Toner processes

A process for the preparation of toner comprised of i) flushing pigment into a sulfonated polyester resin, and which resin has a degree of sulfonation of from between about 0.5 and about 2.5 mol percent based on the repeat unit of the polymer; ii) dispersing the resulting pigmented sulfonated polyester resin in warm water, which water is at a temperature of from about 40.degree. to about 95.degree. C., and which dispersing is accomplished by a high speed shearing polytron device operating at speeds of from about 100 to about 5,000 revolutions per minute thereby enabling the formation of toner sized particles, and which particles are of a volume average diameter of from about 3 to about 10 microns with a narrow GSD; iii) recovering said toner by filtration; iv) drying said toner by vacuum; and v) optionally adding to said dry toner charge additives and flow aids.

PENDING APPLICATIONS 
Illustrated in copending patent application U.S. Ser. No. 663,420 pending, 
filed concurrently herewith, the disclosure of which is totally 
incorporated herein by reference, is a process for the preparation of 
toner compositions comprised of 
i) flushing pigment into a sulfonated polyester resin and which resin has a 
degree of sulfonation of from between about 2.5 and about 20 mol percent 
based on the repeat unit of the polymer; 
ii) dispersing the resulting pigmented sulfonated polyester resin in warm 
water, which water is at a temperature of from about 40.degree. to about 
95.degree. C., and which dispersing is accomplished by a high speed 
shearing polytron device operating at speeds of from about 100 to about 
5,000 revolutions per minute thereby enabling the formation of toner sized 
particles, and which particles are of a volume average diameter of from 
about 3 to about 10 microns with a narrow GSD; adding an alkali halide 
solution 
iii) recovering said toner particles by filtration; 
iv) drying said toner particles by vacuum; and 
v) optionally adding to said dry toner particles charge additives and flow 
aids. 
Illustrated in copending patent application U.S. Ser. No. 664,597 pending, 
filed concurrently herewith, the disclosure of which is totally 
incorporated herein by reference, is a process for the preparation of inks 
comprised of 
i) flushing pigment into a sulfonated polyester resin and which resin 
possesses a degree of sulfonation of from between about 2.5 and about 20 
mol percent; 
ii) dispersing the pigmented polyester resin in water at a temperature of 
from about 40.degree. C. to about 95.degree. C. by a polytron shearing 
device operating at speeds of from about 100 to about 5,000 revolutions to 
yield stable pigmented submicron sized particles of from about 5 to about 
150 nanometers; and thereafter separating said submicron particles and 
mixing said submicron particles with water. 
BACKGROUND OF THE INVENTION 
The present invention is generally directed to toner processes, and more 
specifically, to aggregation and coalescence processes for the preparation 
of toner resins, especially polyesters, and toner compositions thereof. In 
embodiments, the present invention is directed to the economical in situ, 
chemical or direct preparation of toners and toner resins without the 
utilization of the known pulverization and/or classification methods, and 
wherein in embodiments toner compositions with an average volume diameter 
of from about 1 to about 25, and preferably from 1 to about 10 microns, 
and narrow GSD of, for example, from about 1.16 to about 1.26, or from 
about 1.18 to about 1.28 as measured on the Coulter Counter can be 
obtained, and wherein flushed pigments are selected thus enabling toners 
with low melting characteristics and which toners contain certain 
polyester resins. With flushed pigments, there is enabled a superior 
uniform dispersion of the pigment within the low melt resin, permitting 
optimum pigment/polymer loading and improved toner quality. Embodiments of 
the present invention relate to a process for the preparation of dry toner 
compositions comprised of resin and pigment, and which process comprises 
flushing a pigment into a sulfonated polyester resin, referred to as a 
flushed pigmented system, followed by dissipating the flushed pigmented 
system in water to obtain pigmented particles. The degree of sulfonation 
during the preparation of the sulfonated polyester resin is a primary 
factor in determining the size of the toner particles obtained during the 
dissipating step. The process of the present invention relates to the 
preparation of toner particles by (i) dissipation of a flushed pigmented 
sulfonated polyester in warm water (&gt;60.degree. C.) to obtain submicron 
pigmented sulfonated polyester particles which are in the range of 50 to 
200 nanometers in size; followed by heating the resulting mixture below 
about the glass transition temperature of the sulfonated polyester. In 
embodiments, there can be added to the mixture resulting a metal salt 
halide, such as magnesium halide and preferably an aqueous magnesium 
chloride solution wherein the concentration of the solution is in the 
range of from about 0.5 to about 5 weight percent; or optionally adding 
the magnesium chloride solution during the heating from room temperature 
to a temperature below the resin Tg (chemical toner); or (ii) preparing 
pigmented toner size particles directly from the flushed pigment system 
upon dissipating in water where the particles obtained are in the size 
range of from about 3 to about 7 microns in volume average diameter. The 
resulting toners can be selected for known electrophotographic imaging 
methods, printing processes, including color processes, and lithography 
(direct toner). More specifically, with the processes of the present 
invention, the use of surfactants can be avoided, for example nonionic 
surfactant is not needed to disperse the pigment selected, cationic 
surfactant is not needed to perform the aggregation, and the anionic 
surfactant selected to stabilize the aggregated particles when heated to 
20.degree. to 40.degree. C. above the resin Tg during the coalescence, 
reference for example U.S. Pat. No. 5,403,693, the disclosure of which is 
totally incorporated herein by reference, followed by washing to remove 
surfactants is eliminated (chemical toner). The process of the present 
invention enables the utilization of polymers obtained by polycondensation 
reactions, such as polyesters, and more specifically, the sulfonated 
polyesters as illustrated in U.S. Pat. No. 5,348,832, and copending 
application U.S. Ser. No. 595,143, now U.S. Pat. No. 5,604,076 the 
disclosures of which are totally incorporated herein by reference, and 
which polyesters can be selected for low melting toner. With the processes 
of the present invention, there are generated flushed pigmented polyesters 
wherein the polyester has a varying degree of sulfonation which upon 
dissipation in warm water results in particles of (i) about 3 to about 7 
microns in size (direct toner), and (ii) submicron pigmented particles of 
from about 50 to about 200 nanometers in size, which particles are then 
aggregated to toner size, about 3 to about 7 microns, wherein the charging 
and fusing of the toners containing these polyesters is not substantially 
adversely affected by residual surfactants (chemical toner). 
There is illustrated in U.S. Pat. No. 4,996,127, the disclosure of which is 
totally incorporated herein by reference, a toner of associated particles 
of secondary particles comprising primary particles of a polymer having 
acidic or basic polar groups and a coloring agent. The polymers selected 
for the toners of the '127 patent can be prepared by an emulsion 
polymerization method, see for example columns 4 and 5 of this patent. In 
column 7 of this '127 patent, it is indicated that the toner can be 
prepared by mixing the required amount of coloring agent and optional 
charge additive with an emulsion of the polymer having an acidic or basic 
polar group obtained by emulsion polymerization. Also, see column 9, lines 
50 to 55, wherein a polar monomer, such as acrylic acid, in the emulsion 
resin is necessary, and toner preparation is not obtained without the use, 
for example, of the acrylic acid polar group, see Comparative Example I. 
In U.S. Pat. No. 4,983,488, the disclosure of which is totally 
incorporated herein by reference, there is disclosed a process for the 
preparation of toners by the polymerization of a polymerizable monomer 
dispersed by emulsification in the presence of a colorant and/or a 
magnetic powder to prepare a principal resin component, and then effecting 
coagulation of the resulting polymerization liquid in such a manner that 
the particles in the liquid after coagulation have diameters suitable for 
a toner. It is indicated in column 9 of this patent that coagulated 
particles of 1 to 100, and particularly 3 to 70, are obtained. Other prior 
art may include U.S. Pat. Nos. 3,674,736; 4,137,188 and 5,066,560. 
Emulsion/aggregation processes for the preparation of toners are 
illustrated in a number of patents, the disclosures of which are totally 
incorporated herein by reference, such as U.S. Pat. Nos. 5,290,654, 
5,278,020, 5,308,734, 5,346,797, 5,370,963, 5,344,738, 5,403,693, 
5,418,108, 5,364,729, and 5,346,797. 
SUMMARY OF THE INVENTION 
It is an object of the present invention to provide dry toner compositions 
comprised of a sulfonated polyester resin and flushing a pigment into the 
resin, which is then dissipated in warm water (&gt;60.degree. C.), resulting 
in (i) direct preparation of toner size particles; or to provide (ii) 
submicron pigmented size particles which are then aggregated and coalesced 
by the addition of alkali halides (chemical toner) and processes thereof 
with many of the advantages illustrated herein. 
In another object of the present invention, there are provided simple and 
economical chemical processes for the direct preparation of black and 
colored toner compositions with, for example, excellent pigment dispersion 
and narrow GSD, and wherein a pigment is flushed into a sulfonated 
polyester resin, resulting in a uniform distribution of the pigment into 
the sulfonated polyester, which upon dissipation in warm water (40.degree. 
C. to 60.degree. C.) and stirring at speeds of 100 to 5,000 rpm, resulting 
in either pigmented toner size particles or submicron pigmented particles. 
The degree of sulfonation during the synthesis of the polyester resin 
determines the particle size obtained upon dissipation. Flushed sulfonated 
polyester pigmented resin refers to a flushed pigmented system, and can 
readily be obtained in pressed cakes from Sun Chemicals. Typically, a 
flushed pigmented system is prepared as follows. First, a presscake of a 
pigment is generated from an aqueous pigment dispersion by removing water 
using techniques, such as filtration, to the extent that a presscake of 
pigment in water is obtained containing 50 to about 70 percent of the 
pigment solids by weight. Approximately 50 percent of the presscake is 
then introduced into a reactor containing molten sulfonated polyester 
resin, accompanied by a high power to volume mixing for a period of of 15 
to 30 minutes, whereby the pigment transfers itself spontaneously from the 
aqueous phase to the organic phase. As the pigment begins to disperse, the 
remaining 50 percent of pigment presscake is slowly added over a period of 
an additional 60 to 90 minutes. Alternatively, about 50 percent of the 
presscake is introduced into a reactor containing a sulfonated 
resin/solvent (such as toluene, xylene, THF, and the like) solution, 
accompanied by a high power to volume mixing for a period of 15 to 30 
minutes, whereby the pigment transfers itself spontaneously from the 
aqueous phase to the organic phase. As the pigment begins to disperse, the 
remaining 50 percent of pigment presscake is slowly added over a period of 
an additional 60 to 90 minutes. The water molecules separating the primary 
pigment particles and soft agglomerates in the presscake are displaced by 
or flushed out by the resin chains, ensuring that an excellent dispersion 
quality of the pigment is maintained. In embodiments the pigmented 
polyester resin obtained with the processes of the present invention can 
easily be dispersed in warm, about 40.degree. C. to about 100.degree. C., 
water. The polyester flushed pigment mixture can be obtained from Sun 
Chemicals. 
In another object of the present invention, there are provided simple and 
economical chemical processes for the direct preparation of black and 
colored toner compositions with, for example, excellent pigment dispersion 
and narrow GSD, and wherein flushed pigments, especially flushed pigment 
pressed cakes obtained from Sun Chemicals, are selected, or wherein the 
pigmented resin is dissipated in hot, about 40.degree. C. to 60.degree. 
C., water. 
Another object of the present invention provides a simple and a direct 
direct process for the preparation of toner size particles in the range of 
3 to 7 microns with a narrow GSD in the range of 1.18 to 1.26, wherein the 
toner particles are comprised of a pigment and sulfonated polyester resin. 
The direct preparation of pigmented toner particles involves synthesizing 
a sulfonated polyester resin having a degree of sulfonation in the range 
of about 0.5 to about 2.5 mol percent, followed by obtaining a flushed 
pigmented system as indicated. The flushed system obtained is then 
dissipated into warm water at a temperature in the range of about 
40.degree. C. about 95.degree. C., depending on the resin Tg, by stirring 
at speed of 100 to 5,000 rpm for a period of 1 to 20 minutes, resulting 
directly in toner size particles in the range of 3 to 10 microns (direct 
toner). 
Another object of the present invention resides in providing a method for 
the preparation of submicron pigmented particles in the range of 50 to 200 
nanometers in size, which are then aggregated and coalesced in the 
presence of aqueous magnesium chloride solution. The preparation of 
pigmented toner particles in the range of 3 to 10 microns comprises (i) 
synthesizing a sulfonated polyester resin having a degree of sulfonation 
in the range of 2.5 to 20 mol percent; (ii) followed by obtaining a 
flushed pigmented system; (iii) thereafter dissipating the flushed 
pigmented system into warm water, which water is at a temperature in the 
range of about 40.degree. C. to about 95.degree. C., depending on the 
resin Tg, by stirring at speed of 100 to 5,000 rpm for a period of 1 to 20 
minutes, resulting in submicron pigmented size particles in the range of 
50 to 200 nanometers; (iv) optionally adding an aqueous magnesium chloride 
solution, the concentration of which is in the range of 0.5 to 5 percent 
by weight of water, to the submicron particles during heating up to a 
temperature of from about 3.degree. C. to about 10.degree. C. below the 
resin Tg, or adding the magnesium chloride solution upon reaching a 
temperature of from about 3.degree. C. to about 10.degree. C. below the 
resin Tg to induce aggregation over a period of from about 30 to about 90 
minutes; and (v) washing and drying the resulting toners. These toners 
possess excellent pigment dispersion, high gloss, and low melt 
characteristics. 
The chemical toner process of aggregation can be kinetically controlled in 
that an increase in temperature at which the aggregation/coalescence is 
executed leads to, or results in larger particle size. Since no extra 
stabilizer is utilized between the aggregation and coalescence step then 
the temperature control as well as the rate of the addition of the 
magnesium chloride solution needs to be monitored precisely (chemical 
toner). 
Another object of the present invention resides in the preparation of 3 to 
7 micron pigmented toner particles by directly dissipating the flushed 
pigmented sulfonated polyester system in warm water of temperatures of 
60.degree. C. (direct toner). Moreover, depending on the degree of 
sulfonation, submicron pigmented sulfonated polyester particles can be 
formed wherein the submicron pigmented particles act as anionically 
charged particles, which are then aggregated and coalesced with the 
addition of an alkali halide. These submicron pigmented sulfonated 
polyesters are obtained by utilizing a flushed pigmented system, which can 
be obtained from a number of sources, such as Sun Chemicals. The flushed 
pigmented system can also be obtained from a molten flushing process. For 
this process, examples of the alkali halides that may be selected include 
berylium chloride, berylium bromide, berylium iodide, magnesium chloride, 
magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, 
calcium iodide, strontium chloride, strontium bromide, strontium iodide, 
barium chloride, barium bromide, and barium iodide (chemical process). 
Another object of the present invention resides in 
emulsion/aggregation/coalescence processes for the chemical preparation of 
toners wherein the use of surfactants are avoided and wherein flushed 
pigments are selected, and which flushing pigments can be obtained from a 
number of sources, such as Sun Chemicals, or wherein the flushing pigments 
can be prepared by displacing the water in the pigment presscake with 
either molten sulfonated polyester or a sulfonated polyester/solvent 
mixture, removing excess water by vacuum drying, dispersing the toner 
pigment in warm (&gt;60.degree. C.) water with a polytron, and wherein the 
pigment loading can be varied to be 45 to 50 weight percent, and wherein 
the pigmented particles are submicron in size, for example from about 30 
to about 150 nanometers (chemical toner). 
In a further object of the present invention there is provided a process 
for the preparation of toner compositions with an average particle volume 
diameter of from between about 1 to about 20 microns, and preferably from 
about 1 to about 7 microns, and with a narrow GSD of from about 1.2 to 
about 1.3 and preferably from about 1.16 to about 1.25 as measured by a 
Coulter Counter. 
In a further object of the present invention there is provided a process 
for the preparation of toners with particle size distribution which can be 
improved from 1.4 to about 1.16 as measured by the Coulter Counter by 
increasing the temperature of aggregation from about 25.degree. C. to 
about 45.degree. C. (chemical toner). 
Moreover, in a further object of the present invention there is provided a 
process for the preparation of toner compositions which after fixing to 
paper substrates results in images with a gloss of from 20 GGU (Gardner 
Gloss Units) up to 70 GGU as measured by Gardner Gloss meter matching of 
toner and paper. 
In another object of the present invention there is provided a composite 
toner of sulfonated polymeric resin with pigment and optional charge 
control agent in high yields of from about 90 percent to about 100 percent 
by weight of toner without resorting to classification. 
In yet another object of the present invention there are provided toner 
compositions with low fusing temperatures of from about 110.degree. C. to 
about 150.degree. C. and with excellent blocking characteristics at from 
about 50.degree. C. to about 60.degree. C. 
Moreover, in another object of the present invention there are provided 
toner compositions with a high projection efficiency, such as from about 
75 to about 95 percent efficiency as measured by the Match Scan II 
spectrophotometer available from Milton-Roy. 
In a further object of the present invention there are provided toner 
compositions which result in minimal, low or no paper curl. 
These and other objects of the present invention are accomplished in 
embodiments by the provision of toners and processes thereof. In 
embodiments of the present invention, there are provided processes for the 
economical preparation of toner compositions comprising a sulfonated 
polyester flushed with a pigment, and which product is then dispersed into 
warm water to either (i) obtain the desired toner size particles directly, 
(ii) obtain submicron pigmented particles, which are then aggregated to 
toner size by adding an alkali halide, such as magnesium chloride, while 
heating to a temperature in the range of about 3.degree. to about 
10.degree. C. below the resin Tg; or heating the submicron particles to a 
temperature in the range of 3.degree. C. to 10.degree. C. below the resin 
Tg while stirring, followed by the addition of the magnesium chloride 
solution to enhance the aggregation; followed by further heating for a 
period of 30 to 90 minutes to enable coalescence of the submicron 
pigmented particles, and thereafter washing with, for example, water to 
remove any residual salts, and then drying. 
Embodiments of the present invention include a process for the preparation 
of toner particles comprised of resin and pigment, and which process 
comprises 
i) flushing a pigment into a sulfonated polyester, and thereafter adding 
the product resulting to warm water, which water is at a temperature of 
from about 40.degree. C. to about 95.degree. C.; a process for the 
preparation of toner compositions comprised of flushing pigment into a 
sulfonated polyester resin, and which resin has a degree of sulfonation of 
from between about 0.5 and about 2.5 mol percent based on the repeat unit 
of the polymer; 
ii) dispersing the resulting pigmented sulfonated polyester resin in warm 
water, which water is at a temperature of from about 40.degree. C. to 
about 95.degree. C., and which dispersing is accomplished by a high speed 
shearing polytron device operating at speeds of from about 100 to about 
5,000 revolutions per minute thereby enabling the formation of toner sized 
particles, and which particles are of a volume average diameter of from 
about 3 to about 10 microns with a narrow GSD; 
iii) optionally recovering said toner composition, or said toner particles 
by filtration; 
iv) drying said toner particles by vacuum; and 
v) adding to said dry toner particles charge additives and flow aids; a 
process for the preparation of toner compositions comprised of 
i) flushing pigment into a sulfonated polyester resin, and which resin has 
a degree of sulfonation of from between about 0.5 and 2.5 mol percent 
based on the repeat unit, or segment of the polymer; 
ii) dispersing the resulting pigmented sulfonated polyester resin in warm 
water, which water is at a temperature of from about 40.degree. to about 
95.degree. C., and which dispersing is accomplished with a high speed 
shearing device; and 
iii) optionally recovering said toner particles by filtration; 
iv) drying said toner particles by vacuum (chemical toner); a process for 
the preparation of toner compositions comprised of 
i) flushing a pigment into a sulfonated polyester resin, and which resin 
has a degree of sulfonation of from between about 2.5 and 20 mol percent 
based on the repeat unit of the polymer; 
ii) dispersing the resulting sulfonated pigmented polyester resin into warm 
water, which water is at a temperature of from about 40.degree. C. to 
about 95.degree. C., by a high speed shearing polytron device operating at 
speeds of from about 100 to about 5,000 revolutions per minute thereby 
enabling the formation of stable toner sized submicron particles, and 
which particles are of a volume average diameter of from about 5 to about 
150 nanometers; 
iii) allowing the resulting solution to cool to from about 5.degree. C. to 
about 10.degree. C. below the glass transition temperature of said 
pigmented sulfonated polyester resin; 
iv) adding an alkali halide solution, which solution contains from about 
0.5 percent to about 5 percent by weight of water, followed by stirring 
and heating from room temperature to a temperature below the resin Tg to 
induce aggregation of said submicron pigmented particles to obtain toner 
size particles of from about 3 to about 10 microns in volume average 
diameter and with a narrow GSD; or subsequently stirring and heating to a 
temperature below the resin Tg, followed by the addition of alkali metal 
halide until the desired toner size of from about 3 to about 10 microns in 
volume average diameter and with a narrow GSD is achieved; and 
v) recovering said toner by filtration and washing with cold water, drying 
said toner particles by vacuum, and thereafter optionally blending charge 
additives and flow additives; and a process for the preparation of toner 
compositions comprised of 
i) flushing a pigment into a sulfonated polyester resin; 
ii) dispersing the resulting sulfonated pigmented polyester resin into warm 
water, which water is at a temperature of from about 40.degree. C. to 
about 95.degree. C., by a high speed shearing device operating at speeds 
of from about 100 to about 5,000 revolutions per minute thereby enabling 
the formation of stable toner sized submicron particles, and which 
particles are of a volume average diameter of from about 5 to about 150 
nanometers; 
iii) permitting the resulting solution to cool to from about 5.degree. C. 
to about 10.degree. C. below the glass transition temperature of said 
pigmented sulfonated polyester resin; and 
iv) adding a alkali halide solution, which solution contains from about 0.5 
percent to about 5 percent by weight of water, followed by stirring and 
heating from room temperature to a temperature below the resin Tg to 
induce aggregation of said submicron pigmented particles to obtain toner 
size particles of from about 3 to about 10 microns in volume average 
diameter and with a narrow GSD; followed by the addition of alkali metal 
halide until the desired toner size of from about 3 to about 10 microns in 
volume average diameter is achieved; and optionally recovering said toner 
by filtration and washing with cold water, drying said toner by vacuum. 
Various known colorants or pigments together with the polyester resin 
obtained and present in the toner in an effective amount of, for example, 
from about 1 to about 65, and preferably from about 2 to about 35 percent 
by weight of the toner, and preferably in an amount of from about 1 to 
about 15 weight percent, include carbon black like REGAL 330.RTM.; 
magnetites, such as Mobay magnetites MO8029.TM., MO8060.TM., and the like. 
As colored pigments, there can be selected known cyan, magenta, yellow, 
red, green, brown, blue or mixtures thereof. Specific examples of pigments 
include phthalocyanine HELIOGEN BLUE L6900.TM., D6840.TM., D7080.TM., 
D7020.TM., cyan 15:3, magenta Red 81:3, Yellow 17, the pigments of U.S. 
Pat. No. 5,556,727, the disclosure of which is totally incorporated herein 
by reference, and the like. Examples of specific magenta materials that 
may be selected as pigments include, for example, 2,9-dimethyl-substituted 
quinacridone and anthraquinone dye identified in the Color Index as CI 
60710, CI Dispersed Red 15, diazo dye identified in the Color Index as CI 
26050, CI Solvent Red 19, and the like. Illustrative examples of specific 
cyan materials that may be used as pigments include copper tetra(octadecyl 
sulfonamido) phthalocyanine, x-copper phthalocyanine pigment listed in the 
Color Index as CI 74160, CI Pigment Blue, and Anthrathrene Blue, 
identified in the Color Index as CI 69810, Special Blue X-2137, and the 
like; while illustrative specific examples of yellow pigments that may be 
selected are diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a 
monoazo pigment identified in the Color Index as CI 12700, CI Solvent 
Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index 
as Foron Yellow SE/GLN, CI Dispersed Yellow 33 
2,5-dimethoxy-4-sulfonanilide phenylazo-4'-chloro-2,5-dimethoxy 
acetoacetanilide, and Permanent Yellow FGL. Colored magnetites, such as 
mixtures of MAPICO BLACK.TM., and cyan components may also be selected as 
pigments with the process of the present invention. All the pigments 
selected are flushed pigments as indicated herein and not dry pigments. 
More specifically, pigment examples include Pigment Blue 15:3 having a 
Color Index Constitution Number of 74160, magenta pigment Pigment Red 81:3 
having a Color Index Constitution Number of 45160:3, and Yellow 17 having 
a Color Index Constitution Number of 21105. 
The toner may also include known charge additives in effective amounts of, 
for example, from 0.1 to 5 weight percent such as alkyl pyridinium 
halides, bisulfates, and the charge control additives of U.S. Pat. Nos. 
3,944,493; 4,007,293; 4,079,014; 4,394,430 and 4,560,635, which 
illustrates a toner with a distearyl dimethyl ammonium methyl sulfate 
charge additive, the disclosures of which are totally incorporated herein 
by reference, negative charge enhancing additives like aluminum complexes, 
and the like. 
Surface additives that can be added to the toner compositions after washing 
or drying include, for example, metal salts, metal salts of fatty acids, 
colloidal silicas, fumed silicas, mixtures thereof, and the like, which 
additives are usually each present in an amount of from about 0.1 to about 
2 weight percent, reference U.S. Pat. Nos. 3,590,000; 3,720,617; 3,655,374 
and 3,983,045, the disclosures of which are totally incorporated herein by 
reference. Preferred additives include zinc stearate and flow aids, such 
as fumed silicas, like AEROSIL R972.RTM. available from Degussa in amounts 
of from 0.1 to 2 percent which can be added during the aggregation process 
or blended into the formed toner product. 
Developer compositions can be prepared by mixing the toners obtained with 
the processes of the present invention with known carrier particles, 
including coated carriers, such as steel, ferrites, and the like, 
reference U.S. Pat. Nos. 4,937,166 and 4,935,326, the disclosures of which 
are totally incorporated herein by reference, for example from about 2 
percent toner concentration to about 8 percent toner concentration. 
Imaging methods are also envisioned with the toners of the present 
invention, reference for example a number of the patents mentioned herein, 
and U.S. Pat. No. 4,265,660, the disclosure of which is totally 
incorporated herein by reference.

The following Examples are being submitted to further define various 
species of the present invention. These Examples are intended to be 
illustrative only and are not intended to limit the scope of the present 
invention. Also, parts and percentages are by weight unless otherwise 
indicated. 
EXPERIMENTAL 
Preparation of Sulfonated Polyesters 
Preparation of Linear Low Sulfonated Polyester A: 
A linear low sulfonated random copolyester resin containing on a mol 
percent basis of the polyester polymer repeat unit of approximately 0.475 
of terephthalate, 0.025 of sodium sulfoisophthalate, 0.475 of 
1,2-propanediol, and 0.025 of diethylene glycol is prepared as follows. In 
a one liter Parr reactor equipped with a bottom drain valve, double 
turbine agitator, and distillation receiver with a cold water condenser 
were charged 388 grams of dimethylterephthalate, 31.23 grams of sodium 
dimethylsulfoisophthalate, 304.43 grams of 1,2-propanediol (1 mole excess 
of glycols), 22.30 grams of diethylene glycol, (1 mole excess of glycols), 
and 0.8 gram of butyltin hydroxide oxide as the catalyst. The reactor was 
then heated to 165.degree. C. with stirring for 3 hours whereby 115 grams 
of distillate were collected in the distillation receiver, and which 
distillate was comprised of about 98 percent by volume of methanol and 2 
percent by volume of 1,2-propanediol as measured by the ABBE refractometer 
available from American Optical Corporation. The mixture was then heated 
to 190.degree. C. over a one hour period, after which the pressure was 
slowly reduced from atmospheric pressure to about 260 Torr over a one hour 
period, and then reduced to 5 Torr over a two hour period with the 
collection of approximately 122 grams of distillate in the distillation 
receiver comprised of approximately 97 percent by volume of 
1,2-propanediol and 3 percent by volume of methanol as measured by the 
ABBE refractometer. The pressure was then further reduced to about 1 Torr 
over a 30 minute period whereby an additional 16 grams of 1,2-propanediol 
were collected. The reactor was then purged with nitrogen to atmospheric 
pressure, and the polymer discharged through the bottom drain onto a 
container cooled with dry ice to yield 460 grams of 2.5 mol percent 
(percent sulfonated)sulfonated-polyester resin, 
copoly(1,2-propylene-diethylene)terephthalate-copoly(sodium 
sulfoisophthalate dicarboxylate). The 2.5 mol percent sulfonated-polyester 
resin glass transition temperature was measured to be 53.7.degree. C. 
(onset) utilizing the 910 Differential Scanning Calorimeter available from 
E. I. DuPont operating at a heating rate of 10.degree. C. per minute. The 
number average molecular weight was measured to be 1,570 grams per mole, 
and the weight average molecular weight was measured to be 3180 grams per 
mole using tetrahydrofuran as the solvent. This resin was used to prepare 
toner particles in Example IA and IB. 
Preparation of Flushed Pigmented Sulfonated Polyesters 
Molten Flushed Process: 
To a sample (200 grams) of the molten polyester A (&gt;150.degree. C.) in an 
explosion proof stainless steel batch mixer equipped with a high power to 
volume ratio sigma blade was rapidly added 50 percent of a Sun Fast cyan 
15:3 wet presscake, available from Sun Chemicals, which was comprised of 
50 to 70 percent pigment solids by weight. Initial mixing was continued 
for 15 minutes, after which the remaining 50 percent of the presscake was 
slowly added to the reaction mixture over a 2 hour period. The reactor was 
then allowed to cool to 50.degree. C. The water at the top of the reactor 
was decanted and the remaining water removed by vacuum drying. Pigmented 
polyester A was heated to 175.degree. C. and then discharged. The 
resulting composition of the dry toner resin prepared by this process was 
85 percent of sulfonated polyester A and 15 percent of the flushed cyan 
pigment 15:3. 
Solvent Flushed Process: 
To a room temperature, about 25.degree. C., THF solution of the polyester A 
(200 grams of resin in 200 milliliters of THF) in an explosion proof 
stainless steel batch mixer equipped with a high power to volume ratio 
sigma blade was rapidly added 50 percent of a Sun Fast cyan wet presscake, 
available from Sun Chemicals. Initial mixing was continued for 15 minutes, 
after which the remaining 50 percent of the presscake was slowly added to 
the reaction mixture over a 2 hour period. The reactor was then allowed to 
cool to 50.degree. C. The water at the top of the reactor was decanted and 
the remaining water removed by vacuum drying. The product resulting was 
heated to 175.degree. C. and then discharged. The composition of the 
resulting dry toner resin prepared by this process was 85 percent of 
sulfonated polyester A and 15 percent of the flushed cyan pigment. 
Preparation of Toner 
Example IA 
Using a Molten Flushed Pigmented Sulfonated Polyester: 
A 200 gram sample of the pigmented linear sulfonated polyester A with a low 
sulfonation (2.5 mol percent) prepared by the molten flushing process 
illustrated herein was dissipated within 20 minutes by the addition of 
pigmented polyester A with stirring in 500 milliliters of hot water 
(75.degree. C.). Stable toner sized particles (4 microns) with an 
acceptable GSD (1.25) comprised of 8.5 parts by weight of sulfonated 
polyester and 1.5 parts of cyan, 15:3 flushed pigment by weight, were 
obtained. The toner particles were recovered by first filtering and then 
vacuum drying the sample. Toners obtained by this process exhibit a fusing 
performance which was comparable to toners obtained by conventional melt 
mixing processes. 
Example IB 
Using a Solvent Flushed Pigmented Sulfonated Polyester: 
A 200 gram sample of the pigmented linear sulfonated polyester A with a 
degree of sulfonation of 2.5 mol percent prepared by the solvent flushing 
process illustrated herein was dissipated readily within 20 minutes by the 
addition of the pigmented polyester A material, with stirring, to 500 
milliliters of hot water (75.degree. C.). Stable toner sized particles (5 
microns) with an acceptable GSD (1.25) comprised of 8.5 parts by weight of 
sulfonated polyester and 1.5 parts of cyan flushed pigment were obtained. 
The toner particles were recovered by first filtering and then vacuum 
drying the sample. Toners obtained by this process exhibited a fusing 
performance which was comparable to toners obtained by conventional 
process. 
Other modifications of the present invention may occur to those skilled in 
the art subsequent to a review of the present application and these 
modifications, including equivalents thereof, are intended to be included 
within the scope of the present invention.