Toner aggregation processes

A process for the preparation of toner compositions comprising PA1 (i) preparing a pigment dispersion in water, which dispersion is comprised of a pigment, an ionic surfactant and optionally a charge control agent; PA1 (ii) shearing the pigment dispersion with a latex containing a controlled solid contents of from about 50 weight percent to about 20 percent of polymer or resin, counterionic surfactant and nonionic surfactant in water, counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant thereby causing a flocculation or heterocoagulation of the formed particles of pigment, resin and charge control agent to form a dispersion of solids of from about 30 weight percent to 2 percent comprised of resin, pigment and optionally charge control agent in the mixture of nonionic, anionic and cationic surfactants; PA1 (iii) heating the above sheared blend at a temperature of from about 5.degree. to about 25.degree. C. about below the glass transition temperature (Tg) of the resin while continuously stirring to form toner sized aggregates with a narrow size dispersity; and PA1 (iv) heating the electrostatically bound aggregated particles at a temperature of from about 5.degree. to about 50.degree. C. about above the (Tg) of the resin to provide a toner composition comprised of resin, pigment and optionally a charge control agent.

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 compositions comprised, for example, of toner resins, or 
polymers, pigment, and toner additives, such as charge control agents. In 
embodiments, the present invention is directed to 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 0.5 to about 25, and preferably from 1 to about 10 
microns and narrow GSD 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 dispersing a pigment and 
optionally a charge control agent or additive in water containing an ionic 
surfactant, and shearing this mixture with a latex mixture, comprised of 
suspended resin particles of from about 0.05 micron to about 1 microns in 
volume diameter, in water containing a counterionic surfactant in amounts 
of from about 0.5 to 5 percent (weight percent) of the mass of the latex 
with opposite charge to the ionic surfactant of the pigment dispersion, 
and nonionic surfactant, thereby causing flocculation of the resin 
particles, pigment particles and optional charge control particles, 
followed by heating, below, for example from about 5.degree. to about 
20.degree. C., the Tg of the resin, and stirring of the flocculent mixture 
which is believed to form statically bound aggregates of from about 0.5 
micron to about 5 microns, comprised of resin, pigment and optionally 
charge control and thereafter heating at, for example, from about 
10.degree. to about 50.degree. C., above the Tg of the latex resin to 
generate toners ,with an average particle volume diameter of from about 1 
to about 25 microns and wherein the concentration of the latex is 
decreased from 40 percent to 1 percent by weight of the total suspension 
of latex, pigment, surfactant in water and preferably from 30 percent to 5 
percent by weight in the aggregating suspension while maintaining the same 
or similar coagulant surfactant/latex surfactant ratio of from about 
0.5:1.0 to 4:1 thereby enabling the formation of toner aggregates the size 
of which depend primarily inversely on the latex particle concentration in 
the blend. Specifically for example, the size of the aggregate produced 
when a particular latex is aggregated in this manner, under conditions 
where the ratio of counterionic surfactant coagulant to latex ionic 
surfactant is fixed, is small, for example 2 microns in volume average 
diameter at high latex loadings (30 percent solids) and larger, for 
example 8 microns in volume average diameter at low loadings (5 percent 
solids). The process of aggregating identical lattices at differing solids 
loadings of the latex in the dispersion while maintaining a constant ratio 
of counterionic surfactant coagulant to latex ionic surfactant ensures 
aggregates of a uniform chemical composition and allows for the formation 
of a wide variety of toner particles of preselected sizes, each with a 
narrow size distribution (GSD) of, for example, from about 1.16 to about 
1.26 as measured on the Coulter Counter. It is believed that during the 
higher temperature heating stage, the aggregate particles fuse together to 
form toners. In another embodiment thereof, the present invention is 
directed to an in situ process comprised of first dispersing a pigment, 
such as HELIOGEN BLUE.TM. or HOSTAPERM PINK.TM., in water containing a 
cationic surfactant such as benzalkonium bromide (SANIZOL B-50.TM.), 
utilizing a high shearing device such as a Brinkmann Polytron, 
microfluidizer or sonicator, thereafter shearing this mixture with a latex 
of suspended resin particles such as PLIOTONE.TM., comprised of 
poly(styrenebutadiene) and of particle size ranging from 0.01 to about 0.5 
micron in average volume diameter as measured by the Brookhaven nanosizer, 
in an aqueous surfactant mixture containing an anionic surfactant such as 
sodium dodecylbenzene sulfonate (for example NEOGEN R.TM. or NEOGEN 
SC.TM.) and nonionic surfactant such as alkyl phenoxy 
poly(ethylenoxy)ethanol (for example IGE 897.TM. or ANTAROX 897.TM.), 
thereby resulting in a flocculation, or heterocoagulation of the resin 
particles with the pigment particles; and which on further, from for 
example about 1 to about 3 hours, stirring while heating below the Tg of 
the latex resin results in formation of statically bound aggregates 
ranging in size of from about 0.5 microns to about 10 microns in average 
diameter size as measured by the Coulter Counter (Microsizer II); and 
thereafter heating to, for example, from about 5.degree. to about 
50.degree. C. above the Tg of the latex resin, of, for example, from about 
60.degree. to about 95.degree. C., to provide for particle fusion or 
coalescence of the polymer and pigment particles; followed by washing 
with, for example, hot water to remove surfactant, and drying whereby 
toner particles comprised of resin and pigment with various particle size 
diameters can be obtained, such as from 1 to 12 microns in average volume 
particle diameter and wherein the solids loading of the latex in the 
dispersion is decreased by diluting with water from the range of about 40 
percent to 2 percent with a preferred range of decrease being from about 
30 percent to 5 percent. The aforementioned toners are especially useful 
for the development of colored images with excellent line and solid 
resolution, and wherein substantially no background deposits are present. 
While not being desired to be limited by theory it is believed that the 
flocculation or heterocoagulation is formed by the neutralization of the 
pigment mixture containing the pigment and cationic surfactant absorbed on 
the pigment surface, with the resin mixture containing the resin particles 
and anionic surfactant absorbed on the resin particle. The high shearing 
stage ensures the formation of a uniform homogeneous flocculated system, 
or gel, from the initial inhomogeneous dispersion which results from the 
flocculation action, and allows the formation of stabilized aggregates 
that are negatively charged and comprised of the resin and pigment 
particles of about 0.5 to about 5 microns in volume diameter. Thereafter, 
heating is applied to fuse the aggregated particles or coalesce the 
particles to toner comprised of polymer and pigment, and optionally charge 
control agent. Furthermore, in other embodiments the ionic surfactants can 
be exchanged, such that the pigment mixture contains the pigment particle 
and anionic surfactant, and the suspended resin particle mixture contains 
the resin particles and cationic surfactant; followed by the ensuing steps 
as illustrated herein to enable flocculation by homogenization, to form 
statically bounded aggregate particles by stirring of the homogeneous 
mixture, and toner formation after heating. The latex resin particles for 
the aggregation is selected for its functional performance in the 
xerographic process, especially the process involved with fixing the image 
to the final receptor medium, usually paper. The utilization of a constant 
counterionic pigment dispersion surfactant to latex surfactant ratio when 
aggregating the latex under differing solid loadings ensures a consistent 
toner chemical composition while also providing a means to obtain narrow 
size toner distributions. The solids content decrease by diluting with 
water enables, for example, toner particle size control. 
In reprographic technologies, such as xerographic and ionographic devices, 
toners with average volume diameter particle sizes of from about 9 microns 
to about 20 microns have been effectively utilized. Moreover, in some 
xerographic systems, such as the high volume Xerox Corporation 5090 
copier-duplicator, high resolution characteristics and low image noise are 
highly desired, and can be attained utilizing the small sized toners of 
the present invention with an average volume particle of less than 11 
microns, preferably less than about 7 microns and more preferably from 1 
to about 7 microns, and with narrow geometric size distribution (GSD) of 
from about 1.2 to about 1.3. Additionally, in some xerographic systems 
wherein process color is utilized such as pictorial color applications, 
small particle size colored toners of from about 3 to about 9 microns are 
desired to avoid paper curling. Paper curling is especially observed in 
pictorial or process color applications wherein three to four layers of 
toners are transferred and fused onto paper. During the fusing step, 
moisture is driven off from the paper due to the high fusing temperatures 
of from about 130.degree. to 160.degree. C. applied to the paper from the 
fuser. Where only one layer of toner is present such as in black or in 
highlight xerographic applications, the amount of moisture driven off 
during fusing is reabsorbed proportionally by paper and the resulting 
print remains relatively flat with minimal curl. In pictorial color 
process applications wherein three to four colored toner layers are 
present, a thicker toner plastic level present after the fusing step 
inhibits the paper from sufficiently absorbing the moisture lost during 
the fusing step, and image paper curling results. These and other 
disadvantages and problems are avoided or minimized with the toners and 
processes of the present invention. It is preferable to use small toner 
particle sizes such as from about 1 to 7 microns and with higher pigment 
loading such as from about 5 to about 12 percent by weight of toner, such 
that the mass of toner layers deposited onto paper is reduced to obtain 
the same quality of image and resulting in a thinner plastic toner layer 
onto paper after fusing, thereby minimizing or avoiding paper curling. 
Toners prepared in accordance with the present invention enable the use of 
lower fusing temperatures such as from about 120.degree. to about 
150.degree. C. thereby avoiding or minimizing paper curl. Lower fusing 
temperatures minimize the loss of moisture from paper, thereby reducing or 
eliminating paper curl. Furthermore, in process color applications and 
especially in pictorial color applications, toner to paper gloss matching 
is highly desirable. Gloss matching is referred to as matching the gloss 
of the toner image to the gloss of the paper. For example, when a low 
gloss image of preferably from about 1 to about 30 gloss is preferred, low 
gloss paper is utilized such of from about 1 to about 30 gloss units as 
measured by the Gardner Gloss metering unit, and which after image 
formation with small particle size toners of from about 3 to about 5 
microns and fixing thereafter results in a low gloss toner image of from 
above about 1 to about 30 gloss units as measured by the Gardner Gloss 
metering unit. Alternatively, when higher image gloss is desired, such as 
from about above 30 to about 60 gloss units as measured by the Gardner 
Gloss metering unit, higher gloss paper is utilized such as from above 
about 30 to about 60 gloss units, and which after image formation with 
small particle size toners of the present invention of from about 3 to 
about 5 microns and fixing thereafter results in a higher gloss toner 
image of from about 30 to about 60 gloss units as measured by the Gardner 
Gloss metering unit. The aforementioned toner to paper matching can be 
attained with small particle size toners such as less than 7 microns and 
preferably less than 5 microns, such as from about 1 to about 4 microns 
such that the pile height of the toner layer(s) is low. 
Numerous processes are known for the preparation of toners, such as, for 
example, conventional processes wherein a resin is melt kneaded or 
extruded with a pigment, micronized and pulverized to provide toner 
particles with an average volume particle diameter of from about 9 microns 
to about 20 microns and with broad geometric size distribution of from 
about above 1.4 to about 2.0. In such processes it is usually necessary to 
subject the aforementioned toners to a classification procedure such that 
the geometric size distribution of from about 1.2 to about 1.4 is 
attained. Also, in the aforementioned conventional process, low toner 
yields after classifications may be obtained. Generally, during the 
preparation of toners with average particle size diameters of from about 
11 microns to about 15 microns, toner yields range from about 70 percent 
to about 85 percent after classification. Additionally, during the 
preparation of smaller sized toners with particle sizes of from about 7 
microns to about 11 microns, lower toner yields are obtained after 
classification, such as from about 50 percent to about 70 percent. With 
the processes of the present invention in embodiments, small average 
particle sizes of from about 3 microns to about 9, and preferably 5 
microns are attained without resorting to classification processes, and 
where in narrow geometric size distributions are attained, such as from 
about 1.16 to about 1.35, and preferably from about 1.16 to about 1.30. 
High toner yields are also attained such as from about 90 percent to about 
98 percent in embodiments. In addition, by the toner particle preparation 
process of the present invention in embodiments, small particle size 
toners of from about 3 microns to about 7 microns can be economically 
prepared in high yields such as from about 90 percent to about 98 percent 
by weight based on the weight of all the toner material ingredients. 
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. 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. The process of the present invention need not utilize polymers with 
polar acid groups, and toners can be prepared with resins such as 
poly(styrenebutadiene) or PLIOTONE.TM. without containing polar acid 
groups. Additionally, the toner of the '127 patent does not appear to 
utilize counterionic surfactant and flocculation 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 the use of coagulants, such as inorganic magnesium sulfate which 
results in the formation of particles with wide GSD. Furthermore, the '488 
patent does not, it is believed, disclose the process of counterionic 
flocculation, and the importance of solid contents to control particle 
size. 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, wherein 
similar to the '127 patent polar resins of oppositely charges are 
selected; 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. Other patents mentioned are 3,674,736; 
4,137,188 and 5,066,560. 
In U.S. Pat. No. 5,290,645, the disclosure of which is totally incorporated 
herein by reference, there is disclosed a process for the preparation of 
toners comprised of dispersing a polymer solution comprised of an organic 
solvent, and a polyester and homogenizing and heating the mixture to 
remove the solvent and thereby form toner composites. Additionally, there 
is disclosed in U.S. Pat. No. 5,278,020, the disclosure of which is 
totally incorporated herein by reference, a process for the preparation of 
in situ toners comprising an halogenization procedure which, for example, 
chlorinates the outer surface of the toner and results in enhanced 
blocking properties. More specifically, this patent application discloses 
an aggregation process wherein a pigment mixture, containing an ionic 
surfactant, is added to a resin mixture, containing polymer resin 
particles of less than 1 micron, nonionic and counterionic surfactant, 
thereby causing a flocculation to statically bound aggregates of about 0.5 
to about 5 microns in volume diameter as measured by the Coulter Counter, 
and thereafter heating to form toner composites or toner compositions of 
from about 3 to about 7 microns in volume diameter. 
In U.S. Pat. No. 5,308,734, the disclosure of which is totally incorporated 
herein by reference, there is illustrated a process for the preparation of 
toner compositions which comprises generating an aqueous dispersion of 
toner fines, ionic surfactant and nonionic surfactant, adding thereto a 
counterionic surfactant with a polarity opposite to that of said ionic 
surfactant, homogenizing and stirring said mixture, and heating to provide 
for coalescence of said toner fine particles. 
In copending patent application U.S. Ser. No. 022,575 (D/92577), the 
disclosure of which is totally incorporated herein by reference, there is 
disclosed a process for the preparation of toner compositions comprising 
(i) preparing a pigment dispersion in a water, which dispersion is 
comprised of a pigment, an ionic surfactant and optionally a charge 
control agent; 
(ii) shearing the pigment dispersion with a latex mixture comprised of a 
counterionic surfactant with a charge polarity of opposite sign to that of 
said ionic surfactant, a nonionic surfactant and resin particles, thereby 
causing a flocculation or heterocoagulation of the formed particles of 
pigment, resin and charge control agent to form electrostatically bound 
toner size aggregates; and 
(iii) heating the statically bound aggregated particles to form said toner 
composition comprised of polymeric resin, pigment and optionally a charge 
control agent. 
Disadvantages that can be associated with the process of U.S. Ser. No. 
022,575 (D/92577) is that toners of different size cannot usually be 
obtained, rather the size of the toner is altered only by alteration of 
the starting latex resin size and composition and the quantity of 
coagulant added to form the aggregates. When toner particles are prepared 
by varying the coagulant/resin ratio the chemical composition of the 
obtained toner, particularly the surface properties of the toner, can 
differ from one aggregate size to another, and this can cause differences 
in the xerographic behavior of the material as indicated in U.S. Pat. No. 
5,213,938, the disclosure of which is totally incorporated herein by 
reference, since, for example, the xerographic toner charging process is, 
for example, very dependent on the toner surface chemistry. 
In copending patent application U.S. Ser. No. 082,651, filed concurrently 
herewith, the disclosure of which is totally incorporated herein by 
reference, there is illustrated a process for the preparation of toner 
compositions with controlled particle size comprising: 
(i) preparing a pigment dispersion in water, which dispersion is comprised 
of pigment, an ionic surfactant and an optional charge control agent; 
(ii) shearing at high speeds the pigment dispersion with a polymeric latex 
comprised of resin, a counterionic surfactant with a charge polarity of 
opposite sign to that of said ionic surfactant, and a nonionic surfactant 
thereby forming a uniform homogeneous blend dispersion comprised of resin, 
pigment, and optional charge agent; 
(iii) heating the above sheared homogeneous blend below about the glass 
transition temperature (Tg) of the resin while continuously stirring to 
form electrostatically bound toner size aggregates with a narrow particle 
size distribution; 
(iv) heating the statically bound aggregated particles above about the Tg 
of the resin particles to provide coalesced toner comprised of resin, 
pigment and optional charge control agent, and subsequently optionally 
accomplishing (v) and (vi); 
(v) separating said toner; and 
(vi) drying said toner. 
In copending patent application U.S. Ser. No. 083,146, (not yet assigned 
D/93106), filed concurrently herewith, the disclosure of which is totally 
incorporated herein by reference, there is illustrated a process for the 
preparation of toner compositions with a volume median particle size of 
from about 1 to about 25 microns, which process comprises: 
(i) preparing by emulsion polymerization a charged polymeric latex of 
submicron particle size; 
(ii) preparing a pigment dispersion in water, which dispersion is comprised 
of a pigment, an effective amount of cationic flocculant surfactant, and 
optionally a charge control agent; 
(iii) shearing the pigment dispersion (ii) with a polymeric latex (i) 
comprised of resin, a counterionic surfactant with a charge polarity of 
opposite sign to that of said ionic surfactant thereby causing a 
flocculation or heterocoagulation of the formed particles of pigment, 
resin and charge control agent to form a high viscosity gel in which solid 
particles are uniformly dispersed; 
(iv) stirring the above gel comprised of latex particles, and oppositely 
charged pigment particles for an effective period of time to form 
electrostatically bound relatively stable toner size aggregates with 
narrow particle size distribution; and 
(v) heating the electrostatically bound aggregated particles at a 
temperature above the resin glass transition temperature (Tg) thereby 
providing said toner composition comprised of resin, pigment and 
optionally a charge control agent. 
In copending patent application U.S. Ser. No. 083,157, filed concurrently 
herewith, the disclosure of which is totally incorporated herein by 
reference, there is illustrated a process for the preparation of toner 
compositions with controlled particle size comprising: 
(i) preparing a pigment dispersion in water, which dispersion is comprised 
of a pigment, an ionic surfactant in amounts of from about 0.5 to about 10 
percent by weight of water, and an optional charge control agent; 
(ii) shearing the pigment dispersion with a latex mixture comprised of a 
counterionic surfactant with a charge polarity of opposite sign to that of 
said ionic surfactant, a nonionic surfactant and resin particles, thereby 
causing a flocculation or heterocoagulation of the formed particles of 
pigment, resin and charge control agent; 
(iii) stirring the resulting sheared viscous mixture of (ii) at from about 
300 to about 1,000 revolutions per minute to form electrostatically bound 
substantially stable toner size aggregates with a narrow particle size 
distribution; 
(iv) reducing the stirring speed in (iii) to from about 100 to about 600 
revolutions per minute and subsequently adding further anionic or nonionic 
surfactant in the range of from about 0.1 to about 10 percent by weight of 
water to control, prevent, or minimize further growth or enlargement of 
the particles in the coalescence step (iii); and 
(v) heating and coalescing from about 5.degree. to about 50.degree. C. 
above about the resin glass transition temperature, Tg, which resin Tg is 
from between about 45.degree. to about 90.degree. C. and preferably from 
between about 50.degree. and about 80.degree. C., the statically bound 
aggregated particles to form said toner composition comprised of resin, 
pigment and optional charge control agent. 
In copending patent application U.S. Ser. No. 082,741, filed concurrently 
herewith, the disclosure of which is totally incorporated herein by 
reference, there is illustrated a process for the preparation of toner 
compositions with controlled particle size and selected morphology 
comprising 
(i) preparing a pigment dispersion in water, which dispersion is comprised 
of pigment, ionic surfactant, and optionally a charge control agent; 
(ii) shearing the pigment dispersion with a polymeric latex comprised of 
resin of submicron size, a counterionic surfactant with a charge polarity 
of opposite sign to that of said ionic surfactant and a nonionic 
surfactant thereby causing a flocculation or heterocoagulation of the 
formed particles of pigment, resin and charge control agent, and 
generating a uniform blend dispersion of solids of resin, pigment, and 
optional charge control agent in the water and surfactants; 
(iii) (a) continuously stirring and heating the above sheared blend to form 
electrostatically bound toner size aggregates; or 
(iii) (b) further shearing the above blend to form electrostatically bound 
well packed aggregates; or 
(iii) (c) continuously shearing the above blend, while heating to form 
aggregated flake-like particles; 
(iv) heating the above formed aggregated particles about above the Tg of 
the resin to provide coalesced particles of toner; and optionally 
(v) separating said toner particles from water and surfactants; and 
(vi) drying said toner particles. 
In copending patent application U.S. Ser. No. 082,660, filed concurrently 
herewith, the disclosure of which is totally incorporated herein by 
reference, there is illustrated a process for the preparation of toner 
compositions comprising: 
(i) preparing a pigment dispersion, which dispersion is comprised of a 
pigment, an ionic surfactant, and optionally a charge control agent; 
(ii) shearing said pigment dispersion with a latex or emulsion blend 
comprised of resin, a counterionic surfactant with a charge polarity of 
opposite sign to that of said ionic surfactant and a nonionic surfactant; 
(iii) heating the above sheared blend below about the glass transition 
temperature (Tg) of the resin to form electrostatically bound toner size 
aggregates with a narrow particle size distribution; and 
(iv) heating said bound aggregates above about the Tg of the resin.

SUMMARY OF THE INVENTION 
It is an object of the present invention to provide toner processes with 
many of the advantages illustrated herein. 
In another object of the present invention there are provided simple and 
economical processes for the direct preparation of black and colored toner 
compositions with, for example, excellent pigment dispersion and narrow 
GSD. 
In another object of the present invention there are provided simple and 
economical in situ processes for black and colored toner compositions by 
an aggregation process comprised of (i) preparing a cationic pigment 
mixture, containing pigment particles, and optionally charge control 
agents and other known optional additives dispersed in a water containing 
a cationic surfactant by shearing, microfluidizing or ultrasonifying; (ii) 
shearing the aforementioned pigment mixture with a latex mixture comprised 
of a polymer resin, and suitable surfactants in water thereby causing a 
flocculation or heterocoagulation, which on shearing and further stirring 
for from about 1 to about 4 hours allows the formation of 
electrostatically stable aggregates of from about 0.5 to about 5 microns 
in volume diameter as measured by the Coulter Counter; and (iii) 
coalescing or fusing the aggregated particles by heating in the range, for 
example, of from about 60.degree. to about 95.degree. C., to form toner 
composites, or a toner composition comprised of resin, pigment, and charge 
additive, wherein the concentration of the latex, such as 
polystyrene/polybutylacrylate and polyacrylic acid, is decreased from 40 
percent to 2 percent solids and preferably from 30 percent to 5 percent 
by weight solids. 
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 0.5 to about 20 microns, and preferably from about 1 to 
about 10 microns, and with a narrow GSD of from about 1.15 to about 1.35 
and preferably from about 1.2 to about 1.3 as measured by the Coulter 
Counter. 
Moreover, in a further object of the present invention there is provided a 
process for the preparation of toners which after fixing to paper 
substrates result in images with gloss of from 20 GGU up to 70 GGU as 
measured by Gardner Gloss meter matching of toner and paper. 
In another object of the present invention there are provided composite 
polar or nonpolar toner compositions in high yields of from about 90 
percent to about 100 percent by weight of toner without resorting to 
classification, and wherein by varying the latex concentration and 
maintaining the latex/coagulant ratio provides toner aggregates at various 
size diameters. 
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 high projection efficiency such as from about 75 
to about 95 percent efficiency as measured by the Match Scan 11 
spectrophotometer available from Milton-Roy. 
In a further object of the present invention there are provided toner 
compositions which result in low or no paper curl. 
Another object of the present invention resides in processes for the 
preparation of small sized toner particles with narrow GSDs, and excellent 
pigment dispersion by the aggregation of latex particles, with pigment 
particles dispersed in water and surfactant, and wherein the aggregated 
particles, of toner size, can then be caused to coalesce by, for example, 
heating. In embodiments, factors of importance with respect to controlling 
particle size and GSD include the concentration of the surfactant used for 
the pigment dispersion, concentration of the component, like acrylic acid 
in the latex, the temperature of coalescence, the solids contents, and the 
time of coalescence. 
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 direct preparation of toner compositions by an improved 
flocculation or heterocoagulation, and coalescence processes and wherein 
the cationic coagulant surfactant amount selected is in a fixed proportion 
to the latex anionic surfactant present in the mixture and the final toner 
particle size, that is average volume diameter and GSD is controlled by 
varying the solids loading of the latex dispersion in the range of from 
about 40 percent to about 2 percent, and preferably from 30 percent to 5 
percent. 
In embodiments, the present invention is directed to a process for the 
preparation of toner compositions comprising 
(i) preparing a pigment dispersion in water, which dispersion is comprised 
of pigment, a counterionic surfactant with a charge polarity of opposite 
sign to the anionic surfactant of (ii) surfactant and optionally a charge 
control agent; 
(ii) shearing the pigment dispersion with a latex comprised of resin, 
anionic surfactant, nonionic surfactant, and water; and wherein the latex 
solids content, which solids are comprised of resin, is from about 50 
percent to about 20 weight percent thereby causing a flocculation or 
heterocoagulation of the formed particles of pigment, resin and optional 
charge control agent; diluting with water to form a dispersion of total 
solids of from about 30 percent to 1 weight percent, which total solids 
are comprised of resin, pigment and optional charge control agent 
contained in a mixture of said nonionic, anionic and cationic surfactants; 
(iii) heating the above sheared blend at a temperature of from about 
5.degree. to about 25.degree. C. below about the glass transition 
temperature Tg of the resin while continuously stirring to form toner 
sized aggregates with a narrow size dispersity; and 
(iv) heating the electrostatically bound aggregated particles at a 
temperature of from about 5.degree. to about 50.degree. C. above about the 
Tg of the resin to provide a toner composition comprised of resin, pigment 
and optionally a charge control agent. 
In embodiments, the present invention is directed to processes for the 
preparation of toner compositions which comprises initially attaining or 
generating an ionic pigment dispersion, for example by dispersing an 
aqueous mixture of a pigment or pigments such as phthalocyanine, 
quinacridone or Rhodamine B type with counterionic surfactant, such as a 
cationic surfactant such as benzalkonium chloride by utilizing a high 
shearing device such as a Brinkmann Polytron, thereafter shearing this 
mixture by utilizing a high shearing device such as a Brinkmann Polytron, 
a sonicator or microfluidizer with a controlled solids content of 
suspended resin mixture comprised of polymer or resin particles such as 
poly(styrene butadiene) or poly(styrenebutylacrylate) and of particle size 
ranging from 0.01 to about 0.5 micron, in an aqueous surfactant mixture 
containing an anionic surfactant such as sodium dodecylbenzene sulfonate 
and nonionic surfactant; resulting in a flocculation, or heterocoagulation 
of the resin particles with the pigment particles caused by the 
neutralization of cationic surfactant absorbed on the pigment particle 
with the oppositely charged anionic surfactant absorbed on the resin 
particles; and further for from about 1 to about 4 hours stirring the 
mixture using a mechanical stirrer at 250 to 500 rpm and allowing the 
formation of electrostatically stabilized aggregates ranging in diameter 
of from about 0.5 micron to about 10 microns; and heating for 1 to 6 hours 
from about 60.degree. to about 95.degree. C. to provide for particle 
fusion or coalescence of the polymer and pigment particles; followed by 
washing with, for example, hot water to remove surfactant, and drying such 
as by use of an Aeromatic fluid bed dryer whereby toner particles 
comprised of resin and pigment with various particle size diameters can be 
obtained, such as from about 1 to about 10 microns in average volume 
particle diameter as measured by the Coulter Counter. 
Embodiments of the present invention include a process for the preparation 
of toner compositions comprising 
(i) preparing a pigment dispersion in a water, which dispersion is 
comprised of a pigment, an ionic surfactant and optionally a charge 
control agent; 
(ii) shearing the pigment dispersion with a latex mixture comprised of a 
counterionic surfactant with a charge polarity of opposite sign to that of 
said ionic surfactant, a nonionic surfactant and resin particles, thereby 
causing a flocculation or heterocoagulation of the formed particles of 
pigment, resin and charge control agent; and 
(iii) diluting with water and stirring the sheared blend at elevated 
temperature, for example from about 30.degree. to about 50.degree. C., but 
about below the resin Tg, for example from about 5.degree. to about 
15.degree. C. below the resin Tg, to form electrostatically bound or 
attached toner size aggregates; heating, for example from about 5.degree. 
to 50.degree. C. above the resin Tg, the statically bound aggregated 
particles to form a toner composition comprised of polymeric resin, 
pigment and optionally a charge control agent and wherein the solids 
concentration of the latex of resin such as a copolymer of styrene, butyl 
acrylate and acrylic acid is varied from about 40 percent to about 1 
percent by weight, and preferably from 30 percent to 5 percent by weight, 
to obtain toner particles with narrow size distributions of similar 
chemical composition whose size depends inversely on the solids loading of 
the latex used. Thus, by increasing the solids content the particle size 
of aggregates can be caused to decrease. 
Also, in embodiments the present invention is directed to processes for the 
preparation of toner compositions which comprises (i) preparing an ionic 
pigment mixture by dispersing a pigment such as carbon black like REGAL 
330.TM., HOSTAPERM PINK.TM., or PV FAST BLUE.TM. of from about 2 to about 
10 percent by weight of toner in an aqueous mixture containing a cationic 
surfactant such as dialkylbenzene dialkylammonium chloride like SANIZOL 
B-50.TM. available from KAO or MIRAPOL.TM. available from Alkaril 
Chemicals of from about 0.5 to about 2 percent by weight of water, 
utilizing a high shearing device such as a Brinkmann Polytron or IKA 
homogenizer at a speed of from about 3,000 revolutions per minute to about 
10,000 revolutions per minute for a duration of from about 1 minute to 
about 120 minutes; (ii) adding the aforementioned ionic pigment mixture to 
an aqueous suspension of resin particles comprised of, for example, 
poly(styrene-butylmethacrylate), PLIOTONE.TM. or poly(styrenebutadiene) of 
from about 88 percent to about 98 percent by weight of the toner, and of 
about 0.1 micron to about 3 microns polymer particle size in volume 
average diameter, and counterionic surfactant such as an anionic 
surfactant like sodium dodecyl sulfate, dodecylbenzene sulfonate or NEOGEN 
R.TM. from about 0.5 to about 2 percent by weight of water, a nonionic 
surfactant such polyethylene glycol or polyoxyethylene glycol nonyl phenyl 
ether or IGE 897.TM. obtained from GAF Chemical Company, of from about 
0.5 to about 3 percent by weight of water, thereby causing a flocculation 
or heterocoagulation of pigment, charge control additive and resin 
particles; (iii) diluting the aggregate particle mixture with water from 
about 30 percent solids to about 25 to 2 percent solids; (iv) homogenizing 
the resulting flocculent mixture with a high shearing device such as a 
Brinkmann Polytron or IKA homogenizer at a speed of from about 3,000 
revolutions per minute to about 10,000 revolutions per minute for a 
duration of from about 1 minute to about 120 minutes, thereby resulting in 
a homogeneous mixture of latex and pigment and further stirring with a 
mechanical stirrer at from about 250 to 500 rpm to form electrostatically 
stable aggregates of from about 0.5 microns to about 5 microns in average 
volume diameter; (v) heating the statically bound aggregate composite 
particles of from about 60.degree. C. to about 95.degree. C. for a 
duration of about 60 minutes to about 600 minutes to form toner sized 
particles of from about 3 microns to about 7 microns in volume average 
diameter and with a geometric size distribution of from about 1.2 to about 
1.4 as measured by the Coulter Counter; and (vi) isolating the toner sized 
particles by washing, filtering and drying thereby providing a toner 
comprised of polymeric resin, pigment and optionally charge control agent. 
Additives to improve flow characteristics and charge additives to improve 
charging characteristics may be optionally added by blending with the 
toner, such additives including AEROSILS.RTM. or silicas, metal oxides 
like tin, titanium and the like, of from about 0.1 to about 10 percent by 
weight of the toner. 
In some instances, pigments which are available in the wet cake or 
concentrated form containing water, can be easily dispersed utilizing a 
homogenizer or with stirring. In other instances, pigments are available 
in a dry form, whereby a dispersion in water can be effected by 
microfluidizing using, for example, a M-110 microfluidizer and passing the 
pigment dispersion from about 1 to 10 times through the fluidizer chamber, 
or by sonication, such as using a Branson 700 sonicator, with the optional 
addition of dispersing agents such as the aforementioned ionic or nonionic 
surfactants. 
Embodiments of the present invention include a process for the preparation 
of toner compositions comprising 
(i) preparing a pigment dispersion in water, which dispersion is comprised 
of a pigment and a cationic surfactant; 
(ii) shearing the pigment dispersion with a latex containing a controlled 
resin solid contents of from about 50 percent to about 20 percent of 
polymer or resin, an anionic surfactant and nonionic surfactant in water, 
thereby causing a flocculation or heterocoagulation of the formed 
particles of pigment, resin and charge control agent to form a dispersion 
of total solids of from about 30 percent to 2 percent comprised of resin 
and pigment particles contained in the mixture of nonionic, anionic and 
cationic surfactants; 
(iii) heating the above sheared blend at a temperature of from about 
5.degree. to about 25.degree. C. below about the glass transition 
temperature Tg of the resin, or about equal to the Tg while continuously 
stirring to form toner sized aggregates with a narrow size dispersity; and 
(iv) heating the electrostatically bound aggregated particles at a 
temperature of from about 5.degree. to about 50.degree. C. above about the 
Tg of the resin to provide said toner composition comprised of resin and 
pigment. 
Embodiments of the present invention include a process for the preparation 
of toner compositions with controlled particle size comprising 
(i) preparing a pigment dispersion in water, which dispersion is comprised 
of a pigment and counterionic surfactant; 
(ii) shearing the pigment dispersion with a latex, which latex contains a 
resin solid content of from about 50 percent by weight to about 20 percent 
by weight, an anionic surfactant, and nonionic surfactant in water thereby 
causing a flocculation or heterocoagulation of the formed particles of 
pigment and resin to form a uniform dispersion of total solids from about 
30 percent by weight to about 2 percent by weight, comprised of resin and 
pigment particles dispersed in the mixture of nonionic, anionic and 
counterionic surfactants; 
(iii) heating the above sheared blend at a temperature of from about 
5.degree. to about 25.degree. C. below the glass transition temperature Tg 
of the resin while continuously stirring to form toner sized aggregates 
with a narrow size dispersity; 
(iv) heating the electrostatically bound aggregated particles at a 
temperature of from about 5.degree. to about 50.degree. C. above the Tg of 
the resin to provide said toner composition comprised of resin and 
pigment; and optionally 
(v) separating said toner particles from the water in (i) by filtration, or 
centrifugation; and 
(vi) drying the said toner particles. 
Illustrative examples of resins selected for the process of the present 
invention include known polymers like poly(styrene-butadiene), 
poly(para-methyl styrene-butadiene), poly(meta-methyl styrenebutadiene), 
poly(alpha-methyl styrene-butadiene), poly(methylmethacrylate-butadiene), 
poly(ethylmethacrylate-butadiene), poly(propylmethacrylate-butadiene), 
poly(butylmethacrylate-butadiene), poly(methylacrylate-butadiene), 
poly(ethylacrylate-butadiene), poly(propylacrylate-butadiene), 
poly(butylacrylate-butadiene), poly(styrene-isoprene), poly(para-methyl 
styrene-isoprene), poly(meta-methyl styrene-isoprene), 
poly(alpha-methylstyrene-isoprene), poly(methylmethacrylate-isoprene), 
poly(ethylmethacrylate-isoprene), poly(propylmethacrylate-isoprene), 
poly(butylmethacrylate-isoprene), poly(methylacrylate-isoprene), 
poly(ethylacrylate-isoprene), poly(propylacrylate-isoprene), and 
poly(butylacrylate-isoprene), terpolymers such as 
poly(styrene-butadiene-acrylic acid), poly(styrene-butadiene-methacrylic 
acid), PLIOTONE.TM. available from Goodyear, polyethylene-terephthalate, 
polypropylene-terephthalate, polybutylene-terephthalate, 
polypentylene-terephthalate, polyhexalene-terephthalate, 
polyheptadene-terephthalate, polyoctalene-terephthalate, POLYLITE.TM. 
(Reichhold Chemical Inc), PLASTHALL.TM. (Rohm & Haas), CYGAL.TM. (American 
Cyanamide), ARMCO.TM. (Armco Composites), CELANEX.TM. (Celanese Eng), 
RYNITE.TM. (DuPont), STYPOL.TM., and the like. The resin particles 
selected, which generally can be in embodiments styrene acrylates, styrene 
butadienes, styrene methacrylates, or polyesters, are present in various 
effective amounts, such as from about 85 weight percent to about 98 weight 
percent of the toner, and can be of small average (resin) particle size 
such as from about 0.01 micron to about 1 micron in average volume 
diameter as measured by the Brookhaven nanosize particle analyzer. 
The resin selected for the process of the present invention can be prepared 
by emulsion polymerization techniques, and the monomers utilized in such 
processes can be selected from the group consisting of styrene, acrylates, 
methacrylates, butadiene, isoprene, and optionally acid or basic olefinic 
monomers such as acrylic acid, methacrylic acid, acrylamide, 
methacrylamide, quaternary ammonium halide of dialkyl or trialkyl 
acrylamides or methacrylamide, vinylpyridine, vinylpyrrolidone, 
vinyl-N-methylpyridinium chloride, and the like. The presence of acid or 
basic groups is optional and such groups can be present in various amounts 
of from about 0.1 to about 10 percent by weight of the polymer resin. 
Known chain transfer agents such as dodecanethiol or carbon tetrachloride 
can also be selected when preparing resin particles by emulsion 
polymerization. Other process of obtaining resin particles of from about 
0.01 micron to about 3 microns can be selected from polymer 
microsuspension process, such as disclosed in U.S. Pat. No. 3,674,736, the 
disclosure of which is totally incorporated herein by reference, polymer 
solution microsuspension process, such as disclosed in U.S. Pat. No. 
5,290,654, the disclosure of which is totally incorporated herein by 
reference, mechanical grinding process, or other known processes. Also, 
the resins selected can be purchased. 
Various known colorants or pigments 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., 
REGAL 400.RTM., REGAL 660.RTM.; magnetites, such as Mobay magnetites 
MO8029.TM., MO8060.TM.; Columbian magnetites; MAPICO BLACKS.TM. and 
surface treated magnetites; Pfizer magnetites, CB4799.TM., CB5300.TM., 
CB5600.TM., MCX6369.TM.; Bayer magnetites, BAYFERROX 8600.TM., 8610.TM.; 
Northern Pigments magnetites, NP-604.TM., NP-608.TM.; Magnox magnetites 
TMB-100.TM., or TMB-104.TM.; and other equivalent black pigments. 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., 
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, red, blue, green, brown, or yellow pigments, and mixtures 
thereof. 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. 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. The pigments or dyes selected are present in various 
effective amounts, such as from about 1 weight percent to about 65 weight 
and preferably from about 2 to about 12 percent of the toner. 
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, 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. 
Surfactants in amounts of, for example, 0.1 to about 25 weight percent in 
embodiments include, for example, nonionic 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 octylphenyl ether, polyoxyethylene oleyl 
ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl 
ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy) 
ethanol (available from Rhone-Poulenac 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.. 
An effective concentration of the nonionic surfactant is, for example, 
from about 0.01 to about 10 percent by weight, and preferably from about 
0.1 to about 5 percent by weight of monomers selected to prepare the 
copolymer resin, or in amounts as indicated herein. 
Examples of ionic surfactants include cationic and anionic surfactants with 
examples of anionic surfactants being, for example, sodium dodecyl sulfate 
(SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, 
dialkyl benzenealkyl, sulfates and sulfonates, abitic acid, available from 
Aldrich, NEOGEN R.TM., NEOGEN SC.TM. from Kao and the like. An effective 
concentration of the anionic surfactant generally employed is, for 
example, from about 0.01 to about 10 percent by weight, and preferably 
from about 0.1 to about 5 percent by weight of monomers selected to 
prepare the copolymer resin, or in amounts as indicated herein. 
Examples of cationic surfactants selected for the processes of the present 
invention are, for example, dialkyl benzenealkyl ammonium chloride, lauryl 
trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl 
benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium 
bromide, C.sub.12, C.sub.15, C.sub.17 trimethyl ammonium bromides, halide 
salts of quaternized polyoxyethylalkylamines, dodecylbenzyl triethyl 
ammonium chloride, MIRAPOL.TM. and ALKAQUAT.TM. available from Alkaril 
Chemical Company, SANIZOL.TM. (benzalkonium chloride), available from Kao 
Chemicals, and the like, and mixtures thereof. This surfactant is utilized 
in various effective amounts, such as, for example, from about 0.1 percent 
to about 5 percent by weight of water. Preferably the molar ratio of the 
cationic surfactant used for flocculation to the anionic surfactant used 
in the latex preparation is in range of about 0.5 to 4, preferably from 
about 0.5 to 2. 
The temperature for the aggregation is preferably accomplished in the range 
of from about 5.degree. to about 20.degree. C. below the resin Tg, which 
resin Tg is, for example, from about 45.degree. to about 80.degree. C., 
and preferably from about 30.degree. to about 50.degree. C., while being 
stirred for from about 1 to about 4 hours for example. The resulting total 
solids comprise latex particles and pigment particles. The aggregate 
particles are then coalesced by raising the temperature to about 5.degree. 
to about 50.degree. C. above the resin Tg, for example, from about 
60.degree. to about 95.degree. C. 
Surface additives that can be added to the toner compositions after washing 
or drying include, for example, metal salts, metal salts of fatty acids, 
like zinc stearate, colloidal silicas, mixtures thereof and the like, 
which additives are usually 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 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. 
Latex solids refers in embodiments to the amount of resin, such as 50 to 20 
weight percent of the latex of (ii); and total solids refers in 
embodiments to resin, pigment, and optional charge additive or charge 
control agent. The solids contents, that is resin, is reduced by diluting 
with water, for example, to from about 30 to about 1 percent by weight of 
total solids. Various effective amounts of water can be selected for 
dilution as indicated herein. 
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. 
EXAMPLES 
Preparation of the Toner Resin 
A latex was prepared by emulsion polymerization as follows: 
Latex A: 4,920 Grams of styrene, 1,080 grams of butyl acrylate, 120 grams 
of acrylic acid, 60 grams of carbon tetrabromide and 210 grams of 
dodecanethiol were mixed with 9,000 grams of deionized water in which 135 
grams of sodium dodecyl benzene sulfonate (SDBS) anionic surfactant 
(NEOGEN R.TM. which contains 60 percent of active component and 40 percent 
of water component), 129 grams of polyoxyethylene nonyl phenyl 
ether--nonionic surfactant (ANTAROX 897.TM.--70 percent 
active--polyethoxylated alkylphenols), and 60 grams of ammonium persulfate 
initiator were dissolved. The emulsion was then polymerized at 80.degree. 
C. for 5 hours. A latex containing 40 percent solids of polymeric or resin 
particles of a copolymer of styrene, butylacrylate and acrylic acid 
(88/12/2 parts) with a particle size of 150 nanometers, as measured on 
Brookhaven nanosizer, was obtained. Tg=53.degree. C., as measured on 
DuPont DSC. M.sub.w =20,000, and M.sub.n =6,000 as determined on Hewlett 
Packard GPC. The aforementioned latex was then selected for the toner 
preparation of Examples I to IV. 
Preparation of the Pigment Dispersion 
A pigment dispersion was prepared as follows: 
Pigment Dispersion B: 280 Grams of dry PV FAST BLUE.TM. pigment and 58.5 
grams of the cationic or counterionic surfactant SANIZOL B-50.TM. were 
suspended in 8,000 grams of distilled water and subsequently passed 
through a microfluidizer until the dispersion was homogeneous. This 
mixture was then utilized to form the toner in Examples I and II. 
Pigment Dispersion C: 15 Grams of SUN FAST BLUE L.TM. pigment and 8.8 grams 
of the cationic surfactant SANIZOL B-50.TM. were suspended in 500 grams of 
distilled water and homogenized using the inline homogenizer IKA SD41. 
This mixture was then utilized to form the toner in Example III. 
PREATION OF TONER TICLES 
Example I 
417 Grams of the PV FAST BLUE.TM. dispersion (Pigment B) and 650 grams of 
the latex (Latex A) were simultaneously added into a SD41 continuous 
blending device which contained and was diluted with 1,200 grams of water. 
Homogenization was achieved by recirculating the contents of the SD41 
continuously through the shearing chamber at 10,000 rpm for 8 minutes. 
The product resulting was then transferred to a controlled temperature 
kettle and heated at 45.degree. C. while gently stirring for 3 hours. The 
aggregate produced had a diameter of 5.1 microns average volume diameter 
with a GSD of 1.21 as determined by particle diameter measurements using 
the Coulter Counter (Microsizer II). At this point, 40 grams of a 20 
percent by weight solution of NEOGEN R.TM. in water was added to the 
kettle to prevent the formed aggregates from further aggregating and 
increasing in size during the following coalescence stage of the process. 
The kettle contents were then heated to 85.degree. C. while stirring for 
about 4 hours. The particle size was measured again on the Coulter 
Counter. Toner particles of 5.1 microns were obtained with a GSD=1.21, 
indicating no further growth in the particle size. The particles were then 
washed with water and dried. The aforementioned cyan toner was comprised 
of 88 parts of polystyrene, 12 parts of polybutylacrylate, 2 parts of 
polyacrylic acid and 5.5 percent (5.61 parts) of cyan pigment particles 
prepared under conditions of 11.5 percent solids or resin loading of the 
latex in the blend of (ii) of resin, pigment, nonionic, anionic, cationic 
surfactant and water. The yield of the toner particles was 98 percent. 
Example II 
417 Grams of the PV FAST BLUE.TM. dispersion (pigment dispersion B), which 
contains 50 grams of pigment and 366 grams of water, and a mixture of 324 
grams of the latex containing 210 grams of water and 140 grams of the 
polymeric particles, and 325 grams of water were simultaneous added into a 
SD-41 inline homogenizing device which contained and was diluted with 
1,200 grams water. The aggregation was performed in a kettle under the 
same conditions as described in Example I. In this Example the aggregate 
was found to have a diameter of 8.1 microns with a GSD of 1.25. The 
addition of 40 grams of a 20 percent by weight solution of NEOGEN R.TM. in 
water and heating at 85.degree. C. for 4 hours provided a toner of 
dimensional characteristics unchanged from that observed for the 
aggregate. The cyan toner particles obtained were comprised of 88 parts of 
polystyrene, 12 parts of polybutylacrylate, 2 parts of polyacrylic acid 
and 5.5 percent of pigment (5.7 percent solids loading) possess the same 
Tg (Tg=53.degree. C.) as the latex and the toner yield was 98 percent. 
Example III 
418 Grams of the SUN FAST BLUE.TM. dispersion (pigment dispersion C) was 
mixed with an additional 5.9 grams of SANIZOL B50.TM. in 100 grams of 
water and this pigment mixture and 975 grams of the latex were 
simultaneously added into the SD-41 inline homogenizing device which 
contained as the diluent 500 grams of water. The aggregation was performed 
in a continuously stirred kettle which was heated to 45.degree. C. The 
aggregates formed were found to have a diameter of 2.9 microns with a GSD 
of 1.22. 50 Grams of a 20 percent by weight solution of NEOGEN R.TM. in 
water was then added followed by heating at 85.degree. C. for four hours 
to provide toner comprised of 88 parts of polystyrene, 12 parts of 
polybutylacrylate, 2 parts of polyacrylic acid and 5.5 percent of pigment, 
which toner is 3.0 microns in volume diameter with a volume GSD of 1.22. 
The cyan toner particles prepared (20.0 percent solids) have the same Tg 
(Tg =53.degree. C.) as the latex, and the toner yield was 98 percent. 
The dependence of the final aggregate and toner size on the latex solids or 
resin loadings is summarized in the following table and FIG. 1, where the 
x axis represents the percent latex resin loading, calculated 
theoretically, while the y axis represents the particle size (average 
volume diameter) as measured on the Coulter Counter as is the GSD. 
______________________________________ 
LATEX AGGREGATE 
RESIN AND TONER TONER 
LOADING TICLE SIZE GSD 
______________________________________ 
20.0 3.1 1.22 
11.5 5.1 1.21 
5.7 8.1 1.25 
______________________________________ 
Other embodiments and modifications of the present invention may occur to 
those skilled in the art subsequent to a review of the information 
presented herein; these embodiments and modifications, as well as 
equivalents thereof, are also included within the scope of this invention.