CA1136915A - Toner containing a thermoadhesive agent, pigment and an intumescing agent - Google Patents

Abstract

ABSTRACT OF THE INVENTION
The subject invention pertains to a dry transfer imaging technique comprising electrophotographic deposition of an image onto the rear side of a carrier sheet, said carrier sheet being further characterized by being abhesive to the image deposited thereupon; contacting said image-bearing rear side of said carrier sheet with an exterior surface and applying pressure to the front side of said carrier sheet, whereby transfer of said image to said exterior surface is effectuated.
The carrier sheets which are abhesive to the deposited image form a part of the invention. In addition, novel colorless toners have been developed which, when deposited upon the image-bearing carrier sheet, enhance the adherability of said image to the exterior surface.

Description

113~
`~`
The present invention l~ertains to a method, product and appara-tus for forming an electrophotographic image on a suitable carrier sheet, said sheet forming a novel portion of the invention, and transferring said image, thereafter, to a desired surface where it adheres thereto.
This application, being a division of application Serial Number 303,293 filed May 15, 1978, is directed to a toner composition for use in the invention which is disclosed below in its entirety.
There ls disclosed in the prior art (United States 3,013,917) a method for producin~ dry transfer of lettering, symbols, indicia, emblems and the like from a substrate sheet to a receptor sheet, by contacting the substrate sheet containing various print, rear side down, with the receptor sheet, and rubbing the substrate sheee, thereby releasing the lettering etc., and transferring the same to the receptor sheet. The substrate sheet may comprise translucent paper, onion skin, films, paper, cellulose acetate and the like. The characters or designs are printed on the rear surface of the sheet, in reverse position as viewed from the rear of the sheet. The rear surface is treated with a release coating to facilitate transfer of the lettering upon application of pressure to the front surface. The patent limits the method by which the ink is applied to the release coated rear surface of the substrate sheet (dry transfer sheet) to: (1) printing in a flat or rotary press; (2) application with a printing brush; or (3) printing with the aid of a silk screen stencil.
The above process has proved to be inadequate in several respects. The process requires huge inventories of typeface because of the many different typefaces which may be required. There are approximately 22,000 different type fonts, not taking into consideration the eight to ten sizes available in each type font, resulting in enor~ous dealer inventories.

~. ' 113~gl5 The majority of dry transfer sheets are now manufactured by the silk-screen method of reproduction which directly encompasses the above problem of large inventories to the dealers. In addition, it has been found that the quality of print which becomes ultimately adhered to the receptor sheet, I-as been ` ~3~3L5 inadequate. Ill addition, the time regllired to produce the transfer sl~eets has proven to be rather e~tended.
The hi~h cost associated with the above process had led to a need for a dry transfer technique of lower cost and greater overall qu~lity and efficiency, allowing the consumer the flexibility of making hls own transfer as needed.
In accordance with the present invention, there is provided a method, procluct, and apparatus for forming an electrophotographic image on a carrier sheet, said carrier sheet possessing front and rear surfaces, said image being deposited on one of the surfaces of said carrier sheet. The carrier sheet composition provides a novel part of this invention. Said imagc pre-ferably possesses a discernible thickness and, accordingly~, upper and lower surfaces, and is further characterized by having pressure-sensitive qualities at least on the upper surface, so that when the image bearing side of the sheet is brought into contact with a desired surface and pressure is applied to the other side of the carrier sheet, such as by rubbing, a substantially complete transfer of said image from the carrier sheet to the desired surface results.
The image, when viewed from the rear of the sheet, is in reverse position and, as viewed from the front of the sheet, is in normal reading position. The present invention overcomes the disadvantages associated with dry transfer systems taught in the prior art and provides an efficient and relatively low-cost method and apparatus for accomplishing the transfer of the heretofore mentioned images from one surface to another without the necessity for main-taining extensive inventories of typeface, symbols, logos, trademarks and other indicia. In addition, the invention contemplates the consumer purchasing blank carrier sheets and provides him with the flexibility of providing whatever characters he desires to place on the surface of the carrier sheet, whenever he requires the same.

- ~13~9~

The gist of the instan~ invention relates to a dry transfer technique and co~prises the electrophotographic deposition of an image onto a suitable carrier sheet possessing front and rear sides, the said image being deposited on ehe rear side of said carrier sheet, said image possessing pressure sensitive qualities, so that upon bringing at least a portion of the image-bearing rear side of the carrier sheet into contact with a desired surface and, thereupon, applying pressure to the non-image bearing front side of the carrier sheet, a transfer of the image from the carrier sheet to the desired surface is effectuated.
The image deposition referred to hereinabove may be accomplished by any suitable electroptlotographic technique, such as, for example, by the well-known xerographic method, as fully described in United States 2,297,691 and by the so-called electrofax method as more fully described in United States Patents 2,862,815; 2,979,402 and 2,990,279. See generally, Schaffert, Electro-photography (1965).
In a preferred embodiment of the invention to be described in detail hereinbelow, the image is deposited by means of xerographic techniques as descrlbed in United States 2,297,691 to Carlson. Thus, such techniques comprise forming an electrostatic image on a carrier sheet corresponding to information to be recorded and forming a pattern of a xerographic toner on said carrier sheet, corresponding to said electrostatic image.
The efficiency with which the image transfer may be-accomplished in this embodiment is related, in part, to the nature of the carrier sheet;
the composition of the toner whictl is utilized to produce the image; and the thickness of the image produced on the carrier sheet.
The carrier sheets are characterized by possessing abhesive qualities vis-a-vis the image produced thereuron. Accordingly, and in contra-distinction to the generally desired goals in xerographic and electrofax 113~91~
. ~
printing, L~ wit, irremova~le adhesion of the image to the substrate, there is now generated, by virtue of the process o~ this invention, an image which, by virtue of its composition in conjunction with the unique nature of the carrier sheet, itself, is removable from its substrate, i.e. the carrier sheet.
The unique properties of the carrier sheet may, in one embodi-ment of the invention, be obtained by coating a substrate surface Witll an abhesive coating, i.e. coating which is abhesive towards tlle xerographic toner deposited thereon, by any suitable method, such as, for example, by the well-known process of xerograplly, as more fully described in U.S. Pat. No. 2,297,691.
The abhesive or releasing coating may comprise any suitable material or comblnatioll o materials which impart the desired abhesive qualities to the carrier sheet. The coating, in one embodiment of the invention, may comprise one or more (in combination) of the following materials:
a. Fatty acids, such as Stearic acid, Oleic acid, Coconut oil fatty acids, mixed-Castor oil fatty acids, ricinoleic acid, Azelaic acid, Suberic Acid, pellargonic acid.
b. Fatty alcohols, such as Oleyl alcohol, myristyl alcohol.
c. Fatty acid esters, notably polyvinyl stearate.
d. ~letathenic soaps of fatty acids; calcium stearate, barium laurate, Barium-cadmium soap of Lanolin fatty acids.
e. ~letallic complexes of fatty acids, such as sodium stearate, potassium oleate, Sterato-chromic Chloride (~uilon~ made by DuPont) (Chrome Complex).
f. Organic complexes of Silicon such as poly alkyl siloxanes such as G.E. 2054 mixed with 2055C catalyst made by the Ceneral Electric Company, Schenectady~New York, "Silicone" emulsions, solutions and waxes as sold by *

Dow-Corning.

g. Hydrocarbon waxes.
*

Trademark ~136~15 ~ .
Il ve~table based waxes such as hydrogenate~ castor oil.
i. Glycols and polyglycols such as "Carbowax" (Union Carbide Corp.) and polyethylene-glycol-Laurate.
j. Synthetic slip-agents such as the halo carbons and fluoro-carbons, their polymers and co-polymers. As to the mode of applicatioll or incorporation of the release agents (abhesive agents) to the substrate, any convenient mode of application may be used, including, saturation and surface coatlng.
In another embodiment of the invention, a substrate may be selected which is` inherently abhesive, (sui generis), towards the deposited toner image, such as, for example, polyethylene, polypropylene, polyamides, polyfluoro-carbons, proteinaceous films, polyvinyl alcoholj regenerated cellulose films, any pellucid material, and the like.
The substrate which comprises the carrier sheet may consist of any suitable surface which may be utilized in the xerographic process and includes:
1. Fibrous sheets of natural fibers such as cellulose, silk, hemp, abaca or synthetic fibers such as nylon, dacron acrylic polymers, glass.

2. Woven and non-woven fabrics preferably somewhat trans-parentized by coating or saturating with a film - former having a refractive index close to the refractive index of the fabric being transparentized.
Generally polystyrene resin or a thermoplastic acrylic polymer such as a methyl-methacrylate or a butyl methacrylate polymer.

3. Non-fibrous sheets such as vellum, parchment, "synthetic paper" (reputedly a clear or translucent plastic fllm) as witness the "synthetic paper" sold by the Union Carbide Corp., New York City, New York.
The image which is deposited upon the carrier is the product of the well-known process of Carlson United States Patent 2,297,691. The general *Trademark _ 5 _ - - , -i~" 113~i915 thickness of the ima~e will range from 0.00001 to 0.00015 inches, preferably from 0.00002S to 0.005 inches and most preferably will be thicker than 0.0005 inches, i.e., a raised xerographic image having tllickness and body with co-hesiveness simulating the image deposited by a silk-screen process.
Generally, the thicker the image, the more facile the transfer.
In the broadest embodiment of the invention, as it applics to the xerographic method, any convcntional toncr composition may bc utilized such as that presently available in xerograyhy, including, e.g. the Xerox toner made by the Xerox Corp., Roches~er, New York espccially Toner 660, Toner 813, Toner 914, Toner 2400, Toner 3600-3, Color Toners I.B.M. Toner for Copier 2:
~lunt Chemical Company, Palisades Park, New Jersey Toners for various copiers:
Imaging Systems, Inc., Latrobe, Pennsylvania Nashua Corp., Nashua, New Hampshire Van Dyck Research, Whippany, New Jersey Eastman Kodak Inc., Rochester, New York Dennison Mfg. Co., Framingham, Massachusetts A. B. Dick Inc., Chicago, Illinois The nature of the specific toner is dependent upon, in part, the particular model and make of xerographic machine utilized. llowever, the thickness of image obtained with conventional toner will only range between 0.00001 and 0.00005 inches depending on the substrate. It is preferable, when using such con-ventional toner, to enhance the thickness of the image by any suitable mcans such as by repeated copying onto the same image from the same subject matter.
This method of multiple copying to densify the image is taught in United States 2,955,935 to Walkup, Trademark r^;` 1136915 In a l~ss pre~erred eml!odiment of tlle invention, t1~e need for multiple pass-through usin~ conventional toner may be obviated by incomplete fusion and thermoadhesion by varying the 1-eat settings in the copiers so that less heat is available for the fusion of image to substrate. Accordingly, the releasability of tl1e image is enhanced, thereby eliminating the need for thick imaging, as for exa~ple, by tl-e Walkup technique, supra.
In anot}1er embodiment of the invention, a toner composition has been developed which achieves the desired density and thickness paramaters for facile transfer of image from the carrier sheet of this invention to the receptor surface. The toner composition and method for its formation are set forth in United States 3,924,019 and United Statcs 3,945,934, to Jacob.
In essence, the toner composition comprises a stable, dry, free~flowing sel~-contained intumescent electroscopic powder mixture including a Lher1noadhesive agent, a pigment and a dry lntumescing agent being comprised of plastic microspheres containing occluded gas there within at ambient temperatures and being expandible in size upon being subjected to elevated temperature. This e~cpandibility concept has been referred to as "raised xerographic printing".
The above Loner preparation comprises the steps of (a) producing an electrostatlc latent image on a xerographic member, (b) contacting said member with a dry, free-flowing, self-contained intumescent electroscopic toner mixture to develop said electrostatic latent image, (c) transferring tl1e dis-tributed toner from said member to a transfer surface and (cl) sub~ecting said transferred toner to heat sufficient to cause intumescence thereof and thereby provide a raised image on said surface.
As alrcady noted, supra, the image which is formed on the carrier sheet possesses pressure-sensitive, adherable properties, at least on its top or upper surface, i.e., the surface which is not in contact with the 1~3t~91S

carrier sheet, thereby enhancirlg the alllerability of said image to an exterior or desired surface (recept~r surface) brought into contact wlth said image.
The pressure-sensitive property, referred to supra, may be obtained in any suitable and convenient manner such as by: post-coating of the image after it is formed on the carrier slleet; utilizing a novel toner composition to form an image possessing the desired pressure-sensitive qualities; or admixing aerosol and/or po~der cloud toners, as described in Schaffert, Electrophotography (1965) at pp. 157, 307-309, 362, 373, 378, with the novel pressure-sensitive composi-tions of this invention. Tlle above techniques are more fully detailed in the exampLes set forth llereinbelow.
The post-coating of tllc image may bc o~tained in any suitable manner such as by applying the adhesive coating to the image alone or to the entire image-bearing surface of the carrier sheet, the adhesive coating com-prising, in one embodiment of the invention, a wax in combination with a tackifying resin, preferably in liquid suspension. The liquid is a solvent or an emulsifying liquid plus bridging solvent. The liquid must not be a solvent for the thermoadhesive material contained in the toner, otherwise the image will be dissolved or attacked, thereby losing its integrity. Thus, for example, *

tackifying resin can be shellac, and the wax can be "Carbowax" (Union Carbide Corp., New York City, New York). The shellac and the "Carbowax" are dissolved in denatured alcohol. The denatured alcohol, used as solvent, will not attack most xerographic images and is very suitable for making up a tackifying solution.
The post-coating of the image may be achieved non-xerographically, i.e. outside of the photography machine, by any suitable application teclmique known in the art.
The coating may also be applied, xerographically, over the entire image and carrier sheet, utilizing the novel compositions of this invention, by xerographically copying an overall black pattern onto the image-*T~

~ 113~91S

bearing surface of Lhe carrier shcet. This serves to distribu~e tlle pressure-sensitive adherable coating uniformly over the entire surfàce of the carrier sheet. In anotller embodiment, tlle coatin~ may be applied only to the visible and palpable xerographically produced image (and not to the sheet itself) by using the same master sheeL from which the image was first produced (using the conventional colored toner). In yet another embodiment, the master sheet will comprise the same image configuration as that on the carrier sheet but will be slightly larger in area than the image on which it will be superimposed. This insures substantially complete coverage of the image with the clear adhesive coating, wllich, in tllrn, facll.ltates substantially complete adllesion of the imagc to a receptor surface brougllt into contact with said image. In thesc embodlments, two "toner" depositlons are required, one, with conventional toner, to produce the visible image upon the carrier sheet, and the second, with the novel compositions of this invention, to produce the pressure-sensitive coating.
The adhesive composition which is applied xerograyhically includes most theremoadhesive unpigmented particulate matter having a melting point below 300 degrees F.. They may consist of waxes and/or polyethylene in micronized form such as "Polymekon" and "Mekon" sold by l~estern Petrochemical Inc., Chanute, Kansas, various polyethylenes, polypropylenes, and Fischer-Tropsch waxes.
While it is preferred that the adhesive composition be liquid, it may, alternatively, be applied in a powder form which, upon application of lleat, fuses into an adllerent film. ~s above in the case of the liquid adhesive, the powder may be applied eitller xerograpllically or non-xero~raphically. Thcsc powders are generally referred to as thermoadhesive substances.
In another embodiment of the invention, the necessity for passing the carrier sheet tllrough the xerographic copier twice may be avoided by use of the novel toners of this invention, which are adhesive "sui generis".

* Trademar~
_ g _ ~13~i~15 "
By way of background, ~ IIC conventional toner compositiolls comprise relatively high-melting thermoadhesive resins which generally exhibit melting points of around 248 F.. Tlle resins or resin blends contain a pigment, such as carbon black, to generate a visible image on the image-recciving surface.
Carlson's toner (United States 2,297,691) was powdered asphaltum. Modern toners comprise natural or synthetic thermoplastic resins, such as wood rosin, its esters and derivatives, polyterpenes, cumarone-indene resins, styrene polymers and co-polymers, acrylic resins and the like. Thcy are all thermoplastics.
See, for example, Scl~affcrt, E1ectroplloto~raplly at pp. 46-48.
Thc modified toncrs wllicll arc uscd in this embodiment of the invention possess lower mclting points, relative to the convelltional toners>
and are generally tacky at room temperature. These modified toners have in-herent adherability. I~len farmed into an image on a suitable carrier slleet, said image acquires an adherable upper surface.
In general, the modified toners comprise free-flowing conventional toners with additives that lower their melting points. A typical conventional toner may be made as follows:
CONVENTION~L TONER: (PART ~) Low ~I.P. Polystyrene Resin "PS3"
Dow Chemical Co., Midland, Michigan 100 grams Carbon Black, Monarch #71 from Cabot Corp., 125 High Street, Boston, Massachusetts, 02110 1I grams Processing aids, free-flowing agcnts, depolari~ers, and the likc (generally in the trade secret category)4 grams To make the adhesive toner a small amount of plasticizer is added, as follows:
~DHESION PROMOTING ~DDITIVES: (PART B) B.l Butyl Ben~yl Phthalate B.2 Paraffinic Oil Sunpar 110*
Sun Oil Co., Philadelphia, Pennsylvanla * Trademark 13691~
, ~
B.3 Solid Plasl.iclzer Camphor B.4 Solid Plasticizer Di-cyclohexyl Phthalate B.5 Solid Plasticizer *
"Santolite" ~IPor i-H
Monsanto Chemical Co., St. Louis, Missouri Generally lesser amounts of liquid plasticizers are needed to acilieve the same plasticizing efficiency of higher amounts of solid plasticlzers. The following ratios are preferred:
~DHESIVE TONI:R NO.
Conventiollal Toner, Part A100 grams B.1 from Part B 2 grams ADHESIVE TONER NO. 2 Conventional Toner Part A100 grams B.2 from Part B 5 grams ADHESIVE TONER NO. 3 Conventional Toner Part A100 grarns - B.3 from Part B 12 grams ADHESIVE TONER NO. 4 Conventional Toner Part A100 grams B.4 from Part B 30 parts ADHESIVE TONER NO. 5 Conventional Toner Part A100 grams B.5 from Part B 50 grams The addition of Part B to Part A may be accomplished in any convenient manner, of which two methods are preferred:

* Trademark . . .. . . .
-- . .. . . ~ . . . .. . . , .. . . . ..... .. . . ... _ . . .. .

'' ~i` 113~glS

First Method: ~leIt ,Ind mix illtO thc ~ omposition of Part A prior to cooling and pulverizing, tllus creating a plasti-cizer containing toner of homogeneous particles, each particle of the same chemical composition Second Method: Physically blend Part B with Part A particles thus producing a two-component blend. Homogeniety will be achieved late- on after the image has been formed zerographically and heated in the normal operation oE the zerographic copier, said heating serving to melt the two components by flowing them together in the molten condition.
It must be recogni~ed that the lower the melting point of toner, the more difficult it is to deposit xerographically due to poor flowability properties and a tendency to pack down.
Accordingly, as another feature of this invention, the novel toners are preferably refrigerated in a special developer housing maintained within the photocopy machine. The housing is designed to maintain the tacky toner at a temperature which is low enough to permit substantial flowability of said toner.
In another embodiment of the invention, the toner may be refrigerated outside of the photocopier and then, immediately before use, inserted into the developer housing of the photocopier.
In an effort to alleviate tlle necessity of refrigerating the toner,`the invention also perceives the use of a composite two component toner which is not tacky ae room temperature but becomes tackifiable at elevated temperatures, such as experienced during the fusion of the toner onto the carrier sheet. The composite comprises conventional toner and a paraffin wax emulsion which is intimately incorporated into the toner, presumably as a . .

'`'''"~ ll~glS
~r-discrete coating on the individual toner particlcs. This incorporation may be achieved in any convenient manner including spraying the emulsion into the tonerin a suitable blending container then drying to a free-flowing state. ~or the dry free-flowing xerographic toners mixing is carried out dry or moist with a non-solvPnt m~nstruum which has negligible solvent action on the toner. For Electrofax toners, which are liquids containing particulate material and solvents, the ~ixing is effected in the solvent, which is generally an iso-paraffinic liquid. The isoparaffinic liquid has negligible solvent action on most of the adhesive additives. In the present invention, Fischer-Tropsch Waxes, * *
Stcarone and Laurone (Argus Che~ xooklyn, New Yor~k) Micronized polyethylene, foammable microspheres of Jacob U.S. Pat. 3924019 an~ Jacob U.S. Pat. 3945934, all can practically an~ satisfactorily be u~ed in the solvents of i~opara~finic liquid toners.
The waxed toner particles are then used as the toner in a con-ventional photocopier, without the necessity of refrigeration. ~lile the exact mechanism is not known, it is speculated that the waxy coating liquifies during the fusion operation and forms a coating on the deposited image which is characterized by being adhesive to an exterior or receptor surface brought in contact therewith.
In a further embodiment of the instant invention, a unique xerographic toner has been prepared in part by the process of Jacob as it is taught in U.S. Pat. 3,~24,Q19. The starting composition c~mprises the foammable microspheres taught by Jacob in combination with conventional toner yielding an intumescent toner. Low melting, free-flowing, powdered waxy material is combined with this composition.
Prior to fusion, it is speculated that the toner and foammable microspheres are enveloped in the wax. ~fter fusion, at least a portion of the foammable microspheres have "exploded" or otherwise expanded in volume.
* Trademark .- ~

f~ 3~915 .~.
The composition so fo~ed is then used as toner in a conventional photocopier. A more detailed discussion of the novel features of this toner composition is set forth in the examples appearing hereinbelow. Suffice-it-to-say, the resulting image on the carrier slleet is raised and of appreciable thickness and densification. In addition, the image shows a substantial affinity for an exterior surface when the latter is brought into contact with said image and pressure is applied to the non-image bearing side of the carrier sheet.
Other novcl asyects of the invention are more fully understood in tllc context of the cxamples sct forth hereinbelow.
~s ind1cated above, the novel features of the invention encompass any electrophotographic image-producing process including the electrofax process.
This process provides a photoconductive layer consisting of zinc oxide pigment in a resin binder, bonded to a paper backing. This medium serves both as the photosensitive surface and as the finished print after development and fixing.
Thus, the combination of photo-conductor and paper become a consumable item, as contrasted with the "xerox" process in which the photoconductive layer, usually amorphous selenium, is a reusable item and a replaceable component of the copy-ing machine. See, ~nerally, Schaffert, Electrophotography (1965) at 18.
In the instant invention, a novel photoconductor is prepared comprising, preferably, a binder and photoconductive particles such as zinc oxide (or non-particulate photoconductors such as solutions, suspensions and emulsions).
The conventional binder resin is now made novel by imparting ablleslve qualities to it, so that the electrofax photocon~uctor will itself have abhesive qualities.
Removal of the dry image ls impossible from a conventional electrofax copy for the purpose of making a dry transfer. When such an image is removed, it takes with it the white zinc oxide coating into which it has been firmly embedded. A removable and transferrable electrofax image was never ` ~ ~13~15 desired nor invented. ~ccordi1lg to the present inventioll, a separator stratum is interposed between the photoconductor and the deposited image. The separator layer must not be soluble in the liquid toner. Thus, most liquid toners contain isoparaffins as the solvent. The isoparaffins will not attack or dissolve a separator layer consisting of an abhesive substance such as Stearone or Laurone (Argus Chemlcal Co., ~rooklyn, New York) Syloff (Dow Chemical, Midland Michigan) or Calcium Stearate. Accordingly, an electrofax conductor is pre-pared for the instant novel purpose of dry-transfer by coating tllereon a thin layer of Stearone, Laurone, Syloff , Calcium Stearate or the like. The photo-conductor is then uscd in the conventional manner to iecelve an electrophoto-graphic image. This image will now be removable. In order for the image to be transferrable by dry-transfer, the image forming particles are made by combining a thermoadhesive resin with the pigment. Conventionally, the pigment is sub-stantially pure carbon black which is not thermoadhesive. Accordingly, a powdered wax is admixed with the pigment-containing liquid toner as follows:
Liquid Toner 100 grams Powdered Po*lyethylene Microthene (U.S.I., New York City New York) 1/2 gram The quantity may be varied to secure any desired adherability. Instead of powdered polyethylene, other powdered thermoadhesives may be used, and the quality of adherability will thusly be varied. Unlike the requirements of Xerography for a relatively high melting powdered adhesive, we can use lower M.P. powdered adhesives for the wet toners. Thus, powdered fatty acids as low as C12 fatty acid can be used. The use of lower m.p. adhesives will permit adherability of the transferred image with less rubbing and less burnishing pressure. Alternatively and preferably, the pigmentary substance in the liquid toner could be a single component pigment, consisting of a pigmented thermo~
adhesive substance. Pigmented polyethylene made according to Lerman, et al.
*Trademark . ~

~ ~ 113f~9~5 United States Patent 3,5~6,G54 is pr~ferred.
The carrier sheets of the instant invention have also found utility in other processes relating to the dry transfer field. ~t present, the consumer (user) must purchase his/her type, symbols, logos, etc. from their particular source of supply, mainly art material stores. These stores are now overloaded with type inventory (dry transfer sheets). There are 24,000 different typefaces in approximately 16 si~.es for each typeface. The standard typefaccs such as th~ helveticas, caslons, romans, commcrcial scripts, old english, etc.
are probably the largest selling ltcm ln a dcaler's store. ~any,times, a con-sumer runs out of a particular lctter and must thereby purchase more transfer sheets, and in many instances, the dealer has to wait until his stock is re-plenished to supply his accounts, meaning that the dealer `cannot order too many of any one kind otllerwise he would be stocked to the ceiling.
To take care of the above problem, chemically treated trans-parent sheets are provided. These sheets initially are similar to the carrier sheets referred to hereinabove. These sheets may be pellucid films or p~per.
The sheets are chemically treated with a non-photographic coating, such as a resin coating and may be pigmented. A master sheet is placed into close proximity of the carrier sheet in a contact or volume frame. The master sheet comprises a fllm positive consisting of typefaces, logos, symbols and the like.
The master sheet and carrier sheet are then irradiated by a suitable source of energy which may comprise light (ultra violet, fluorescent); laser energy;
x-ray and the like. The irradiation activates those chcmically-treated areas of the carrier sheet which are not covered by the image appearing on thc master slleet, resulting in a chemical or physical change in the exposed areas of tlle contact sheet. The unexposed areas (those areas covered by the master sheet image) remain unchanged and, accordingly, become an identical copy of the master sheet image. The non-photographic coating preferable includes an adhesive ` ~ 113~91S

component so ~llat the form~d image 011 ~he carrier sheet is adhesive at least on its upper surface. In addition, the untreated carrier sheet is abhesive to the formed image so that, upon contacting the exposed carrier sl~cet with a desired surface, image down, and rubbing or burnishing the opposite side of the carrier sheet, a substantially complete transfer of the image to the desired surface takes place. Thus, the image-bearing carrier sheets formed by this technique, are substantially the same as those prepared by the electrophotographic process already defined.
The preferred embodiment is set forth in the following example:
EX~MPLE 1 An image was produced xerographically in SUCIl a way as to have very poor attachment to the substrate. Because of this poor attachment the image could be removed and transferred to a surface which was placed in contact with such image. Removal and transferrence was effected by vlgorous rubbing, in the manner used in the dry-transfer lettering art. Dry transfer lettering is taught in United States 2,501,495; 2,588,367; 2,611,313; 2,626,226; 2,777,781 and 3,013,917. Poor attaclmlent to the substrate was achieved by coating the substrate with an abhesive coating, i.e. a coating which would be abhesive towards the xerographic toner which was deposited thereon by the well-known process of Xerography. The process of Xerography is described in Carlson, United States 2,297,691. The abhesive coating consisted of: (either one or more in co~bination) a. Fatty acids, such as Stearic acid, Oleic acid, Coconut oil fatty acids, mixed Castor oil fatty acids, ricinoleic; Azelaic acid, suberic Acid, pellargonic acid.
b. Fatty alcohols, Oleyl alcohol, myristyl alcohol, cetyl alcohol.
c. Fatty acid esters, notably polyvinyl Stearate.

13~915 d. Metatllenic soaps ol fatty acids; calcium stearate barium laurate> Barium-cadmium soap of Lanolin fatty acids.

e. Metallic complexes of fatty acids, such as sodiùm stearate, potassium oleate, Sterato-chromic Chloride ("Quilon'l made by DuPont?.
f. Organic complexes of Silicon such as poly alkyl siloxanes;
e.g. C.~. 2054 mixed with 2055C catalyst; "Silicone" emulsions, solutions and waxes as sold by Dow-Corning.
g. ~Iydrocarbon waxes.
h. Vegetable based waxes such as hydrogenated castor oil.

i. Clycols and polyglycols such as "Carbowax" (Union Carbide Corp.) and polyethylene-glycol-laurate.
~ . Synthetic slip-agents such as the halocàrbons and fluoro-carbons, their polymers and co-polymers.
As to the mode of application or incorporation of the release agents (abhesive agents) to the substrate, any convenient mode of application may be used, including, saturation and surface-coating. Instead of using a substrate with an abhesive coating, a substrate may be selected which is abhesive towards the deposited toner by its very nature.
An abhesive substrate, sui generis, may include, polyethylene, polypropylene, polyamides, polyfluoro-carbons, proteinaceous films, polyvinyl alcohol, regenerated cellulose films, and the like.

In this example, it was desired to increase the density, cover-ing power, coherence and opacity produced in Example 1 of the lmage in or~er to improve its transferability. Therefore the image was increased in thickness by repeated copying on to the same image from the same subject matter. With each copying operation, the thickness of the xerographic print was increased by about three tenths of one thousandth of an inch (0.0003"). After a thickness of *Trademark 113~i91~
~7 0.0015" was attaincd, t~lc thickness Or the toner d~posit was satisfactory for transferrence. This metllod of multiple copying to denslfy the image is shown in Walkup, United Scates Patent 2,955,935. In this example a sheet of poly-ethylene terephthalate ("~SYLAR") about five thousandths of an inch thick (0.005") was repeatedly fed through a Xerox copying machine for multiple im-pressions of the subject matter superimposed upon each other. The Xerox copier used was a ~o. 4000 which is well suited for multiple copies, due to the fact that a given copy can bc rcpeatively fed into the machine to receive subsequent impressions.
EX~SPLE 3 To attain a greater degrce of image clarity vis-a-vis Example 2 product, the raised xerographic printing process was used wherein a thick image is produced in but a single pass through the xerograpllic copier. Raised Xero-graphic printing is described in Jacob, United States, 3,924,019 and 3,945,934.
In this example, 100 volumes of a commercially available Xerox Toner, 8 volumes - of foamable microspheres were added. By using the appropriate toner for a particular Xerox model machine, and by simply therein adding the foamable micro-spheres, raised copies were obtained (0.003" thick) immediately upon use, without any need to adjust the heat in the fusing sectlon, the exposure time, the dwell time and other variables. Other compositions of intumescent toners are taught by the '019 disclosures and these can be used at any intended temperature depending upon the thermal stability of the carrier sheet selected. These in-tumescent toners muy or may not libcrate a gas upon heating, but in evcry case they attain great expansion. Foamable microsplleres are made by the Dow Chemical Co. of Midland ~lichigan. It is a powder composed of vinylidene chloride-acrylonitrile-isobutane having a particle size of about 1/2 to 20 micron with an average of 8 microns. This powder is electroscopic. The characters so produced were very sharp and the background very clean. ~Sagnified 25 times the characters *Trademark .

L1369~5 i~printed showed a well packed raised ;tructure llaving a grained appearance rather like many brown to black balloons closely compacted together instead of the usual Xerox characters which have a molten and solidified flowed lava like appearance with fissures, cracks and dusting. The thickness of the print was 0.003" as indicated, upon transfer to the receptor surface, yet by pressing and rubbing, the thickness shrank down to 0.0015" with increase in the density and coverage, probably due to the initial low density of the raised Zerographic print, initially. The substrate used was a vellum wllich has a surface coating of a well-known abhc.sLve matcrial - "Quilon C" made by Du~ont.
EX~LE 4 A substrate was used Witllout any abhesive coating. A xero-graphic print was made thereon, but the print was not comF`letely fused and thermoadhesively attached. This incompletely-fused print could be transferred to a receptor surface by vigorous rubbing and pressure. To prepare an in-completely fused print, it was necessary to alter the heat settings within the Xerographic copier. In some copiers this is not possible. In working with the Xerox 813 copier and the Xerox 660 copier, the result was achieved by using a substrate that was two or three times tlle thickness of the substrate which is normally used for firm thermoadhesive attachment of the print. The heavier mass of material in the substrate, with its higher specific heat, absorbed much of the heat available in the copier, leaving insufficient heat for adequate fusion of the print. This inadequately fused print could be transferred to a receptor surface.
EXA~LE 5 In order to facilitate transferrence of the image from the carrier sheet to the receptor sheet, the surface of the image as it rested on its abhesive substrate was given an adhesive coating. This adhcsivc coating serves to wet the surface of the receptor tenaciously witll very little pressure *Trademark ' ,.

,. 113~g~5 and rubbing. The adilesive coating stieks Elrmly to the receptor and pulls off the xerographic print away from its abhesive substrate for firm attachment to tlle receptor.
The adhesive coating used was a wax plus tackifying resin as in United States 3,013,917 in solvent suspension. Both natural and synthetic waxes may be used. Solvents used in the adhesive coating tend to damage a xerographic print. A xcrographic print is based on a styrene resin, or a styrene acrylic res$n which is readily soluble in solvent. Therefore, in order to minimize solvent attack, it has bcen found that a water dispersion of the adhesive agents used in the coating over the print, is most desirable.
Eor a xerographic print made with Xerox 813 toner whicll is based on styrene acrylic resin, a suitable coating is an acrylic`pressure-sensitive adhesive in aqueous emulsion. In this example, nine parts of Rohm and Haas Latex ~ HA8 and one part o Rohm and Haas Latex HA-12 were used. The mixture was diluted with water to about 400 cps., sprayed onto the xerographic print and allowed to dry. A dry transfer xerographic print made as above will transer readily to a receptor surface and peel away the print from the carrier very cleanly and rapidly. A minimum of rubbing and pressure are needed to produce the desired effect.
X~LE 6 The dry transfer sheets made as in Example 5 may tend to block when the sheets are arranged into fairly low piles. Therefore, the substrate was coated with an abhesive coating on both its front and back surfaces. The frone surface served as the abhesive substrate for the xerographic print (image), while the back surface acted as a releasing liner to free adheslve coated surface of the sheet that lay in contact with it. Thus, the blocking could be minimized for all but the severest conditions of shipping and storage.
*Trademark ` .~li 1~3~9iS
E~LE 7 The ~ esive coating in Example 6 was replaced by a colorless powder coating applied, preferably, xerograpllically or by a]iy other powder-coating method, such as, e.g., fluidized bed. The powdered thermoad}lesive material used was a low melting Ethylene-vlnyl acetate to co-polymer sold by U.S.I. division of National Distillers, under the trademark "Microthene".
After the powder coating was applied, heat was used to fuse the powder into a film that was adherent.
EX~I.E 8 The xerographic application of a colorless powdered thermo-adllesive substance as in Example 7 was modified so that the deposit of the adhesive powder occurred only on the print areas. This wa~ cffected by using the same master sheet from which the original xerographic print was made and by making a second copy thereof on the original xerographic print, utili~ing as "toner" the colorless particulate thermoadhesive powder.
EX~LE 9 In order to overlap the outline of ehe printed character with adhesive, the master sheet comprised an image of slightly larger area than that of the print which was to be covered.

In order to obviate the need for two passes of the carrier sheet tllrough the xerographic copier (one for the print, and one for the overlay of adhesive) a toner was devised which would be adhesive "sui generis" (by its very nature). ~lile the toners used in Exàmples 1-4 were unmodified xerographic toners of a relatively high-melting thermoadhesive resin, the toners used in this and following examples are lower melting and can be transferred without excessive pressure and frictional heat. Conventional toner resins melt at 120 C.
The following formula was used. The toner resulting therefrom was lower melting, 1~ 5 and could be ground illtO ~ fine electr~scopic powder 5 to 20 microns.

Cumarone-Indene resin 60 C.~l.P.100 grams Carbon Black, ~lonarch 71 lO grams Zinc Ste*rate 2 grams Santocel (~lonsanto) a silica aerogel 3 grams Beeswax 1 gram The above composition was dispersed at 100C, then cooled and ground. This toner could be transferred from its substrate uith less rubbing and pressure than was needed in the conventional 120 C toners in Examples 1-4.
XA~LE 11 In order to achieve facile transferrence of the image, a toner of low melting point was tried. The resin uscd was a 40 C melting point poly-styrene tllercules Co.) instead of the 60C resin used in Example 10. This toner has a tendency to pack down and not flow freely in the manner of an electro-scopic powder. Therefore, lt was refrigerated to 0C and dispersed in the developer of the Xerox ~lodel 813 whicll also had been pre-cooled to 0C. The entire developer housing with the developer in it was removed from the Xerox 813 and placed in the refrigerator overnight prior to use.
EXJ~LE 12 In this example a two component toner was utilized. This composition results in a pressure sensitive print from the Xerox copier, wlthout the need for using a low melting toner which must be stored and used below room temperature and which also requires refrigera~ion of the developer and the developer housing, as in Example 11. The composition used herein was:

Xerox 813 Toner 100 grams Paraffin wax emulsion-~ura-Commodities Corp.
Paraffin Wax Emulsion S-9 10 grams The emulsion was sprayed into the toner while it was being mixed.
The ideal way to do this is in a Patterson-Kelley double cone mixer with in-tensifier bar. The intensifier bar which is approximately in the central hori-zontal axis of the tumbling toner, is provided with a series of perforations or ~Tradcmark ` ;.~ 1~L3~i915 ~r nozzles. Tllese perforatiolls are used as ti-e outlet of a pressure-fed stream of Paraffin ~ax emulsion. The fine emulsion droplets are slowly and cvenly in-corporated into the toner. Thereafter a stream of dry air is sparged across and through tlle tumbling Toner until the volatiles have been removed.
The waxed toner particles are then used as the Toner in the Xerox 813. In the copying process, it is speculated that while the toner is being fused on to the carrier, the waxy envelope surroundin~ the toner melts and liquefies. The liquefied wax then, (it being incompatible with and sub-stantially incapable of remaining in solution with the toner at room temperature) will form a coating on the deposited image. Furthermore, some of the liquefied wax coating will spill over the boundaries of the image and make contact with the abhesive coating on the substrate. l~lere the coating ~n the substrate comprises a compatible wax, as in Example lG, there will be created in effect a perimeter of wax as an envelope, encasing the image, and protecting its extre-mities from abrasion and rough handling. This waxy envelope being actually the adhesive which will transfer on to the dcsired surface, ensures faithful transfer of the extremities of the image.
Where the abhesive coating on the substrate is not compatible with the thusly created liquefied wax coating on the image, there will never-theless still exist a protective action on the extremities of the image by the wax which had melted and spilled over. Instead of paraffin wax other waxes may be used or combinations of waxes and resins may be used or combinations of elastomer-resin-wax may be used such that the coating created on the image will be of a pressure-sensitive, dry, nature and will adhere to the receptor surface with a minimum of pressure and rubbing. Of course the amount of waxy coating on the toner particlcs as givcn in the starting formulation in this example, can be varied so as to increase the wax coating for those images whicll are to be transferred to suraces of greater rugosity than the surface of a shect of 20-lb. bond payer.

, .

1SL36~

~LE 13 In tl-is example we have created a novel composition and method for a single-deposition of toner whicll achieves dry-transfer desiderata, in addition to image density and thickness In this example a raised xerograpllic toner sucl- as taught in Jacob, United States 3,924,019 is used. We used Example 7 of said patent. Additionally, we tumbled into the formulation, 10 parts o~ the lowest melting free-flowing powdered waxy material in this case the Ethylene Vinyl ~cetate from U.S.I.. Any other low melting pressure-sensitive solid material may be used provided it is free flowing in powder form at room temperature. At this state it is speculated that toner and foamable microsphere particles are enveloped in a wax envelope.
After fusion in the Xerox copier, a novel print was produced which was not only raised, but also carried on the microsphere's inflated walls some of the powdered waxy material. Some microspheres were exploded so that t1-e walls had waxy material both within and without the Eragments. (Stage 2) The final stage 3 gave a novel product. The print when transferred to the receptor surface showed that the waxy product was re-aligned and re-agglomerated by the rubbing action of the transfer process. Thus was created a surface re-concentration of waxy material, away from the microsphere fragments, a further fragmentation of the microsphere walls with some compaction, and a densification of the image. The densified image was from 0.001" to 0.0015"
thick and was a coherent film which could be removed from its abhesive substrate with a pair of tweezers. Thus a thickness of film was achieved which was most desirable for dry-transfer images, and comparable to the material now being sold as dry transfer images. See, United States 3,013,917. Tlle novel feature is that the step of transferrence is now a functional part of the process of creating a raised xerographic dry-transfer image. It compacts the image, re-distributes the adhesive particles, substantially expels them from the microspheres ~-- 1136915 i and microspllere fragments, crcates a greater and more cffective adhesive surface by re-aggregating displaced wax (adhesive) particles in the vicinity of and in contact with the rcceptor surface.
A novel feature of the Print when it is in stage 2, the stage in which it is stacked and sold or used, is that the exploded or inflated micro-splleres in the raised xerograpllic print provide an anti-block surface so that the sheets do not block upon cacll othcr. The surfacc of thc print is multi-planar.
EXl~IPLE 14 A novel singlc particle toner was formulated by utilizing a thermoadilcsLve con~position, tlle latter not being usable as a free flowing powder. In effect a "tacky" toner was created, whicll nevertheless would be free-flowing and capable of particulate deposition in a Xerox copier.

Wax or incompatible room temp. plasticizer -see below: 100 gm.
Natural Rubber tPale Crepe)100 grams Monarch 71 Carbon Black 10 grams Piccotoner resin (reputedly Styrene-acrylic-Hercules Co.)100 grams Shell "Ionol"* l gram The natural rubber, was broken down for 10 minutes [with Butylated Hydroxy toluene (antioxidant)] on a 10" rubber mill (cool water was run through the mill rolls. After the rubber has been broken down or "masticated" to a ~1ooney of 55, the water was shut off. This takes about 10 minutes as stated. The Piccotoner resin was added using only fricitional heat of the mill. The compo-sition was milled for about 10 more minutes. The Carbon Black and antioxidant were then added and dispersed thorough;y. This takes lO more minutes.
scraper blade was used on the back roll.
The incompatible drying agent, a wax incompatible at room temperatures was milled in, said drying agent spewing to tllc surfacc as a dry bloom. The composition works best wlth Ceresin Wax 85C. M.P.. Some waxes sold *Trademark - ~13~gl5' as antlozonailts in tire ma~ufacture a]so work well.
This composition is very tacky when hot and can only be removed from the mill rolls by using the scraper blade. ~len cool it is dry and non-blocking. This composition is capable of being air-milled under refrigerated conditions to the size suitable for xerographic toners, namely from 5 to 20 microns.
EX~LE 15 In Example 13 we propose to use adhesive containing microspheres instead of the foamable microspheres. Thcse microspheres measure from one micron to 30 microns in diameter. Thcy consist of a iiquld core or a tacky balsamic solid core instead of the pure isobutane normally used for foammable microspheres. The cncapsulatltlg shell may bc of thermoplastic thcrmoadllcsivc material such as the shell of the foammable microsphere and it may be dyed or undyed natural material. The encapsulating shell may also be incapable of thermally being softened such as the shell made of gum arabic. The encapsulated tacky material is preferably of low viscosity to facilitate spray drying during manufacture. A higher viscosity balsamic material might equally be used and liquefied by heat during the spray drying step of microsphere manufacture.
Suitable tacky liquids are: Polybutene "Indopol" sold by Amoco: Polyterpenes sold by Hercules Co. (Wilmington, Delaware) Atactic polypropylene; Wood Rosin oils and derivatives "Hercolyn" "Abalyn" sold by ~lercules.
We prefer a composition in which the encapsulating shell will be tllermoadhesive, will not be solvated by the contents at ambient conditions but will be solvated by a post heating after xerographic deposition. We prefer therefore a styrene-acrylonitrile shell and polybutene tackifying liquid. This produccs a Toner wllicll is dry alld frce flowiog whcn used ln a pllotocopyil)g machine but becomes tacky when thermoadhesively affixed to the carrier sheet in tlle Xerographic process. It ~s a single microsphere which can be used as the sole toner in our process.
*Trademark - 27 -~.~ 3~.915 .~LE 16 In ~xample 15 we propose to use adhesive containing microspheres as an admixture with foamable microspheres of Jacob United States Patent 3,924,019 (~xampLe 7). About 10 to 50 volumes of adhesive-containing micro-spheres would be blended into the self-rising Jacob Toner composition.
EX1~LE 17 We propose to use foamable microspheres whicll also contain an adhesive, say, polybutcne, dissolved in the isobutane (or other similar hydro-carbon) which is encapsulatcd in said microsphere, in combination with con-ventional toner. This would be a viable method of securing a raised xerographic print, and "pari passu" crcate an adhesivc coating. It would yield a tacky toner, whicll is dry and free flowing before deposition on-~he substrate, and will also result in a raised xerographic print. If the microspheres are also colored, (such as with Carbon Black), then they could constitute the sole toner, which would embody firstly the pigmented thermoadhesive "dry ink", secondly a method for creating a raised xerographic print, and thirdly a sourcc of the dry-transerred adhesive.
EX1~LE 18 This illustrates another method for creating a tacky surface on a xerographic print prepared as in Example 1 and Example 3. It involves post-plasticization. After the raised print has been made according to Example 3, a sheet of paper or other carrier is placed upon it. This sheet contains a plasticizer and will function as a plasticizer-donor. We used a 25 lb. glassine very lightly coated with dibutyl sebacàte - about 5 lbs. per ream. This plasti-cizer migratcd into the xerographic print. The presence of thc foamed micro-spheres in the print helpcd in this migratioll. Thc print bccamc tacky on its surface after one week. (This could be accelerated by short heating and pressure).
The tacky print could be transferred to the receptor surface very easily compared 1136~15 with control (whicll ls Ixample 3) . TI~JS, We can usc the normal 120C Loner in the normal raised xerograpl-ic printing J alld achieve by this novel process the end result of having a tacky surface suitable for dry transfer.
EXA~LE 19 In this method a xerographic print or image is produced on an abhesive carrier sheet as in ~xamplc 1, 2, 3. ~n adhesive donor sheet is placed in contact with the print. This ad~esive donor sheet is made of glassine paper -about 15 lbs./rcam~coated with a 2 mil. thickness of a blend of Beeswax, 80 parts by weight, and a resin (SUCII as Wood rosin) 20 parts by weigl~t. The two sheets 1~ togetller are passed under an inEra-red heat source. The black print becomes hot and melts the superposed wax mixture. The wax mixture is thus leached from the donor sheet and becomes part of the surface of the pri~t. The print has thus acquired a dry adhesive coating which will facilitate its attachment to a transfer sheet by the dry transfer method.
Both the following examples use the two novel aspects of the invention namely abhesiveness and adhesiveness to create tlle invented dry-transfer sheet by the simple expedient of combining both processes into a coating onto a sheet which when copies upon automatically becomes a dry-transfer sheet.
The thusly created transfer sheet has everything included in it so tllat if it is fed through the conventional xerographic copier operating in conventional manner and printed upon with conventional toner, the resulting product is a dry-transfer image.
The image will transfer from the substrate because it will be abhesive to the substrate and will also transfer, dry, to a foreign surface because the image will have acquired pressure scnsitive qualities and adhera-bility by the mere act of passage througll a heating chamber, aftcr it has received the Xerographic image. These heating chambers usually exist within L3~915 the ~erogr~phic copicr but tllcy may be scparate units as in the "l~icoh 1'1ate Fuser Machine" made by Ricoh in Japan.
E.YA~LE 20 An abhesive sheet is first secured. This abhesive sheet is either prepared by coating as detailed, supra or is abhesive sui generis.
The abhesive sheet is next coated with what is here called a "HOT ~LT PLASTICIZER" and which is llere defined as a substance dry to the touch at room temperatures, and which is capable of meltlng at temperatures above room temperatures, and whicll in TIIE ~IOLTEN STATE can combine chemically and/or physical1y with a Xerographic image deposited from conventional Xero-~raphic toner when sucll image is in a heat-softened state. After such combina-tion has been effected tile resulting toner image is unlikc~any conventional toner image in that it has acquired adhesive qualities. The "I~OT ~IELT PLASTI-CI%ER" (H.~l.P.) is coated upon the abhesive sheet such that the tllickness of the deposited coating can be 0.0003" to 0.003". The "}I.~l.P." coating may bc applied from solution, from a liquid emulsion, from a hot-molten mass, or by the technique of "powder coating" where discrete powder particles are deposited and then flowed together by heat or pressure or both into a cohesive coating.
The "H.M.P." varieties devised include:
C12 Fatty Acid with 0.5% Dow Corning Silicone Oil 1~200 C14 Fatty Acid with 0.75% Dow Corning Silicone Oil #200 C16 Fatty Acid with 0.9% Dow Corning'Silicone Oil ~200 C18 Fatty Acid with 1.5~ Dow Corning Silicone Oil ~200 plus 5~ Dicyclo-hexyl ~Ithalate.
EXA~LE 21 In this example the simplest method is shown. A single composi-tion is coated upon a carrier sheet, and this formulation has a combination of abhesive and adhesive properties. The coated sheet is selectively abhesive to the substrate and simultaneously is selcctively adhesive to the toncr image.

*Trademark `,.'~, 113~g~5 T~le ~'URP~)SL of this e~m~le is to securc a ulliform coated pro~uct combining ab and ad properties, and to overcome one of the recurring problems Witll Example 20.
In ~xample 20 the second coating operation would generally scrape off to some extent, the first or abhesive coating, thus resulting in non-unifonm quality of release in use. Some sections and some products would release readily and some sections would not release and would not transfer.
In tllis example, a glassine paper (20 lb. approx.) was used as tlle substrate.
This was coated witll 0.0015" molten stcaric acid and coolcd to room tempcrature.
This slleet was then fcd tllrou~ll tlle Dennison BC14 copicr using conventional toner. The copy, while hot upon emergence from the heating chamber of the copier, showed the stearic acid in molten condition being sucked into and amalgamated with the toner image. Upon cooling which took place rapidly, a finished dry-transfer sheet had been created. This experiment was repeated with the Jacob toner, with Red colored Ja~ob toner, with Blue colored Jacob toner with the same results. A clear differentiation between toners is possible in the Dennison Xerographic B.C. 14 copier, because it permits the removal of the entire Developer-Toner housing and replacement with another developer-toner housing containing a different toner. The entire developer-toner combination is uncontaminated. Additional formulations were tried to achieve this result.
Such formulations consisted of the same formulations used in Example 20, except that the percentages of Dow Corning Silicone Oil were doubled, and the per-centage of the dicyclohexyl phthalate had also been doubled where used. The reason is that where these additives were used in Example 20 there was no need for additional abhesiveness. The sheet was already abhesive. The additives were only to secure bctter running in thc coating macllinc. In Example 21 it was imperative to increase the Silicone Oil because it is the sole abhesive donor.
Perfect Dry-Transfers were made. All the abhesive materials mentioned at pages 5-6 of tl~le specification can bc used.
*Tradcmark - 31 -

Claims (6)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A toner composition comprising a powder mixture of a thermo-adhesive agent, a pigment and an intumescing agent, in which the thermo-adhesive agent comprises microspheres carrying or containing adhesive.

2. A composition according to claim 1 in which the microspheres comprise encapsulating shells comprising a thermoplastic, thermoadhesive material, and an inner core comprising a tackifying balsamic solid or a tackifying liquid.

3. A composition according to claim 2 in which the core comprises a polybutene.

4. A composition according to claim 1 in which the microspheres contain occluded gas and are coated with adhesive.

5. A composition according to any one of claims 1, 2 or 3 in which the microspheres are formed of a styrene-acrylonitrile copolymer.

6. A toner composition comprising a powder mixture of a thermo-adhesive agent, a pigment and an intumescing agent, in which the thermo-adhesive agent comprises microspheres carrying or containing adhesive, the microspheres being formed of encapsulating shells comprising a thermoplastic, thermoadhesive material, and an inner core comprising a tackifying balsamic solid or a tackifying liquid.