Method of Fusing Electrostatographic Toners to Provide Enhanced Gloss

This invention relates to fusing electrostatographic toner images. More particularly, this invention relates to fusing an electrostatographic particulate toner image using a multi-zone or multi-stage process to provide a fused toner image having enhanced gloss. In a specific aspect, this invention pertains to a method for fusing an electrostatographic toner image comprising toner particles that, upon fusing with heat and pressure, exhibit a loss tangent of at least 1.2.

In electrostatography an image comprising an electrostatic field pattern, usually of non-uniform strength, (also referred to as an electrostatic latent image) is formed on an insulative surface of an electrostatographic element by any of various methods For example, the electrostatic latent image may be formed electrophotographically (i.e., by imagewise photo-induced dissipation of the strength of portions of an electrostatic field of uniform strength previously formed on a surface of an electrophotographic element comprising a photoconductive layer and an electrically conductive substrate), or it may be formed by dielectric recording (i.e., by direct electrical formation of an electrostatic field pattern on a surface of a dielectric material). Typically, the electrostatic field pattern is developed into an electrostatographic toner pattern by contacting the field pattern with an electrostatographic developer containing an electrostatographic toner. If desired, the latent electrostatic field pattern can be transferred to another surface before such development. Although such techniques are typically used for black and white reproductions such as copying business correspondence, they are capable of forming a variety of single color or multicolor toner images.

A typical method of making a multicolor copy involves trichromatic color synthesis by subtractive color formation. In such synthesis successive latent electrostatic images are formed on a substrate, each representing a different color, and each image is developed with a toner of a different color and is transferred to a support (receiver). Typically, but not necessarily, the images will correspond to each of the three primary subtractive colors (cyan, magenta and yellow), and black as a fourth color, if desired. For example, light reflected from a color photograph to be copied can be passed through a filter before impinging on a charged photoconductive layer so that the latent electrostatic image on the photoconductive layer corresponds to the presence of yellow in the photograph. That latent image can be developed with a yellow toner and the developed image can be transferred to a support. Light reflected from the photograph can then be passed through another filter to form a latent electrostatic image on the photoconductive layer which correspond to the presence of magenta in the photograph, and that latent image can then be developed with a magenta toner and transferred to the same support. The process can be repeated for cyan (and black, if desired).

In the systems described previously herein, the toner images may be provided on a support such as paper, film, plastic or glass to which they are permanently fixed. A common technique for fixing such toner images to a support involves employing thermoplastic polymeric toner particles which include a colorant to form the unfixed or unfused image and then fusing the particles to the support by the application of heat and pressure thereto. A suitable method involves passing the support with the toner particles thereon through a pair of opposed rolls, one a heated fuser roll and the other a non-heated or heated backup roll.

It is known to use toner fusing processes to provide toner images having certain enhanced characteristics. For example, U.S. Pat. No. 4,913,991, issued Apr. 3, 1990, describes a process for preparing glossy electrostatographic toner images which the patent indicates presents a pleasing appearance to a viewer, particularly where such images are multicolor toner images.

In the process described in U.S. Pat. No. 4,913,991 a toner image is formed on a recording sheet and fused by passing the sheet between a heat application roll coated with a fluorine-containing resin and a pressure application roll. The toner image has rheological characteristics such that its loss tangent (tan .delta.) is in the range of 1.70 to 3.00 at a storage elastic modulus (G') of 10.sup.5 dyne/cm.sup.2. U.S. Pat. No. 4,913,991 indicates that the aforementioned loss tangent ranges are critical to obtaining acceptable fused toner images having the required gloss and presents comparative data to illustrate this point. The process described in U.S. Pat. No. 4,913,919 is adequate to provide glossy toner images but, it does have some drawbacks. For example, the process is not as flexible a process as would be desired since it is limited to use with toner images having the aforementioned limited range in loss tangent values.

It is also known in the prior art that it is a problem to provide colored toner images having maximum color saturation and, in colored transparencies, maximum chroma or color clarity. Color desaturation in a colored toner image can result from light scattering or multiple reflections within the toner image. This is a problem in reflection color copies but it is particularly troublesome in subtractive color images in transparencies where such light reflection can also result in color shifts upon projection and a failure to faithfully reproduce the colors of the original image. For example, bright yellow in an original image may appear as a muddy yellow. The term often used in the prior art to describe the quality of an image projected by a transparency is "chroma" and high chroma refers to a faithful reproduction of the original colored image while low chroma refers to less than faithful or inaccurate representation of the original colored image. U.S. Pat. No. 4,791,447, issued Dec. 13, 1988, addresses the problem of providing glossy opaque toner images and high chroma transparencies using a fusing system comprising three roll members which cooperate to form a pair of roll nips.

In light of the previous discussion, it is obvious that it would be desirable to have a fusing method capable of providing a wide variety of electrostatographic toner images exhibiting enhanced gloss. Likewise, it would be desirable for such fusing method to have the capability of providing color transparencies exhibiting excellent color clarity, i.e. high chroma. This invention provides such a fusing method.

In accordance with this invention, electrostatographic toner images having enhanced gloss are obtained when the toner particles forming the images in the pattern exhibit certain specified viscoelastic flow characteristics as evidenced by their loss tangent values, measured at a storage elastic modulus (G') of 10.sup.5 dynes/cm.sup.2 as described hereinafter, and such images are subjected to a fusing method comprising three zones i.e. a fusing zone, a cooling zone and a release zone. Accordingly, this invention pertains to a method of fusing an electrostatographic toner image to provide enhanced gloss which method comprises (a) providing an element having a support bearing the image in unfused toner particles that exhibit a loss tangent (tan .delta.) of at least 1.2 upon fusing the image with heat and pressure, (b) passing the element successively through a fusing zone, a cooling zone and a release zone, (c) within the fusing zone, bringing the image into pressure contact with a surface of a fusing member to form a fused image, (d) maintaining contact between the fused image and the fusing member within the cooling zone while reducing the temperature of the fusing member and (e) separating the fused image from the fusing member within the release zone at a temperature where no toner image offset occurs.

A significant feature of this invention is that a transparent support can be used in the aforementioned method to provide a transparency exhibiting excellent color clarity or high chroma, i.e. a transparency that faithfully reproduces the colors in the original image.

The method of this invention provides a technique for separating the contact fusing and fusing member release events that occur during the process by a substantial cooling phase. This is a significant distinction from roll fusing processes of the type employed in U.S. Pat. No. 4,913,991 where such events take place substantially simultaneously. Separating the contact fusing and fusing member release events according to the process of this invention makes it possible to use a fusing temperature which will cause unfused toner particles to flow sufficiently to form a smooth toner image surface capable of exhibiting enhanced gloss and then releasing the image only when it exhibits sufficient elasticity that it does not offset onto the fusing member. Accordingly, the method of this invention is capable of providing enhanced gloss to toner images having a wider range of viscoelasticities and is not limited to those having the loss tangent values of 1.70 to 3.00, as described in U.S. Pat. No. 4,913,991. Accordingly, the process of this invention represents an obvious advantage over roll fusing techniques of the type described in U.S. Pat. No. 4,913,991. Other advantages of this invention will be described or become obvious from the following description.

FIG. 1 is a schematic illustration of apparatus suitable for carrying out the method of this invention.

FIG. 2 is a schematic illustration of other apparatus suitable for carrying out the method of this invention.

The unfixed or unfused toner image that is fused in the method of this invention can be generated using any electrostatographic image-forming process that forms at least one toner image comprising discrete toner particles having a loss tangent of at least 1.2, as described previously herein. Such images can comprise line copy, continuous tone images and half-tone images as well as combinations thereof. The toner images are conveniently generated using electrostatographic processes of the type described hereinbefore, and particularly the colored toner images described in U.S. Pat. No. 4,913,991.

FIG. 1 illustrates preferred apparatus suitable for fusing or fixing an electrostatographic toner image according to the method of this invention. FIG. 1 depicts a fusing device 1 which comprises a heating roll 2, a roll 3 spaced from the heating roll 2, a fusing member which is trained about heating roll 2 and roll 3 as an endless or continuous web or belt 4 which is conveyed in a counterclockwise direction, as viewed in FIG. 1, upon rotation of the heating roll 2 and roll 3. Backup or pressure roll 5 is biased against the heating roll 2 and the continuous belt 4 is cooled by impinging air provided by blower 6 disposed above belt 4. In operation, support 7 bearing the unfused toner image 8 is transported in the direction of the arrow into the nip between heating roll 2 and backup or pressure roll 5 which can be heated if desired, where it enters a fusing zone extending about 2.5 cm laterally along continuous belt 4. Following fusing in the fusing zone, the fused image then continues along the path of the belt 4 and into the cooling zone (about 5 to 25 cm in length) in the region following the nip between heating roll 2 and pressure roll 3. Upon exiting the fusing zone, belt 1 is cooled slightly upon separation from heating roll 3 and then additionally cooled in a controlled manner by air that is caused to impinge upon belt 4 by blower 6. The fused toner image on support 7 then exits the cooling zone, separates from belt 4 as the belt passes around roll 3 and is transported to copy collection means such as a tray (not shown). Support 7 bearing the fused image is separated from the fusing member within the release zone at a temperature where no toner image offset occurs. Separation is expedited by using a roll 3 of relatively small diameter, e.g. a diameter of about 2.5 to 4 cm. As a result of passing through the three distinct zones, i.e. the fusing zone, cooling zone and release zone, the fused toner image exhibits an enhanced level of gloss which is normally readily perceptible to the unaided eye. The extent of each of the three zones and the duration of time the toner image resides in each zone can be conveniently controlled simply by adjusting the velocity or speed of belt 4. The velocity of the belt in a specific situation will depend upon several variables, including, for example, the temperature of the belt in the fusing zone, the temperature of the cooling air and the composition of the toner particles. U.S. Pat. No. 3,931,618, issued Jun. 5, 1990, describes an image glazing device that is used to apply a gloss to a fused toner image or a dye image. Such device has several features in common with the fusing apparatus depicted in FIG. 1 which features are described in detail in the patent. Accordingly, U.S. Pat. No. 3,931,618 is hereby incorporated by reference herein.

FIG. 2 illustrates another device suitable for fusing an electrostatographic toner image to provide differential gloss according to this invention. In this device the fusing member is a roll rather than a continuous web as shown in FIG. 1. As shown in FIG. 2, the fusing device 9 comprises a roll 10, forming a nip with backup or pressure roll 11 and another nip with roll 12 and continuous conveyor means 17 trained partly about rolls 10 and 12, and scive 18. Roll 10 rotates in a counterclockwise direction while rolls 11 and 12 rotate in a clockwise direction, as viewed in FIG. 2. The surface of roll 10 is heated by radiant heat from a heater 13 and is cooled by air provided by a blower 14. Support 16 bears unfused toner image 15. In operation, support 16 bearing unfixed or unfused toner image 15 is conveyed in the direction of the arrow on conveyor means 17 through the nip between rolls 10 and 11 around roll 10 and continues through the nip between rolls 10 and 12. The toner image passes through the fusing zone extending through of the nip between rolls 10 and 11 and proceeds through the cooling zone where blower 14 impinges air upon conveyor 17 which cools support 16 bearing fused toner image and the surface of roll 10. Upon exiting the cooling zone support 16 bearing the fused image is separated by scive 18 from roll 10 (now in a cooled condition) after exiting the nip between roll 10 and roll 12. Upon separation, support 16 bearing the fused image is transported by copy handling means to copy collection means such as a tray (not shown). The fused image is separated from the cooled surface of roll 10 at a temperature where no toner image offset occurs.

It is essential to this invention that the toner image fused in the inventive method comprises toner particles that exhibit a loss tangent of at least about 1.2, typically about 1.2 to 8.5 and often about 1.2 to 5.5. As discussed in U.S. Pat. No. 4,913,991, issued Apr. 3, 1990, loss tangent (tan .delta.) describes the rheological characteristics of a toner and is the ratio of the loss modulus (G") to the storage modulus (G'). This relationship can be described by the following equation: ##EQU1## This relationship is also discussed in Japanese laid-open Application Number 88/300,254, published Dec. 7, 1988.

The rheological characteristics of the toner particles from which such loss tangent can be determined can be measured using equipment known to those skilled in the art, for example, a rheometer. An example of a suitable rheometer is a Rheometrics Model RDA 700 (commercially available from Rheometrics Inc., Piscataway, N.J.) Another example is the Rheometrics Dynamic Spectrometer RDS-7700 made by Rheometrics, Inc., which is mentioned in the aforementioned U.S. Pat. No. 4,913,991 and Japanese laid-open application Number 88/300,254. The rheological characteristics of the toners used in the present invention were measured with a Rheometrics Model RDA using parallel plates in a sinusoidal shear mode. Measurements were made at temperatures ranging from 100.degree. to 250.degree. C. and at frequencies ranging from 0.1 to 100 rad./sec. The loss tangent values referred to in this specification and claim are determined for a storage modulus (G') of 10.sup.5 dynes/cm.sup.2 and, therefore, can be directly compared to the loss tangent values reported in U.S. Pat. No. 4,913,991 and Japanese laid-open Application Number 88/300,254.

The aforementioned loss tangents largely depend upon the toner binder polymer since it is the principle determinant of the viscoelastic properties of the toner particles used in the practice of this invention. As understood by those skilled in the art, and as illustrated by the following Examples, Japanese laid-open Application Number 88/300,254 and U.S. Pat. No. 4,913,991; the loss tangent of a given binder material depends upon several variables, including polymer architecture (chain-branching, crosslinking or lack thereof) molecular weight distribution, glass transition temperature and additives. Accordingly, the toner particles must be formulated with a binder polymer or combination of such polymers which meet the criteria needed to provide a desired loss tangent. Suitable toner binder materials having the low loss tangent values can comprise an additive which adjusts the loss tangent of a binder polymer to less than 1.2. Such additives can be used in concentrations up to 50 weight percent, of the toner binder material, and include vinyl addition and/or polycondensation polymers that are high molecular weight and optionally highly cross-linked. Such additive polymers frequently have T.sub.g values in the range of about 65.degree. to 125.degree. C. Polymeric beads, e.g. polymethylmethacrylate beads, are useful additives. A wide variety of binder polymer materials can be employed in the method of this invention, including vinyl addition polymers and condensation polymers. Such binder polymers are chosen for their loss tangent values as well as good combinations of advantageous properties, such as toughness, transparency, and adequate adhesion to supports. Vinyl addition polymers that are useful as binder polymers in the toner particles can be linear, branched or lightly cross-linked. The most widely used condensation polymers are polyesters which are polymers in which backbone recurring units are connected by ester linkages. Like the vinyl addition polymers, polyester useful as binder polymers in toner particles can be linear, branched or lightly cross-linked. They can be fashioned from any of many different monomers, typically by polycondensation of monomers containing two or more carboxylic acid groups (or derivatives thereof, such as anhydride or ester groups) with monomers containing two or more hydroxy groups. Specific examples of useful binder polymers include olefin homopolymers and copolymers, such as polyethylene, polypropylene, polyisobutylene, and polyisopentylene; polyfluoroolefins such as polytetrafluorethylene; polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam; acrylic resins, such as polymethylmethacrylate, polyacrylonitrile, polymethylacrylate, polyethylmethacrylate and styrene-methymethacrylate or ethylene-methyl acrylate copolymers, ethylene ethyl acrylate copolymers, ethylene-ethyl methacrylate copolymers, polystyrene and copolymers of styrene with unsaturated acrylic monomers of the type mentioned hereinbefore, cellulose derivatives, such as cellulose acetate, cellulose acetate butyrate, cellulose propionate, cellulose acetate propionate, and ethyl cellulose; polyvinyl resins such as polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate and polyvinyl butyral, polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl acetate copolymers, and ethylene-allyl copolymers such as ethylene-allyl alcohol copolymers, ethylene-allyl acetone copolymers, ethylene-allyl benzene copolymers ethylene-allyl ether copolymers, ethylene-acrylic copolymers and polyoxymethylene, polycondensation polymers, such as, polyesters, polyurethanes, polyamides and polycarbonates.

Binder materials that are useful in the toner particles used in the method of this invention typically are amorphous polymers having a glass transition temperature (Tg) in the range of about 45.degree. to 120.degree. C., and often about 50.degree. to 70.degree. C. Such polymers can be heat-fixed to smooth-surfaced film supports as well as to more conventional substrates, such as paper, without difficulty. Tg can be determined by any conventional method, e.g., differential scanning calorimetry (DSC).

Fusable toner particles used in this invention typically have fusing temperatures of less than about 200.degree. C., often less than about 100.degree. so they can be fused to paper sheets, even resin coated paper sheets without deformation (blistering) of the resin coating. Of course, if the toner images are fused to supports which can withstand higher temperatures, toner particles of higher fusing temperatures can be used.

Numerous colorant materials selected from dyestuffs or pigments can be employed in the toner particles used in the invention. Such materials serve to color the toner and/or render it more visible. Suitable toners can be prepared without the use of a colorant material where it is desired to have developed toner image of low optical densities. In those instances where it is desired to utilize a colorant, the colorants can, in principle, be selected from virtually any of the compounds mentioned in the Colour Index Volumes 1 and 2, Second Edition. Included among the vast number of useful colorants are those dyes and/or pigments that are typically employed as blue, green, red and yellow colorants used in electrostatographic toners to make color copies. Suitable colorants include those typically employed in primary substrative cyan, magenta and yellow colored toners. Examples of useful colorants are Hansa Yellow G (C.I. 11680) CI Yellow 12, CI Solvent Yellow 16, CI Disperse Yellow 33, Nigrosine Spirit soluble (C.I. 50415), Chromogen Black ETOO (C.I. 45170), Solvent Black 3 (C.I. 26150), Fuchsine N (C.I. 42510 ) C.I. Pigment Red 22, C.I. Solvent Red 19, C.I. Basic Blue 9 (C.I. 52015) and Pigment Blue 15. Carbon black also provides a useful colorant. The amount of colorant added may vary over a wide range, for example, from about 1 to 20 percent of the weight of binder polymer used in the toner particles. Good results are obtained when the amount is from about 1 to 10 percent.

To utilize a binder polymer in an electrostatographic toner, the polymer particles are mixed in any convenient manner with any other desired addenda, to form a free-flowing powder of toner particles containing the binder polymer. Useful toner particles can simply comprise the binder polymer but, it is often desirable to incorporate addenda such as waxes, release agents, change control agents, and other toner addenda well known in the art.

Charge control agents suitable for use in toners are disclosed for example in U.S. Pat. Nos. 3,893,935; 4,079,014; 4,323,634 and British Patent Nos. 1,501,065 and 1,420,839. Charge control agents are generally employed in small quantifies such as, about 0.1 to 3, weight percent, often about 0.2 to 1.5 weight percent, based on the weight of toner.

Toner images fused according to this invention can be formed from electrostatographic developers comprising toner particles that are mixed with a carrier vehicle. Carrier vehicles which can be used to form suitable developer compositions, can be selected from a variety of materials. Such materials include carrier core particles and core particles overcoated with a thin layer of film-forming resin. Examples of suitable resins are described in U.S. Pat. Nos. 3,547,822; 3,632,512; 3,795,618; 3,898,170; 4,545,060; 4,478,925; 4,076,857; and 3,970,571.

The carrier core particles can comprise conductive, non-conductive, magnetic, or non-magnetic materials. See, for example, U.S. Pat. Nos. 3,850,663 and 3,970,571. Especially useful in magnetic brush development schemes are iron particles such as porous iron particles having oxidized surfaces, steel particles, and other "hard" or "soft" ferromagnetic materials such as gamma ferric oxides or ferrites, such as ferrites of barium, strontium, lead, magnesium, or aluminum. See for example, U.S. Pat. Nos. 4,042,518; 4,478,925; and 4,546,060.

A typical developer composition containing toner particles and carrier vehicle generally comprises about 1 to 20 percent, by weight, of particulate toner particles and from 80 to 99 percent, by weight, carrier particles. Usually, the carrier particles are larger than the toner particles. Conventional carrier particles have a particle size on the order of about 20 to 1200 micrometers, generally about 30 to 300 micrometers. Alternatively, the toners can be used in a single component developer, i.e., with no carrier particles.

The toner and developer compositions described in the previous paragraphs can be used in a variety of ways to develop electrostatic charge latent images to provide the unfused electrostatographic toner images that can be fused by the method of this invention. Such developable charge latent images can be prepared by a number of means and be carried for example, on a light sensitive photoconductive element or a non-light-sensitive dielectric-surfaced element such as an insulator-coated conductive sheet. One suitable development technique involves cascading the developer composition across the electrostatic charge latent image, while another technique involves applying toner particles from a magnetic brush. This latter technique involves the use of a magnetically attractable carrier vehicle in forming the developer composition. After image-wise deposition of the toner particles to form an electrostatographic unfused toner image, the image can be fixed or fused by the method of this invention to the support carrying the toner image. If desired, the unfused toner image can be transferred to a support such as a blank sheet of copy paper and then fused thereon to form a permanent image.

Typical toner particles generally have an average particle size in the range of about 0.1 to 100 micrometers, a size of about 8 to 15 micrometers being particularly useful in the practice of this invention to form high resolution images.

In the method of this invention the toner image is brought into pressure contact with the surface of the fusing member in the fusing zone. The temperature applied to fuse the toner particles causes such particles to adhesively adhere to the support bearing the toner particles and to flow sufficiently to form a fused toner mass having a relatively smooth surface in which the toner particles substantially lose their particulate identity. Upon cooling in the cooling zone while in contact with the fusing member, the toner image retains the aforementioned surface characteristics and is separated in the release zone at a temperature where no toner image offset occurs. Typical temperatures used in the fusing zone are less than about 140.degree., generally in the range of about 100.degree. to 140.degree. C., often 105.degree. C. to 135.degree. C. and preferably 115.degree. C. to 130.degree. C. The pressure used in this invention in combination with the aforementioned fusing temperature to fuse the toner image includes those conventionally employed in contact fusing processes in the prior art. They typically are in the range of about 3 kg/cm.sup.2 to 15 kg/cm.sup.2, often about 10 kg/cm.sup.2.

The fusing member employed in the practice of this invention can be in any physical form suitable for applying heat in a face-to-face relationship with the toner image and maintaining such relationship through the cooling zone to the separation zone. Examples are the continuous belt 4 indicated in FIG. 1 and the roll 10 indicated in FIG. 2, although the fusing member can also be in the form of a plate. A continuous belt is preferred because temperature control is reasonably simple and a belt provides a straight, flat fusing path which reduces curl problems that can be introduced by a roll. The surface of the fusing member is generally smooth, although a textured surface can be used, provided the surface is not so rough that it reduces the overall gloss of the fused toner image to an undesirable level. When a continuous belt is employed, the belt must be reasonably flexible and heat resistant; it is preferably made with a material such as stainless steel or polyester which meet such criteria. The outer surface of the fusing member which contacts the unfused toner image can comprise any of the materials known in the prior art to be suitable for use in such fusing surfaces, including aluminum, steel, various alloys as well as polymeric materials such as thermoset resins. Fusing members with fluoroelastomer surfaces can improve the release characteristics of the fuser member. Also release agents, for example, polymeric release oils such as polydiorganosiloxane release oils can be used. However, such additional release agents are normally unnecessary in the practice of this invention because the toner images are cooled in the cooling zone to a level where they readily release from the fusing member without toner image offset i.e. there is no significant transfer of toner image to the surface of the fusing member. The toner image to be fused typically moves through the fusing zone at a velocity of at least about 2.5 cm/sec., normally about 2.5 to 10 cm/sec. The velocity is generally kept constant as the element bearing the toner image moves through the cooling and release zones.

In the cooling zone, cooling of the fused toner image is controlled so that it can be released at a temperature where no toner image offset occurs. The temperature of the fused image is generally reduced at least about 40.degree. C., often about 65.degree. to 90.degree. C. in the cooling zone. As previously indicated herein, cooling can conveniently be controlled simply by adjusting the velocity of the fusing member, for example, the velocity of a continuous belt or roll while cooling air is impinged upon the belt, or upon the element, as illustrated in FIGS. 1 and 2, although other cooling means such as a chill roll or plate could be used in place of air impingement. When a continuous belt is used as the fusing member, it usually is not necessary to press the element against the fusing member to maintain contact between the fusing member and the fused toner image because the image is heated in the fusing zone to a point where the fused image surface acts as an adhesive which temporarily bonds to the fusing member as the fused toner image moves through the cooling zone.

In the release zone the fused toner image is separated from the fusing member. Such release is not effected until the fusing member is cooled to a temperature where no toner image offset occurs. Such temperature is typically no more than about 75.degree. C. and is normally in the range of about 30.degree. to 60.degree. C. The specific temperature used to achieve such separation will vary considerably as it depends upon the flow properties of the toner particles having a loss tangent of at least 1.2. The release temperature chosen is such that toner image adheres to the support and exhibits sufficient cohesiveness such that it will not offset on the fuser member at the particular temperature used. Upon separation from the fusing member in the release zone, the fused toner image exhibits a degree of gloss that will vary considerably depending upon the specific processing conditions such as amount and duration of pressure and temperature and the vicoelastic characteristics of the toner particles used in the method of this invention. However, the gloss levels for fused toner images formed in this invention are typically at least 20 and often in the range of about 50 to 100. Such gloss levels are readily perceptible to the unaided eye but they can be measured by a specular glossmeter at 20.degree. using conventional techniques well known to those skilled in the art for this purpose for example, the method described in ASTM-523-67. A typical method utilizes a single reflectivity measurement, as of a type which measures the amount of light from a standard source which is specularly reflected in a defined path. A suitable device for this purpose is a Glossgard II 20.degree. glossmeter (available commercially from Pacific Scientific, Inc., Silver Springs, Md.) which produces a reading, on a standardized scale, of a specularly reflected ray of light having angles of incidence and reflection of 20.degree. to the normal. The standard scale of such meter has a range from 0 to 100, the instrument being normally calibrated or adjusted so that the upper limit corresponds to a surface that has substantially less than the complete specular reflection of a true mirror. Reflectivity readings are indicated as gloss numbers. As previously indicated herein, the method of this invention provides not only fused toner images having enhanced gloss, but it can also provide transparencies having colored toner images on transparent supports which images exhibit good color clarity. As known to those skilled in the art, color clarity can be defined as the ratio of specular to total transmitted light expressed in percent. Such color clarity can be conveniently determined by placing an image on a transparent support in an optical light path and separately measuring or reading the specular and totally transmitted light with a suitable device, e.g., a photometer.

Various conductive or nonconductive materials can be used as supports for the toner images fused in the method of this invention. Such supports are well known to those skilled in the art and include various metals such as aluminum and copper and metal-coated plastic films as well as organic polymeric films and various types of paper. Polyethylene terephthalate is an excellent transparent polymeric support for use in forming transparencies.

The following preparation and fusing techniques and examples are presented to further illustrate this invention.

In some of the preparations and examples polymer names contain an indication of the molar or weight ratios of the various units in the polymer, as specified. In some of the preparations and examples (as indicated therein), the relative concentrations of units are expressed as ratios or amounts of the monomers used to prepare the polymer.

Toner particles employed to form the toner images in the following examples were formulated from 100 parts binder polymer, 0-20 parts colorant, 0-20 parts addenda and 0-2 parts of charge agent for 100 parts binder polymer. The mixtures were melt-compounded at temperatures in the range of 110 to 150.degree. C. on a 2-roll rubber mill, the mass cooled to room temperature, and coarse ground and fluid energy-milled to produce toner particles having a particle size in the range of about 8 to 15 micrometers.

The toner particles were then mixed with carrier particles in a closed container on a 2-roll mill for 30 seconds to form a triboelectrically-charged 2-component dry electrostatographic developer comprising about 12 weight percent toner particles. The carrier particles employed were strontium ferrite particles coated with a thin poly(vinylidene fluoride) film.

The electrostatographic developer was used to develop a toner image on a bond paper support. Biased development was carried out in an electrophotographic copying apparatus having an organic photoconductor film, a magnetic brush developing station and a biased roll transfer station for transferring the toner image from the photoconductor film to the bond paper support. The toner image was a half-tone screen toner image of toner particles having a loss tangent of 1.2 or more.

The toner image was fused using a fusing device of the type illustrated in FIG. 1 in which the fusing member was a continuous highly polished smooth steel belt. The fusing conditions used were as follows:

The fusing method of this invention is effective to provide toner images exhibiting desirable gloss characteristics. To illustrate, a developer composition comprising the following toner was prepared as described previously in the Developer Formulation, Imaging and Fusing section.

Toner particles were formulated from 100 parts of a binder polymer comprising a branched polyester of terephthalic acid, glutaric acid, propanediol and glycerol (87/13/95/5 molar ratios) having an inherent viscosity of 0.4 dl/g in dichloromethane, and a T.sub.g of 62.degree. C. a weight-average molecular weight of 70,000 and a M.sub.n of 10,000,6 parts of a cyan colorant and 1 part of a quaternary ammonium charge agent. The pulverized toner particles were classified to provide cyan toner particles having a loss tangent of 2.1 determined for a storage modulus, G', of 10.sup.5 dynes/cm.sup.2 (G' of 2.01.times.10.sup.3 dynes/cm.sup.2, G" of 1.05.times.10.sup.4 dynes/cm.sup.2 and a melt viscosity of 1.07.times.10.sup.4 poise measured at a temperature of 150.degree. C. and 1 rad/sec.) all measured using a Rheometrics Model RDA 700 rheometer, commercially available from Rheometrics Inc., Piscataway, N.J., using parallel plates in a sinusoidal shear mode. This toner was used to develop a half-tone screen image as described in the Developer Formulation, Imaging and Fusing section.

The gloss of the fused half-tone screen toner image was determined using a MICRO TRI glossmeter (commercially available from Byk Gardner Inc., Silver Springs, Md.) at an angle of 20.degree.. The average gloss for 5 readings on the image was determined to be 65.

As previously indicated herein, the fusing method of this invention is useful for forming transparent image-recording materials exhibiting excellent color clarity upon projection. To illustrate this feature of the invention, this Example 1 was repeated except that the unfused toner image was developed on a transparent poly(ethylene) terphthalate film 101.6 micrometers thick, coated with a subbing layer comprising a terpolymer of acrylonitrile, vinylidene chloride and acrylic acid. Upon projection in an overhead projector the fused cyan half-tone screen image showed high color density and saturation comparable to the original image. The color clarity for the image, determined as described previously herein was approximately 90 percent.

The procedure of Example 1 was repeated except that a toner prepared as follows was used in place of the toner described in Example 1. Toner particles were formulated from 100 parts of a binder polymer comprising poly(styrene-co-n-butylacrylate)[80/20 weight percent] crosslinked with 1.3 parts per hundred divinylbenzene, having a T.sub.g of 65.degree. C. and a weight-average molecular weight (M.sub.w) of 410,000, and a number average molecular weight (M.sub.n) of 10,000, 6 parts of a black colorant and 1 part of a quaternary ammonium charge agent. The pulverized toner particles were classified to provide black toner particles having a particle size of 6-8 micrometers and a loss tangent of 1.2 determined for a storage modulus, G', of 10.sup.5 dynes/cm.sup.2 (G' of 4.98.times.10.sup.3 dynes/cm.sup.2 G" of 1.01.times.10.sup.4 dynes/cm.sup.2 and melt viscosity of 1.12.times.10.sup.4 poise measured at a temperature of 150.degree. C. and 1 rad/sec.) measured as described in Example 1. This toner was used to develop the half-tone screen image, as described in Example 1. The gloss of the fused image, determined as in Example 1, was 20.

The procedure of Example 1 was repeated except that a toner prepared as follows was used in place of the toner described therein. Toner particles were formulated from 100 parts of a binder polymer comprising poly(styrene-co-n-butylacrylate)[80/20 weight percent] having a T.sub.g of 68.degree. C. a weight-average molecular weight (M.sub.w) of 47,000 and a number-average molecular weight (M.sub.n) of 23,000, 8 parts of a blue colorant and 1 part of a quaternary ammonium charge agent. The pulverized toner particles were classified to provide blue toner particles having a particle size of 7-9 micrometers and a loss tangent of 2.6 determined for a storage modulus, G', of 10.sup.5 dynes/cm.sup.2 (G' of 5.84.times.10.sup.1 dynes/cm.sup.2 G" of 1.86.times.10.sup.3 dynes/cm.sup.2 and melt viscosity of 1.86.times.10.sup.3 poise measured at a temperature of 150.degree. C. and 1 rad/sec.) measured as described in Example 1. This toner was used to develop the half-tone screen image, as described in Example 1. The gloss of the fused image, determined as in Example 1, was 70.

Toner particles prepared according to the procedure of this Example from the following high loss tangent binder polymers provide similar high levels of gloss;

(1) Poly(styrene-co-n-butylacrylate) [80/20 weight percent] having a T.sub.g of 68.degree. C., a weight-average molecular weight (M.sub.w) of 23,000, a number-average molecular weight (M.sub.n) of 12,000 and a loss tangent of 3.2 determined for a storage modulus, G', of 10 dynes/cm.sup.2 (G' of 2.46.times.10.degree. dynes/cm.sup.2, G" of 4.651.times.10.sup.2 dynes/cm.sup.2 and melt viscosity of 4.651.times.10.sup.2 poise measured at a temperature of 150.degree. C. and 1 rad/sec.) measured as described in Example 1.

(2) Polystyrene having a T.sub.g of 59.degree. C., a weight-average molecular weight (M.sub.w) of 9,000, a number-average molecular weight (M.sub.n) of 2,500 and a loss tangent of 5.4 determined for a storage modulus, G', of 10 dynes/cm.sup.2 (G" of 4.061.times.10 dynes/cm.sup.2, G" of 3.356.times.10.sup.1 dynes/cm.sup.2 and melt viscosity of 3.381.times.10.sup.1 poise measured at a temperature of 150.degree. C. and 1 rad/sec.) measured as described in Example 1.

(3) Polystyrene having a T.sub.g of 68.degree. L C., a weight-average molecular weight (M.sub.w) of 4,400 a number-average molecular weight (M.sub.n) of 1,700 and a loss tangent of 8.0 determined for a storage modulus, G', of 10.sup.5 dynes/cm.sup.2 (G' of 8.6.times.10.sup.-1 dynes/cm.sup.2, G" of 2.71.times.10.sup.2 dynes/cm.sup.2 and melt viscosity of 2.71.times.10.sup.2 poise measured at a temperature of 150.degree. C. and 1 rad/sec.) measured as described in Example 1.

It is evident from the foregoing specification, and particularly the Examples, that the fusing method of this invention makes it possible to obtain toner images exhibiting very desirable levels of gloss from toner particles having widely varying viscoelastic properties, as evidenced by the wide range of loss tangent values that such particles exhibit upon fusing by the combined action of heat and pressure. It is also evident that color transparencies that faithfully reproduce the color of an original image can be prepared using the fusing method of this invention.

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it should be appreciated that variations and modification can be effected within the spirit and scope of the invention.