Thermal Transfer Systems Having Delaminating Coatings

The present invention concerns delaminating coatings for use in thermal transfer systems. Specifically, the invention concerns delaminating coatings that provide both delaminating properties and antistatic properties to intermediate carrying sheets in thermal transfer systems. The delaminating property allows a recepted image layer to be transferred from the intermediate carrying sheet to other supports of interest, such as films, glass, or paper. The preferred delaminating coating is formed from a composition of a vanadium oxide colloidal dispersion.

Thermal transfer systems for thermal imaging utilize a recording method in which a donor sheet, having a colorant (i.e., dye or pigment) layer thereon, and a receptor sheet are brought into contact and heated with a localized heat source, such as a laser or a thermal print head. The heat source directly contacts the backside of the donor sheet. A thermal print head contains small electrically heated elements that can be selectively heated, thereby transferring colorant from the donor sheet to the receptor sheet and forming a desired image. This imaging process can involve either mass transfer of colorant in a binder or state-altered transformation of a dye, as by melting or sublimation of the colorant. In a mass transfer process, the colorant, e.g., dye or pigment, is dispersed within a binder and both the dye and its binder are transferred from a donor sheet to a receptor sheet:. In a dye transfer process, the colorant (present on the donor with or without a binder) is transferred without binder by melting, melt-vaporization, propulsive ablation, sublimation, or vaporization to a receptor sheet where the colorant adheres to or diffuses into an image-receiving layer.

Such thermal transfer systems generally require the use of receptor sheets with certain specific requirements. For example, the thickness, flatness, flexibility, and shape of a receptor sheet are limited, such that the receptor sheet can be used in typical thermal printing devices. Such restrictions limit the applicability of thermal imaging. Thus, there is a need for a thermal imaging process that can transfer an image to an arbitrarily shaped object, such as paper, film, metal, glass, cardboard, etc.

In thermal dye transfer systems, this has been accomplished with the use of an intermediate sheet that can act as both a receptor and a donor. In such a system, a donor sheet, having a colorant layer thereon, and an intermediate carrying sheet are brought into contact and heated with a thermal print head, thereby transferring colorant from the donor sheet to the intermediate carrying sheet and forming an intermediate image. In this way the intermediate carrying sheet acts as a receptor sheet. This intermediate carrying sheet is then typically placed in contact with a final receptor. Under the application of heat and pressure the image is transferred from the intermediate carrying sheet to the final receptor.

The retransfer process for thermal dye-transferred image systems is well known in the art. U.S. Pat. No. 3,906,138 discloses the retransfer process of a sublimation dye from a formed image to a transparent receptor. U.S. Pat. No. 4,923,848 discloses a process for retransferring a thermal dye-imaged layer to an objective body. U.S. Pat. No. 5,055,444 discloses an intermediate dye receptor and a process for retransferring dye images alone out of the dye receiving layer to an objective body. However, the process for transferring a thermal mass-transferred image to an objective body using an intermediate carrying sheet has not been shown. Unlike thermal dye transfer imaging, the colorants and their binder in a thermal mass transfer donor sheet are all transferred upon initial imaging. This makes the retransfer of the formed mass-transferred image to other surfaces theoretically possible because of the presence of a meltable binder in the image. However, such a retransfer has proven to be difficult because of the problems involved in conforming a sheet having a mass-transferred image thereon to an irregular object. Thus, a need exists for a thermal mass transfer system for imaging irregular objects.

Whether a retransfer process involves mass transfer of dye transfers, foreign substances, such as dust, can create areas of noncontact between the donor and receptor sheets or between the donor sheet and the print heads, for example. Such noncontact areas adversely effect the transfer of an image. For example, a single particle of dust can easily get trapped under a print head and streak an image. This detrimental effect can occur whether the transfer occurs via a mass transfer or dye transfer. Generally, foreign substances such as dust are attracted to the donor and/or receptor sheets as a result of electrostatic attraction to built-up electrical charges.

There is a growing interest in the use of antistatic materials and coatings to solve the problems created by the build-up of electric charges, i.e., "static electricity" in various fields of technology, such as the photographic, electronics, and magnetic recording industries. Antistatic materials, i.e., antistats, are electrically conductive materials that are capable of transporting charges away from areas where they are not desired. This conduction process results in the dissipation of the static electricity. In certain situations this results in a decrease in the buildup of dust.

A typical antistatic layer comprises an organic or inorganic conductive material in a binder. The layer dissipates electrical charges by the conduction of charged particles, which can be either ions or electrons. Ionically conductive antistatic coatings are thought to act as electrolytic solutions through which ions are transported under the influence of an electric field. They are typically salts or hydrophilic chemicals that are applied to the surface of an article. As such, they threaten contamination and/or corrosion of material, e.g., electronic components, and may interfere with the function of materials with which they come in contact. Furthermore, being hydrophilic or water soluble, they lack permanence in contact with water. The use of ionically conductive coatings is especially difficult in applications in which the surface coatings must be incident to air. For example, low friction layers, dye donor layers, and dye receptor layers must typically not be overcoated by materials that interfere with their function. Also, the function of ionically conductive antistatic coatings is dependent upon humidity. At low humidity, the coating is not sufficiently conductive to provide rapid dissipation of triboelectrically generated charges, i.e., changes resulting from friction-causing events such as unwinding and handling. Furthermore, at high humidity the coating can become soft, sticky, and can undergo a large volume change.

Preferable antistats for many applications are those that conduct electrons by a quantum mechanical mechanism rather than by an ionic mechanism. This is because antistats that conduct electrons by a quantum mechanical mechanism are generally effective independent of humidity. They are suitable for use under conditions of low relative humidity, without losing effectiveness, and under conditions of high relative humidity, without becoming sticky. Furthermore, such electronically conductive antistatic coatings remain effective when overcoated by, for example, an adhesive layer or a low adhesion layer. A major problem, however, with such electron-conducting antistats is that they generally cannot be provided as thin, transparent, lightly colored or relatively colorless coatings by solution coating methods.

Metal particle, metal oxide particle, or carbon black dispersions can be used to provide electronically conductive coatings via solution deposition methods; however, such coatings tend to be darkly colored and opaque. This is generally not desirable for use in thermal transfer systems. Although there have been many attempts to do so, such as by using defect semiconductor oxide particle dispersions and conductive polymers, there has been very little success in depositing thin, transparent, lightly colored or relatively colorless electronically conductive antistatic coatings.

The present invention describes an intermediate carrying sheet that can be used in a thermal transfer process to provide advantageous image transfer to an irregular object, i.e., an arbitrarily shaped object. This process can be used in a thermal mass transfer process as well as a thermal dye transfer process. The process involves the steps of: providing a thermal transfer donor sheet in an image-wise distributed manner and a thermal transfer intermediate carrying sheet in a facing relationship; and applying heat to the donor sheet to cause material on the donor sheet to form an intermediate image, preferably a mass-transferred image. If this image on the intermediate carrying sheet is a reverse image, it can be directly transferred to a final receptor. This is done by placing the intermediate carrying sheet in contact with a final receptor such that the intermediate image is in contact with the final receptor, and transferring the image to the final receptor. Alternatively, if the image on this first intermediate carrying sheet is a positive image, the image can be transferred to a second intermediate carrying sheet and subsequently transferred to a final receptor.

The final receptor can be a sheet material or an arbitrarily shaped object. This method is particularly suited for image formation on arbitrarily shaped objects, i.e., irregularly shaped objects, having a variety of surfaces. Such objects include, for example, round containers, packaging boxes, tubes, and the like. The intermediate carrying sheet preferably consists of a film-forming substrate having coated thereon optional layers that improve antistatic properties, printer feedability, image receptivity, and image releasability.

The present invention also provides vanadium oxide coatings that can be used advantageously in thermal retransfer systems. That is, vanadium oxide coatings can be used to provide antistatic characteristics, as well as delaminating characteristics, to an intermediate carrying sheet in a thermal transfer system, preferably a thermal dye transfer system. Furthermore, the vanadium oxide coatings can be tailored to provide varying degrees of delaminating characteristics, which is advantageous for intermediate carrying sheets.

A vanadium oxide coating, i.e., layer, can be used on either side of an intermediate carrying sheet, i.e., film. That is, in an intermediate carrying sheet, the vanadium oxide layer can be either coated on a substrate frontside, i.e., the side which receives an image from a donor sheet, or on its backside. The vanadium oxide layer is preferably coated under an image-receiving layer on the substrate frontside, i.e., it is positioned between the substrate and an image-receiving layer (if such image-receiving layer is present). Although the donor sheet of a thermal retransfer system can include a vanadium oxide antistatic layer on either side of a film-forming substrate, the vanadium oxide layer is advantageously coated on the intermediate carrying sheet. Preferably, in a thermal retransfer system, the intermediate carrying sheet is the only sheet with the vanadium oxide antistatic layer, i.e., delaminating coating, thereon.

Preferred vanadium oxide sols, i.e., colloidal dispersions, used in the deposition of the vanadium oxide layers of the present invention are prepared by hydrolyzing vanadium oxoalkoxides with an excess of water, preferably deionized water. Herein, "vanadium oxoalkoxides" refer to vanadium complexes with an oxide (.dbd.O) ligand and at least one alkoxide (--OR) ligand per vanadium atom. It is to be understood, however, that complexes referred to herein as vanadium oxoalkoxides can also include ligands other than the oxide and alkoxide groups.

Preferably, the vanadium oxoalkoxide is a trialkoxide of the formula VO(OR).sub.3, wherein each R is substituted or unsubstituted and is independently selected from a group consisting of aliphatic, aryl, heterocyclic, and arylalkyl groups. Herein, "substituted" R groups, i.e., substituted organic groups, mean that one or more hydrogen atoms are replaced by a functional group that is nonreactive to hydrolysis, and noninterfering with the formation of colloidal dispersions. Preferably, such functional groups include halide, hydroxide, thiol, and carbonyl groups, or mixtures thereof.

Each R is preferably independently selected from a group consisting of C.sub.1-10 alkyl, C.sub.1-10 alkenyl, C.sub.1-10 alkynyl, C.sub.1-18 aryl, and C.sub.1-18 arylalkyl groups. These groups can also be substituted, or they can be unsubstituted, i.e., contain only hydrogen atoms. If substituted, they are preferably substituted with a functional group such as a halide, hydroxide, thiol, carbonyl, or mixtures thereof. More preferably, each R is independently selected from a group consisting of unsubstituted C.sub.1-6 alkyl groups. When it is said that each R is "independently" selected from a group, it is meant that not all R groups in the formula VO(OR).sub.3 are required to be the same.

In the context of the present invention, the term "aliphatic" means a saturated or unsaturated linear, branched, or cyclic hydrocarbon group. This term is used to encompass alkyls, alkenyls such as vinyl groups, and alkynyls, for example. The term "alkyl" means a saturated linear or branched hydrocarbon group. The term "alkenyl" means a linear or branched hydrocarbon group containing at least one carbon-carbon double bond. The term "alkynyl" means a linear or branched hydrocarbon group containing at least one carbon-carbon triple bond. The term "heterocyclic" means a mono- or polynuclear cyclic group containing carbons and one or more heteroatoms such as nitrogen, oxygen, or sulfur or a combination thereof in the ring or rings, such as furan, thymine, hydantoin, and thiophene. It is preferred that any nitrogen atoms in the heterocyclic group be no more than weakly basic. The term "aryl" means a mono- or polynuclear aromatic hydrocarbon group. The term "arylalkyl" means a linear, branched, or cyclic alkyl hydrocarbon group having a mono- or polynuclear aromatic hydrocarbon or heterocyclic substituent. The aliphatic, aryl, heterocyclic, and arylalkyl groups can be unsubstituted, or they can be substituted with various substituents such as Br, Cl, F, I, OH groups, and the like.

Herein, "vanadium oxide" colloidal dispersions refer to colloidal dispersions of mixed valence vanadium oxide, wherein the formal oxidation states of the vanadium ions are typically +4 and +5. In this field, such species are often referred to as V.sub.2).sub.5. Herein, the terms "sol," "colloidal dispersion," and "colloidal solution" are used interchangeably. They all refer to a uniform suspension of finely divided particles in a continuous liquid medium. The average particle size in a sol or colloidal dispersion is usually between about 5.0.times.10.sup.-4 .mu.m and about 5.0.times.10.sup.-1 .mu.m.

The vanadium oxide colloidal dispersions of the present invention contain at least a minimum effective amount of vanadium and preferably no greater than about 3.5 weight-percent (wt-%) vanadium. Preferably they contain about 0.3 wt-% vanadium to about 2.0 wt-% vanadium. Herein, these weight percentages are calculated from the amount of vanadium in the vanadium oxoalkoxide starting material, and are based on the total weight of the dispersion. In preferred embodiments, the ratio of V.sup.4+ ions to the total concentration of vanadium ions, i.e., V.sup.4+ +V.sup.5+ ions, is at least about 0.01:1.0, preferably at least about 0.05:1.0, and more preferably at least about 0.30:1.0.

The antistatic material useful in the present invention is a dispersed form of vanadium oxide which is extremely effective for the preparation of antistatic coatings. Such antistatic coatings, i.e., layers, impart a reduced tendency to attract dust. Furthermore, the alkoxide hydrolysis methods of the present invention produce preferred vanadium oxide colloidal dispersions capable of forming effective and advantageous antistatic coatings with significantly less material than do known alkoxide hydrolysis methods. The use of the preferred coatings prepared from the alkoxide hydrolysis methods described herein, as well as the other vanadium oxide coatings of the prior art, on thermal transfer sheets has proven to be extremely effective in reducing static problems without interfering with the transferability or developability of the image.

It is to be understood that for certain embodiments thermal mass transfer is the focus of the present invention, and for other embodiments thermal dye diffusion transfer is the focus.

FIG. 1 is a schematic representation of a preferred intermediate carrying sheet having a vanadium oxide layer coated on a substrate and beneath an image-receiving layer.

FIG. 2 is a schematic representation of the preferred embodiment of FIG. 1 in which the vanadium oxide layer and image-receiving layer are shown in a partially delaminated position.

Coatings of vanadium oxide are particularly beneficial and desirable in thermal transfer systems, either thermal mass transfer or thermal dye transfer systems, and preferably in thermal dye transfer systems. With this type of coating, both antistatic and delaminating properties are imparted to a substrate. This is particularly advantageous in thermal retransfer systems that use an intermediate carrying sheet to transfer an image from a donor sheet to a receptor without direct contact between the donor and the receptor.

Because of the antistatic properties of vanadium oxide, the thermal transfer sheets remain static resistant during both imaging and processing. This helps prevent dust-induced defects in the imaged sheets. Thus, the present invention provides a thermal transfer system containing at least one vanadium oxide antistatic layer, preferably this layer is incorporated into an intermediate carrying sheet in a thermal retransfer system.

In contrast to many traditional antistats, the vanadium oxide antistatic layers can be coated under layers in thermal transfer sheets, such as the image-receiving layer, and the dye donor layer, i.e., the donor colorant layer. This is because the vanadium oxide antistatic layers do not need humidity to be operative. Traditional antistats that function using an ionic mechanism need to be coated on the outermost surfaces of the donor and receptor sheets, or at least mixed with the material in the outermost layers. This can generally interfere with the imaging process in a thermal transfer process. Furthermore, even if an overcoat of an antistatic layer did not interfere with the function of, for example, the image-receiving layer and the donor colorant layer, such overcoated layers are typically difficult to obtain. That is, such layers as the donor colorant layer, for example, can be difficult to overcoat because they do not generally have easily wettable surfaces. It is to be understood, however, that the vanadium oxide antistat of the present invention can be coated on the outermost surfaces of thermal transfer sheets, or alternatively mixed with the material in the outermost layers, if the vanadium oxide does not substantially interfere with the imaging process.

The use of vanadium oxide in thermal transfer donor and receptor sheets is disclosed in U.S. patent application Ser. No. 08/015,419 entitled "Thermal Transfer Systems Having Vanadium Oxide Antistatic Layers," the disclosure of which is incorporated herein by reference. Thus, in a transfer system that involves use of an intermediate carrying sheet (a system referred to herein as a retransfer system), the donor, final receptor, and any of the intermediate carrying sheets can advantageously incorporate vanadium oxide. Preferably, vanadium oxide is incorporated into at least one intermediate carrying sheet in a retransfer system.

The present invention is also based in part on the discovery that an intermediate carrying sheet can be used in a thermal transfer process, preferably a mass transfer process, to provide advantageous image transfer to an irregular object. The process involves the steps of: providing a thermal transfer donor sheet and a thermal transfer intermediate carrying sheet in a facing relationship; and applying heat to the donor sheet in an imagewise fashion to cause material on the donor sheet to transfer to the intermediate carrying sheet to form an intermediate image, preferably a mass-transferred image. Any number of subsequent transfers can be carried out. Generally, however, only one to two subsequent transfers occur. For example, if the transferred image is a reverse image, it can be directly transferred to a final receptor. Alternatively, if the transferred image on the intermediate carrying sheet is a positive image, the image can be transferred to a second intermediate carrying sheet and subsequently transferred to a final receptor. This process can be carried out with a thermal transfer sheet containing vanadium oxide. In this embodiment, the transfer can be either mass transfer or dye transfer. If no vanadium oxide is incorporated into a thermal transfer sheet used in the process, the process preferably involves a mass transfer process with the formation of a mass-transferred image.

Thermal retransfer printing systems involve the use of a donor sheet; at least one intermediate receptor carrying sheet; a final receptor; means for applying heat for transfer of an image from the donor sheet to the intermediate carrying sheet; and means for applying heat and/or pressure for retransfer of the image from the intermediate carrying sheet to a second intermediate carrying sheet or to the final receptor.

The donor sheet consists of a flexible substrate on which is coated a colorant, i.e., dye or pigment. The intermediate carrying sheet consists of a flexible substrate, preferably with an image-receiving layer coated thereon. The final receptor can consist of a flexible substrate, as do the donor sheet and intermediate carrying sheets; however, in a retransfer system the final receptor is typically an arbitrarily shaped object. Both the donor and intermediate carrying sheets can include adhesive layers, i.e., primer layers, if desired. The thicknesses of the various layers are the same as those typically used in thermal transfer systems.

Either the donor sheet or the intermediate carrying sheet (or both) can include a vanadium oxide coating. Preferably, the intermediate carrying sheet has the vanadium oxide layer coated thereon. In this way, the delaminating characteristics of the vanadium oxide can be advantageously applied to the intermediate carrying sheet, which acts as a receptor sheet in a first transfer step and a donor in a second transfer step.

The substrate, i.e., support, for both the donor sheet and the intermediate carrying sheet is a flexible substrate that can be smooth or rough, transparent, translucent, or opaque, porous or nonporous. It can be formed from a film-forming material, such as paper, polymeric film, and the like. Most polymers used in the flexible substrate, however, are nonconductive and have inherent electrostatic problems. Thus, an antistatic layer is advantageous.

For most commercial purposes, the substrate is a polymeric resin such as a polyester (e.g., polyethylene terephthalate), polyolefin, polyvinyl resin (polyvinyl chloride, polyvinylidene chloride, etc.), polystyrene, polycarbonate, polyvinyl butyral, polyamide, polyimide, polyether sulfone, and cellulose ester. Preferably the substrate for the intermediate carrying sheet is a polyester film. It is to be understood that colored substrates, reflective substrates, and laminated substrates can be used in the thermal transfer systems of the present invention.

The substrates for a donor sheet can be about 2-100 .mu.m thick, but are typically about 3-8 .mu.m thick to be able to feed through currently available printers. The substrates for an intermediate carrying sheet can be about 3-500 .mu.m thick, but are typically about 5-250 .mu.m thick to be able to feed through currently available printers, and for effective heat conduction.

Conventional thermal transfer donor sheets include a colorant layer, having a colorant and binder, coated on a substrate. The binder in a thermal mass transfer donor system is thermoplastic resins with Tg below 100.degree. C. and low melting waxes. These materials have a low enough melting or softening point that they are capable of transferring with the colorant to the receptor sheet. Examples of such binders include, but are not limited to copolymers of vinyl chloride and vinyl acetate, butadiene and styrene copolymers, hydrocarbon waxes, epoxy resins, and chlorinated waxes. Examples of such thermal mass transfer donor sheets are disclosed in U.S. Pat. Nos. 4,839,224 and 4,847,237. The binder in a thermal dye transfer donor sheet is typically a thermoplastic resin with Tg (glass transition temperature) of about 25.degree.-180.degree. C., and preferably about 50.degree.-160.degree. C. Useful binders are those that do not transfer themselves, but allow the colorant to diffuse, sublime, melt, or vaporize, etc. out of the colorant layer thereby leaving the binder on the donor sheet. Examples of such binders include, but are not limited to, vinyl chloride/vinyl acetate copolymers, polyesters, polycarbonates, polyacrylates, cellulose, polyvinyl chloride (PVC), and chlorinated PVC. Examples of such thermal dye transfer donor sheets are disclosed in U.S. Pat. No. 4,847,238.

The colorant can be a pigment, a stable dye, a polymeric dye, or any combination of these. It can be physically absorbed in the binder as when a dye is used. Alternatively, the colorant can be physically adsorbed to the binder as when a pigment is used, or chemically bound to the binder as occurs in a polymeric dye. Examples of colorant compositions are disclosed in U.S. Pat. Nos. 4,822,643; 5,061,678; 4,847,237; and 4,847,238. Preferably the colorant is a dye such as azo, indoaniline, anthraquinone, styryl, cyanine, mesocyanine, phenolic, ketomethylene, tricyanostyryl, diazine, and oxazine. Typically the molecular weight range is from about 100 to about 800.

The colorant layer can also include additives to help solubilize and stabilize the dye or pigment. These include polyurethanes, UV stabilizers, heat stabilizers, plasticizers, surfactants, silicones, low Tg polymers (Tg no greater than about 80.degree. C.), elastomers, etc. The additives can be added in concentrations of about 0.1-20 wt-%, based on the total colorant concentration.

The donor sheet can also include an antistick layer, i.e., a layer of a heat-resistant material that prevents the donor sheet from sticking to the thermal print head. The antistick layer is coated on the backside of the substrate, i.e., the side of the substrate opposite the side on which the colorant is coated. This backside coating of an antistick material can include a silicone, polyurethane, higher fatty acid, fluorocarbon resin, etc. Examples of materials used in antistick layers are disclosed in U.S. Pat. No. 5,141,915.

If present on the intermediate carrying sheet, the image-receiving layer is typically in direct contact with the donor colorant layer during thermal transfer imaging. It is designed to effectively receive an image from a donor sheet and to hold the image until it is retransferred, and ultimately yield a desired image with high optical image density, brightness, and stability on the final receptor.

In a typical intermediate carrying sheet, the image-receiving layer can be bonded to the substrate through an intervening adhesive layer, or directly bonded to the substrate without such an adhesive layer. Furthermore, the image-receiving layer can have an optional barrier layer between it and the adhesive layer to prevent solvent migration or dye diffusion into the substrate. An example of such a barrier layer is polyvinyl alcohol.

In preferred embodiments, the intermediate carrying sheet consists of a flexible substrate on which is coated a vanadium oxide layer. On this vanadium oxide layer is coated the image-receiving layer. If desired, an adhesive layer can be coated be coated between these two layers. The vanadium oxide layer can also be tailored to allow for various levels of delamination. This can be accomplished, for example, by combining the vanadium oxide with varying amounts of polymeric materials. This is discussed in further detail below.

In a thermal dye transfer system, the image-receiving layer, i.e., the dye-receiving layer, generally consists of a thermoplastic resin that has a strong compatibility with dyes. Because the dye-receiving layer is in intimate contact with a dye donor sheet under pressure and heat during imaging, it must have adequate adhesion to prevent substantial peeling from its substrate during the imaging step. Furthermore, the imaged dye-receiving layer on an intermediate carrying sheet must also be able to separate from its substrate and transfer to other surfaces of interest in a subsequent image layer transfer process under appropriate conditions. In a mass transfer system, because of total transfer of meltable binder and colorant, the receptor film may need or may not need an additional image-receiving layer. In either case, the resultant mass-transferred image must also be able to separate from its base and transfer to an object of interest under appropriate conditions.

Suitable polymeric resins for use in image-receiving layers can be thermoplastic, cross-linked, heat-cured, radiation-cured, etc. Preferably, they are thermoplastic resins. Several classes of thermoplastic resins are known for use as an image receiver, including, but not limited to, polyesters, polyamides, polycarbonates, polyurethanes, polyvinylchlorides, polycaprolactones, poly(styrene-coacrylonitriles), and mixtures thereof. Desired properties for effective image receptivity include inherent viscosity, molecular weight, glass transition temperature, compatibility, etc. Examples of thermal dye transfer intermediate carrying sheets are described in U.S. Pat. Nos. 5,055,444; 5,077,263; and 4,923,848. In thermal dye transfer systems, the donor colorant layer and the image-receiving layer preferably contain the same binder resin for advantageous diffusion.

It is to be understood that the thermal transfer systems of the present invention can also include a lubricating layer coated over the image-receiving layer to improve separability of the donor sheet from the intermediate carrying sheet after image transfer. Lubricating layers permeable to colorants under normal conditions are well known. They are generally characterized by low surface energy and include silicone and fluorinated polymers. Examples include fluorinated polymers such as polytetrafluoroethylene, and vinylidene fluoride/vinylidene chloride copolymers, and the like, as well as dialkylsiloxane-based polymers.

Furthermore, the image-receiving layer can include other additives, such as UV stabilizers, heat stabilizers, antioxidants, plasticizers, surfactants, delaminating agents, etc. It can also include a white pigment for improving the whiteness of the receptor sheet.

It can be desirable to adjust the adherent properties of the image-receiving layer to the flexible substrate. This can be done by adjusting the delaminating properties of the vanadium oxide coating. Alternatively, for more adhesion when vanadium oxide is used alone or with a polymer that is not readily adherent to a chosen substrate, a primer or priming process may be advantageous. For example, a priming process such as corona discharge, plasma treatment, laser ablation, and the like, can be used to alter the physical properties of the substrate and thereby improve its adhesive characteristics.

Also, a thermal adhesive layer, i.e., an adhesive that softens at elevated temperatures, can be added to the intermediate dye receptor, i.e., intermediate carrying sheet, as an underlayer to facilitate multiple retransfer of the dye-imaged receiving layer. Thermal adhesives, also known as hot melt adhesives, are well known in the art. They typically include a thermoplastic polymeric composition of a polyamide, polyacrylate, polyolefin, polystyrene, polyvinyl resin, and copolymers and blends of these polymers. If a thermal adhesive is used it preferably has a melting temperature of about 50.degree.-100.degree. C.

In a typical thermal transfer imaging process, the colorant layer on the donor sheet is placed in contact with the image-receiving layer on the intermediate carrying sheet, i.e., the thermal transfer donor sheet and the thermal transfer receptor sheet are placed in a facing relationship. The donor sheet is selectively heated according to a pattern of information signals, i.e., in an imagewise distributed manner, whereby the material on the donor sheet, i.e., the dye or pigment (and in a mass transfer process, the binder as well) is transferred from the donor sheet to the intermediate carrying sheet. A pattern is formed thereon in a shape and density according to the intensity of heat applied to the donor sheet. The heating source can be an electrical resistive element, a laser, an infrared flash, a heated pen, or the like. The quality of the resulting image can be improved by readily adjusting the size of the heat source that is used to supply the heat energy, the contact place of the donor sheet and the intermediate carrying sheet, and the heat energy. The applied heat energy is controlled to give light and dark gradation of the image. Furthermore, in thermal dye transfer systems the applied heat energy is controlled for the efficient diffusion of the dye from the donor sheet to ensure continuous gradation of the image as in a photograph.

The mass-transferred image on the intermediate carrying sheet can be either directly transferred to a final receptor or transferred to a second intermediate carrying sheet and subsequently transferred to a final receptor. This depends on the orientation of the initial mass-transferred image, i.e., whether it is a positive or reverse image. The transfer to a final receptor and the transfer to a second intermediate carrying sheet are typically carried out under heat and pressure. This can be done using a laminating machine, such as a 3M Model 1147 Laminator available from 3M Company, St. Paul, Minn.

The thermal retransfer system of the present invention, wherein at least one of the donor and intermediate carrying sheets has a vanadium oxide antistatic coating thereon, can be used in the print preparation of a photograph by printing, facsimile, or magnetic recording systems wherein various printers of thermal printing systems are used. It can be used in the print preparation for a television picture, or cathode ray tube picture by operation of a computer, or a graphic pattern or fixed image for suitable means such as a video camera.

A thermal transfer system of the present invention can include a vanadium oxide layer on either the donor sheet, the intermediate carrying sheet, or it can be on both the donor sheet and the intermediate carrying sheet. Furthermore, although less advantageous it can also be on the final receptor. Preferably, the vanadium oxide is incorporated into at least one intermediate carrying sheet. More preferably, it is incorporated into the first intermediate carrying sheet, i.e., the carrying sheet that comes into direct contact with the donor sheet. A discussion of thermal transfer donor sheets incorporating vanadium oxide is in U.S. patent application Ser. No. 08/015,419 entitled "Thermal Transfer Systems Having Vanadium Oxide Antistatic Layers," which is incorporated herein by reference.

In a thermal transfer intermediate carrying sheet, the vanadium oxide layer can be coated on a substrate either on its frontside, i.e., the side on which the image-receiving layer is coated, or its backside. FIG. 1 is a schematic representation of a preferred intermediate coating sheet (21) having a substrate (23) on which is coated a vanadium oxide layer (25). An image-receiving layer (27) is coated on the vanadium oxide layer (25). In certain preferred embodiments, an adhesive layer (not shown) is positioned between the vanadium oxide layer (25) and the image-receiving layer (27). Alternatively, the substrate may not have any image-receiving layer coated thereon.

FIG. 2 is a schematic representation of the preferred embodiment of the intermediate carrying sheet of FIG. 1, shown with a portion of the vanadium oxide layer (25) and image-receiving layer (27) delaminated from the substrate (23). This situation typically occurs in a subsequent transfer of the image from the intermediate carrying sheet to either a second intermediate carrying sheet or a final receptor. Although this represents one preferred orientation, i.e., one in which the vanadium oxide layer is capable of delaminating with the image-receiving layer, it may also be desirable to delaminate the image-receiving layer and leave the vanadium oxide coating on the substrate. This can be done, for example, by altering the delaminating characteristics of the vanadium oxide through the use of organic polymers having various degrees of priming properties, i.e., adhesion to the substrate of choice.

Although FIGS. 1 and 2 show particularly preferred embodiments of an intermediate carrying sheet, i.e., a thermal transfer sheet capable of acting as a receptor and a donor sheet, the vanadium oxide can also be on the backside of the substrate or incorporated into the image-receiving layer. In embodiments wherein the image-receiving layer includes the vanadium oxide, there is no distinct vanadium oxide layer separate from the image-receiving layer. That is, there is one layer incorporating both desired materials, i.e., an image-receiving material and vanadium oxide. It should be understood, however, that because of the fibrous structure of a vanadium oxide coating, the overcoated layer can penetrate the vanadium oxide layer. Thus, there may be no completely "distinct" and "separate" vanadium oxide layers in any embodiments of the present invention.

Significantly, effective antistatic coatings of vanadium oxide can be deposited in transparent, substantially colorless thin films by coating from aqueous dispersions. This is advantageous for many reasons, particularly from an ecological perspective. Thus, the process of the present invention for providing an image using a thermal transfer process decreases, and often substantially eliminates, problems associated with the use of organic solvents.

Vanadium oxide has three unique properties, i.e., its conduction mechanism, dispersibility, and morphology, which distinguish it from other antistatic coating materials. The latter two properties are generally highly dependent upon the method of synthesis, the first somewhat less so. The conduction mechanism in vanadium oxide is primarily a quantum mechanical mechanism known as small polaron hopping. By this mechanism, electrons are transported through the material by transference (i.e., by "hopping") from one vanadium (V) ion to the next. This conduction mechanism does not require the presence of a well-developed crystalline lattice or a specific defect structure, as do defect semiconductors such as doped tin oxide or doped indium oxide.

Because small polaron hopping electronic conduction does not require a well-developed crystalline structure there is no need for an annealing step when a film or coating is made from vanadium oxide. Furthermore, vanadium oxide is conductive simply upon precipitation or formation in solution, without being adversely affected by changes relative humidity. Thus, a highly dispersed form of vanadium oxide that exhibits electronic conductivity, and desirable morphology, particle size, and dispersion properties is useful for the preparation of conductive antistatic coatings.

In the mid-1970's, Claude Guestaux of Eastman Kodak reported that a previously known synthetic method provides a vanadium oxide colloidal dispersion which, at the time, was considered uniquely useful for the preparation of antistatic coatings. Guestaux's method was based on a process originally described by Muller in 1911. The method is described in U.S. Pat. No. 4,203,769 and consists of pouring molten vanadium pentoxide into water. The process produces a good antistatic coating, which is useable in the present invention, although there are some drawbacks. These drawbacks include high energy requirements, the need for special reactor materials and equipment, and the creation of conditions which generate toxic vanadium oxide fumes. Furthermore, the Guestaux method results in incomplete dispersion of vanadium oxide. The nondispersed vanadium oxide must then be removed from the viscous dispersion; however, such viscous vanadium oxide dispersions are usually very difficult to filter. Also, in some situations, the vanadium oxide coatings prepared using this method may impart undesirable color.

There are several other methods known for the preparation of vanadium oxide colloidal dispersions. These include inorganic methods such as ion exchange acidification of NaVO.sub.3, thermohydrolysis of VOCl.sub.3, and reaction of V.sub.2 O.sub.5 with H.sub.2 O.sub.2. Although vanadium oxide colloidal dispersions prepared by these methods are also useable in the present invention, they are less effective for the preparation of antistatic coatings than colloidal dispersions prepared by the process described by Guestaux in U.S. Pat. No. 4,203,769. To provide coatings with effective antistatic properties from dispersions prepared from inorganic precursors typically requires substantial surface concentrations of vanadium. Higher surface concentrations of vanadium generally result in the loss of desirable properties such as transparency, adhesion, and uniformity. Furthermore, vanadium oxide coatings prepared using this method may impart undesirable color.

One reaction known to yield particularly useful vanadium oxide colloidal dispersions useful as antistatic coatings in thermal transfer systems is the hydrolysis of vanadium alkoxides. This hydrolysis reaction typically gives preferred antistatic layer products that are not gels, discrete particles, or products similar to those obtained from other inorganic precursors of which applicants are aware. Instead, hydrolysis of vanadium oxoalkoxides under appropriate conditions gives vanadium oxide colloidal dispersions that are exceptionally useful precursors for antistatic coatings. Highly effective vanadium oxide colloidal dispersions prepared by these methods are characterized by: high aspect ratio colloidal particles, as observed in the final coating state by field emission scanning electron microscopy; and well-dispersed particles, i.e., not unacceptably agglomerated or flocculated particles. They may also be characterized by an effective concentration of vanadium(IV) ions, which are believed to be a source of mobile electrons in the quantum mechanical small polaron hopping mechanism. These and other aspects of this area of technology are disclosed in U.S. patent application Ser. No. 08/072,548 entitled "Vanadium Oxide Colloidal Dispersions and Antistatic Coatings," which is incorporated herein by reference.

The alkoxide-derived vanadium oxide colloidal dispersions preferred in the practice of the present invention are similar to those prepared by the process of U.S. Pat. No. 4,203,769 (Guestaux), if a further aging step is used subsequent to the Guestaux method. In the preferred alkoxide-derived dispersions the V.sup.4+ concentrations are much higher than in the products prepared by the Guestaux method. In fact, V.sup.4+ concentrations can, predictably and reproducibly, be made to vary over a surprisingly wide range, i.e., over a range of about 1-40% of total vanadium content in the colloidal dispersions of the present invention. Both dispersions are useful in the formation of the antistatic coatings of the present invention. The alkoxide process for the preparation of vanadium oxide colloidal dispersions offers advantages over the process of U.S. Pat. No. 4,203,769. This includes variable V.sup.4+ concentrations, energy savings, convenience, elimination of conditions whereby highly toxic vanadium-containing fumes may be generated, absence of any need to filter the resultant colloidal dispersions, and ability to prepare the colloidal dispersion in situ (e.g., in organic polymer solutions).

The effectiveness of a dispersed form of vanadium oxide, i.e., a vanadium oxide colloidal dispersion, for the preparation of antistatic coatings can be expressed in terms of the surface concentration of vanadium. The surface concentration is described as the mass of vanadium per unit surface area, i.e., mg of vanadium per m.sup.2 of substrate surface area, required to provide useful electrostatic charge decay rates. Generally, the lower the surface concentration of vanadium needed for effective conductivity in an antistatic coating, the more desirable the vanadium oxide colloidal dispersion. This is because with a lower surface concentration of vanadium, there is typically less color imparted to the coating, the coating is more transparent and uniform, and in some circumstances the coating generally adheres better to the substrate and may even provide better adhesion for subsequent layers. Thus, altering the surface concentration of vanadium can improve the delaminating characteristics of a vanadium oxide coating.

Generally, preferred vanadium oxide sols for the preparation of antistatic coatings are those which exhibit the greatest effectiveness, that is, those which provide antistatic properties with the lowest possible surface concentrations of vanadium, i.e., the lowest coating weight of the vanadium oxide dispersion. High surface concentrations of vanadium may result in undesirable coloration, are more expensive, and may adversely affect adhesion of subsequently applied layers; however, this latter characteristic may be used to advantage.

Preferred vanadium oxide antistatic coatings consist of a network of electrically conductive fibers on the surface of the substrate. Because of this open network, most of the surface of the substrate is uncovered, allowing for bonding of an image-receiving layer, for example, as if no antistatic layer were present between it and the receptor substrate. Although a vanadium oxide antistatic layer may exhibit priming properties itself, the open network and partial surface coverage of the antistatic layer allow insertion of the antistatic layer between a substrate and an image-receiving layer, antistick layer, and colorant layer, for example.

An antistatic layer containing vanadium oxide alone (other than optional additives such as a surfactant for wetting), and an antistatic layer containing vanadium oxide plus a sulfonated polyester exhibit useful properties unrelated to the antistatic feature. The special property of both antistatic layers is the level of adhesion. The vanadium oxide only layer generally exhibits a rather low level of adhesion which allows the image-receiving layer plus image to be transferred from an intermediate carrying sheet, i.e., an receptor/donor film. A delamination phenomenon is advantageous for various applications as discussed herein.

In contrast, the vanadium oxide plus sulfonated polyester layer typically provides excellent adhesion to a substrate. Thus, this combination can be used as a separate priming layer, although this use is not broadly applicable. For example, vanadium oxide/sulfopolyester layers do not provide good priming for some silicone release coatings and gelatin emulsions. Thus, the vanadium oxide/sulfopolyester layer may also act as a delaminating layer in certain situations.

An antistatic vanadium oxide layer with a controlled, tailored level of delamination is also within the scope of the present invention. The adhesion of the image-receiving layer is generally a function of sulfonated polymer concentration. Thus, a three component system is desirable to tailor the level of delamination of an image from an intermediate carrying substrate. This three-component system includes vanadium oxide, a sulfonated polymer, and a polymer that is a poor primer for adhering the image-receiving layer to the substrate of choice. Examples of poor priming polymers, i.e., polymers having low adhesion to the substrate, are polyvinyl alcohol and cellulosic polymers.

In sum, the vanadium oxide only layer (which is preferred for most intermediate carrying sheets) and the controlled delaminating layer are directed towards the same end, e.g., a transferrable image layer. For either of these transferrable image-receiving layer constructions, or for the non-transferrable image-receiving layer construction, surface modification (e.g., flame treating, corona treating, and flash lamp treating) of the substrate may be useful.

The preferred vanadium oxide products are produced by the hydrolysis of vanadium alkoxides. The products of this hydrolysis reaction typically include solutions of partially hydrolyzed vanadium alkoxide species, V.sub.2 O.sub.5 gels, and V.sub.2 O.sub.5 particulates. None of the products produced by this reaction, however, has been described as a vanadium oxide colloidal dispersion with properties similar to those of the dispersion prepared according to the process of U.S. Pat. No. 4,203,769 (Guestaux), particularly if an aging step is subsequently used. The products produced by the known hydrolysis methods require more relatively thick coatings for effective conduction. That is, using vanadium oxide colloidal dispersions produced from the hydrolysis of vanadium alkoxides according to known methods, the amount of vanadium oxide required in a coating, i.e., the surface concentration of vanadium, for effective antistatic properties is relatively high. Thus, using vanadium oxide colloidal dispersions produced by known alkoxide hydrolysis methods, there are problems with color formation, transparency, adhesion, and uniformity in the antistatic coatings; however, these problems are generally tolerable in thermal transfer systems.

A report by C. Sanchez et al. in Mat. Res. Soc., Symp. Proc., 121, 93 (1988) discusses the hydrolysis of vanadium oxoalkoxides by an excess of water. Therein, it is stated that the chemical pathway leading to V.sub.2 O.sub.5 solutions and gels from this hydrolysis method is similar to the pathway leading to V.sub.2 O.sub.5 solutions from inorganic precursors such as NaVO.sub.3 and VOCl.sub.3 Sanchez et al. also state that the V.sub.2 O.sub.5.nH.sub.2 O gels so obtained have structural and physical properties close to that of vanadium pentoxide gels prepared by polymerization of decavanadic acid. Because sols and gels prepared from inorganic precursors, including decavanadic acid, generally do not form advantageous antistatic coatings, it has therefore been generally understood that vanadium oxide colloidal dispersions produced from the hydrolysis of vanadium oxoalkoxides do not form advantageous antistatic coatings. However, these materials are useful in thermal transfer systems, as are V.sub.2 O.sub.5 materials made from inorganic precursors.

Preferred vanadium oxide colloidal dispersions used in the present invention are prepared by hydrolyzing vanadium oxoalkoxides with an excess of water, preferably deionized water. The vanadium oxoalkoxides can be any of a variety of compounds that can produce colloidal dispersions capable of forming, i.e., usable to produce, antistatic coatings with the properties desired as herein defined.

The preferred vanadium oxoalkoxides used in the present invention are vanadium complexes with one oxide ligand (.dbd.O) and at least one alkoxide ligand (--OR) per vanadium atom. They may also include ligands other than the oxide and alkoxide groups, such as carboxylyates, sulfides, selenides, .beta.-diketonates, halides, and pseudohalides such as --SCN.sup.- and --CN.sup.-. The vanadium oxoalkoxides useful in the methods of the present invention can be monomeric, dimeric, or polymeric.

Preferably, the vanadium oxoalkoxides are of the formula VO(OR).sub.3, i.e., vanadium oxotrialkoxides, wherein each substituent R is substituted or unsubstituted and is independently selected from the group consisting of aliphatic, aryl, heterocyclic, and arylalkyl groups. Preferably each R is independently selected from the group consisting of C.sub.1-10 alkyl, C.sub.1-10 alkenyl, C.sub.1-18 aryl, and C.sub.1-18 arylalkyl groups. Each of these preferred alkoxide R groups may be substituted or unsubstituted. They may be substituted with halides, hydroxides, thiols, carbonyls, or mixtures thereof. More preferably each R group is independently selected from the group consisting of unsubstituted C.sub.1-6 alkyl groups. Examples of usable vanadium oxotrialkoxides include, but are not limited to, VO(OEt).sub.3, VO(O-i-Pr).sub.3, VO(O-n-Pr).sub.3, VO(O-i-Bu).sub.3, VO(O-n-Bu).sub.3, VO(O-t--Amyl).sub.3, VO(O-n-pentyl).sub.3, and VO(O-CH.sub.2 CMe.sub.3).sub.2.3 (O-i-Bu).sub.0.7. It is understood that the hydrolysis process can involve hydrolyzing one or more vanadium oxoalkoxides, i.e., a mixture of oxoalkoxides.

The vanadium oxoalkoxides can also be prepared in situ prior to use from a vanadium oxide precursor species and an alcohol. That is, the vanadium oxoalkoxides can be prepared without isolation and/or purification from a vanadium oxide precursor species and an alcohol. For example, the vanadium oxoalkoxides can be generated by combining a vanadium oxide precursor species, such as, for example, a vanadium oxyhalide (VOX.sub.3).sub., preferably VOCl.sub.3, or vanadium oxyacetate (VO.sub.2 OAc), with an appropriate alcohol, such as i-BuOH, i-PrOH, n-PrOH, n-BuOH, t-BuOH, and the like. It is understood that if vanadium oxoalkoxides are generated from a vanadium oxide precursor species and an alcohol, they may contain ligands other than oxide and alkoxide ligands. For example, the product of the reaction of vanadium oxyacetate with an alcohol is a mixed alkoxide/acetate. Thus, herein the term "vanadium oxoalkoxide" is used to refer to species that have one oxide (.dbd.O) ligand and at least one alkoxide (--OR) ligand per vanadium atom, particularly if prepared in situ, i.e., without isolation and/or purification of the vanadium oxoalkoxide. Preferably, however, the vanadium oxoalkoxides are trialkoxides with one oxide and three alkoxide ligands.

The in situ preparations of the vanadium oxoalkoxides are preferably carried out under a nonoxidizing atmosphere such as nitrogen or argon. The vanadium oxide precursor species is typically added to an appropriate alcohol at room temperature. Preferably, it is added at a controlled rate such that the reaction mixture does not greatly exceed room temperature, if the reaction is exothermic. The temperature of the reaction mixture can be further controlled by placing the reaction flask in a constant temperature bath, such as an ice water bath. The reaction of the vanadium oxide precursor species and the alcohol can be done in the presence of an oxirane, such as propylene oxide, ethylene oxide, or epichlorohydrin, and the like. The oxirane is effective at removing by-products of the reaction of the vanadium oxide species with alcohols. If desired, volatile starting materials and reaction products can be removed through distillation or evaporative techniques, such as rotary evaporation. The resultant vanadium oxoalkoxide product, whether in the form of a solution or a solid residue after the use of distillation or evaporative techniques, can be combined directly with water to produce the vanadium oxide colloidal dispersions preferably used in the present invention.

The coatings may be made by combining a vanadium oxoalkoxide and an excess of water, preferably with stirring until a homogeneous colloidal dispersion forms. By an "excess" of water, it is meant that a sufficient amount of water is present relative to the amount of vanadium oxoalkoxide such that there is greater than 1 equivalent of water per equivalent of vanadium oxoalkoxide. That is, there is greater than a 1:1 molar ratio of water to vanadium-bound alkoxide ligands. Preferably, a sufficient amount of water is used such that the final colloidal dispersion formed contains no greater than about 3.5 wt-% vanadium and at least a minimum effective amount of vanadium. This typically requires a molar ratio of water to vanadium alkoxide of at least about 45:1, and preferably at least about 150:1. Herein, by "minimum effective amount" of vanadium it is meant that the colloidal dispersion contains an amount of vanadium in the form of vanadium oxide, whether diluted or not, which is sufficient to form an effective antistatic coating for the use desired.

For most uses, an effective antistatic coating has a surface concentration of vanadium, i.e., coating weight, ([V].sub.eff, calculated in mg of vanadium per m.sup.2 of substrate surface area) of less than about 12 mg/M.sup.2 ; however, for some end uses a value of [V].sub.eff of less than about 20 mg/m.sup.2 can be tolerated. For preferred uses, however, it is desirable that the antistatic coating have a [V].sub.eff of less than about 6.0 mg/m.sup.2, and more preferably less than about 3.0 mg/m.sup.2, most preferably less than about 2.0 mg/m.sup.2. Generally, the lower the surface concentration of vanadium required for effective conduction of electrostatic charges, the thinner the coating, which is advantageous and commercially desirable because thinner vanadium oxide coatings are generally less colored, more transparent, more uniform, and in certain circumstances possess better adhesion properties than do thicker coatings.

The value of [V].sub.eff is the calculated surface concentration of vanadium required to provide an electrostatic charge decay time of less than 0.10 second for decay of a 5000 V potential to less than 50 V. The surface concentration of vanadium in antistatic coatings can be calculated from: (1) formulation data, assuming 100% conversion of the vanadium oxoalkoxide to the vanadium oxide colloidal dispersion, and also assuming the density of each successively diluted vanadium oxide colloidal dispersion is that of water (1.0 g/mL); and (2) the wet coating thickness (the wet coating thickness applied using a No. 3 Mayer Bar is 6.9 .mu.m).

Colloidal dispersions with a vanadium concentration greater than about 3.5 wt-% are not generally desirable because they typically have poor dispersion properties, i.e., they are not dispersed well and are too gelatinous, and the coatings produced therefrom have poor antistatic properties. A coating with "poor" antistatic properties is one with a [V].sub.eff value of greater than about 20 mg/m.sup.2. Interestingly, colloidal dispersions originally prepared containing above about 3.5 wt-% vanadium do not typically exhibit improved properties if diluted to a colloidal dispersion containing a lesser amount of vanadium prior to formation of the coating. That is, the properties of a vanadium oxide colloidal dispersion containing above about 3.5 wt-% vanadium can not be easily improved upon dilution of the colloidal dispersion. It is possible, however, to improve the quality and stability of the colloidal dispersions containing above about 3.5 wt-% vanadium by adding an amine, such as, for example, N,N-diethylethanolamine. Although not intending to be limiting, it is believed that this increases the degree of ionization of colloidal particles by deprotonating V-OH groups.

In preparing preferred embodiments of the vanadium oxide colloidal dispersions, a sufficient amount of water is used such that the colloidal dispersion formed contains about 0.3 wt-% to about 2.0 wt-% vanadium. Most preferably, a sufficient amount of water is used so that the colloidal dispersion formed upon addition of the vanadium-containing species contains about 0.6 wt-% to about 1.7 wt-% vanadium.

Preferably, the water used in these methods is deionized water. By "deionized" water, it is meant that the water has had a significant amount of any Ca.sup.2+, Mg.sup.2+, and Fe.sup.2+ ions originally present removed. Preferably, the deionized water contains less than about 50 parts per million (ppm) of these multivalent cations (total concentration of all multivalent cations), and more preferably less than about 5 ppm. Most preferably, the deionized water of the present invention contains less than about 50 ppm of a total cation concentration, including multivalent cations and monovalent cations, such as Na.sup.+.

Multivalent cations cause the greatest detrimental effect to the quality of the dispersions of the present invention. That is, the dispersions are much more tolerant of monovalent cations, such as Na.sup.+, than they are of multivalent cations, such as Ca.sup.2+, Mg.sup.2+, and Fe.sup.2+. For example, the dispersions of the present invention can tolerate a total concentration of multivalent cations of up to about 50 ppm (parts per million), and a total concentration of monovalent cations of up to about 500 ppm, before flocculation occurs and the quality of the dispersion is significantly diminished.

As long as the water is deionized, there is no requirement that it be distilled. Thus, deionized tap water or well water can be used. Depending on the charge balance of the water, it can be neutral, slightly acidic, or slightly basic. The "deionized" water of the present invention can also be prepared using "softening" agents, such as Na.sub.2 CO.sub.3, which replace the multivalent cations with Na.sup.+. Thus, the term deionized water, as used herein, includes within its scope "soft" water, which contains Na.sup.+ ions; however, for soft water to be usable in the preparation of good quality dispersions, it is preferred that the water contain less than about 500 ppm Na.sup.+ ions.

Water useful in the methods of the present invention generally has a pH sufficient to render colloidal dispersions with a pH of about 1.5 to about 8.0. If the pH of the colloidal dispersion is less than about 1.5, the dispersion properties are usually detrimentally affected such that they produce inadequate antistatic coatings. If the pH of the colloidal dispersion is more than about 8.0, the dispersion properties are also detrimentally affected typically because of the dissolution of vanadium oxide to form vanadate compounds. Typically, deionized water with a pH within a range of about 5.0 to about 9.0 will produce a colloidal dispersion with a pH within a range of about 1.5 to about 8.0.

In a preferred preparation process for the antistatic coatings used in the present invention, a vanadium oxoalkoxide is preferably hydrolyzed by adding the vanadium oxoalkoxide to the water, as opposed to adding the water to the vanadium oxoalkoxide. This is advantageous because it typically results in the formation of a desirable colloidal dispersion and generally avoids excessive gelling. Whether the vanadium oxoalkoxide is added to the water or the water is added to the vanadium oxoalkoxide, the vanadium oxoalkoxide can be at least partially hydrolyzed before it is combined with the excess water. This can be done, for example, by spray drying the oxoalkoxide in the presence of water. The spray dried vanadium oxoalkoxide can then be combined with the excess water.

In these processes, the water initially reacts with the vanadium oxoalkoxides in a hydrolysis reaction. The hydrolyzed product then subsequently undergoes a condensation reaction to form a mixed valence vanadium oxide colloidal dispersion. That is, the vanadium oxide colloidal dispersions formed contain vanadium atoms in both the +4 and +5 formal oxidation states. Often the product is referred to as vanadium pentoxide (V.sub.2 O.sub.5); however, its molecular formula can be more accurately represented by V.sub.2 O.sub.4.67.

The homogeneous solution resulting from hydrolysis is preferably subjected to an aging process to allow for initially formed vanadium oxide fibrils to coalesce. Although this is preferred and advantageous for certain applications, the colloidal dispersions of the present invention do not need to be aged to be useful or to provide advantage over the vanadium oxide colloidal dispersions produced by known alkoxide hydrolysis methods. The aging process typically involves storing the solution in a constant temperature bath until a thixotropic colloidal dispersion is formed. Preferably, the aging is conducted for about 1-6 days in a 20.degree.-90.degree. C. water bath, more preferably a 40.degree.-60.degree. C. water bath. Improvement can be observed, however, with aging conditions of up to about 10 days. Most preferably, aging is conducted for a short period of time, such as for about 8-24 hours. Typically, an aged colloidal dispersion provides a more advantageous coating than one that has not been aged. For example, a coating made from an unaged colloidal dispersion can require a surface vanadium concentration 8 times greater than a material aged at 90.degree. C. for 8 hours (to provide an electrostatic charge decay time of less than 0.10 seconds for decay of a 5000 V potential to less than 50 V). Thus, the aging process results in a colloidal dispersion capable of forming thinner coatings, i.e., coatings with less color.

As long as there is an excess of water used in the hydrolysis and subsequent condensation reactions of the vanadium oxoalkoxides, water-miscible organic solvents can also be present. That is, in certain preferred embodiments the vanadium oxoalkoxides can be added to a mixture of water and a water-miscible organic solvent. Miscible organic solvents include, but are not limited to, alcohols, low molecular weight ketones, dioxane, and solvents with a high dielectric constant, such as acetonitrile, dimethylformamide, dimethylsulfoxide, and the like. Preferably, the organic solvent is acetone or an alcohol, such as i-BuOH, i-PrOH, n-PrOH, n-BuOH, t-BuOH, and the like.

Preferably, the reaction mixture also contains an effective amount of hydroperoxide, such as, for example, H.sub.2 O.sub.2 or t-butyl hydroperoxide. An "effective amount" of a hydroperoxide is an amount that positively or favorably affects the formation of a colloidal dispersion capable of producing an antistatic coating with a value of [V].sub.eff of less than about 2.0 mg/m.sup.2. The presence of the hydroperoxide enhances the reaction by facilitating production of an antistatic coating with highly desirable properties. Furthermore, the presence of the hydroperoxide appears to improve the dispersive characteristics of the colloidal dispersion. That is, when an effective amount of hydroperoxide is used the resultant colloidal dispersions are less cloudy, less turbid, and more well dispersed. The hydroperoxide is preferably present in an amount such that the amount of vanadium in the vanadium oxoalkoxide added to the hydroperoxide is within a range of about 1-4 moles of vanadium per mole of hydroperoxide originally present. While not wishing to be held to any particular theory, it is believed that the hydroperoxide accelerates the formation of acicular, i.e., needle-like, vanadium oxide colloidal particles.

The vanadium oxide antistatic layer may optionally contain an organic polymer. Preferred polymers are sulfonated organic polymers, i.e., those containing a salt of an --SO.sub.3 H group, as disclosed in U.S. patent application Ser. No. 07/893,279 bearing Attorney's Docket No. 48349USA1A and entitled "Sulfopolymer/Vanadium Oxide Antistatic Compositions," which is incorporated herein by reference. The vanadium oxide/sulfopolymer composite layer preferably contains about 0.2-50 wt-% vanadium oxide and about 50-99.8 wt-% polymer.

Sulfonated polymers are known to be useful primer layers. If used for this purpose, the priming function of the sulfonated polymer is not adversely affected by the inclusion of vanadium oxide in an amount sufficient to provide excellent antistatic properties. That is, an antistatic layer containing vanadium oxide and a sulfonated polymer can provide advantageous adherent properties to the substrate. Thus, such an antistatic layer can improve the adhesion of the colorant layer and/or the antistick layer to the base substrate of the donor sheet. Similarly, an antistatic layer with a sulfonated polymer can improve the adhesion of the image-receiving layer to the base substrate of the final receptor sheet.

An intermediate carrying sheet can also include a vanadium oxide/sulfonated polymer layer; however, the adhesive properties of the sulfonated polymer are typically decreased by the addition of a second polymer with poor adhesive properties. In this way, the adhesive characteristics, and thereby delaminating characteristics, of a vanadium oxide layer can be tailored for desired results.

Preferred embodiments of this invention contain antistatic layers comprising vanadium oxide plus a polymer binder, such as a sulfonated polymer. However, it is important to note that vanadium oxide can be coated without a binder, which may be desirable if the polymer is one that interferes with thermal transfer properties. Such a vanadium oxide layer is preferably very thin, i.e., the vanadium oxide is applied in a low coating weight, to enhance the adhesion between the substrate and the layer overcoating the antistatic layer. Alternatively, use of an antistatic layer that shows a low level of adhesion to a substrate can be advantageously used as a delaminating liner as well as an antistatic layer.

Advantageously, the process of the present invention can be carried out in the presence of an organic polymer or prepolymer. Ill this way, colloidal dispersions of vanadium oxide can be prepared in situ in solutions or dispersions of organic polymers or prepolymers with which colloidally dispersed vanadium oxide is otherwise incompatible, as evidenced by flocculation of the colloidal dispersion. The organic polymers or prepolymers that are usable in this in situ manner are those that are soluble or dispersible in water or water plus a water-miscible solvent. Such organic polymers or prepolymers include, but are not limited to, polyacrylic acid; polyols such as those available from Dow Chemical under the trademark VORANOL.TM.; polyvinyl alcohols; hydroxyethyl cellulose; polymethyl methacrylate; polyethyl acrylate; polystyrene; polystyrene/butadiene copolymers; polyvinylidene chloride; and the like. Preferably, the useful organic polymers or prepolymers are "soluble" in water or a mixture of water and a water-miscible organic solvent as described above. The ratio of the number of moles of vanadium oxoalkoxide initially added to the number of moles of an organic polymer or prepolymer can vary within a range of about 1:1 to about 1:499.

Generally, the hydrolysis and condensation reactions of the vanadium oxoalkoxides using an excess of water, can be carried out in air. Also, although it is preferred that the alkoxide be added to the water, the rate of addition is not typically crucial. It is desirable, however, that the mixture be stirred during the hydrolysis and condensation reactions. Furthermore, the initial hydrolysis can be carried out at any temperature in which the solvent (i.e., water or a mixture of water and a water-miscible organic solvent) is in a liquid form, e.g., within a range of about 0.degree.-100.degree. C. It is preferred, however, that the initial hydrolysis, and subsequent condensation, reactions be carried out within a temperature range of about 20.degree.-30.degree. C., i.e., at about room temperature.

The concentration of V.sup.4+ in the resultant colloidal dispersions can be determined by titration with permanganate. Preferably, the mole fraction of V.sup.4+ to (V.sup.4+ +V.sup.5+), i.e., V.sup.4+ /total vanadium, is at least about 0.01:1.0, preferably at least about 0.05:1.0, and more preferably at least about 0.30:1.0. The concentration of V.sup.4+ in the resultant colloidal dispersions can be easily varied, however, simply by removing volatile reaction products through distillation subsequent to hydrolysis of the vanadium oxoalkoxide. Significantly, the V.sup.4+ concentrations can be varied over a range of about 1-40% of the total vanadium content. Although not intending to be limited by any theory, it is believed that the concentration of V.sup.4+ may contribute to the intrinsic conductivity of the coatings. Furthermore, it is believed that the V.sup.4+ ions contribute to the formation of the colloidal dispersions, perhaps acting as polymerization initiators or by controlling intercalation.

The vanadium oxide colloidal dispersions of the present invention can be diluted as desired with water or a water-miscible organic solvent prior to coating onto a substrate. The water-miscible organic solvent can be any of those listed above that can be present in the reaction mixture during the preparation of the colloidal dispersions. Preferably, the organic solvent with which the colloidal dispersion is diluted, prior to forming a film, is acetone or an alcohol.

Typically, the colloidal dispersions can be stored at any concentration. Preferably, they are stored at a concentration of about 0.3 wt-% to 2.0 wt-% vanadium. If necessary, the originally formed dispersions can be diluted to this concentration with water or a water-miscible organic solvent. No particular precautions need be observed during storage other than maintaining the temperature above the freezing point of the colloidal dispersions. If allowed to freeze, the colloidal dispersion is generally destroyed. The colloidal dispersions can be stored in any type of container, preferably glass or plastic. Furthermore, they can be stored in the presence or absence of light. Typically, as long as the colloidal dispersions are kept in a sealed container (to avoid evaporation of water), they are stable for at least about 6 months.

The vanadium oxide colloidal dispersions can be coated onto any flexible substrate used in the thermal transfer systems of the present invention, which are generally nonconductive substrates, or substrates that have less than a desirable conductivity. For example, the colloidal dispersions can be coated onto materials such as paper, cloth, flexible ceramic materials, and a variety of polymeric materials, including cellulose esters, polyesters, polycarbonates, polyolefins, copolymers, and terpolymers. The colloidal dispersions of the present invention can be coated directly onto any of these substrates or over an intermediate layer of a material that promotes or reduces adhesion, as needed for the desired properties, between the antistatic coating and the substrate.

The vanadium oxide colloidal dispersions, as well as the other coating materials used in thermal transfer systems, can be applied to a substrate by a variety of conventional solution coating methods. These include, but are not limited to, roll coating, brush coating, hopper coating, curtain coating, slide coating, knife coating, and rotogravure coating. Advantageously, the colloidal dispersions are coated using a slide coating, roll coating, or rotogravure coating process. These methods, and the techniques by which they are implemented, are all well known in the coating industry. The methods of manufacturing thermal transfer sheets can also include drying steps between coating the various layers for removing solvent, although this is not always required. Generally, if desirable, the drying steps are conducted at temperatures of no greater than about 100.degree. C. These methods are well known in the thermal transfer imaging industry.

The amount of vanadium oxide colloidal dispersion used in the coating process can be widely varied. The upper limit of the amount used is generally controlled by the quality of the particular dispersion and the desire for a transparent and relatively colorless coating, i.e., one that is difficult to detect by the human eye. That is, although coatings can be prepared with coverages of 100 mg/m.sup.2 and higher, for many uses it is preferable to have as thin a coating as possible, e.g., no more than about 3.0 mg/m.sup.2, to decrease the color imparted to the coating, increase its transparency, improve uniformity, and in certain circumstances improve adhesion. Such thin coatings typically require a high quality colloidal dispersion, such as can be produced using the methods of the present invention, because the lower the quality of the colloidal dispersion, the more material needed to produce an acceptable antistatic coating. Because the vanadium oxide colloidal dispersions are colored, the more material used the more the coating is colored; however, if the colloidal dispersions are coated thinly enough on a substrate, they do not appear colored. Typically, an apparently "colorless" coating can be obtained with a coverage of no more than about 3.0 mg/m.sup.2, preferably with no more than about 1.5 mg/m.sup.2, and more preferably with no more than about 1.0 mg/m.sup.2. By "colorless" it is meant that the coatings do not show significant absorption in the visible region of the spectrum (typically, they display an absorbance of less than 0.1) during a UV-VIS spectral analysis, and the coatings are substantially undetectable using a Macbeth Densitometer Model RD 514 (Nuburg, N.Y.).

The coatings prepared from the vanadium oxide colloidal dispersions preferred in the present invention typically contain whisker-shaped or needle-shaped particles. These particles have a high aspect ratio, i.e., the ratio of the length to the width of the particles, and are generally evenly distributed. By "high aspect ratio" it is generally meant that the ratio of the length to the width of the particles, as observed in the coatings produced from the colloidal dispersions invention by Field Emission Electron Microscopy, is greater than about 25.

The particles of vanadium oxide exist as a porous layer of particles (generally as fibers, fibrils or particles with one dimension significantly greater than the other dimensions) in intimate contact with each other. By intimate contact it is meant that particles physically contact other particles. The contact may be only at crossover or intersection points or may be more extensive. Across the length of the layer, a conductive path is created by the particle-to-particle contact. The particles may or may not be actually bound to particles at the point of contact. There may be only physical contact, electronic attraction, or some chemical bonding, as long as the conductive mechanism of the particles is maintained.

The vanadium oxide colloidal dispersions and antistatic coatings preferred in the present invention can contain a variety of additives as desired. They preferably contain wetting agents, i.e., surfactants, such as fluorinated surfactants and other commercially available surfactants, that promote coatability. They can contain polymeric binders that improve the mechanical properties of the antistatic coatings; metal dopants or modifiers such as VO.sub.2, Ag.sub.2 O, Cu.sub.2 O, MnO, ZnO, Nb.sub.2 O.sub.5, MoO.sub.3, WO.sub.3, Sb.sub.2 O.sub.3, GeO.sub.2, Nd.sub.2 O.sub.3, Sm.sub.2 O.sub.3, Gd.sub.2 O.sub.3, Yb.sub.2 O.sub.3, and Eu.sub.2 O.sub.3 that alter the dispersion properties, color, and/or electrical conductivity; dyes such as methylene blue, crystal violet, and acid violet; biocides; preservatives; antifreeze agents; and anti-foam agents. Metal dopants can be added as metal alkoxides, salts, or compounds during the hydrolysis of the vanadium oxide dispersions, or after the vanadium oxide dispersions are formed.

The invention has been described with reference to various specific and preferred embodiments and will be further described by reference to the following detailed examples. It is understood, however, that there are many extensions, variations, and modifications on the basic theme of the present invention beyond that shown in the examples and detailed description, which are within the spirit and scope of the present invention.

Vanadium oxide colloidal dispersions were prepared as described below. Coating dispersions, i.e., vanadium oxide colloidal dispersions suitable for coating, were prepared with successively greater dilution (each successive coating dispersion was one half the concentration of the previous coating dispersion). Unless otherwise noted, coatings were prepared by hand spreading using a No. 3 Mayer bar onto poly(vinylidene chloride) (PVDC) primed polyester film (available from Specialty Film Division, 3M Company, St. Paul, Minn.). Each subsequent vanadium oxide coating had one half the surface vanadium concentration, i.e., coating weight, as the previous one. The effectiveness of the vanadium oxide colloidal dispersions for the preparation of antistatic coatings was determined as the surface concentration of vanadium ([v].sub.eff, in mg of vanadium per m.sup.2 of substrate surface area) required to provide an electrostatic charge decay time of less than 0.10 second for decay of a 5000 V potential to less than 50 V. The surface concentration of vanadium reported in the following examples was calculated from formulation data assuming the density of each successively diluted vanadium oxide colloidal dispersion to be that of water (1.0 g/mL), and the wet coating thickness obtained with the No. 3 Mayer Bar to be 6.86 .mu.m. An Inductively Coupled Plasma (ICP) Spectroscopic analysis of vanadium surface concentration of several coated film samples showed that the actual vanadium surface concentration was consistently about 40% of that calculated from the amount coated from a particular concentration of coating dispersion. Times required for decay of a 5000 V charge (to less than 50 V) were determined using a model 406C Static Decay Meter from Electro-Tech Systems, Inc., Glenside, Pa.

All reagents were obtained from Aldrich Chemical Co., Milwaukee, Wis., unless otherwise noted. The deionized water used in the examples below was prepared by pumping well water through a cation exchange bed (regenerated with sulfuric acid) and then through an anion exchange bed (regenerated with NaOH). The cation exchange resins used were sulfonated polystyrenes crosslinked with vinyl benzene, and the anion exchange resins used were quartenary ammonium styrenes crosslinked with vinyl benzene. These resins are commonly available under the trade designation AMBERLITE.TM. from Rohm & Haas, Philadelphia, Pa. In the process, cations were exchanged for H.sup.+ ions and anions were exchanged for OH.sup.- ions. After passing through the exchange resins, the water was held in a tank prior to use.

A vanadium oxide colloidal dispersion was prepared by adding VO(O-i-Bu).sub.3 (15.8 g, 0.055 mol, product of Akzo Chemicals, Inc., Chicago, Ill.) to a rapidly stirring solution of H.sub.2 O.sub.2 (1.56 g of 30% aqueous solution, 0.0138 mol, product of Mallinckrodt, Paris, Ky.) in deionized water (252.8 g), giving a solution with a vanadium concentration of 0.22 mole/kg (2.0% V.sub.2 O.sub.5, 1.1% vanadium). Upon addition of VO(O-i-Bu).sub.3, the mixture became dark brown and gelled within five minutes. With continued stirring, the dark brown gel was broken up giving an inhomogeneous, viscous dark brown colloidal solution. This colloidal solution became homogeneous in about 45 minutes of continued stirring. The sample was allowed to stir for 1.5 hours at room temperature and was then transferred to a polyethylene bottle and aged in a constant temperature bath at 50.degree. C. for 4 days to give a dark brown thixotropic gelatinous colloidal dispersion, i.e., a colloidal dispersion in which the dispersed phase has combined to produce a semi-solid material with a three-dimensional solid network containing a large volume of interconnecting pores filled with a liquid.

The surface concentration of vanadium required to provide static decay of 5000 V to less than 50 V in less than 0.10 second, [V].sub.eff, was determined for the vanadium oxide colloidal dispersion as follows. Portions of the vanadium oxide colloidal dispersion containing 1.1% vanadium, prepared as described above, were diluted with deionized H.sub.2 O and TRITON.TM. X-100 surfactant to provide colloidal dispersions with 0.084, 0.042, 0.021, and 0.011% vanadium and 0.1% TRITON.TM. X-100. Each diluted dispersion was coated by hand using a No. 3 Mayer bar on PVDC primed polyester film to give vanadium oxide coatings with calculated surface vanadium concentrations of 5.76, 2.88, 1.44, and 0.72 mg/m.sup.2, respectively. The static decay times for decay of a 5000 V potential to less than 50 V were measured for each of these coatings, and the value of [V].sub.eff was determined to be 1.4 mg/m.sup.2.

Calculation of coating weight:

Mol. Wt. of V=50.94 g/mole

Mol. Wt. of VO(O-i-Bu).sub.3 =286.02 g/mole

Density of Vanadium Dispersion.apprxeq.1 g/mL or 1 g/cm.sup.3

Coating Thickness=6.9.times.10.sup.-6 meters

In this example, 0.055 mole VO(O-i-Bu).sub.3 was used, which is equivalent to 0.055 mole V in 1.56 g H.sub.2 O.sub.2 +252.8 g H.sub.2 O=254.36 g total solvent mixture. ##EQU1## Assuming the density of the dispersion is 1 g/cm.sup.3, then 6.9 grams is spread over 1 m.sup.3 of substrate. ##EQU2## But, the dispersions are diluted, so for example if 1.1% sol is diluted with the addition of 547 mL of H.sub.2 O to give a 0.17% sol, the calculated surface vanadium concentration is 11.5 mg/m.sup.2 .

This example demonstrates the preparation of a V.sub.2 O.sub.5 dispersion according to U.S. Pat. No. 4,203,769. V.sub.2 O.sub.5 (15.6 g, 0.086 mol, product of Aldrich, Milwaukee, Wis.) was heated in a covered platinum crucible for 10 minutes at 1100.degree. C. and then poured into 487 g of rapidly stirring deionized H.sub.2 O. The resulting liquid plus gelatinous black precipitate was warmed to 40.degree.-45.degree. C. for 10 minutes and allowed to stir for 1 hour at room temperature to give a soft, thixotropic black gel which was diluted with 1,041.0 g deionized H.sub.2 O to give a vanadium oxide colloidal dispersion containing 1.0% V.sub.2 O.sub.5. The viscous colloidal dispersion was filtered to remove undispersed V.sub.2 O.sub.5.

The surface concentration of vanadium required to provide static decay of 5000 V to less than 50 V in less than 0.1 second, [v].sub.eff, was determined as follows. Portions of the vanadium oxide colloidal dispersion, containing 0.56 wt-% vanadium (1.0% V.sub.2 O.sub.5), were diluted with deionized water and TRITON.TM. X-100 surfactant to provide colloidal dispersions with 0.17, 0.084, 0.042, and 0.21% vanadium and 0.1% TRITON.TM. X-100. Each diluted dispersion was coated by hand spreading using a No. 3 Mayer bar onto PVDC primed PET film to produce vanadium oxide coatings with calculated surface vanadium concentrations of 11.6, 5.8, 2.9, and 1.4 mg/m.sup.2, respectively. The static decay times for decay of a 5000 V potential to less than 50 V were determined for each of these coatings, and the value of [V].sub.eff was determined to be 11.6 mg/m.sup.2.

This example shows that solutions prepared according to U.S. Pat. No. 4,203,769 are less effective for the preparation of antistatic coatings than those prepared by the alkoxide process of the present invention. Furthermore, the former process is not particularly preferred because of the need for special containers, the generation of highly toxic V.sub.2 O.sub.5 fumes by heating to high temperatures, and the difficulty in filtering out nondispersed V.sub.2 O.sub.5.

This example demonstrates the preparation of a vanadium oxide colloidal dispersion by an ion exchange process. Sodium metavanadate (6.0 g, 0.049 mol, product of Alfa Products, Ward Hill, Mass.) was dissolved by warming in 144 g deionized H.sub.2 O. The resulting solution was filtered to remove insoluble material. The filtered solution was pumped through a 15 mm.times.600 mm chromatography column containing 600 mL of AMBERLITE.TM. IR 120 Plus (H.sup.+) (available from Aldrich Chemical, Milwaukee, Wis.) to give a light orange solution containing 1.7% vanadium. The solution became a soft opaque brick red gel upon standing at room temperature for 24 hours.

Before evaluating, the dispersion had aged for 14 months at room temperature. The sample was then diluted to give a hazy orange-red colloidal dispersion containing 0.17% vanadium. The value of [V].sub.eff for the colloidal dispersion, determined as described in Example 1, was 23.2 mg/m.sup.2.

This example shows that solutions prepared by an ion exchange process are less effective for the preparation of antistatic coatings than the colloidal dispersions of the alkoxide hydrolysis products.

This example demonstrates the preparation of a sulfopolyester. A one gallon polyester kettle was charged with 126 g (6.2 mol-%) dimethyl 5-sodiosulfoisophthalate, 625.5 g (56.8 mol-%) dimethyl terephthalate, 628.3 g (47.0 mol-%) dimethyl isophthalate, 854.4 g (200 mol-% glycol excess) ethylene glycol, 365.2 g (10 mol-%, 22 wt-% in final polyester) PCP-200.TM. polycaprolactone diol (Union Carbide), 0.7 g antimony oxide, and 2.5 g sodium acetate. The mixture was heated with stirring to 180.degree. C. at 138 kPa (20 psi) under nitrogen, at which time 0.7 g zinc acetate was added. Methanol evolution was observed. The temperature was increased to 220.degree. C. and held for 1 hour. The pressure was then reduced, vacuum applied (0.2 torr), and the temperature increased to 260.degree. C. The viscosity of the material increased over a period of 30 minutes, after which time a high molecular weight, clear, viscous sulfopolyester was drained. This sulfopolyester was found by Differential Scanning Calorimetry to have a Tg of 41.9.degree. C. The theoretical sulfonate equivalent weight was 3954 g polymer per mole of sulfonate. 500 g of the polymer were dissolved in a mixture of 2000 g water and 450 g isopropanol at 80.degree. C. The temperature was then raised to 95.degree. C. in order to remove the isopropanol and a portion of the water, yielding a 21% solids aqueous dispersion.

This example demonstrates the preparation of an antistatic thermal dye transfer intermediate carrying film containing an antistatic layer comprising vanadium oxide prepared by the hydrolysis of VO(O-i-Bu).sub.3. A coating solution was prepared by adding 27.2 g deionized water and 0.3 g 10% TRITON.TM. X-100 surfactant (available from Aldrich Chemical Co., Milwaukee, Wis.) to 4.5 g of 1% colloidal vanadium oxide prepared as described in Example 1. The coating solution contained 0.084 weight percent (wt-%) vanadium and was applied to unprimed and untreated 4 mil (100 micron) PET (polyethylene terephthalate) using a No. 3 Mayer bar (product of RD Specialties, Webster, N.Y.) and dried for 5 minutes at 100.degree. C. to give an antistatic substrate film with surface concentration of vanadium=5.8 mg/m.sup.2. The static decay time of the substrate film was 0.01 second.

A hot melt adhesive layer was formed on the antistatic layer by coating a 45 wt-% SYNTHEMUL.RTM. 97-603 acrylic resin emulsion (Reichhold Chemicals, Inc., Dover, Del.) with No. 10 Mayer bar, followed by drying at 220.degree. F. (104.degree. C.) for 2 minutes. The adhesive layer was then overcoated with an image-receiving layer composed of 5.0 g/m.sup.2 of UCAR.RTM. VYNS-3 (a vinyl chloride/vinyl acetate copolymer, 9:1 by weight, Mn=44,000, Union Carbide, Danbury, Conn.), 0.46 g/m.sup.2 of MR-120 (a vinyl chloride copolymer, hydroxy equivalent weight 1,890 g/mol, sulfonate equivalent weight 19,200 g/mol, epoxy equivalent weight 2,400 g/mol, Tg=65.degree. C., Mw=30,000 from Nippon Zeon Co., Tokyo, Japan), and 0.004 g/m.sup.2 of KF-393 (amino-modified silicone from Sin-Etsu Silicone of America, Inc., Torrance, Calif.). The addition of the antistatic, adhesive, and image-receiving layers to the clear polyester base did not significantly change its transparency. The difference in reflectance optical density between the substrate itself and the coated film was only 0.05 in yellow color as measured by a Gretag SPM 50 Spectrophotometer.

The resulting intermediate carrying sheet was imaged on a 3M RAINBOW.TM. Desktop Color Proofer using four color dye transfer ribbon and self-print pattern. A uniform full-color image was printed on the image-receiving layer, showing no peeling of the coating from the substrate. A 3M Model 1147 Laminator (3M Co., St. Paul, Minn.) was used to make image layer retransfer. The above imaged intermediate carrying sheet, with image side down, was mated to a 3 mil (76 .mu.m) polyester film, i.e., a second intermediate carrying sheet, whose surface was coated with the same SYNTHEMUL.RTM. 97-603 hot melt adhesive as described earlier. The composite was passed through the laminator at 290.degree. F. (143.degree. C.) at 0.8 inch/sec (2.0 cm/sec). After being cooled to room temperature, the polyester backing of the intermediate carrying sheet was peeled off, leaving a clean and glossy print on the 3 mil (76 .mu.m) PET receptor. No image splitting or air bubble was observed. The retransferred image is now in a reverse reading from (i.e., mirror image) on the second intermediate receptor.

This reverse image was further transferred to a 10 mil (250 .mu.m) thick white MATCHPRINT.RTM. Base (3M Co., St. Paul, Minn.) by the same laminator at the same condition. After cooling, the 3 mil (76 .mu.m) polyester backing was easily peeled off, producing a clean, glossy, and positive image on the white base. The reflectance optical densities (ROD) of the resultant image, as measured by a Gretag SPM 50 Spectrophotometer were 1.84 for cyan, and 2.93 for black. The unimaged area had a slight yellowish but acceptable background of 0.05 ROD.

In a comparative experiment, the same image-receiving layer was applied to the same polyester base but without an antistatic coating to form a non-antistatic intermediate carrying receptor sheet. The resultant receptor sheet did not exhibit decay of a triboelectrically generated charge and could not be charged by the Electro-tech Static Decay Meter. The imaging and retransfer properties were not as good as those with the antistatic coating.

This example shows that an antistatic layer of vanadium oxide prepared according to Example 1 can be inserted between a substrate film and an image-receiving layer on an intermediate carrying sheet, with the effect of providing excellent antistatic properties and improved imaging and retransfer properties.

This example demonstrates the preparation of an antistatic thermal dye intermediate carrying film containing an antistatic layer comprising vanadium oxide prepared by the process of U.S. Pat. No. 4,203,769. A coating solution was prepared by adding 20.7 g deionized water and 0.3 g 10% TRITON.TM. X-100 surfactant to 9.0 g of 1% colloidal vanadium oxide prepared as described in Example 2. The coating solution contained 0.17 wt-% vanadium and was applied to unprimed and untreated 4 mil (100 .mu.m) PET film using a No. 3 Mayer bar and dried for 5 minutes at 100.degree. C. to give an antistatic substrate film with surface concentration of vanadium=11.6 mg/m.sup.2. The static decay time of the substrate film was 0.01 second.

The antistatic layer was overcoated with the same adhesive and image-receiving layers, imaged on the same printer, and tested under the same conditions as described in Example 5. The addition of the antistatic, adhesive, and image-receiving layers to the clear polyester base caused significant coloration with a yellow ROD of 0.08. The resulting transferred image was retransferred to the white MATCHPRINT.RTM. base using the same procedure and the same laminator under the same condition as in Example 5. This also produced a clean, glossy, and positive image on the white base. The reflectance optical densities (ROD) of the resultant image are 2.02 for cyan, and 2.65 for black. The unimaged area, however, showed a yellowish background of 0.08 ROD.

This example shows that an antistatic layer of vanadium oxide prepared according to Example 2 can be inserted between a substrate film and a thermal image-receiving layer on an intermediate carrying substrate, with the effect of providing excellent antistatic properties and improved imaging and retransfer properties. However, with this particular vanadium oxide dispersion, a certain degree of undesirable coloration occurred.

This example demonstrates the preparation of an antistatic thermal dye intermediate carrying film containing an antistatic layer comprising vanadium oxide prepared by ion exchange acidification of sodium metavanadate. A coating solution was prepared by adding 6.9 g deionized water and 0.1 g 10% TRITON.TM. X-100 surfactant to 3.0 g of 2% colloidal vanadium oxide prepared as described in Example 3. The 2% colloidal vanadium oxide had aged for 14 months at room temperature before using. The coating solution containing 0.34 wt-% vanadium was applied to unprimed and untreated 4 mil PET using a No. 3 Mayer bar and dried for 5 minutes at 100.degree. C. to give an antistatic substrate film with calculated surface concentration of vanadium equal to 23.2 mg/m.sup.2. The static decay time of the antistatic substrate film was 0.05 second.

The antistatic layer was overcoated with the same adhesive and image-receiving layers, imaged on the same printer, and tested under the same conditions as described in Example 5. The addition of the antistatic, adhesive, and dye receiving layers to the clear polyester base caused significant coloration with a yellow ROD of 0.11.

The resulting image was retransferred to the white MATCHPRINT.RTM. base using the same procedure and the same laminator under the same conditions as in Example 5. This also produced a clean, glossy, and positive image on the white base. The reflectance optical densities (ROD) of the resultant image were 1.72 for cyan, and 2.71 for black. The unimaged area, however, showed a yellowish background of 0.11 ROD.

This example shows that an antistatic layer of vanadium oxide prepared according to Example 3 can be inserted between a substrate film and an image-receiving layer on an intermediate carrying sheet, with the effect of providing excellent antistatic properties and improved imaging and retransfer properties. However, with this particular vanadium oxide dispersion, there was a certain degree of undesirable coloration produced.

This example describes the process for the formation of a mass transfer image and subsequent transfer of the image to another surface.

Step 1: Formation of a mass transfer image on an intermediate receptor. A thermal mass transfer donor ribbon (three color patches, yellow, cyan, and magenta, on 11 .mu.m thick backing) manufactured by Fuji K. K. (Tokyo, Japan) was placed on a 9.5 .mu.m polyester film (3M Company, St. Paul, Minn.). The composite was run through a thermal printer to make a mass transfer image on the intermediate receptor at 6.5 volts and a 4 msec burn time using EPROM (Electronically Programmable Read Only Memory) pattern. The printer was equipped with a Hewlett Packard thermal print head (H. P. Part No. 07317-60050, Hewlett Packard Co.) with 4 dots per mm and 470 ohms resistive heating elements. After imaging, the donor ribbon was peeled off, leaving a clean reverse mass transfer image on the polyester receptor.

Step 2: Retransfer the formed mass transfer image to other surface. The intermediate receptor with the image side facing down was placed on top of a SCOTCHCAL.RTM. vinyl film (3M Company, St. Paul, Minn.) and run through a hot-press roller at medium speed (about 1 inch per second) at 150.degree. F. (65.6.degree. C.). The image on the intermediate sheet was transferred to the final SCOTCHCAL.RTM. receptor under heat and pressure. The substrate of the intermediate receptor was peeled off from the composite, leaving a clean, sharp, and positive image on the SCOTCHCAL.RTM. receptor.

The disclosures of all patents, patent applications, patent documents, and publications cited herein are incorporated by reference. The foregoing detailed description and examples have been given for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described, for variations obvious to one skilled in the art will be included within the invention defined by the claims.