Toner compositions

A toner composition comprised of pigment, and a sulfonated polyester of the formula or as essentially represented by the formula ##STR1## wherein M is an ion independently selected from the group consisting of hydrogen, ammonium, an alkali metal ion, an alkaline earth metal ion and a metal ion; R is independently selected from the group consisting of aryl and alkyl; R' is independently selected from the group consisting of alkyl and oxyalkylene; and wherein n and o represent random segments; and wherein the sum of n and o are equal to 100 mole percent.

BACKGROUND OF THE INVENTION 
This invention is generally directed to toner and developer compositions, 
and more specifically, the present invention is directed to developer and 
toner compositions containing a novel sulfonated polyester resin, and 
process for the preparation thereof. In embodiments, there are provided in 
accordance with the present invention, toner compositions comprised of 
certain sulfonated polyester resin particles and pigment particles 
comprised of, for example, carbon black, cyan, magenta, or yellow, thereby 
providing for the development and generation of black and/or colored 
images. In embodiments, there are provided in accordance with the present 
invention processes for the preparation of toner and developer 
compositions, and more specifically emulsion aggregation toner processes. 
In embodiments, the present invention relates to processes which comprise 
the preparation of a sulfonated polyester resin represented by the formula 
##STR2## 
derived from at least one dicarboxylic acid or diester component, at 
least one diol component, and at least 0.5 mole percent to about 8 mole 
percent of a sulfonated difunctional monomer, and wherein M is an ion such 
as hydrogen, ammonium, lithium, sodium, potassium, an alkali earth or a 
metal ion; R and R' are as illustrated herein such as alkyl, aryl, 
oxyalkylene and the sum of o+n equals 100 percent, and o is preferably 
from about 0.5 to about 8 mole percent. In another embodiment, the present 
invention relates to an in situ process for the preparation of toner 
compositions which comprises homogenizing a polymer, especially a 
sulfonated polyester resin utilizing a Gaulin homogenizer, available from 
APV Gaulin Incorporated, containing an aqueous solution containing an 
ionic and nonionic surfactant at a temperature of from about 120.degree. 
C. to about 170.degree. C., subsequently homogenizing the mixture and 
generating suspended particles of about 0.05 micron to about 2 microns in 
volume diameter; aggregating the resulting microsuspension with a mixture 
of cationic surfactant, pigment and optional charge enhancing additives in 
an aqueous solution; followed by coalescence of the aggregates by heating 
thereby providing toner particles with an average particle volume diameter 
of from between about 3 to about 21 microns. The present invention is thus 
directed to a toner composition comprised of a sulfonated polyester and 
the economical preparation of toners without the utilization of the known 
pulverization and/or classification methods, and wherein toners with an 
average volume diameter of from about 3 to about 21 microns can be 
obtained. The resulting toners can be selected for known 
electrophotographic imaging and printing processes, including color 
processes, and lithography. In embodiments, the present invention is 
directed to a process comprised of homogenizing a molten resin, preferably 
a sulfonated polyester resin, exhibiting a melt viscosity of from about 10 
poise to about 10,000 poise in a sealed vessel heated of from about 
120.degree. to about 170.degree. C. containing an aqueous solution 
comprised of at least two surfactants, wherein one surfactant is nonionic 
and the other is ionic, thereby generating suspended resin particles from 
about 0.05 micron to about 2 microns in volume diameter, followed by 
cooling the mixture to below the glass transition temperature of the resin 
of from about 45.degree. to about 65.degree. C., and subsequently 
aggregating the aforementioned suspended particles with an aqueous mixture 
of pigment, counterionic surfactant and optionally charge control 
additives to generate toner aggregates with an average particle volume 
diameter of from about 3 to about 21 microns, followed by heating the 
toner aggregates above the glass transition temperature causing 
coalescence of the toner aggregates to toner composites with an average 
particle volume diameter of from about 3 to about 21 microns. In 
embodiments, the present invention is directed to a process comprised of 
homogenizing a sulfonated polyester, such as one derived from about 42 
mole percent to about 49.5 mole percent of a dicarboxylic diester monomer 
such as dimethylterephthalate, about 50 mole percent of a diol such as 
propylene glycol or diethylene glycol, and from about 0.5 to about 8 mole 
percent of a sulfonated difunctional monomer, such as dimethyl 
5-sulfo-isophthalate sodium salt, in an aqueous solution containing at 
least two surfactants, one of which is a nonionic surfactant of from about 
0.1 to about 5 percent by volume of an aqueous fraction such as 
polyethylene glycol nonyl phenyl ether, and the other or second surfactant 
is an ionic surfactant such as dodecyl benzene sulfonate sodium salt of 
from about 0.1 to about 1.5 percent by volume of the aqueous fraction in a 
heated pressurized vessel at high temperature of, for example, from about 
120.degree. C. to about 170.degree. C., which vessel contains a Gaulin 
homogenizer, operated at from about 1,000 to about 10,000 revolutions per 
minute for a duration of from about 1 minute to about 3 hours, thereby 
generating suspended particles of from about 0.01 micron to about 2 
microns in volume average diameter; followed by cooling the mixture to 
ambient temperature of from about 10.degree. C. to about 40.degree. C. and 
adding thereto a mixture comprised of from about 1 to about 10 percent by 
weight of pigment particles, such as carbon black, or other colored 
pigments like HELIOGEN BLUE.TM. or HOSTAPERM PINK.TM. in an aqueous 
mixture containing from about 0.1 to about 5 percent by volume of a 
counterionic surfactant such as alkylbenzene tetraalkylammonium chloride; 
followed by dispersing the resulting mixture and thereby obtaining 
suspended aggregate particles of from about 2 microns to about 21 microns 
in volume diameter; followed by coalescence of the aforementioned 
aggregated pigment-sulfonated polyester particles by heating to a 
temperature of from about 5.degree. C. to about 40.degree. C. above the 
glass transition temperature of the resin particle to generate toners with 
an average particle diameter of from about 3 to about 21 microns in volume 
average diameter. The aforementioned toners are especially useful for the 
development, especially xerographic development, reference U.S. Pat. No. 
4,265,990, the disclosure of which is totally incorporated herein by 
reference, of colored images with excellent line and solid resolution, and 
wherein substantially no background deposits are present. 
In color reprography, especially process color reprography wherein 
pictorial images are generated, high gloss of from about 50 gloss units to 
about 80 gloss units as measured by the Gardner Gloss meter is highly 
desirable. Additionally, toners which fix onto paper at low fusing 
temperatures, such as from about 125.degree. C. to about 140.degree. C., 
are desirable to prolong the lifetime of the fuser and reduce its energy 
consumption. Accordingly, in order to satisfy the aforementioned high 
gloss and low fusing temperature requirements, it is advantageous to 
utilize conventional toners comprised of polyesters as the resin binder. 
However, the process for obtaining conventional toners usually requires 
the utilization of pulverization and cumbersome classification methods 
which are expensive, especially wherein small size toners of from about 3 
microns to about 7 microns are desired. The toner process of this 
invention is directed to the economical preparation of toners containing, 
for example, polyester resins without the utilization of the known 
pulverization and attrition methods, and wherein a solvent is not needed, 
and wherein toners with an average volume diameter of from about 3 to 
about 7 microns can be obtained. Additionally, with the toners of this 
invention, high gloss of from about 50 to about 80 gloss units as measured 
by the Gardner gloss meter, and low fixing temperature of from about 
125.degree. C. to about 150.degree. C. are attained in embodiments. 
Certain in situ emulsion aggregation processes are known, and usually 
involve the use of polar emulsion resins, which are, for instance, 
comprised of an acidic functionality such as carboxylic acids or basic 
functionalities such as a tertiary or a quaternized amine to render the 
polymeric resin highly charged necessary for the controlled aggregation 
step with a pigment, by properly mixing the ionic and counterionic 
surfactants, followed by coalescence. The preparation of addition type 
emulsion resins with polar groups such as styrene acrylate-acrylic acid or 
methacrylic acid in the main chain wherein the acid group is from about 2 
to about 8 percent of the polymer chain are known and utilized in the 
aggregation and coalescence step, wherein the resins have sufficient 
charge, such as mentioned in U.S. Pat. No. 4,996,127. However, such 
addition type polymeric resin is not effective for toner compositions 
wherein a low fixing temperature of from about 125.degree. C. to about 
140.degree. C. is required with high gloss of from about 50 to about 80 
gloss units as measured by the Gardner gloss meter, and nonvinyl offset 
properties such that the image does not offset to vinyl covers utilized in 
binding the images. Hence, there is a need for polyester based toner 
compositions wherein the aforementioned low fixing temperature, high gloss 
and nonvinyl offset properties are attained, and moreover there is a need 
for the preparation of toner by an economical in situ process which does 
not require the utilization of pulverization and cumbersome classification 
methods. Also, certain polyesters are considered neutral with low acid 
values present at the chain ends, and thus they usually do not provide the 
high polar charge necessary for proper aggregation control. In the present 
invention, a novel sulfonated polyester is utilized, wherein the 
sulfonated ion is present in the main chain of the polyester in an amount 
of, for example, from about 0.5 to about 8 percent by weight thereby 
providing adequate charging characteristics for effective use in in situ 
emulsion aggregation processes, and enabling the generation of toner 
particles comprised of sulfonated polyesters with a number of advantages, 
including a low fixing temperature of from about 120.degree. C. to about 
140.degree. C., high gloss of from about 50 to about 80 gloss units as 
measured by the Gardner gloss metering unit, nonvinyl offset 
characteristics, and avoidance of charge control agents in embodiments. 
There is illustrated in U.S. Pat. No. 4,996,127 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 this '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. Additionally, this 
process involves the preparation of emulsion addition type resins, such as 
that obtained from styrene, ethyl acrylate and the like, and wherein it is 
believed that polyesters cannot be effectively obtained. Also, note 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 acrylic acid polar group, see Comparative Example 
I of the '127 patent. With the present invention, polyester resins are 
utilized, and more specifically sulfonated polyester emulsions with polar 
charges induced by the sulfonated ion groups, and wherein the emulsion 
particles are prepared by a high shear and high temperature processes. In 
U.S. Pat. No. 4,983,488, 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. This process is thus directed 
to emulsion type resins and monomers therefrom, and coagulants are 
utilized. With the process of the present invention, addition type resins 
are avoided and sulfonated polyester resin particles are selected thereby 
enabling low toner fusing temperatures and high gloss with nonvinyl offset 
properties, and without the use of charge control agents. Similarly, the 
aforementioned disadvantages are noted in other prior art, such as U.S. 
Pat. No. 4,797,339, wherein there is disclosed a process for the 
preparation of toners by resin emulsion polymerization and spray drying; 
and U.S. Pat. No. 4,558,108, wherein there is disclosed a process for the 
preparation of a copolymer of styrene and butadiene by specific suspension 
polymerization processes. More specifically, the present invention is 
directed to a toner comprised of a sulfonated polyester resin prepared by 
an in situ emulsion aggregation, which sulfonated polyester is 
microsuspended to from about 0.05 to about 1 micron in volume diameter 
utilizing a high shearing device, such as a Gaulin homogenizer, at 
elevated temperature followed by cooling to ambient temperature, 
aggregating with pigmented particles and counterionic surfactant to toner 
size pigment-resin aggregated particles of from about 3 microns to about 7 
microns in volume diameter as measured by the Coulter Counter, followed by 
heating the resulting aggregate composite above the glass transition resin 
of the polyester to effect coalescence and to generate toner particles of 
from about 3 to about 21 microns. These toners exhibit low fixing 
temperatures of from about 125.degree. to about 140.degree. C., high gloss 
of from about 50 to about 80 gloss units as measured by the Gardner Gloss 
device, excellent triboelectric charge induced, it is believed, by the 
sulfonated ion groups on the polyester resin, hence avoiding or minimizing 
the use of charge control agents. 
Illustrated in U.S. Pat. No. 5,290,654 is an in situ process for the 
preparation of toner compositions which comprises dispersing a polymer, a 
pigment and an optional charge enhancing additive in an aqueous media 
containing a surfactant, or mixture of surfactants; stirring the mixture 
with optional heating to remove the organic solvent thereby obtaining 
suspended particles of about 0.05 micron to about 2 microns in volume 
diameter; subsequently homogenizing the resulting suspension with an 
optional pigment in water and surfactant; and followed by aggregating the 
mixture by heating thereby providing toner particles with an average 
particle volume diameter of from between about 3 to about 21 microns when 
said pigment is present. Disadvantages associated with this process 
include the use of solvents that can be toxic, which solvent is to be 
disposed of, or redistilled before reuse; thus, for example, adding to the 
process cost. Additionally, the polyesters of U.S. Pat. No. 5,290,654 do 
not contain sulfonated groups, hence are not polar charged and do not 
provide, it is believed, process latitude. Furthermore, with the 
sulfonated polyester of the present invention, excellent negative 
triboelectrification of toners with carriers are obtained, such as from 
about -10 to about -80 microcoulombs per gram, especially when the Xerox 
Corporation 9200 carrier comprised of, for example, a ferrite or steel 
core with a polymeric coating thereover of a terpolymer of styrene, 
methacrylate and an organosiloxane, and excellent admix properties are 
obtained, such as from about 30 seconds to about 2 minutes, without the 
use of charge control agents. 
There is also disclosed in a Japanese Laid Open Patent H4-51251, a process 
for the preparation of polyester emulsion particles and toners comprised 
of a mixture of styrene based particles with polyester particles, however, 
the sulfonated polyesters of the present invention are not mentioned, and 
additionally pH adjusting agents must be utilized with the process of the 
H4-51251 patent and in situ toner particles comprised of exclusively a 
polyester resin with pigment and optionally charge control agent are not 
disclosed and cannot be obtained due to the nonpolar nature of the 
polyester utilized. The present invention discloses sulfonated polyester 
particles which are polar charged due to the sulfonated ions, and hence do 
not require pH adjusting agents during the process, and can be aggregated 
and coalesced with pigments and without the use of polar charged styrene 
based particles and without the use of charge control agents. 
Water soluble sulfonated polyester resins are also known, such as 
illustrated in U.S. Pat. No. 3,564,008 wherein water-dissipatible 
sulfonated polyesters useful for sizing textiles, such as yarn, hemp rope 
and tie cord, are disclosed and wherein the polyester is derived from one 
dicarboxylic acid component, at least one diol component being a 
poly(ethylene glycol), and a difunctional monomer containing a metal 
sulfonate group attached to an aromatic nucleus. In the '008 patent, a 
sulfo-monomer component constitutes at least about 8 mole percent to about 
45 mole percent of the polyester to achieve water-dissipatibility. 
Furthermore, sulfonated water-dissipatible polyester amides are disclosed 
in U.S. Pat. No. 3,779,993 which in addition to the polyesters of the '008 
patent include amine monomers. 
There is a need for a toner composition of low fixing temperature of from 
about 125.degree. to about 140.degree. C. with high gloss of from about 20 
to about 50 gloss units and wherein toner offset to vinyl covers is 
avoided or minimized, and moreover there is a need for an economical in 
situ preparation without resorting to conventional pulverization and 
classification process. There is also a need for toner compositions 
containing no charge control agents to provide for excellent toner 
triboelectrification and admix properties. These and other needs are 
attained with this invention in embodiments by providing a toner 
composition comprised of a pigment, optionally a charge control additive, 
and a sulfonated polyester resin, and wherein the toner can be prepared 
from an in situ emulsion aggregation process as illustrated herein. 
SUMMARY OF THE INVENTION 
It is an object of the present invention to provide toner and developer 
compositions with many of the advantages illustrated herein. 
In another object of the present invention there are provided toner 
compositions with sulfonated polyester resins, and which toners are useful 
for the development of electrostatic latent images including color images. 
In yet another object of the present invention there are provided processes 
for the preparation of toner compositions comprised of a sulfonated 
polyester, pigment and optional charge control agent. 
Moreover, in another object of the present invention there are provided 
toner compositions comprised of a sulfonated polyester with low melt 
fusing temperatures of from about 125.degree. C. to about 140.degree. C. 
Moreover, in another object of the present invention that are provided 
toner compositions comprised of a sulfonated polyester with a high gloss 
of from about 40 to about 80 gloss units, and which polyesters can be 
prepared without utilizing solvents and with high shearing. 
In yet another object of the present invention there are provided in situ 
toners with excellent triboelectrification and excellent admix properties. 
Moreover, in another object of the present invention that are provided 
toner compositions comprised of a sulfonated polyester with nonvinyl 
offset properties. 
Moreover, in another object of the present invention that are provided 
toner compositions comprised of a sulfonated polyester derived from at 
least one dicarboxylic acid or diester component, at least one diol 
component, and at least from about 0.5 to about 8 mole percent of a 
sulfonated difunctional monomer. 
In another object of the present invention there are provided simple and 
economical in situ processes for black and colored toner compositions by 
an in situ emulsion aggregation process and, more specifically, by heating 
a polyester like S II.TM. with pigment to a low melt viscosity state in 
a pressure reactor containing an aqueous surfactant solution, followed by 
dispersing the mixture and subsequently aggregation. 
In a further object of the present invention there is provided a process 
for the preparation of toners with an average particle diameter of from 
between about 3 to about 50 microns, and preferably from about 3 to about 
21 microns. 
In another object of the present invention there are provided in situ 
toners prepared by dispersing certain polyester resins, pigment and 
optional toner additives at elected temperatures in a pressurized vessel 
containing an aqueous solution of ionic and nonionic surfactants, such as 
sodium dodecylsulfate and polypropylene glycol nonyl phenyl ether to yield 
directly toner sized particles or emulsion sized particles, followed by 
aggregation. 
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 toner 
compositions comprised of a sulfonated polyester resin of the formula 
illustrated herein, and processes for the economical direct preparation of 
toners by an emulsion suspension, aggregation process. 
The polyesters of the present invention can be considered sulfonated 
polyesters obtained from the melt esterification of at least one, such as 
1 to about 10 and preferably from one to two, dicarboxylic acid or diester 
components, such as dimethyl terephthalate, isophthalic acid or mixtures 
of such components with from about 42 mole percent to about 49.5 mole 
percent of the polyester, at least one, that is preferably one or two, 
diol components such as 1,2-propylene glycol, or propoxylated bisphenol A 
diethylene glycol or mixtures of the diol components with from about 50 
mole percent of the polyester resin, a sulfonated difunctional monomer 
such as dimethyl-5-sulfo-isophthalate sodium salt, or sodium 
2-sulfo-phthalic anhydride or mixtures of such components which is from 
about 0.5 to about 8 mole percent of polyester, and using a 
polycondensation catalyst such as dibutyl tin oxide hydroxide of from 
about 0.01 to about 0.1 mole percent of the polyester. The toners of the 
present invention can be prepared by an in situ emulsion aggregation 
process comprised of the steps of (a) homogenizing from about 80 to about 
97 percent by toner weight of a sulfonated polyester resin comprised, for 
example, of about 42 mole percent of terephthalate, 50 mole percent of 
1,2-propylene glycol, and 8 mole percent of sodio 5-sulfonoisophthalate in 
an aqueous mixture containing about 1.5 percent by weight of sodium 
dodecyl benzene sulfonate, and 1.5 percent by weight of propylene glycol 
nonylphenyl ether available from Rhoune-Poulenac as Antarox 897, 
utilizing a Gaulin homogenizer available from APV Gaulin Incorporated, and 
which mixture is heated at from about 120.degree. C. to about 160.degree. 
C. at a speed of from about 4,000 revolutions per minute to about 10,000 
revolutions per minute for a duration of from about 1 minute to about 1 
hour thereby generating suspended sulfonated polyester particles of from 
about 0.01 micron to about 2 microns in average particle diameter; (b) 
subsequently adding to the resulting emulsion suspension a pigment 
dispersion comprised of about 3 to about 7 percent by weight of toner of a 
pigment such as cyan, magenta, yellow, black, and the like, such as 
HOSTAPERM PINK.TM., in an aqueous mixture containing a counterionic 
surfactant such alkylbenzene tetraalkylammonium chloride of from about 1.5 
percent by weight and resulting in the aggregation of resin particles and 
pigment of from about 3 to about 21 microns; (c) heating the said 
pigment-resin aggregates at from about 5.degree. C. to about 40.degree. C. 
above the glass transition temperature of the resin for a duration of from 
about 30 minutes to about 6 hours thereby providing toner particles with 
an average particle volume diameter of from between about 1 to about 100 
microns, and preferably from between about 3 to about 21 microns; and (d) 
cooling the mixture to ambient temperature, about 25.degree. C., washing 
with water from about three to about six times, and drying the toner 
product by known methods such as fluid bed dryer. 
Specific examples of the diol utilized for the derivation of the sulfonated 
polyesters of this invention are selected from the group consisting of 
ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene 
glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentylene glycol, 
1,3-pentylene glycol, 1,4-pentylene glycol, 1,5-pentylene glycol, 
1,2-hexylene glycol, 1,3-hexylene glycol, 1,4-hexylene glycol, 
1,5-hexylene glycol, 1,6-hexylene glycol, heptylene glycols, octylene 
glycols, decylne glycol, dodecylyne glycol, 2,2-dimethyl propane diol, 
propoxylated bisphenol A, ethoxylated bisphenol A, 1,4-cyclohexane diol, 
1,3-cyclohexane diol, 1,2-cyclohexane diol, 1,2-cyclohexane dimethanol, 
2-propene-diol, mixtures thereof and the like, and which diols are 
employed in effective amounts of, for example, from about 45 to about 55 
mole percent by weight of the resin. 
Specific examples of dicarboxylic acids utilized in preparing the 
aforementioned sulfonated polyesters, include malonic acid, succinic acid, 
2-methyl succinic acid, 2,3-dimethylsuccinic acid, dodecylsuccinic acid, 
glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, azeilic 
acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, 
1,2-cyclohexanedioic acid, 1,3-cyclohexanedioic acid, 1,4-cyclohexanedioic 
acid, glutaric anhydride, succinic anhydride, dodecylsuccinic anhydride, 
mixtures thereof in effective amounts of, for example, from about 45 to 
about 55 mole percent by weight of the resin. 
Specific examples of dicarboxylic diesters utilized in preparing the 
aforementioned sulfonated polyesters, include alkyl esters, wherein the 
alkyl groups contain from 1 to about 23 carbons and are esters of 
malonate, succinate, 2-methyl succinate 2,3-dimethyl succinate, dodecyl 
succinate, glutarate, adipic acid, 2-methyladipate, pimelate, azeilate, 
sebacate acid, terephthalate, isophthalate, phthalate, 
1,2-cyclohexanedioate, 1,3-cyclohexanedioate, 1,4-cyclohexanedioate, 
mixture thereof and the like. Effective diester amounts of, for example, 
from about 45 to about 55 mole percent by weight of the resin are 
selected. 
Specific examples of sulfonated difunctional monomers utilized in preparing 
the aforementioned sulfonated polyesters include the ion salts of 
sulfonated difunctional monomers wherein the ion is a hydrogen, ammonium, 
an alkali or alkaline earth such as lithium, sodium, potassium, cesium, 
magnesium, barium, or a metal ion such as vanadium, copper, iron cobalt, 
manganese, mixtures thereof and the like, and the sulfonated difunctional 
moiety is selected from the group including dimethyl-5-sulfo-isophthalate, 
dialkyl-5-sulfo-isophthalate-4-sulfo-1,8-naphthalic anhydride, 
4-sulfo-phthalic acid, dimethyl 4-sulfo-phthalate, dialkyl 
4-sulfo-phthalate, 4-sulfophenyl-3,5-dicarbomethoxybenzene, 
6-sulfo-2-naphthyl-3,5-dicarbomethoxybenzene, sulfo-terephthalic acid, 
dimethyl-sulfo-terephthalate, dialkyl-sulfo-terephthalate, 
sulfo-ethanediol, 2-sulfopropanediol, 2-sulfobutanediol, 
3-sulfopentanediol, 2-sulfo hexanediol, 3-sulfo-2-methylpentanediol, 
2-sulfo-3,3-dimethylpentanediol, sulfo-p-hydroxybenzoic acid, mixtures 
thereof and the like. Effective difunctional amounts of, for example, from 
about 0.5 to about 8 mole percent by weight of the resin are selected. Two 
preferred monomers are dimethyl-5-sulfo-isophthalate sodium salt, and 
N,N-bis(2-hydroxyethyl)-2-aminoethane sulfonate available as BES from 
Aldrich Chemical Company. 
Various known colorants present in the toner in an effective amount of, for 
example, from about 1 to about 25 percent by weight of the toner, and 
preferably in an amount of from about 1 to about 15 weight percent, that 
can be selected include carbon black like REGAL 330.RTM.. As colored 
pigments, there can be selected known cyan, magenta, or yellow. Specific 
examples of pigments include HELIOGEN BLUE L6900.TM., D6840.TM., 
D7080.TM., D7020.TM., PYLAM OIL BLUE.TM., PYLAM OIL YELLOW.TM., PIGMENT 
BLUE 1.TM. available from Paul Uhlich & Company, Inc., PIGMENT VIOLET 
1.TM., PIGMENT RED 48.TM., LEMON CHROME YELLOW DCC 1026.TM., E.D. 
TOLUIDINE RED.TM. and BON RED C.TM. available from Dominion Color 
Corporation, Ltd., Toronto, Ontario, NOVAPERM YELLOW FGL.TM., HOSTAPERM 
PINK E.TM. from Hoechst, and CINQUASIA MAGENTA.TM. available from E.I. 
DuPont de Nemours & Company, and the like. Generally, colored pigments 
that can be selected are cyan, magenta, or yellow pigments. Examples of 
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 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 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. Cyan components may also be 
selected as pigments with the process of the present invention. The 
pigments selected are present in various effective amounts, such as from 
about 1 weight percent to about 15 weight percent, and preferably from 1 
to about 10 weight percent of the toner. 
The toner may also include known charge additives such as alkyl pyridinium 
halides, bisulfates, 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, and the like. 
Surface additives that can be added to the toner compositions of the 
present invention include, for example, metal salts, metal salts of fatty 
acids, colloidal silicas, mixtures thereof and the like, which additives 
are usually present in an amount of from about 0.1 to about 1 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 AEROSIL R972.RTM. 
available from Degussa. 
Surfactants in effective amounts of, for example, 0.1 to about 25 weight 
percent in embodiments include, for example, non ionic surfactants such as 
polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethyl 
cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl 
cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, 
polyoxyethylene octyl ether, polyoxyethylene octyphenyl ether, 
polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, 
polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether 
(available from GAF as IGE CA-210.TM., IGE CA-520.TM., IGE 
CA-720.TM., IGE CO-890.TM., IGE CO-720.TM., IGE CO-290.TM., 
IGE CA-210.TM., ANTAROX 890.TM. and ANTAROX 897.TM. available from 
Rhone-Poulenac, dialkylphenoxy poly(ethyleneoxy)ethanol, ionic surfactants 
such as sodium dodecyl sulfate, sodium dodecyl-benzene sulfate, sodium 
dodecylnaphthalene sulfate, dialkyl benzenealkyl ammonium chloride, 
MIRAPOL.TM., SANIZOL.TM., mixtures thereof and the like. The surfactant is 
utilized in various effective amounts, and preferably, for example, from 
about 0.1 percent to about 5 percent by weight of water. 
Specific examples of polycondensation catalysts include tetraalkyl 
titanates, dialkyltin oxide, tetraalkyltin, dialkyltin oxide hydroxide, 
aluminum alkoxides, alkyl zinc, dialkyl zinc, zinc oxide, stannous oxide, 
dibutyltin oxide, butyltin oxide hydroxide, tetraalkyl tin such as 
dibutyltin dilaurate, mixtures thereof and the like selected in effective 
amounts of from about 0.01 mole percent to about 1 mole percent of resin. 
Specific examples of sulfonated polyesters include the hydrogen, ammonium, 
alkali or alkali earth metals such as lithium, sodium, potassium, cesium, 
magnesium, barium, iron, copper, vanadium, cobalt, calcium of the random 
copoly(ethylene-terephthalate)-copoly-(ethylene-5-sulfo-isophthalate), 
copoly(propylene-terephthalate)-copoly-(propylene-5-suifo-isophthalate), 
copoly(diethylene-terephthalate)-copoly-(diethylene-5-sulfo-isophthalate), 
copoly(propylene-diethylene-terephthalate)-copoly(propylene-diethylene-5-s 
ulfo-isophthalate), 
copoly(propylene-butylene-terephthalate)-copoly-(propylene-butylene-5 
-sulfo-isophthalate), copoly-(propoxylated 
bisphenol-A-fumarate)-copoly(propoxylated bisphenol 
A-5-sulfo-isophthalate), copoly(ethoxylated 
bisphenol-A-fumarate)-copoly(ethoxylated bisphenol 
A-5-sulfo-isophthalate), copoly(ethoxylated 
bisphenol-A-maleate)-copoly(ethoxylated bisphenol A-5-sulfo-isophthalate), 
mixtures thereof and the like, and wherein the sulfonated copoly portion 
is present in an amount of, for example, from about 0.5 to about 8 mole 
percent of the resin. For the aforementioned sulfonated polyester resins, 
the glass transition temperature can be selected to be from about 
45.degree. C. to about 65.degree. C. as measured by the Differential 
Scanning Calorimeter, the number average molecular weight can be selected 
to be from about 2,000 grams per mole to about 150,000 grams per mole, the 
weight average molecular weight can be selected to be from about 3,000 
grams per mole to about 300,000 grams per mole as measured by the Gel 
Permeation Chromatograph, and the polydispersity can be selected to be 
from about 1.6 to about 100 as calculated by the ratio of the weight 
average to number average molecular weight. 
Percentage amounts of components are based on the total toner components 
unless otherwise indicated. 
In embodiments, the present invention is directed to a toner composition 
comprised of a pigment, and a sulfonated polyester of the formula or as 
essentially represented by the formula 
##STR3## 
wherein M is an ion independently selected from the group consisting of 
hydrogen, ammonium, an alkali metal ion, an alkaline earth metal ion and a 
metal ion; R is independently selected from the group consisting of aryl 
and alkyl; R' is independently selected from the group consisting of alkyl 
and oxyalkylene; and wherein n and o represent random segments, and 
wherein o is from about 0.5 to about 8 mole percent, and wherein the sum 
of n and o are equal to 100 mole percent; and an in situ process for the 
preparation of toner compositions which comprises the dispersion of the 
above sulfonated polyester in a sealed vessel containing an aqueous media 
of an anionic surfactant, and a nonionic surfactant at a temperature of 
from about 100.degree. C. to about 180.degree. C. thereby obtaining 
suspended particles of about 0.05 micron to about 2 microns in volume 
average diameter; subsequently homogenizing the resulting suspension at 
ambient temperature; followed by aggregating the mixture by adding thereto 
a mixture of cationic surfactant and pigment particles to effect 
aggregation of said pigment and sulfonated polyester particles; followed 
by heating the pigment-sulfonated polyester particle aggregates above the 
glass transition temperature of the sulfonated polyester causing 
coalescence of the aggregated particles to provide toner particles with an 
average particle volume diameter of from between about 3 to about 21 
microns. Alkyl includes components with from 1 to about 25 carbon atoms, 
such as methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl, nonyl and the 
like; aryl includes components with from 6 to about 24 carbon atoms such 
as phenyl, naphthyl, benzyl, and the like; and oxyalkylene includes 
alkylene with from 1 to about 25 carbon atoms like methylene, ethylene, 
propylene, butylene hexylene, and the like. The subscripts n and o 
represent various amounts of the segments indicated providing the sum 
thereof is equal to 100 percent; preferably o is from about 0.5 to about 8 
mole percent, and n is from about 95.5 to about 92 mole percent. 
Known additives may be included in or with the toner of the present 
invention, such as charge additives like quaternary compounds, alkyl 
pyridium halides, distearyl dimethyl ammonium methyl sulfate, mixtures 
thereof, and the like, in effective amounts of, for example, from about 
0.1 to 10 weight percent; waxes like polypropylene and polyethylene, 
preferably of a molecular weight of from 1,000 to about 20,000; surface 
additives like metal salts of fatty acids; colloidal silicas like AEROSIL 
R972.RTM.; metal oxides like tin oxide, titanium oxides and the like, 
present in effective amounts, such as from about 0.1 to 3 weight percent; 
and the like. Developer compositions comprised of the toners illustrated 
herein and carrier particles, including those as illustrated in U.S. Pat. 
Nos. 4,937,166 and 4,935,326, the disclosures of which are totally 
incorporated herein by reference, are also encompassed by the present 
invention. 
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.

EXAMPLE I 
Preparation of sulfonated polyester resin derived from 46 mole percent of 
dimethyIterephthalate, 4 mole percent of dimethyl-5-sulfoisophthalate 
sodium salt, 42.5 mole percent of 1,2-propylene glycol and 7.5 mole 
percent of diethylene glycol: 
A one liter Parr reactor equipped with a bottom drain valve, double turbine 
agitator and distillation receiver with a cold water condenser was charged 
with 361 grams of dimethylterephthalate, 20.76 grams of 
dimethyl-5-sulfo-isophthalate sodium salt, 274.6 grams of 1,2-propanediol 
(1 mole excess), 31 grams of diethylene glycol and 0.8 gram of tetrabutyl 
titanate as the catalyst. The reactor was then heated to 165.degree. C. 
with stirring for 16 hours whereby 115 grams of distillate was collected 
in the distillation receiver, 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 over a one hour period 
to about 260 Torr, and then reduced to 5 Torr over a two hour period with 
the collection of approximately 120 grams of distillate in the 
distillation receiver, which distillate was 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 18 
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 454 grams of 
copoly(1,2-propylene-diethylene-terephthalate) 
copoly(1,2-propylene-diethylene-5-sulfo-isophthalate) sodium salt resin. 
The glass transition temperature of the resin resulting was then measured 
to be 53.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 2,050 grams per mole and the weight average molecular weight was 
measured to be 3,400 grams per mole using tetrahydrofuran as the solvent 
and obtained with the 700 Satelite WISP gel permeation chromatograph 
available from Waters Company equipped with a styrogel column. 1.8 Grams 
of this sulfonated polyester resin was then pressed into a pellet of about 
1 centimeter in diameter and about 10 centimeters in length using the 
press and die set supplied by Shimadzu with the Flowtester 500 series. The 
pressed sample pellet was then loaded in the flowtester and subjected to 
the standard Shimadzu conditions using 20 killigrams/cm.sup.2, and where 
the barrel temperature heated from 20.degree. C. to 130.degree. C. at a 
rate of 10.degree. C. per minute. For the resin of this Example, a 
softening point of 68.degree. C., beginning of flow temperature T.sub.1 of 
82.degree. C., and flow temperature T.sub.2 of 98.degree. C. were 
obtained. 
EXAMPLE II 
A 5.0 micron toner comprised of the sulfonated polyester of Example I, and 
HOSTAPERM PINK E.TM. pigment was prepared as follows. 
One hundred (100) grams of the sulfonated polyester of Example I were 
dispersed in an aqueous mixture containing 400 grams of one percent by 
weight of polyoxyethylene nonylphenyl ether (available from Rhone Poulenac 
as ANTAROX 897.TM.) and one percent by weight of sodium dodecylsulfate, 
utilizing a homogenizer available from APV Gaulin Incorporated, operating 
at 10,000 revolution per minute for a duration of 720 seconds at an 
elevated temperature of 150.degree. C. The resultant mixture was then 
cooled to about 25.degree. C. resulting in a mixture of microsuspended 
polyester particles with average volume particle size of about 150 
nanometers as measured using the Brookhaven nanosizer. In a separate 200 
milliliter vessel was dispersed HOSTAPERM PINK E.TM. (Hoechst Celanese) in 
100 grams of an aqueous solution containing one percent of MIRAPOL.TM. 
(available from Miranol Inc.) utilizing a Brinkmann homogenizer operating 
at 10,000 revolutions per minute for a duration of 720 seconds. The 
dispersed pigment solution was then added to the 2 liter kettle containing 
the microsuspended polyester particles resulting in a flocculation of 
polyester particles and pigment. This mixture was then dispersed utilizing 
a Brinkmann homogenizer operating at 4,000 revolutions per minute for a 
duration of 3 minutes, wherein an aggregated composite of sulfonated 
polyester and pigment particles were obtained with an average volume 
diameter particle size of 4.8 microns as measured utilizing the Coulter 
Counter. The resulting aggregate composite was subsequently heated to 
60.degree. C. for a duration of 1 hour. The mixture was then cooled to 
ambient temperature, about 25.degree. C., filtered off and washed 
repeatedly three times with about 1 liter of water. The wet toner cake was 
then fluidized in an Aeromatic AG bed dryer operated at 30.degree. C. for 
a duration of 3 hours. The dry toner particles had a volume average 
particle size of 5 microns in diameter and a geometric distribution of 
1.33 as determined by a Coulter Counter. 
A developer composition was prepared by roll milling the aforementioned 
toner, 3 parts by weight with 100 parts by weight of a Xerox Corporation 
9200 carrier comprised of a steel core with a 1.75 coating weight of a 
terpolymer of styrene, butylmethacrylate and triethoxysilane. The tribo 
data was obtained using the known blow-off Faraday Cage apparatus, and the 
charge was measured to be -29 microcoulombs per gram. Unfused copies were 
then produced using a Xerox Corporation 9200 imaging apparatus with the 
fusing system disabled. The unfused copies were then subsequently fused on 
a test fuser using a process speed of 11.9 inches per second. Fusing 
evaluation of the toner indicated a minimum fixing temperature of about 
131.degree. C., and a hot-offset temperature of 180.degree. C. 
EXAMPLE III 
A 4.7 micron toner comprised of the sulfonated polyester of Example I, and 
HELIOGEN BLUE.TM. pigment (available from BASF) was prepared as follows. 
One hundred (100) grams of the sulfonated polyester of Example I were 
dispersed in an aqueous mixture containing 400 grams of one percent by 
weight of polyoxyethylene nonylphenyl ether (available from Rhone Poulenac 
as ANTAROX 897.TM.), and one percent by weight of sodium dodecylsulfate, 
utilizing a Gaulin homogenizer available from APV Gaulin Incorporated, 
operating at 10,000 revolutions per minute for a duration of 720 seconds 
at an elevated temperature of 150.degree. C. The resultant mixture was 
then cooled to about 25.degree. C., resulting in a mixture of 
microsuspended polyester particles with an average volume particle size of 
about 150 nanometers as measured using the Brookhaven nanosizer. In a 
separate 200 milliliter vessel was dispersed HELIOGEN BLUE.TM. (BASF) in 
100 grams of an aqueous solution containing one percent of MIRAPOL.TM. 
(available from Miranol Inc.) utilizing a Brinkmann homogenizer operating 
at 10,000 revolutions per minute for a duration of 720 seconds. The 
dispersed pigment solution was then added to the 2 liter kettle containing 
the prepared microsuspended polyester particles resulting in a 
flocculation of polyester particles and pigment. This mixture was then 
dispersed utilizing a Brinkmann homogenizer operating at 4,000 revolutions 
per minute for a duration of 3 minutes, wherein an aggregated composite of 
the sulfonated polyester and pigment particles were obtained with an 
average volume diameter particle size of 4.7 microns as measured utilizing 
the Coulter Counter. The resulting aggregate composite was subsequently 
heated to 60.degree. C. for a duration of 1 hour. The mixture was then 
cooled to ambient temperature, about 25.degree. C., filtered off and 
washed three times with about 1 liter of water. The wet toner cake was 
then fluidized in an Aeromatic AG bed dryer operated at 30.degree. C. for 
a duration of 3 hours. The resulting dry toner particles had a volume 
average particle size of 4.7 microns in diameter and a geometric 
distribution of 1.35 as determined by a Coulter Counter. 
A developer composition was prepared by roll milling the aforementioned 
toner, 3 parts by weight, with 100 parts by weight of the aforementioned 
Xerox Corporation 9200 carrier comprised of a steel core. The tribo data 
was obtained using the known blow-off Faraday Cage apparatus, and the 
charge was measured to be -32 microcoulombs per gram. Unfused copies were 
then produced using a Xerox Corporation 9200 imaging apparatus with the 
fusing system disabled. The unfused copies were then subsequently fused on 
a test fuser like the 9200 using a process speed of 11.9 inches per 
second. Fusing evaluation of the toner indicated a minimum fixing 
temperature of about 133.degree. C., and a hot-offset temperature of 
180.degree. C. 
EXAMPLE IV 
Preparation of sulfonated polyester resin derived from 46 mole percent of 
dimethylterephthalate, 6 mole percent of dimethyl-5-sulfoisophthalate 
sodium salt, 42.5 mole percent and 1,2-propylene glycol and 7.5 percent of 
diethylene glycol: 
A one liter Parr reactor equipped with a bottom drain valve, double turbine 
agitator and distillation receiver with a cold water condenser was charged 
with 353 grams of dimethylterephthalate, 31.14 grams of 
dimethyl-5-sulfo-isophthalate sodium salt, 274.6 grams of 1,2-propanediol 
(1 mole excess), 31 grams of diethylene glycol and 0.8 gram of tetrabutyl 
titanate as the catalyst. The reactor was then heated to 165.degree. C. 
with stirring for 16 hours whereby 112 grams of distillate was collected 
in the distillation receiver, 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 over a one hour period 
to about 260 Torr, 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 18 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 450 grams of 
copoly(1,2-propylene-diethylene-5-sulfo-isophthalate) sodium salt resin. 
The glass transition temperature was then measured to be 58.degree. C. 
(onset) utilizing the 910 Differential Scanning Calorimeter available from 
DuPont operating at a heating rate of 10.degree. C. per minute. The number 
average molecular weight was measured to be 2,900 grams per mole and the 
weight average molecular weight was measured to be 4,100 grams per mole 
using tetrahydrofuran as the solvent and obtained with the 700 Satelite 
WISP gel permeation chromatograph available from Waters Company equipped 
with a styrogel column. 1.8 Grams of this sulfonated polyester resin was 
then pressed into a pellet of about 1 centimeter in diameter and about 10 
centimeters in length using the press and die set supplied by Shimadzu 
with the Flowtester 500 series. The pressed sample pellet was then loaded 
in the flowtester and subjected to the standard Shimadzu conditions using 
20 killigrams/cm.sup.2, and wherein a barrel temperature from 20.degree. 
C. to 130.degree. C. at a rate of 10.degree. C. per minute was selected. 
For the resin of this Example, a softening point of 75.degree. C., 
beginning of flow temperature T.sub.1 of 89.degree. C., and flow 
temperature T.sub.2 of 103.degree. C. were obtained. 
EXAMPLE V 
A 7 micron (average volume diameter throughout unless otherwise indicated) 
toner comprised of the sulfonated polyester of Example IV, and HELIOGEN 
BLUE.TM. (BASF) pigment was prepared as follows. 
One hundred (100) grams of the sulfonated polyester of Example IV were 
dispersed in an aqueous mixture containing 400 grams of one percent by 
weight of polyoxyethylene nonylphenyl ether (available from Rhone Poulenac 
as ANTAROX 897.TM.), and 1 percent by weight of sodium dodecylsulfate, 
utilizing a Gaulin homogenizer available from APV Gaulin Incorporated 
operating at 10,000 revolution per minute for a duration of 720 seconds at 
an elevated temperature of 150.degree. C. The resultant mixture was then 
cooled to about 25.degree. C., resulting in a mixture of microsuspended 
polyester particles with average volume particle size of about 130 
nanometers as measured using the Brookhaven nanosizer. In a separate 200 
milliliter vessel was dispersed HELIOGEN BLUE.TM. (BASF) in 100 grams of 
an aqueous solution containing one percent of MIRAPOL.TM. (available from 
Miranol Inc.) utilizing a Brinkmann homogenizer operating at 10,000 
revolutions per minute for a duration of 720 seconds. The dispersed 
pigment solution was then added to the 2 liter kettle containing the above 
prepared microsuspended polyester particles resulting in a flocculation of 
polyester particles and pigment. This mixture was then dispersed utilizing 
a Brinkmann homogenizer operating at 4,000 revolutions per minute for a 
duration of 3 minutes, and an aggregated composite of sulfonated polyester 
and pigment particles was obtained with an average volume diameter 
particle size of 7 microns, as measured by the Coulter Counter. The 
resulting aggregate composite was subsequently heated to 65.degree. C. for 
a duration of 2 hours. The mixture was then cooled to ambient temperature, 
about 25.degree. C., filtered off and washed three times with about 1 
liter of water. The wet toner cake was then fluidized in an Aeromatic AG 
bed dryer operated at 30.degree. C. for a duration of 3 hours. The 
resulting dry toner particles had a volume average particle size of 7 
microns in diameter and a geometric distribution of 1.32 as determined by 
a Coulter Counter. 
A developer composition was prepared by roll milling the aforementioned 
toner, 3 parts by weight, with 100 parts by weight of the aforementioned 
carrier comprised of a steel core with a terpolymer coating. The tribo 
data was obtained using the known blow-off Faraday Cage apparatus, and the 
charge (toner throughout unless otherwise indicated) was measured to be 
-21 microcoulombs per gram. Unfused copies were then produced using a 
Xerox Corporation 9200 imaging apparatus with the fusing system disabled. 
The unfused copies were then subsequently fused on a test fuser using a 
process speed of 11.9 inches per second. Fusing evaluation of the toner 
indicated a minimum fixing temperature of about 138.degree. C., and a 
hot-offset temperature of 190.degree. C. 
EXAMPLE VI 
Preparation of sulfonated polyester resin derived from 46 mole percent of 
dimethylterephthalate, 2 mole percent of dimethyl-5-sulfoisophthalate 
sodium salt, 42.5 mole percent of 1,2-propylene glycol and 7.5 mole 
percent of diethylene glycol: 
A one liter Parr reactor equipped with a bottom drain valve, double turbine 
agitator and distillation receiver with a cold water condenser was charged 
with 368 grams of dimethylterephthalate, 10.4 grams of 
dimethyl-5-sulfo-isophthalate sodium salt, 274.6 grams of 1,2-propanediol 
(1 mole excess), 31 grams of diethylene glycol and 0.8 gram of tetrabutyl 
titanate as the catalyst. The reactor was then heated to 165.degree. C. 
with stirring for 16 hours whereby 110 grams of distillate was collected 
in the distillation receiver 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 over a one hour period to about 260 
Torr, and then reduced to 5 Torr over a two hour period with collection of 
approximately 124 grams of distillate 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 18 
grams of 1,2-propanediol was 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 445 grams of 
copoly(1,2-propylene-diethylene-5-sulfo-isophthalate) sodium salt resin. 
The glass transition temperature was then measured to be 59.degree. C. 
(onset) utilizing the 910 Differential Scanning Calorimeter available from 
DuPont operating at a heating rate of 10.degree. C. per minute. The number 
average molecular weight was measured to be 2,990 grams per mole and the 
weight average molecular weight was measured to be 4,300 grams per mole 
using tetrahydrofuran as the solvent and obtained with the 700 Satelite 
WISP gel permeation chromatograph available from Waters Company equipped 
with a styrogel column. 1.8 Grams of this sulfonated polyester resin were 
then pressed into a pellet of about 1 centimeter in diameter and about 10 
centimeters in length using the press and die set supplied by Shimadzu 
with the Flowtester 500 series. The pressed sample pellet was then loaded 
in the flowtester and subjected to the standard Shimadzu conditions using 
20 killigrams/cm.sup.2, and a barrel temperature heated from 20.degree. C. 
to 130.degree. C. at a rate of 10.degree. C. per minute. For the resin of 
this Example, a softening point of 76.degree. C., beginning of flow 
temperature T.sub.1 of 91.degree. C., and flow temperature T.sub.2 of 
105.degree. C. were obtained. 
EXAMPLE VII 
A 6 micron toner comprised of the sulfonated polyester of Example VI, and 
HELIOGEN BLUE.TM. pigment (BASF) was prepared as follows. 
One hundred (100) grams of the sulfonated polyester of Example VI was 
dispersed in an aqueous mixture containing 400 grams of one percent by 
weight of polyoxyethylene nonylphenyl ether (available from Rhone Poulenac 
as ANTAROX 897.TM.), and one percent by weight of sodium dodecylsulfate, 
utilizing a Gaulin homogenizer available from APV Gaulin Incorporated, 
operating at 10,000 revolution per minute for a duration of 720 seconds at 
an elevated temperature of 150.degree. C. The resultant mixture was then 
cooled to about 25.degree. C., resulting in a mixture of microsuspended 
polyester particles with average volume particle size of about 130 
nanometers as measured using the Brookhaven nanosizer. In a separate 200 
milliliter vessel was dispersed HELIOGEN BLUE.TM. (BASF) in 100 grams of 
an aqueous solution containing one percent of MIRAPOL.TM. (available from 
Miranol Inc.) utilizing a Brinkmann homogenizer operating at 10,000 
revolutions per minute for a duration of 720 seconds. The dispersed 
pigment solution was then added to the 2 liter kettle containing the above 
prepared microsuspended polyester particles resulting in a flocculation of 
polyester particles and pigment. This mixture was then dispersed utilizing 
a Brinkmann homogenizer operating at 4,000 revolutions per minute for a 
duration of 3 minutes, wherein an aggregated composite of sulfonated 
polyester and pigment particles were obtained with an average volume 
diameter particle size of 6 microns was measured utilizing the Coulter 
Counter. The resulting aggregate composite was subsequently heated to 
70.degree. C. for a duration of 1 hour. The mixture was then cooled to 
ambient temperature, about 25.degree. C., filtered off and washed three 
times with about 1 liter of water. The wet toner cake was then fluidized 
in an Aeromatic AG bed dryer operated at 30.degree. C. for a duration of 3 
hours. The resulting dry toner particles had a volume average particle 
size of 6 microns in diameter and geometric distribution of 1.34 as 
determined by a Coulter Counter. 
A developer composition was prepared by roll milling the aforementioned 
toner, 3 parts by weight, with 100 parts by weight of the aforementioned 
terpolymer coated carrier. The tribo data was obtained using the known 
blow-off Faraday Cage apparatus, and the toner charge was measured to be 
-28 microcoulombs per gram. Unfused copies were then produced using a 
Xerox Corporation 9200 imaging apparatus with the fusing system disabled. 
The unfused copies were then subsequently fused on a test fuser using a 
process speed of 11.9 inches per second. Fusing evaluation of the toner 
indicated a minimum fixing temperature of about 142.degree. C., and a 
hot-offset temperature of 200.degree. C. 
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.