CA1132176A - Magnetic printing process and apparatus - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The present invention provides a magnetic printing member comprising a ferromagnetic material forming a magnetic layer on a support which comprises an electrically conductive material, whereby the member is adapted in use to discharge electric charges at all times from substantially the entire surface of the magnetic layer through the thickness of the magnetic layer to the electrically conductive material, said surface being adapted to record a magnetic image thereon and print a substrate using a ferromagnetic toner, which is useful in magnetic copying e.g. magnetic textile printing.

Description

- ~323L~7~

BACKGROUND OF THE INVE~TION
1. Field of the Invention This invention relates to magnetic printing - processes and devices.

2. Description of the Prior Art One form of copying process in wide usage is the electrostatic copying process. Operation of such a process may provide difficulties in that large black areas may not be amendable to copying and the document to be copied may have to be reimaged each time a copy is made.
The overcoming of these difficulties may be economically prohibitive. It is well known that audio signals and digital data can be recorded on magnetic materials.
Magnetic field configurations in the form of alphabetical characters and pictures can also be produced by selective magnetization or demagnetization of the surface of a ferromagnetic chromium dioxide film. The resultant fields are strong enough to attract and hold small magnetic particles such as iron powder. The development, that is, the making visible, of such a latent magnetic image can be effected by contacting the image surface with a magnetic developer, usually referred to as a magnetic toner, consisting of ferromagnetic particles and pigments encapsulated in a thermoplastic resin binder.
Such a development process is commonly known as decoration of the latant magnetic image. The developed image can then be transferred to and fixed on paper, thus providing a black-on-white copy of the latent image. Operation of such magnetic processes, however, may not be completely free of difficulties. For example, since most magnetic ~3~7~

toner particles are attracted by both electrostatic and magnetic fields, stray electrostatic charges which are present on the magnetic surface or toner particles may interfere with the interaction of the magnetic image and the magnetic toner particles. More specifically, a portion of the magnetic sur-face other than that containing the magnetic image may attract enough magnetic toner particles to render unsatisfactory the paper print which subsequently is produced.
There i5 ~x~ensive prior ar~ in the fields of magnetic recording tapes and thermomagnetic recording. ~-U.S. 3,476,595 discloses a magnetic recording tape which is coated with a thin layer of a cured complex of silica and a preformed org2nic polymer containing a plurality of alcoholic hydroxy groups. The disclosure includes coated, ferromagnetic, chromium dioxide, magnetic recordins tapes.
Discussions of acicular chromium dioxide and magnetic recording members bearing a layer of such ma~erial may also be found in U.S. 2,956,gS5 and 3J512,930. U.S. 3,~54,798 discloses a magnetic recording member which is relatively transparent to light (transmits 5 to 95~) and which includes a plurality of discrete areas of hard magnetic particulate material supported thereon and bound thereto. A magnetically hard ~aterial is a material which is permanently ma~neti~able below the Curie point of the material,as opposed to a magne~ically soft material which is substantially non-permanently magne~izable under similar conditions below tne Curie point of the material. Chromium dioxide is disclosed as an example of a hard masnetic mat~rial. Decoration of the ~maqe may be effected by means of a m~gne~ic pi~men~, for

3~ ex~ple, a dilute, alkyd-oil/water cmulsion, carbon blac~-based ~ 3'~6 printing lnX. U~S7 3,522,090 1~ ~imilar in disclosur~ to .S. 3t5~4,798 in that it al~o discloses a l~ght-transp~ren~
recording member. ~owever, ~t also discloses ~hat the ~gnetic material which ~s capable of maqnetization to a hard ~a~netic state (on the xecording mem~er) may haYe a coating of a reflective material which is so disposed that the magnetic material is shielded from exposing xadiation while the adjacent uncoated portion of the recording member transmits 10 to 90% of the exposing radiation. The reflective coating can be a metallic reflector, such as aluminum, or a diffuse reflective pig~en~, such as titanium dioxide. U.5. 3,555,556 - discloses a direct thermomagnetic recording (TMR) process wherein the document to be copied is imaged by light which passes through the document. U.S. ~,555,~57 discloses a reflex thermomagnetic recording process wherein the light passes through the recording member and reflec~s off o~f th~ documen~
which is to be copied. Thus, in the direct process, the document must be transparent but the recording member need not be transparent, whereas in the reflex process, the recording member must be transparent but the document need not be transparent. For the recording mem~er to ~e transparent, ~t must hav~ regions which are free of magnetic particles, that is, a non-continuous ma~netic surface must be used.
U.S. 3,627,58~ discloses fcrromagnetic toner particles, for dcveloping magnet;c ima~es, that include ~inary mixturcs of a magnetically hard material and a magnctically soft material, an ~nc~psulatin~ rcsin and, ~pti~nally, carbon black or blac~ or colored dycs ~o provide ~ blac~er or colored copy~ ~N;grosine~ SSU is discloscd as an ex~mple of a black dyc~ ThC enca~sulating rcsin aids '1~3~6 txans f er of the decorated magnetic lmage to paper and ean be heated, pressed or ~apor softened to adher~ or fix ~he ~agnetic particles to the surface fibers of the paper.
~erromagnetic toncr particles of the type disclosed in U.S. 3,627,682 are disclosed as being useful in the dry thermomagnetic copying process of U.S. 3,698,005.
The latter patent discloses such a dry thermomagnetic copying process wherein the magnetic r~cording ~ember is coated with a polysilicic acidl The use of the polysilicic acid coating on ~he recording member is particularly useful when the magnetic materi~1 on the recording member comprises a plurality of discrete areas of particulate magn~tic material because a greater number of clean copies can be produced. The polysilicic acid, which is relatively non-conductive, ex~ibits good non-stic~
properties. Thus, toner particles which are held to the surface of the recording member by nonmagnetic forces can be easily removed without removing the toner particles which are held to ~he surface o~.the recording member by magnetic ~orces. U.S. 2,826,634 discloses the use of iron or ~ron oxide magnetic particlcs, either alone or encapsulated itl low-melting resins, for developing .magne tic images .
Such toners have ~ecn employed to develop magnetic images recorded on magnetic tapes, films, drums and printing plates.
Japancse ~0/52044 discloscs a n~ethod wllic~
comprises adhering iron particl~s ~earing a photoscnsitivc dia~snium compo~d on~o an elcctrophotographic matcrial to ~orm an image, tr3nsfcring thc imaqc onto a sup~ort 30 having a coupl~r which is a~le to form an azo dyc by rcaction ~3Z~7~

~th ~he d~azonium compound, reac~ing the diazonium ~ompound ~nd ~he coupler and thereaf~er removing She iron particles~
~.S. 3,530,794 discloses ~ magnetic printing arrangement-wherein a thin, flexible master sheet having magnetizable, character-representing, mirror-reversed printing portions .~s employed in combination with ~ rotary printing cylinder.
5he ~aster sheet,which consists of a thin, flexible non-magnetizable layer, such as paper, is placed on top of and in contact with a layer of iron oxide or ferrite which is adhesively attached to a base sheet. The combined layer and base sheet are imprinted, for example, by the impact of type faces, so that mirror-reversed, character representing por~ions of the iron oxide layer a~here to the non-magnetizable layer, thus forming magnetizable prin~ing portions on same. Thereafter, the printing p~rtions ~re masnetized and a magnetizable toner powder, such as iron powderg is applied to and adheres to ~he magneti~ed printing portions. The powder is then transferred from the prin~ing portions to a copy sheet and permanently ~0 attached ~hereto, for example, by heating. U.S 3,052,564 discloses a magnetic printing process employing a magnetic ~n3c consisting of granules of iron coated wi~h a colored ~r uncolored thermoplastic wax composition. The magnetic ink is employed in effecting the tra~sfer of a printPd ~ecord, using magnetic me~ns, to paper. U.S. 3,735,416 discloscs a magnetic printing proce~s whcrein characters or other data to be prin~cd are formcd on a ma~nctic rccording surface by mcas3s of a rccording hcad. ~ m~ tic toner which ~ s composcd of x~sin-coated magnetic p~rticl~s is 30 employ~d to efect: trans cr of 'ch~ char~cters or othcr d~ta 3'~

from ~he recordi~g surface ~o a rec~ving sheet, ~.S.
3,250,636 discloses ~ direct ~maging process and apparatus whexein a uniform magnetic field is applied to a ferromagnetic ~maging layeri the magnetized, ferromagnetic imagin~ layer is exposed to a pattern of heat conforming to the shape of the image to be reproduced, the heat being sufficient to raise the heated psrtions of the layer above the Curie point temperature of the ferromagnetic imaging layer so as to foxm a latent magnetic image on the imaging layer; the latent magnetic image is developed hy depositing a finely divided magnetically attractable material on the surface of the ferromagnetic imaging layer; the imaging layer is uniformly heated above its Curie point temperature after the development to uniformly demaqnetize it; and,finally, the loosely adhering magnetically attractable mat~rial is transferred from the imaging layer to a transfer layer.
German 2,4S2,530 discloses electrophotographic toners comprising a magnetic material coated with an organic substance containing a dye which vaporizes at 100 to 220C, pre~er~bly 160 to 200CC, at atmospheric pressure. The ma~netic matexial is preferably granular iron and/or iron oxide and the coating is a water-insoluble polymer melti~g at about 150C, e.gO, polyamudes, epoxy resins and cellulose ethers and esters. Both basic ~nd di~perse dyes c~n be used in ~he ton~rs. ~he toners are from 1 to 10 microns in diameter and ~ay also contain silic~c acid as anti static a~ent. Colored or bl~c~ copies are formed ~y toner dcvclopmcn~ o thc l~tent im~ge on ~ photo-conduc~in~ shcct of ZnO paper, followcd by tr~nsfcr of ~Ic dy~ in the vapor pllasc to a rcc~;~ing sheot by applic~ion of heat and ~essure.

_7_ ~13Z~6 osJEcTs AND SUMMA~Y OF TH~: INVENTIO~
In carrying out prior art thermomagnetic recording processes, generally, only reddish-brown or black images can be obtained on paper because of the dark hard magnetic components, for example, the iron oxides (y-Fe203 or Fe304), and the dark soft magnetic components, for example, iron, in the ferromagnetic toners employed therein;
because the magneti.c components are retained in and may be essential to the formation of the visible images; and because the magnetic components are bound to the paper by the encapsulating resins employed in the ferromagnetic toners. It is an object of the present invention to provide magnetic printing processes and devices which can be used to print, in a broad range of colors, if desixed, a variety of substrates, including textiles, such as fabric and yarn, film, including paper and wood. It also is an object to provide such processes and devices which utili2e either hard magnetic componen~s or soft magnetic components or a mixture of hard and soft magnetic components.
Another object is to provide a magnetic printing process whic~ inclu&es the step of scouring the print to rer.ove t~e nard a~a/or soft ~.agnetic com~onents an~ ti~e encapsulatin~ resin for sucll magnetic components. It is a further object to provide such a process by means of which can be obtained a print which is substantially free of hard and soft magnetic components an~ encapsulating resin.
Still another object is to provide a process ~or applying chemi~al treating agents to a substrate. A fur~her o~ject is to provide a proccss and an appropriate device by 30 means of whicll a sllarp print can be obtained, that is, without objectionable bac~ground caused by ferromagnetic tonex particles undesira~ly adhering, for exampleL
electrostatically, to certain areas of tne ferromagnetic material during formation of the magnetic image thereon.
The tenm "textile" is intended to include any natural or synthetic material, such as natural or regenerated cellulose, cellulose derivatives, natural polyamides, suc~
as wool, synthetic polyamides, polyesters, acryl~nitrile polymers and mixtures thereof, which is suitable for spinning into a filament, fiber or yarn. The term ".abric"
is intended to include any woven, knitted or non~toven cloth comprised of natural or synthetic fibers, filar.ents or yarns.
In summary, tlle invention herein resides in a magnetic printing process~ and a device for carrving out same, which process comprises the steps:
~a) forming a magnetic image on a ferromagnetic material whlch is imposed on an electrically conductive support;
(b) developing the magnetic image by decora.lns sam~ with a ferromagnetic toner comprising a ferromagnetic component and a re~in which substantiallv encapsulates the ferromagnetic component; and (c~ transferring the developed image to a substrate.
- In magnetic textile printing, preferred embodimen~s or the process include those wherein the ferromagnetic toner of step (b) additionally con~ai~s a dye and/or che.~lcal treating agent and whereln, after transferring the developed image ~o a substrate in s~ep (c), _ g _ ~32~

the dye and/or chemical t-eating agent of tne ima~e is permanently fixed on the sllbstrate, step (d~, and the ferromagn~tic component and the resin are removed from tne imase on the substrate, step (e). Furtner preCerred embodiments of the process include those wherein the developed image, after being transferred to the substr2te in step (c), is adhered to the substrate by means or hea' and/or water, with or withcut pressure, which means fuses and/or partially dissolves the encapsulating resin; wherein the developed image is transrerred to a first substrate, such as paper, in step (c), and adhered thereto, an~ then transferred, by heat-transfer means, to a second substrate whereon, in step (d), the dye and/or chemical treating asent o the image is permanently fixed; and wherein the resin of the rerromagnetic component is water-soluble or water-solubilizable and the removal of the ferromagnetic component and resin is effected, in step (e), by means of an aqueous scour.
BRI}:F DESCRIPTIO~ OF T~r DRAWINGS

Figure 1 represents an enlarged cross-sectional view of a cylindrical, continuously surface-coated, conductive magnetic printing member. ~igures 2A and 2B
represent top and side views, respectively, in rectilinear form, of the printing member of Figure 1 before orientation of the acicular CrO~ of layer 2; Figures 2C and 2D represent the same views a~ter orientation Oc the aclcular CrO2.
Figure 3~ represents a side view, in rectilinear form, of the acicular CrO2 o. layer 2 but before the CrO2 is ~agnetically structured; Figure 3~ represents the same ~iew after the CrO~ of layer 2 has been magnetically struct~re~. Fisure 4 represents an enlarged cross-sectional ~3~6 view of a cylindrical, intermittently surf~ce-coate2 (in grooves) conductive masne.ic printing member.
Figures S to 9 represent certain steps of the invention magnetic printing process as they apply to the use of the magnetically structured printins member represented by ~igure 3B. Figure 5 depicts the formation of a latent magnetic image on the printing member by Xenon flashing an appropriate film positive. Figure 6 depicts the printing member having the latent magnetic image imposed thereon.

Figure 7 depicts the printing member, after the latent magnetic image has been decorated with ferromagnetic toner particles, as it is a~out to be brough_ into contact with the substrate which is to be printed. ~igure 8 depicts the substrate after the image consisting o~ ferromagne'ic toner particles has been transferred thereto from the magnetic printing member. Figure 9 depicts the substrate after the image has been adhered thereto. Fisure 10, representing a side view, in rectilinear form, of the printing member of ~igure 1, depicts the path o' the electrostatic charge ~eing dissipated from the acicular CrO2 of laye~ 2 to ground .hrough conductive layer 4. Fisure 11, in schematic form, depicts a single color magnetic printing device which can be used to carry out certain steps of the invention magnetic printing process. Figure 12, in 6chematic form, depicts a three color magnetic printing de~ice which can be used to carry out certain steps of the invention magnetic printing proc~ss.
DETAILED D~SCRIPTION OF T~E INVENTION

The formation of the magnetic lmage on a erro-magnetic material which is im~osed on an electrically conductive support can be carried out ~y techniques well know~ in the art OI magnetic recording. One of tne 1 _ --~3~76 unusual features o~ the instant in~ention is the substantial abs~nce of background dye and/or chemical treating agent ir.
the substrate being p~inted. ~y bac~ground dye andtor chemical treating agent is meant tne presence ~f dye and/or agent on un2esirable areas of the substrate whicn has been subjected to the magnetic printing process. rt has been discovered that such background can be substan-tially avoided if any charge on the ferromagnetic material is dissipated, at some stage of the magnetic prin~fng process prior to transfer of the decorated image to the substrate, the purpose being to preclude the affixing of and/or to facilitate the removal of ferromag-netic toner on and/or from areas of the ferromasnetic mate-rial other than those areas whe_e the desired image appears.
It has been observed that such undesirable-toner deposition on the ferromagnetic material may occur during the afore-said image decorating step (b) if the ferromagnetic material is electrostatically charged. It has been dis-covered in this invention that the formation of such an electrostatic charge can be avoided by imposing ferromag-netic material having adequate charge dissipating conductance through its thickness on an electrically conductive support.
Ano~her unusual feature of the present invention resides in the discovery that the decorated image resultins from the aforesaid step (b) can be transferred bv pressure, electrostatic or magnetic means, or a combir.a.ion thereof, directly to ~e su~strate which is to be printed, for example, a textile fabric, or it ran be transferre~ to a first substrate, for example, paper, and subsequently, 33 if desi_ed, after storage, transfer_ed, by w211 known i ~3'~7~
procedu-es, ~o 2 second substrate, t:~e ultimate substrate which is to be printed.
A further unusual feature o the invention resides in the discovery that the ?~inted substrate, after completion o the aforesaid step (d), can be conveniently anc facileiy scou ea to remove and, if Gesire~, ~ecover, the ferro~lmagnetic com~onent and tile resin ori~inally present in the toner. ~artlcularly in the case of dye-containing tcners, this feature, coupled with previously-discussed features, ma~es possible the utilization ofmagnetic recording techniques to effect the color printing, in one or more colors, of a variety o substrates.
Moreover, in the case of che~ical treating a~ent-containing toners, with or withou~ dye, this invention makes possible the utilization of magnetic printing techniqu~s for th~
application of a variety of chemical treating ag~llts to a variety of substrates.
Although the invention herein resides in magnetic printing processes and ~evices, since an important aspect of the invention process xesides in the use of a particular type of ferromagnetic toner, the following disc~ssion of toners is provided. The ferromagne~i~ toner comprises:
~a~ at least one ferromagnetic compo~ent;

(b) optionally, but preferably, at least one member of the group consisting of dye and chemical treating agent; and (c) a readily fusible resin which substantially encapsulates (a) and the optional component (b).
The resin may be solvent-soluble or, pref~rably, water-soluDle or water-solubilizable. Solvent,'as useZ
3~ hereln, is meant to include any known organic solvent, such ~2~
as a hydrocarbon, a halo-genated hydrocarbon, an alcohol, a ketone, an ester, an acid, an amide, and the like, solvent, as well as aqueous solutions of such solvents wnich 2' e miscible with water.
A pre-erred embodiment includes the use of toners which include the optional component, comprise, based on the total weight of (a), (b) and (c), 14 to 83~ of (a), 0.10 to 25~ of (b) and 9 to 74~ of (c), and have a resin to ferromagnetic component ratio of 0.11 to 3.3. An especially preferred embodiment is one wherein the toner used comprises 55 to 70~ of (a), 0.10 to 15~ of (b) and 30 to 40~ of (c) and has a resin to ferromagnetic component ratio of 0.40 to 1Ø
The ferromagnetic component can consist of hard magnetic particles, soft magnetic particles or a binary mixture of hard and soft magnetic par~icles. The ~agnetically soft particles can be iron or another high-permeability, low-remanence material, such as iron car~onyl, certain of the ferrites, for example, ~Zn, Mn)-Fe204, or permalloys. The magnetically hard particles can be an iron oxide, preferably Fe304, Y-Fe203, other ferrites, ~or example, BaFel20l~, chi-iron car~ide, chromium dioxide or alloys of Fe304 and nic~el or cobalt.
Preferred mixtures of soft and hard magnetic particles include mixture5 or iron particles and either Fe304 particles or CrO2 Darticles. Magnetically hard and magnetically sort particles are substances which are, respectively, permanently magneti7able and substantially non-permanently magnetizable under similar conditions below the Curie point of the subs.ances. .~ magneticallv ~3~

hard substance has a high-intr~nsic coercivity, ra~.gins from a few tens of oersteds (Oe), for example, 40 Oe, to as much as several thousand oersteds and a relativel~
high remanence (20 percent or more Or the satura.ion magnetization) when removed from a magnetic field.
Such su~stances are of low permeability and require hign fields for magnetic saturation. Magnetically hard substances are used as permanent magnets for applications such as loud speakers and other acoustlc transducers, in motors, Senerators, meters and instruments and as the recording layer in most magnetLc tapes. A magnetically soft substance has low coerci~ity, for example, one oersted or less, high permeability, permitting sat~ration to be obtained with a small applied field, and exhibits a remanence of less than 5 percent of the satura.ion magnetization. ~lagnetically soft substances are usually found in solenoid cores, recording heads, large industrial magnets, motors and other electrically excited devices wherein a hish flux density is xequired. Preferred soft magnetic substances include iron-based pisments, such as carbonyl iron, iron fla~es and iron alloys.
The dye which is used in the ferromagnetic toner can be selectcd from virtually all of the con:pounds ~entioned in the Colour Index, Vols. 1, 2 and 3, 3rd Edition, ~71. Such dyes are of a variety of chemical types;
the choice of dye ~s determincd by the nature of tllc Rubstrate being printed. For example, premetalized dyes ~1:1 and 2:1 dye:metal complexes) are suitable for synthetic p~lyamide fibers. The majority of such dyes 3? are monoa70 or disazo dyes; a lesser number are i anthraquinone dyes. Such dyes can have or be free from water-so~u3ilizing groups, such as sulfonic acid and carboxy groups, and sulfonamido groups. Acid wool dyes, including the monoazo, disazo and anthraquinone mem~ers of this class which bezr water-solubilizing sulfonic acid groups, may also be suitable for syn~hetic polyzm~e textiles. Dis?erse dyes can be used for printin~ syn'.he,ic polyamide, polyester and regenerated cellulosic fibers.
A common feature of such dyes is the absence of water-solubilizing grou?s. HoweYer, they are, for ~he most part,thermosoluble in synthetic polvmers, notably polyesters, polyamides and cellulose esters. Disper~e dyes include dyes of the monoazo, polyazo, anthra~uinone, styryl, nitro, phthaloperinone, quinophthalone, thiazine and.oxazine series and-vat dyes in the leuco or o~idized form. For polyacrylonitrile and acid-modified polyester fibers, preference usually is given to cationic dyes containing a carbonium ion or a quaternary ammonium grou?. Catio~ic disperse dyes, that is, water-insoluble salts or dye cations and selected arylsulfonate anions, are well-known in ~he art for dyeing acid-modified polyester and acrylic fibers. Cotton fibers can be printed with vat dyes and with fiber rcactive dycs, including those which are employed ~or polyamide fibers. Other suitable dyes for cotton are ~he water-soluble and water-insoluble sulfur dyes. Water-swellabl~ cellulos~c fibers, or mixtures or blends thereof with synthetic fibers, can ~lso be uniformly printed ~ith ~ater-insoluble disperse dyes using a~eous ethylene glycol or polyethylene glycol type sol~ents, as described I,~
~n the art.

The amount of dye, if present, in the ferromas-netic toner can vary over a wide range, for example, 0.1 to 25~ by welght of the total weight of com~onents (a), (b) and (c) ln the toner. Particularly good ~esults can be obtained when the zmount is 0.1 to 15~ by weight.
A wide vari.ety of chemical treating asents, such as flame-retardins agents, hiocides, ultra~iolet llght absorbers, fluorescent brighteners, dyeability modifiers and soil-rel~asé and ~ater-proofing agents, can be present in the ferromagnetic toner. Such agents have utility on cotton, regenerated cellulose, wood pulp, paper, syn~hetic ibers, such as oolyesters and polyamides, and blends of cotton with polye~ter or poly~mide. By dyeability modifier is meant a chemical substance that can he chemically or physically bound to the substrate, such as a fiber, to change the dyeability of the substrate, ~or example, the degree of dye fixation or the type or class of dye that can be employed. A specific ex~mple of a useful dyeability modifier is a treating agent which provides printcd chcmical resis~s, that is, prin~ed areas ~hich remain unstained during a subsequent dyein~ oleration.
Since many chemical treating a~ents~ including those of the afore~a$d types, are well-known in the prior art, no urther discussion thereof is necessary, The chemical treating agént in the toner c3n be present in the same amount as the dye, that is, 0.1 to 2~, prefera~ly 0.1 to li~, of the to~al weight of components (a~, ~b) and (c).
The resin which is used in the ferromagnetic toner includes any of the ~nown, readily fusible, natural, modi-ied natural or synthetic resins or polymers w-nlch 7~

are soluble ar solubilizable in an organlc solvent or water, or mixtures thereo~, that is, either directly soluble or made soluble through a simple chemical treatment. The solubility must he such that the ferromagnetic component and the encapsulating resin can be removed ~rom the substrate, after permanent fixation of the dye and/or chemical trea~ing agent, if present, by means of a scour, in a short time, as will be described in greater detail hereinafter. Organic solvents which may be used lnclude 1~ hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, acids, amides,or mixtur~s thereof, in which the resin of the toner exhibits significant solubility. A
wide ~ariety of useful solvents are well-known in the art and are commercially avaiLable. Examples of useful solYent- -soluble or solvent-solubilizable resins include low molecular weight polyamides, ethylene/vin~l acetate copoly~ers, styrene/acrylate and styrene/acrylonitrile copolymers, fluorine-containing copolymers, such as tetrafluoro-ethyiene/vinyl acetate copolymers, hydrocarbon-type polymers, such as Carnau~a wax and microcrystalline paraffin, and the like. It is generally preferred, however, to use resins wnich are water-soluble or wa~er-solubilizable and can be removed by an aqueous scour.
Examples or water-solubilizable resins are those resins or polymers which contain salt-forming groups, which th~reby render them soluble in an alkaline aqueous solution, and those which can be hydrolyzed by acids or alXalis so as to become water-soluble. Exemplary of useful natural resins are rosin (also known as cqlophony) JJ and modified derivatives thereof, such as rosin ~3Z~7~

esterified wlth glycerin or pentaerythritol, dimerized and polymerized rosin, unsaturated or hydrated rosin and derivatives thereor and rosin, and derivatives thereo~, which has been modiried with phenolic or maleic resins.
Other natural resins with properties similar to rosin, such as dammar, copal, sandarak, shellac and tolloel, can be successrully used in the rerromagnetic toners.
Examples or water-solublizable synthetic ~esins which are useful include vinyl polymers, such as polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetals, polyvinyl acetate, polyvinyl acetate copolymers, and polyvinyl pyrrolidone; poly-acrylic acid and polyacrylamide; methyl-, ethyl- a~d butyl methacrylate-methacrylic acid co~olymers; styrene-maleic.acid copolymers; methyl vinyl ether-maleic acid copolymers; carboxyester lactone polymers; polyethylene oxide polymers; nonhardening phenolformaldhyde copolymers;
polyester resins, such as linear polyesters prepared from dicarboxylic acids and alkyle~e glycols, for example, from phthalic, terephthalic, isophthalic or sebacic acid and ethylene slycol; cellulose ethers, such as hydroxypropyl-cellulose; polyurethanes; and polyamides, such as tnose prepared from sebacic acid and hexamethylenediamine.
. The re~in used in the toner is preferably o~ the thermoplastic ty~e in order to permit adhesion thereof to the substrate by melting or fusion. Particularly prefer~ed resins are adducts of rosin, a dicarbo~lic acid or-~nhydride, a polymeric fatty acid and an alkylene polyamide; hydr3:~yp~0pylcell~1Ose pre?ared by reacting 3~5 to 4.2 ~ules o~ propylene oxide per D-glucopyranosyl - 19 - .

~ 13~
~nit of the cellulose, and poly~inyl aceta~e copolymers ha~ing a free carboxy group content equivalent ~o 0.002 to 0.01 equivalcnt of ammonium hydroxide per gram of dry copolymer. The prefcrred resins possess a high elec-trical resistivi~y for good transfcr in an electrostatic field "lav~ good in~rared and steam fusion properties and do no~ inter~ere wi~l pcnetration of the dye or chcmical trcatin~ agent into the substratc during the final (permanent) fixation operation. Moreover, after the dye and/or chemical treating agent, if present, has been fixed within the substrate, the resin must be easily removable in a scouxing operation in a short time, for example, in an aqueous scour in less than five minutes at less than 100C, preferably in less than 60 seconds at less than 90C.
The ferromagnetic toner can be prepared by intimately mixing together, for example, by ball milling or by hiyh frequency viscous milling, an aqueous or organic solvent solution or slurry containing the desired proportion~ o optional dye~s) and/or chemical treating agent(s), ferromagnetic component(s) and encapsulating resin and then spray-drying to remove the water or solvent, as the case may be. Particularly good results usually can be obtained by ball milling for 1-17 hours at about 60 percent by weight nonvolatiles content.
The solution or dispersion resulting from ball milling is separated ~xom the ceramic balls, sand or other grinding means and spray-dried at a nonvolatiles content of 10 to 40 percent by weightO Spray-drying is accomplished by conventional means, for example, by dropping the solution or dispersior. onto a disk rotating at high speed or by .

~ , , using a conventional spray-dryin~ nozzle, as described in the art. Spray-drying consists of atomizing the toner solution or dispersion into small droplets, mixing these with a gas, and holding the droplets in suspension in tne gas until the water or solvent in the droplets evaporates and heat and surface tension forces cause t~e resi~
particles in each droplet to coalesce and encase the ferromagnetic component and the dye and/or treating agent which are included in the droplet. Most frequently, spray-drying is carried out with air as the gas for the drying step. The gas is heated sufficiently to remove the water ox sol~ent and so that the many small particles in any one droplet formed during atomization can come together to form a small, hard, spherical toner particle ; which entraps the materials initially included within that droplet.
By maintaining uniformity of dispersion of dye and resin in the ~ter or solven~ and by controlling solids concentration in the final dye-water or dye-sol~ent mixture, the paxticle size of the toner can be controlled by the size of the droplet produced by the atomizing head in the spray-drying equlpment. Moreover, by controlling the toner slurry feed rate, the viscosity of the toner slurry, the spray-dryins temperature and the disc xpm for a disc atomizer, the pres-sure for a single-fluid nozzle atomizer or the pressure and air to feed ratio for a two-fluid nozzle atomi zer, spherical ~oner particles having diameters within the range of 2 to 100 micro~s, preferably 10 to 25 microns, can be readily obtained. Toners passing a 200 mesh screen ~U.S. Sieve 30 Series~, thus being less than 74 micxons in 'che longest particle dimensionl are especially useful.

'7~
Other suitable well known encapsulation processes can be employed to produce the ferromagnetic toner. These include coacervation, interfacial polymerization and melt extrusion techniques.
The relative amounts of resinous material and ferromagnetic component in the toner usually are deter-mined by the desired adhesive and magnetic properties of the toner particle. Generally, the ratio of resinous material to ferromagnetic material is 0.11 to 3.3, 10 preferably 0.40 to 1Ø The preferred ratio especially provides toners having good decoration~ transfer and fusion properties.
It is to be understood that, in some cases, it may be advisable to add one or more known chemical assistants to enhance the functional behavior of the ferromagnetic toner, for example, dispersing agents and/or surfactants and/or materials which promote dye and/or treating agents fixation in the substrate. Further examples of such chemical assistants include urea; latent oxidizing agents, such as sodium chlorate and sodium m-nitrobenzene sulfonate; latent reducing agents; acid or alkali donors, such as ammonium salts and sodIum trichloroacetate;
and dye carriers, usually pres-ent in amounts of Q.l to 8%
by weight based on the total toner weight, such as benzyl alcohol, benzanilide, ~-naph*hol, o-phenylphenol and butyl benzoate. Conventional commercial dispersing agents, such as the lignin sulfonates and salts of sulfonated naphthalene-formaldehyde condensates, can be employed.
Such agents include Polyfon*, a sodium salt of sulfonated lignin; P~eax*, the sodium salts of sulfonated lignin derivatives; Marasperse*, a partially desulfonated sodium * denotes trade mark liynosulfonate; Lignosol*, sulfonated lignin derivatives;
Blancol*, "slancol" N and Tamol*, the sodium salt of sulfonated naphthalene-formaldehyde condensates; and Daxad* 11 KLS and "Daxad" 15, the polymerized potassium and sodium salts, respectively, of alkyl naphthalenesulfonic acid. Other known use.Eul auxiliary chemicals can assist in the prevention of "bleeding" of a dye pattern by preventing the swelling or coagulation of the resin.
Exemplary of such auxiliary chemicals are starch, starch derivatives, sodium alginate and locust bean flour and its derivatives. Cationic surfactants, such as quaternary ammonium compounds, reduce the static propensity of the toner particles for the image-bearing magnetic film.
Lower toner pickup in background or nonimage areas can be acheived by incorporating such surfactants into the toner.
Dimethyldistearylammonium chloride has been found to be particularly useful for this purpose. Still other auxiliary chemicals which may be present in the toner include known addi.tives for improving the bri.ghtness and. tinctorial strength of the dyeing, for example, ci.tric acid, which is commonly used with cationic dyes, and ammonium oxalate, which i.s. commonly used wi.th.acid dyes.
A free-flow agent, usually present in an amount within the range 0.01 to 5% by weight, preferably Q~01 to Q.4~ by weight, based on total toner we-i.ght, can be added to keep the indi.vidual toner particles from sticking together and to increase the bulk of the toner powder.
This facilitates an even depositi.on of toner particles on the latent magnetic image. Free-flow or dispersing agents, such.as microfine silica, alumina and fumed silica * denotes trade mark sold under the trade names ~uso* and Cab-O-Sil*, are useful.
The invention PrOceSS and device are applicable to all types of printable substrates. Particularly preferred are fabric substrates, such as those prepared from natural and regenerated cellulose, cellulose derivatives, wool and synthetic fibers, such as polyamides, polyesters and polyacrylics, and mixtures of any of such ~abrics. Film substrates, such as commercially available polyester film and paper, are also preferred.
The following discussion relates to process and equipment details of the invention. It is to be understood that any specific reference solely to color printing or to the printing of substrates with a chemical treating agent, or any speci.fic reference to only certain aspects of either type of printing, is not intended to be limiting on the invention. Furthermore, the following references to and/or discussions of the accompanying drawings are intended to facilitate understanding of the invention rather than to impose limitations thereon. Based on the following discus-sion of process and equipment details, one skilled in the art will readily be able ko envision other (undescribed~
embodiments of the inventi.on.
~ s already suggested, the invention i.s useul for producing multiple color prints (:reproductions) of an original desi.gn. The invention has parti.cular appli.cabilIty-to the formation of colored prints of an original desi:gn consisting of multiple colors. In such.a system a plurality of toner decorated magnetic images- corresponding to a series of color separati.on fi.lm posi.tives of the original multicolored design are successively transferred to a * denotes trade mark ~ . ~

substrate in register and superimposed one on top of th~
other so as to fGrm a multicolored print composed of th~
diffcrent color imagcs.
Either multicolor or full color separation film positives are prepared from ~he original deslgn. Multicolor film separations (that is, one film separation for each color in a pattern) can be made either manually by tracing the design or by using a color recognition electronic scanner. The preparation of full color (that is, process color) separation film positives can be made either with a camera and colored filters or by using a process color electronic scanner. With the former technique, the original design is photographed through three filters, each corresponding in color and light transmussion to one of the additive blue, green and red primaries. Placing a red filter over the camera lens produces a negative recording of all the red light reflected or transmitted ~rom the original. This is Xnown as the red separation negative.
~hen a film positive is made from this negative, the sil~er in the film will correspond to areas which did not contain red but contained the other two colors of light, that is, blue and green. In effect, the negative has subtracted the red light from the original design. The positive is a recording of the blue and green in the original design and is called the cyan film positive. Photographing through a green filter produces a negative recording of the green in the original design, The positive is a recording of the red and blue additive primaries and is called the mage~ta film positive. The use of a blue filter produc~s a ncgative which records all of the blue in the o~iginal design. The positive records the red and green which, when combined as additive colors, pro~uce yellow.
This is called the yellow film positive. For some designs, a black film positive i~ necded. This is ob~ilin d ~y photographing the original design through re~, blue and grccn filters in succession, ~ detailed discussion of tne preparation of process color film positives can be found in "Principles of Color Reproduction," J. A. C. Yule, Chapters l and 3, John ~1iley and Sons, Inc., 1967.
Electronic scanners can be use~ for both full 10 color (based on the four process colors) or multicolor ~individual color recognition) film separations. In bo~
types of scanners, the original design is mounted on a horizon~ally rotating drum which is driven by a step motor operating at approximately 2,000 steps per second. A
horizontally moving scanning head is mounted in front of the arum. T~e desi~n pattern is illuminated and the reflected colored light is interce~ted by the sca~nins head at each step. A series of prisms and mirrors splits the xe~lected light into red, green and blue components which are then converted into three separate electronic signals. In full color separation scanners, the red, green and blue components are processed through an optical elec~ronic con~er~er which pro~ides the yellow, magenta, cyan and blac~ film separation positives. In multicolor separation scann~xs, ~he red, green and blue components are compared to the amounts of red, green and bluc components stored in the scanl1ers computcr mcn-ory. Thc ou~put is a film scpara~ion positivc corres~ol1din~ to each color l~at~ern in tl~e ori~inal de~i~n. ~s maJ1y ~s t~elve -diffcrcn~ color~ c~n be store~ in thc conlp~er memoryoP ~ mul~icolor s~aration ~c~nncr. Suiti~ electronic color scaJ)Ilcrs ~rc ~ca~ily availa~lc comn1e~rci;l11y.
Elect onic scanners have obvious adYantages over manual separation techniques due to their lower processing cost, higher speeds (2 to 3 hours as compared to 100 to 200 hours) and greater resolution capabilities.
The aforesaid color separation film positives are used to form a plurality of latent magnetic images, as described below, one latent magnetic image corresponding to each colo; film positi~e. Each latent magnetic image is then decorated with dye-containing ferromagnetic toner particles to form a series of toner-decorated latent magnetic images corresponding to the color separation images. In a typical subtractive multiple color processing system in accord with this invention, each laten~ magnetic image is decorated witll toner particles having a dye color complementary to the original color separation filter.
Thus, the cyan latent magnetic image corresponding to the red color filter is decorated with toner containing a blue dye; the yellow latent magnetic image corresponding to the blue ilter is decorated with a ~ellow dye toner and the magenta latent magDetic image corresponding to the green color filter is decorated with a red dye toner.
The dye images from each of the individual toner-decorated images are transferred in register and superimposed, one on top of the other, on the substrate to form the final multicolor print of the original printed ~lesign.
The most important force for magnetic printing is, of course, of magnetic origin. However, stray electro-static forces can exceed magnetic forces. Since ferro-magnetic toner particles are attracted by both electro-static ~nd magnetic fields, any high electrostatic charge density on the magnetic printing surface (that is, the ~3~

ferromagnetic material) will generate fields eaual to or greater than the magnetic field from the masnetic imase.
The background region, that is, that portion of the printLng surface other than that containing the magnetic image, will thus attract enough toner particles to ren~e- -the final print unattractive, if not indiscernible. Static charges usually ~uild up at a sufficiently slow rate so that at least one clear print can be made, but unless some means is provided to dissipate the static charges, after a few prints have been made, the buildup of static charge becomes large enough to cause serious background problems.
As already discussed hereinabove,in the invention process and device, the background problem is 21iminated ~y having the se~iconductive ferromagnetic CrO2 plus binder continuously coated on the conductive support, for example, as shown in Figure 1. Preferably, at least two static neutralizing means, such as two AC coronas, as shown in ~igures 11 and 12, are employed in conjunction withthe continuously CrO2-coated 2Q conductive support to neutralize any residual charges on the toner.
Since the surface resistivity of the CrO2 coating is approximately 108 ohms/s~uare, the time required for comple~e static charge dissipation must be less than the time elapsed between electrostatic toner transfer and subsequent toner redecoration; otherwise, static charge will build up on the printing surface. As can be seen from Figure 10, using the conductive CrO2-coated printing ~ember 1 of this invention, the elec~rostatic sur~ace charge on the CrO2 2 travels ~hrough the thickness of the CrO2, that is, ~ the Y direction, instead of along ~he entire leng'h o~ the CrO2 surface, that is, in the 7~

direction, ~n order to reach ground t}lrough ~e ~onductiYe ~ upport 4. Grounding i; accomplished by clamping the CrO2-coated printing member 1 to printing drum 12 depicted in Yigure 11. For a 5-inch (12.7 cm.) ~tide printina surLace, the X/Y ratio is approximately 104 and, thus, rapid charge dissipation occurs and background free prints are obtained.
In one e~bodiment of the invention process, the electrically conductive support providing the path to ground for the electrostatic charge can be either continuously coated with a layer of ferromagnetic CrO2 or can be provided with a series df grooves which are in turn filled with the CrO2. Figure 1 shows an enlarged cross-sectional view of the continuously surface-coated conductive magnetic printing member 1 of ~his invention com?rising a conductive support which is continuously coated with a 50 to 1,000 microinch (1.27 to 25.4 x 10 4 cm), preferably 100 to 500 microinch (2.54 to 12.7 x 10 4 cm), layer 2 of ferromagnetic CrO2 in a xesin binder. Acicular CrO2 is particularly preferred due to it5 high coercivity, which allows i~ to be magnetically oriented to giv~ a high xemanence. A unique aspect of CrO2 is its outstanding magnetic properties togeth~r with its easily attainable Curie temperature o 116~C. ~cicular CrO2 can be produce~
by techniques ~ell known in thc art. The conduc~ive support can be any appropriate material, for example, a polyethylene terephthalate film 3, about 125 micxons in thickness, coated with a thin conductive layer of aluminum 4. Commer-ciaily aYailable alumini~ed po}yestex fi~n is particularly uscful as a conductive support. The conductive support can 30 ~e a metallized plas~ic material, for example, a sleeve of a pla~tic ~aterial, such as an acetal resin, coated with ~luminum, nickel, copper or other conductive metal, or i~

7~

can be a metal sleeve coated with a thin layer of elastomericmaterial, such as polychlorobutadiene (neoprene~, poly-butadi~ne, polyisoprene, butadiene-styrene copoly~ers, acrylonitrile-buta~iene copolymers, etc., or with an epoxy resin, containing conductive particulate matter, for example, carbon black, graphite or silver, uniformly dispersed therein.
The conductive support can also be the conductive metal itself.
` The coating o~ the conductive support with acicular CrO2 can be accomplished in a variety of ways, for example, by gravure coating a slurry of CrO2 and resin in tetra-hydrofuran-cyclohexanone on a web of aluminized polyester or by spra~-coatillg a conductive metal sleeve. Ilowever, regardless of the coating technique used, it is desirable to orient the CrO2 by passins the wet coated conductive ~upport ~etween`the pole pieces of two bar magnets ~approximately 1,500 gauss average field strength) aligncd wi~l tlle same poles facing one another. TJIe magnetic flux lincs oriellt th~ acicular CrO2. Figures ~ and 2B

show top and side views, respcctively, of prin~in~ mcmbcr 1 of Figurc 1 be~ore oricn~ation; ~igures 2C and 2~ sl~ow - th~sc res~ective YiCWS af~er oricnta~ion. ~atios o~ magnetic - rcm~n~ncc to ma~llctic sa~ur~tion ~r/n5) of up to 0. no an intri~lsic cocrcivi~y (ill~) o~ 510 to 5S0 o~rs~ ave ~e~n ~ in~ on SllCil printin~ menlber~.
I~ the oriented CxO2 ~agnetized pxinting æurface is decorated with ferromagnetic toner particles (for example, 10 to 30 micron partisles consisting of a dye and a ferromagnetic component encapsulated in a water-soluble resin binder), the particles will be magnetic lly attracted to only the edges of the surface as depicted in Flgure 3A. In order to achieve even toner decoration of the entire magnetic printing surface, the oontinuous ~ ~ ~Z~7 ~

CrO2 coating is magnetically structured, as illustrated in Figure 3B, so as to createmagnetic flux gradients that uniformly attract tne magnetic toner particles. A numDer of different techniques can be used to magnetically structure the ma~netic printing surface. An alternating signal, equivalent to 100 to 1,500 magnetic lines per inch (39 to 590 lines per cm), can be recorded on th~
CrO2 surface using a magnetic write head. A magnetic line consists of two magnetic flux reversals. Alternatively, 0 2 Ronchi ruled transparent film can be placed on top of ~he uniformly magnetized CrO2 surface and the assembly can then be exposed to a Xenon flash passing through the transparent ruled film. ~he CrO2 under the clear areas of the film is thermally demagneti~ed to provide tlle requisite magnetic pattern. The technique of roll-in magnetization also can ~e used to structure the CrO2 surface. In this method, a high permeability material, such as nickel, which has been surface structured to the desired groove width is placed in contact with the u~magnetized CrO~ surface.
A permanent magnet or an electromagnet is placc~ on the backside of the highly permeable material. As the struc-tured high permeability material is brougllt into contactw~th the CrO2 surface, thc magnet concentrates the magnetic flux lines at the points of contact, resulting in ~he magnetization of the CrO2 coating. The CrO2 surface can ~lso be thexmoremanently structured by placing the continu-ously coa ed CrO2 surface on top of a magnetic ma~ter which has the desired magnetic line pattern recorded on it.
Thermoremanent duplication of the master pattern on the CrO2 surface is effected by heating the surface above the _, 7~

116-C CrO~ Curie temperature. As the surface cools down below the Curie temperature, it picks up the magnetic signal from the magnetic master and is selectively magnetized.
In still another method, a scanning laser beam can be used to structure the magnetic CrO2 surface.
Figure 4 shows an enlarged cross-secticnal view of the permanently structured conductive magnetic printing member 1' of this invention, comprising a grooved COIl-ductive support with the CrO2 and resin bindex 2' in the grooves. In this embodiment, the conductive support is preferably a plastic support material 3' which has been structured to the desired groove width and depth. The grooved plastic support 3' is plated with a thin layer of a conductive metal 4', such as aluminum, copper, nickel or ~he like,and the grooves are filled with the CrO2 and resin binder 2'. If desired, the grooved support can consist solely of the conductive metal, for example, copper~
As in the case of the continuously coated magnetic printing member illustrated in Figure 1, the CrO2 must be oriented during the groove filling operation. Maqnetization of the grooved conductive magnetic printing surface can be readily accomplished by passing the surface in front of a magnetic field.
~ urther aspects of the invention are depicted in ~igures 5 to 9 (shown for simplification as comprising flat surfaces) which show the stepwise formation of the latent magne~ic image on the structured printing member 1 (~igures 5 and 6), the aecoration thereof with toner particles (Figure 7), the trans~er of the toner particles 3~ to ~he substrate (Figure 8) and the toner particles adhered ~ 7~
to the substrate (Figure 9). The aforesaid sequence of steps can be carried out using the continuously CrO2-coated magnetic printing member 1 depicted in Figure 1, the CrO2 surface cf which has been oriented (depicted in Figure 2) and magnetically structured (depicted in Figure 3), Figures 2 a~d 3 shown for simplification as comprising flat surfaces. A similar se~uence of steps can be envisaged for the grooved magnetic printing member depicted in Figure 4.
1~ It is to be understood, and it will be obvious to one skilled in the art, that the structured printing member can be imaged in such a way that the substrate will be uniformly chemically treated and/cr dyed, depending on the type of ferromagnetic toner used, ovex a wide area.
In other words, instead of a pattern-type print, the print can provide a total coloration and/or chemical treatment of the substrate.
Referring further to Figure 5, a latent magnetic image is formed on the surface of the magnetic printing 2;J member 1 by placing an image-bearing photocolor separation film positive, prepared as described abo~e, in face-to face contac~ with the structured printing surface and uniformly heating, from the backside o~ the film positive, with a short burst of high energy from a Xenon lamp. The dark areas of the film positive, that is, the imaqe areas, absor~ the energy of the Xenon flash, while the transparent areas of the film transmit the energy, thereby heating the CrO2 to a~ove the 116C Curie point. As can be seen from Figure 6, the suxface of ~he magnetic printing 3~ member i~ selectively demagnetized to form a latent magne~ic ~3~7~

$m~ge which consists of a reproduction of the darX areas of the film positive.
Instead of using a photocolor separation film positive, an electronic color scanner can also be used to form the latent magnetic image. The output signal from the scanner drives a magnetic write head which is in contact with the surface of continuously CrO2-coated printing member 1. There is no need to prestructure the printing surface since the data recording of the magnetic write head can provide the required magnetic flux lines to attract the toner particles. A permanent record of the latent magnetic image can be obtained by decorating the latent magnetic image with a black toner and transferring and fusing it onto a transparent film~ The output of the scanner can also consist of digital color separa~ion data recorded on a magnetic tape and this tape can be used to drive the magnetic write head directly on the printing surface.
Ferromagnetic toner particles are applied to tne latent magnetic image to form a decorated magnetic image (as shown in ~igure 7) and the substrate to ~e printcd is brought into juxtaposition therewith to effect transfer of the image to the substrate (Figure 8).
The latent magnetic image can be developed hy e~nvenient methods which are well known in the art.
Typical methods include cascade, magnetic brush, magnetic roll, powder cloud and dusting by hand. In cascade development, finely d~vided ferromagnetic toner particles are conveyed to and rolled or cascaded across the latent 30 ~agnetic image-bearing surface, whereupon the ~erromagnetic 3~

~oner parti~les are ~agne~ically a~tracted and ~ecured to the magnetized portion of the latent image. In magnetic brush or roll development, ferromagnetic toner particles are carried by a magnet~ The magnetic field of the magnet causes alignment of the magnetic toner par~icles into a brushlike arrangement. The magnetic brush or roll is then engaged with the magnetic image-bearing surface and the ferromagnetic toner particles are drawn from ~he brush to the latent image by magnetic attraction. The transfer of the ferxomagnetic toner particles to the substrate can be accomplished either by pressure, magnetic or electrostatic means, or a combination thereof. In the preferred electrostatic means, a positive or negative charge is applied to the backside of the substrate which is in contact with the toner-decorated latent magnetic image. In connection with the use of pressure transfer means, the use of high force, for exam~le, about 40 pounds per linear inch (about 70 N~ewtons per linear cm), generally results in shorter printing surface life, poorer transfer efficiency and poorer image definition on the ~ubstxate. Such problems are avoided by using electrostatic transfer means wherein there is no substantial amount of pressure between the printing surface and th~ substrate and, therefore, no abrasion occurs.
The ~ransferred image is temporarily adhered to ~he substrate (as shown in Figure 9) until permanent fixation of the dye and/or chemical treating agent thereon and/or therein is effected. Temporary adhering of the transferred image to the substrate conveniently can be effected by application of heat and/or a suitablc solvent ~ 3 (water or an oryanic solvent), the latter either in the form of a spray or as vapors, for example, water or steam.
Heating at 90 to 170C and steam fusing at 100C for l to 15 seconds at 760 mm (of Hg) pressure are particularly preferred herein. The adhesion of the image to the substrate results from the melting and/or the partial dissolution (in the solvent~ of the encapsulating resin.
Final (~permanent) fixation of the dye and/or chemical treating agent of the toner can be accomplishea in any way which is consistent with the type of substrate and dye and/or agent which are used. For example, dry-heat treatment, for example, Thermosol* treatment, at 190 to 230C, particularly 200 to 210C, for up to 100 seconds can be used to fix disperse dyes on polyester and mixed disperse-fiber reactive dyes on polyester-cotton. The application of pressure, for example, up to about 1.5 psi,g (10,350 Pascal gauge), may be advantageous. High pressure steaming at pressures of 10 to 25 psig (69,000 to 172,500 Pascal gauge)accelerates the fixation of disperse dyes on polyester and c~llulose triacetate. ~apid disperse dye fixation ~an also be obtained by high-temperature steaming at 150 to 205C for 4 to 8 minutes. High-temperature steaming combines the advantages of short treatment times without the need to use pressure seals-. High molecular weight disperse dyes can be -Eixed to polyester-cotton using aqueous ethylene glycol- or polyethylene glycol-type solvents according to well known prior art procedures. Cottage-steaming and pressure-steaming can be used to fix cationic dyes to acid-modi,fied acrylic and polyester fibers and to fix acid dyes, including premetalized dyes, to polyamide and wool fibers. Cottage-steaming uses saturated steam at a pressure of 1 to 7 * denotes trade mark .~, ~`~3'~17~i psig (6,900 to 48,300 Pascal gauge) and 100~ relative humidity. It may be noted that there is no tendency to remove moisture from the fabric when saturated steam is used. As ~he fabric is initially contacted by the steam, a deposit of condensed water quic~ly forms on its cold surface. Such water serves various functions, such as swelling the fiber and activating the chemical treating agent and/or dye, thereby creating the conditions necessary for the diffusion of the dye and~or agent into the fiber.
Rapid aging at 100 to 105C for 15 to 45 minutes at 760 mm (g ~g) pressure can be used to fix disperse dyes to ceilulose acetate fibers and cationic dyes to acid-modified acrylic fibers. The aforesaid fixation procedures are all known in the art, for example, as described by Clarke in ~An Introduction to Textile Printing," Third Edition, 1971, pages 58 to 66.
Depending on the nature of the toner dye and/or chemical treating agent, it may be necessary or desirable to treat the fabric with known auxiliary agents, to achieve certain effects, before final (permanent) fixation of ~oner dye and/or chemical treating agent. For example, it may be necessary to impregnate the fabric with an aqueous solution of an acid or an alkali, such as citric acid, ammonium oxalate or sodium bicar~onate t or in some cases, a reducing agent for the dye. Alternati~ely, thcse auxiliary agents can be incorporated directly lnto tne toner composition.
After permanent fixation of the dye and/or chemical treating agent, the printed fabric is scoured to remo~e the ferromagnetic component, encapsulating resin ~2~
and any unfixed dye and/or chemical treating agent. Although the severity of the scouring treatment generally depends on the type of resi~ and solvent employed, with ferromagnetic toners containing water-soluble or water-solubilizable resins, only a few seconds immersion in a conventional aqueous scour, for example, an aqueous surfactant solution or aqueous alXali, at less than 90C, is sufficient to dissolve away the resin and release the ferromagnetic material from the fabric surface. In the case of dye-containing toners, a well-defined colored print is obtained on the fabric. Thetransfer of the dye- and/or chemucal treating agent-containing ferromagnetic toner to the substrate and the temporary adhering thereof on the substrate can be carried out in a continuous operation, that is, in an immediately sequential manner. The final ~permanent) fixation of the dye and/or chemical treating agent and scouring can be carried out separately in a later operation~
As already suggested above, the magnetic printing process of the invention involves a delicate balance of forces in that the areas of the magnetic printing surface which are to retain ferromagnetic toner particles, that is, the image areas, must magnetically attract toner particles, whereas the image-frce areas of the printing surface must no~. On the other hand, the force of ~agnetic attxaction must not be so great as to prevent the substantially complete transfer of the toner fxom the printing surface to the substrate. The strength of the magnetic attraction between the ~oner particles and the printing surface depends on the physical properties of the pri~ting ~urface, such as the coercivity (iHC) and ~3~

remanence.(Br) of the CrO2 coating, the degree of orientatisn of ~he CrO2 crystals (Br/Bs), the tnickness of the CrO2 coating, the ~umber of magnetic lines on the surface and the properties of the ferromagnetic toner particles, for example, their magnetic susceptibility, shape and size.
It has been found that optimum decoration, transfer and fusion properties are obtained using a CrO~ coating having a thickness range of 50 to 1,000 microinches (1.27 to 25.4 x 10 4 cm), prefexably 100 to 500 microinches (2.54 to 12.7 x 10 4 cm), a coercity of 200 to 600 oersteds, preferably 350 to 580 oersteds, and an orientation (Br/Bs) of 0.4 to 0.9, preferably 0.6 to 0.9. The surface of the printing member can be magnetically structured to 100 to 1,500 magnetic lines per inch (39 to 590 per cm), preferably 150 to 400 magnetic lines per inch (59 to 157 per cm).
Further to the above disc~lssion, Figure 11 shows a schematic diagram of a single color magnetic printing device which is useful in performing the invention magnetic printing process. The substrate 5 to be printed is fed from feed roll 6, around dancer rolls 7, 8 and 9 to the nip betwee~ feed rolls 10 and 11, which rolls cooperate to feed the substrate into physical contact with the surface of magnetic printing member 1, shown in cross-sectional vi~w in Figure 1. Magnetic printing member 1 can be a continuously CrO2-coated aluminized polyester film which is secured and grounded to the outer circumferential surface of a rotating aluminum or copper printing drum 12~
Prior to mounting printing drum 12 in the apparatus, the CrO2 suxface of the aluminized polyester film affixed thereto 3~ is magnetically structured, using a magnetic write head ~ 2~ ~ 6 ~s previously described, into a line pattern contai~ing 300 magnetic lines per inch ~118 magnetic lines per cm).
Aft.er structuring the printing surface, a latent magnetic image is formed thereon by placing a photocolor-separated film positive of a design in ~ace-to-face contact with the magnetically structured printing surface on drum 12 and then uniformly heating the printing surface with successive short bursts from a high energy Xenon lamp flashed through the film positive. After exposure, the CrO2 printing 10 surface on drum 12 co~tains magnetized areas of CxO2 corresponding to the printed areas of the film positive.
Printing drum 12 is then mounted in the apparatus and is driven in the direction shown by the arrow by a commer-cially a~ailable drive motor (not shown) which is provided with a speed control unit~ The printing member containing the latent magnetic image is then decorated (de~eloped) with toner using a suitable decorating means 13. ~n the particular embodiment illustrated, the decorating means 13 is a magnetic brush decorating means comprising a trough 14 containing a supply of the toner particles 15.
The tonex particles are magnetically attracted to the surface of the magnetic brush 16 and are co~eyed to the surface of printing member 1 where they are stripped from the surface of magnetic brush 16 by a stationary doctor blade 17. Toner particles are drawn from the brush to the latent ma~netic image by magnetic attraction;
8urp1us toner falls back into trough 14 for recirculation.
~l~hough this represents a convenient means for depositing toner on the printing member, any of the numerous decorating 3~ m~ans known to ~hose skilled in the ar~ can he used.

~3~ 6 Preferably, triboelectric charses generated in toner ~rough 14 are eliminated by neutralization using AC corona 18. An~
toner particles a~ventitiously adhering to the demagnetize~

areas of the CrO2 surface are removed by vacu~m knife lg.
The printing member, bearing the clean decorated image, is tl~en contacted with substrate 5 past DC corona device 20, tnus causing the toner par~icles to be transferred to substrate 5 upon its separation from printing member 1.

A neqative DC corona device potential of 3 to 20 10 kilovolts, preferably 4 to 8 kilovolts, is used. There is only an insignificant amount of pressure between substrate and the surface of printing member 1, which pressure is generated entirely by the electrostatic charge on substrate 5.
Alternatively, trans~~r o_ the image can take place in the nip between a resilient pressure roll (nct shown) and printing mem~er 1, in which case the pressure roll replaces the corona device 20. Applied pressure agalnst the drum can range from lO to 40 pounds per linear inch (17.6 to 69.6 ~ewtons per llnear cm~. However, the most efficient trans.er, about 20 90 percent of ~he toner particles are transferred, occurs at the upper limi~ of this range. Such high pressures, how-ever, have a destructive e.fect on the life of the printing member; hence, lower pressures are preferred if printing member li~e is a concern. Pollowing transfer of the image, the substrate 5 containing the toner image particles is conveyed around idler roller 23 to thermal fusing means 24 which temporarily adheres the toner particles to substrate ~.
The fuslng means can be a bank of infrare~ heaters, a contact hot roll or a ste m fuser. The substrate 5 ls then conveyed 30 over idler rcll 2; to the nip between ~olls 26 and 27 whic;~

~3~7~j cooperate to ~eed substrate 5 onto final taXe-up roll 28.
After transfer, toner particles remaining on the surface of magnetic printin~ member 1 are removed by means o vacuum brush 21. ~referablv, residual electrostatic c;narges are neutralized ~y .~C neutraLizing corona ~ ..2ces3ar-~, dn AC corona is also used after DC corona device 20 and before vacuum brush 21 to remove the electrostatic char~e on the toner particles which do not transfer, thus enhancing the action of vacuum brush 21. Alternatively, a vacuum ~nife such as 19 is used instead of vacuum brush 21. In this case, an AC corona preferably is also u~ a~ter D~ coro~2 device 20 and before the vacuum knife to remove the electro-static charge on the toner particles which do not transfer.
AC neutralizing corona 22 can then be elimlnated. ~he clean electrostatic charge-free surface of printing nember 1 is then again decorated with toner in trough 14 and the neutralizing, vacuum knife cleaning, electrostatic transferring, fusing, vacuum brush cleaning and neutraliz-ing steps are continued until the printing cycle i5 com-pleted.
The aforesaid apparatus and description formthe basis for a commercial single-color magnetic printer, for example, capable of printing speeds of up to 240 feet (73 meters~per minute, having the ability to provide multiple prints from a single latent magnetic image.
As mentioned above, ~he invention magnetic printing pro ess and device have particular applicability to the printin~ of colored prints of an original design composed o~ multiple colors. Figure 12 shows a schematic view of a multicolor (three color) m2gnetic printins .

~3'~ 6 device embodiment of this invention. The substrate 2g to be printed is fed from feed roll 30 into contast with endless belt 31 which is made of a dielectric film, such as polyethylene terephthalate. Rollers 32 and 33 serve to drive, in the direction shown by the arrows, ar.d suide endless belt 31. The substrate 29 is electrostatically attracted to endless belt 31 by means of DC (dlrect current) corona device 34 or by other conventional dry fabric bonding techniques. Any electrostatic charge buildup on subs~rate 29 is neutralized by AC (al~ernating current) neutralizing co~ona 35. The charge-free substrate is conveyed by endless belt 31 to the toner-decorated surface of m~snetic printing mem~er 1 positioned at printing statlon A. The ferromagnetic toner is electro-statically transferred from the surface OL this printing member 1 to substrate 29 by means of DC corona device 36. After transfer, the toner is.fused to substrate 29 using fusing means 37 which is an infrare~
or steam ~using device. The process of applying toner - 20 to the surface of magnetic prin~ing member 1 is essentially the same as shown in Figure 11 for the single color magnetic printer.
As further shown at station ~ in Figure 12, a latent magnetic image o~ one of the colors (yellow, cyan or magenta) m2~ing up the design to ~e printed is formed on the surface of the magnetic printing member 1 mounted on drum 12. The latent mag~etic image is decorated with ferromagnetic toner particlcs lS using a suitable decorating means 13. In the particular embodiment illustrated, decorating means 13 consists of hopper 3a having a narrow orificP from which toner particles 15 are smoothly and 1 ~ 3'~

uniformly dispensed onto the surface of ~agnetized roll 39 The toner particles adhering to magnetic roll 39 are su~sequentl~ driven by magnetic attraction from the roll to the latent magnetic image on the surface of printing member 1. The surface of toner decorated printing member 1 preferably is neutralized with AC neutrallzing corona 1 and vacuum cleaned with vacuum knife 19 to remove toner par-ticles which have adventitiou5lybecome attracted to the demagnetized bac~ground area. After transfer of the toner to substrate 29 using DC corona 36, t~e surface of printing member 1 is vacu~m cleaned with vacuum brush 21 and t~e resid~al electrostatic charges preferably are neutralized using AC corona 22. Prefera~ly, an AC corona ean also be used a^~ ear DC corona 35 and before vacuum ~rush 2L to remove the electrostatic charge o~ the toner particles which do not transfer, thus enhancing the action o- vacuum brush 21.
The clean, electrostatic charge-free printing surface is then xeady for redecoration followed by the steps of neutralization, vacuum knife cleaning, electrostatic transfer, fusion, vacuum brush cleaning and neutraliz~-tion. ~his sequence of steps is continued until the pri~ting cycle is completed.
Latent magnetic images of the remaining two colors making up the design to be printed in this embodiment are similarly decorated, transferred and fused at printing stations B and C. The fused mul~icolor printed ~abric is ~aken u~ by take up roll 40. The imase alignment of printing stations A, B and C is achieved ~lectronically by placing a magnetic read head 41, commonly available~ at the edge of each printing drum 12. The ~ead head 41 senses t~e signal on the ~32~ ~

~gnetic ~urface that is in registry with the image at each pxinting station. This signal is sent to a synchro-nization control box tnot shown). The speed of endless belt 31 is set manually by a belt drive motor (not shown).
A belt speed signal is sent to the synchronization control box which controls the speeds of each of the motors driving the drums at printing stations A, B and C. Thus, all of the drums are placed in register by means of the feedback signal from the magnetic read head 41 on each of the drums.
It is to be understood that the aforesaid discussions of figures are de~oid of descriptions of the permanent fixation (of dye and/or chemical treating agent) and the ~erromagnetic component- and resin-removal (for example, by aqueous scouring) steps of the invention magnetic printing process since these steps, and the equipment which can be employed in connection therewith, are familiar to one s~illed in the art of dye chemistry.
In addition to direct abric printing, the invention process also affords the capabili y of indirectly printing fabrics by utilizing the process in combination with heat-transer printing. In magnetic/heat transfer printing, ferromagnetic toners containing sublimable dyes are first direc~ly printed to a paper substrate, fused thereon as described above and then subsequently heat-transfer printed from the paper substrate to a fabric substrate employing a combination of heat, pressure and ~well time.
~eat-transfer printing at 160 to 250C, prefera~ly l90 to 220C, at 1 to 2 psi ~6,900 to 13,800 Pascal) pressure for up to lO0 seco~ds dwell time provi~es good results in tl~e invention magnetic/heat-transfer printing proccss. Under ~l132~76 such conditions, the dye sublimes and is transferred to and is fixed within the ~abric substrate. The resin and ferromagnetic components are subse~uently removed by scouring the printed fabric substrate as described above for the magnetic printing process.
The invention magnetic pxinting process provides numerous advantages over conventional wet printing pxocesses. ~or example, prints can be produced having half-tone or large solid areas which exhibit excellent optical density. Since the printing surface is reusable, there is no need for conventional printing screens and rollers. A dry toner system is used and no print paste makeup is re~uired. This provides minimum water pollution (by dye) on cleanup. No additional ~uxiliary chemicals or gums are requir~d since the ferromagnetic toners can be formulated so as to contain all of the necessary materials.
Moreover, lower printing costs are obtainable due to lower engxaving costs and shorter changeQver times.
EXAMPLES
In the following examples, unless othexwise noted, all parts and percentages are by weight and all materials employed are readily commercially available.
Example 1 This example illustrates th~ preparation, by manual mixing of ~he ingredients fol~owed by spray-drying, of a ferroma~ne~ic toner containing a blue disperse dye, magnetic components and an aqucous alkali soluble resin, and the application therco~ to bo~h papc~ and polyester. A magnetic tcner was prepared ~rom 32.7~ o car~onyl iron, 32.7~ o~
~e304, 1.8~ of C.I. Dispexse Blue 5G, 5.5~ of li~ninsulfonate ~ispersant ~nd 27.3~ of a polyvinyl acetate ~opoIymer resin.
~he carbonyl ixon, used as the soft magnetic material and commercially available under the tracle name "Carbonyl Iron" GS-6, is substantially pure iron powder produced ~y the pyrolysis of iron carbonyl. A suitable Fe3O4 is sold under -the trade name Mapico* slack Iron Oxide and the polyvinyl acetate copolymer resin, under the trade name Gelva* C5-VIOM. "Gelva" C5-VIOM is an aqueous alkali-soluble copolymer of vlnyl acetate and a monomer containing the requisite number of carboxy groups and has a softening point of 123C.
A 20% aqueous alkaline solution (450 parts) of the polyvinyl acetate copolymer resin was manually stirred with 500 parts of water until thorough mixing was effected.
Carbonyl Iron GS-6 (108 parts) and "Mapico" Black Iron Oxide (108 parts) were added and the mixture was thoroughly stirred. C.I. Disperse Blue 56 (24 parts of a 24.6%
standardized powder) was stirred in 455 parts of water until completely dispersed, then added to the above resin solution. The resultant toner slurry was stirred for 30 minutes with a high shear mixer and then spray-dried in a Niro* electric spray-dryer. The toner slurry was atomized by dropping it onto a disc rotating at 20,000 to 50,000 rpm in a chamber through which heated air was swirling at a high velocity. Precautions were taken to stir the ~ner slurry and maintain a uniform feed composition.
The exact temperature and air velocity depend mainly on the softening point of the resin. An air inlet temperature of 225C, an outlet temperature of 85C and an atomizer air pressure of 85 psig (586,500 Pascal gauge~ provided satis-factory results. The resulting discrete toner particles o~ magnetic resin-encapsulated dye had a particle size * denotes trade mark _~7_ :
~, ...

within the range of 2 to 100 microns, mostly within the range of 10 to 25 microns. The particles were collected in a collection chamber. Toner adhering to the sides of the drying chamber was removed by brushing into a bottle and combined with the initial fraction. The toner sample was finally passed through a 200 mesh screen (U.S. Sieve Series), thus being less than 74 microns in particle size.
The ferromagnetic toner was mechanically mixed with 0.2%
of a fumed silicate, ~uso WR-82, to improve powder flow characteristics.
Toner evaluation was made on a 2 mil (0.0508 mm) aluminized Mylar* polyester film continuously coated with 170 microinches (43,180 A) of acicular CrO2 in a resin binder. Suitable acicular CrO2 can be prepared by well known prior art techniques. The CrO2 film was magnetically structured to 300 lines per inch (12 lines per mm~ by re-cording a sine wave with a magnetic write head. A film positive of the printed image to be copied was placed in contact with the magnetically structured CrO2-coated alum-inized polyester film and uniformly illuminated by a Xenonflash,passing through,the film positive. The dark areas of the film positive corresponding to the printed message absorbed the energy of the Xenon flash, whereas the clear areas transmitted the ligh,t and heated the CrO2 beyond lts 116C Curie point, thereby demagnetizing the exposed -magnetic CrO2 lines. The latent magnetic image was manually decorated by pouring the fluidized toner powder over the partially demagnetized CrO2 film and then blowing off the excess. The magnetic ima~e became visible by vir-tue of the toner being magnetically attracted to the magnetized areas.
* denotes trade mark $j The toner decorated image was separately transferred to paper and to Polyester fabric substrates by applying a 20 kv positive potential from the backside of the substrate by means of a DC corona. Other transfer means can also be employed, such as bly means of a pressure of 10-40 pounds per linear inch (17.6-69.6 Newtons per linear cm). However, such means may lead to shorter film life, poorer transfer efficiency and poorer image definition on the substrate. After transfer to the paper or fabric substrate, the toner was fused thereon by infrared radiation, backside fusion (140C) or by steam fusion (100C for 10-15 seconds at 1 atm pressure). The latter method is the most economical but is only possible with water-soluble resins.
The image which had been transferred to the paper was then heat transfer printed from the paper to polyester fabric by placing the fused image-bearing paper face-down on the polyester and applying 1.5 to 2.0 psi --(10,350 to 13,800 Pascal] pressure for 30 seconds 20 at 205-210C. After direct transfer and fusion to polyester fabric, the dye was fixed in the fabric by heating for 30 seconds at 205-210C and 1.5 to 2.0 psi pressure (10,350 to 13,800 Pascal).
Both fabric samples which had been printed as described above, that is, either dlrectly printed or heat transfer printed from paper, following :Eixatibn of the dye, were scoured by immersion in cold water and then in hot detergent. A detergent consi-sting of sodium phosphates, sodium carbonates- and biodeyradable anionic and nonionic surfactants (Lakeseal*) was used. The samples were finally rinsed in cold water and dried. A deep blue print was obtained on each fabric.
* denontes trade mark ExamE~e 2 This example illustxates the preparation, by ball-millins of the ingredients followed by spray-drying, of a ferromagnetic toner containing a blue disperse dye, m~gnetic components and an aqueous alkali-soluble resin, and the a~plication thereof to polyester. A magnetic toner was prepared from 30~ of carbonyl iron, 30~ of Fe3O4, 10 of C~I~ Disperse Blue 56 and 30~ of a polyvinyl acetate copolymer resin ~"Gelva" C5-VIOM).
A mixture of 300 parts of a 20% aqu~ous alkaline solution of the polyvinyl acetate copolymer resin, 20 parts of C.I. Disperse Blue 56 crude pow~er, 60 parts of ~Mapico" Black Iron Oxide, 60 parts of Carbonyl Iron GS-6 and 100 parts of water was ball-milled for 17 hours .at 37~ nonvolatilesO A ceramic ball-mill was selected of such size that when the ball-mill was about one-half to two thirds full of 0.5 inch (1.27 cm) high density ceramic.balls, the above ingredients just covexed the balls.
After discharging the ball-mill and diluting with 460 parts of water to reduce the total nonvolatile solids to approximat~ly 20~, the slurry was spray-dried in a-Niro `;
spray-dryer using an air inlct temperature of 200C, an ~ir outlet temperature of 80C an~ an atomizer air prcssure of 80 psig (552,000 Pascal gauge). The toner particles wer~ brush~d from the d~ying chamber, collected and passed through a 200 mesh scree~. The toner sample was fluidized with 0.2~ of Quso WR- 82 and then used to dccorate the latent magnetic image on a 300 line per inch (1~ per mm) CrO2-coated aluminized ~Mylar" film as descri~ed in ~xample 1. The ton~r decorated m~ge was electrostatically txansferred directly to 100S polyester double-knit fabric , ~3'~
by applying a 20 KV negative potential to the backside of the fabric. The toner was steam fused to the fabric at 100C for 10-15 seconcls at 1 atm pressure. After fusion, the dye was fixed in the fabric by heating at 205C for 40 seconds at 1.5 psi (10,350 Pascal). The printed fabric was then scoured at 65C in a mixture of 2 parts per liter of caustic soda, 2 parts per liter of sodium hydrosulfite and 2 parts per liter of a poly-oxyethylated tridecanol surface acti.ve agent to remove resin, Fe, Fe3O4 and any unfi.xed dye and then dried. A
bright blue print was obtained.
Example 3 This example illus.trates the preparation o a solvent ball-milled and spray-dri.ed, ferromagnetic resi.n encapsulated, disperse dye toner and the application there-of to polyester.
A magnetic toner was- prepared by ball-milling a mixture of 120 parts of an aqueous alkali-soluble polyamide res.in-di.carboxylic acid adduct (commercially available 20 as TPX*-1002), 136 parts of "~Mapi.co" Black Iron O ~de, 136 parts of Carbonyl Iron GS-6, 8 parts of C.I. Disperse Red 60 crude powder and 267 parts of a 50:50 mixture of toluene: isopropanol for 16 hours at 60% nonvolatile solids. The ball-mill was discharged and the content was diluted with 666.ml of 50:5Q mixture of toluene:i.sopropanol to approximately 30% nonvolati.le solids. The solvent toner slurry was spray-dried in a ~owen* spray-dryer using a feed rate of 152 ml per minute, an air inlet temperature of 143C, an air outlet temperature of 62C and an 30 atomizer air pressure of 85 psig (:586,5Q0 Pascal gauge~.
The toner particles were classified to some extent by a * denotes trade mark .~, ~13Z~7~

cyclone collection system~ The main toner fraction (81%, 238 parts) collected from the dryer chamber consisteZ of nearly spherical spray-dried particles having an average particle size of lO to 15 microns (a range of 2 to 50 microns~.
The resultant magnetic toner consisted of 30g of poly~i~e r~in adduct, 34~ o~ carbonyl iron, 34% of ~e~O4 and 2% of C.l. Disperse Red 60. The toner wac fluiâized with 0.3~
of Quso WR 82 and then applied to decorate tho latent image on a 300 line per inch (12 per mm) magnetically structurod CrO2 coated aluminized "Mylar" film as described in Example l. The toner decorated image was electrostatically transferred directly to 100% polyester woven fabric by applying a 20 KV negative potential to the backside of the fabric. The fabric was steam fused and the dve was fixed by heating at 205C for 40 seconds at 1.5 psi (10,350 Pasc?1).
The printed fabric was then scoured as in Exam le 2 and dried.
Examples 4 to 33 .

Dispersc dye toncrs were prepared by eithcr manually mixing or ball-milling thc appropriate in~redicllts and spray-drying thc slurry as describcd in E~mplcs 1 an~
2. Dctails are summarizcd in Tablc I. ~anually mixe~
ton~rs were prepared in all cascs except Examples 13, 14, i9 and 32, i~ these the toners were prepared by ball-milling.
~he compositions of the inal spray-dried toners as well ~s ~he ratio of resin to total magnetic component present are aiso shown in the table~ Ball-milled toners exhibited optic~l densities, when printed on polyester, which were superior to those of manually mixed toners of comparable dye co~cent~-tion. This diffcrence is p~rticularly evident when ~he toner contains high concentrations of dye.

~l~Z~76 The standardized disperse dye powders (and pastes) used in the manually mixed toners contained ligninsulfonate and sulfonated naphthalene-formaldehyde condensate dis~ersing asents. At high dispersant levels, the quantity of magnetic component in ~he toner becomes limited a.nd decoration of the latent magnetic image may becom~ impaire~.
Toner compositions containing 9 to 74~ (Examples 12 and 25) of water-soluble resin and 14 to 83% (Examples 1 and 12) of total magnetic component and ~ompositions having a resin to magnetic component ratio of 0.11 to 3.3 (Examples 12 and 25) exhibited sa~isfactory magnetic, transfer and fusion properti~s. Various disperse dye types, for example, quinophthalone (Exa~ple 4), anthraquinone (Examples 5 to 25, 32 and 33) and azo (Examples 26 to 31) dyes, provide a wide range of colored magnetic toners.
The amount of dye present in t~e toner depends on thc amount of rcsin and magnetic component present. Dye concentra-tions of 0.10~ (~xample 33) to 25~ (Example 32) wcre used with satisfactory rcsults. Toner com~ositions containing 20 both hard and soft ma~Jnetic compolleots are exemplificd in Tabl~ I. A bin~ry mixture of m~gnctic particl~s is not essentia1~ howeverO Equally good results are obtained using only a hard ma~netic component (Examples 18 to 21).
Ferric oxide is a preferred hard magnetic component based on its magnetic prope~ties and its cost. Chromium dioxide can also be used but it is much more expensive.
A free-flow agent, present in ~uantities of 0.01 to 5%
(preferably 0.01 to 0.4~, based on total toner weight, was used to keep the individual toner particles from stic~ing toge.her and to increase the bul~ of the toner powder. ~hese factors facilitate even deposition of , ~L~3217~;

toner over the imaging mem~er. Free-flow agents such as microfine silica and alumina are useful. Quso ~IR-82 provides satis~actory flow properties when added to tne toners described herein.

The toners were evaluated as descri~ed in ExaMple 1. The latent magnetic image on a 300 line ~er inch (12 per mm) magnetically str~ctured CrO2 coated aluminized "Mylar" film was manuallv decorated and the decorated image was electrostatically transferred to (that is, printed on3 a substxate (shown in Table I).
The toner fusion and dye fi~ation conditions and the scouring procedure for removing resin, magnetic component(s) and unfixed dye from the printed substrate are also given in the table. For instance, in Example 4 the designation "DP(Pap)t~ indicates that the toner was directly printed on paper and infrared fused at 160-170C; the desi~n~tion "~ITP(PE)f'g" mcans that the toncr was heat trans~er print~d from papcr to polycster ~y hcatin~ a~

205C for 40 seconds and 1~5 psi (10,350 Pascal) and the printed polyester was scoured at 65C in a~ueous deterg nt solution; and the desLgnation "DPlPE~t'f'g"
~e ns that the toner was directly printed on polyester, ~nfrared fused ~t 163-170C, the dye was fixed at 205C for 40 seconds and 1.5 psi (10,350 Pascal) and the printed poly~stex fabric Wa5 scoured a~ 65C. in aqueous detergent.
~ number of different ~ixation pxocedures, for example, dry heat, hot air, high temperature steam and high pressure steam, were used to fix the dyes in the substrate.
3~ Such procedures are well-known in the art for fixing disperse dyes in polyester and nylon.

_ j4 -~3Z~7 ~

Exam~les 27, 29, 30 and 31 3how ~he effect of~ncorporating 2, 4, 6 and 8% of a ~enzanilide dye carrier.
in the toner compositions. The carrier gave increased tinctorial strength over toner without the carrier.
Concentra~ons of 2 to 4% ~of carrier) provided optimum results.
Example 34 This example illustrates the effect of various chemicals which are normally used in the conventional printing of polyester to prevent side effects during fixation of the dye.
The toncr of Example 27 containing 2~ of benzanilide carricr was directly printed on 100% polyester woven ~abric according to the procedure o~ Example 1. The toner was steam fused at 100C and 1 atm pressure for 10-15 seconds. Thc fabric was spraycd with a solution of 100 parts of urea and 10 par~s of sodium chlorate in 1,000 parts of water ~o prevent reduction of the dye during the fixation step. The dye was fixed by high pressure steaming ~t 22 psig ~151,800 Pascal) for 1 hour. The printed f abxic was scoure~ in 2 parts per liter o~ sodium hydxo-sulfite, 2 parts per liter of soda caustic and 2 parts per ~ter of a po~yethoxylated trideca~ol surfactant at 65C.
A deep red print was obt~ined; it exhibited superior tinctorial strength as compared to a corresponding print which had not been sprayed prior to fixation.
Example 35 This example illustrates the effect of various chemicals which are normally used in the conventional print~ng of nylon ~o preven~ si~e effects durins fixation o~ ~he dye~

~3~

~ he toner of Example 27 containing 2~ of benz-anilide carrier ~as directly printed on "Qiana" nylon fabri~

according to the procedure of Example 1. .The toner was steam fused at 100C and 1 atm pressure for 10-15 seconds.
m e abric was then sprayed with a solution of 100 parts of urea, 10 parts of sodium chlorate and 10 parts of citric acid in 1,000 parts of water and the dye was fixed by high pressure steaming at 22 psig (151,800 Pascal) for 1 hour. After scourillg, a deep red print was obtained; it was tinctorially stronger than a corrcsponding red print which had not been sprayed prior to fixatiQn.
Example 36 This cxample illustrates thc preparation and application o~ a fcxromagnetic disperse dy~ toner to a poly~stcr/cottoll blcnd ~abric.
A 6-inch ~15 cm~ wide, 3-yard (274 cm) length of 65/35 polyest~r/cotton blend fabric was pretreated ~y padding to a~ou~ 55~ pic~up with an aqueo~s solution containing 120 parts per liter of metho?~ypolyethylene glycol, M.W. 350.
2~ The padded fabric was heated at 72C for 1 ~our ~n a hot -air oven to evaporate water, leaving the cotton fibers in a swollen state.
A magnetic toner was~prepared by spray-drying a ~ixt~re containing 29~'4% of polyvinyl ace~a~e copolymer ~ . ~
resin ~ "(;elva" C5-VIO~ , 33 . 3~ of Carbonyl Iron GS-6, 33~3~ of "Mapico" Blac~ Iron Oxide, 2% of a dye of the ~ormula shown as ~A) in Table VII and 2~ of a sul~onated naphthalene-formaldehyde dispersant. The spray-dried product was sieved through a 200 mesh screen and a . 2~ of 30 Quso W~-82 w~s added to rPnder the toner free 1Owing.

-- ~6 --~13'hl~

A latent magnetic ~mage such as described in -Example 1 was manually decorated with the abo~e toner and txansferred electrostatically to both untreated and pretreated 65/35 polyester/cotton by a procedure such as described in Example 1. Following trans~er, the toner was stea.m fused at 100C and 1 atm pressure for 10 to is seconds and the dye was hot air fixed at 205C for 100 seconds.
Following fixation of the dye, the print was scoured at 65C in aqueous detergent. The pretreated polyesterfcotton ~abric was printed in a deep bright red shade, whereas the untreated fabric was only lightly stained. Similar r~sults were obtained when thc dispcrse dye toner was trans~erred to the pretreated and untreated fabrics, steam fused and then dry heat fixcd at 205~C for 100 s~conds at 1.5 psig (10,350 Pascal gauge).
xample 37 This example illustrates the preparation of a ferromagnetic toner containing a cationic dye, magnetic com~o-nents and an aqueous alkali-soluble resin and the application thereof to acid-modified polyester and polyacrylonitrile~
A solutio~ of 21 parts of C.I~ Basic Blue 77, as a 24.4% standardized powder (containing boric ~cid as a diluent) in 300 ml of hot water, was added, with thorougn stirring, to 400 parts of a 20% aqueou.s alkaline solution of a polyvinyl acetate resin. ~ "Gelva" CS-VIOM) . Ca~bonyl Iron GS-6 (91 parts3, "Mapico" 81ack Iron Oxide (91 parts) and 510 parts o~ water were then added and~ stirring was ~on~inued for an additional 30 minutes. The toner slur-y was spray-dried to give a final toner composi~ion containing 28.3% of polyvinyl acetate copolymer resin, 32.2% o~
C~rbonyl Irsn GS-6, 3~.2~ of ~apico~ Black Iron Oxide, - g7 -7~;

1~8~ of C.I. Rasic Bl~e 77 and 5.5 weight percent of boric acid diluent. The toner was sieYed throug~ a 2Q0 ~esh ~creen and fluidLzed with O . 2% of Quso ~R-82.
A latent magnetic image such as described in Example 1 was manually decorated with the above toner and transferred electxostatically to acid-modified polyester fabric as described in Example 1. After transfer, the toner was steam fused at 100C and 1 atm pxessure for 10 to 15 seconds and the cationic dye was fixed by high-pressure ~teaming at 22 psig (151,800 Pascal gauge) fo- 1 hour.
~he printed ~ahric was scouxed as described in ~xample 2.
A blue print was obtained.
~ ~econd toner trans fcr was made to polyacrylo-nitrile fabric in a similar manner. The toner was steam ~used, ~he dye was fixed by cottage-steaming ~k 7 psig (48,300 Pascal gauge) for 1 hour and the printed fabric was scoured as described above; a deep blue print was obtained, In conventional prin~ing with rationic dyes, a ~steady acid" is normally used in the print paste to insure 20 that an acid pH is maintained during ~ixation of the dye.
Accoraingly, in ano her set of experiments, after transfer and steam fusion of the above cationic dye toner to ~oth ~he acid-modified polyester and the polyacrylonitrile fabrics, the printed fabrics were oversprayed with a 50% aqueous ~olution of citric acid and then ~ixed by high-pressure - steaming and cottage~steaming, respectively, as described abo~e. The printed ~abrics were then scoured. Bright blue prints were obtained, exhibiting superior image definition as compared to the prints which were prepared withou~ the overspray step.
xamples 38 to 43 ~erromagn tic cationic dye toners were prepared ,~ ,L~.X,~
by manually mi~lng the ap~ropriate ingredients and spray-drying the slurries as described in Example 37 After drying, 0.2 to 1.2% of ~uso WR-82 was added to obtain toner fluidity. Details are summarized in Table II. The ferromagnetic cationic dye toners were directly printed to both acid-modified polyester and polyacrylonitrile substrates, steam fused and fixed by either high pressure steam developmen-t at 22 psig (151,800 Pascal gauge) for 1 hour or by cottage-steaming at 7 psig (48,300 Pascal gauge) for 1 hour.
Cationic dyes of the triarylmethane (Example 37), azomethine (Example 38), styryl (.Examples 39 and 41-43) and rhodamine (Example 40) series, with both water-soluble hydroxypropyl cellulose ("Klucel" LF) and polyvinyl acetate copolymer ("Gelva" C5-VIOM) resins, are exemplified.
Klucel* LF is a cellulose ether containing propylene glycol groups attached by an ether linkage ana not more than 4.6 hydroxypropyl groups per anhydroglucose unit and having a molecular weight of approximately 100,000. The cati.onic 20 dye toners of Ex~mples 42 and 43 containing l and 2%, respectively, of citric acid provided brighter and tinctorially stronger prints on both acid-modified poly-ester and polyacrylonitri.le as compared to the corresponding toners without the citric acid.
Example 44 Thi~s example illustrates the preparation of a ferromagnetic toner containing an acid dye, magnetic compo-nents and an aqueous alkali-soluble resin and the application thereof to nylon.
A solution of 12.7 parts of C.I. Acid Blue 40 * denotes trade mark ~r ~

tC.I. ~2,125), as a 31.6~ standardized powder ~containing dextrin as a diluent) in 150 ml of hot water, was added, with thorough stirring, to 300 parts of a ~0% aqueous alkaline solution of a polyamide resin (TPX-1002). Carbonyl Iron G~-6 (63.4 parts), "Mapico" Black Iron Oxide (64 parts) and 410 parts of water were added and the slurry was stirred on a high shear mixex for 20 minutes. The toner slurry was spray-dried to give a final toner composition containing 30~ o~ polyamide resin, 31.7~ of Carbonyl Iron GS-6, 32~
of ~Mapico" Black Iron Oxi~e, 2~ of C.I. Aci~ Blue 40 and

4.~% o~ dextrin diluent. The toner was sieved through a 200 mesh screen and ~luidi~ed with 0.6% of Quso WR-8~.
~ latent magnetic ~mage such as described i~
Example 1 was manually decorated with the a~ove toner and transferred electrostatically to 100~ nylon 66 jersey fabric and steam fused at 100C and 1 atm pressure for 10 to 15 seconds. The acid dye was fixed by cot~age-steaming the printed ~abric at 7 psiy ~48,300 Pascal gauge) for 1 hour.
m e fabric was scoured at 60C with an aqueous solution of 2 par~s per liter of a polyethoxylated ol~yl alcohol and 2 parts per liter of al~yl trimethylammonium bromide surface-active agents7 A bright blue print was obtained.
xamples 45 to 53 _ Fexromasnetic acid dye toners werP prepared by ~anually mixing the appropria~e ingredients and spray-drying the slurries as desrribed in Example 44. The toners were fluidized with 0.2 to 1.4% of Quso WR-8~. Detai;s are swnmarized in Table III. A latent magnetic image such as descxlbed ~n Example 1 was ~anually decorated and the toner 3 de~orated image was electros~atically trans~2rred directly ~3'~

to nylon 66 jersey. The toners were steam fused and the acid dyes were ixed by cottage-steaming at 7 psig (48,300 Pascal gauge) for 1 hour. After scouring, bright well~de~ined prints were obtained.
Toners containing monosulfonated azo (Examples 45, 46 and 51) and monosulfonated anthraquinone (Examples 47 ~o 50) dyes, with water soluble polyvinyl acetate copolymer (nGelva" C5-VIOM), hydroxypropylcellulose ("Xlucel" L~) and polyamide (TPX-1002) rcsins, are exemplificd. ~xamples 52 and 53 include a speciàl disulfonated bis-anthraquinone dye whi~h is notcd for its good light- and wetfastness properties on nylon. Examples 47, 50, 51 and 53, with acid dyes and containing 1~ of ammonium oxalate, ~rovided brighter and tinctorially stronger prints on nylon than the corres-ponding toners without ammonium oxalate. Citric acid, present either in the toner tExample 49) or sprayed on the toner fused nylon (Example 48), was found to significantly improve dye fixation.
Example 54 This example illustrates the preparation of a ferromagnetic toner containing a ~iber~reactive d~e~ magnetic components and an aqueou~ alkali-soluble resin and the ~pplication thereof to cottonO
A magnetic toner was prepared by spray-drying a mixture containing 30% of polyvinyl acetate copolymer xesin ("Gelva" C5-VIO~), 3~% of Carbonyl Iron GS-6, ~3% of - n~apico" Black Iron Oxide, 2~ of C.II ~eactive Blue 7 (~.I. 611Z5) and ~ of inorganic diluent. The spray-dried pr~duct was sieved througll a 2~0 mesh screen and fluidized ~h Q.3~ ~uso WR-8~. A latent magnetic image such as described in Example 1 was manually decorated with the above toner and the decorated image was electrostatically trans-ferred to 100% cotton twill fabric by applying a 20 ~V
negative potential to the bac~side of the fabric. The printed fabric was steam fused at 100C and l atm pressure for 10 seconds. The toner fused cotton fabric was then sprayed with an aqueou~ solution containing 100 ~arts per liter of urea and 15 parts pcr liter of sodium bicarbonat~.
This overspray is required to chomically link the reactive dye to ~le cot~on by forming a covalent dyc-fiber ~ond.
Following th~ spray application, the cottGn abric was dricd and thc dye was fixcd by heating at 190C for 3 n~inutes ~n a hot aix oven. The fabric was then scoured at 65C
~n a~ueous detergent. A brilliant blue print having excellent washfastness properties was obtained.
Example 55 A spray-dried magnetic toner con~aining 30~ of -polyvinyl acetate copolymer resin ("Gelva" C5-~IOM), 33 of Carbonyl Iron GS-6, 33% of "Mapico" Black Iron Oxide, 2% of Reactive Yellow 2 and 2~ of inorganic diluent was directly printed on 100% cotton twill fabric in general accord with the procedure descxibed in Example 54. The ts~ner was steam fused and the printed fabric was sprayed with an aque~us solution containing 100 parts per liter of urea and 15 parts per liter of sodium bicarbonate. The dye ~as fixed by heating at lY2C for 3 minutes and t~e fabric was scoured at 65C in aqueous detergent. A bright yellow print was obtained.
Example 56 3 Foll~wing the proced~re of Example 55, a spray-dri d fer~omagnetic toner containin~ 30~ of polyvinyl ~3Zl~i acetate copolymer resin (nGelva" CS-VIOM), 33~ of Carbonyl Iron GS-6, 33~ of "Mapico" Black Iron Oxide, 2% C.I.
Reactive Red 2 and 2% of diluent was directly printed on 100~ cotton twill fabric. The toner was steam fused, the printed fabric was oversprayed with aqueous urea/sodium bicarbonate and the dye was fixed. A~ter scourins, a bright red print was obtained.
Example 57 This example illustrates the prepara~ion o~ a fe~romagnetic toner containing a reactive dye, a dispcrse dyc, ma~netic components and an aqueous alkali-soluble resin .~nd the a~plication thereof to polyester/cotton-blend fabric.
A magnetic toner was prepared by spray-drying a mix~ure containing 30~ of polyvinyl acetate copolymer resin ~Gelva" C5-VIOM~, 30~ of Carbonyl Iron GS-6, 31.1% of ~Mapico" Blac~ Iron Oxide, 3% o~ a 60/40 mixture of a yellow disperse dye of the formula shown as (B) in Table V~I and C.I. Reactive Yellow 2 and S.9~ of inoxganic diluent. The ~oner was sieved through a 200 mesh screen and fluidized with 0.2% of Quso WR-82. Toner decora~ion of a latent magnetic image was carried out as described in ~xample 1. The toner decorated image was electrostatically transferred directly to 65~35 polyes ter/cotton poplin fabric and steam fused at 100C and 1 a~m pressure for 10 seconds. Dye fixation was accomplished by heating the fabric at 210C for 100 seconds in a hot air oven. The printed fabric was finally scoured at 60~C in aqueous detergent. A bright yellow well-defined print was obtained.
Example 58 J~ A ~pray-dried magnetic toner containing 30~ of ~ 6 polyvinyl acetate copolymer resin tHGelva" C5-VIOM), 30~
of Carbonyl Iron GS-6, 30.1% of "Mapico" Black Iron Oxide, 3% of a 76/24 mixture of a blue disperse dye of`tne formula shown as (C) in Table VII and C.I. Reactive Blue 7 and 6.9~ of inorganic diluent was dir~ctly printed on 65/35 polyester/cotton poplin and steam fused as described in Example 57. The printed fabric was fixcd by heating at 200C for 100 seconds and then scoured at 60~C in aqueous deterg~nt. A bright blue print was obtained.

This example illustrates the preparation of a ferromagnetic toner containing a sulfur dye, masnetic components and an aqueous alkali-soluble resin and the application thereof to cotton.
A spray-dried magnetic toner containing 32.6%
of polyvinyl acetate copolymer resin ("Gel~a" C5-VIOM), 32.6% of Caxbo-ny1 Ixon GS-6, 32.6% of nMapico" Black Iron Oxide and ~.2~ of C.I. Leucd Sulfur Blue 13 (C.I. 53450) was prepared, sieved through a 200 mesh screen and fluidized with 0 . 2~ of Quso WR-82. A~ toner decorated latent magnetic image was electrostatically transferred, by a procedure such as described in Example 1, to 100~ cotton fabric.
The toner was steam fused at 100C and 1 atm pressure for 10 se~onds. The printed fabric was subsequently padded f~om an aqueous bath containing 300 parts per liter of ~odium sulfhydrate at a pickup of approximately 50~. The leuco dye was then immediately steam fixed at 100C and 1 atm pressure for 60 sec~nds. A~tex fixation, the printed fabric was developed by oxidation a~ 50C in an a~ueous ,~ b~th containing ~ pa~s per liter of sodium perborate.

~ ~2~ ~ 6 The fabric was finally scoured at 60C ~n an aqueous bath containing 2 parts per liter of diethanolamine oleyl sulfate surface-active agent. A blue print was obtained.
Examp 1 e 6 0 This example illustrates the preparation of a ferromagnctic toner containing a vat dye,. magnetic components and àn aqu~ous alkali-soluble resin-and the application thereof to cotton fa~ric.
A ~pray-dried ma~nctic toner containing 29~ of polyvinyl acetate copolymer resin tnGelva~ C5-V~CM~, 32.9 of Carbonyl`Iron GS-6, 32.~% of ~Mapico" Black Iron Oxide, 2.7~ of C.I. Vat Red 10 (C.I. 67,000) and 2.5% of dilue~t was used to manually decorate a latent magnetic image on a 300 line per inch (12 per mm) magnetically structured CrO2 coated aluminized "Mylar" film. T~e toner decorated latent image was electrostatically transferred to 100% cotton twill fabric and the toner was steam fused at 100C and 1 atm pressur for 10 seconds. The printed co~ton fa~ric was then padded from a reducing ba~h containing 34 parts per liter of soda caustic 60 parts per liter of soda ash 60 paxts per liter of sodium hydrosulfitP
2 parts per liter of sodium octyl/decyl zulfate surface-active agent 15 parts per liter of amylopectin ~hic~ening agent 2 parts per liter of 2-ethylhexanol at a pic~up of 70 to 80~ and f lash aged at 132C for 4$
~econds. The fabric was rinsed in cvld water, oxidized fox 1 minute at 60C ~n a bath containing 2% hydrogen peroxide ~ 65 -and 2% glacial acetic acid~ rinsed and scoured for 5 minutes at 82~C i~ 0.S part per liter (aqueous) of a diethanolamine oleyl sulfate surface-active agent. A bright red print was ohtained.
xample 61 A spray-~ried ferromagnetic toner containing 30 of polyvinyl acetate copolymer resin (UGelva" C5-VIOM), 33~ of Carbonyl Iron GS-6, 33~ of "Mapico" Black Iron Oxide-, 2~ of C.I. Vat Blue 6 (C.I. 69825) and 2% of diluent was~
prcpaxed and the lat~nt ima~e producc~ therewith was transferred dircctly to 100~ cotton twill fabric. The toner was fused, the vat dye was fixed and the printed ~abric was scoured as described in Example 60. ~ bright ~lue print was obtained.
~xample 62 ` . ~`
A spray-dried ferromagnetic toner containing 30%~
of polyvinyl acetate copolymer resin (~Gelva" C5-VIOM), 33~ of~ Carbonyl Iron G5-6, 33% of "~apico" Black Iron Oxide, ~% of C.~. Vat Yellow 22 and 2~ of diluent was prepared 2~ a~d printed on 100% cotton twill fabric by a procedure substantially as described in Example 60. A yellow print was obtainedO

~his example illustrates the preparation of a ferromagnetic toner containing a premetalized acid dye, ~agnetic componen~s and an aqueous alkali-soluble resin and the application thereof to nylon.
A spray-dried magnetic toner was prepared so as ~o contain 30% of polyvinyl acetate copolymer resin (~GelYa~ C5-V~O~, 31.4~ of ~arbonyl Iron GS-6, 31.4~ of "Mapico" Black Iron Oxide, 2% of C.I. Acid Yellow 151 (a sulfonated premetalized azo dye) and 5.2% of inorganic diluent. The toner was sieved through a 200 mesh screen and fluidized with 0.2% of Quso WR-82. A toner decorated latent magnetic image such as described in Example 1 was electrostatically transferred to nylon 66 jersey fabric and steam fused at 100°C and 1 atm pressure for 10 seconds.
The premetalized acid dye was fixed by cottage-steaming the fabric at 7 psig (48,300 Pascal gauge) for 1 hour.
The printed fabric was then scoured at 65°C in an aqueous solution of 2 parts per liter of each of sodium hydrosulfite, soda caustic and polyethoxylated tridecanol surfactant. A
second toner transfer was made to nylon 66 jersey fabric.
The toner was steam fused and the fabric was oversprayed with a 50% aqueous solution of citric acid. The dye was fixed by cottage-steaming at 7 psig (48,300 Pascal gauge) for 1 hour and the printed fabric was caustic-hydro scoured as above.
In both cases, strong well-defined yellow prints were obtained.
Example 64 Using the procedures substantially as disclosed in Example 63, a spray-dried ferromagnetic toner containing 30% of polyvinyl acetate copolymer resin ("Gelva" C5-VIOM), 32.1% of Carbonyl Iron GS-6, 33% of "Mapico" Black Iron Oxide, 2% of C.I. Acid Red 182 (premetallized azo dye) and 2.9% of inorganic diluent was prepared and electrostatically transferred to nylon 66 jersey fabric. After steam fusing, cottage-steaming and scouring, a well-defined bright red print fabric was obtained. A similar sharp red print was obtained when the fabric was oversprayed with 50% aqueous citric acid prior to cottage-steaming.

7t~

Examples 65 to 68 Examples 65 to 68 illustrate the preparation of ferromagnetic toners containing cationic-disperse dyes, magnetic compo~ents and an aqueous alkali-soluble resin and the application thereof ~o acid-modified polyester, polyacrylonitrile and cellulose acetate.
Cationic-disperse dyes, 'hat is, water-insoluble salts o~ dye cations and selected arylsulfonate anions, are well-known in the art for dyeing acid-modified polyestcr ~nd acrylic fibers. Cationic-disperse dye toners were prcpared by manu~lly mixing ~hc appropriate ingredicnts (20% non~olatile solids) and spray-drying. The spray-dried toners were sieved through a 200 mesh screen and fluidized with O.2~ of Quso ~7R-82. Details are summariæed in ~able IV. Examples 65 to 67 use 1,5-naphthalenedisulfonate as ~he anion and Example 68 uses 2,4-dinitrobenzenesulfonate as the anion. Toner decoration of a latent magnetic image and electrostatic transfer to the fabric substrate were preformed as d~scribed in Example 1. The toners were steam fused and the printed abrics were oversprayed witn 50~
a~ueous citric acid to aid in dye fixationq The dyes were ~ixed by either cottage~steaming or high-pressure steaming ~he spxayed fabrics. Arter scouring, in each example, ~ well-defined print was obtained.
Example 69 This example illustrates the preparation of a ferromagnetic toner containing a fluorescent brightening agent, magnetic components and an aqueous alkali-soluble ~esin and the ap~lication thereof to cotton.
A ~agne~ic toner containing 30% of polyvinyl ~13~

acetate copolymer resin ~nGel~a~ C5-VIOM~, 34% of Carbonyl Iron GS-6, 34% of ~Mapico~ BlacX Iron Oxide and 2~ of C.I. Fluorescent Brightener 102 was prepared by spray-drying an a~ueous 20~ nonvolatile solids mixture of the i~gredients. The spray-dried toner was sieved through a 200 mesh screen and fluidized with 0.2% of Quso WR-82.
A latent magnetic image such as described in Ex~mple l was toner decorated and the image was electrostatic~lly transferred to 100~ c~tton shceting. The toner was steam fused and the bright~ner was ~ixed by heating the fabric at 100C and l atm pressurc for 25 minutcs. The printbd fabric was ~hen scoured at 60C in an aquQous solution of 2 parts per liter of soda caustic and 2 parts per liter of polyethoxylatPd tridecanol surfactant. Upon exposure to ~n ultraviolet light source, the printed fabric strongly fluoresced in the imaged areas.
Examples 70 to 74 These examples illustrate the preparatio~ of ferro-~agnetic toners containing a chemical-resist agent, magnetic components and an aqueous alXali-soluble resin and the application thereof ~o nylon. The toners were prepared by spray-drying an aqueous 20% no~volatile solids slurry of the appropriate ingredients. The spray-dried toners were sieved through a 200 mesh screen and fluidized with 0.2 of Quso W~-82, Details are summarized in Table Y. The ~hemical-resist toners were evalua~ed by manual decoration of ~he latent magnetic image o~ a 300 line per inch (12 per r~) ~agnetically structured CrO2 coated aluminized "Mylar" ~ilm by proc~dures substantially the ~ame ~s described in Example l.
~h~ toner-deco~ated images were transferred electrostatically 3~

to nylon 66 jersey fabric and steam fused at 100C and 1 atm pressure for 10 to 15 seconds. The che~ucal resist in each example was ~ixed by steaming (atmospheric) the fabrir for 20 minutes. Each printed fabric was rinsed in water to remove the resin and the magnetic component(s) and ~inally dried. Each resultant resist printed nylon fabric was then overdyed with either a red biscationic dye of the formula shown as ~D) or a blue diacidic (anionic) dye o~ the formula shown as (E), or a mixture thereof, the 'O (D) and (E) formulas bein~ given in Table VII, by the following procedurc:
Resist-printed nylon fabric t5 par~s) was added to 300 parts of water containing:
ethylenediaminetetraacetic a~id, t~trasodium salt ~,...... 0.013 part ~0.25% owf) a sulfobetaine of the formula shown a~ (F) in Table VII ..~. 0.05 part ~1.0% owf) te~rasodium pyrophosphate ... ~...... 0.010 part (9.2~ owf).
~he dye bath was adjusted to pH 6 wi~h monosodium phosphate and the temperature was raised to 27C and held at this temperature for 10 minutes. The cationic dye ( 0 . 025 part;
0.5% owf, that is, on weight of fiber) and~or the acidic dye (O.a25 part; O.S~ owr) were added. When both types of dyes were employed, the bath containing the cationic dye was held-at 27GC for 5 minutes prior to the addition of the anionic dye. After completion of the dye(s) addition ~he bath was mai~tained at 27~C for 10 minutes, the temperatuxe was r~ised at about 2C per minute to 100~C
and held at this temperature for 1 hour. Each fa~ric was rinsed in cold water and dried. The printed-resist fabrics remained unstained in the imaged areas during the subsequent overdyeing process.
Toners containing 2, 4, 6 and 8% of a chemical-resist agent of the formula shown as (G) in Table VII
and binary soft tFe) and hard (Fe3O4) magnetic materials are illustrated in Examples 70 to 73; they showed excellent chemical-resist properties on nylon. An analogous magnetic-resist toner containing only chromium dioxide 10 as the hard magnetic component (Example 74) also ~3rovided satisfactory printed resist on nylon.
Example 75 A ferromagnetic disperse dye toner containing 30% of a polyamide resin (Versamid* 930), 34% of Carbonyl Iron GS-6, 34% of "Mapico" Black Iron Oxide and 2% of C.I. Disperse Yellow 54 was prepared by ball-milling and spray-drying a 20% nonvolatile soli.ds toluene-isopropanol slurry of the ingredients by a procedure substantially as described in Example 3. "Versamid" 930 is a water-20 insoluble resin having a molecular weight of about 3,100and a softening temperature of 105-115C. Such. water-insoluble resins are disclosed as having utility in prior art, known magnetic toners, for example, such as disclosed by Hall and Young in U.S. 3,627,682.
A magnetic disperse dye toner containing 31.1%
of polyvinyl acetate copolymer resin (."Gelva" C5-VIOM), 30.7% of Carbonyl Iron GS-6, 30.7% of "Mapico" Black Iron Oxide, 1.9% of C.I. Disperse Blue 56 and 5.6% of dispersant was prepared by spray-drying an aqueous slurry of the 30 ingredients containing 2Q% of nonvolatile solids.
* denotes trade mark ~3~17~

Bo~h of the afsresaid toners were manually applied to the latent images on a CrO2-coated aluminized "~ylar"
film and electrostatically transferred to 100% polyester double-knit fabric by procedures substantially the same as described in Example 1. The toners were steam fused and the disperse dyes were fixed by heating the printed fabrics at 210C and 1 atm pressure for 15 seconds. ~he printed fabrics were then scoured at 75C in an aqueous solution of 4 parts per liter of caustic soda, 4 parts per liter of sodium hydrosulfite and 2 parts pcr liter of "Lakeseal"
detergent. The fabric printed with the disperse dye toner containins the watcr-soluble resin was completcly clear of resin and magnctic componcnts after just a fcw seconds of gen~le stirring in the scouring medium, The fabric printed with the watcr-insolublc resin was not clear of resin and magnetic components cvcn after 15 minutes scouring at 75C. Thus, the resin impregnated masnetic particles were much more easily removed by aqueous scour from the printed fabric using the dye toner containing the water-soluble resin as compared to the toner containing the w~ter-insoluble resin This clearly shows that the scouring medium must be suitable for the resin being used since the presence of the black iron-iron oxide on the fabric surface effectively mas~s the color of the dye fixed in the fabric. In the aforesaid experiment employing the water-soluble polyvinyl acetate resin, scoured fabric was printed to a bright blue whereas in the experiment employing the water-insoluble polyamide resin, the aqueous scoured fabric was printed to a dark brown to blacX, completely masking the bright yellow color of the dye employed. Scouring with a 50-50 mixture of isopropanol-toluene at 60C provided a significantly hetter print in that the yellow color of the dye was evident.
Example 76 This example illustrates the preparation of a ferromagnetic dye toner containing a yellow disperse dye, magnetic components and a water-soluble natural resin, and the a~plication thereof to paper and polyester.
A mixture of 350 parts of a commercially available 20% aqueous solution of a maleic anhydride-rosin derivative 10 tUnirez* 7057), 28.~ parts of C.I. Disperse ~ellow 54 as a 28.2% standardized powder containing a 50/50 mixture of li.gnin sulfonate and sulfonated naphthalene-formaldehyde as a dispersant, 60 parts of "Mapico" Black Iron Oxide and 59.6 parts of Carbonyl Iron GS-6 was stirred for 30 minutes on a high-speed shear mixer. Water (,502 parts) was added and the resultant slurry was spray dried to give a final toner composition containing 35% of esterified rosi.n, ~% of C.I. Disperse Yellow 54, 1.2% of the li.gnin sulfonate/sulfonated naph.thalene-formaldehyde dispersant, 3Q% of "Mapico" Black Iron Oxide and 29.8% of Carbonyl I,ron GS-6. The toner was sieved through a 200 mesh.
(U.S. Sieve Series) screen and flui.dized with 2% of ,Ouso WR-82. A latent magnetic i.mage such as described in Example 1 was manually decorated with the toner and the toner decorated image was transferred electrostatically to both.pape,r and polyester subs.trates. by applying a 20 KV
negative potential, using a DC corona, to the back.side of the substrate. After transfer the image was steam-fused on each,substrate~ After direct transfer and fusion to the polyester fabric, the dye image was fixed by heating for 30 seconds~ at 210C and 1 to 1.5 psi (6,900 to 10,350 Pascal) * denotes trade mark ,;, h~J~i pressure. The dye was also heat transfer printed from the paper to polyester fabric by placing the fused image-bear-ing paper face down on the polyester and applying l to 1.5 psi (6,900 to 10,350 Pascal) pressure for 30 seconds at 210C. Each of the fabrics~ after dye fixation, was scoured with hot aqueous alkaline detergent. Deep yellow prints were obtained on each, that is, the polyester which was directly printed and the polyester which was heat transfer printed from paper.
Example 77 This example illustrates the preparation of a ferromagnetic dye toner containing a yellow disperse dye, magnetic components and an aqueous alkali-soluble poly-acrylic acid resin, and the application thereof to paper and polyester.
A ferromagnetic toner was prepared by spray-drying a mixture containing 35% of a commercially available, aqueous alkali-soluble polyacrylic acid resin (Joncryl*
678), 4% of C.I. Disperse Yellow 54, 1.2% of a 50/50 mixture of lignin sulfonate and sulfonated naphthalene-formaldehyde dispersant, 30% of "~apico" Black Iron Oxide and 29.8% of Carbonyl Iron GS-6. The spray-dried toner was sieved through a 200 mesh (U.S. Sieve Series) screen and fluidized with 0.1% of Ouso WR-82. The toner was used to manually decorate a latent magnetic image on the surface of a printing base such as described in Example 1.
The decorated image was then electrostatically transferred and steam fused to paper and suhsequently heat transfer printed from the paper to 100% polyester fabric as describ-ed in Example 76. The image was also directly printed to* denotes trade mark lO0~ polyester fabric as described in Example 76. In both cases the fixed printed fabrics were scoured at 65C
in an aqueous polyethoxylated tridecanol surfactant solution; deep yellow prints were obtained on both fabrics.
Example 78 This example illustrates the preparation of a erromagnetic dye toner containing a red disperse dye, a magnetically hard component and an aqueous alkali-soluble polyvinyl acetate copolymer resin, and the application thereof to paper and polyester film and fabric.
A ferromagnetic toner was prepared by spray-drying a mixture containing 30% of polyvinyl acetate copolymer resin, 65.8% of a commercially available Fe304-cobalt alloy (HiEN* - 527) containing 1 to 2 mole percent of cobalt, 1% of C.I. Disperse Red 60 and 3.2% of a lignin sulfonate dispersant. The toner was passed through a 200 mesh screen. The toner flow properties were excellent. The toner was used to manually decorate a latent magnetic image on the surface of a printing base such as described in Example 1. The decorated image was electrostatically transferred to paper, steam fused and then heat transfer printed from the paper to 100% polvester fabric. The image was also directly transferred to both 100% polyester fabric and "~ylar" polyester film and then steam fused. In each case permanent dye fixation was achie~ed by heating the printed film or fabric substrate at 205-210C and 1.5 psi (lOr350 ~ascal) pressure for 40 seconds. The printed substrates were finally scoured at 82C in an a~ueous solution of 2 parts/liter of caustic soda, 2 parts/liter of hydrosulfite and 2 parts/liter * denotes trade mark ~3~
of a polyethoxylated tridecanol sur~actant. Bright red prints were obtained in each case.
~xample 79 This example illustrates the preparation of a ferromagnetic dye toner containing a yellow disperse dye, magnetic components and a water-soluble polyacrylic acid resin, and the application thereof to both paper and poly-ester.
A ferromagnetic toner was prepared by spray-drying a mixture containing 35% of a polyacrylic acid resin~ oncryl" 678, 4% of C.I. Disperse Yellow 54, 1.2% of a 1 to 1 mixed lignin-sulfonate/sulfonated naphthalene-formaldehyde dispersant, 30% of "Mapico" Black Iron Oxide and 29.8% of Carbonyl I:ron GS-6. The spray-dried toner was sIeved through a 20Q mesh screen (U.S. Sieve Series) and fluidized with Quso WR-82 in a high-speed Waring*
blender. Outstanding toner flow and decoration properties were obtained using from 0.1 to 0.2% of Quso WR-82 at low blending speeds for 20 to 30 seconds. The toner was used to develop the latent magnetic image on the surface of a CrO2-coated aluminized polyester printing member (such as 1 as shown in Figure 1) using a printing apparatus such as depicted in Figure 11. Any subsequent numbered references in thi.s example refer to said Fi.gure 11. A continuous 0.18 mil (.4.6 micron) coating of CrO2 dispersed in a resi.n bi-nder was uniformly applied to the surface of an aluminized 2 mil (50.8 micron~ poly-ester fi~mbase (:"~ylar"). The CrO2 particles dispersed in the resin binder were applied to the aluminized polyester film in the presence of a magnetic i.eld to orient the particles parallel to the length o the film. The film * denotes trade mark ~3'~

was then magnetically structured into a 253 to 450 lines per inch (98 to 178 lines per cm) magnetic pa~tern using a 0.5 inch (1.3 cm) wide magne~ic write head. The structured film was imagewise demdgneti~ed by ex?osure to a short burst from a Xenon lamp flashed through an image-bearing photographic transparency. The resultant partially demagneti~ed aluminized CrO2 film was then mounted on a rotary drum (such as 12 of Figure 11). The magnetic image on the CrO2-coated aluminized polyester film was developed with toner particles 15 applied by means of magnetic brush 16. Both the brush and the film drum were driven at the same surface speed of 40 ft/min (12.2 meters per minute). Excess toner W2S removed from the background of the decorated printing member by means OL neutralizina AC corona 18 and air ~nife 19. In this exa.mple, a preferrQd-embodimen~, the AC corona 18 -was em?loyQd to neutrGlize the stat~c charge on the toner particLes. ThQ
pressure of the air stream sup~lied by the air knife was adjusted to the point where only the excess toner and not the toner decorating the magnetic image was removed. Air supplied a a pressure of 0.4 inch tl cm) of water from ~n orifice held 0.25 inch (0.6 cm) from the suxface of the printing member fulfilled these conditions. The toner-decorated image on the printing member was electrostatically transferred to polyethylene terephthalate fabric 5 hy cha_ging ~Ihe back of the îabric with DC corona device 20 which com~rised a corona wire spaced about 0.5 inch (1.3 c~) from the ~abric and maintained at 5,000 volts negative ~otenti21. Following transfer, the toner particles were Cused ~o the faDric by heating at 90 to 120aC

.

using two banks of 500 watt infrared lamps 24 placed approximately 1 ir.~h ~2.5 cm) from the fabric and operatins ~t 93% efficiency. ~e printed polyethylene tereph.halate fabric was finally removed on take-up roll 28. Toner particles remaining on .the surface of printing member 1 were removed by.vacuum brush 21 and the ~urface was neutralized with AC corona 22 prior to redecoration.

The use of AC corona 22 represents a preferred embodiment wherein the,corona neutrali~es the static charge on the 1~ toner particles remaining on the aurface.

A similar run, made in a similar fashion and providing similar ~esults, was made using paper as the substrate.
Exam~le 80 This example illustrates the preparation of a ferromagnetic dye toner containins a red disperse dye, a soft magnetic component and an aqueous al~ali-soluble resin, and ~hç application there~f to pa?er.

A ferromagnetic toner was prepared by spraY-2~
drying a mixture containins 10~ of polyvinyl acetate copolymer resin t~lGelvall CS-VIOM), 1% of C.I. Disperse Red 60, 3.2~ of lignLn sulfonate dispérsant and 8S.8% of Carbonyl Iron GS-6. The!spray-dried toner was fluidized with l~ of Quso WR-82 and used to develop the latent .
magnetic image on the surface of a continuously CrO2-coated (220 microinches) (5.59 x 10 4 cm) aluminized "~yla-"~
polyester printing member (such as 1 depicted in Figure l) usins a printing appa-atus sucn 25 that depicted in Figu_e ll. ~he CrO~ s~rface of the printing member was magnetically structured into a 500 lines per inch (197 .f~

lines per cm) magnetic pattern using a magnetic write head;
it was then imagewise demagnetiz2d by exposure to a short burst from a Xenon lamp flashed t~rough an image-bearing photographic transparency. The resultant latent magnetic image was developed with the toner particles and the tor.er decorated image was electrcstatically transferred to paper al~d fused thereon as described in Example 79. A

~ell-defined, ~c~ground-free red print was obtained.
~xample 81 10 . A ferromagnetlc toner containing ~6~ of pol~yvinyl acetate copolymer resin ("Gelva" C5-VIOM), 1~ of C.I.
Disperse ~ed 60, 3.2~ of lignin sulfonate dispersant and 59.8% of Carbonyl Iron GS-~ was similarly prepared and applied to paper as described in Example 80 The results were comparable to those of Example 80.
Exam~le 82 .
This example illustrates the magnetic transfer printing of a ferromagnetic dye toner containing a blue disperse dye, magnetic components and an aq~eous alkali-sol~ble resin.
A ferromagnetic toner was prepared by spray-drying a mixture containing ~S~ of polyvinyl acetate c~polymer resin (~&elva" C5-VIOM), 2% of C.I. Disperse Blue 59 crude powder, 37~ of "Mapico~ Blac~ Iron Oxide and 36% of Carbonyl Iron GS-6. The toner, which had a particle ~ize within the range 3 to 20 microns, was used to develop the latent magnetic image on the surface of a 197 lines per cm, magnetically structured, CrO2-coated, alumini~ed YMylar" polyes~er film. The toner i~age was magnetically -' transferred from the decorated film to paper by ap~lication ~32~7~;

of a magnetic field o~ approximately 625 gauss averase strength supplied by a permanent magnet (approximately 1,200 gauss) placed behind the paper. The toner particles transferred completely from the latent magnetic imase on the film to the paper.
Example _83 The ~oner of Example 82 was used to develop the la~ent ~gnet~c i~age on the sur~ace of a CrO2-coated aluminized polyester printing member (such as 1 as shown in Figure 1) using a printing apparatus such as depictea in ~igure 11. The tone~ decorated imase on the printing member was magnetically transferred to paper using a 1,200 gauss permanent magnet in place of the DC corona device 20 depicted in Figure 11. Usins a field strensth of 540 gauss, good transfer of the ~oner particles from the printins member to the paper was obtained.
Exam~ie 84 The toner of Example 82 was magnetically transferred to p~er uslng a printing apparatus such as depicted in Figure 11. In this case, however, DC corona device 20 shown in ~igure 11 was replaced by a meta~ pressure roll wrapped with a 0.25 inch (0.64 cm) layer of a flexible/ permanent magnetic material,` such as a rubDer bo~ded barium ferxite (commercially aYailable under the trademarX "Plasti'orm"). At a surface field stre~gth of 370 gauss, the magnetic roll pressed the paper against the decorated image and good toner transfe~ was obtain ed .

~ ~ 32 Exam~l~ 85 A ferromagn~tlc toner con~ainln~ 25~ of P~ solvent- -~~oluble pol~amide resin ("VersP~mid" 93O~, 36~ of "~laplco" Bi~c'.
Iron Oxlde, 36$ of Caroonyl Iron GS-6 ~nd 3~ of C,I. Disperse Red 60 crude powder ~as prepared by ball-mllllng and spray-d~ying a 3O~ non~olatile solids mlxture of the ingredients in 5O:5O toluene-isopropanol. The spr~y-drled toner was sie~ed through a 200 mesh screen, fluid~zed with 0.5~ of Quso WR-82 and used to develop the latent magnetic image on the surfac~ of a 35O microlnch CrO2-coated aluminized "~Y1Pr~ polyester print-~ng ~ember (~uch as 1 depicted in Figure l) uslng a prlntinO

apparatus such ~s that deplcted in Figure ll. The C~02 surface o~ the printlng member was magneticPlly structured into a 333 llnes per ~nch magnetic pattern using a ma~netic ~rite hezd;
it was then ima3ewise dema~netized by exposure to a short burst from a Xenon lamp fl_shed through an ~age-bearin~ pho~o~rP?hic transparency, The resultant latent ma~,netic ima~e was de~eloped with the toner particles and the toner decorated image was elec-trostatically transferred to polyet~ylene terephthalate ~abric and fused thereon as described in Exam?le 79O The dye was fixed by steaming at 14 psig (96,600 Pascal) for one hour. The printed fabric was scoured at 60C for 5 minutes in a mixture o ;0:50 isopropanol-toluene and then rinsed for 90 seconds with i0:50 isopropanol-toluene. A red print was obtained.
Exam~le 86 -A toluene-isopropanol ball-milled and spray-dried ferromagnetic toner contalning 21% of Carnauba wax, 37~ of "Mapico" Blac~ Iron Oxide, 38~ of Carbonyl Iron GS-o and 4 or C.I. Dispers~ Red 60 crude pcwder was electrostatically ~^~ transrerred to ?olyethylene t-rephthalate rabric and ~used .- 81 -~13~7~i thereon as described in Example 85. The ~e wzs ~ixed b~
s~eaming at 14 psig (96,600 Pzscal) for 1 hour. The printed fabric W2S scoured at 60C for 5 minutes in toluene and then rinsed for 90 seconds with 50:50 isopropanol-~oluere to glve a red print.
Exam~le 87 A ferromagnetic toner containing 30~ of a solvent-soluble polyamide resin ("Versamid" 930~, 30~ of "Ma2ico"
Blac~ Iron Oxide, 29.6~ of Carbonyl Iron GS-6, 2~ of C.I.
Basic Red 14 and 8.4~ of inert diluent,for example-, boric acid, was prepared by ball-milling and spray-d~ying a 30 nonvolatile solids mixture o~ the ingredients in 50:50 toluene-isopropanol. The spray-dried toner was sieved through a 200 mesh sc~een and fluidized with 0.4~ of Quso WR-82. The latent magnetic image on a 300 lines ~er inch CrO2-coated aluminized "~ylar" film was manually decorzted and the toner transferred electrostatically to polyacrylo-nitrile fabric as described in Example l. The toner was steam-fused and the cationic dye fixed by steàming zt 2 psig (13,800 Pascal) for 1 hour. Th~ printed fabrlc was scoured in an aqueous bath containing 2 parts/liter or soda caustic and 2 partq/liter Or a polyethoxylated tridecanol surf2ctznt. After scouring for 30 minutes at 50 to 6GC, the res~n and ferrom20netlc components were only ?2rtially re~.oYed .rom tne prir.ted ~abric, thus illustratin~ the in-fi'ectiveness o:' convention21 zau-ous al~aline scour-r.O
procedu-es for removinO ~olvent-soluble resin-im~re~nzted .erro~20netic ~art'cles from the ?rlnt-d f~b--c. A scou~-in~ solvent ~hlch is comcatible wi~h tne resin, :'or -xamp e, 31^ isopr3p2nol-toluen-, czn oe usad to ?ro~ide ~rin~s wnic;~

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are signlficarvly better (in exhibltin$ the color of the dye) than those obtained from the aqueous scour.
Ex m~te 88 _ A toluene-isoprop~nol ball-milled and spray-dried ferrom2~netic toner containing 30~ OL "Versamid" 930, 33~ of "Mapico" Black Iron Oxide, 32.4p of "Carbonyl" Iron GS-6, 2~ of C.I. Acld Red 151, 1~ of oxalic acid and l.o~
of inert diluent was electrostatically transferred directlv to nylon 66 ~ersey fabric as described in Example 1. The toner was steam-fused and the acid dye was fixed by steam-in~ at 2 psi~ tl3,800 Pascal) for 1 hour. Scouring in aqueous alkaline surfactant ~t 50 to 60C L ailed to com-pletely remove the resin-imbedded ferrom2gnetic parvicles from the printed nylon fabric. The printed fab~ic C2n bS
scoured with 50:50 isopropanol-toluene to give a r~d print.
Examples 89 to 110 Tone~ Examples 89 to 102 and 105 to 110 ~ere prepared by ball-millin& and spray-drying a 40 to 60a~ r.Gr.-volatile solids slurry of dye (or pi~ment), fer~omag~etlc component(s) and solvent-soluble resin ln a 50:50 mixvure of toluene-isopropanol. The percent nonvclatile solids concentration and the spray-d~yin~ conditions were varied in ord~r to produce spherical, large-size toner particles.
Toner Examples 103 and 104 were prep2red oy a ?rocess of "he2t sphericallzation" ~herein the solvent-soluble resi and ferromagne~lc p~rticles ~ere irst combinea -n ~ 70:30 ~xture of toluene-zcetone and s?r2y-dried. The dye ~as then added ~t 205~C âO that th- dye parti^i-~ ere embecàec on the su-f'ace OLt the toner. The com?osi~ions of th_ 3 ferroma~netic tor.ers are ~iven in Tzble VIII. The ton-rs / ~ ~
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were fluidized by the addition of from 0.1 to n. 3% of Quso WR-82.
Toner Examples 89 to 105 contain disperse dyes and solvent-soluble resins and can be magnetically printed on polyethylene terephthalate fabric as described in Example 85. After scouring in a suitable organic solvent, red, blue or yellow prints can be obtained. Carbon black pigment toners are described in Examples 106 to 110 and can be used to provide optically dense black prints when mag-netically printed to a substrate such as paper or poly-ethylene terephthalate fabric. The Darco* Carbon Black G-60 which was used is a commercially available premium grade of powdered activated carbon which generally is used for decolorizing, purifying and refining and is made by the activation of lignite with heat and steam. In these Examples 106 to 110 it is not necessary to remove the ferromagnetic component and the resin.
It is to be understood that each above example does not necessarily recite all details regarding the mag-netic printing process and/or apparatus of the invention.Any unrecited details relative to the invention can readily be ascertained by one skilled in the art from other examples and/or from the non-example portions of this specification.
The following experiments illustrate the need to use a conductive printing member in order to eliminate static charge buildup on the printing surface when using electro-static transfer.
E periment 1 A 180 microinch ~4.6 x 10 4 cm) thick coating of CrO2 in a resin binder was applied to the surface of a

5 mil (0.013 cm) polyester film ("Mylar"). The resultant * denotes trade mark ~3~7~

CrO2 film had a coercivity of 567 oers~eds a~d a resistivity of approximately 108 ohms/square. The film was mounted an~ electrically connecteZ to a 5-inch (12.7 cm) wlde, S-incn (12.7 cm) diameter grounded aluminum drum.The C~2 sur_zce was revolved past a DC corona at a speed of 0.4 to 1.5 seconds per revolution. At only 7,000 volts positive corona potential, a surface charge was found to rapidly build up (resulting i~ a fiel~ increase of approximately 1,000 volts per cm per revolu-tion of the drum) on the CrO2 film. Thus, the CrO2 film 10 surface was not conductive enough to dissipate the charge from the corona.
eriment 2 The conductivity experiment described in Experi-ment 1 was repeated, exce?t that two AC coronas were placed about 0.25 lnch ~0.6 cm) ~rom the film surface in order to neutralize surface charges. At 2,000 volts negative DC corona potential, no surlace charge buildup was detec'ed on the CrO2 film. At 8,000 volts negative DC potential, only a 600 volt per cm buildup was measured on the rihm surface.
Thus, the AC coronas effectively dissipated the surface char~es below 2 ,000 volts DC potential on the corona device but did not completely remove all the charse from the film surface at higher potentials.
~XDerim.ent 3 .. . .. .
A 120 microinch (3 x 10 4 cm~ thic.~ layer or CrO2 in a resin binder was applied to the surface of a t;~in copper sheet. The CrO2-coated copper sh~et was mounted on a grounded drum and subjected to a 3,500 volt positive potenti~l ~rom z DC corona as described in ~xDeriment 1.

When tested ror static charse buildup usi.~ a commercially 8~

~3'~17~;

availa~le static voltmeter, th.e CrO2 surface was found to be highly resistant to charge buildup.
Experiment 4 A 65 microinch (1.65 ~ 10 4 cm) coating of CrO2 in a resin binder was applied to the surfac~ of a 2 mil ~0.005 cm) aluminized polycster film ("Mylar"). During the coating operation, the CrO2 was magnetically-oriented by passing the coated film hetwcen identical poles of two ~ar magnets havin~ an approximate field strength of 13 1 500 ~auss. Ihe coated fllm was c~iencered by hcatin~
contact wlth hot ro~;ers at 90C under high pressure. The resultant CrO2-coated ~ilm had a coerclvity of 526 oersteds and an orientation of 0.80. When tested for static buildup properties zs described in Experiment 1, the CrO2-coated aluminlzed film W2S found to be highly resistant to char~e buildup when electric211y connected to the grounded drum.
Ex~eriment 5 -A 5-inch (12.1 cm) wide by 5-inch (12.7 c~) dia-meter copper sleeve W2S directly coated with a 200 micro-inch (5 x lQ-4 cm) layer of CrO2 in a resin binder. The sleeve wa~ dip coated from a slurry OL- CrO2 and resin in tetranydro~uran-cyclohexano~e (25:75 by wei~ht) and the solvenks were slowly removed by evaporation. A pair of perm2nent magnets t~as used to orient tne GrC2 as described in Ex~er'.~ent 4. The CrO2 sur~ace sho~ed little tendency to sustain 2 st~tic charOe when electrically connected to the ~rounded drum.
The coppe~ sleev- can also be chemic211y etchec into a 250 to 350 lines per inch (98 to 138 lines ~er c~.) ~rooved p2ttern and the ~rooves L 111ed wi~h th- CrG2 ~r.i r~sln binder. This would provide a h2rd~ conductive, per..anently structurec .~.agne lc p.~n~in~ su~f~ce.
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Claims (21)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A magnetic printing member comprising a ferro-magnetic material forming a magnetic layer on a support which comprises an electrically conductive material, whereby the member is adapted in use to discharge electric charges at all times from substantially the entire surface of the magnetic layer through the thickness of the magnetic layer to the electrically conductive material, said surface being adapted to record a magnetic image thereon and print a substrate using a ferromagnetic toner.

2. A magnetic printing member of Claim 1 in which the support additionally comprises a dielectric material.

3. A magnetic printing member which comprises a ferromagnetic material forming a magnetic layer on a di-electric support and having an electrically conductive layer disposed therebetween whereby the member is adapted in use to discharge electric charges through the thickness of the mag-netic layer to the electrically conductive layer, said print-ing member having a surface which is adapted to record a mag-netic image thereon and print a substrate using a ferro-magnetic toner.

4. Printing member of Claim 1 wherein the ferro-magnetic material is a continuous coating on the support.

5. Printing member of Claim 2 wherein the ferro-magnetic material is a continuous coating on the support.

6. Printing member of Claim 3 wherein the ferro-magnetic material is a continuous coating on the support.

7. Printing member of Claim 4 wherein the support is a metallized dielectric film.

8. Printing member of Claim 5 wherein the support is a metallized dielectric film.

9. Printing member of Claim 6 wherein the support is a metallized dielectric film.

10. Printing member of Claim 4 wherein the support is a metal sleeve coated with a layer of elastomeric material containing conductive particulate material uniformly dispersed therein.

11. Printing member of Claim 5 wherein the support is a metal sleeve coated with a layer of elastomeric material containing conductive particulate material uniformly dispersed therein.

12. Printing member of Claim 6 wherein the support is a metal sleeve coated with a layer of elastomeric material containing conductive particulate material uniformly dispersed therein.

13. Printing member of Claims 10, 11 or 12 wherein the conductive particulate material is carbon black.

14. Printing member of Claims 1, 2 or 3 wherein the ferromagnetic material is acicular CrO2.

15. Printing member of Claims 7, 8 or 9 wherein the metallized dielectric film is an aluminized polyester film.

16. Printing member of Claim 1 wherein the support contains grooves and the ferromagnetic material is in the grooves.

17. Printing member of Claim 2 wherein the support contains grooves and the ferromagnetic material is in the grooves.

18. Printing member of Claim 3 wherein the support contains grooves and the ferromagnetic material is in the grooves.

19. Printing member of Claims 16, 17 or 18 wherein the ferromagnetic material is acicular CrO2.

20. Printing member of Claims 16, 17 or 18 wherein the support is a grooved plastic support which is plated with a conductive metal.

21. Printing member of Claim 16 wherein the support is an electrically conductive metal support.