above 650C, preferably above 1000C, and more preferably in the range of from about 100 to about 180 degrees Celsius ("C). In addition, the powdered thermoplastic polymer is preferably composed of particles having diameters of about 50 micrometers, more preferably from about 2 to 50 micrometers, and most preferably from about 1 to about 20 micrometers.

In other embodiments, each of the film-forming binders and powered thermoplastic polymers melt in the range from 800C to above 1200C, preferably in the range of from about 1000C to about 1200C.

The function of the powdered thermoplastic polymer is to assist in the transferring of an image to a fabric, both in terms of ease of transfer and the permanence of the transferred image.

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. In preferred embodiments, the film-forming binder has, at the transfer temperature, a lower melt viscosity than the powdered thermoplastic polymer. As a practical matter, water-dispersible ethylene-acrylic acid copolymers have been found to be especially effective film forming binders.

In general, the powdered thermoplastic polymer can be any thermoplastic polymer which meets the criteria set forth herein. Preferably, the powdered thermoplastic polymer is selected from the group consisting of polyolefins, polyesters, and ethylene- vinyl acetate copolymers.

The powdered thermoplastic polymer flow partially into the fiber matrix of the fabric to which an image is being transferred. The result is a fabric having an image which does not render the fabric stiff. Moreover, the image itself is neither rubbery nor rough to the feel and is stable to repeated washings.

The melt-transfer film layer comprises a film- forming binder as already described. The image- receptive film layer preferably comprises from about 15 to about 80 percent by weight of a film-forming binder (e.g. ethylene-acrylic acid copolymers; polyolefins and waxes which melt in the range of about 65 to about 180 degrees Celsius) . The melt transfer layer may also contain from about 85 to about 20 percent by weight of a powdered thermoplastic polymer, each of which are as already defined.

As a general rule, the amount of powdered thermoplastic polymer employed can be reduced if larger particle sizes are employed.

If desired, any of the foregoing film layers can contain other materials, such as processing aids, release agents, pigments, deglossing agents, antifoam agents, and the like. The use of these and other like materials is well known to those having ordinary skill in the art.

Representative binders and powdered thermoplastic polymers are as follows: Binder A Binder A is Michems 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 1020C and a Brookfield viscosity of 0.65 pa s (650 centipoise) at 1400C.

Binder B This binder is Michemo Prime 4983R (Michelman, Inc., Cincinnati, Ohio). The binder is a 25 percent solids dispersion of Primacoro 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 430C and a ring and ball softening point of 1000C. The melt index of the copolymer is 500 g/10 minutes (determined in accordance with ASTM D- 1238).

Binder C Binder C is Michem 4990 (Michelman, Inc., Cincinnati, Ohio). The material is 35 percent solids dispersion of Primacors 5990 made by Dow Chemical Company. Primacors 5990 is a copolymer of 20 percent acrylic acid and 80 percent ethylene. It is similar to Primacors 5983 (see Binder B), except that the ring and ball softening point is 930C. The copolymer has a melt index of 1,300 g/10 minutes and Vicat softening point of 390C.

Binder D This binder is Michemo 37140, a 40 percent solids dispersion of a Hoechst-Celanese high density polyethylene. The polymer is reported to have a melting point of 1000C.

Binder E This binder is Michemo 32535 which is an emulsion of Allied Chemical Company's AC-325, a high density polyethylene. The melting point of the polymer is about 1380C. Michemo 32535 is supplied by Michelman, Inc., Cincinnati, Ohio.

Binder F Binder F is Michemo 48040, an emulsion of an Eastman Chemical Company microcrystalline wax having a melting point of 88"C. The supplier is Michelman, Inc., Cincinnati, Ohio.

Powdered Thermoplastic Polymer A This powdered polymer is Microtheneo FE 532, an ethylenevinyl acetate copolymer supplied by Quantum Industries, Cincinnati, Ohio. The particle size is reported to be 20 micrometers. The vicat softening point is 750C and the melt index is 9 g/10 minutes.

Powdered Thermoplastic Polymer B Powdered Thermoplastic Polymer B is Aqua Polysilk 19. It is a micronized polyethylene wax containing some polytetrafluoroethylene. The average particle size is 18 micrometers and the melting point of the polymer is 1020-1180C. The material is supplied by Micro Powders, Inc., Scarsdale, N.Y.

Powdered Thermoplastic Polymer C This material is Microthenes FN-500, a polyethylene powder supplied by USI Chemicals Co., Cincinnati, Ohio.

The material has a particle size of 20 micrometers, a Vicat softening point of 830C, and a melt index of 22 g/10 minutes.

Powdered Thermoplastic Polymer D This polymer is Aquawax 114, supplied by Micro Powders, Inc., Scarsdale, N.Y. The polymer has a reported melting point of 910-936C and an average particle size of 3.5 micrometers; the maximum particle size is stated to be 13 micrometers.

Powdered Thermoplastic Polymer E Powdered Thermoplastic Polymer E is Corvels 23- 9030, a clear polyester from the Powder Coatings Group of the Morton Chemical Division, Morton Thiokol, Inc., Reading, Pa.

Powdered Thermoplastic Polymer F This material is Corvels natural nylon 20-9001, also supplied by Morton Thiokol, Inc.

Powdered Thermoplastic Polymer G This polymer powder is Corvels clear epoxy 13-9020, supplied by Morton Thiokol, Inc.

Powdered Thermoplastic Polymer H Powdered Thermoplastic Polymer H is AClyns 246A, which has a melting temperature of about 95"C as determined by differential scanning calorimetry. The polymer is an ethylene-acrylic acid magnesium ionomer.

The material is supplied by Allied-Signal, Inc., Morristown, N.J.

Powdered Thermoplastic Polymer I This polymer is AC-316A, an oxidized high density polyethylene. The material is supplied by Allied Chemical Company, Morristown, N.J.

Powdered Thermoplastic Polymer J This polymer is Texture 5380, supplied by Shamrock Technologies, Inc., Newark, N.J. It is powdered polypropylene having a melting point of 165"C and an average particle size of 40 micrometers.

The binders and thermoplastic polymers may be combined and blended as desired. For example, Binder A (e.g. 80 parts) may be blended with powdered thermoplastic polymer A (e.g. 80 parts) and optionally with a fluorocarbon dispersion such as Zonyl 7040 (e.g.

0.20 parts) obtained from dupont. Another example includes combining Binder B (e.g. 400 parts) and Polymer B (e.g. 70 parts) and blending in a standard laboratory colloid mill. Also, Binder A (e.g. 286 parts) may be combined with Polymer C (e.g. 65 parts) . Binder B (e.g.

400 parts) may be combined with Polymer D (e.g. 70 parts). Binder C (e.g. 200 parts) may be combined with Polymer E (e.g. 35 parts) and optionally with propylene glycol (e.g. 20 parts) and water (e.g. 20 parts) Similarly, Binder C (e.g. 200 parts) may be combined

with Polymer F (e.g. 54 parts) and optionally with propylene glycol (e.g. 20 parts) and water (e.g. 20 parts). Also, Binder A (e.g. 200 parts) may be combined with Polymer G (e.g. 30 parts) and optionally with propylene glycol (e.g. 20 parts) and water (e.g. 20 parts). Binder D (e.g. 200 parts) may be combined with Polymer H (e.g. 30 parts) and optionally water (e.g. 40 parts) and blended. Binder A (e.g. 286 parts) may be combined with Polymer J (e.g. 40 parts) and optionally with propylene glycol (e.g. 50 parts).

In another embodiment of the invention, the transfer layer is located between the support and at least one silver halide light sensitive emulsion layer, but at least one of the emulsion layers may contain the transfer material of the invention, or a mixture of the transfer material of the invention and a conventional binder. This type of system, but without the separate transfer layer of the invention, is described in provisional application 60/026,917.

Referring to Figure 1, there is generally illustrated a cross-sectional view of the silver halide photographic transfer element 10 of the present invention. The transfer element 10 comprises a suitable support or substrate 20 which may be any type of material ordinarily used as a support for photographic materials. Examples thereof include cellulose acetate films, cellulose acetate propionate films, cellulose nitrate films, cellulose acetate butyrate films, polyethylene terephthalate films, polystyrene films, polycarbonate films, and laminated sheets of these films and papers. Suitable papers include papers coated with a polymer of an alpha oleo in and preferably an alpha oleo in having 2 to 10 carbon atoms, such as polyethylene, polypropylene, etc., and baryta coated papers, etc. The only limitation on the support is that it must separate from the transfer layer 30 upon application of heat. If conventional polyolefin paper

interferes with transfer due to poor separation from the transfer layer, fiber based paper which does not contain a resin coated layer nearest the support layer or on both surfaces is preferably used.

One preferred application of this invention is directed to photographic transfer elements capable of producing multicolor dye images. Such a photographic transfer element comprises a support and a plurality of color forming layers coated thereon. The color forming layers include at least one blue light recording yellow dye image forming layer, at least one green light recording magenta dye image forming layer, and at least one red light recording cyan dye image forming layer.

Interlayers may be positioned between the color forming layers. Each image forming layer includes at least one silver halide emulsion layer. A dye image providing material can be located in the emulsion layer, in an adjacent layer, or introduced during development. The blue sensitive emulsion layers can rely on native sensitivity to blue light or contain a blue sensitizing dye adsorbed to the silver halide grains of the blue sensitive layers. Spectral sensitizing dyes capable of absorbing green and red light are adsorbed to silver halide grain surfaces in the emulsions of the green and red recording color forming layers, respectively.

To prevent color contamination of adjacent color layers, oxidized development product scavengers including an oxidized developing agent and oxidized electron transfer agents can be incorporated at any location in the color forming layers or in an interlayer separating adjacent color forming layers. Suitable scavengers include alkyl substituted aminophenols and hydroquinones as disclosed in U.S. Patent Nos. 2,336,327 and 2,937,086, sulfoalkyl substituted hydroquinones as disclosed in U.S. Patent 2,701,197, and sulfonamido substituted phenols as disclosed in U.S. Patent 4,205,987.

The order of the photographic layers on the support and transfer layer is any order conventional in the art.

For example, in color print paper, the order of layers starting from the support is a blue sensitive layer, an interlayer, a green sensitive layer, an U.V. layer, a red sensitive layer, an U.V. layer and a surface overcoat.

In the photographic materials of the present invention various conventionally known hydrophilic colloids may optionally be used in combination with the transfer layer of the invention, so long as the transfer properties of the present transfer layer are capable of performing the desired function (e.g. transfer, adherence, colorfast). Examples of typical hydrophilic colloids used as the binders for photographic silver halide emulsions and other emulsions such as non-light sensitive emulsions (e.g., surface overcoat, interlayers, etc.) for the photographic layers include gelatin; sugar derivatives such as agar agar, sodium alginate, starch derivatives, etc.; casein; cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose etc.; colloidal albumin; synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, maleic anhydride copolymers, polyacrylamide, the derivatives or partially hydrolyzed products thereof and water-dispersed vinyl polymers in the form of a latex. A mixture of two or more of these colloids may be used when the combination is compatible with each other.

The silver halide photographic emulsion 40 used in the present invention may be prepared by mixing an aqueous solution of a water-soluble silver salt such as silver nitrate with an aqueous solution of a water soluble halogen salt such as potassium bromide. The silver halide may be silver chloride, silver bromide, etc., or mixed silver halides such as silver

chlorobromide, silver chloriodide, etc. These silver halide grains may be prepared according to conventionally known processes. Examples of such known processes include the so-called single jet method, the so-called double jet method, or the controlled double jet method. In addition, two or more different silver halide emulsions separately prepared may be used together.

The silver halide photographic emulsions may also contain compounds to prevent the formation of fog during production, processing or preserving the photographic material, and to prevent a reduction in sensitivity.

Suitable compounds for this purpose include 1-phenyl-5- mercaptotetrazole, 3-methylbenzothiazole, 4-hydroxy-6- methyl-1,3,3a,7-tetrazaindene and many metal salts, mercury-containing compounds, mercapto compounds and heterocyclic compounds, etc.

The silver halide emulsions may be chemically sensitized in a conventionally known manner. Suitable chemical sensitizers include gold compounds such as gold trichloride, salts of noble metals such iridium and rhodium; sulfur compounds capable of forming silver sulfide by causing reaction with a silver salt such as sodium thiosulfate; amines, stannous salts, and other reducing compounds.

Moreover, the silver halide photographic emulsions may be spectrally sensitized or super dye sensitized using cyanine dyes such as merocyanine, carbocyanine, or cyanine alone or in combinations thereof or using a combination of cyanine dyes and styryl dyes. The selection of such dyes depends upon the object and use of the photographic materials including the desired sensitivity and the wavelength regions.

The hydrophilic colloid layers may be hardened with cross-linking agents such as vinyl sulfate compounds, active halogen compounds, carboiimide compounds, etc.

The dye forming couplers suitably used in this invention include cyan, magenta and yellow dye forming couplers. These couplers may be 4-equivalent couplers or 2-equivalent couplers as described in U.S. Patent Nos. 3,458,315 and 3,277,155.

Examples of suitable yellow dye-forming couplers include those described in U.S. Patent Nos. 3,384,657, 3,277,155, 3,253,924, 3,227,550, 4,026,706, 2,428,054, 2,908,573, 2,778,658, 2,453,661 and 2,499,966.

Examples of suitable magenta dye forming couplers include those described in U.S. Patent Nos. 4,206,706, 2,725,292, 3,227,550, 2,600,788, 3,252,924, 3,062,653, 2,908,573, 3,152,896 and 3,311,476.

Examples of suitable cyan dye forming couplers which can be used in the invention include those described in U.S. Patent Nos. 3,043,892, 4,026,706, 2,275,292, 3,253,294, 2,474,293, 3,227,550, 2,423,730, 2,908,573 and 2,895,826.

A further general discussion of suitable couplers is described in Photogranhic Chemistry by Glafkides, Volume 2, pages 596-615 and EncvcloDedia of Chemical Technolosv, Vol. 5, pages 822-825.

The couplers may either be incorporated into the emulsion layers containing silver halide grains or added to the material upon processing (e.g. adding color couplers to the color developer such as by the Kodachrome process).

Dyes may be formed by the reaction of the couplers with an oxidized aromatic primary amine silver halide developing agent during conventional processing.

Typical processing steps for color negative films and color print papers are development, bleach, fix, washing, optionally stabilization and then drying. Two or more of these steps may be combined into a single step. For instance, the bleaching and fixing steps may be combined into a single bleach-fix step. Color development is usually carried out in an alkaline

solution containing an aromatic primary amine developing agent such as aminophenol, phenylenediamine or a mixture thereof.

Where it is desired to reverse the sense of the color image, such as in color slide processing, reversal processing can be undertaken. A typical sequence for reversing color processing includes black and white development, stop, washing, fogging, washing, color development, washing, bleaching, fixing, washing, stabilizing and drying. An optional prehardening bath prior to black and white development may be employed.

The washing step can be omitted or relocated in the sequence. The fogging bath can be replaced by uniform light exposure or by the use of a fogging agent in the color development step to render the silver halide not developed in the black and white step developable.

When the color photographic material of the present invention is a color photographic diffusion transfer film unit the processing of the photographic material is carried out automatically in the photographic material.

In these instant product type units, the color developer containing a color developing agent is contained in a rupturable container. Suitable developing agents include 1-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, <BR> <BR> <BR> <BR> 1-phenyl-3-pyrazolidone, N-methylamino-phenol, 1-phenyl- 4, 4-dimethyl-3-pyrazolidone, and 3-methoxy-N, N- diethyl-p-phenylene-diamine.

Accordingly, in order to form color images in photographic materials various known methods can be used, including the coupling reaction of the above- described dye-forming color couplers and the oxidation products of a p-phenylenediamine series color developing agent; the oxidation cleavage reaction of DRR compounds, the dye releasing reaction upon coupling of DDR couplers; the dye forming reaction upon the coupling reaction of DDR couplers and a silver dye bleaching process.

Therefore, the present invention can be applied to various types of color photographic materials such as color positive films, color papers, color negative films, color reversal films, color diffusion transfer film units, silver dye bleaching photographic materials, black and white films and papers, etc.

Methods for preparing silver halide photographic elements of the present invention are well known in the art. Representative methods thereof are set forth in U.S. Patent Nos. 4,822,728, 4,743,533, 4,710,455, 4,705,747, 4,680,247, 4,659,647, 4,654,293, 4,636,457, 4,634,661, 4,619,884, 4,588,672, 4,565,778, 5,552,834, 4,529,690, 4,459,353, 4,499,174, 4,144,070, 4,379,837 and Reissue 32,149.

The following examples are provided for a further understanding of the invention, however, the invention is not to be construed as being limited thereto.

EXAMPLE 1 A silver halide photographic transfer element is prepared as follows: The following silver halide emulsion is coated on the base sheet of Example 1 of U.S. Patent No. 5,501,902.

Silver halide grains are prepared by mixing a solution of .3 M silver nitrate with a solution of .4 M sodium chloride. Silver halide grains are grown in a traditional single jet conformation in 4% (w/total weight) gelatin.

Thus, in this example, the silver halide grains are coated on top of the transfer layer in the same manner as in conventional photographic systems.

The sensitized paper is exposed to room light for about 30 seconds and then developed in color development chemistry known in the art as RA-4 (Eastman Kodak).

The working solution RA-4 is a paper development color process. The coupler magenta, cyan or yellow color

coupling dye is added to the RA-4 working solution before development. Therefore, it is similar to the color development process known as the K-14 Kodachrome process (Eastman Kodak). The test sample is a sample of what a magenta layer (red-blue hue) would look like if separated. The resulting uniform image contains both the silver and color coupler dyes. Both the material and dye image can withstand bleaching to remove silver, thereby leaving only the color image. The material is then dried.

EXAMPLE 2 A silver halide photographic transfer element is prepared as follows. A conventional package of color paper silver halide photographic light sensitive emulsions (utilizing gelatin as the carrier) is coated on the base sheet of Example 1 of U.S. Patent No.

5,501,902.

All quantities below are in terms of grams per square meter unless otherwise specified.

Layer 1 comprises 1.5g of gelatin, 0.32 g of a blue-sensitive silver chlorobromide emulsion, and 0.3 g of dioctyl phthalate (DOP) in which 1.2 x 10-3 mol of a- (1-benzyl-2-phenyl-3, 5-dioxo-1,2,4-triazolidinyl)-a- pivalyl-2-chloro-5-[a(dodecyloxycarbonyl) ethoxy carbonyl] acetanilide as a yellow coupler and 0.015 g of 2,5-di-t-ocytl hydroquinone (HQ).

Layer 2 is an interlayer which comprises 0.9 g of gelatin and 0.6 g of DOP in which 0.09 of HQ is dissolved.

Layer 3 comprises 1.3 g of gelatin, 0.27 g of a green sensitive silver chlorobromide emulsion, and 0.2 g of DOP in which 0.59 x 10-3 mol of 1-(2,4,6- trichlorophenyl)-3-(2-chloro-5-octadecylsuccinimide- anilino)-5-pyrazolone as a magenta coupler and 0.015 g of HQ are dissolved.

Layer 4 comprises 1.5 g of gelatin and 0.6 g of DOP in which 0.8 g benzophenone as an ultraviolet absorbent and 0.04 g of HQ are dissolved.

Layer 5 comprises 1.6 g of gelatin, 0.3 g of a red sensitive silver chlorobromide emulsion and 0.2 g of DOP in which 0.75 x 10-3 mol of 2,4-dichloro-3-methyl-6-[a- (2,4-di-t-amylphenoxy)-butylamide]phenol as a cyan coupler and 0.005 g of HQ are dissolved.

Layer 6 is a surface overcoat (e.g., protective layer) and comprises 1.0 g of gelatin.

The color print paper thus produced is exposed to light through a standard negative.

The exposed color print paper sample is processed as follows. The sample is processed in a color developer having a temperature of 330C for 3.5 minutes.

The developed sample is placed in a solution of bleach- fix at a temperature of 330C for 1.5 minutes. The sample is washed for 3 minutes with water maintained at 300-340C. Finally, the sample is dried for 2 minutes at a temperature of 60"-800C.

The composition of the above-mentioned color developer is listed below: Pure water 800 ml Ethylene glycol 15 ml Benzyl alcohol 15 ml Hydroxylamine sulfate 2g Potassium carbonate 32 g Potassium bromide 0.65 g Sodium chloride 1.0 g Potassium sulfite 2.0 g N-ethyl-N-beta-methanesulfonamide 4. 5g ethyl-3-methyl-4-aminoaniline sulfate Whitex BB (in 50% aqueous solution) 2 ml (Optical whitening agent, mfd. by Sumitomo Chemical Ind. Co. Ltd., Japan) 1-hydroxyethylidene- 1,1 2 ml diphosphonic acid (in 60% aqueous solution) Pure water is added therein to make 1 liter and the pH value thereof is adjusted by the use of 10% potassium hydroxide or dilute sulfuric acid solution to pH = 10.1.

The composition of the bleach-fix solution is listed below: Pure water 550 ml Color Developer 200 ml Iron (III) ammonium ethylenediamine 65 g tetraacetic acid Ammonium thiosulfate 85 g Sodium hydrogensulfite 10 g Sodium metahydrogensulfite 2g Di-ethylenediaminetetraacetate 12 g Sodium bromide 10 g Potassium chloride 1.0 g Pure water is added thereto to make 1 liter and the pH value is adjusted to pH = 7.0 with the use of dilute sulfuric acid or concentrated aqueous ammonia.

EXAMPLE 3 Referring to Figure 2, the method of applying a photographic image to a receptor element will be described. More specifically, Figure 2 illustrates how the step of heat transfer from the silver halide photographic transfer element (50) to a tee shirt or fabric (62) is performed.

The silver halide photographic transfer element is prepared, exposed and developed to form a photographic image as in Example 1. A tee shirt (62) is laid flat, as illustrated, on an appropriate support surface, and the front surface of the silver halide photographic transfer element (50) is positioned onto the tee shirt.

An iron (64) set at its highest heat setting is run and pressed across the back (52A) of the silver halide photographic transfer element. The image is transferred to the tee shirt and the support is removed and discarded.

EXAMPLE 4 An integral imaging receiver (IIR) element is prepared by coating the following layers in the order

recited on a transparent poly(ethylene terephthalate) film support which has been coated on one side with the same transfer layer as described in Example 1 of US Patent 5,242,739. The following layers are coated on top of the transfer layer. Quantities are parenthetically given in grams per square meter unless otherwise stated.

(1) Image receiving layer of poly(styrene-co-N- benzyl-N, N-dimethyl-N-vinylbenzyl-ammonium chloride-co- divinylbenzene) (molar ratio 49/49/2) (1.1) and gelatin as carrier (1.2); (2) Image receiving layer of poly(styrene-co-l- vinylimidazole-co-3-benzyl-1-vinylimidazolium chloride) (50:40:10 mole ratio) (1.6) and gelatin as carrier (0.75); (3) Reflecting layer of titanium dioxide (17) and gelatin as carrier (2.6); (4) Opaque layer of carbon black (0.95) and gelatin as carrier (0.65); (5) Gelatin as carrier for interlayer !0.54); (6) Gelatin as carrier for interlayer (0.65); (7) Cyan redox dye-release layer; (8) Gelatin as carrier for interlayer; (9) Red sensitive silver halide emulsion layer and gelatin as carrier; (10) Gelatin as carrier for interlayer; (11) Magenta-redox dye-releaser layer; (12) Green-sensitive silver halide emulsion layer and gelatin as carrier; (13) Gelatin as carrier for interlayer; (14) Yellow redox dye-releaser layer; (15) Blue-sensitive silver halide emulsion layer and gelatin as carrier; and (16) Gelatin as carrier for overcoat layer.

Layers 8-16 are similar to those described in Example I of U.S. Patent No. 4,356,250.

A cover sheet and processing pod are prepared and assembled into film assemblages. (For example, see Example I of U.S. Patent No. 4,356,250).

The above film assemblages are exposed to a test object. The assemblages are processed in a conventional manner by spreading the contents of the processing pod between the cover sheet and the Integral Imaging Receiver by using a pair of juxtaposed rollers.

EXAMPLE 5 The method of Example 3 is repeated using the IIR element of Example 4. A tee shirt is laid flat on a suitable support surface and the front surface of the IIR element is positioned onto the tee shirt. An iron is run and pressed across the back of the IIR element and the image is transferred to the tee shirt.

EXAMPLE 6 A multilayer light sensitive color reversal element comprising layers having the following composition is coated on a cellulose triacetate film support: A transfer layer as in Example 1.

(2) An antihalation layer comprising gelatin as a carrier containing black colloidal silver at a silver coating weight of 0.2 g/m2.

(3) A red sensitive low speed emulsion layer of gelatin as a carrier comprising a silver bromo-iodide emulsion (silver iodide: 7% by mol; average grain size: 0.65 ) at a silver coating weight of 0.62 g/m2 and a silver/carrier (Gelatin) ratio of 0.30, sensitizing dye I in an amount of 0.000135 mol per mol of silver, sensitizing dye II in an amount of 0.000316 mol per mol of silver, Coupler A in an amount of 0.211 mol per mol of silver dispersed in tricresylphosphate and diethylauramide;

(4) A red sensitive high speed emulsion layer of gelatin as a carrier comprising a silver bromo-iodide emulsion (silver iodide: 7% by mol; average grain size: 1.18 ») at a silver coating weight of 0.57 g/m2 and a silver/gelatin ratio of 0.30, sensitizing dye I in amount of 0.00Q123 mol per mol of silver, Coupler A in an amount of 0.221 mol per mol of silver dispersed in tricresylphosphate and diethyl-lauramide.

(5) An intermediate layer of gelatin as a carrier comprising 2,5-ditert-octylhydroquinone dispersed in tricreslphosphate.

(6) A green sensitive high speed emulsion layer of gelatin as a carrier comprising a silver bromo-iodide emulsion (silver iodide: 7% of mol, average grain size: 1.18 ) at a silver coating weight of 0.53 g/m2 and a silver/gelatin ratio of 0.46, sensitizing dye III in an amount of 0.000866 mol per mol of silver sensitizing dye IV in an amount of 0.000190 mol per mol of silver, Coupler B in an amount of 0.183 mol per mol of silver.

(7) A green sensitive low speed emulsion layer of gelatin as a carrier comprising a blend of a silver bromo-iodide emulsion (silver iodide: 7% by mol; average grain size: 0.65 y) and a silver bromo-iodide emulsion (silver iodide: 5% by mol; average grain size 0.29 y) at a total silver coating weight of 0.46 g/m2 and a total silver/gelatin ratio of 0.41, sensitizing dye III in an amount of 0.000935 mol per mol of silver, sensitizing dye IV in an amount of 0.00021 mol per mol of silver and Coupler B in an amount of 0.132 mol per mol of silver.

(8) An intermediate layer the same as layer (4).

(9) A yellow filter layer of gelatin as a carrier comprising dispersed yellow colloidal silver.

(10) A blue sensitive high speed emulsion layer of gelatin as a carrier comprising a blend of a silver bromo-iodide emulsion (silver iodide: 7% by mol, average grain size: 1.18 ») and a silver bromo-iodide emulsion (silver iodide: 14% by mol; average grain size: 1.4 p)

at a total silver coating weight of 0.85 g/m2 and a total silver/gelatin ratio of 0.52, sensitizing dye V in an amount of 0.00015 mol per mol of silver, Coupler C in an amount of 0.145 mol per mol of silver and Coupler D in an amount of 0.071 mol per mol of silver both dispersed in tricresylphosphate and diethylalauramide.

(11) A blue sensitive low speed emulsion layer of gelatin as a carrier comprising a silver bromo-iodide emulsion (silver iodide: 7% by mol; average grain size: 0.65 p) at a silver coating weight of 0.55 g/m2 and a silver/gelatin ratio of 0.46, sensitizing dye V in an amount of 0.000133 mol per mol of silver, Coupler C in an amount of 0.147 mol per mol of silver and Coupler D in an amount of 0.071 mol per mol of silver both dispersed in tricresylphosphate and diethyllauramide.

(12) A protective layer of gelatin as a carrier comprising polymethylmethacrylate particles of mean diameter 2 y and 2-(2-hydroxy-35-di-t-butylphenyl)-5- t-butyl-benzotriazole W absorber dispersed in tricresylphosphate and dibutylphthalate.

Surface active agents and antifogging agents are also added to the layers.

The element is exposed and processed through a reversal color process E6 described in "Using Process E6, Kodak Publication N2-119".

Compounds which may be used for preparing the above-described element are the following.

Sensinziu£ Dye 1: Sensitizing Dye II: Coupler A: Sensitizing We III: Sensitizing Dye IV: Coupler B: Sensitizing Dye V: Coupler C: Coupler D:

EXAMPLE 7 The multilayer light sensitive color reversal element of Example 4 is applied to a tee shirt in the manner set forth in Example 3.

EXAMPLE 8 A paper support which is not coated on both sides with polyethylene is coated with a transfer layer consisting of a mixture of Michemo 58035 and Michemæ Prime 4983. Both materials are available from Michelman, Inc., Cincinnati, Ohio. A ratio of four or five to one of 58035 to 4983 is used. The basis weight of the melt-transfer layer is 8 g/m2. Michem 58035 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 1020C. and a Brookfield viscosity of 0.65 Pas (650 centipoise) at 1400C. Michem Prime 4983 is a 25 percent solids dispersion of Primacor5983 made by Dow Chemical Company. The polymer contains 20 percent acrylic acid and 80 percent ethylene. The copolymer has a Vicat softening point of 430C. and a ring and ball softening point of 100°C. The melt flow rate of the copolymer is 500 g/10 minutes.

The transfer layer then is coated with an emulsion containing silver halide grains formed as in Example 1.

When the thermoplastic binder and/or the binder are the variables, the cationic polymer in every case is an amide-epichlorohydrin copolymer, namely, either Kymenes 557 or Retens 204LS, both being supplied by Hercules Inc., Wilmington, Del. The cationic polymer is included at a level of 5 weight percent, based on the weight of the thermoplastic polymer. The transfer layer is dried by heating at 800-950C. The basis weight of the transfer layer is 15 g/m2.

In general, a minimum amount of binder is used.

For example, 10 weight percent of a polyacrylate, Rhoplexo B-15 (Rohm and Haas Company) may be used.

Another binder which may be used at the 10 weight percent level is Micheme 58035, described above. The binder must be compatible with the cationic polymer.

Two binders which are more compatible with the cat ionic polymer and which yellow less than the Michems 58035 are Airflexo 124 and Airflexs 125, both poly(vinyl alcohol) stabilized ethylene-vinyl acetate copolymers. The materials are available from Air Products and Chemicals, Inc., Allentown, Pa.

Several thermoplastic polymers may be used including Microthenes FE 532, an ethylene-vinyl acetate copolymer supplied by US Chemicals Co., Cincinnati, Ohio. The particle size is reported to average approximately 20 micrometers. The Vicat softening point is 750C. The melt flow rate of the copolymer is 9 g/10 minutes and it is reported to have a density of 0.928 g/cm3. Another thermoplastic polymer is Microthene FN 500, a low density polyethylene powder also supplied by USI Chemicals Co. The material has an average particle size of 20 micrometers, a Vicat softening point of 830C., a melt flow rate of 22 g/10 minutes, and a density of 0.915 g/cm3.

The material is exposed, developed and transferred as in Example 3.

EXAMPLE 9 Example 8 is repeated, but using the following thermoplastic polymers: Thermoplastic Polymer A This polymer is Microtheneo FE 532, described in Example 8.

Thermoplastic Polymer B This material is Microtheneo FN-500, also described in Example 8.

Thermoplastic Polymer C Thermoplastic Polymer C is Corvels 2093. It is a polyester. The average particle size is 20 micrometers, the melting point of the polymer is approximately 800C., and the melt flow rate is reported to be "high". The material is supplied by Powder Coatings Group of the Morton Chemical Division, Morton Thiokol, Inc., Reading, Pa.

Thermoplastic Polymer D This polymer is MP 22, described in Example 8.

Thermoplastic Polymer E Thermoplastic Polymer E is MPP 611, also described in Example 8.

Thermoplastic Polymer F This material is MPP 635, also a polyethylene supplied by Micro Powders, Inc. The average particle size of the polymer is 5 micrometers, the melting point is reported to be 124, and the melt flow rate is 'high".

Thermoplastic Polymer G This polymer is Accumists B6, supplied by Allied Chemical Company, Morristown, NJ. The polymer is a polyethylene having a melting point of 126°C. The average particle size of the polymer is 6 micrometers and the melt flow rate is "high".

Thermoplastic Polymer H Thermoplastic Polymer H is Accumist9 B12, also supplied by Allied Chemical Company. The polymer is a high density polyethylene having a melting point of 1260C. The average particle size of the polymer is 12 micrometers.

Thermoplastic Polymer I This polymer is DPP 714, a polystyrene dispersion supplied by Dow Chemical Company, Midland, Mich.

Thermoplastic Polymer J This material is Piccotexo LC55R, a styrene-methyl styrene copolymer dispersion supplied by Hercules, Inc.

Thermoplastic K Thermoplastic Polymer K is DL 256, a polystyrene dispersion also supplied by Dow Chemical Company.

Thermoplastic L This polymer is BN 4901X, a polystyrene dispersion available from BASF Corporation, Sarnia, Ontario, Canada.

Thermoplastic M This material is Ropaque, a polystyrene dispersion supplied by Rohm and Haas Company, Philadelphia, Pa.

Four different binders are used: Binder A Binder A is Carbosets 514H, a polyacrylate binder dispersed in water, supplied by B.F. Goodrich Company, Cleveland, Ohio.

Binder B This binder is Rhoplexs B15, described in Example 8.

Binder C Binder C is Michems 58035, also described in Example 8.

Binder D This binder is Marklubes 542, a cationic low density polyethylene emulsion from Ivax Industries, Inc., Rock Hill, S.C.

The composition of the transfer layer layer is summarized in Table 1 below. In the Table, the "TP" column identifies the thermoplastic polymer by letter, the "Type" column identifies the binder by letter, and basis weights are given in g/m2.

TABLE 1 Summary of Transfer layer Composition with Various Thermoplastic Polvmers Binder Basis TP Type Wt.k Weight A A 10 21 A B 10 23 A C 10 23 A C 20 23 B C 50 31 B C 10 23 C C 10 32 D C 10 30 E C 10 23 E C 12.5 28 E C 12.5 8 E C 12.5 13 F C 10 23 F C 12.5 13 F C 18 11 F C 20 13 F D 25 13 G C 18 13 H C 18 13 I C 10 17 J C 10 17 K C 10 8 L C 10 8 M C 10 8 M C 30 8 M C 40 8

EXAMPLE 10 A base sheet of fiber based paper which is not coated with polyethylene on both sides is coated with a low molecular weight polymer film layer, referred to hereinafter as the first layer. The next layer was a film based on a polymer having a higher molecular weight, referred to hereinafter as the second layer.

Finally, on top of the second layer silver halide grains as described in Example 1.

A number of multi layered samples (including the base sheet) are evaluated. In every case, the transfer layer consisted of 77 weight percent MPP 635 (Thermoplastic Polymer F), 8 weight percent of BN 4901X (Thermoplastic Polymer L), 10 weight percent Michem 58035 (Binder C), 4 weight percent Reten 204LS (cationic polymer), and 1 weight percent Triton X-OO, a surfactant, all based on the total weight of the layer (excluding silver halide grains) . These weights of binder, cationic polymer, and surfactant are equivalent to 12, 5 and 1 weight percent, respectively, based on the weight of thermoplastic polymer.

A preferred sample using this format contains the following: First layer: The layer consisted of 45 weight percent Michemo 4983 and 55 weight percent Chemawaxs 40.

The layer is applied as a mixed latex. The basis weight of the layer was 8 g/m2.

Second layer: The layer, located adjacent to the paper, consisted of Epolenes C13 which is formed by melt extrusion at a basis weight of 20 g/m2. The polymer is a 200 melt flow rate low density polyethylene obtained from Eastman Chemical Products, Inc., Kingsport, Tenn.

Another material which may be used as the second layer and which can be extrusion coated on the paper base sheet is Nucrels RX 62, supplied by E. I. Du Pont de Nemours and Company, Inc., Wilmington, Del. The

polymer is an ethylene-methacrylic acid copolymer having 10 weight percent methacrylic acid and a melt flow rate of around 500 g/10 min.

The material is exposed, developed and transferred as in Example 3.

EXAMPLE 11 This Example evaluates various cationic polymers.

Two types of transfer layers are employed, in which the cationic polymer is included as a component. Type A consists of Microtheneo FE 532 (Thermoplastic Polymer A), 13 weight percent of Michems 58035 binder (Binder C), based on the weight of the thermoplastic polymer, 1 weight percent Triton X-100 surfactant, and the cationic polymer. The basis weight of the layer is 15 g/m2. The Type B layer consists of MPP 635 (Thermoplastic Polymer F), 18 weight percent of Michem 58035 binder (Binder C), based on the weight of the thermoplastic polymer, 1 weight percent Tritons X-100 surfactant, and the cationic polymer. The basis weight of the layer is 13 g/m2. When The Type B second layer is employed, a third layer consisting of Michem 58035 at a basis weight of 17 g/m2 is employed, adjacent to the paper support. The various cationic polymers evaluated are as follows: Cat ionic Polymer A Cationic Polymer A is Kymenes 557, an amide- epichlorohydrin copolymer available from Hercules, Inc.

Cat ionic Polymer B This polymer is Calgans 261LV, a quaternary polymer. It is available from Calgon Corporation.

Cationic Polymer C This material is Corcato P145. It is a polyethyleneimine supplied by Cordova Chemical Company.

Cationic Polymer D Cationic Polymer D is Pares 631NC, a polyacrylamide available from American Cyanamide.

Cationic Polymer E This material is Betzo 1260. It is obtained from Betz Paperchem, Trevose, Pa.

Cationic Polymer F This polymer is Reteno 204LS, an amide- epichlorohydrin copolymer available from Hercules, Inc.

Cat ionic Polymer G Verona 3 C-300 from Miles Inc., Pittsburgh, Pa.

Cat ionic Polymer H Aquaproxs UP103 from Synthron, Morgantown, N.C.

Cationic Polymer I Tinofixs EW from Ciba-Geigy Corporation, Hawthorn, N.Y.

Cat ionic Polymer J Reactofixs ES from Ivax Industries, Inc.

Cat ionic Polymer K Protefixs TS, a cationic carbamide from Synthron.

In the table, the column "CP" Type" identifies the cationic polymer, whereas the column "Type" identifies the type of transfer material employed, as described above.

TABLE 4 Evaluation of Various Cat ionic Polymers CP Tvoe Amount Tvoe A 2 A A 4 A A 6 A B 2 A B 4 A C 2 A C 4 A D 2 A D 4 A E 2 A

F 5 A F 4 A F 8 A G 8 B H 8 B I 8 B J 8 B K 8 B The silver halide grains as described in Example 1 are coated on top of the transfer layer, which is coated on (i) a fiber base paper which is not coated on both sides with polyethylene and (ii) transparent polyacetate film. The material is exposed, developed and transferred as described in Example 3.

EXAMPLE 12 The formulations involving Cat ionic Polymer F as reported in Example 11 are modified further since yellowing may be encountered when images are heat transferred.

In the experiments, the paper base which is not coated on both sides with polyethylene is extrusion coated with 44 g/m2 of Nucrels RX62, an ethylene- methacrylic acid copolymer having a melt flow rate of 600 g/10 minutes supplied by E. I. Du Pont de Nemours and Co., Inc. The second layer had a basis weight of approximately 13 g/m2.

The binder employed in the transfer layer is either Airflexs 124 (Binder E) or Airflex 125 (Binder F). The binder is present at a level of 26 weight percent, based on the weight of the thermoplastic polymer. The cationic polymer used is Reteno 204LS, the humectant is Polyglycolo E200, a poly(ethylene glycol) from Dow Chemical Company having a weight-average molecular weight of about 200; the humectant level is 10 weight percent, based on the weight of the thermoplastic

polymer. The surfactant is Tritons X-100 at a level of 3 weight percent, based on the weight of thermoplastic polymer employed. The fluid viscosity modifier is Polyox3 N80 at a level of 3 weight percent, also based on the weight of the thermoplastic polymer. The thermoplastic polymers to be evaluated include micropowders MPP 635 and Accumists A-12, from Micropowders and Allied Chemical Company, respectively.

The material is exposed, developed and transferred as described in Example 3.

The experiments are summarized in Table 5. In the table, the "TP" column identifies the thermoplastic polymer by letter (see Example 9), the "WT.-h CP" column identifies the amount of Retens 204LS employed in the second layer in weight percent, based on the weight of the thermoplastic polymer, and the "WT.-k Acid" column identifies the amount of citric acid included in the transfer layer, in weight-percent based on the weight of the thermoplastic polymer.

TABLE 5 Summary of Cat ionic Polymer F Formulation Modifications Sample Binder TP Parts CP Wt.-W Acid 1 F H 8 None 2 F H 8 4 3 E H 8 None 4 F F 8 None 5 F F 12 None 6 F F 16 None EXAMPLE 13 Foto-Wear!, Inc. Print n' Wear paper marketed under the name Print n' Wear (comparative support Substrate A) is directly compared to (inventive support) Substrate B after both are coated with a photographic emulsion.

Substrate A is " TRANS E ZE " having a Singapore Dammar

Resin coated thereon, and was manufactured by Kimberly- Clark in 1990, and stored under fluctuating temperature and humidity. Substrate B was manufactured by Kimberly- Clark in the past 12 months in accordance with U.S.

Patent 5,501,902, under the name Foto-Wear! Jet Wear (Green-Line Hot Peel) and stored under the same conditions.

A 5k gelatin (e.g. a 225 Bloom) AgCl photographic emulsion as described in Example 1, at 320C, is hand coated onto both substrates under a Kodak Safelight #1.

A synthetic bristle paintbrush is used to coat 2ml of emulsion uniformly onto each substrate. Two sheets of substrate A and two sheets of substrate B are coated in this manner. Emulsion setting time is accelerated by cool forced air for ten minutes.

Once dried, a contact exposure of keys, placed directly on the paper, is chosen as an indication for resolution qualities during development, transfer, and washing. A seventeen-second full room light exposure is made to all samples.

Processing of the latent image involves a two- minute development bath at 200C with constant agitation.

The developer is Kodak PolymaxT with a dilution of one part liquid concentrate to nine parts tap water. The development bath is followed by a five-minute non- hardening fixer bath at 200C with constant agitation.

The final step in processing is a fifteen-minute running water bath to remove any remaining chemicals from the emulsion coating and the substrate base. Both sheets are allowed to dry at room temperature.

Substrate A paper is discolored (yellowed) and has a distinctive odor. Both Substrates A and B retain a photographic image, develop to proper image density, and transfer to a receiving fabric. However, the transfer using Substrate B adheres uniformly and throughout the fabric whereas Substrate A is inferior in comparison to Substrate B with respect to adhesion. Moreover,

washability and mechanical stability of the Substrate B transfer material is far superior. Thus, when utilizing the same emulsion package, the transfer layer of the invention is far superior to Substrate A.

All cited patents, publications, copending applications, and provisional applications referred to in this application are herein incorporated by reference.

The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the present invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.