Note: Descriptions are shown in the official language in which they were submitted.
- ~323L~7~
BACKGROUND OF THE INVE~TION
1. Field of the Invention
This invention relates to magnetic printing
- processes and devices.
2. Description of the Prior Art
One form of copying process in wide usage is
the electrostatic copying process. Operation of such a
process may provide difficulties in that large black areas
may not be amendable to copying and the document to be
copied may have to be reimaged each time a copy is made.
The overcoming of these difficulties may be economically
prohibitive. It is well known that audio signals and
digital data can be recorded on magnetic materials.
Magnetic field configurations in the form of alphabetical
characters and pictures can also be produced by selective
magnetization or demagnetization of the surface of a
ferromagnetic chromium dioxide film. The resultant
fields are strong enough to attract and hold small
magnetic particles such as iron powder. The development,
that is, the making visible, of such a latent magnetic
image can be effected by contacting the image surface
with a magnetic developer, usually referred to as a
magnetic toner, consisting of ferromagnetic particles
and pigments encapsulated in a thermoplastic resin binder.
Such a development process is commonly known as decoration
of the latant magnetic image. The developed image can
then be transferred to and fixed on paper, thus providing
a black-on-white copy of the latent image. Operation
of such magnetic processes, however, may not be completely
free of difficulties. For example, since most magnetic
- 2 -
~3~7~
toner particles are attracted by both electrostatic and
magnetic fields, stray electrostatic charges which are present
on the magnetic surface or toner particles may interfere with
the interaction of the magnetic image and the magnetic toner
particles. More specifically, a portion of the magnetic sur-
face other than that containing the magnetic image may attract
enough magnetic toner particles to render unsatisfactory the
paper print which subsequently is produced.
There i5 ~x~ensive prior ar~ in the fields of
magnetic recording tapes and thermomagnetic recording. ~-
U.S. 3,476,595 discloses a magnetic recording tape which is
coated with a thin layer of a cured complex of silica and
a preformed org2nic polymer containing a plurality of
alcoholic hydroxy groups. The disclosure includes coated,
ferromagnetic, chromium dioxide, magnetic recordins tapes.
Discussions of acicular chromium dioxide and magnetic recording
members bearing a layer of such ma~erial may also be found
in U.S. 2,956,gS5 and 3J512,930. U.S. 3,~54,798 discloses
a magnetic recording member which is relatively transparent
to light (transmits 5 to 95~) and which includes a plurality
of discrete areas of hard magnetic particulate material
supported thereon and bound thereto. A magnetically hard
~aterial is a material which is permanently ma~neti~able
below the Curie point of the material,as opposed to a
magne~ically soft material which is substantially non-
permanently magne~izable under similar conditions below tne
Curie point of the material. Chromium dioxide is disclosed
as an example of a hard masnetic mat~rial. Decoration of the
~maqe may be effected by means of a m~gne~ic pi~men~, for
3~ ex~ple, a dilute, alkyd-oil/water cmulsion, carbon blac~-based
~ 3'~6
printing lnX. U~S7 3,522,090 1~ ~imilar in disclosur~ to
.S. 3t5~4,798 in that it al~o discloses a l~ght-transp~ren~
recording member. ~owever, ~t also discloses ~hat the
~gnetic material which ~s capable of maqnetization to a hard
~a~netic state (on the xecording mem~er) may haYe a coating
of a reflective material which is so disposed that the
magnetic material is shielded from exposing xadiation while
the adjacent uncoated portion of the recording member transmits
10 to 90% of the exposing radiation. The reflective coating
can be a metallic reflector, such as aluminum, or a diffuse
reflective pig~en~, such as titanium dioxide. U.5. 3,555,556
- discloses a direct thermomagnetic recording (TMR) process wherein
the document to be copied is imaged by light which passes
through the document. U.S. ~,555,~57 discloses a reflex
thermomagnetic recording process wherein the light passes
through the recording member and reflec~s off o~f th~ documen~
which is to be copied. Thus, in the direct process, the
document must be transparent but the recording member need
not be transparent, whereas in the reflex process, the
recording member must be transparent but the document need
not be transparent. For the recording mem~er to ~e transparent,
~t must hav~ regions which are free of magnetic particles,
that is, a non-continuous ma~netic surface must be used.
U.S. 3,627,58~ discloses fcrromagnetic toner
particles, for dcveloping magnet;c ima~es, that include
~inary mixturcs of a magnetically hard material and a
magnctically soft material, an ~nc~psulatin~ rcsin and,
~pti~nally, carbon black or blac~ or colored dycs ~o provide
~ blac~er or colored copy~ ~N;grosine~ SSU is discloscd
as an ex~mple of a black dyc~ ThC enca~sulating rcsin aids
'1~3~6
txans f er of the decorated magnetic lmage to paper and
ean be heated, pressed or ~apor softened to adher~ or fix
~he ~agnetic particles to the surface fibers of the paper.
~erromagnetic toncr particles of the type disclosed
in U.S. 3,627,682 are disclosed as being useful in the
dry thermomagnetic copying process of U.S. 3,698,005.
The latter patent discloses such a dry thermomagnetic
copying process wherein the magnetic r~cording
~ember is coated with a polysilicic acidl The use of the
polysilicic acid coating on ~he recording member is
particularly useful when the magnetic materi~1 on the
recording member comprises a plurality of discrete areas
of particulate magn~tic material because a greater number
of clean copies can be produced. The polysilicic acid,
which is relatively non-conductive, ex~ibits good non-stic~
properties. Thus, toner particles which are held to the
surface of the recording member by nonmagnetic forces can be
easily removed without removing the toner particles which
are held to ~he surface o~.the recording member by magnetic
~orces. U.S. 2,826,634 discloses the use of iron or
~ron oxide magnetic particlcs, either alone or encapsulated
itl low-melting resins, for developing .magne tic images .
Such toners have ~ecn employed to develop magnetic images
recorded on magnetic tapes, films, drums and printing
plates.
Japancse ~0/52044 discloscs a n~ethod wllic~
comprises adhering iron particl~s ~earing a photoscnsitivc
dia~snium compo~d on~o an elcctrophotographic matcrial
to ~orm an image, tr3nsfcring thc imaqc onto a sup~ort
30 having a coupl~r which is a~le to form an azo dyc by rcaction
~3Z~7~
~th ~he d~azonium compound, reac~ing the diazonium ~ompound
~nd ~he coupler and thereaf~er removing She iron particles~
~.S. 3,530,794 discloses ~ magnetic printing arrangement-
wherein a thin, flexible master sheet having magnetizable,
character-representing, mirror-reversed printing portions
.~s employed in combination with ~ rotary printing cylinder.
5he ~aster sheet,which consists of a thin, flexible
non-magnetizable layer, such as paper, is placed on top
of and in contact with a layer of iron oxide or ferrite
which is adhesively attached to a base sheet. The combined
layer and base sheet are imprinted, for example, by the
impact of type faces, so that mirror-reversed, character
representing por~ions of the iron oxide layer a~here to
the non-magnetizable layer, thus forming magnetizable
prin~ing portions on same. Thereafter, the printing p~rtions
~re masnetized and a magnetizable toner powder, such as
iron powderg is applied to and adheres to ~he magneti~ed
printing portions. The powder is then transferred from
the prin~ing portions to a copy sheet and permanently
~0 attached ~hereto, for example, by heating. U.S 3,052,564
discloses a magnetic printing process employing a magnetic
~n3c consisting of granules of iron coated wi~h a colored
~r uncolored thermoplastic wax composition. The magnetic
ink is employed in effecting the tra~sfer of a printPd
~ecord, using magnetic me~ns, to paper. U.S. 3,735,416
discloscs a magnetic printing proce~s whcrein characters or
other data to be prin~cd are formcd on a ma~nctic rccording
surface by mcas3s of a rccording hcad. ~ m~ tic toner
which ~ s composcd of x~sin-coated magnetic p~rticl~s is
30 employ~d to efect: trans cr of 'ch~ char~cters or othcr d~ta
-6-
3'~
from ~he recordi~g surface ~o a rec~ving sheet, ~.S.
3,250,636 discloses ~ direct ~maging process and apparatus
whexein a uniform magnetic field is applied to a ferromagnetic
~maging layeri the magnetized, ferromagnetic imagin~ layer
is exposed to a pattern of heat conforming to the shape
of the image to be reproduced, the heat being sufficient to
raise the heated psrtions of the layer above the Curie
point temperature of the ferromagnetic imaging layer so as
to foxm a latent magnetic image on the imaging layer; the
latent magnetic image is developed hy depositing a finely
divided magnetically attractable material on the surface
of the ferromagnetic imaging layer; the imaging layer is
uniformly heated above its Curie point temperature after the
development to uniformly demaqnetize it; and,finally, the
loosely adhering magnetically attractable mat~rial is
transferred from the imaging layer to a transfer layer.
German 2,4S2,530 discloses electrophotographic
toners comprising a magnetic material coated with an organic
substance containing a dye which vaporizes at 100 to 220C,
pre~er~bly 160 to 200CC, at atmospheric pressure. The ma~netic
matexial is preferably granular iron and/or iron oxide and
the coating is a water-insoluble polymer melti~g at about
150C, e.gO, polyamudes, epoxy resins and cellulose ethers and
esters. Both basic ~nd di~perse dyes c~n be used in ~he
ton~rs. ~he toners are from 1 to 10 microns in diameter and
~ay also contain silic~c acid as anti static a~ent. Colored
or bl~c~ copies are formed ~y toner dcvclopmcn~ o thc
l~tent im~ge on ~ photo-conduc~in~ shcct of ZnO paper,
followcd by tr~nsfcr of ~Ic dy~ in the vapor pllasc to a
rcc~;~ing sheot by applic~ion of heat and ~essure.
_7_
~13Z~6
osJEcTs AND SUMMA~Y OF TH~: INVENTIO~
In carrying out prior art thermomagnetic
recording processes, generally, only reddish-brown or black
images can be obtained on paper because of the dark hard
magnetic components, for example, the iron oxides (y-Fe203
or Fe304), and the dark soft magnetic components, for
example, iron, in the ferromagnetic toners employed therein;
because the magneti.c components are retained in and may
be essential to the formation of the visible images; and
because the magnetic components are bound to the paper
by the encapsulating resins employed in the ferromagnetic
toners. It is an object of the present invention to
provide magnetic printing processes and devices which can
be used to print, in a broad range of colors, if desixed,
a variety of substrates, including textiles, such as fabric
and yarn, film, including paper and wood. It also
is an object to provide such processes and devices which
utili2e either hard magnetic componen~s or soft magnetic
components or a mixture of hard and soft magnetic components.
Another object is to provide a magnetic printing process
whic~ inclu&es the step of scouring the print to
rer.ove t~e nard a~a/or soft ~.agnetic com~onents an~ ti~e
encapsulatin~ resin for sucll magnetic components. It is
a further object to provide such a process by means of which
can be obtained a print which is substantially free of
hard and soft magnetic components an~ encapsulating resin.
Still another object is to provide a process ~or applying
chemi~al treating agents to a substrate. A fur~her o~ject
is to provide a proccss and an appropriate device by
30 means of whicll a sllarp print can be obtained, that is,
without objectionable bac~ground caused by ferromagnetic
tonex particles undesira~ly adhering, for exampleL
electrostatically, to certain areas of tne ferromagnetic
material during formation of the magnetic image thereon.
The tenm "textile" is intended to include any natural
or synthetic material, such as natural or regenerated
cellulose, cellulose derivatives, natural polyamides, suc~
as wool, synthetic polyamides, polyesters, acryl~nitrile
polymers and mixtures thereof, which is suitable for
spinning into a filament, fiber or yarn. The term ".abric"
is intended to include any woven, knitted or non~toven
cloth comprised of natural or synthetic fibers, filar.ents
or yarns.
In summary, tlle invention herein resides in a
magnetic printing process~ and a device for carrving out
same, which process comprises the steps:
~a) forming a magnetic image on a ferromagnetic
material whlch is imposed on an electrically conductive
support;
(b) developing the magnetic image by decora.lns
sam~ with a ferromagnetic toner comprising a ferromagnetic
component and a re~in which substantiallv encapsulates the
ferromagnetic component; and
(c~ transferring the developed image to a
substrate.
- In magnetic textile printing, preferred
embodimen~s or the process include those wherein the
ferromagnetic toner of step (b) additionally con~ai~s a
dye and/or che.~lcal treating agent and whereln, after
transferring the developed image ~o a substrate in s~ep (c),
_ g _
~32~
the dye and/or chemical t-eating agent of tne ima~e is
permanently fixed on the sllbstrate, step (d~, and the
ferromagn~tic component and the resin are removed from tne
imase on the substrate, step (e). Furtner preCerred
embodiments of the process include those wherein the
developed image, after being transferred to the substr2te
in step (c), is adhered to the substrate by means or hea'
and/or water, with or withcut pressure, which means fuses
and/or partially dissolves the encapsulating resin; wherein
the developed image is transrerred to a first substrate,
such as paper, in step (c), and adhered thereto, an~ then
transferred, by heat-transfer means, to a second substrate
whereon, in step (d), the dye and/or chemical treating
asent o the image is permanently fixed; and wherein the
resin of the rerromagnetic component is water-soluble or
water-solubilizable and the removal of the ferromagnetic
component and resin is effected, in step (e), by means of
an aqueous scour.
BRI}:F DESCRIPTIO~ OF T~r DRAWINGS
Figure 1 represents an enlarged cross-sectional
view of a cylindrical, continuously surface-coated,
conductive magnetic printing member. ~igures 2A and 2B
represent top and side views, respectively, in rectilinear
form, of the printing member of Figure 1 before orientation
of the acicular CrO~ of layer 2; Figures 2C and 2D represent
the same views a~ter orientation Oc the aclcular CrO2.
Figure 3~ represents a side view, in rectilinear form, of
the acicular CrO2 o. layer 2 but before the CrO2 is
~agnetically structured; Figure 3~ represents the same
~iew after the CrO~ of layer 2 has been magnetically
struct~re~. Fisure 4 represents an enlarged cross-sectional
- 10 -
~3~6
view of a cylindrical, intermittently surf~ce-coate2
(in grooves) conductive masne.ic printing member.
Figures S to 9 represent certain steps of the invention
magnetic printing process as they apply to the use of
the magnetically structured printins member represented
by ~igure 3B. Figure 5 depicts the formation of a latent
magnetic image on the printing member by Xenon flashing
an appropriate film positive. Figure 6 depicts the printing
member having the latent magnetic image imposed thereon.
Figure 7 depicts the printing member, after the latent
magnetic image has been decorated with ferromagnetic toner
particles, as it is a~out to be brough_ into contact with
the substrate which is to be printed. ~igure 8 depicts
the substrate after the image consisting o~ ferromagne'ic
toner particles has been transferred thereto from the
magnetic printing member. Figure 9 depicts the substrate
after the image has been adhered thereto. Fisure 10,
representing a side view, in rectilinear form, of the
printing member of ~igure 1, depicts the path o' the
electrostatic charge ~eing dissipated from the acicular CrO2
of laye~ 2 to ground .hrough conductive layer 4. Fisure 11,
in schematic form, depicts a single color magnetic printing
device which can be used to carry out certain steps of
the invention magnetic printing process. Figure 12, in
6chematic form, depicts a three color magnetic printing
de~ice which can be used to carry out certain steps of the
invention magnetic printing proc~ss.
DETAILED D~SCRIPTION OF T~E INVENTION
The formation of the magnetic lmage on a erro-
magnetic material which is im~osed on an electrically
conductive support can be carried out ~y techniques well
know~ in the art OI magnetic recording. One of tne
1 _ --
~3~76
unusual features o~ the instant in~ention is the substantial
abs~nce of background dye and/or chemical treating agent ir.
the substrate being p~inted. ~y bac~ground dye andtor
chemical treating agent is meant tne presence ~f dye
and/or agent on un2esirable areas of the substrate whicn
has been subjected to the magnetic printing process. rt
has been discovered that such background can be substan-
tially avoided if any charge on the ferromagnetic material
is dissipated, at some stage of the magnetic
prin~fng process prior to transfer of the decorated
image to the substrate, the purpose being to preclude the
affixing of and/or to facilitate the removal of ferromag-
netic toner on and/or from areas of the ferromasnetic mate-
rial other than those areas whe_e the desired image appears.
It has been observed that such undesirable-toner deposition
on the ferromagnetic material may occur during the afore-
said image decorating step (b) if the ferromagnetic
material is electrostatically charged. It has been dis-
covered in this invention that the formation of such an
electrostatic charge can be avoided by imposing ferromag-
netic material having adequate charge dissipating conductance
through its thickness on an electrically conductive support.
Ano~her unusual feature of the present invention
resides in the discovery that the decorated image resultins
from the aforesaid step (b) can be transferred bv pressure,
electrostatic or magnetic means, or a combir.a.ion thereof,
directly to ~e su~strate which is to be printed, for
example, a textile fabric, or it ran be transferre~ to a
first substrate, for example, paper, and subsequently,
33 if desi_ed, after storage, transfer_ed, by w211 known
- 12 -
i ~3'~7~
procedu-es, ~o 2 second substrate, t:~e ultimate substrate
which is to be printed.
A further unusual feature o the invention
resides in the discovery that the ?~inted substrate, after
completion o the aforesaid step (d), can be conveniently
anc facileiy scou ea to remove and, if Gesire~, ~ecover,
the ferro~lmagnetic com~onent and tile resin ori~inally
present in the toner. ~artlcularly in the case of dye-
containing tcners, this feature, coupled with previously-
discussed features, ma~es possible the utilization ofmagnetic recording techniques to effect the color
printing, in one or more colors, of a variety o substrates.
Moreover, in the case of che~ical treating a~ent-containing
toners, with or withou~ dye, this invention makes possible
the utilization of magnetic printing techniqu~s for th~
application of a variety of chemical treating ag~llts to a
variety of substrates.
Although the invention herein resides in magnetic
printing processes and ~evices, since an important aspect
of the invention process xesides in the use of a particular
type of ferromagnetic toner, the following disc~ssion of
toners is provided. The ferromagne~i~ toner comprises:
~a~ at least one ferromagnetic compo~ent;
(b) optionally, but preferably, at least one member of the
group consisting of dye and chemical treating agent; and
(c) a readily fusible resin which substantially encapsulates
(a) and the optional component (b).
The resin may be solvent-soluble or, pref~rably,
water-soluDle or water-solubilizable. Solvent,'as useZ
3~ hereln, is meant to include any known organic solvent, such
- 13 -
~2~
as a hydrocarbon, a halo-genated hydrocarbon, an alcohol,
a ketone, an ester, an acid, an amide, and the like, solvent,
as well as aqueous solutions of such solvents wnich 2' e
miscible with water.
A pre-erred embodiment includes the use of toners
which include the optional component, comprise, based on
the total weight of (a), (b) and (c), 14 to 83~ of (a),
0.10 to 25~ of (b) and 9 to 74~ of (c), and have a resin
to ferromagnetic component ratio of 0.11 to 3.3. An
especially preferred embodiment is one wherein the toner
used comprises 55 to 70~ of (a), 0.10 to 15~ of (b) and
30 to 40~ of (c) and has a resin to ferromagnetic component
ratio of 0.40 to 1Ø
The ferromagnetic component can consist of hard
magnetic particles, soft magnetic particles or a binary
mixture of hard and soft magnetic par~icles. The
~agnetically soft particles can be iron or another
high-permeability, low-remanence material, such as iron
car~onyl, certain of the ferrites, for example, ~Zn, Mn)-
Fe204, or permalloys. The magnetically hard particles
can be an iron oxide, preferably Fe304, Y-Fe203, other
ferrites, ~or example, BaFel20l~, chi-iron car~ide,
chromium dioxide or alloys of Fe304 and nic~el or cobalt.
Preferred mixtures of soft and hard magnetic particles
include mixture5 or iron particles and either Fe304
particles or CrO2 Darticles. Magnetically hard and
magnetically sort particles are substances which are,
respectively, permanently magneti7able and substantially
non-permanently magnetizable under similar conditions
below the Curie point of the subs.ances. .~ magneticallv
- 14 -
~3~
hard substance has a high-intr~nsic coercivity, ra~.gins
from a few tens of oersteds (Oe), for example, 40 Oe,
to as much as several thousand oersteds and a relativel~
high remanence (20 percent or more Or the satura.ion
magnetization) when removed from a magnetic field.
Such su~stances are of low permeability and require hign
fields for magnetic saturation. Magnetically hard substances
are used as permanent magnets for applications such as loud
speakers and other acoustlc transducers, in motors, Senerators,
meters and instruments and as the recording layer in most
magnetLc tapes. A magnetically soft substance has low
coerci~ity, for example, one oersted or less, high
permeability, permitting sat~ration to be obtained with a
small applied field, and exhibits a remanence of less
than 5 percent of the satura.ion magnetization. ~lagnetically
soft substances are usually found in solenoid cores,
recording heads, large industrial magnets, motors and other
electrically excited devices wherein a hish flux density
is xequired. Preferred soft magnetic substances include
iron-based pisments, such as carbonyl iron, iron fla~es and
iron alloys.
The dye which is used in the ferromagnetic
toner can be selectcd from virtually all of the con:pounds
~entioned in the Colour Index, Vols. 1, 2 and 3, 3rd
Edition, ~71. Such dyes are of a variety of chemical types;
the choice of dye ~s determincd by the nature of tllc
Rubstrate being printed. For example, premetalized
dyes ~1:1 and 2:1 dye:metal complexes) are suitable for
synthetic p~lyamide fibers. The majority of such dyes
3? are monoa70 or disazo dyes; a lesser number are
- 15 -
i
anthraquinone dyes. Such dyes can have or be free
from water-so~u3ilizing groups, such as sulfonic acid and
carboxy groups, and sulfonamido groups. Acid wool dyes,
including the monoazo, disazo and anthraquinone mem~ers
of this class which bezr water-solubilizing sulfonic acid
groups, may also be suitable for syn~hetic polyzm~e
textiles. Dis?erse dyes can be used for printin~ syn'.he,ic
polyamide, polyester and regenerated cellulosic fibers.
A common feature of such dyes is the absence of water-
solubilizing grou?s. HoweYer, they are, for ~he most part,thermosoluble in synthetic polvmers, notably polyesters,
polyamides and cellulose esters. Disper~e dyes include
dyes of the monoazo, polyazo, anthra~uinone, styryl, nitro,
phthaloperinone, quinophthalone, thiazine and.oxazine
series and-vat dyes in the leuco or o~idized form. For
polyacrylonitrile and acid-modified polyester fibers,
preference usually is given to cationic dyes containing a
carbonium ion or a quaternary ammonium grou?. Catio~ic
disperse dyes, that is, water-insoluble salts or dye cations
and selected arylsulfonate anions, are well-known
in ~he art for dyeing acid-modified polyester and acrylic
fibers. Cotton fibers can be printed with vat dyes and
with fiber rcactive dycs, including those which are employed
~or polyamide fibers. Other suitable dyes for cotton are
~he water-soluble and water-insoluble sulfur dyes. Water-
swellabl~ cellulos~c fibers, or mixtures or blends thereof
with synthetic fibers, can ~lso be uniformly printed
~ith ~ater-insoluble disperse dyes using a~eous ethylene
glycol or polyethylene glycol type sol~ents, as described
I,~
~n the art.
- 16 -
The amount of dye, if present, in the ferromas-
netic toner can vary over a wide range, for example, 0.1 to
25~ by welght of the total weight of com~onents (a), (b)
and (c) ln the toner. Particularly good ~esults can be
obtained when the zmount is 0.1 to 15~ by weight.
A wide vari.ety of chemical treating asents,
such as flame-retardins agents, hiocides, ultra~iolet llght
absorbers, fluorescent brighteners, dyeability modifiers
and soil-rel~asé and ~ater-proofing agents, can be
present in the ferromagnetic toner. Such agents
have utility on cotton, regenerated cellulose, wood pulp,
paper, syn~hetic ibers, such as oolyesters and polyamides,
and blends of cotton with polye~ter or poly~mide. By
dyeability modifier is meant a chemical substance that
can he chemically or physically bound to the substrate,
such as a fiber, to change the dyeability of the substrate,
~or example, the degree of dye fixation or the type or
class of dye that can be employed. A specific ex~mple of
a useful dyeability modifier is a treating agent which
provides printcd chcmical resis~s, that is, prin~ed areas
~hich remain unstained during a subsequent dyein~ oleration.
Since many chemical treating a~ents~ including those of
the afore~a$d types, are well-known in the prior art, no
urther discussion thereof is necessary, The chemical
treating agént in the toner c3n be present in the same
amount as the dye, that is, 0.1 to 2~, prefera~ly 0.1 to
li~, of the to~al weight of components (a~, ~b) and (c).
The resin which is used in the ferromagnetic
toner includes any of the ~nown, readily fusible, natural,
modi-ied natural or synthetic resins or polymers w-nlch
7~
are soluble ar solubilizable in an organlc solvent or water,
or mixtures thereo~, that is, either directly soluble or
made soluble through a simple chemical treatment. The
solubility must he such that the ferromagnetic component
and the encapsulating resin can be removed ~rom the
substrate, after permanent fixation of the dye and/or
chemical trea~ing agent, if present, by means of a scour, in
a short time, as will be described in greater detail
hereinafter. Organic solvents which may be used lnclude
1~ hydrocarbons, halogenated hydrocarbons, alcohols, ketones,
esters, acids, amides,or mixtur~s thereof, in which the
resin of the toner exhibits significant solubility. A
wide ~ariety of useful solvents are well-known in the art
and are commercially avaiLable. Examples of useful solYent- -
soluble or solvent-solubilizable resins include low molecular
weight polyamides, ethylene/vin~l acetate copoly~ers,
styrene/acrylate and styrene/acrylonitrile copolymers,
fluorine-containing copolymers, such as tetrafluoro-
ethyiene/vinyl acetate copolymers, hydrocarbon-type
polymers, such as Carnau~a wax and microcrystalline
paraffin, and the like. It is generally preferred,
however, to use resins wnich are water-soluble or wa~er-
solubilizable and can be removed by an aqueous scour.
Examples or water-solubilizable resins are those resins
or polymers which contain salt-forming groups, which
th~reby render them soluble in an alkaline aqueous
solution, and those which can be hydrolyzed by acids or
alXalis so as to become water-soluble. Exemplary of
useful natural resins are rosin (also known as cqlophony)
JJ and modified derivatives thereof, such as rosin
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~3Z~7~
esterified wlth glycerin or pentaerythritol, dimerized and
polymerized rosin, unsaturated or hydrated rosin and
derivatives thereor and rosin, and derivatives thereo~,
which has been modiried with phenolic or maleic resins.
Other natural resins with properties similar to rosin,
such as dammar, copal, sandarak, shellac and tolloel,
can be successrully used in the rerromagnetic toners.
Examples or water-solublizable synthetic
~esins which are useful include vinyl polymers, such as
polyvinyl alcohol, polyvinyl chloride, polyvinylidene
chloride, polyvinyl acetals, polyvinyl acetate, polyvinyl
acetate copolymers, and polyvinyl pyrrolidone; poly-
acrylic acid and polyacrylamide; methyl-, ethyl- a~d
butyl methacrylate-methacrylic acid co~olymers; styrene-
maleic.acid copolymers; methyl vinyl ether-maleic acid
copolymers; carboxyester lactone polymers; polyethylene
oxide polymers; nonhardening phenolformaldhyde copolymers;
polyester resins, such as linear polyesters prepared from
dicarboxylic acids and alkyle~e glycols, for example, from
phthalic, terephthalic, isophthalic or sebacic acid and
ethylene slycol; cellulose ethers, such as hydroxypropyl-
cellulose; polyurethanes; and polyamides, such as tnose
prepared from sebacic acid and hexamethylenediamine.
. The re~in used in the toner is preferably
o~ the thermoplastic ty~e in order to permit adhesion
thereof to the substrate by melting or fusion. Particularly
prefer~ed resins are adducts of rosin, a dicarbo~lic
acid or-~nhydride, a polymeric fatty acid and an alkylene
polyamide; hydr3:~yp~0pylcell~1Ose pre?ared by reacting
3~5 to 4.2 ~ules o~ propylene oxide per D-glucopyranosyl
- 19 - .
~ 13~
~nit of the cellulose, and poly~inyl aceta~e copolymers
ha~ing a free carboxy group content equivalent ~o 0.002
to 0.01 equivalcnt of ammonium hydroxide per gram of
dry copolymer. The prefcrred resins possess a high elec-
trical resistivi~y for good transfcr in an electrostatic
field "lav~ good in~rared and steam fusion properties and
do no~ inter~ere wi~l pcnetration of the dye or chcmical
trcatin~ agent into the substratc during the final
(permanent) fixation operation. Moreover, after the dye
and/or chemical treating agent, if present, has been
fixed within the substrate, the resin must be easily
removable in a scouxing operation in a short time, for
example, in an aqueous scour in less than five minutes at
less than 100C, preferably in less than 60 seconds at less
than 90C.
The ferromagnetic toner can be prepared by
intimately mixing together, for example, by ball
milling or by hiyh frequency viscous milling, an
aqueous or organic solvent solution or slurry containing
the desired proportion~ o optional dye~s) and/or chemical
treating agent(s), ferromagnetic component(s) and
encapsulating resin and then spray-drying to remove the
water or solvent, as the case may be. Particularly good
results usually can be obtained by ball milling for 1-17
hours at about 60 percent by weight nonvolatiles content.
The solution or dispersion resulting from ball milling
is separated ~xom the ceramic balls, sand or other grinding
means and spray-dried at a nonvolatiles content of 10 to
40 percent by weightO Spray-drying is accomplished by
conventional means, for example, by dropping the solution
or dispersior. onto a disk rotating at high speed or by
- 20 -
.
~ , ,
using a conventional spray-dryin~ nozzle, as described
in the art. Spray-drying consists of atomizing the toner
solution or dispersion into small droplets, mixing these
with a gas, and holding the droplets in suspension in tne
gas until the water or solvent in the droplets evaporates
and heat and surface tension forces cause t~e resi~
particles in each droplet to coalesce and encase the
ferromagnetic component and the dye and/or treating agent
which are included in the droplet. Most frequently,
spray-drying is carried out with air as the gas for the
drying step. The gas is heated sufficiently to remove
the water ox sol~ent and so that the many small particles
in any one droplet formed during atomization can come
together to form a small, hard, spherical toner particle
; which entraps the materials initially included within
that droplet.
By maintaining uniformity of dispersion of dye
and resin in the ~ter or solven~ and by controlling solids
concentration in the final dye-water or dye-sol~ent mixture,
the paxticle size of the toner can be controlled by the size
of the droplet produced by the atomizing head in the spray-
drying equlpment. Moreover, by controlling the toner slurry
feed rate, the viscosity of the toner slurry, the spray-dryins
temperature and the disc xpm for a disc atomizer, the pres-
sure for a single-fluid nozzle atomizer or the pressure and
air to feed ratio for a two-fluid nozzle atomi zer, spherical
~oner particles having diameters within the range of 2 to
100 micro~s, preferably 10 to 25 microns, can be readily
obtained. Toners passing a 200 mesh screen ~U.S. Sieve
30 Series~, thus being less than 74 micxons in 'che longest
particle dimensionl are especially useful.
-- 21 --
'7~
Other suitable well known encapsulation processes
can be employed to produce the ferromagnetic toner. These
include coacervation, interfacial polymerization and melt
extrusion techniques.
The relative amounts of resinous material and
ferromagnetic component in the toner usually are deter-
mined by the desired adhesive and magnetic properties of
the toner particle. Generally, the ratio of resinous
material to ferromagnetic material is 0.11 to 3.3,
10 preferably 0.40 to 1Ø The preferred ratio especially
provides toners having good decoration~ transfer and
fusion properties.
It is to be understood that, in some cases,
it may be advisable to add one or more known chemical
assistants to enhance the functional behavior of the
ferromagnetic toner, for example, dispersing agents and/or
surfactants and/or materials which promote dye and/or
treating agents fixation in the substrate. Further examples
of such chemical assistants include urea; latent oxidizing
agents, such as sodium chlorate and sodium m-nitrobenzene
sulfonate; latent reducing agents; acid or alkali donors,
such as ammonium salts and sodIum trichloroacetate;
and dye carriers, usually pres-ent in amounts of Q.l to 8%
by weight based on the total toner weight, such as benzyl
alcohol, benzanilide, ~-naph*hol, o-phenylphenol and
butyl benzoate. Conventional commercial dispersing agents,
such as the lignin sulfonates and salts of sulfonated
naphthalene-formaldehyde condensates, can be employed.
Such agents include Polyfon*, a sodium salt of sulfonated
lignin; P~eax*, the sodium salts of sulfonated lignin
derivatives; Marasperse*, a partially desulfonated sodium
* denotes trade mark
-22-
liynosulfonate; Lignosol*, sulfonated lignin derivatives;
Blancol*, "slancol" N and Tamol*, the sodium salt of
sulfonated naphthalene-formaldehyde condensates; and
Daxad* 11 KLS and "Daxad" 15, the polymerized potassium
and sodium salts, respectively, of alkyl naphthalenesulfonic
acid. Other known use.Eul auxiliary chemicals can assist
in the prevention of "bleeding" of a dye pattern by
preventing the swelling or coagulation of the resin.
Exemplary of such auxiliary chemicals are starch, starch
derivatives, sodium alginate and locust bean flour and
its derivatives. Cationic surfactants, such as quaternary
ammonium compounds, reduce the static propensity of the
toner particles for the image-bearing magnetic film.
Lower toner pickup in background or nonimage areas can be
acheived by incorporating such surfactants into the toner.
Dimethyldistearylammonium chloride has been found to be
particularly useful for this purpose. Still other auxiliary
chemicals which may be present in the toner include known
addi.tives for improving the bri.ghtness and. tinctorial
strength of the dyeing, for example, ci.tric acid, which is
commonly used with cationic dyes, and ammonium oxalate,
which i.s. commonly used wi.th.acid dyes.
A free-flow agent, usually present in an amount
within the range 0.01 to 5% by weight, preferably Q~01
to Q.4~ by weight, based on total toner we-i.ght, can be
added to keep the indi.vidual toner particles from sticking
together and to increase the bulk of the toner powder.
This facilitates an even depositi.on of toner particles on
the latent magnetic image. Free-flow or dispersing
agents, such.as microfine silica, alumina and fumed silica
* denotes trade mark
-23-
sold under the trade names ~uso* and Cab-O-Sil*, are
useful.
The invention PrOceSS and device are applicable
to all types of printable substrates. Particularly preferred
are fabric substrates, such as those prepared from natural
and regenerated cellulose, cellulose derivatives, wool and
synthetic fibers, such as polyamides, polyesters and
polyacrylics, and mixtures of any of such ~abrics. Film
substrates, such as commercially available polyester film
and paper, are also preferred.
The following discussion relates to process and
equipment details of the invention. It is to be understood
that any specific reference solely to color printing or to
the printing of substrates with a chemical treating agent,
or any speci.fic reference to only certain aspects of either
type of printing, is not intended to be limiting on the
invention. Furthermore, the following references to and/or
discussions of the accompanying drawings are intended to
facilitate understanding of the invention rather than to
impose limitations thereon. Based on the following discus-
sion of process and equipment details, one skilled in the
art will readily be able ko envision other (undescribed~
embodiments of the inventi.on.
~ s already suggested, the invention i.s useul for
producing multiple color prints (:reproductions) of an
original desi.gn. The invention has parti.cular appli.cabilIty-
to the formation of colored prints of an original desi:gn
consisting of multiple colors. In such.a system a plurality
of toner decorated magnetic images- corresponding to a
series of color separati.on fi.lm posi.tives of the original
multicolored design are successively transferred to a
* denotes trade mark
-24-
~ . ~
substrate in register and superimposed one on top of th~
other so as to fGrm a multicolored print composed of th~
diffcrent color imagcs.
Either multicolor or full color separation film
positives are prepared from ~he original deslgn. Multicolor
film separations (that is, one film separation for each
color in a pattern) can be made either manually by tracing
the design or by using a color recognition electronic
scanner. The preparation of full color (that is, process
color) separation film positives can be made either with
a camera and colored filters or by using a process color
electronic scanner. With the former technique, the original
design is photographed through three filters, each
corresponding in color and light transmussion to one of the
additive blue, green and red primaries. Placing a red
filter over the camera lens produces a negative recording
of all the red light reflected or transmitted ~rom the
original. This is Xnown as the red separation negative.
~hen a film positive is made from this negative, the sil~er
in the film will correspond to areas which did not contain
red but contained the other two colors of light, that is,
blue and green. In effect, the negative has subtracted
the red light from the original design. The positive is a
recording of the blue and green in the original design
and is called the cyan film positive. Photographing
through a green filter produces a negative recording of
the green in the original design, The positive is a
recording of the red and blue additive primaries and is
called the mage~ta film positive. The use of a blue filter
produc~s a ncgative which records all of the blue in the
o~iginal design. The positive records the red and green
- 2S -
which, when combined as additive colors, pro~uce yellow.
This is called the yellow film positive. For some
designs, a black film positive i~ necded. This is ob~ilin d
~y photographing the original design through re~, blue and
grccn filters in succession, ~ detailed discussion of tne
preparation of process color film positives can be found
in "Principles of Color Reproduction," J. A. C. Yule,
Chapters l and 3, John ~1iley and Sons, Inc., 1967.
Electronic scanners can be use~ for both full
10 color (based on the four process colors) or multicolor
~individual color recognition) film separations. In bo~
types of scanners, the original design is mounted on a
horizon~ally rotating drum which is driven by a step motor
operating at approximately 2,000 steps per second. A
horizontally moving scanning head is mounted in front of
the arum. T~e desi~n pattern is illuminated and the
reflected colored light is interce~ted by the sca~nins
head at each step. A series of prisms and mirrors splits
the xe~lected light into red, green and blue components
which are then converted into three separate electronic
signals. In full color separation scanners, the red, green
and blue components are processed through an optical
elec~ronic con~er~er which pro~ides the yellow, magenta,
cyan and blac~ film separation positives. In multicolor
separation scann~xs, ~he red, green and blue components
are compared to the amounts of red, green and bluc
components stored in the scanl1ers computcr mcn-ory. Thc
ou~put is a film scpara~ion positivc corres~ol1din~ to each
color l~at~ern in tl~e ori~inal de~i~n. ~s maJ1y ~s t~elve -
diffcrcn~ color~ c~n be store~ in thc conlp~er memoryoP ~ mul~icolor s~aration ~c~nncr. Suiti~ electronic
- 26 -
color scaJ)Ilcrs ~rc ~ca~ily availa~lc comn1e~rci;l11y.
Elect onic scanners have obvious adYantages over manual
separation techniques due to their lower processing cost,
higher speeds (2 to 3 hours as compared to 100 to 200
hours) and greater resolution capabilities.
The aforesaid color separation film positives
are used to form a plurality of latent magnetic images,
as described below, one latent magnetic image corresponding
to each colo; film positi~e. Each latent magnetic image
is then decorated with dye-containing ferromagnetic toner
particles to form a series of toner-decorated latent
magnetic images corresponding to the color separation
images. In a typical subtractive multiple color processing
system in accord with this invention, each laten~ magnetic
image is decorated witll toner particles having a dye
color complementary to the original color separation filter.
Thus, the cyan latent magnetic image corresponding to the
red color filter is decorated with toner containing a
blue dye; the yellow latent magnetic image corresponding
to the blue ilter is decorated with a ~ellow dye toner
and the magenta latent magDetic image corresponding to the
green color filter is decorated with a red dye toner.
The dye images from each of the individual toner-decorated
images are transferred in register and superimposed, one
on top of the other, on the substrate to form the final
multicolor print of the original printed ~lesign.
The most important force for magnetic printing
is, of course, of magnetic origin. However, stray electro-
static forces can exceed magnetic forces. Since ferro-
magnetic toner particles are attracted by both electro-
static ~nd magnetic fields, any high electrostatic charge
density on the magnetic printing surface (that is, the
~3~
ferromagnetic material) will generate fields eaual to or
greater than the magnetic field from the masnetic imase.
The background region, that is, that portion of the
printLng surface other than that containing the magnetic
image, will thus attract enough toner particles to ren~e- -
the final print unattractive, if not indiscernible. Static
charges usually ~uild up at a sufficiently slow rate so
that at least one clear print can be made, but unless some
means is provided to dissipate the static charges, after
a few prints have been made, the buildup of static charge
becomes large enough to cause serious background problems.
As already discussed hereinabove,in the invention
process and device, the background problem is 21iminated ~y
having the se~iconductive ferromagnetic CrO2 plus binder
continuously coated on the conductive support, for example,
as shown in Figure 1. Preferably, at least two
static neutralizing means, such as two AC coronas,
as shown in ~igures 11 and 12, are employed in
conjunction withthe continuously CrO2-coated
2Q conductive support to neutralize any residual
charges on the toner.
Since the surface resistivity of the CrO2 coating
is approximately 108 ohms/s~uare, the time required for
comple~e static charge dissipation must be less than the
time elapsed between electrostatic toner transfer and
subsequent toner redecoration; otherwise, static charge
will build up on the printing surface. As can be seen
from Figure 10, using the conductive CrO2-coated printing
~ember 1 of this invention, the elec~rostatic sur~ace
charge on the CrO2 2 travels ~hrough the thickness of the
CrO2, that is, ~ the Y direction, instead of along ~he
entire leng'h o~ the CrO2 surface, that is, in the
- 28 -
7~
direction, ~n order to reach ground t}lrough ~e ~onductiYe
~ upport 4. Grounding i; accomplished by clamping the
CrO2-coated printing member 1 to printing drum 12 depicted
in Yigure 11. For a 5-inch (12.7 cm.) ~tide printina surLace, the
X/Y ratio is approximately 104 and, thus, rapid charge
dissipation occurs and background free prints are obtained.
In one e~bodiment of the invention process,
the electrically conductive support providing the path to
ground for the electrostatic charge can be either continuously
coated with a layer of ferromagnetic CrO2 or can be
provided with a series df grooves which are in turn
filled with the CrO2. Figure 1 shows an enlarged cross-
sectional view of the continuously surface-coated conductive
magnetic printing member 1 of ~his invention com?rising
a conductive support which is continuously coated with a
50 to 1,000 microinch (1.27 to 25.4 x 10 4 cm), preferably
100 to 500 microinch (2.54 to 12.7 x 10 4 cm), layer 2
of ferromagnetic CrO2 in a xesin binder. Acicular CrO2
is particularly preferred due to it5 high coercivity,
which allows i~ to be magnetically oriented to giv~ a high
xemanence. A unique aspect of CrO2 is its outstanding
magnetic properties togeth~r with its easily attainable
Curie temperature o 116~C. ~cicular CrO2 can be produce~
by techniques ~ell known in thc art. The conduc~ive support
can be any appropriate material, for example, a polyethylene
terephthalate film 3, about 125 micxons in thickness,
coated with a thin conductive layer of aluminum 4. Commer-
ciaily aYailable alumini~ed po}yestex fi~n is particularly
uscful as a conductive support. The conductive support can
30 ~e a metallized plas~ic material, for example, a sleeve of
a pla~tic ~aterial, such as an acetal resin, coated with
~luminum, nickel, copper or other conductive metal, or i~
- 29 -
7~
can be a metal sleeve coated with a thin layer of elastomericmaterial, such as polychlorobutadiene (neoprene~, poly-
butadi~ne, polyisoprene, butadiene-styrene copoly~ers,
acrylonitrile-buta~iene copolymers, etc., or with an epoxy
resin, containing conductive particulate matter, for example,
carbon black, graphite or silver, uniformly dispersed therein.
The conductive support can also be the conductive metal itself.
` The coating o~ the conductive support with acicular
CrO2 can be accomplished in a variety of ways, for example,
by gravure coating a slurry of CrO2 and resin in tetra-
hydrofuran-cyclohexanone on a web of aluminized polyester
or by spra~-coatillg a conductive metal sleeve. Ilowever,
regardless of the coating technique used, it is desirable
to orient the CrO2 by passins the wet coated conductive
~upport ~etween`the pole pieces of two bar magnets
~approximately 1,500 gauss average field strength) aligncd
wi~l tlle same poles facing one another. TJIe magnetic
flux lincs oriellt th~ acicular CrO2. Figures ~ and 2B
show top and side views, respcctively, of prin~in~ mcmbcr 1
of Figurc 1 be~ore oricn~ation; ~igures 2C and 2~ sl~ow
- th~sc res~ective YiCWS af~er oricnta~ion. ~atios o~ magnetic
- rcm~n~ncc to ma~llctic sa~ur~tion ~r/n5) of up to 0. no
an intri~lsic cocrcivi~y (ill~) o~ 510 to 5S0 o~rs~ ave
~e~n ~ in~ on SllCil printin~ menlber~.
I~ the oriented CxO2 ~agnetized pxinting æurface
is decorated with ferromagnetic toner particles (for
example, 10 to 30 micron partisles consisting of a dye
and a ferromagnetic component encapsulated in a water-
soluble resin binder), the particles will be magnetic lly
attracted to only the edges of the surface as depicted
in Flgure 3A. In order to achieve even toner decoration
of the entire magnetic printing surface, the oontinuous
- 30 -
~ ~ ~Z~7 ~
CrO2 coating is magnetically structured, as illustrated
in Figure 3B, so as to createmagnetic flux gradients that
uniformly attract tne magnetic toner particles. A numDer
of different techniques can be used to magnetically
structure the ma~netic printing surface. An alternating
signal, equivalent to 100 to 1,500 magnetic lines per
inch (39 to 590 lines per cm), can be recorded on th~
CrO2 surface using a magnetic write head. A magnetic
line consists of two magnetic flux reversals. Alternatively,
0 2 Ronchi ruled transparent film can be placed on top of
~he uniformly magnetized CrO2 surface and the assembly can
then be exposed to a Xenon flash passing through the
transparent ruled film. ~he CrO2 under the clear areas of
the film is thermally demagneti~ed to provide tlle requisite
magnetic pattern. The technique of roll-in magnetization
also can ~e used to structure the CrO2 surface. In this
method, a high permeability material, such as nickel, which
has been surface structured to the desired groove width
is placed in contact with the u~magnetized CrO~ surface.
A permanent magnet or an electromagnet is placc~ on the
backside of the highly permeable material. As the struc-
tured high permeability material is brougllt into contactw~th the CrO2 surface, thc magnet concentrates the magnetic
flux lines at the points of contact, resulting in ~he
magnetization of the CrO2 coating. The CrO2 surface can
~lso be thexmoremanently structured by placing the continu-
ously coa ed CrO2 surface on top of a magnetic ma~ter which
has the desired magnetic line pattern recorded on it.
Thermoremanent duplication of the master pattern on the
CrO2 surface is effected by heating the surface above the
_,
- 31 -
7~
116-C CrO~ Curie temperature. As the surface cools down
below the Curie temperature, it picks up the magnetic
signal from the magnetic master and is selectively magnetized.
In still another method, a scanning laser beam can be used
to structure the magnetic CrO2 surface.
Figure 4 shows an enlarged cross-secticnal view
of the permanently structured conductive magnetic printing
member 1' of this invention, comprising a grooved COIl-
ductive support with the CrO2 and resin bindex 2' in
the grooves. In this embodiment, the conductive support
is preferably a plastic support material 3' which has
been structured to the desired groove width and depth. The
grooved plastic support 3' is plated with a thin layer of
a conductive metal 4', such as aluminum, copper, nickel
or ~he like,and the grooves are filled with the CrO2 and
resin binder 2'. If desired, the grooved support can
consist solely of the conductive metal, for example, copper~
As in the case of the continuously coated magnetic printing
member illustrated in Figure 1, the CrO2 must be oriented
during the groove filling operation. Maqnetization of the
grooved conductive magnetic printing surface can be
readily accomplished by passing the surface in front of
a magnetic field.
~ urther aspects of the invention are depicted
in ~igures 5 to 9 (shown for simplification as comprising
flat surfaces) which show the stepwise formation of the
latent magne~ic image on the structured printing member 1
(~igures 5 and 6), the aecoration thereof with toner
particles (Figure 7), the trans~er of the toner particles
3~ to ~he substrate (Figure 8) and the toner particles adhered
- 32 -
~ 7~
to the substrate (Figure 9). The aforesaid sequence of
steps can be carried out using the continuously CrO2-coated
magnetic printing member 1 depicted in Figure 1, the
CrO2 surface cf which has been oriented (depicted in Figure
2) and magnetically structured (depicted in Figure 3),
Figures 2 a~d 3 shown for simplification as comprising flat
surfaces. A similar se~uence of steps can be envisaged
for the grooved magnetic printing member depicted in
Figure 4.
1~ It is to be understood, and it will be obvious
to one skilled in the art, that the structured printing
member can be imaged in such a way that the substrate will
be uniformly chemically treated and/cr dyed, depending
on the type of ferromagnetic toner used, ovex a wide area.
In other words, instead of a pattern-type print, the
print can provide a total coloration and/or chemical
treatment of the substrate.
Referring further to Figure 5, a latent magnetic
image is formed on the surface of the magnetic printing
2;J member 1 by placing an image-bearing photocolor separation
film positive, prepared as described abo~e, in face-to
face contac~ with the structured printing surface and
uniformly heating, from the backside o~ the film positive,
with a short burst of high energy from a Xenon lamp. The
dark areas of the film positive, that is, the imaqe areas,
absor~ the energy of the Xenon flash, while the transparent
areas of the film transmit the energy, thereby heating
the CrO2 to a~ove the 116C Curie point. As can be seen
from Figure 6, the suxface of ~he magnetic printing
3~ member i~ selectively demagnetized to form a latent magne~ic
~3~7~
$m~ge which consists of a reproduction of the darX areas
of the film positive.
Instead of using a photocolor separation film
positive, an electronic color scanner can also be used to
form the latent magnetic image. The output signal from
the scanner drives a magnetic write head which is in
contact with the surface of continuously CrO2-coated
printing member 1. There is no need to prestructure the
printing surface since the data recording of the magnetic
write head can provide the required magnetic flux lines to
attract the toner particles. A permanent record of the
latent magnetic image can be obtained by decorating the
latent magnetic image with a black toner and transferring
and fusing it onto a transparent film~ The output of
the scanner can also consist of digital color separa~ion
data recorded on a magnetic tape and this tape can be
used to drive the magnetic write head directly on the
printing surface.
Ferromagnetic toner particles are applied to tne
latent magnetic image to form a decorated magnetic image
(as shown in ~igure 7) and the substrate to ~e printcd is
brought into juxtaposition therewith to effect transfer
of the image to the substrate (Figure 8).
The latent magnetic image can be developed hy
e~nvenient methods which are well known in the art.
Typical methods include cascade, magnetic brush, magnetic
roll, powder cloud and dusting by hand. In cascade
development, finely d~vided ferromagnetic toner particles
are conveyed to and rolled or cascaded across the latent
30 ~agnetic image-bearing surface, whereupon the ~erromagnetic
-- 34 --
3~
~oner parti~les are ~agne~ically a~tracted and ~ecured
to the magnetized portion of the latent image. In magnetic
brush or roll development, ferromagnetic toner particles
are carried by a magnet~ The magnetic field of the magnet
causes alignment of the magnetic toner par~icles into a
brushlike arrangement. The magnetic brush or roll is then
engaged with the magnetic image-bearing surface and the
ferromagnetic toner particles are drawn from ~he brush
to the latent image by magnetic attraction. The transfer
of the ferxomagnetic toner particles to the substrate
can be accomplished either by pressure, magnetic or
electrostatic means, or a combination thereof. In the
preferred electrostatic means, a positive or negative
charge is applied to the backside of the substrate which
is in contact with the toner-decorated latent magnetic
image. In connection with the use of pressure transfer
means, the use of high force, for exam~le, about
40 pounds per linear inch (about 70 N~ewtons per linear cm),
generally results in shorter printing surface life, poorer
transfer efficiency and poorer image definition on the
~ubstxate. Such problems are avoided by using electrostatic
transfer means wherein there is no substantial amount of
pressure between the printing surface and th~ substrate
and, therefore, no abrasion occurs.
The ~ransferred image is temporarily adhered
to ~he substrate (as shown in Figure 9) until permanent
fixation of the dye and/or chemical treating agent thereon
and/or therein is effected. Temporary adhering of the
transferred image to the substrate conveniently can be
effected by application of heat and/or a suitablc solvent
~ 3
(water or an oryanic solvent), the latter either in the
form of a spray or as vapors, for example, water or steam.
Heating at 90 to 170C and steam fusing at 100C for l to
15 seconds at 760 mm (of Hg) pressure are particularly
preferred herein. The adhesion of the image to the
substrate results from the melting and/or the partial
dissolution (in the solvent~ of the encapsulating resin.
Final (~permanent) fixation of the dye and/or chemical
treating agent of the toner can be accomplishea in any way
which is consistent with the type of substrate and dye and/or
agent which are used. For example, dry-heat treatment, for
example, Thermosol* treatment, at 190 to 230C, particularly
200 to 210C, for up to 100 seconds can be used to fix
disperse dyes on polyester and mixed disperse-fiber reactive
dyes on polyester-cotton. The application of pressure, for
example, up to about 1.5 psi,g (10,350 Pascal gauge), may
be advantageous. High pressure steaming at pressures
of 10 to 25 psig (69,000 to 172,500 Pascal gauge)accelerates
the fixation of disperse dyes on polyester and c~llulose
triacetate. ~apid disperse dye fixation ~an also be obtained
by high-temperature steaming at 150 to 205C for 4 to 8
minutes. High-temperature steaming combines the advantages
of short treatment times without the need to use pressure
seals-. High molecular weight disperse dyes can be -Eixed
to polyester-cotton using aqueous ethylene glycol- or
polyethylene glycol-type solvents according to well known
prior art procedures. Cottage-steaming and pressure-
steaming can be used to fix cationic dyes to acid-modi,fied
acrylic and polyester fibers and to fix acid dyes, including
premetalized dyes, to polyamide and wool fibers. Cottage-
steaming uses saturated steam at a pressure of 1 to 7
* denotes trade mark
-36-
.~,
~`~3'~17~i
psig (6,900 to 48,300 Pascal gauge) and 100~ relative
humidity. It may be noted that there is no tendency to
remove moisture from the fabric when saturated steam
is used. As ~he fabric is initially contacted by the steam,
a deposit of condensed water quic~ly forms on its cold
surface. Such water serves various functions, such as
swelling the fiber and activating the chemical treating
agent and/or dye, thereby creating the conditions necessary
for the diffusion of the dye and~or agent into the fiber.
Rapid aging at 100 to 105C for 15 to 45 minutes at 760 mm (g
~g) pressure can be used to fix disperse dyes to ceilulose
acetate fibers and cationic dyes to acid-modified acrylic
fibers. The aforesaid fixation procedures are all known
in the art, for example, as described by Clarke in
~An Introduction to Textile Printing," Third Edition,
1971, pages 58 to 66.
Depending on the nature of the toner dye and/or
chemical treating agent, it may be necessary or desirable
to treat the fabric with known auxiliary agents, to
achieve certain effects, before final (permanent) fixation
of ~oner dye and/or chemical treating agent. For example,
it may be necessary to impregnate the fabric with an
aqueous solution of an acid or an alkali, such as citric
acid, ammonium oxalate or sodium bicar~onate t or in some
cases, a reducing agent for the dye. Alternati~ely, thcse
auxiliary agents can be incorporated directly lnto tne
toner composition.
After permanent fixation of the dye and/or
chemical treating agent, the printed fabric is scoured to
remo~e the ferromagnetic component, encapsulating resin
- 37 -
~2~
and any unfixed dye and/or chemical treating agent. Although
the severity of the scouring treatment generally depends
on the type of resi~ and solvent employed, with ferromagnetic
toners containing water-soluble or water-solubilizable resins,
only a few seconds immersion in a conventional aqueous scour,
for example, an aqueous surfactant solution or aqueous alXali,
at less than 90C, is sufficient to dissolve away the resin
and release the ferromagnetic material from the fabric
surface. In the case of dye-containing toners, a well-
defined colored print is obtained on the fabric. Thetransfer of the dye- and/or chemucal treating agent-containing
ferromagnetic toner to the substrate and the temporary
adhering thereof on the substrate can be carried out in a
continuous operation, that is, in an immediately sequential
manner. The final ~permanent) fixation of the dye
and/or chemical treating agent and scouring can
be carried out separately in a later operation~
As already suggested above, the magnetic
printing process of the invention involves a delicate
balance of forces in that the areas of the magnetic printing
surface which are to retain ferromagnetic toner particles,
that is, the image areas, must magnetically attract
toner particles, whereas the image-frce areas of the
printing surface must no~. On the other hand, the force
of ~agnetic attxaction must not be so great as to
prevent the substantially complete transfer of the toner
fxom the printing surface to the substrate. The strength
of the magnetic attraction between the ~oner particles
and the printing surface depends on the physical properties
of the pri~ting ~urface, such as the coercivity (iHC) and
- 38 -
~3~
remanence.(Br) of the CrO2 coating, the degree of orientatisn
of ~he CrO2 crystals (Br/Bs), the tnickness of the CrO2
coating, the ~umber of magnetic lines on the surface and
the properties of the ferromagnetic toner particles,
for example, their magnetic susceptibility, shape and size.
It has been found that optimum decoration, transfer and
fusion properties are obtained using a CrO~ coating having
a thickness range of 50 to 1,000 microinches (1.27 to
25.4 x 10 4 cm), prefexably 100 to 500 microinches
(2.54 to 12.7 x 10 4 cm), a coercity of 200 to 600 oersteds,
preferably 350 to 580 oersteds, and an orientation (Br/Bs)
of 0.4 to 0.9, preferably 0.6 to 0.9. The surface of the
printing member can be magnetically structured to 100 to
1,500 magnetic lines per inch (39 to 590 per cm), preferably
150 to 400 magnetic lines per inch (59 to 157 per cm).
Further to the above disc~lssion, Figure 11 shows
a schematic diagram of a single color magnetic printing
device which is useful in performing the invention magnetic
printing process. The substrate 5 to be printed is fed
from feed roll 6, around dancer rolls 7, 8 and 9 to the
nip betwee~ feed rolls 10 and 11, which rolls cooperate
to feed the substrate into physical contact with the
surface of magnetic printing member 1, shown in cross-
sectional vi~w in Figure 1. Magnetic printing member 1
can be a continuously CrO2-coated aluminized polyester film
which is secured and grounded to the outer circumferential
surface of a rotating aluminum or copper printing drum 12~
Prior to mounting printing drum 12 in the apparatus, the CrO2
suxface of the aluminized polyester film affixed thereto
3~ is magnetically structured, using a magnetic write head
- 39 -
~ 2~ ~ 6
~s previously described, into a line pattern contai~ing
300 magnetic lines per inch ~118 magnetic lines per cm).
Aft.er structuring the printing surface, a latent magnetic
image is formed thereon by placing a photocolor-separated
film positive of a design in ~ace-to-face contact with
the magnetically structured printing surface on drum 12 and
then uniformly heating the printing surface with successive
short bursts from a high energy Xenon lamp flashed through
the film positive. After exposure, the CrO2 printing
10 surface on drum 12 co~tains magnetized areas of CxO2
corresponding to the printed areas of the film positive.
Printing drum 12 is then mounted in the apparatus and
is driven in the direction shown by the arrow by a commer-
cially a~ailable drive motor (not shown) which is provided
with a speed control unit~ The printing member containing
the latent magnetic image is then decorated (de~eloped)
with toner using a suitable decorating means 13. ~n the
particular embodiment illustrated, the decorating
means 13 is a magnetic brush decorating means comprising
a trough 14 containing a supply of the toner particles 15.
The tonex particles are magnetically attracted to the
surface of the magnetic brush 16 and are co~eyed to the
surface of printing member 1 where they are stripped
from the surface of magnetic brush 16 by a stationary
doctor blade 17. Toner particles are drawn from the brush
to the latent ma~netic image by magnetic attraction;
8urp1us toner falls back into trough 14 for recirculation.
~l~hough this represents a convenient means for depositing
toner on the printing member, any of the numerous decorating
3~ m~ans known to ~hose skilled in the ar~ can he used.
- 40 -
~3~ 6
Preferably, triboelectric charses generated in toner ~rough 14
are eliminated by neutralization using AC corona 18. An~
toner particles a~ventitiously adhering to the demagnetize~
areas of the CrO2 surface are removed by vacu~m knife lg.
The printing member, bearing the clean decorated image,
is tl~en contacted with substrate 5 past DC corona
device 20, tnus causing the toner par~icles to be transferred
to substrate 5 upon its separation from printing member 1.
A neqative DC corona device potential of 3 to 20
10 kilovolts, preferably 4 to 8 kilovolts, is used. There is
only an insignificant amount of pressure between substrate
and the surface of printing member 1, which pressure is
generated entirely by the electrostatic charge on substrate 5.
Alternatively, trans~~r o_ the image can take place in the
nip between a resilient pressure roll (nct shown) and printing
mem~er 1, in which case the pressure roll replaces the corona
device 20. Applied pressure agalnst the drum can
range from lO to 40 pounds per linear inch (17.6 to 69.6 ~ewtons
per llnear cm~. However, the most efficient trans.er, about
20 90 percent of ~he toner particles are transferred, occurs
at the upper limi~ of this range. Such high pressures, how-
ever, have a destructive e.fect on the life of the printing
member; hence, lower pressures are preferred if printing
member li~e is a concern. Pollowing transfer of the image,
the substrate 5 containing the toner image particles is
conveyed around idler roller 23 to thermal fusing means 24
which temporarily adheres the toner particles to substrate ~.
The fuslng means can be a bank of infrare~ heaters, a contact
hot roll or a ste m fuser. The substrate 5 ls then conveyed
30 over idler rcll 2; to the nip between ~olls 26 and 27 whic;~
- 41
~3~7~j
cooperate to ~eed substrate 5 onto final taXe-up roll 28.
After transfer, toner particles remaining on the surface of
magnetic printin~ member 1 are removed by means o vacuum
brush 21. ~referablv, residual electrostatic c;narges are
neutralized ~y .~C neutraLizing corona ~ ..2ces3ar-~, dn
AC corona is also used after DC corona device 20 and before
vacuum brush 21 to remove the electrostatic char~e on the
toner particles which do not transfer, thus enhancing the
action of vacuum brush 21. Alternatively, a vacuum ~nife
such as 19 is used instead of vacuum brush 21. In this
case, an AC corona preferably is also u~ a~ter D~ coro~2
device 20 and before the vacuum knife to remove the electro-
static charge on the toner particles which do not transfer.
AC neutralizing corona 22 can then be elimlnated. ~he
clean electrostatic charge-free surface of printing
nember 1 is then again decorated with toner in trough 14
and the neutralizing, vacuum knife cleaning, electrostatic
transferring, fusing, vacuum brush cleaning and neutraliz-
ing steps are continued until the printing cycle i5 com-
pleted.
The aforesaid apparatus and description formthe basis for a commercial single-color magnetic printer,
for example, capable of printing speeds of up to 240 feet
(73 meters~per minute, having the ability to provide
multiple prints from a single latent magnetic image.
As mentioned above, ~he invention magnetic
printing pro ess and device have particular applicability
to the printin~ of colored prints of an original design
composed o~ multiple colors. Figure 12 shows a schematic
view of a multicolor (three color) m2gnetic printins
.
- 42 -
~3'~ 6
device embodiment of this invention. The substrate 2g
to be printed is fed from feed roll 30 into contast with
endless belt 31 which is made of a dielectric film, such
as polyethylene terephthalate. Rollers 32 and 33 serve to
drive, in the direction shown by the arrows, ar.d suide
endless belt 31. The substrate 29 is electrostatically
attracted to endless belt 31 by means of DC (dlrect current)
corona device 34 or by other conventional dry
fabric bonding techniques. Any electrostatic charge
buildup on subs~rate 29 is neutralized by AC (al~ernating
current) neutralizing co~ona 35. The charge-free substrate
is conveyed by endless belt 31 to the toner-decorated
surface of m~snetic printing mem~er 1 positioned at
printing statlon A. The ferromagnetic toner is electro-
statically transferred from the surface OL this printing
member 1 to substrate 29 by means of DC corona
device 36. After transfer, the toner is.fused to
substrate 29 using fusing means 37 which is an infrare~
or steam ~using device. The process of applying toner
- 20 to the surface of magnetic prin~ing member 1 is essentially
the same as shown in Figure 11 for the single color
magnetic printer.
As further shown at station ~ in Figure 12, a
latent magnetic image o~ one of the colors (yellow, cyan or
magenta) m2~ing up the design to ~e printed is formed on
the surface of the magnetic printing member 1 mounted on
drum 12. The latent mag~etic image is decorated with
ferromagnetic toner particlcs lS using a suitable decorating
means 13. In the particular embodiment illustrated,
decorating means 13 consists of hopper 3a having a narrow
orificP from which toner particles 15 are smoothly and
- 43 -
1 ~ 3'~
uniformly dispensed onto the surface of ~agnetized roll 39
The toner particles adhering to magnetic roll 39 are
su~sequentl~ driven by magnetic attraction from the roll
to the latent magnetic image on the surface of printing
member 1. The surface of toner decorated printing member 1
preferably is neutralized with AC neutrallzing corona 1
and vacuum cleaned with vacuum knife 19 to remove toner par-
ticles which have adventitiou5lybecome attracted to the
demagnetized bac~ground area. After transfer of the toner
to substrate 29 using DC corona 36, t~e surface of printing
member 1 is vacu~m cleaned with vacuum brush 21 and t~e
resid~al electrostatic charges preferably are neutralized
using AC corona 22. Prefera~ly, an AC corona ean also be
used a^~ ear DC corona 35 and before vacuum ~rush 2L to remove
the electrostatic charge o~ the toner particles which do not
transfer, thus enhancing the action o- vacuum brush 21.
The clean, electrostatic charge-free printing surface
is then xeady for redecoration followed by the steps of
neutralization, vacuum knife cleaning, electrostatic
transfer, fusion, vacuum brush cleaning and neutraliz~-
tion. ~his sequence of steps is continued until the
pri~ting cycle is completed.
Latent magnetic images of the remaining two
colors making up the design to be printed in this
embodiment are similarly decorated, transferred and fused
at printing stations B and C. The fused mul~icolor
printed ~abric is ~aken u~ by take up roll 40. The imase
alignment of printing stations A, B and C is achieved
~lectronically by placing a magnetic read head 41,
commonly available~ at the edge of each printing
drum 12. The ~ead head 41 senses t~e signal on the
~32~ ~
~gnetic ~urface that is in registry with the image at
each pxinting station. This signal is sent to a synchro-
nization control box tnot shown). The speed of endless
belt 31 is set manually by a belt drive motor (not shown).
A belt speed signal is sent to the synchronization control
box which controls the speeds of each of the motors
driving the drums at printing stations A, B and C. Thus,
all of the drums are placed in register by means of the
feedback signal from the magnetic read head 41 on each of
the drums.
It is to be understood that the aforesaid
discussions of figures are de~oid of descriptions of the
permanent fixation (of dye and/or chemical treating agent)
and the ~erromagnetic component- and resin-removal (for
example, by aqueous scouring) steps of the invention magnetic
printing process since these steps, and the equipment
which can be employed in connection therewith, are familiar
to one s~illed in the art of dye chemistry.
In addition to direct abric printing, the
invention process also affords the capabili y of indirectly
printing fabrics by utilizing the process in combination
with heat-transer printing. In magnetic/heat transfer
printing, ferromagnetic toners containing sublimable dyes
are first direc~ly printed to a paper substrate, fused
thereon as described above and then subsequently heat-
transfer printed from the paper substrate to a fabric substrate
employing a combination of heat, pressure and ~well time.
~eat-transfer printing at 160 to 250C, prefera~ly l90 to
220C, at 1 to 2 psi ~6,900 to 13,800 Pascal) pressure for
up to lO0 seco~ds dwell time provi~es good results in tl~e
invention magnetic/heat-transfer printing proccss. Under
-- 45 --
~l132~76
such conditions, the dye sublimes and is transferred to
and is fixed within the ~abric substrate. The resin and
ferromagnetic components are subse~uently removed
by scouring the printed fabric substrate as described above
for the magnetic printing process.
The invention magnetic pxinting process provides
numerous advantages over conventional wet printing
pxocesses. ~or example, prints can be produced having
half-tone or large solid areas which exhibit excellent
optical density. Since the printing surface is reusable,
there is no need for conventional printing screens and
rollers. A dry toner system is used and no print paste
makeup is re~uired. This provides minimum water pollution
(by dye) on cleanup. No additional ~uxiliary chemicals
or gums are requir~d since the ferromagnetic toners can be
formulated so as to contain all of the necessary materials.
Moreover, lower printing costs are obtainable due to
lower engxaving costs and shorter changeQver times.
EXAMPLES
In the following examples, unless othexwise noted,
all parts and percentages are by weight and all materials
employed are readily commercially available.
Example 1
This example illustrates th~ preparation, by
manual mixing of ~he ingredients fol~owed by spray-drying, of
a ferroma~ne~ic toner containing a blue disperse dye, magnetic
components and an aqucous alkali soluble resin, and the
application therco~ to bo~h papc~ and polyester. A magnetic
tcner was prepared ~rom 32.7~ o car~onyl iron, 32.7~ o~
~e304, 1.8~ of C.I. Dispexse Blue 5G, 5.5~ of li~ninsulfonate
~ispersant ~nd 27.3~ of a polyvinyl acetate ~opoIymer resin.
~he carbonyl ixon, used as the soft magnetic material
- 46 -
and commercially available under the tracle name "Carbonyl
Iron" GS-6, is substantially pure iron powder produced ~y
the pyrolysis of iron carbonyl. A suitable Fe3O4 is sold
under -the trade name Mapico* slack Iron Oxide and the
polyvinyl acetate copolymer resin, under the trade name
Gelva* C5-VIOM. "Gelva" C5-VIOM is an aqueous alkali-
soluble copolymer of vlnyl acetate and a monomer containing
the requisite number of carboxy groups and has a softening
point of 123C.
A 20% aqueous alkaline solution (450 parts) of
the polyvinyl acetate copolymer resin was manually stirred
with 500 parts of water until thorough mixing was effected.
Carbonyl Iron GS-6 (108 parts) and "Mapico" Black Iron
Oxide (108 parts) were added and the mixture was thoroughly
stirred. C.I. Disperse Blue 56 (24 parts of a 24.6%
standardized powder) was stirred in 455 parts of water
until completely dispersed, then added to the above resin
solution. The resultant toner slurry was stirred for
30 minutes with a high shear mixer and then spray-dried
in a Niro* electric spray-dryer. The toner slurry was
atomized by dropping it onto a disc rotating at 20,000 to
50,000 rpm in a chamber through which heated air was
swirling at a high velocity. Precautions were taken to
stir the ~ner slurry and maintain a uniform feed composition.
The exact temperature and air velocity depend mainly on the
softening point of the resin. An air inlet temperature of
225C, an outlet temperature of 85C and an atomizer air
pressure of 85 psig (586,500 Pascal gauge~ provided satis-
factory results. The resulting discrete toner particles
o~ magnetic resin-encapsulated dye had a particle size
* denotes trade mark
_~7_
:
~, ...
within the range of 2 to 100 microns, mostly within the
range of 10 to 25 microns. The particles were collected
in a collection chamber. Toner adhering to the sides
of the drying chamber was removed by brushing into a bottle
and combined with the initial fraction. The toner sample
was finally passed through a 200 mesh screen (U.S. Sieve
Series), thus being less than 74 microns in particle size.
The ferromagnetic toner was mechanically mixed with 0.2%
of a fumed silicate, ~uso WR-82, to improve powder flow
characteristics.
Toner evaluation was made on a 2 mil (0.0508 mm)
aluminized Mylar* polyester film continuously coated
with 170 microinches (43,180 A) of acicular CrO2 in a resin
binder. Suitable acicular CrO2 can be prepared by well
known prior art techniques. The CrO2 film was magnetically
structured to 300 lines per inch (12 lines per mm~ by re-
cording a sine wave with a magnetic write head. A film
positive of the printed image to be copied was placed in
contact with the magnetically structured CrO2-coated alum-
inized polyester film and uniformly illuminated by a Xenonflash,passing through,the film positive. The dark areas of
the film positive corresponding to the printed message
absorbed the energy of the Xenon flash, whereas the clear
areas transmitted the ligh,t and heated the CrO2 beyond
lts 116C Curie point, thereby demagnetizing the exposed
-magnetic CrO2 lines. The latent magnetic image was manually
decorated by pouring the fluidized toner powder over the
partially demagnetized CrO2 film and then blowing off the
excess. The magnetic ima~e became visible by vir-tue of the
toner being magnetically attracted to the magnetized areas.
* denotes trade mark
-48-
$j
The toner decorated image was separately
transferred to paper and to Polyester fabric substrates
by applying a 20 kv positive potential from the backside
of the substrate by means of a DC corona. Other
transfer means can also be employed, such as bly means of
a pressure of 10-40 pounds per linear inch (17.6-69.6 Newtons
per linear cm). However, such means may lead to shorter
film life, poorer transfer efficiency and poorer image
definition on the substrate. After transfer to the paper
or fabric substrate, the toner was fused thereon by infrared
radiation, backside fusion (140C) or by steam fusion
(100C for 10-15 seconds at 1 atm pressure). The latter
method is the most economical but is only possible with
water-soluble resins.
The image which had been transferred to the
paper was then heat transfer printed from the paper to
polyester fabric by placing the fused image-bearing paper
face-down on the polyester and applying 1.5 to 2.0 psi --
(10,350 to 13,800 Pascal] pressure for 30 seconds
20 at 205-210C. After direct transfer and fusion to polyester
fabric, the dye was fixed in the fabric by heating for
30 seconds at 205-210C and 1.5 to 2.0 psi pressure
(10,350 to 13,800 Pascal).
Both fabric samples which had been printed as
described above, that is, either dlrectly printed or heat
transfer printed from paper, following :Eixatibn of the
dye, were scoured by immersion in cold water and then in
hot detergent. A detergent consi-sting of sodium phosphates,
sodium carbonates- and biodeyradable anionic and nonionic
surfactants (Lakeseal*) was used. The samples were
finally rinsed in cold water and dried. A deep blue print
was obtained on each fabric.
* denontes trade mark
-49-
ExamE~e 2
This example illustxates the preparation, by
ball-millins of the ingredients followed by spray-drying,
of a ferromagnetic toner containing a blue disperse dye,
m~gnetic components and an aqueous alkali-soluble resin,
and the a~plication thereof to polyester. A magnetic toner
was prepared from 30~ of carbonyl iron, 30~ of Fe3O4, 10
of C~I~ Disperse Blue 56 and 30~ of a polyvinyl acetate
copolymer resin ~"Gelva" C5-VIOM).
A mixture of 300 parts of a 20% aqu~ous alkaline
solution of the polyvinyl acetate copolymer resin, 20
parts of C.I. Disperse Blue 56 crude pow~er, 60 parts of
~Mapico" Black Iron Oxide, 60 parts of Carbonyl Iron
GS-6 and 100 parts of water was ball-milled for 17 hours
.at 37~ nonvolatilesO A ceramic ball-mill was selected
of such size that when the ball-mill was about one-half
to two thirds full of 0.5 inch (1.27 cm) high density
ceramic.balls, the above ingredients just covexed the balls.
After discharging the ball-mill and diluting with 460
parts of water to reduce the total nonvolatile solids to
approximat~ly 20~, the slurry was spray-dried in a-Niro `;
spray-dryer using an air inlct temperature of 200C, an ~ir
outlet temperature of 80C an~ an atomizer air prcssure
of 80 psig (552,000 Pascal gauge). The toner particles
wer~ brush~d from the d~ying chamber, collected and passed
through a 200 mesh scree~. The toner sample was fluidized
with 0.2~ of Quso WR- 82 and then used to dccorate the
latent magnetic image on a 300 line per inch (1~ per mm)
CrO2-coated aluminized ~Mylar" film as descri~ed in
~xample 1. The ton~r decorated m~ge was electrostatically
txansferred directly to 100S polyester double-knit fabric
,
- 50 -
~3'~
by applying a 20 KV negative potential to the backside
of the fabric. The toner was steam fused to the fabric
at 100C for 10-15 seconcls at 1 atm pressure. After
fusion, the dye was fixed in the fabric by heating at
205C for 40 seconds at 1.5 psi (10,350 Pascal). The
printed fabric was then scoured at 65C in a mixture of
2 parts per liter of caustic soda, 2 parts per liter of
sodium hydrosulfite and 2 parts per liter of a poly-
oxyethylated tridecanol surface acti.ve agent to remove
resin, Fe, Fe3O4 and any unfi.xed dye and then dried. A
bright blue print was obtained.
Example 3
This example illus.trates the preparation o a
solvent ball-milled and spray-dri.ed, ferromagnetic resi.n
encapsulated, disperse dye toner and the application there-
of to polyester.
A magnetic toner was- prepared by ball-milling a
mixture of 120 parts of an aqueous alkali-soluble polyamide
res.in-di.carboxylic acid adduct (commercially available
20 as TPX*-1002), 136 parts of "~Mapi.co" Black Iron O ~de,
136 parts of Carbonyl Iron GS-6, 8 parts of C.I. Disperse
Red 60 crude powder and 267 parts of a 50:50 mixture
of toluene: isopropanol for 16 hours at 60% nonvolatile
solids. The ball-mill was discharged and the content was
diluted with 666.ml of 50:5Q mixture of toluene:i.sopropanol
to approximately 30% nonvolati.le solids. The solvent
toner slurry was spray-dried in a ~owen* spray-dryer using
a feed rate of 152 ml per minute, an air inlet temperature
of 143C, an air outlet temperature of 62C and an
30 atomizer air pressure of 85 psig (:586,5Q0 Pascal gauge~.
The toner particles were classified to some extent by a
* denotes trade mark
-51-
.~,
~13Z~7~
cyclone collection system~ The main toner fraction (81%,
238 parts) collected from the dryer chamber consisteZ of
nearly spherical spray-dried particles having an average
particle size of lO to 15 microns (a range of 2 to 50 microns~.
The resultant magnetic toner consisted of 30g of poly~i~e
r~in adduct, 34~ o~ carbonyl iron, 34% of ~e~O4 and 2% of
C.l. Disperse Red 60. The toner wac fluiâized with 0.3~
of Quso WR 82 and then applied to decorate tho latent image
on a 300 line per inch (12 per mm) magnetically structurod
CrO2 coated aluminized "Mylar" film as described in
Example l. The toner decorated image was electrostatically
transferred directly to 100% polyester woven fabric by
applying a 20 KV negative potential to the backside of the
fabric. The fabric was steam fused and the dve was fixed
by heating at 205C for 40 seconds at 1.5 psi (10,350 Pasc?1).
The printed fabric was then scoured as in Exam le 2 and
dried.
Examples 4 to 33
.
Dispersc dye toncrs were prepared by eithcr
manually mixing or ball-milling thc appropriate in~redicllts
and spray-drying thc slurry as describcd in E~mplcs 1 an~
2. Dctails are summarizcd in Tablc I. ~anually mixe~
ton~rs were prepared in all cascs except Examples 13, 14,
i9 and 32, i~ these the toners were prepared by ball-milling.
~he compositions of the inal spray-dried toners as well
~s ~he ratio of resin to total magnetic component present
are aiso shown in the table~ Ball-milled toners exhibited
optic~l densities, when printed on polyester, which were
superior to those of manually mixed toners of comparable
dye co~cent~-tion. This diffcrence is p~rticularly
evident when ~he toner contains high concentrations of dye.
- 52 -
~l~Z~76
The standardized disperse dye powders (and pastes) used
in the manually mixed toners contained ligninsulfonate
and sulfonated naphthalene-formaldehyde condensate
dis~ersing asents. At high dispersant levels, the quantity
of magnetic component in ~he toner becomes limited a.nd
decoration of the latent magnetic image may becom~ impaire~.
Toner compositions containing 9 to 74~ (Examples
12 and 25) of water-soluble resin and 14 to 83% (Examples 1
and 12) of total magnetic component and ~ompositions
having a resin to magnetic component ratio of 0.11 to 3.3
(Examples 12 and 25) exhibited sa~isfactory magnetic,
transfer and fusion properti~s. Various disperse dye types,
for example, quinophthalone (Exa~ple 4), anthraquinone
(Examples 5 to 25, 32 and 33) and azo (Examples 26 to 31)
dyes, provide a wide range of colored magnetic toners.
The amount of dye present in t~e toner depends on thc amount
of rcsin and magnetic component present. Dye concentra-
tions of 0.10~ (~xample 33) to 25~ (Example 32) wcre used
with satisfactory rcsults. Toner com~ositions containing
20 both hard and soft ma~Jnetic compolleots are exemplificd
in Tabl~ I. A bin~ry mixture of m~gnctic particl~s is not
essentia1~ howeverO Equally good results are obtained
using only a hard ma~netic component (Examples 18 to 21).
Ferric oxide is a preferred hard magnetic component based
on its magnetic prope~ties and its cost. Chromium
dioxide can also be used but it is much more expensive.
A free-flow agent, present in ~uantities of 0.01 to 5%
(preferably 0.01 to 0.4~, based on total toner weight,
was used to keep the individual toner particles from
stic~ing toge.her and to increase the bul~ of the toner
powder. ~hese factors facilitate even deposition of
- 53 -
,
~L~3217~;
toner over the imaging mem~er. Free-flow agents such as
microfine silica and alumina are useful. Quso ~IR-82
provides satis~actory flow properties when added to tne
toners described herein.
The toners were evaluated as descri~ed in
ExaMple 1. The latent magnetic image on a 300 line ~er
inch (12 per mm) magnetically str~ctured CrO2 coated
aluminized "Mylar" film was manuallv decorated and the
decorated image was electrostatically transferred to
(that is, printed on3 a substxate (shown in Table I).
The toner fusion and dye fi~ation conditions and the
scouring procedure for removing resin, magnetic component(s)
and unfixed dye from the printed substrate are also
given in the table. For instance, in Example 4 the
designation "DP(Pap)t~ indicates that the toner was directly
printed on paper and infrared fused at 160-170C; the
desi~n~tion "~ITP(PE)f'g" mcans that the toncr was heat
trans~er print~d from papcr to polycster ~y hcatin~ a~
205C for 40 seconds and 1~5 psi (10,350 Pascal) and
the printed polyester was scoured at 65C in a~ueous
deterg nt solution; and the desLgnation "DPlPE~t'f'g"
~e ns that the toner was directly printed on polyester,
~nfrared fused ~t 163-170C, the dye was fixed at
205C for 40 seconds and 1.5 psi (10,350 Pascal) and
the printed poly~stex fabric Wa5 scoured a~ 65C. in
aqueous detergent.
~ number of different ~ixation pxocedures, for
example, dry heat, hot air, high temperature steam and high
pressure steam, were used to fix the dyes in the substrate.
3~ Such procedures are well-known in the art for fixing
disperse dyes in polyester and nylon.
_ j4 -
~3Z~7 ~
Exam~les 27, 29, 30 and 31 3how ~he effect of~ncorporating 2, 4, 6 and 8% of a ~enzanilide dye carrier.
in the toner compositions. The carrier gave increased
tinctorial strength over toner without the carrier.
Concentra~ons of 2 to 4% ~of carrier) provided optimum
results.
Example 34
This example illustrates the effect of various
chemicals which are normally used in the conventional
printing of polyester to prevent side effects during
fixation of the dye.
The toncr of Example 27 containing 2~ of
benzanilide carricr was directly printed on 100% polyester
woven ~abric according to the procedure o~ Example 1. The
toner was steam fused at 100C and 1 atm pressure for
10-15 seconds. Thc fabric was spraycd with a solution of
100 parts of urea and 10 par~s of sodium chlorate in 1,000
parts of water ~o prevent reduction of the dye during the
fixation step. The dye was fixed by high pressure steaming
~t 22 psig ~151,800 Pascal) for 1 hour. The printed
f abxic was scoure~ in 2 parts per liter o~ sodium hydxo-
sulfite, 2 parts per liter of soda caustic and 2 parts per
~ter of a po~yethoxylated trideca~ol surfactant at 65C.
A deep red print was obt~ined; it exhibited superior
tinctorial strength as compared to a corresponding print
which had not been sprayed prior to fixation.
Example 35
This example illustrates the effect of various
chemicals which are normally used in the conventional
print~ng of nylon ~o preven~ si~e effects durins fixation
o~ ~he dye~
- 55 -
~3~
~ he toner of Example 27 containing 2~ of benz-
anilide carrier ~as directly printed on "Qiana" nylon fabri~
according to the procedure of Example 1. .The toner was
steam fused at 100C and 1 atm pressure for 10-15 seconds.
m e abric was then sprayed with a solution of 100 parts
of urea, 10 parts of sodium chlorate and 10 parts of citric
acid in 1,000 parts of water and the dye was fixed by high
pressure steaming at 22 psig (151,800 Pascal) for
1 hour. After scourillg, a deep red print was obtained; it
was tinctorially stronger than a corrcsponding red print
which had not been sprayed prior to fixatiQn.
Example 36
This cxample illustrates thc preparation and
application o~ a fcxromagnetic disperse dy~ toner to a
poly~stcr/cottoll blcnd ~abric.
A 6-inch ~15 cm~ wide, 3-yard (274 cm) length of
65/35 polyest~r/cotton blend fabric was pretreated ~y padding
to a~ou~ 55~ pic~up with an aqueo~s solution containing
120 parts per liter of metho?~ypolyethylene glycol, M.W. 350.
2~ The padded fabric was heated at 72C for 1 ~our ~n a hot -
air oven to evaporate water, leaving the cotton fibers in
a swollen state.
A magnetic toner was~prepared by spray-drying
a ~ixt~re containing 29~'4% of polyvinyl ace~a~e copolymer
~ . ~
resin ~ "(;elva" C5-VIO~ , 33 . 3~ of Carbonyl Iron GS-6,
33~3~ of "Mapico" Blac~ Iron Oxide, 2% of a dye of the
~ormula shown as ~A) in Table VII and 2~ of a sul~onated
naphthalene-formaldehyde dispersant. The spray-dried
product was sieved through a 200 mesh screen and a . 2~ of
30 Quso W~-82 w~s added to rPnder the toner free 1Owing.
-- ~6 --
~13'hl~
A latent magnetic ~mage such as described in -
Example 1 was manually decorated with the abo~e toner and
txansferred electrostatically to both untreated and pretreated
65/35 polyester/cotton by a procedure such as described
in Example 1. Following trans~er, the toner was stea.m
fused at 100C and 1 atm pressure for 10 to is seconds and
the dye was hot air fixed at 205C for 100 seconds.
Following fixation of the dye, the print was scoured at
65C in aqueous detergent. The pretreated polyesterfcotton
~abric was printed in a deep bright red shade, whereas
the untreated fabric was only lightly stained. Similar
r~sults were obtained when thc dispcrse dye toner was
trans~erred to the pretreated and untreated fabrics, steam
fused and then dry heat fixcd at 205~C for 100 s~conds
at 1.5 psig (10,350 Pascal gauge).
xample 37
This example illustrates the preparation of a
ferromagnetic toner containing a cationic dye, magnetic com~o-
nents and an aqueous alkali-soluble resin and the application
thereof to acid-modified polyester and polyacrylonitrile~
A solutio~ of 21 parts of C.I~ Basic Blue 77,
as a 24.4% standardized powder (containing boric ~cid as a
diluent) in 300 ml of hot water, was added, with thorougn
stirring, to 400 parts of a 20% aqueou.s alkaline solution of a
polyvinyl acetate resin. ~ "Gelva" CS-VIOM) . Ca~bonyl Iron
GS-6 (91 parts3, "Mapico" 81ack Iron Oxide (91 parts) and
510 parts o~ water were then added and~ stirring was
~on~inued for an additional 30 minutes. The toner slur-y
was spray-dried to give a final toner composi~ion containing
28.3% of polyvinyl acetate copolymer resin, 32.2% o~
C~rbonyl Irsn GS-6, 3~.2~ of ~apico~ Black Iron Oxide,
- g7 -
7~;
1~8~ of C.I. Rasic Bl~e 77 and 5.5 weight percent of boric
acid diluent. The toner was sieYed throug~ a 2Q0 ~esh
~creen and fluidLzed with O . 2% of Quso ~R-82.
A latent magnetic image such as described in
Example 1 was manually decorated with the above toner and
transferred electxostatically to acid-modified polyester
fabric as described in Example 1. After transfer, the toner
was steam fused at 100C and 1 atm pxessure for 10 to 15
seconds and the cationic dye was fixed by high-pressure
~teaming at 22 psig (151,800 Pascal gauge) fo- 1 hour.
~he printed ~ahric was scouxed as described in ~xample 2.
A blue print was obtained.
~ ~econd toner trans fcr was made to polyacrylo-
nitrile fabric in a similar manner. The toner was steam
~used, ~he dye was fixed by cottage-steaming ~k 7 psig
(48,300 Pascal gauge) for 1 hour and the printed fabric was
scoured as described above; a deep blue print was obtained,
In conventional prin~ing with rationic dyes, a
~steady acid" is normally used in the print paste to insure
20 that an acid pH is maintained during ~ixation of the dye.
Accoraingly, in ano her set of experiments, after transfer
and steam fusion of the above cationic dye toner to ~oth
~he acid-modified polyester and the polyacrylonitrile fabrics,
the printed fabrics were oversprayed with a 50% aqueous
~olution of citric acid and then ~ixed by high-pressure
- steaming and cottage~steaming, respectively, as described
abo~e. The printed ~abrics were then scoured. Bright
blue prints were obtained, exhibiting superior image
definition as compared to the prints which were prepared
withou~ the overspray step.
xamples 38 to 43
~erromagn tic cationic dye toners were prepared
- 58 -
,~ ,L~.X,~
by manually mi~lng the ap~ropriate ingredients and spray-
drying the slurries as described in Example 37 After
drying, 0.2 to 1.2% of ~uso WR-82 was added to obtain toner
fluidity. Details are summarized in Table II. The
ferromagnetic cationic dye toners were directly printed
to both acid-modified polyester and polyacrylonitrile
substrates, steam fused and fixed by either high pressure
steam developmen-t at 22 psig (151,800 Pascal gauge) for
1 hour or by cottage-steaming at 7 psig (48,300 Pascal
gauge) for 1 hour.
Cationic dyes of the triarylmethane (Example 37),
azomethine (Example 38), styryl (.Examples 39 and 41-43)
and rhodamine (Example 40) series, with both water-soluble
hydroxypropyl cellulose ("Klucel" LF) and polyvinyl acetate
copolymer ("Gelva" C5-VIOM) resins, are exemplified.
Klucel* LF is a cellulose ether containing propylene glycol
groups attached by an ether linkage ana not more than 4.6
hydroxypropyl groups per anhydroglucose unit and having
a molecular weight of approximately 100,000. The cati.onic
20 dye toners of Ex~mples 42 and 43 containing l and 2%,
respectively, of citric acid provided brighter and
tinctorially stronger prints on both acid-modified poly-
ester and polyacrylonitri.le as compared to the corresponding
toners without the citric acid.
Example 44
Thi~s example illustrates the preparation of a
ferromagnetic toner containing an acid dye, magnetic compo-
nents and an aqueous alkali-soluble resin and the
application thereof to nylon.
A solution of 12.7 parts of C.I. Acid Blue 40
* denotes trade mark
-59-
~r ~
tC.I. ~2,125), as a 31.6~ standardized powder ~containing
dextrin as a diluent) in 150 ml of hot water, was added,
with thorough stirring, to 300 parts of a ~0% aqueous alkaline
solution of a polyamide resin (TPX-1002). Carbonyl Iron
G~-6 (63.4 parts), "Mapico" Black Iron Oxide (64 parts)
and 410 parts of water were added and the slurry was stirred
on a high shear mixex for 20 minutes. The toner slurry
was spray-dried to give a final toner composition containing
30~ o~ polyamide resin, 31.7~ of Carbonyl Iron GS-6, 32~
of ~Mapico" Black Iron Oxi~e, 2~ of C.I. Aci~ Blue 40 and
4.~% o~ dextrin diluent. The toner was sieved through
a 200 mesh screen and ~luidi~ed with 0.6% of Quso WR-8~.
~ latent magnetic ~mage such as described i~
Example 1 was manually decorated with the a~ove toner and
transferred electrostatically to 100~ nylon 66 jersey fabric
and steam fused at 100C and 1 atm pressure for 10 to 15
seconds. The acid dye was fixed by cot~age-steaming the
printed ~abric at 7 psiy ~48,300 Pascal gauge) for 1 hour.
m e fabric was scoured at 60C with an aqueous solution
of 2 par~s per liter of a polyethoxylated ol~yl alcohol and
2 parts per liter of al~yl trimethylammonium bromide
surface-active agents7 A bright blue print was obtained.
xamples 45 to 53
_
Fexromasnetic acid dye toners werP prepared by
~anually mixing the appropria~e ingredients and spray-drying
the slurries as desrribed in Example 44. The toners were
fluidized with 0.2 to 1.4% of Quso WR-8~. Detai;s are
swnmarized in Table III. A latent magnetic image such as
descxlbed ~n Example 1 was ~anually decorated and the toner
3 de~orated image was electros~atically trans~2rred directly
-- 60 -
~3'~
to nylon 66 jersey. The toners were steam fused and the
acid dyes were ixed by cottage-steaming at 7 psig (48,300
Pascal gauge) for 1 hour. After scouring, bright
well~de~ined prints were obtained.
Toners containing monosulfonated azo (Examples 45,
46 and 51) and monosulfonated anthraquinone (Examples 47
~o 50) dyes, with water soluble polyvinyl acetate copolymer
(nGelva" C5-VIOM), hydroxypropylcellulose ("Xlucel" L~)
and polyamide (TPX-1002) rcsins, are exemplificd. ~xamples
52 and 53 include a speciàl disulfonated bis-anthraquinone
dye whi~h is notcd for its good light- and wetfastness
properties on nylon. Examples 47, 50, 51 and 53, with acid
dyes and containing 1~ of ammonium oxalate, ~rovided brighter
and tinctorially stronger prints on nylon than the corres-
ponding toners without ammonium oxalate. Citric acid,
present either in the toner tExample 49) or sprayed on the
toner fused nylon (Example 48), was found to significantly
improve dye fixation.
Example 54
This example illustrates the preparation of a
ferromagnetic toner containing a ~iber~reactive d~e~ magnetic
components and an aqueou~ alkali-soluble resin and the
~pplication thereof to cottonO
A magnetic toner was prepared by spray-drying
a mixture containing 30% of polyvinyl acetate copolymer
xesin ("Gelva" C5-VIO~), 3~% of Carbonyl Iron GS-6, ~3% of
- n~apico" Black Iron Oxide, 2~ of C.II ~eactive Blue 7
(~.I. 611Z5) and ~ of inorganic diluent. The spray-dried
pr~duct was sieved througll a 2~0 mesh screen and fluidized
~h Q.3~ ~uso WR-8~. A latent magnetic image such as
- 61 -
described in Example 1 was manually decorated with the above
toner and the decorated image was electrostatically trans-
ferred to 100% cotton twill fabric by applying a 20 ~V
negative potential to the bac~side of the fabric. The
printed fabric was steam fused at 100C and l atm pressure
for 10 seconds. The toner fused cotton fabric was then
sprayed with an aqueou~ solution containing 100 ~arts
per liter of urea and 15 parts pcr liter of sodium bicarbonat~.
This overspray is required to chomically link the reactive
dye to ~le cot~on by forming a covalent dyc-fiber ~ond.
Following th~ spray application, the cottGn abric was dricd
and thc dye was fixcd by heating at 190C for 3 n~inutes
~n a hot aix oven. The fabric was then scoured at 65C
~n a~ueous detergent. A brilliant blue print having
excellent washfastness properties was obtained.
Example 55
A spray-dried magnetic toner con~aining 30~ of
-polyvinyl acetate copolymer resin ("Gelva" C5-~IOM), 33
of Carbonyl Iron GS-6, 33% of "Mapico" Black Iron Oxide,
2% of Reactive Yellow 2 and 2~ of inorganic diluent was
directly printed on 100% cotton twill fabric in general
accord with the procedure descxibed in Example 54. The ts~ner
was steam fused and the printed fabric was sprayed with an
aque~us solution containing 100 parts per liter of urea
and 15 parts per liter of sodium bicarbonate. The dye ~as
fixed by heating at lY2C for 3 minutes and t~e fabric
was scoured at 65C in aqueous detergent. A bright yellow
print was obtained.
Example 56
3 Foll~wing the proced~re of Example 55, a spray-
dri d fer~omagnetic toner containin~ 30~ of polyvinyl
- 62 -
~3Zl~i
acetate copolymer resin (nGelva" CS-VIOM), 33~ of Carbonyl
Iron GS-6, 33~ of "Mapico" Black Iron Oxide, 2% C.I.
Reactive Red 2 and 2% of diluent was directly printed on
100~ cotton twill fabric. The toner was steam fused, the
printed fabric was oversprayed with aqueous urea/sodium
bicarbonate and the dye was fixed. A~ter scourins, a bright
red print was obtained.
Example 57
This example illustrates the prepara~ion o~ a
fe~romagnetic toner containing a reactive dye, a dispcrse dyc,
ma~netic components and an aqueous alkali-soluble resin .~nd
the a~plication thereof to polyester/cotton-blend fabric.
A magnetic toner was prepared by spray-drying a
mix~ure containing 30~ of polyvinyl acetate copolymer resin
~Gelva" C5-VIOM~, 30~ of Carbonyl Iron GS-6, 31.1% of
~Mapico" Blac~ Iron Oxide, 3% o~ a 60/40 mixture of a
yellow disperse dye of the formula shown as (B) in Table
V~I and C.I. Reactive Yellow 2 and S.9~ of inoxganic
diluent. The ~oner was sieved through a 200 mesh screen
and fluidized with 0.2% of Quso WR-82. Toner decora~ion of
a latent magnetic image was carried out as described in
~xample 1. The toner decorated image was electrostatically
transferred directly to 65~35 polyes ter/cotton poplin
fabric and steam fused at 100C and 1 a~m pressure for
10 seconds. Dye fixation was accomplished by heating the
fabric at 210C for 100 seconds in a hot air oven. The
printed fabric was finally scoured at 60~C in aqueous
detergent. A bright yellow well-defined print was obtained.
Example 58
J~ A ~pray-dried magnetic toner containing 30~ of
- 63 -
~ 6
polyvinyl acetate copolymer resin tHGelva" C5-VIOM), 30~
of Carbonyl Iron GS-6, 30.1% of "Mapico" Black Iron Oxide,
3% of a 76/24 mixture of a blue disperse dye of`tne
formula shown as (C) in Table VII and C.I. Reactive Blue 7
and 6.9~ of inorganic diluent was dir~ctly printed on
65/35 polyester/cotton poplin and steam fused as described
in Example 57. The printed fabric was fixcd by heating
at 200C for 100 seconds and then scoured at 60~C in aqueous
deterg~nt. A bright blue print was obtained.
This example illustrates the preparation of
a ferromagnetic toner containing a sulfur dye, masnetic
components and an aqueous alkali-soluble resin and the
application thereof to cotton.
A spray-dried magnetic toner containing 32.6%
of polyvinyl acetate copolymer resin ("Gel~a" C5-VIOM),
32.6% of Caxbo-ny1 Ixon GS-6, 32.6% of nMapico" Black Iron
Oxide and ~.2~ of C.I. Leucd Sulfur Blue 13 (C.I. 53450)
was prepared, sieved through a 200 mesh screen and fluidized
with 0 . 2~ of Quso WR-82. A~ toner decorated latent magnetic
image was electrostatically transferred, by a procedure
such as described in Example 1, to 100~ cotton fabric.
The toner was steam fused at 100C and 1 atm pressure for
10 se~onds. The printed fabric was subsequently padded
f~om an aqueous bath containing 300 parts per liter of
~odium sulfhydrate at a pickup of approximately 50~. The
leuco dye was then immediately steam fixed at 100C and
1 atm pressure for 60 sec~nds. A~tex fixation, the printed
fabric was developed by oxidation a~ 50C in an a~ueous
,~ b~th containing ~ pa~s per liter of sodium perborate.
- 64 -
~ ~2~ ~ 6
The fabric was finally scoured at 60C ~n an aqueous bath
containing 2 parts per liter of diethanolamine oleyl
sulfate surface-active agent. A blue print was obtained.
Examp 1 e 6 0
This example illustrates the preparation of
a ferromagnctic toner containing a vat dye,. magnetic
components and àn aqu~ous alkali-soluble resin-and the
application thereof to cotton fa~ric.
A ~pray-dried ma~nctic toner containing 29~ of
polyvinyl acetate copolymer resin tnGelva~ C5-V~CM~, 32.9
of Carbonyl`Iron GS-6, 32.~% of ~Mapico" Black Iron Oxide,
2.7~ of C.I. Vat Red 10 (C.I. 67,000) and 2.5% of dilue~t
was used to manually decorate a latent magnetic image on a
300 line per inch (12 per mm) magnetically structured CrO2
coated aluminized "Mylar" film. T~e toner decorated latent
image was electrostatically transferred to 100% cotton
twill fabric and the toner was steam fused at 100C and
1 atm pressur for 10 seconds. The printed co~ton fa~ric
was then padded from a reducing ba~h containing
34 parts per liter of soda caustic
60 parts per liter of soda ash
60 paxts per liter of sodium hydrosulfitP
2 parts per liter of sodium octyl/decyl
zulfate surface-active agent
15 parts per liter of amylopectin ~hic~ening
agent
2 parts per liter of 2-ethylhexanol
at a pic~up of 70 to 80~ and f lash aged at 132C for 4$
~econds. The fabric was rinsed in cvld water, oxidized fox
1 minute at 60C ~n a bath containing 2% hydrogen peroxide
~ 65 -
and 2% glacial acetic acid~ rinsed and scoured for 5 minutes
at 82~C i~ 0.S part per liter (aqueous) of a diethanolamine
oleyl sulfate surface-active agent. A bright red print
was ohtained.
xample 61
A spray-~ried ferromagnetic toner containing 30
of polyvinyl acetate copolymer resin (UGelva" C5-VIOM),
33~ of Carbonyl Iron GS-6, 33~ of "Mapico" Black Iron Oxide-,
2~ of C.I. Vat Blue 6 (C.I. 69825) and 2% of diluent was~
prcpaxed and the lat~nt ima~e producc~ therewith was
transferred dircctly to 100~ cotton twill fabric. The
toner was fused, the vat dye was fixed and the printed
~abric was scoured as described in Example 60. ~ bright
~lue print was obtained.
~xample 62 ` . ~`
A spray-dried ferromagnetic toner containing 30%~
of polyvinyl acetate copolymer resin (~Gelva" C5-VIOM),
33~ of~ Carbonyl Iron G5-6, 33% of "~apico" Black Iron Oxide,
~% of C.~. Vat Yellow 22 and 2~ of diluent was prepared
2~ a~d printed on 100% cotton twill fabric by a procedure
substantially as described in Example 60. A yellow print
was obtainedO
~his example illustrates the preparation of a
ferromagnetic toner containing a premetalized acid dye,
~agnetic componen~s and an aqueous alkali-soluble resin
and the application thereof to nylon.
A spray-dried magnetic toner was prepared so as
~o contain 30% of polyvinyl acetate copolymer resin
(~GelYa~ C5-V~O~, 31.4~ of ~arbonyl Iron GS-6, 31.4~ of
- 66 -
"Mapico" Black Iron Oxide, 2% of C.I. Acid Yellow 151
(a sulfonated premetalized azo dye) and 5.2% of inorganic
diluent. The toner was sieved through a 200 mesh screen
and fluidized with 0.2% of Quso WR-82. A toner decorated
latent magnetic image such as described in Example 1 was
electrostatically transferred to nylon 66 jersey fabric
and steam fused at 100°C and 1 atm pressure for 10 seconds.
The premetalized acid dye was fixed by cottage-steaming
the fabric at 7 psig (48,300 Pascal gauge) for 1 hour.
The printed fabric was then scoured at 65°C in an aqueous
solution of 2 parts per liter of each of sodium hydrosulfite,
soda caustic and polyethoxylated tridecanol surfactant. A
second toner transfer was made to nylon 66 jersey fabric.
The toner was steam fused and the fabric was oversprayed with
a 50% aqueous solution of citric acid. The dye was fixed by
cottage-steaming at 7 psig (48,300 Pascal gauge) for 1 hour
and the printed fabric was caustic-hydro scoured as above.
In both cases, strong well-defined yellow prints were obtained.
Example 64
Using the procedures substantially as disclosed
in Example 63, a spray-dried ferromagnetic toner containing
30% of polyvinyl acetate copolymer resin ("Gelva" C5-VIOM),
32.1% of Carbonyl Iron GS-6, 33% of "Mapico" Black Iron
Oxide, 2% of C.I. Acid Red 182 (premetallized azo dye) and
2.9% of inorganic diluent was prepared and electrostatically
transferred to nylon 66 jersey fabric. After steam fusing,
cottage-steaming and scouring, a well-defined bright red
print fabric was obtained. A similar sharp red print was
obtained when the fabric was oversprayed with 50% aqueous
citric acid prior to cottage-steaming.
- 67 -
7t~
Examples 65 to 68
Examples 65 to 68 illustrate the preparation of
ferromagnetic toners containing cationic-disperse dyes,
magnetic compo~ents and an aqueous alkali-soluble resin and
the application thereof ~o acid-modified polyester,
polyacrylonitrile and cellulose acetate.
Cationic-disperse dyes, 'hat is, water-insoluble
salts o~ dye cations and selected arylsulfonate anions,
are well-known in the art for dyeing acid-modified polyestcr
~nd acrylic fibers. Cationic-disperse dye toners were
prcpared by manu~lly mixing ~hc appropriate ingredicnts
(20% non~olatile solids) and spray-drying. The spray-dried
toners were sieved through a 200 mesh screen and fluidized
with O.2~ of Quso ~7R-82. Details are summariæed in
~able IV. Examples 65 to 67 use 1,5-naphthalenedisulfonate
as ~he anion and Example 68 uses 2,4-dinitrobenzenesulfonate
as the anion. Toner decoration of a latent magnetic image
and electrostatic transfer to the fabric substrate were
preformed as d~scribed in Example 1. The toners were steam
fused and the printed abrics were oversprayed witn 50~
a~ueous citric acid to aid in dye fixationq The dyes were
~ixed by either cottage~steaming or high-pressure steaming
~he spxayed fabrics. Arter scouring, in each example,
~ well-defined print was obtained.
Example 69
This example illustrates the preparation of a
ferromagnetic toner containing a fluorescent brightening
agent, magnetic components and an aqueous alkali-soluble
~esin and the ap~lication thereof to cotton.
A ~agne~ic toner containing 30% of polyvinyl
- 68 -
~13~
acetate copolymer resin ~nGel~a~ C5-VIOM~, 34% of Carbonyl
Iron GS-6, 34% of ~Mapico~ BlacX Iron Oxide and 2~ of
C.I. Fluorescent Brightener 102 was prepared by spray-
drying an a~ueous 20~ nonvolatile solids mixture of the
i~gredients. The spray-dried toner was sieved through
a 200 mesh screen and fluidized with 0.2% of Quso WR-82.
A latent magnetic image such as described in Ex~mple l was
toner decorated and the image was electrostatic~lly
transferred to 100~ c~tton shceting. The toner was steam
fused and the bright~ner was ~ixed by heating the fabric
at 100C and l atm pressurc for 25 minutcs. The printbd
fabric was ~hen scoured at 60C in an aquQous solution of
2 parts per liter of soda caustic and 2 parts per liter
of polyethoxylatPd tridecanol surfactant. Upon exposure to
~n ultraviolet light source, the printed fabric strongly
fluoresced in the imaged areas.
Examples 70 to 74
These examples illustrate the preparatio~ of ferro-
~agnetic toners containing a chemical-resist agent, magnetic
components and an aqueous alXali-soluble resin and the
application thereof ~o nylon. The toners were prepared by
spray-drying an aqueous 20% no~volatile solids slurry of
the appropriate ingredients. The spray-dried toners were
sieved through a 200 mesh screen and fluidized with 0.2
of Quso W~-82, Details are summarized in Table Y. The
~hemical-resist toners were evalua~ed by manual decoration
of ~he latent magnetic image o~ a 300 line per inch (12 per r~)
~agnetically structured CrO2 coated aluminized "Mylar" ~ilm by
proc~dures substantially the ~ame ~s described in Example l.
~h~ toner-deco~ated images were transferred electrostatically
- 69 -
3~
to nylon 66 jersey fabric and steam fused at 100C and
1 atm pressure for 10 to 15 seconds. The che~ucal resist
in each example was ~ixed by steaming (atmospheric) the
fabrir for 20 minutes. Each printed fabric was rinsed in
water to remove the resin and the magnetic component(s)
and ~inally dried. Each resultant resist printed nylon
fabric was then overdyed with either a red biscationic dye
of the formula shown as ~D) or a blue diacidic (anionic)
dye o~ the formula shown as (E), or a mixture thereof, the
'O (D) and (E) formulas bein~ given in Table VII, by the
following procedurc:
Resist-printed nylon fabric t5 par~s) was added
to 300 parts of water containing:
ethylenediaminetetraacetic a~id,
t~trasodium salt ~,...... 0.013 part ~0.25% owf)
a sulfobetaine of the formula shown
a~ (F) in Table VII ..~. 0.05 part ~1.0% owf)
te~rasodium
pyrophosphate ... ~...... 0.010 part (9.2~ owf).
~he dye bath was adjusted to pH 6 wi~h monosodium phosphate
and the temperature was raised to 27C and held at this
temperature for 10 minutes. The cationic dye ( 0 . 025 part;
0.5% owf, that is, on weight of fiber) and~or the acidic
dye (O.a25 part; O.S~ owr) were added. When both types of
dyes were employed, the bath containing the cationic dye
was held-at 27GC for 5 minutes prior to the addition of the
anionic dye. After completion of the dye(s) addition
~he bath was mai~tained at 27~C for 10 minutes, the
temperatuxe was r~ised at about 2C per minute to 100~C
and held at this temperature for 1 hour. Each fa~ric
- 70 -
was rinsed in cold water and dried. The printed-resist
fabrics remained unstained in the imaged areas during the
subsequent overdyeing process.
Toners containing 2, 4, 6 and 8% of a chemical-
resist agent of the formula shown as (G) in Table VII
and binary soft tFe) and hard (Fe3O4) magnetic materials
are illustrated in Examples 70 to 73; they showed excellent
chemical-resist properties on nylon. An analogous
magnetic-resist toner containing only chromium dioxide
10 as the hard magnetic component (Example 74) also ~3rovided
satisfactory printed resist on nylon.
Example 75
A ferromagnetic disperse dye toner containing
30% of a polyamide resin (Versamid* 930), 34% of Carbonyl
Iron GS-6, 34% of "Mapico" Black Iron Oxide and 2% of
C.I. Disperse Yellow 54 was prepared by ball-milling and
spray-drying a 20% nonvolatile soli.ds toluene-isopropanol
slurry of the ingredients by a procedure substantially
as described in Example 3. "Versamid" 930 is a water-
20 insoluble resin having a molecular weight of about 3,100and a softening temperature of 105-115C. Such. water-
insoluble resins are disclosed as having utility in prior
art, known magnetic toners, for example, such as disclosed
by Hall and Young in U.S. 3,627,682.
A magnetic disperse dye toner containing 31.1%
of polyvinyl acetate copolymer resin (."Gelva" C5-VIOM),
30.7% of Carbonyl Iron GS-6, 30.7% of "Mapico" Black Iron
Oxide, 1.9% of C.I. Disperse Blue 56 and 5.6% of dispersant
was prepared by spray-drying an aqueous slurry of the
30 ingredients containing 2Q% of nonvolatile solids.
* denotes trade mark
-71-
~3~17~
Bo~h of the afsresaid toners were manually applied
to the latent images on a CrO2-coated aluminized "~ylar"
film and electrostatically transferred to 100% polyester
double-knit fabric by procedures substantially the same
as described in Example 1. The toners were steam fused and
the disperse dyes were fixed by heating the printed fabrics
at 210C and 1 atm pressure for 15 seconds. ~he printed
fabrics were then scoured at 75C in an aqueous solution
of 4 parts per liter of caustic soda, 4 parts per liter of
sodium hydrosulfite and 2 parts pcr liter of "Lakeseal"
detergent. The fabric printed with the disperse dye toner
containins the watcr-soluble resin was completcly clear
of resin and magnctic componcnts after just a fcw seconds
of gen~le stirring in the scouring medium, The fabric
printed with the watcr-insolublc resin was not clear of
resin and magnetic components cvcn after 15 minutes scouring
at 75C. Thus, the resin impregnated masnetic particles were
much more easily removed by aqueous scour from the printed
fabric using the dye toner containing the water-soluble resin
as compared to the toner containing the w~ter-insoluble resin
This clearly shows that the scouring medium must be suitable
for the resin being used since the presence of the black iron-
iron oxide on the fabric surface effectively mas~s the color
of the dye fixed in the fabric. In the aforesaid experiment
employing the water-soluble polyvinyl acetate resin, scoured
fabric was printed to a bright blue whereas in the experiment
employing the water-insoluble polyamide resin, the aqueous
scoured fabric was printed to a dark brown to blacX, completely
masking the bright yellow color of the dye employed. Scouring
with a 50-50 mixture of isopropanol-toluene at 60C provided a
significantly hetter print in that the yellow color of the
dye was evident.
Example 76
This example illustrates the preparation of a
ferromagnetic dye toner containing a yellow disperse dye,
magnetic components and a water-soluble natural resin,
and the a~plication thereof to paper and polyester.
A mixture of 350 parts of a commercially available
20% aqueous solution of a maleic anhydride-rosin derivative
10 tUnirez* 7057), 28.~ parts of C.I. Disperse ~ellow 54
as a 28.2% standardized powder containing a 50/50 mixture
of li.gnin sulfonate and sulfonated naphthalene-formaldehyde
as a dispersant, 60 parts of "Mapico" Black Iron Oxide
and 59.6 parts of Carbonyl Iron GS-6 was stirred for
30 minutes on a high-speed shear mixer. Water (,502 parts)
was added and the resultant slurry was spray dried to
give a final toner composition containing 35% of esterified
rosi.n, ~% of C.I. Disperse Yellow 54, 1.2% of the li.gnin
sulfonate/sulfonated naph.thalene-formaldehyde dispersant,
3Q% of "Mapico" Black Iron Oxide and 29.8% of Carbonyl
I,ron GS-6. The toner was sieved through a 200 mesh.
(U.S. Sieve Series) screen and flui.dized with 2% of ,Ouso
WR-82. A latent magnetic i.mage such as described in
Example 1 was manually decorated with the toner and the
toner decorated image was transferred electrostatically to
both.pape,r and polyester subs.trates. by applying a 20 KV
negative potential, using a DC corona, to the back.side of
the substrate. After transfer the image was steam-fused
on each,substrate~ After direct transfer and fusion to
the polyester fabric, the dye image was fixed by heating for
30 seconds~ at 210C and 1 to 1.5 psi (6,900 to 10,350 Pascal)
* denotes trade mark
,;,
h~J~i
pressure. The dye was also heat transfer printed from the
paper to polyester fabric by placing the fused image-bear-
ing paper face down on the polyester and applying l to 1.5
psi (6,900 to 10,350 Pascal) pressure for 30 seconds at
210C. Each of the fabrics~ after dye fixation, was scoured
with hot aqueous alkaline detergent. Deep yellow prints were
obtained on each, that is, the polyester which was directly
printed and the polyester which was heat transfer printed
from paper.
Example 77
This example illustrates the preparation of a
ferromagnetic dye toner containing a yellow disperse dye,
magnetic components and an aqueous alkali-soluble poly-
acrylic acid resin, and the application thereof to paper
and polyester.
A ferromagnetic toner was prepared by spray-
drying a mixture containing 35% of a commercially available,
aqueous alkali-soluble polyacrylic acid resin (Joncryl*
678), 4% of C.I. Disperse Yellow 54, 1.2% of a 50/50
mixture of lignin sulfonate and sulfonated naphthalene-
formaldehyde dispersant, 30% of "~apico" Black Iron Oxide
and 29.8% of Carbonyl Iron GS-6. The spray-dried toner
was sieved through a 200 mesh (U.S. Sieve Series) screen
and fluidized with 0.1% of Ouso WR-82. The toner was
used to manually decorate a latent magnetic image on the
surface of a printing base such as described in Example 1.
The decorated image was then electrostatically transferred
and steam fused to paper and suhsequently heat transfer
printed from the paper to 100% polyester fabric as describ-
ed in Example 76. The image was also directly printed to* denotes trade mark
-74-
lO0~ polyester fabric as described in Example 76. In both
cases the fixed printed fabrics were scoured at 65C
in an aqueous polyethoxylated tridecanol surfactant
solution; deep yellow prints were obtained on both fabrics.
Example 78
This example illustrates the preparation of a
erromagnetic dye toner containing a red disperse dye, a
magnetically hard component and an aqueous alkali-soluble
polyvinyl acetate copolymer resin, and the application
thereof to paper and polyester film and fabric.
A ferromagnetic toner was prepared by spray-
drying a mixture containing 30% of polyvinyl acetate
copolymer resin, 65.8% of a commercially available
Fe304-cobalt alloy (HiEN* - 527) containing 1 to 2 mole
percent of cobalt, 1% of C.I. Disperse Red 60 and 3.2% of
a lignin sulfonate dispersant. The toner was passed
through a 200 mesh screen. The toner flow properties
were excellent. The toner was used to manually decorate
a latent magnetic image on the surface of a printing base
such as described in Example 1. The decorated image was
electrostatically transferred to paper, steam fused and
then heat transfer printed from the paper to 100% polvester
fabric. The image was also directly transferred to both
100% polyester fabric and "~ylar" polyester film and then
steam fused. In each case permanent dye fixation was
achie~ed by heating the printed film or fabric substrate
at 205-210C and 1.5 psi (lOr350 ~ascal) pressure for
40 seconds. The printed substrates were finally scoured
at 82C in an a~ueous solution of 2 parts/liter of caustic
soda, 2 parts/liter of hydrosulfite and 2 parts/liter
* denotes trade mark
-75-
~3~
of a polyethoxylated tridecanol sur~actant. Bright red
prints were obtained in each case.
~xample 79
This example illustrates the preparation of a
ferromagnetic dye toner containing a yellow disperse dye,
magnetic components and a water-soluble polyacrylic acid
resin, and the application thereof to both paper and poly-
ester.
A ferromagnetic toner was prepared by spray-
drying a mixture containing 35% of a polyacrylic acid resin~ oncryl" 678, 4% of C.I. Disperse Yellow 54, 1.2% of
a 1 to 1 mixed lignin-sulfonate/sulfonated naphthalene-
formaldehyde dispersant, 30% of "Mapico" Black Iron Oxide
and 29.8% of Carbonyl I:ron GS-6. The spray-dried toner
was sIeved through a 20Q mesh screen (U.S. Sieve Series)
and fluidized with Quso WR-82 in a high-speed Waring*
blender. Outstanding toner flow and decoration properties
were obtained using from 0.1 to 0.2% of Quso WR-82 at
low blending speeds for 20 to 30 seconds. The toner
was used to develop the latent magnetic image on the
surface of a CrO2-coated aluminized polyester printing
member (such as 1 as shown in Figure 1) using a printing
apparatus such as depicted in Figure 11. Any subsequent
numbered references in thi.s example refer to said
Fi.gure 11. A continuous 0.18 mil (.4.6 micron) coating of
CrO2 dispersed in a resi.n bi-nder was uniformly applied to
the surface of an aluminized 2 mil (50.8 micron~ poly-
ester fi~mbase (:"~ylar"). The CrO2 particles dispersed
in the resin binder were applied to the aluminized polyester
film in the presence of a magnetic i.eld to orient the
particles parallel to the length o the film. The film
* denotes trade mark
-76-
~3'~
was then magnetically structured into a 253 to 450 lines
per inch (98 to 178 lines per cm) magnetic pa~tern using
a 0.5 inch (1.3 cm) wide magne~ic write head. The
structured film was imagewise demdgneti~ed by ex?osure
to a short burst from a Xenon lamp flashed through an
image-bearing photographic transparency. The resultant
partially demagneti~ed aluminized CrO2 film was then mounted
on a rotary drum (such as 12 of Figure 11). The magnetic
image on the CrO2-coated aluminized polyester film was
developed with toner particles 15 applied by means of
magnetic brush 16. Both the brush and the film drum were
driven at the same surface speed of 40 ft/min (12.2
meters per minute). Excess toner W2S removed from the
background of the decorated printing member by means
OL neutralizina AC corona 18 and air ~nife 19. In this
exa.mple, a preferrQd-embodimen~, the AC corona 18 -was em?loyQd
to neutrGlize the stat~c charge on the toner particLes. ThQ
pressure of the air stream sup~lied by the air knife was
adjusted to the point where only the excess toner and not
the toner decorating the magnetic image was removed. Air
supplied a a pressure of 0.4 inch tl cm) of water from
~n orifice held 0.25 inch (0.6 cm) from the suxface of the
printing member fulfilled these conditions. The toner-
decorated image on the printing member was electrostatically
transferred to polyethylene terephthalate fabric 5 hy
cha_ging ~Ihe back of the îabric with DC corona
device 20 which com~rised a corona wire spaced about
0.5 inch (1.3 c~) from the ~abric and maintained at 5,000
volts negative ~otenti21. Following transfer, the toner
particles were Cused ~o the faDric by heating at 90 to 120aC
.
- 77 -
using two banks of 500 watt infrared lamps 24 placed
approximately 1 ir.~h ~2.5 cm) from the fabric and operatins
~t 93% efficiency. ~e printed polyethylene tereph.halate
fabric was finally removed on take-up roll 28. Toner
particles remaining on .the surface of printing member 1
were removed by.vacuum brush 21 and the ~urface was
neutralized with AC corona 22 prior to redecoration.
The use of AC corona 22 represents a preferred embodiment
wherein the,corona neutrali~es the static charge on the
1~ toner particles remaining on the aurface.
A similar run, made in a similar fashion and
providing similar ~esults, was made using paper as the
substrate.
Exam~le 80
This example illustrates the preparation of a
ferromagnetic dye toner containins a red disperse dye,
a soft magnetic component and an aqueous al~ali-soluble
resin, and ~hç application there~f to pa?er.
A ferromagnetic toner was prepared by spraY-
2~
drying a mixture containins 10~ of polyvinyl acetate
copolymer resin t~lGelvall CS-VIOM), 1% of C.I. Disperse
Red 60, 3.2~ of lignLn sulfonate dispérsant and 8S.8% of
Carbonyl Iron GS-6. The!spray-dried toner was fluidized
with l~ of Quso WR-82 and used to develop the latent .
magnetic image on the surface of a continuously CrO2-coated
(220 microinches) (5.59 x 10 4 cm) aluminized "~yla-"~
polyester printing member (such as 1 depicted in Figure l)
usins a printing appa-atus sucn 25 that depicted in
Figu_e ll. ~he CrO~ s~rface of the printing member was
magnetically structured into a 500 lines per inch (197
- 78 -
.f~
lines per cm) magnetic pattern using a magnetic write head;
it was then imagewise demagnetiz2d by exposure to a short
burst from a Xenon lamp flashed t~rough an image-bearing
photographic transparency. The resultant latent magnetic
image was developed with the toner particles and the tor.er
decorated image was electrcstatically transferred to
paper al~d fused thereon as described in Example 79. A
~ell-defined, ~c~ground-free red print was obtained.
~xample 81
10 . A ferromagnetlc toner containing ~6~ of pol~yvinyl
acetate copolymer resin ("Gelva" C5-VIOM), 1~ of C.I.
Disperse ~ed 60, 3.2~ of lignin sulfonate dispersant and
59.8% of Carbonyl Iron GS-~ was similarly prepared and
applied to paper as described in Example 80 The results
were comparable to those of Example 80.
Exam~le 82
.
This example illustrates the magnetic transfer
printing of a ferromagnetic dye toner containing a blue
disperse dye, magnetic components and an aq~eous alkali-
sol~ble resin.
A ferromagnetic toner was prepared by spray-
drying a mixture containing ~S~ of polyvinyl acetate
c~polymer resin (~&elva" C5-VIOM), 2% of C.I. Disperse Blue
59 crude powder, 37~ of "Mapico~ Blac~ Iron Oxide and
36% of Carbonyl Iron GS-6. The toner, which had a particle
~ize within the range 3 to 20 microns, was used to develop
the latent magnetic image on the surface of a 197 lines
per cm, magnetically structured, CrO2-coated, alumini~ed
YMylar" polyes~er film. The toner i~age was magnetically
-' transferred from the decorated film to paper by ap~lication
- 79 -
~32~7~;
of a magnetic field o~ approximately 625 gauss averase
strength supplied by a permanent magnet (approximately
1,200 gauss) placed behind the paper. The toner particles
transferred completely from the latent magnetic imase on
the film to the paper.
Example _83
The ~oner of Example 82 was used to develop the
la~ent ~gnet~c i~age on the sur~ace of a CrO2-coated
aluminized polyester printing member (such as 1 as shown
in Figure 1) using a printing apparatus such as depictea
in ~igure 11. The tone~ decorated imase on the printing
member was magnetically transferred to paper using a 1,200
gauss permanent magnet in place of the DC corona
device 20 depicted in Figure 11. Usins a field strensth
of 540 gauss, good transfer of the ~oner particles from
the printins member to the paper was obtained.
Exam~ie 84
The toner of Example 82 was magnetically
transferred to p~er uslng a printing apparatus such as
depicted in Figure 11. In this case, however, DC corona
device 20 shown in ~igure 11 was replaced by
a meta~ pressure roll wrapped with a 0.25 inch (0.64 cm)
layer of a flexible/ permanent magnetic material,` such
as a rubDer bo~ded barium ferxite (commercially aYailable
under the trademarX "Plasti'orm"). At a surface field
stre~gth of 370 gauss, the magnetic roll pressed the paper
against the decorated image and good toner transfe~ was
obtain ed .
- 80 -
~ ~ 32
Exam~l~ 85
A ferromagn~tlc toner con~ainln~ 25~ of P~ solvent- -
~~oluble pol~amide resin ("VersP~mid" 93O~, 36~ of "~laplco" Bi~c'.
Iron Oxlde, 36$ of Caroonyl Iron GS-6 ~nd 3~ of C,I. Disperse
Red 60 crude powder ~as prepared by ball-mllllng and spray-
d~ying a 3O~ non~olatile solids mlxture of the ingredients in
5O:5O toluene-isopropanol. The spr~y-drled toner was sie~ed
through a 200 mesh screen, fluid~zed with 0.5~ of Quso WR-82
and used to develop the latent magnetic image on the surfac~ of
a 35O microlnch CrO2-coated aluminized "~Y1Pr~ polyester print-
~ng ~ember (~uch as 1 depicted in Figure l) uslng a prlntinO
apparatus such ~s that deplcted in Figure ll. The C~02 surface
o~ the printlng member was magneticPlly structured into a 333
llnes per ~nch magnetic pattern using a ma~netic ~rite hezd;
it was then ima3ewise dema~netized by exposure to a short burst
from a Xenon lamp fl_shed through an ~age-bearin~ pho~o~rP?hic
transparency, The resultant latent ma~,netic ima~e was de~eloped
with the toner particles and the toner decorated image was elec-
trostatically transferred to polyet~ylene terephthalate ~abric
and fused thereon as described in Exam?le 79O The dye was fixed
by steaming at 14 psig (96,600 Pascal) for one hour. The printed
fabric was scoured at 60C for 5 minutes in a mixture o ;0:50
isopropanol-toluene and then rinsed for 90 seconds with
i0:50 isopropanol-toluene. A red print was obtained.
Exam~le 86
-
A toluene-isopropanol ball-milled and spray-dried
ferromagnetic toner contalning 21% of Carnauba wax, 37~ of
"Mapico" Blac~ Iron Oxide, 38~ of Carbonyl Iron GS-o and 4
or C.I. Dispers~ Red 60 crude pcwder was electrostatically
~^~ transrerred to ?olyethylene t-rephthalate rabric and ~used
.- 81 -
~13~7~i
thereon as described in Example 85. The ~e wzs ~ixed b~
s~eaming at 14 psig (96,600 Pzscal) for 1 hour. The printed
fabric W2S scoured at 60C for 5 minutes in toluene and then
rinsed for 90 seconds with 50:50 isopropanol-~oluere to glve
a red print.
Exam~le 87
A ferromagnetic toner containing 30~ of a solvent-
soluble polyamide resin ("Versamid" 930~, 30~ of "Ma2ico"
Blac~ Iron Oxide, 29.6~ of Carbonyl Iron GS-6, 2~ of C.I.
Basic Red 14 and 8.4~ of inert diluent,for example-, boric
acid, was prepared by ball-milling and spray-d~ying a 30
nonvolatile solids mixture o~ the ingredients in 50:50
toluene-isopropanol. The spray-dried toner was sieved
through a 200 mesh sc~een and fluidized with 0.4~ of Quso
WR-82. The latent magnetic image on a 300 lines ~er inch
CrO2-coated aluminized "~ylar" film was manually decorzted
and the toner transferred electrostatically to polyacrylo-
nitrile fabric as described in Example l. The toner was
steam-fused and the cationic dye fixed by steàming zt
2 psig (13,800 Pascal) for 1 hour. Th~ printed fabrlc was
scoured in an aqueous bath containing 2 parts/liter or soda
caustic and 2 partq/liter Or a polyethoxylated tridecanol
surf2ctznt. After scouring for 30 minutes at 50 to 6GC,
the res~n and ferrom20netlc components were only ?2rtially
re~.oYed .rom tne prir.ted ~abric, thus illustratin~ the
in-fi'ectiveness o:' convention21 zau-ous al~aline scour-r.O
procedu-es for removinO ~olvent-soluble resin-im~re~nzted
.erro~20netic ~art'cles from the ?rlnt-d f~b--c. A scou~-
in~ solvent ~hlch is comcatible wi~h tne resin, :'or -xamp e,
31^ isopr3p2nol-toluen-, czn oe usad to ?ro~ide ~rin~s wnic;~
- 82 -
~3Z~
are signlficarvly better (in exhibltin$ the color of the
dye) than those obtained from the aqueous scour.
Ex m~te 88
_
A toluene-isoprop~nol ball-milled and spray-
dried ferrom2~netic toner containing 30~ OL "Versamid" 930,
33~ of "Mapico" Black Iron Oxide, 32.4p of "Carbonyl" Iron
GS-6, 2~ of C.I. Acld Red 151, 1~ of oxalic acid and l.o~
of inert diluent was electrostatically transferred directlv
to nylon 66 ~ersey fabric as described in Example 1. The
toner was steam-fused and the acid dye was fixed by steam-
in~ at 2 psi~ tl3,800 Pascal) for 1 hour. Scouring in
aqueous alkaline surfactant ~t 50 to 60C L ailed to com-
pletely remove the resin-imbedded ferrom2gnetic parvicles
from the printed nylon fabric. The printed fab~ic C2n bS
scoured with 50:50 isopropanol-toluene to give a r~d print.
Examples 89 to 110
Tone~ Examples 89 to 102 and 105 to 110 ~ere
prepared by ball-millin& and spray-drying a 40 to 60a~ r.Gr.-
volatile solids slurry of dye (or pi~ment), fer~omag~etlc
component(s) and solvent-soluble resin ln a 50:50 mixvure
of toluene-isopropanol. The percent nonvclatile solids
concentration and the spray-d~yin~ conditions were varied
in ord~r to produce spherical, large-size toner particles.
Toner Examples 103 and 104 were prep2red oy a ?rocess of
"he2t sphericallzation" ~herein the solvent-soluble resi
and ferromagne~lc p~rticles ~ere irst combinea -n ~ 70:30
~xture of toluene-zcetone and s?r2y-dried. The dye ~as
then added ~t 205~C âO that th- dye parti^i-~ ere embecàec
on the su-f'ace OLt the toner. The com?osi~ions of th_
3 ferroma~netic tor.ers are ~iven in Tzble VIII. The ton-rs
- 83 -
/ ~ ~
~3~
were fluidized by the addition of from 0.1 to n. 3% of
Quso WR-82.
Toner Examples 89 to 105 contain disperse dyes
and solvent-soluble resins and can be magnetically printed
on polyethylene terephthalate fabric as described in
Example 85. After scouring in a suitable organic solvent,
red, blue or yellow prints can be obtained. Carbon black
pigment toners are described in Examples 106 to 110 and can
be used to provide optically dense black prints when mag-
netically printed to a substrate such as paper or poly-
ethylene terephthalate fabric. The Darco* Carbon Black
G-60 which was used is a commercially available premium
grade of powdered activated carbon which generally is used
for decolorizing, purifying and refining and is made by the
activation of lignite with heat and steam. In these
Examples 106 to 110 it is not necessary to remove the
ferromagnetic component and the resin.
It is to be understood that each above example
does not necessarily recite all details regarding the mag-
netic printing process and/or apparatus of the invention.Any unrecited details relative to the invention can readily
be ascertained by one skilled in the art from other examples
and/or from the non-example portions of this specification.
The following experiments illustrate the need to
use a conductive printing member in order to eliminate static
charge buildup on the printing surface when using electro-
static transfer.
E periment 1
A 180 microinch ~4.6 x 10 4 cm) thick coating
of CrO2 in a resin binder was applied to the surface of a
5 mil (0.013 cm) polyester film ("Mylar"). The resultant
* denotes trade mark
-84-
~3~7~
CrO2 film had a coercivity of 567 oers~eds a~d a
resistivity of approximately 108 ohms/square. The film was
mounted an~ electrically connecteZ to a 5-inch (12.7 cm) wlde,
S-incn (12.7 cm) diameter grounded aluminum drum.The C~2 sur_zce
was revolved past a DC corona at a speed of 0.4 to 1.5 seconds
per revolution. At only 7,000 volts positive corona potential,
a surface charge was found to rapidly build up (resulting i~ a
fiel~ increase of approximately 1,000 volts per cm per revolu-
tion of the drum) on the CrO2 film. Thus, the CrO2 film
10 surface was not conductive enough to dissipate the
charge from the corona.
eriment 2
The conductivity experiment described in Experi-
ment 1 was repeated, exce?t that two AC coronas were placed
about 0.25 lnch ~0.6 cm) ~rom the film surface in order
to neutralize surface charges. At 2,000 volts negative
DC corona potential, no surlace charge buildup was detec'ed
on the CrO2 film. At 8,000 volts negative DC potential,
only a 600 volt per cm buildup was measured on the rihm surface.
Thus, the AC coronas effectively dissipated the surface
char~es below 2 ,000 volts DC potential on the corona
device but did not completely remove all the charse from the
film surface at higher potentials.
~XDerim.ent 3
.. . .. .
A 120 microinch (3 x 10 4 cm~ thic.~ layer or
CrO2 in a resin binder was applied to the surface of a t;~in
copper sheet. The CrO2-coated copper sh~et was mounted
on a grounded drum and subjected to a 3,500 volt positive
potenti~l ~rom z DC corona as described in ~xDeriment 1.
When tested ror static charse buildup usi.~ a commercially
8~
~3'~17~;
availa~le static voltmeter, th.e CrO2 surface was found
to be highly resistant to charge buildup.
Experiment 4
A 65 microinch (1.65 ~ 10 4 cm) coating of CrO2
in a resin binder was applied to the surfac~ of a 2 mil
~0.005 cm) aluminized polycster film ("Mylar"). During
the coating operation, the CrO2 was magnetically-oriented
by passing the coated film hetwcen identical poles of
two ~ar magnets havin~ an approximate field strength of
13 1 500 ~auss. Ihe coated fllm was c~iencered by hcatin~
contact wlth hot ro~;ers at 90C under high pressure. The
resultant CrO2-coated ~ilm had a coerclvity of 526 oersteds
and an orientation of 0.80. When tested for static buildup
properties zs described in Experiment 1, the CrO2-coated
aluminlzed film W2S found to be highly resistant to char~e
buildup when electric211y connected to the grounded drum.
Ex~eriment 5
-
A 5-inch (12.1 cm) wide by 5-inch (12.7 c~) dia-
meter copper sleeve W2S directly coated with a 200 micro-
inch (5 x lQ-4 cm) layer of CrO2 in a resin binder. The
sleeve wa~ dip coated from a slurry OL- CrO2 and resin in
tetranydro~uran-cyclohexano~e (25:75 by wei~ht) and the
solvenks were slowly removed by evaporation. A pair of
perm2nent magnets t~as used to orient tne GrC2 as described
in Ex~er'.~ent 4. The CrO2 sur~ace sho~ed little tendency
to sustain 2 st~tic charOe when electrically connected to
the ~rounded drum.
The coppe~ sleev- can also be chemic211y etchec
into a 250 to 350 lines per inch (98 to 138 lines ~er c~.)
~rooved p2ttern and the ~rooves L 111ed wi~h th- CrG2 ~r.i
r~sln binder. This would provide a h2rd~ conductive,
per..anently structurec .~.agne lc p.~n~in~ su~f~ce.
- 8~ -
~3Zl~
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t~ P~ P~ ~ r.~ t.l rL~ t.~ r~l rL~ t~l t~ t~ t~ r~ t.~ , t~l
~: ~ r4 ~ ~4 P~ P~P~ P~ P~ a P~ P~ P~ P~ ,z; Z
CJ rl. r4 t~
t~ ~ ~I t~ P- P~ ~4 P~ C4 ~4 P. ~4 P~ t4 ~4 P~ P4 t4 P4 P~
t~ ~ t ~ 1 p F~ Q F~ A ~ t~ ~ Q
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