CA1091001A - Ferromagnetic toner - Google Patents

Abstract

ABSTRACT
Ferromagnetic toner which is useful in magnetic printing processes and devices for printing a variety of sub-strates, including textiles, such as fabric and yarn, film, paper, metal and wood, which toner comprises a ferromagnetic compounds, a dye and/or chemical treating agent and a readily fusible water-soluble or -solubilizable, preferably thermo-plastic, resin which substantially encapsulates the ferro-magnetic component and the dye and/or treating agent.

Description

lO91UOl BACXGROUND OF THE INVENTION
.
1. Field of the Invention This invention relates to ferromagnetic tonerswhich are useful in maqnetic printing processes and deviceq .

2. De~cription of the_Prior Art One form of copying process in wide usage is the electxostatic copying process. Operation of such a process may provide difficulties in that large black areas may not be amenable to copying and the document to be copied may have to be reimaged each time a copy i8 made. The overcoming of these difficulties may be economically prohibitive. It i8 well known that audio signals and digital data can be recorded on magnetic material~. Magnetic field configurations in the form of alphabetical characters and pictures can al~o be produced by selective magnetization or demsgnetiza-tion of the surface of a ferromagnetic chromium dioxide f~lm. The resultant fields are strong enough to attract and hold ~mall magnetic particles such as iron powder. The development, that is, the making visible, of such a latent magnetic image can be effected ~y 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 re~in binder.
Such a development process is commonly known as decoration of the latent 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 maqnetic 109100~

toner particles are attracted by both electrostatic and magnetic fields, any electrostatic field which is pre~ent on the magnetic surface may interfere with the interaction of the magnetic image and the magnetic toner particles.
More ~pecifically, a portion of the magnetic surface other than that containing the magnetic image may attract enough magnetic toner particles to render unsatisfactory the paper print which ~ub e~uently i5 produced.
There is extensive prior art in the field~ 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 organic polymer containing a plurality of alcoholic hydroxy groups. The disclosure includes coated, ferromagnetic, chromium dioxide, magnetic recording tapes.
Discussions of acicular chromium dioxide and magnetic recording members bearing a layer of such material may also be found in U.S. 2,956,955 and 3,512,930. U.S. 3,554,798 discloses a magnetic recording member which is relatively transparent to light ~transmits S to 95~) and which includes a plurality of di~crete areas of hard magnetic particulate material su~ported thereon and bound thereto. A magnetically hard material is a material which is permanently magnetizable below the Curie point of the material,as opposed to a magnetically soft material which is substantially non-permanently magnetizable under similar conditions below the Curie point of the material. Chromium dioxide is disclosed as an example of a hard magnetic material. Decoration of the image may be effected by means of a magnetic pigment, for example, a dilute, alkyd-oil/wate~ emulsion, carbon black-based l(J91001 printing ink. U.S. 3,522,090 is similar in disclosure to U.S. 3,554,798 in that it also discloses a light-transparent recording member. However, it also discloses that the magnetic material which is capable of magnetization to a hard magnetic state (~n the recording member) may have a coating of a reflective material which is so disposed that the magnetic material is shielded from exposing radiation 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 pigment, such as titanium dioxide. U.S. 3,5S5,S56 discloses a dlrect thermomagnetic recording process wherein the document to be copied is imaged by light which passes through the document. U.S. 3,555,557 discloses a reflex thermomagnetic recording process wherein the light passes through the recording member and reflects off of the document 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 member to be transparent, it must have regions which are free of magnetic particles, that is, a non-continuous magnetic surface must be used.
U.S. 3,627,682 discloses ferromagnetic toner particles, for developing magnetic images, that include binary mixtures of a magnetically hard material and a magnetically soft material, an encapsulating resin and, optionally, carbon black or black or colored dyes to provide a blacker or colored copy. "~igrosine" SSB is diQclosed 3V as an example of a black dye. The encapsulating resin aids transfer of the decorated magnetic image to paper and can be heated, pressed or vapor softened to adhere or fix the magnetic particles to the surface fibers of the paper.
Ferromagnetic toner 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 recording member i8 coated with a polysilicic acid. The use of the polysilicic acid coating on the recording member is particularly useful when the magnetic material on the recording member compri~es a plurality of discrete areas of particulate magnetic material because a greater number of clean copies can be produced. The polysilicic acid, which i8 relatively non-conductive, exhibits good non-stick properties. Thus, toner particleQ which are held to the surface of the recording member by nonmagnetic forces can be easily removed without removing the toner particle~ which are held to the surface of the recording member by magnetic forces. U.S. 2,826,634 discloses the use of iron or iron oxide magnetic particles, either alone or encapsulated in low-melting resins, for developing magnetic images.
Such toners have been employed to develop magnetic images recorded on magnetic tapes, films, drums and printing plates.
Japanese 70/52044 discloses a method which comprises adhering iron particles bearing a photosensitive diazonium compound onto an electrophotographic material to form an image, transfering the image onto a support having a coupler which is able to form an azo dye by reaction _ c _ 109100~ , with the diazonium compound, reacting the diazonium compound and the coupler and thereafter removing the iron particles.
U.S. 3,530,794 discloses a magnetic printing arrangement wherein a thin, flexible maRter sheet having magnetizable, character-representing, mirror-reversed printing portions is employed in combination with a rotary printing cylinder.
The master 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 i~ adhesively attached to a base ~heet. The combined layer and base sheet are imprinted, for example, by the impact of type faces, so that mirror-reversed, character represénting portions of the iron oxide layer adhere to the non-magnetizable layer, thus forming magnetizable printing portion8 on same. Thereafter, the printing portions are magnetized and a magnetizable toner powder, such as iron powder, i8 applied to and adheres to the magnetized printing portions. The powder is then transferred fro~
the printing portions to a copy sheet and permanently attached thereto, for example, by heating. U.S. 3,052,564 discloses a magnetic printing process employing a magnetic in~ consisting of granules of iron coated with a colored or uncolored thermoplastic wax composition. The magnetic ink is employed in effecting the transfer of a printed record, using magnetic means, to paper. U.S. 3,735,416 discloses a magnetic printing process wherein characters or other data to be printed are formed on a magnetic recording surface by means of a recording head. A magnetic toner which is composed of resin-coated magnetic particles is employed to effect transfer of the characters or other data from the recording surface to a receiving sheet. U.S.

3,250,636 discloses a direct imaging process and apparatus wherein a uniform magnetic field is applied to a ferromagnetic imaging layer; the magnetized, ferromagnetic imaging 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 portions of the layer above the Curie point temperature of the ferromagnetic imaging layer so as to form a latent magnetic image on the imaging layer; the latent magnetic image is developed by 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 demagnetize it; and,finally, the loosely adhering magnetically attractable material is tran~ferred from the imaging layer to a transfer layer.
German 2,452,530 discloses electrophotographic toners comprising a magnetic component coated with an organic substance containing a dye w~ich vaporizes at 100 to 220C, preferably 160 to 200~C, at atmospheric pressure. The magnetic component is preferably granular iron and/or iron oxide and the coating is a water-insoluble polymer melting at about 150C, e.g., polyamides, epoxy resins and cellulose ethers and esters. Both basic and disperse dyes can be used in the toners. The toners are from 1 to 10 microns in diameter and may also contain silicic acid as anti-~tatic agent. Colored or black copies are formed by toner development of the latent image on a photo-conducting sheet of ZnO
paper, followed by transfer of the dye in the vapor phase to a receiving sheet by application of heat and pressure.

OBJECTS AND SUMMARY OF THE INVENTION
Generally,only reddish-brown or black images can be obtained on paper using prior art ferromagnetic toner~
because of the dark hard magnetic components, for example, the iron oxides ~y-Fe2O3 or Fe3O4), and the dark soft magnet$c components, for example, iron, employed therein;
becau~e the magnetic components are retained in and may be essential to the formation of the vi~ible image~; and because the magnetic components are bound to the paper by 10 the encapsulating resins employed therein. It is an object .:
of the present invention to provide a ferromagnetic toDer which can be employed in magnetic printing proces~es and devices to print, in a broad range of colors, if de~ired, a variety of substrates, including textiles, such a~ fabric snd yarn, film, paper, metal and wood.
It is a further object to provide such a print which is substantially free of hard and soft magnetic components and .-encapsulating resin. Still another object i8 to provide a ferromagnetic toner from which the hard magnetic component and, if present, the soft magnetic component, and the encapsulating resin can be readily.removed by means of an a~ueou~ scour after the toner has been employed in a magnetic printing proce~s and device. The term ~textile~is intended to ; include any natural or synthetic material, such as natural ~: and regenerated cellulose, cellulose derivatives, natural polyamides, such as wool, synthetic polyamidesi polye~ter~, acrylonitrile polymers and mixtures thereof, which i8 8uitable for spinning into a filament, fiber or yarn. The term "fabric" is intended to include any woven, knitted or nonwoven cloth comprised of natural or synthetic fibers, ,, ilaments or yarns.
In summa~y,the invention herein resides in a ferromagnetic toner comprising a ferromagnetic component, a dye and/or a chemical treating agent and a readily fusible, water-soluble or -solubilizable, preferably thermoplastic, resin which substantially encapsulates the ferromagnetic component and the dye and/or treating agent.
DETAILED DESCRIPTION OF THE INVENTION

The invention resides in a ferromagnetic toner comprising:

(a) at least one ferromagnetic component;

~b) at least one mem~er of the group consisting of dye and chemical treating agent; and ~c) a readily fu~ible, water-soluble or water-~olubilizable resin which substantially encapsu-lates ~a) and ~b).

A preferred embodiment includes such toners comprising, ba~ed 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 having a resin to ferromagnetic component ratio of 0.11 to 3.3.

An especially preferred embodiment is one wherein there iS 55 to 70~ of ~a), 0.10 to 15% of ~b) and 30 to 4~%

of ~c) and which 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 particles. The magnetically soft particles can be iron or another high-permeability, low-remanence material, such as iron carbonyl, certain of the ferrite~, for example, (Zn, Mn)Fe204, or permalloys. The magnetically lO9iOOl hard particles can be an iron oxide, preferably Fe3O4, y-Fe2O3, other ferrites, for example, BaFel2Olg, chi-iron carbide, chromium dioxide or alloys of Fe3O4 and nickel or cobalt. As already indicated above, magnetically hard and magnetically soft particles are substances which are, re~pectively, permanently magnetizable and substantially non-permanently magnetizable under similar conditions below the Curie point of the substances. A magnetically hard substance has a high-intrinsic coercivity, ranging from a few tens of oersteds (Oe), for example, 40 Oe, to as much a~ several thou~and oersteds and a relatively high remanence (20 percent or more of the saturation magnetization) when removed from a magnetic field. Such ~ubstances are of low permeability and require high fields for magnetic saturation.
Magnetically hard substances are used as permanent magnets for applications such a~ loud speakers and other acoustic tran~ducers, in motor~, generators, meters and instruments and a~ the recording layer in most magnetic tapes. A
magnetically soft sub~tance has low coercivity, for example, one oersted or less, high permeability, permitting saturation to be obtained with a small applied field, and exhibits a remanence of less than 5 percent of the saturation magnetization. Magnetically soft substances are usually found in solenoid core~, recording heads, large indu~trial maqnets, motors and other electrically excited devices wherein a high flux density i8 required. Preferred soft magnetic substances include iron-based pigments, such as carbonyl iron, iron flakes and iron alloys.
Dyes which are useful in the ferromagnetic toners of this invention can be selected from virtually all lO9iOOl of the compounds mentioned in the Colour ~ndex, Vols. 1, 2 and 3, 3rd Edition, 1971. Such dyes are of a variety of chemical types; the choice of dye is determined by the nature of the substrate being printed. For example, premetalized dyes (1:1 and 2:1 dye:metal complexes) are suitable for synthetic polyamide fibers. The majority of such dyes are monoazo or disazo dyes; a lesser number are anthraquinone dyes. Such dyes can have or be free from water-solubilizing groups, such as sulfonic acid and carboxy groups, and sulfonamido groups. Acid wool dyes, including the monoazo, disazo and anthraquinone members of thi~ class which bear water-solubilizing sulfonic acid group~, may also be suitable for synthetic polyamide textiles. Disperse dyes can be used for printing synthetic polyamide, polyester and regenerated cellulosic fibers.
A common feature of such dyes is the absence of water-solubilizing groups. However, they are, for the most part, thermosoluble in synthetic polymers, notably polyesters, polyamides and cellulose e~ters. Disperse dyes include dyes of the monoazo, polyazo, anthraquinone, styryl, nitro, phthaloperinone, quinophthalone, thiazine and oxazine series and vat dyes in the leuco or oxidized form. For polyacrylonitrile and acid-modified polyester fibers, preference usually is given to cationic dyes containing a carbonium ion or a quaternary ammonium group. Cationic-disperse dyes, that is, water-insoluble salts of cationic dyes and selected arylsulfonate anions, are well-known in the art for dyeing acid-modified polyester and acrylic fibers. Cotton fibers can be printed with vat dyes and with fiber reactive dyes, including those which are employed for polyamide fibers. Other suitable dyes for cotton are the water-soluble and water-insoluble sulfur dyes. Water-swellable cellulosic fibers, or mixtures or blends thereof with synthetic fiber~, can also be uniformly printed with water-insoluble diqperse dyes using aqueous ethylene glycol or polyethylene glycol type solvents, as described -in the art.
The amount of dye present in the ferromagnetic toners of this invention can vary over a wide range, for example, 0.1 to 25% by weight of the total weight of essen-tial components (a), (b) and (c) in the toner. Particularly good results can be obtained when the amount is 0.1 to 15 by weight.
A wide variety of chemical treating agents, ~uch as flame-retarding agent~, biocide~, ultraviolet light absorbers, fluore~cent brighteners, dyeability modifiers and soil-release and water-proofing agents, are useful in the ferromagnetic toner~ of this invention. Such agents have utility on cotton, regenerated cellulose, wood pulp, paper, synthetic fibers, such as polyesters and polyamides, and blend6 of cotton with polyester or polyamide. ~y dyeability modifier is meant a chemical substance that can be chemically or physically bound to the ~ubstrate, such as a fiber, to change the dyeability of the ~ubstrate, for example, the degree of dye fixation or the type or class of dye that can be employed. A specific example of a useful dyeability modifier i5 a treating agent which provides printed chemical resists, that is, printed areas which remain unstained during a subsequent dyeing operation.
Since many chemical treating agents, including those of 1~91~01 the aforesaid types, are well-known in the prior art, no further discussion thereof is necessary. The chemical treating agent in the toner can be present in the same amount as the dye, that is, 0.1 to 25%, preferably 0.1 to 15%, of the total weight of essential components (a), (b) and (c).
The reQins which are useful in the ferromagnetic toners include any ~f the known, readily fusible, natural, mndified natural or synthetic resins or polymers which are soluble or solubilizable in water, that is, either directly soluble in water or made soluble through a simple chemical treatment. The solubility in water must be such that the ferromagnetic component and the encapsulating re~in can be removed from the sub~trate, after permanent fixation of the dye and/or chemical treating agent, by an aqueous -scour, in a Qhort time, as will be described in greater d-tail herelnafter. Examples of solubilizable resins are those resins or polymers which contain salt-forming group~, which thereby render them soluble in an alkaline aqueou~
solution, and those which can be hydrolyzed by acids or alkalis 80 as to become water-~oluble. Exemplary of useful -natural resins are rosin ~also known as colophony) and modified derivatives thereof, such as ro~in esterified with glycerin or pentaerythritol, dimerized and polymerized rosin, unsa~urated or hydrated rosin and derivatives thereof and rosin, and derivatives thereof, which has been modified with phenolic or maleic resins. Other natural resins with properties similar to rosin, such as dammar, copal, sandarak, shellac and talloel, can be successfully used in the ferromagnetic toners.

~09iO01 Examples of synthetic resins which are useful herein include vinyl polymers, such as polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetals, polyvinyl acetate, polyvinyl acetate copolymers, and polyvinyl pyrrolidone; polyacrylic acid and polyacryl- ~-amide; methyl-, ethyl- and butyl methacrylate-methacrylic acid copolymers; styrene-maleic acid copolymers; methyl vinyl ether-maleic acid copolymers; carboxyester lactone polymer~; polyethylene oxide polymers; nonhardening phenol- ~
10 formaldehyde copolymers; polyester resins, such as linear ~-polyesters prepared from dicarboxylic acids and alkylene glycol~, for example, from phthalic, terephthalic, isophthalic or sebacic acid and ethylene glycol; cellulose ethers, such as hydroxypropylcellulo~e; polyurethane~;
and polyamide~, ~uch as those prepared from sebacic acid and hexamethylenediamine.
Resin~ used in the toners herein are preferably of the thermopla~tic type in order to permit adhesion thereof to the substrate by melting or fusion. Particularly preferred resins herein are adducts of rosin, a dicarboxylic acid or anhydride, a polymeric fatty acid and an alkylene polyamide; hydroxypropylcellulose prepared by reacting 3.5 to 4.2 moles of propylene oxide per D-glucopyranosyl unit of the cellulose; and polyvinyl acetate copolymers having a free carboxy group content equivalent to 0.002 to 0.01 equivalent of ammonium hydroxide per gram of dxy copolymer. The preferred resins possess a hiqh elec-trical resistance for good transfer in an electrostatic field, have good infrared and steam fusion properties and do not interfere with penetration of the dye or chemical treating agent into the substrate during the final 1~9~001 (permanent) fixation operation. Moreover, after the dyeand/or chemical treating agent has been fixed within the substrate, the resin must be easily removable in an aqueous washing operation in a short time, for example, in less than five minutes at less than 100C, preferably in less than 60 seconds at less than 90C.
The ferromagnetic toners of this invention can be prepared by intimately mixing together, for example, by ball milling or by high frequency viscous milling, an agueous solution or slurry containing the desired proportions of dye ~8) and/or chemical treating agent~s), ferromagnetic component~s) and encapsulating resin and then spr~y-drying to remove the water. Particularly good re~ults u~ually can be obtained by ball milling for 1-17 hours at about 60 percent by weight nonvolatiles content.
~he solution or disper~ion re~ulting from ball milling i8 ~eparated from the ceràmic balls, ~and or other grinding means, diluted with water and spray-dried at a nonvolatiles content of 10 to 40 percent by weight. Spray-drying is accompli8hed by conventional means, for example, by dropping the ~olution or di~persion onto a disk rotating at high speed or by u~ing a conventional spray-drying nozzle, as described in the art. Spray-drying consists of atomizing the aqueous toner solution or dispersion into small droplet~, mixing these with a gas, and holding the droplet~
in suspension in the gas until the water in the droplets evaporates and heat and surface tension forces cause the resin particles in each droplet to coalesce and enca~e the dye andfor treating agent included in the droplet.
Most frequently, spray-drying is carried out with air a~ the 1O9lOO~

gas for the drying step. The gas is heated sufficiently to remove the water 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 entrap~ any dye and/or treating agent initially included within that droplet.
By maintaining uniformity of dispersion of dye and resin in the water and by controlling solids concen-tration in the final dye-water mixture, the particle size of the toner can be controlled by the size of the droplet produced by the atomizing head in the spray-drying equipment. Moreover, by controlling the toner ~lurry feed rate, the viscosity of the toner slurry, the spray-drying ;
temp-rature and the disc rpm for a disc atomizer, the pEes-sure for a single-fluid nozzle atomizer or the pr~suie and air to feed ratio for a two-fluid nozzle atomizer, spherical toner p~rticles having diameters within the range of 2 to 100 micron~, preferably 10 to 25 microns, can be readily obtained. Toners passing a 200 mesh screen ~U.S. Sieve Ser~es), thus being le~s than 74 micron~ in the longest particle dimension,are eQpecially u~eful.
Other suitable well known encapsulation processe~
can be employed to produce the ferromagnetic toners of this invention. These include coacervation and interfacial polymerization techniques.
The relative amounts of resinous material and ferromagnetic material 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, .~, . . . .

109~00~

preferably 0.40 to 1Ø The preferred ratio especially provides toners having good decoration, transfer and fusion propertie~.
It is to be understood that the ferromagnetic component, dye and/or chemical treating agent and encapsulating resin are essential components of the toners of this invention and the aforesaid percentages are based on the combined weights of these essential components.
In some ca~e~, 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, :~ .
surfactants and materials to promote dye and/or treating agent fixation in the substrate. Purther examples of such chemical assistants include urea; latent oxidizing agent~, such as sodium chlorate and sodium m-nitrobenzene sulfonatet latent reducing agents; acid or alkali donors, such as ammonium salts and sodium trichloroacetate;
and dye carriers, usually present in amounts of 0.1 to 8%
by weight based on the total toner weight, such as benzyl alcohol, ~enzanilide, ~-naphthol, o-phenylphenol and butyl benzoate. Conventional-commercial di~persing agehts, such as the l ignin ~ulfonates and salts of sulfonated naphthalene-formaldehyde condensate~, can be employed.
Such agents include ~Polyfon~ a sodium ~alt of sulfonated lignin; "Reax*n the sodium salts of sulfonated lignin - ~^~r, derivatives; NMarasperse~" a partially desulfonated sodium lignosulfonate; "Lignosol*,U sulfonated lignin derivatives;
"Blancol~n nBlancoln*N and "~amol*~ the sodium salt of sulfonated naphthalene-formaldehyde condensates; and "Daxadn*ll KLS and UDaxadn~15, the polymerized potassium * denotes tr~dem~rk 109100~

and ~odium salts, respectively, of alkyl naphthalenesulfonic acid. Other known useful auxiliary chemicals can assist in the prevention of "bleeding" of the 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 achieved by incorporating such _urfactant_ 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 additiveQ for improving the brightnes~ and tinctorial ~trength of the dyeing, for example, citric acid, which is ¢ommonly u~ed with cationic dyes, and ammonium oxalate, which i~ commonly u~ed with acid dyes.
A free-flow agent, usually present in an amount within the range 0.01 to 5~ by weight, preferably 0.01 to 0~4~ by weight, ba~ed on total toner weight, can be added to keep the individual toner particles from sticking together and to increase the bulk of the toner powder.
This facilitates an even deposition of toner particles on the latent magnetic image. Free-flow or dispersing agents, such as microfine silica, alumina and fumed Qilica sold under the trade names "QusoU*and "Cab-O-Sil~ are u~eful.
The toners of this invention are e~pecially 30 - useful in a process for magnetic printing comprising the denote~ trademark 1091~0~

stepq of forming a latent magnetic image on the surface of a magnetic printing member, developing the latent magnetic image by decoration with the ferromagnetic toner particles, transferring the toner-decorated image to a substrate, temporarily fixing the toner particles to the substrate, permanently fixing the dye and/or chemical treating agent to the substrate,and finally, removing the ancillary substances and any excess dye and/or agent from the substrate. The latent magnetic image can be developed by any convenient known method. Typical methods include cascade, magnetic brush, magnetic roll, powder cloud and dusting by hand. Cascade, magnetic brush, powder cloud and magnetic roll development are well known in the art.
Transfer of the ferromagnetic toner to the sub-~trate can be accomplished either by magnetic, pressure or, preferably, by electrostatic means, that is, by applying a positive or negative potential to the backside of the substrate placed in contact with the toner-decorated latent 2~ magnetic image. The u~e of high pressure, for example, ;~
near 400 pounds per linear inch (about 70 kg per cm), generally results in shorter printing surface life, poorer transfer efficiency and poorer image definition on the substrate. Such problem~ are avoided by using electrostatic transfer means wherein there is no substantial amount of -~
pressure between the printing surface and the ~ubstrate and, therefore, abxasion is minimized.
A~ mentioned hereinabove, the toners can be - printed on all types of printable substrates. Particularly preferred are fabric substrates, especially tho~e prepared .

1~91001 from natural and regenerated cellulose, cellulose deri-vative~, wool and synthetic fibers, such as polyamides, polyesters and polyacrylics, and mixtures of any of these fabrics. Film substrateq, for example, ~Mylar'~polyester film, are also preferred.
The ferromagnetic dye and/or chemical toner can be temporarily fixed to the substrate by melting it by the application of heat or by partially dissolving it in water, either in the form of an aqueous spray or as steam.
Stoam fu~ion at 100C for 1 to 15 seconds at 1 atm pressure i9 particularly preferred.
Permanent fixation can be accomplished in any way which i8 consistent with the type of sub~trate and dye and/or chemical treating agent which are used. For example, dry-heat treatment, ~uch a~ a Thermosol treatment, at 190 to 230C for up to 100 seconds can be used to fix di~perse dyes on polyester and mixed di~perse-fiber reactive dyeq on polyester-cot~on. Moreover, high pressure steaming at pres~ures of 10 to 25 psig ~0.7 to 1.76 kg per sq cm gauge) accelerates the fixation of diqper~e dyes on polyester and cellulose triacetate. Rapid di~perqe dye fixation can also be obtained by high-temperature ~teaming at 150 to 205C for 4 to 8 minutes. High-temperature steam~ng provides the advantage of short treatment times without the need to use pressure seals.
Cottage-steaming and pressure-steaming can be used to fix cationic dyes to acid-modified acrylic and polyester fibers and to fix acid dyes, including premetalized dyes, to polyamide and wool fibers. Cottage-steaming u~es ~aturated steam at a pressure of 1 to 7 psig (0.07 to denotes tradem~rk ~091001 O.49 kg per sq cm gauge) and a relative humidity of 100~.
There is no tendency to remove moisture from the fabric using saturated steam. As the fabric is initially contacted by the steam, a deposit of condensed water quickly forms on its cold surface. Such water serves various functions, such as swelling the fiber and activating the chemicals and dyes, thereby creating the conditions necessary for their diffusion into the fiber. ~apid aging at 100 to 105C
for 15 to 45 minutes at 760 mm of pressure can be used to fix diQperse dyes on cellulose acetate and cationic dyes on acrylic fibers.
Depending on the nature of the dye and/or chemical treating agent, it may also be necessary or desir-able to treat the fabric with an aqueous solution before final fixation. 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 bicarbonste, and, in some cases, a reducing agent for the dye. Such materials may also be incorporated directly into the toner composition. All the afore~aid f Lxstion procedures are well-known in the art.
After permanent fixation of the dye and/or chemical treating agent, the printed fabric is scoured to remove the ferromagnetic component, resin and any unfixed dye and/or chemical treating agent. Although the severity of the scouring treatment generally depends on the type of resin employed, with the ferromagnetic toners of this invention immersion in an aqueous surfactant solution at le-~s than 90C for only a few seconds usually is sufficient to dissolve away the resin and release the magnetic materials from the fabric surface. If the toner contains a dye, a well-defined lU9iOO~

colored print is obtained on the fabric.
The tran~fer of the ferromagnetic toner to the surface of the fabric and the temporary fixation thereof on the fabric are carried out sequentially, one immediately after the other. The permanent fixation and scouring may be done separately in a later operation, if desired.
It is to be understood that the aforesaid description of magnetic printing processes i8 not intended to be a limitation on the use of the ferromagnetic toners of this invention, but rather, it is intended merely to show at least one utility for such toners.
EXAMPLES
In the following examples, unless otherwi~e noted, all parts and percentages are by weight and all materials employed are readily commercially available.
Ex~mple 1 This example illustrates the preparation, by manual mixing of the ingredients followed by spray-drying, of a ferromagnetic toner containing a blue disper~e dye, magnetic components and an aqueous alkali-soluble resin, and the application thereof to both paper and polyester. A magnetic toner was prepared from 32.7% of carbonyl iron, 32.7~ of Fe304, 1.8% of C.I. Disperse Blue 56, 5.5% of ligninsulfonate di~persant and 27.3~ of a polyvinyl acetate copolymer resin.
The carbonyl iron, used as the soft magnetic material and commercialIy available under the trade name Carbonyl Ironn~GS-6, i~ substantially pure iron powder produced by the pyrolysis of iron carbonyl. A suitable Fe304 i9 901a under the trade name "Mapicon*Black Iron Oxide and the polyvinyl acetate copolymer resin, under the trade name "Gelvan*C5-VIOM. "Gelva~ C5-VIOM is an aqueous alkali-soluble * denote8 trademark -22-copolymer of vinyl acetate and a monomer containing the requi~ite 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.
'~arbonyl 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 unt$1 completely dispersed, then added to the above resin ~olution. 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 ~wirling at a high velocity. Precautions were taken to atir the toner slurry and maintain a uniform feed composition.
The exact temperature and air velocity depend mainly on the ~oftening point of the resin. An air inlet temperature of 225C, an outlet temperature of 85C and an atomizer air pre~sure of 85 psig (6 kg per sq cm gauge) provided satisfactory results. The re~ulting discrete toner particles of magnetic resin-encapsulated dye had a particle size 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 me~h screen (U.S. Sieve Series), thus being less than 74 microns in particle size.
The ferromagnetic toner wa~ mechanically mixed with 0.2 of a fumed silicate,'~uaonWR-82, to improve powder flow characteristic~.
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 per mm) by recording a sine wave with a magnetic write head. A film positive of the printed image to be copied wa~ placed in contact with the magnetically structured CrO2-coated aluminized polyester film and uniformly illuminated by a Xenon fla~h pa~sing through the film po~itive. The dark area~ of the film positive corresponding to the printed me~sage ab~orbed the energy of the Xenon flash, whereas the clear area~ transmitted the light and heated the CrO2 beyond its 116C Curie point, thereby demagnetizing the expo~ed 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 exce~s. The magnetic image became visible by virtue of the toner being magnetically attracted to the magnetized areas.
The toner decorated image wa~ separately transferred to paper and to polyester fabric substrates by applying a 20 KV positive potential from the back~ide of the substrate by means of a DC corona. The applied 109100~

potential induced a dipole in the toner and the toner was electrostatically transferred to the substrate. Other ~ ;
transfer means can also be employed, such as by means of a prescure of 20-400 pounds per linear inch (0.36-7.15 kg per linear mm). 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 fu~ed thereon by infrared radiation, backQide fusion (140C) or by steam fusion 10 ~100C for 10-15 second~ at 1 atm pressure). The latter method is the mo~t economical but is only possible with water-soluble resins.
The image which had been tran~ferred to the paper was then heat transfer printed from the paper to polyester fabric by placing the fu~ed image-bearing paper f~c~-down on the polye~ter and applying 1.5 to 2.0 psi (0.11 to 0.14 kg per sq cm) pressure for 30 seconds at 205-210C. After direct tran~fer and fusion to polyester fabric, the dye was fixed in the fabric by heating for 20 30 seconds at 205-210C and 1.5 to 2.0 psi pressure (0.11 to 0.14 kg per sq cm).
~oth fabric samples which had been printed as described above, that is, either directly printed or heat tran~fer printed from paper, following fixation of the dye, were scoured by immersion in cold water and then in hot detergent. A detergent con~isting of sodium pho~phates, sodiwm carbonate~ and biodegradable anionic and nonionic ~urfactants (nLakeseal~ was used. The samples were finally rinsed in cold water and dried. A deep blue print * denotes tr~dem~rk ~ , .

109100~

wa~ obtained on each fabric.
Example 2 `r,~
This example illustrates the preparation, by ball-milling of the ingredients followed by spray-drying, of a ferromagnetic toner containing a blue disperse dye, magnetic components and an aqueous alkali-soluble resin, and the application thereof to polyester. A magnetic toner was prepared from 30~ of carbonyl iron, 30% of Fe3O4, 10%
of C.l. Disperse Blue 56 and 30% of a polyvinyl acetate copolymer re~in ("Gelva" C5-VIOM).
A mixture of 300 part~ of a 20% aqueous alkaline ~olution of the polyvinyl acetate copolymer resin, 20 parts of C.I. Disperse Blue 56 crude powder, 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~ nonvolatiles. A ceramic ball-mill was selected of ~uch ~ize that when the ball-mill was about one-half to two-thirds full of 0.5 inch (1.27 cm) high den~ity ceran~c balls, thé above ingredient~ j w t covered the balls.
After discharging the ball-mill and diluting with 460 parts of water to reduce the total nonvolatile solids to approximately 20~, the slurry was spray-dried in a ~iro~n spray-dryer using an air inlet temperature of 200~C, an air outlet temperature of 80C and an atomizer air pres~ure of ~0 psig (5.6 kg per sq cm gauge). ~he toner particles were brushed from the drying chamber, collected and pas~ed through a 200 mesh screen. The toner sample wa~ fluidized with 0.2~ of"~us~ WR-82 and then used to decorate the latent magnetic image on a 300 line per inch ~12 per mm) * denotcs trademark CrO2 coated aluminized "Mylar" film as described in Example 1. The toner decorated image was electrostatically transferred direct7y to LOO~ polyester double-knit fabric by app~ying a 2~ KV negative potential to the backside of the fabric. The toner was steam f~sed to the fabric at 100 C for 10-15 seconds at 1 atm pressure. After fu~ion, the dye was fixed in the fabric by heating at 205~C
for 40 second~ at 1.5 psi (0.11 kg per ~q cm). The printed fabric was then ~coured at 65C in a muxture of 2 parts per liter of caustic soda, 2 parts per liter of sodium hydrosulfite and 2 parts per liter of a polyoxyethylated tridecanol surface-active agent to remove resin, Fe, Fe3O4 and any unfixed dye and then dried. A bright blue print was obtained.
Exam~le 3 This example illu~trates the preparation of a ~olvent ball-milled and ~pray-dried,ferromagnetic resin encapsulated,disperse dye toner and the application thereof to poly-ster.
A magnetic toner was prepared by Sall-milling a mixture of 120 parts of an aqueous alkali-soluble polyamide resin-dicarboxylic acid adduct lcommercially available as TPX-1002), 136 parts of "Mapico" Black Iron Oxide, 136 parts ofl'Carbonyl Iro~ 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. ~he ball-mill was discharged and the contents was diluted with 666 ml of a 50:50 mixture of toluene:isopropanol to approximately 30% nonvolatile solids. The solvent toner slurry was spray-dried in a Bowen 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 atomizer air pres~ure of 85 psig (6 kg per ~q cm gauge).
The toner particles were cla~sified to some extent by a cyclone collection system. The main toner fraction (81%, 238 parts) collected from the dryer chamber consisted of nearly spherical spray-dried particles having an average particle size of 10 to 15 microns ~a range of 2 to 50 microns).
The resultant magnetic toner consisted of 30% of polyamide resin adduct, 34% of carbonyl iron, 34% of Fe3O4 and 2~ of C.I. Di~perse Red 60. The toner was fluidized with 0.3%
of ~usonWR-82 and then applied to decorate the latent image on a 300 line per inch ~12 per mm) magnetically structured CrO2 coated aluminized "MylarU film as described in Example 1. The toner decorated image was electrostatically tran~ferred directly to 100% polyester woven fabric by applying a 20 KV negative potential to the backside of the fabric. The fabric wa~ steam fused and the dye wa~ fixed by heating at 205C for 40 seconds at 1. 5 p5i ~0. 11 kg per sq cm). The printed fabric was then scoured as in Example 2 and dried.
. ~ .
Disperse dye toners were prepared by either manually mixinq or ball-milling the appropriate ingredients and spray-drying the slurry as described in Examples 1 and ; 2. Details are summarized in Table I. Manually mixed toners were prepared in all cases except Examples 13, 14, 19 and 32; in these the toners were prepared by ball-milling.

109~00~ .

The composition~ of the final pray-dried toners as well a~ the ratio of resin to total magnetic component present are also shown in the table. Ball-milled toners exhibited optical densities, when printed on polyester, which were superior to those of manually mixed toners of comparable dye concentration. This difference is particularly evident when the toner contains high concentrations of dye.
The standardized disperse dye powders (and pastes) used in the manually mixed toners contained ligninsulfonate 10 and sulfonated naphthalene-formaldehyde condensate dispersing agents. At high dispersant levels, the quantity of magnetic component in the toner becomes limited and decoration of the latent magnetic image may become impaired.
Toner composition~ containing 9 to 74% (Examples 12 and 25) of water-soluble resin and 14 to 83~ (Examples ll and 12) of total magnetic component and compositions having a resin to magnetic component ratio of 0.11 to 3.3 ~Examples 12 and 25) exhibited satisfactory magnetic, 20 transfer and fusion properties. Various disperse dye types, s for example, quinophthalone ~Example 4), anthraquinone ~Examples S to 25, 32 and 33) and azo (Examples 26 to 31) dyes, provide a wide range of colored magnetic toners.
~he amount of dye present in the toner depends on the amount of resin and magnetic component present. Dye concentra- -tions of 0.10% (Example 33) to 2~% (Example 32) were used with satisfactory results. Toner compositions containing both hard and soft magnetic components are exemplified in Table I. A binary mixture of magnetic particles is not 10910~1 essential, however. Equally good results are obtained using only a hard magnetic component ~Examples 18 to 21).
Ferric oxide is a preferred hard magnetic component based on its magnetic properties and its cost. Chromium dioxide can al~o be used but it is much more expensive.
A free-flow agent, present in quantities 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 together and to increase the bulk of the toner powder. These factors facilitate even deposition of toner over the imaging member. Free-flow agents such as microfine silica and alumina are useful. Quso WR-82 provides satisfactory flow properties when added to the toners described herein.
The toners were evaluated as described in Ex~mple 1. ~he latent magnetic image on a 300 line per inch tl2 per mm) magnetically structured CrO2-coated aluminized "Mylar" film was manually decorated and the decorated image was electrostatically transferred to ~that is, printed on) a substrate (shown in Table I).
The toner fusion and dye fixation conditions and the scouring procedure for removing resin, magnetic co~ponent~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 designation "HTP(PE)f'9~ means that the toner was heat transfer printed from paper to polyester by heating at 205C for 40 seconds and 1.5 psi (0.11 ~g per sq cm) and 109100~

the printed polyester was scoured at 65C in aqueous detergent solution; and the designation "DP(PE)t'f'g"
means that the toner was directly printed on polyester, infrared fused at 160-170C, the dye was fixed at 205C for 40 seconds and 1.5 psi (0.11 kg per sq cm) and the printed polyester fabric was scoured at 65C. in aqueous detergent.
A number of different fixation procedures, for example, dry heat, hot air, high temperature steam and hiqh pressure ~team, were used to fix the dyes in the substrate.
Such procedures are well-known in the art for fixing disperse dyes in polyester and nylon.
Examples 27, 29, 30 and 31 show the effect of incorporating 2, 4, 6 and 8% of a benzanilide dye carrier. -in the toner compositions. The carrier gave increased tinctorial strength over tonex without the carrier.
Concentrations of 2 to 4% (of carrier) provided optimum re8ults.
Example 34 This example illustrates the effect of vario w chemicals which are nonmally used in the conventional printing of polyester to prevent side effects during fixation of the dye.
The toner of Example 27 containing 2% of benzanilide carrier was directly printed on 100% polyeQter woven fabric according to the procedure of Example 1. The toner was steam fused at lOO~C and 1 atm pressure for 10-15 seconds, The fabric was sprayed with a solution of 109100~

100 parts of urea and 10 parts of sodium chlorate in 1,000 parts of water to prevent reduction of the dye during the fixation step. The dye was fixed by high pressure steaming at 22 psig tl.55 kg per 5q cm gauge) for 1 hour. The printed fabric was scoured in 2 parts per liter of sodium hydro-sulfite, 2 parts per liter of soda caustic and 2 parts per liter of a polyethoxylated tridecanol surfactant at 65C.
A deep red print was obtained; it exhibited superior tinctorial ~trength as compared to a corresponding print which had not been sprayed prior to fixation.
Example 35 Thi~ example illustrates the effect of various chemicals which are normally used in the conventional printing of nylon to prevent side effects during fixation of the dye.
The toner of Example 27 containing 2% of benz-anilide carrier was directly printed on "Qiana'~nylon fabric according to the procedure of Example 1. The toner was steam fused at 100C and 1 atm pressure for 10-15 seconds.
The fabric 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 pre~sure ~teaming at 22 psig (1.55 kg per sq cm gau~e) for 1 hour. After scouring, a deep red print was obtained; it was tinctorially stronger than a corresponding red print which had not been sprayed prior to fixation.
Example 36 This example illustrates the preparation and application of a ferromagnetic disperse dye toner to a polye8ter/cotton blend fabric.
* denotc8 trademark lV91001 A 6-inch (15 cm) wide, 3-yard (274 cm) length of 65/35 polyester/cotton blend fabric was pretreated by padding to about 55% pickup with an aqueous solution containing 120 parts per liter of methoxypolyethylene glycol, M.W. 350.
The padded fabric was heated at 72C for 1 hour in a hot air oven to evaporate water, leaving the cotton fibers in a swollen state.
A magnetic toner was prepared by spray-drying a mixture containing 29.4% of polyvinyl acetate copolymer resin (nGelva" C5-VIOM), 33.3~ of'~arbonyl Iro~' GS-6, 33.3% of NMapico" Black Iron Oxide, 2% of a dye of the formula shown as (A) in Table VII and 2% of a sulfonated naphthalene-formaldehyde dispersant. The spray-dried product was sieved through a 200 mesh screen and 0.2~ of '.
Quso WR-82 was added to render the toner free flowing.
A latent magnetic image swch as described in Example 1 was manually decorated with the above toner and transferred electrostatically to both untreated and pretreated ~;
65/35 polyester/cotton by a procedure such as described in Example 1. Following transfer, the toner was steam fu~ed at 100C and 1 atm pressure for 10 to 15 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 polyester/cotton fabric was printed in a deep bright red shade, whereas the untreated fabric was only lightly stained. Similar results were obtained when the disperse dye toner was transferred to the pretreated and untreated fabrics, steam fused and then dry heat fixed at 205C for 100 seconds at 1.5 psig (0.11 kg per sq cm gauge).
.

309~0Q~

Example 37 This example illustrates the preparation of a ferromagnetic toner containing a cationic dye, magnetic compo-nents and an aqueous alkali-soluble resin and the application thereof to acid-modified polyester and polyacrylonitrile.
A solution of 21 parts of C.I. Basic Blue 77, as a 24.4% standardized powder (containing boric acid as a diluent) in 300 ml of hot water, was added, with thorough stirring, to 400 parts of a 20% aqueous alkaline solution of a polyvinyl acetate re3in ("Gelva" C5-VIOM). "Carbonyl Iron~
GS-6 (91 parts), "Mapico" Black Iron Oxide (91 parts) and 510 parts of water were then added and stirring was continued for an additional 30 minutes. The toner slurry was ~pray-dried to give a final toner composition containing 28.3% of polyvinyl acetate copolymer resin, 32.2% of ~Carbonyl IronnGS-6, 32.2% of "Mapico~ Black Iron Oxide, 1.8~ of C.I. Ba~ic Blue 77 and 5.5 weight percent of boric acid diluent. The toner was sieved through a 200 mesh screen and fluidized with 0.2S of Quso WR-82.
A latent magnetic image such as described in Example 1 was manually decorated with the above toner and transferred electrostatically to acid-modified polyester fabric as de~cribed in Example 1. After transfer, the toner was steam fused at 100~C and 1 atm pressure for 10 to 15 séconds and the cationic dye wa~ fixed by high-pressure steaming at 22 psig (1.55 kg per sq cm gau~e) for 1 hour.
The printed ~abric was scoured as described in Example 2.
A blue print was obtained.
A second toner transfer was made to polyacrylo-'30 nitrile'fabric in a similar manner. The toner was steam s: ., , 109100~

fused, the dye was fixed by cottage-steaming at 7 psig (0.5 kg per sq cm gauge) for 1 hour and the printed fabric was scoured as described above; a deep blue print was obtained.
In conventional printing with cationic dyes, a "steady acid" is normally used in the print paste to insure that an acid pH is maintained during fixation of the dye.
Accordingly, in another set of experiments, after transfer and steam fusion of the above cationic dye toner to ~oth the acid-modified polyester and the polyacrylonitrile fabrics, the printed fabrics were oversprayed with a 50% aqueous solution of citric acid and then fixed by high-pressure steaming and cottage-steaming, respectively, as described above. The printed fabrics were then scoured. Bright blue prints were obtained, exhibiting superior image definition as compared to the prints which were prepared without the overRpray step. ~
Examples 38 to 43 --Ferromagnetic cationic dye toners were prepared -by manually mixing the appropriate ingredients and spray-drying the slurries as described in Example 37. After drying, 0.2 to 1.2~ of~Qus~ WR-82 was added to obtain toner fluidity. Details are summarized in Table II. The ferromaqnetic cationic dye toners were directly printed to both acid-modified polyester and polyacrylonitrile ~ubstrates, steam fused and fixed by either high pres8ure steam development at 22 psig (1.55 kg per sq cm qauge) for 1 hour or by cottage-steaming at 7 psig (0.5 kg per g~ cm gauge) for 1 hour.
Cationic dyes of the triarylmethane (Example 37), 34 azomethine (Example 38), styryl (Examples 39 and 41-43) and rhod~mine (Example 40) series, wi~h both water-soluble hydroxypropyl cellulose ("Klucel'~ LF) and polyvinyl acetate copolymer ("Gelva" C5-VIOM) resins, are exemplified.
"Klucel" L~ is a cellulose ether containing propylene glycol groups attached by an ether linkage and not more than 4.6 hydroxypropyl groups per anhydroglucose unit and having a molecular weight of approximately 100,000. The cationic dye toners of Examples 42 and 43 containing 1 and 2%, re~pectively, of citric acid provided brighter and tinctorially stronger prints on both acid-modified polyester and polyacrylonitrile as compared to the corresponding toners without the citric acid.
Example 44 This example illustrates the preparation of a ferromagnetic toner containing an acid dye, magnetic compo-nents and an aqueou~ alkali-soluble resin and the application thereof to nylon.
A solution of 12.7 parts of C.I. Acid Blue 40 (C.I. 62,125), 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 20% aqueous alkaline solution of a polyamide resin (TPX-1002). "Carbonyl Iron~
GS-6 (63.4 parts), ~Mapico~ Black Iron Oxide (64 parts) and 410 parts of water were added and the ~lurry was stirred on a high shear mixer for 20 minutes. The toner slurry was spray-dried to give a final toner composition coDtaining 30% of polyamide resin, 31.7~ of~Carbonyl Iron" GS-6, 32%
of "Mapico" Black Iron Oxide, 2% of C.I. Acid Blue 40 and

4.3~ of dextrin diluent. The toner was sieved through a 200 mesh screen and fluidized with 0.6% of"QusonW~-82.

* denotes tr~demark lO910Ql A latent magnetic image such as described in Example 1 was manually decorated with the above toner and transferred electrostatically to 100% nylon 66 jersey fabric and steam fused at 100C and 1 atm pressure for 10 to lS
seconds. The acid dye was fixed by cottage-steaming the printed fabric at 7 psig (0.5 ~g per sq cm gauge)for 1 hour.
The fabric was scoured at 60C with an aqueous solution of 2 parts per liter of a polyethoxylated oleyl alcohol and 2 partR per liter of alkyl trimethylam~onium bromide surface-active agents. A bright blue print was obtained.
Examples 45 to 53 Ferromagnetic acid dye toners were prepared by manually mixing the appropriate ingredients and spray-drying the slurries as described in Example 44. The toners were fluidized with 0.2 to 1.4% of ~usonWR-82. Details are summarized in Table III. A latent magnetic image such as described in Example 1 was manually decorated and the toner decorated image was electrostatically transferred directly to nylon 66 jer~ey. The toners were steam fused and the acid dyes were fixed by cottage-~teaming at 7 p8ig (0.5 kg per 5q cm gauge) for 1 hour. After scouring, bright well-defined prints were obtained.
Toners containing monosulfonated azo ~Examples 45, 46 and 51) and monosulfonated anthraquinone (Examples 47 to 50) dyes, with water-soluble polyvinyl acetate copolymer Gelva" C5-VIOM), hydroxypropylcellulose (~Klucel" LF) and polyamide (TPX-100~ reæins, are exemplified. Examples 52 and 53 include a special disulfonated bis-anthraquinone dye which is noted for its good light- and wetfastness properties on nylon. Examples 47, 50, Sl and 53, with acid * denotes tr~dem~rk ~091(~

dyes and containing 1% of ammonium oxalate, provided brighter and tinctorially stronger prints on nylon than the corres-ponding toners without ammonium oxalate. Citric acid, present either in the toner (Example 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 fiber-reactive dye, magnetic components and an aqueous alkali-soluble resin and the application thereof to cotton.
A magnetic toner was prepared by spray-drying a mixture containing 30% of polyvinyl acetate copolymer resin (NGelva" C5-VIOM), 33~ of~Carbonyl Iron"GS-6, 33~ of "Mapico" Black Iron Oxide, 2% of C.I. Reactive Blue 7 ~C.I. 61125) and 2~ of inorganic diluent. The spray-dried product was sieved through a 200 mesh screen and fluidized with 0.3%'1Qus~ WR-82. 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 XV
negative potential to the backside of the fabric. The printed fabric was steam fused at 100C and 1 atm pressure for 10 seconds. The toner fused cotton fabric was then sprayed with an aqueous solution containing 100 parts per liter of urea and 15 parts per liter of sodium bicarbonate.
This overspray is required to chemically link the reactive dye to the cotton by forming a covalent dye-fiber bond.
Following the spray application, the cotton fabric was dried and the dye was fixed by heating at 190C for 3 minutes 109100~

in a hot air oven. The fabric was then scoured at 65C
in aqueouQ detergent. A brilliant blue print having excellent wa~hfastness properties was obtained.
Ex Q le 55 . `:
A spray-dried magnetic toner containing 30% of polyvinyl acetate copolymer re~in (~Gelva" C5-VIOM), 33%
of"Carbonyl Iro~ 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 described in Example 54. The toner was steam fused and the printed fabric was sprayed with an agueous solution containing 100 parts per liter of urea and 15 parts per liter of sodium bicarbonate. The dye was fixed by heating at lB2C for 3 minutes and the fabric wa~ ~coured at 65C in aqueous detergent. A bright yellow print was obtained.
Ex~mple 56 Pollowing the procedure of Example 55, a spray-dried ferromagnetic toner containing 30% of polyvinyl acetate copolymer resin (~Gelva" C5-VqOM), 33~ of"Carbonyl IronnGS-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 over3prayed with a~ueous urea/sodium bicarbonate and the dye was fixed. After scouring, a b A ght ~- red print was obtained.
Example 57 This example illustrates the preparation of a ferromagnetic toner containing a reactive dye, a disperse dye, magnetic components and an aqueous alkali-soluble resin and ~39~

wr . ~ . - - - . . - . . .

the application thereof to polyester/cotton-blend fabric.
A magnetic toner was prepared by spray-drying a mixture containing 30% of polyvinyl acetate copolymer resin (~Gelva" C5-VIOM), 30% of Carbonyl Iron GS-6, 31.1% of ~Mapico~ Black ~ron Oxide, 3% of a 60/40 mixture of a yellow disperse dye of the formula shown as (B) in Table VII and C.I. Reactive Yellow 2 and 5.9% of inorganic diluent. The toner was sieved through a 200 mesh screen and fluidized with 0.2% of"Quso~WR-82. Toner decoration of a latent magnetic image was carried out as described in Example 1. The toner decorated image was electrostatically transferréd directly to 65/35 polyester/cotton poplin fabric and steam fused at 100C and 1 atm 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 ~coured at 60C in aqueous detergent. A bright yellow well-defined print was obtained.
Exampl- 58 A spray-dried magnetic toner containing 30~ of polyvinyl acetate copolymer resin ~"Gelva" C5-VIOM), 30%
ofnCarbonyl Iron"GS-6, 30.1~ of ~Mapico" Black Iron Oxide, 3% of a 76/24 mixture of a blue disperse dye of the formula shown-as ~C) in Table VII and C.I. Reactive Blue ?
and 6.9% of inorganic diluent was directly printed on 65/35 polyester/cotton poplin and steam fused as described ~-; in Example 57. The printed fabric was fixed by heating at 200C for 100 seconds and then scoured at 60C in aqueous detergent. A bright blue print was obtained.

.. , " . . . . . . .

Example 59 ~-This example illustrate~ the preparation of a ferromagnetic toner containing a ~ulfur dye, magnetic components and an aqueous alkali-soluble resin and the application thereof to cotton.
A ~pray-dried magnetic toner containing 32.6%
of polyvinyl acetate copolymer resin ~Gelva~ C5-VIOM), 32.6% of"Carbonyl Iron~GS-6, 32.6~ of HMapico~ Black Iron Oxide and 2.2% of C.I. Leuco Sulfur Blue 13 (C.I. 53450) - 10 wa~ prepared, sieved through a 200 mesh screen and fluidized .
with 0.2% ofqQu~o~WR-82. A toner decorated latent magnetic ; image was electro~tatically transferred, by a procedure , . . .
~uch a~ described in Examplé 1, to 100% cotton fabric.
; Tho toner wa~ ~toam fw ed at 100C and 1 atm pre~sure for ~` 10 econd~. ~he printed fabric was subsequently padded fros an aqueous bath containing 300 parts per liter of 80dium sulfhydrate at a pickup of approximately 50%. The leuco dye was then immediately steam fixéd at 100C and b,',, ~ 1 atm pressure for 60 seconds. After fixation, the pr~nted ,., ~ , .
fabric was developed by oxidation at 50C in an aqueous bath containing 4 part~ per liter of sodium perborate.
,. ~; , The fabric was finally scoured at 60C in an agueou~ bath oontainlng~2 parts per liter of diethanol~;ne oleyl ., .
~ sulfate surface-active agent. A blue print was obtained.
.;, ^ . . .
~ Example 60 g~;~ This example illu~trate~ the preparation of , ~ .
;-- a ferromaqnetic toner containing a vat dye, magnetic ,~
-~ components and an aqueou8 alkali-soluble resin and the application thereof to cotton fabric.
A ~pray-dried magnetic toner containing 29% of :~ .

1091(101 polyvinyl acetate copolymer resin ("Gelva" C5-VIOM), 32.9%
of"Carbonyl Iron'GS-6, 32.9% of "Mapico" Black Iron Oxide, 2.7% of C.I. Vat Red 10 (C.I. 67,000) and 2.5% of diluent 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. The toner decorated latent image was electrostatically transferred to 100% cotton twill fabric and the toner was steam fused at 100C and 1 atm pressure for 10 seconds. -The printed cotton fabric was then padded from a reducing bath containing 30 parts per liter of soda caustic 60 parts per liter of soda ash 60 parts per liter of sodium hydrosulfite 2 parts per liter of sodium octyl/decyl sulfate surface-active agent 15 parts per liter of amylopectin thickening agent 2 parts per liter of 2-ethylhexanol at a pickup of 70 to 80% and flash aged at 132C for ~5 seconds~ The fabric was rin~ed in cold water, oxidized for 1 minute at 60C in a bath containing 2% hydrogen peroxide and 2% glacial acetic acid, rinsed and scouxed for 5 minutes at 82C in 0.5 part per liter ~aqueous) of a diethanol~mine oleyl sulfate surface-active agent. A bright red print was obtained.
Example 61 A spray-dried ferromagnetic toner containing 30%
of polyvinyl acetate copolymer resin ("Gelva" C5-VIOM), 33% of"Car~onyl IronnGS-6, 33% of "Mapico" Black Tron Oxide, 3~ 2% of C.I. Vat Blue 6 tC.I. 69825) and 2% of diluent was prepared and the latent image produced therewith was transferred directly to 100~ cotton twill fabric. The toner was fused, the vat dye was fixed and the printed fabric was scoured as described in Example 60. A bright blue print was obtained.
ExamPle 62 A spray-dried ferromagnetic toner containing 30%
of polyvinyl acetate copolymer resin ("Gelva" C5-VIOM), 33% of"Carbonyl Iron"GS-6, 33% of "Mapico" Black Iron Oxide, 2~ of C.I. Vat Yellow 22 and 2% of diluent was prepared and printed on 100~ cotton twill fabric by a procedure sub8tantially as described in Example 60. A yellow print was obtained~
Example 63 This example illustrates the preparation of a ferromagnetic toner containing a premetalized acid dye, magnetic components and an aqueous alkali-soluble resin and the appl~cation thereof to nylon.
A spray-dried magnetic toner was prepared ~o as to contain 30% of polyvinyl acetate copolymer resin ~Gelva" C5-VIOM), 31.4% of"Carbonyl IronnGS-6, 31.4% of HMapico~ Black Iron Oxide, 2% of C.I. Acid Yellow 151 ~a sulfonated premetalized azo dye) and 5.2~ of inorganic diluent. The toner was ~ieved through a 200 mesh screen and fluidized with 0.2S ofnQu~ WR-82. A toner decorated - latent magnetic image such as described in Example 1 wa~
electrostatically transferred to nylon 66 jersey fabric and steam fused at 100C and 1 atm pressure for 10 seconds.
The premetalized acid dye was fixed by cottage-steaming ~;~ the fabric at 7 psig ~0.5 kg per sq cm 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 ~odium hydro~ulfite, ~09lOOi 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 (0.5 kg per s~ cm gauge) for 1 hour and the printed fabric was caustic-hydro scoured as above.
In both cases, strong well-defined yellow prints were obtained.
_xample 64 Using the procedures substantially as disclosed in Example 63, a spray-dried ferromagnetic toner containing 30% of polyvinyl acetate copolymer resin tnGelva" C5-VIOM), 32.1S 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 jer~ey fabric. After steam fusing, cottage-steaming and scouring, a well-defined bright red print fabr~c wa~ obtained. A similar sharp red print was obtained when the fabric was over~prayed with 50% aqueous citric acid prior to cottage-steaming.
Example8 65 to 6~
Examples 65 to 68 illustrate the preparation of ferromaqnetic toners containing cationic-disperse dyes, magnetic components and an aqueous alkali-soluble resin and the application thereof to acid-modified polyester, polyacrylonitrile and cellulose acetate.
Cationic-disperse dyes, that is, water-insoluble salts of cationic dyes and selected arylsulfonate anions, are well-~nown in the art for dyeing acid-modified polyester and acrylic fibers. Cationic-disperse dye toners were prepared by manually mixing the appropriate ingredients lO91UOl ,.

~20% nonvolatile solids) and spray-drying. The spray-dried toners were sieved through a 200 mesh screen and fluidized with 0.2% of~Qusd'WR-82. Details are summarized in Table IV. Exa~ples 65 to 67 use l,S-naphthalenedisulfonate a~ the anion and Example 68 uses 2,4-dinitrobenzenesulfonate as the anion. Toner decoratiGn of a latent magnetic image and electro~ttatic transfer to the fabric substrate were preformed as described in Example 1. ~he toners were ste~m fused and the printed fabrics were oversprayed with 50 agueous citric acid to aid in dye fixation. The dyes were flxed by either cottage-stteaming or high-pressure steaming ~' the sprayed fabrics. After scouring, in each example, ' ;
~ a well-defined print was obtained.
r',' Exa~ple 69 . .i'" This example illustrates the preparation of a ~' rromagnetic toner containing a fluorescent brightening ;~ agent, magnetlc component~ and an agueous alkali-soluble r~in and the application thereof to cotton.
, ~ ~ , ., ;~, A magnetic toner containing 30% of polyvinyl acetate copolymer resin (~Gelva~ C5-VIOM), 34t of~Carbonyl ~' Ironn,GSt-6, 34% of ~Mapico~ Black Iron Oxide and 2~ of '- ~ C.I. Fluorescent Brightener 102 was prepared by spray-d~ying an aqueous 20% nonvolatile solids mixture of the '' t,~2 , ingr-dients. The ~pray-dried toner was sieved through ~.-,. . .
a 200~me~h screen and fluidized with 0.2% of~Qu~ WR-82.
A latent agnetic image such as de~cri~ted in Example 1 was ~, toner decorated and the image was electrostatically ~"
, transerred to 100% cotton ~heeting. The toner wa~ ~team ~ fused and the brightener was fixed by heating the fabtric -,~ 30 at 100CtC and 1 atm pressure for 25 minutes. The printed ~ ~ -45-1~i0~1 fabric was then scoured at 60C in an aqueous solution of 2 parts per liter of soda caustic and 2 parts per liter of polyethoxylated tridecanol surfactant. Upon exposure to an ultraviolet light source, the printed fabric strongly fluoresced in the imaged areas.
Examples 70 to 74 These examples illustrate the preparation of ferro-magnetic toners containing a chemical-resist agent, magnetic components and an aqueous alkali-soluble resin and the application thereof to nylon. The toners were prepared by spray-drying an aqueous 20% nonvolatile solids slurry of the appropriate ingredients. The spray-dried toners were sieved through a 200 mesh screen and fluidized with 0.2% -r-of QU80 WR-82. DetailQ are summarized in Table V. The chemical-resi~t toners were evaluated by manual decoration of the latent magnetic image on a 300 line per inch 112 per mm) magnetically structured CrO2-coated aluminized "Mylar" film by procedures substantially the same as described in Example 1.
The toner-decorated images were transferred electrostatically to nylon 66 jersey $abric and steam fused at lOO-C and 1 atm pressure for 10 to lS seconds. The chemical resi~t in each example was fixed by steaming (atmospheric) the abric for 20 minutes. Each printed fabric was rin~ed in water to remove the resin and the magnetic componentls) and finally dried. Each resultant resist printed nylon fabric was then overdyed with either a red biscationic dye of the formula shown as ID) or a blue diacidic (anionic) dye of the formula shown as IE), or a mixture thereof, the (D) and (E) formulas being given in Table VII, by the following procedure:

lO9i()01 Resist-printed nylon fabric (S parts) was added to 300 parts of water containing:
ethylenediaminetetraacetic acid, tetrasodium salt ........ 0.013 part (0.25~ owf) a sulfobetaine of the formula shown as (F) in Table VII ..... 0.05 part (1.0% owf) tetrasodium pyrophosphate ........... 0.010 part (0.2% owf).
The dye bath was adjusted to pH 6 with 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 (0.025 part; 0.5% owf) were added. When both types of dyes were employed, the bath containing the cationic dye wa~ held at 27C for 5 minutes prior to the addition of the anionic dye. After completion of the dye(s) addition the bath was maintained at 27C for 10 minutes, the temperature was raised at about 2C per minute to 100C
~nd hela at thi~ temperature for 1 hour. Each fabric was r~nsed 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 IG) in Table VII
and binary soft IFe) and hard (Fe3O4) magnetic materials are illustrated in Examples 70 to 73; they showed excel-lent chemical-resist properties on nylon. An analogous magnetic-resist toner containing only chromium dio~ide as the hard magnetic component (Example 74) also provided satisfactory printed resist on nylon.

~ ':' ' .

~09iOOl Example 75 This example illustrates the multicolor printing of polyester with ferromagnetic disperse dye toners containing water-soluble resins.
A semitransparent nonconductive CrO2 film was prepared by embossing a 5-mil (0.127 mm) thick flexible cellulose acetate film with a 500 line per inch (20 per mm) pattern of parallel groove~. Chromium dioxide mixed in an alkyd binder was doctored over the surface of the embo~sed tran~parent support and then cured to bind the magnetic material to the support by a procedure known in the art, for example, as described in U.S. 3,554,798.
The film was magneti2ed by passing it over the poles of a bar magnet of approximately 1,500 gauss average field strength. A photocolor separation of a printed design was made by photographing the design three times through red, green and blue filter~. Exposure through the red filter produced a negative recording of the red light in the printed original. A cyan film positive recording the remaining green and blue primaries present in the original print was obtained. Exposure through the green filter produced a negative recording of the green in the original print, and a magenta film positive recording the remaining red and blue primaries was obtained. Similarly, exposure through the blue filter produced a negative recording of the blue in the original print, and a yellow film positive was obtained. ~ separate latent magnetic image of each of the cyan, magenta and yellow colors making up the design to be printed was developed by placing the photocolor separated film positive of the desired color in contact ~.09~01 with the aforesaid magnetized semitransparent CrO2 film and uniformly illuminating by a Xenon flash passing through the film positive. The dark areas of the film positive, that i8, the image areas, absorbed the energy of the Xenon flash, whereas the clear areas transmitted the light and heated the CrO2 beyond its 116C Curie point, thereby demagnetizing the exposed magnetic CrO2 lines. A latent magnetic image corresponding to the dark areas of the film positive was obtained. The resultant cyan, magenta and yellow latent magnetic images were manually decorated with the blue, red and yellow disperse dye toners of Example~ 1, 15 and 4, respectively. An AC corona wa~ passed over the surface of each toner decorated image to dissipate any static charge~. The cyan toner-decorated latent image was electrostatically tranqferred at 20 KV negative potentlal directly to 100% polyester woven cloth. The magenta and yellow toner-decorated image~ were similarly successively transferred to the same polyester fabric, thereby providlng a multicolored printed design. Following transfer, the disperae dyea were fixed by heating the printed fabric at 205C and 1.5 p5i (O. 11 kg per ~q cm) for 40 seconds. The printed fabric was then scoured at 60C
in an a~ueou solution of 2 part~ per liter of sodium hydrosulfite and 2 parts per liter of soda caustic.
A well-defined multicolored printed design was o~tained.
Example 76 A ferromagnetic disperse dye toner containing 30~ of a polyamide resin ~nVersamid'~ 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 * denotes tradem~rk 1091~0'1 spray-drying a 20% nonvolatile solids toluene-isopropanol slurry of the ingredients by a procedure substantially as described in Example 3. "Versamid" 930 is a water-insoluble resin having a molecular weight of about 3,100 and 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'~arbonyl Iron" GS-6, 30.7% of "Mapico" Black Iron Oxide, 1.9% of C.I. DisperQe Blue 56 and 5.6% of dispersant wa~ prepared by spray-drying an aqueous slurry of the ingredients containing 20~ of nonvolatile ~olids.
Both of the afore~aid toners were manually applied to the latent images on a CrO2-coated aluminized ~Mylar"
film and electrostatically transferred to 100% polyester double-knit fabric by procedures gubstantially the same-as deQcribed in Example 1. The toners were steam fused and the disperse dyes were fixed by heating the printed fabrics at 210~C and 1 atm pressure for 15 seconds. The printed fabrics were then scoured at 75C in an a~ueous solution of 4 part~ per liter of caustic soda, 4 parts per liter of sodium hydrosulfite and 2 parts per liter of ~Lakeseal~
detergent. m e fabric printed with the disperse dye toner containin~ the water-soluble resin was completely clear of resin and magnetic components after just a few econds of gentle stirring in the scouring medium. The fabric printed with the water-insoluble resin was not clear of ~0 resin and magnetic components even after 15 minutes scouring lV5~00~

at 75C. Thus, the resin impregnated magnetic particles were much more easily removed from the printed fabric using the dye toner containing the water-soluble resin as compared to the toner containing the water-insoluble resin.
~his is a critical feature since the presence of the black iron-iron oxide on the fabric surface effectively masks the color of the dye fixed in the fabric. In the aforesaid experiment employing the water-soluble polyvinyl acetate re~in, scoured fabric was printed to a bright blue whereas in the experiment employing the wster-insoluble polyamide resin, the scoured fabric was printed to a dark brown to black, completely masking the bright yellow color of the dye employed.
Ex~mple 77 Thl~ example ~llu~trates the preparation of a forromagnetic dye toner containing a yellow disper~e dye, magnetic components and a water-~oluble natural resin, and the application thereof to paper and polyester.
A mixture of 350 parts of a commercially available 20~ aqueous solution of a maleic anhydride-rosin derivative ("Unirez"*7057), 28.4 parts of C.I. Disperse Yellow 54 as a 28.2% ~tandardized powder containing a 50/50 mixture of lignin sulfonate and sulfonated naphthalene-formaldehyde as a dispersant, 60 parts of "Mapico" Black Iron Oxide and 59.6 parts o"Carbonyl Irod'GS-6 was stirred for 30 minutes on a high-speed shear mixer. Water (502 parts) wa~ added and the resultant slurry was spray-dried to give a final toner composition containing 35% of esterified rosin, 4S of C.I. Disperse Yellow 54, 1.2% of the lignin sulfonate/sulfonated naphthalene-formaldehyde disper~ant, * d~notea trademark lO~iOOl 30~ of "Mapico" Black Iron Oxide and 29.8% of"Carbonyl Iron"GS-6. The toner was sieved through a 200 mesh ~U.S. Sieve Series) screen and fluidized with 2% of"Quso"
WR-82. A latent magnetic image such as described in Example 1 was manually decorated with the toner and the toner decorated image was transferred electrostatically to both paper and polyester substrates by applying a 20 KV
negative potential, using a DC corona, to the backside of the substrate. After transfer the image was steam-fused 10 on each substrate. After direct transfer and fu~ion to the polyester fabric, the dye image was fixed by heating for 30 seconds at 210C and 1 to 1.5 psi (0.07 to 0.11 kg per 8q cm) pre3sure. The dye wa~ also heat transfer printed from the paper to polyester fabric by placing the fused ~mage-bearing paper face down on the polye~ter and applying 1 to 1.5 psi ~0.07 to 0.11 kg per sq cm) pres~ure for 30 ~econds at 210C. Each of the fabrics, after dye fixation, was scoured with hot aqueous alkaline detergent. Deep yellow prints were obtained 20 on each, that is, the polyester which was directly printed and the polyester which was heat transfer printed from paper.
Example 78 s ~his example illustrates the preparation of a ferromagnetic dye toner containing a yellow disperse dye, magnetic components and an aqueous aIkali-soluble polyacrylic acid resin, and the application thereof to paper and polyester.
A ferromagnetic toner was prepared by spray-30 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-fonmaldehyde dispersant, 30% of "Mapico" Black Iron Oxide and 29.8% of~Carbonyl IronnGS-6. The spray-dried toner was sieved through a 200 mesh (U.S. Sieve Series) screen and fluidized with 0.1% ofnQusonWR-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 subsequently heat transfer printed f,rom the paper to 100% polyester fabric as described in Example 77. The image was also directly printed to 1004 polyester fabric as described in Example 77. In both case~ the fixed printed fabrics were ~coured at 65C
in an aqueous polyethoxylated tridecanol surfactant solutlon; deep yellow prints were obtained on both fabrics.
Example 79 This example illustrates the preparation of a ferromagnetic dye toner containing a red disperse dye, a msgnetically 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 ~pray-drying a mixture containing 30~ of polyvinyl acetate copolymer re~in, 65.8~ of a commercially available Fe304-cobalt alloy (HiE~"*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 pa~sed through a 200 mesh screen. The toner flow properties * denotes trademark 53 lO910Ql were excellent. The oner was used to manually decorate a latent magnetic image on the surface of a printing base such as de~cribed in Example 1. The decorated image was electrostatically transferred to paper, steam fused and then heat transfer printed from the paper to 100% polyester fabric. The image was also directly transferred to both 100% polyester fabric and "Mylar" polyester film and then steam fused. The image was also electrostatically transferred to paper, steam fused and then heat transfer printed from the paper. In each case permanent dye fixation was achieved by heating the printed film or fabric substrate at 205-210C and 1.5 psi (0.11 kg per sq cm) pressure for 40 seconds. The printed substrates were finally scoured at 82C in an aqueous solution of 2 parts/
liter of caustic soda, 2 parts/liter of hydrosulfite and 2 p~rt~/liter of a polyethoxylated tridecanol surfactant.
~right red pr~nt~ were obtained in each case.
Example 80 .

This example illustrates the preparation of a ferromagnetic dye toner containing a red disperse dye, a soft ferromagnetic component and an aqueous alkali-soluble resin, and the application thereof to paper.
A ferromagnetic toner was prepared by spray-drying a mixture containing 10% of polyvinyl acetate copolymer resin (nGelva" C5-VIOM), 1~ of C.I. Disperse Red 60, 3.2~ of lignin sulfonate dispersant and 85.8%
of ~arbonyl IronnGS-6. The spray-dried toner was fluidized with 1~ of"Quso"WR-82. The toner was used to develop the latent magnetic image on the surface of a continuously CrO2-coated (220 microinches) (5.59 x 10 4 cm) al~ nized "Mylar" polyester film as described in Example 1. The ~urface of the CrO2 film was magnetically structured into a 500 lines per inch (197 lines per cm) magnetic pattern using a magnetic write head and then imagewise demagnetized by exposure to a short burst from a Xenon lamp flashed through an image-bearing photographic transparency. The resultant latent magnetic image was manually decorated with toner particles and the toner decorated image wa~
electrostatically transferred to paper and fused thereon as described in Example 1. A well-defined, background-free red print was obtained.
Example 81 A ferromagnetic toner containing 36% of polyvinyl acetate copolymer resin ("Gelva" C5-VIOM), 1% of C.I.
Disperse Red 60, 3.2% of lignin sulfonate dispersant and 59.8~ of"Carbonyl Iron~GS-6 wa~ ~imilarly prepared and appl~ed to paper as de~cribed in Example 80. The results obtained were comparable.

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Claims (52)

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

1. Ferromagnetic toner comprising:
(a) at least one ferromagnetic component;
(b) at least one member of the group consisting of dye and chemical treating agent; and (c) a readily fusible, water-soluble or water-solubilization resin which substantially encapsulates (a) and (b).

2. Ferromagnetic toner for magnetically printing a substrate, said toner comprising:
(a) at least one ferromagnetic component;
(b) at least one member of the group consisting of dye and chemical treating agent, said agent being selected from the group consisting of flame-retarding agent, biocide, ultraviolet light absorber, fluorescent brightener, dye ability modifier, soil-release agent and water-proofing agent; and (c) a readily fusible, aqueous scour-removable water-soluble or water-solubilizable resin which substantially encapsulates (a) and (b).

3. Ferromagnetic toner of Claim 1 comprising, 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 having a resin to ferromagnetic component ratio of 0.11 to 3.3.

4. Ferromagnetic toner of Claim 2 comprising, 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 having a resin to ferromagnetic component ratio of 0.11 to 3.3.

5. Ferromagnetic toner of Claim 3 or 4 comprising 55 to 70% of (a), 0.10 to 15% of (b) and 30 to 40% of (c) and having a resin to ferromagnetic component ratio of 0.40 to 1Ø

6. Ferromagnetic toner of Claim 1 wherein the ferromagnetic component consists of hard magnetic particles.

7. Ferromagnetic toner of Claim 2 wherein the ferromagnetic component consists of hard magnetic particles.

8. Ferromagnetic toner of Claim 6 or 7 wherein the hard magnetic particles are Fe3O4 particles.

9. Ferromagnetic toner of Claim 6 or 7 wherein the hard magnetic particles are chromium dioxide particles.

10. Ferromagnetic toner of Claims 6 or 7 wherein the hard magnetic particles consist of an alloy of Fe304 and cobalt.

11. Ferromagnetic toner of Claims 6 or 7 wherein the hard magnetic particles consist of an alloy of Fe304 and nickel.

12. Ferromagnetic toner of Claim 1 wherein the ferromagnetic component consists of a binary mixture of hard and soft magnetic particles.

13. Ferromagnetic toner of Claim 2 wherein the ferromagnetic component consists of a binary mixture of hard and soft magnetic particles.

14. Ferromagnetic toner of Claims 12 to 13 wherein the hard and soft magnetic particles are Fe304 particles and iron particles, respectively.

15. Ferromagnetic toner of Claims 12 or 13 wherein the hard and soft magnetic particles are chromium dioxide particles and iron particles, respectively.

16. Ferromagnetic toner of Claim 1 wherein the dye is a disperse dye.

17. Ferromagnetic toner of Claim 1 wherein the dye is a cationic dye.

18. Ferromagnetic toner of Claim 1 wherein the dye is an acid dye.

19. Ferromagnetic toner of Claims 1 or 2 wherein the dye is a premetalized acid dye.

20. Ferromagnetic toner of Claims 1 or 2 wherein the dye is a vat dye.

21. Ferromagnetic toner of Claims 1 or 2 wherein the dye is a sulfur dye.

22. Ferromagnetic toner of Claims 1 or 2 wherein the dye is a fiber-reactive dye.

23. Ferromagnetic toner of Claims 1 or 2 wherein the dye is a mixture of a disperse dye and a fiber-reactive dye.

24. Ferromagnetic toner of Claims 1 or 2 wherein the dye is a salt of a cationic dye and an arylsulfonate anion.

25. Ferromagnetic toner of Claims 1 or 2 wherein the chemical treating agent is a fluorescent brightening agent.

26. Ferromagnetic toner of Claims 1 or 2 wherein the chemical treating agent is a dyeability modifier.

27. Ferromagnetic toner of Claims 1 or 2 wherein the chemical treating agent is a flame retarding agent.

28. Ferromagnetic toner of Claims 1 or 2 wherein the chemical treating agent is a biocidal agent.

29. Ferromagnetic toner of Claims 1 or 2 wherein the chemical treating agent is an ultraviolet light absorbing agent.

30. Ferromagnetic toner of Claims 1 or 2 wherein the chemical treating agent is a soil-release agent.

31. Ferromagnetic toner of Claims 1 or 2 wherein the chemical treating agent is a water-proofing agent.

32. Ferromagnetic toner of Claims 1 or 2 wherein the resin is a natural, modified natural or synthetic resin.

33. Ferromagnetic toner of Claims 1 or 2 wherein the resin is a thermoplastic resin.

34. Ferromagnetic toner of Claims 1 or 2 wherein the resin is such that it can be solubilized in water in less than five minutes at less than 90°C.

35. Ferromagnetic toner of Claims 1 or 2 wherein the resin is an adduct of resin, a dicarboxylic acid or anhydride, a polymeric fatty acid and an alkylene polyamide.

36. Ferromagnetic toner of Claims 1 or 2 wherein the resin is a hydroxypropylcellulose prepared by reacting 3.5 to 4.2 moles of propylene oxide per D-glucopyranoayl unit of the cellulose.

37. Ferromagnetic toner of Claims 1 or 2 wherein the resin is a polyvinyl acetate copolymer having a free carboxy group content equivalent to 0.002 to 0.01 equivalent of ammonium hydroxide per gram of copolymer.

38. Ferromagnetic toner of Claim 1 containing from 0.01 to 5% by weight, based on total toner weight, of a free-flow agent.

39. Ferromagnetic toner of Claim 2 containing from 0.01 to 5% by weight, based on total toner weight, of a free-flow agent.

40. Ferromagnetic toner of Claims 38 or 39 containing from 0.01 to 0.4% of a free flow agent, which agent is an alumina or fumed silica.

41. Ferromagnetic toner of Claim 2 wherein the dye is a disperse dye.

42. Ferromagnetic toner of Claims 16 or 41 con-taining a benzanilide dye carrier.

43. Ferromagnetic toner of Claims 16 or 41 con-taining a butyl benzoate dye carrier.

44. Ferromagnetic toner of Claims 16 or 41 con-taining a .beta.-naphthol dye carrier.

45. Ferromagnetic toner of Claims 16 or 41 con-taining an o-phenylphenol dye carrier.

46. Ferromagnetic toner of Claims 16 or 41 con-taining a lignin sulfonate dispersant.

47. Ferromagnetic toner of Claims 16 or 41 con-taining a dispersant which is a salt of a sulfonated naphthalene-formaldehyde condensate,

48. Ferromagnetic toner of Claims 1 or 2 con-taining a static-reducing cationic surfactant.

49. Ferromagnetic toner of Claim 2 wherein the dye is a cationic dye.

50. Ferromagnetic toner of Claims 17 or 49 con-taining citric acid.

51. Ferromagnetic toner of Claim 2 wherein the dye is an acid dye.

52. Ferromagnetic toner of Claims 18 or 51 con-taining citric acid.