Fluorescent toner processes

A process for the preparation of fluorescent toner compositions comprising PA1 (i) preparing a pigment dispersion in a solvent, which dispersion is comprised of a pigment or dye, an ionic surfactant and optionally a charge control agent; PA1 (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 pigment, resin particles and charge control agent to form electrostatically bound toner size aggregates; and PA1 (iii) heating the statically bound aggregated particles to form said toner composition comprised of polymeric resin, pigment and optionally a charge control agent, and wherein the pigment or dye is excitable by ultraviolet light in the frequency range of from about 254 to about 366 nanometers and fluoresces in the visible spectrum of from about 400 to about 700 nanometers.

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 fluorescent security toner compositions. In embodiments, the present 
invention is directed to the economical preparation of fluorescent toners 
without the utilization of the known pulverization and/or classification 
methods, and wherein toners with an average volume diameter of from about 
1 to about 25 and preferably from 1 to about 10 microns, and narrow GSD 
characteristics can be obtained. The resulting toners can be selected for 
known electrophotographic imaging and printing processes, including 
security color processes and lithography. In embodiments, the present 
invention is directed to a process comprised of dispersing a component, 
such as a pigment, excited in the ultraviolet region of the light spectrum 
and which fluoresces in the visible spectral region, such as invisible 
blue dyes, and optionally a charge control agent or additive in an aqueous 
mixture 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 2 microns in volume diameter, in an aqueous solution 
containing a counterionic surfactant with opposite charge to the ionic 
surfactant of the pigment dispersion and nonionic surfactant, thereby 
causing a flocculation of resin particles, pigment particles and optional 
charge control particles, followed by 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 particles, and thereafter heating to generate toners with 
an average particle volume diameter of from about 1 to about 25 microns in 
embodiments, a luminescent dye or pigment is dispersed in an aqueous 
cationic solution by ultra sonification or microfluidization methods, and 
the pigment or dye solution iS simultaneously introduced with latex 
particles into a high shear device containing water, and wherein blending 
is accomplished at high speeds of, for example, about 7,000 to about 
12,000 revolutions per minute, followed by aggregating and coalescing, 
reference U.S. Pat. Nos. 5,370,963, 5,344,738, 5,403,693, 5,418,108, 
5,364,729, and 5,405,728, the disclosures of which are totally 
incorporated herein by reference. It is believed that during the heating 
stage, the aggregate particles fuse together to form toners. In 
embodiments thereof, the present invention is directed to an in situ 
process comprised of first dispersing a pigment, such as an invisible blue 
fluorescent dye, in an aqueous mixture containing a cationic surfactant, 
such as benzalkonium bromide (SANIZOL B-50.TM.), utilizing a high shearing 
device, such as a Brinkman Polytron, microfluidizer or sonicator; 
thereafter shearing this mixture with a latex of suspended resin 
particles, such as PLIOTONE.TM., comprised of styrene butadiene and of a 
particle size ranging from 0.01 to about 0.5 micron, 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; which on further stirring 
results in formation of statically bound or attached aggregates ranging in 
size of from about 0.5 micron to about 10 microns in average diameter size 
as measured by the Coulter Counter (Microsizer II); and thereafter, 
heating 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 volume average particle diameter. 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 
or dye, 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 disperses the big 
initially formed flocculants, and speeds up formation of stabilized 
aggregates negatively charged and comprised of the pigment and resin 
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 composites. 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; and form statically bound aggregate particles by stirring 
of the homogeneous mixture and toner formation after heating. 
SUMMARY OF THE INVENTION 
It is an object of the present invention to provide toner processes with 
many of the advantages illustrated herein. Specifically, the present 
invention provides a means for the incorporation of water insoluble, 
visibly fluorescent dyes and pigments into toner particles which 
circumvents the more costly and energy conventional melt mixing process. 
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, and wherein the pigment is excited in the UV portion of the light 
spectrum, that is from about 254 to about 366 nanometers. 
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 invisible dye or pigment particles, and optionally 
charge control agents and other known optional additives dispersed in 
water containing a cationic surfactant by shearing, microfluidizing or 
ultrasonifying; (ii) shearing the pigment mixture with a latex mixture 
comprised of a polymer resin, anionic surfactant and nonionic surfactant 
thereby causing a flocculation or heterocoagulation, which on further 
stirring 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 aggregate particle 
mixture by heat to toner composites, or a toner composition comprised of 
resin, pigment, and charge additive. 
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 1 to about 50 microns, and preferably from about 1 to about 
7 microns, and with a narrow GSD of from about 1.2 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 results 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. 
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 II 
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, or the 
aggregation of MICR suspension 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, and the time of coalescence. 
These and other objects of the present invention are accomplished in 
embodiments by the provision of fluorescent toners and authentication 
processes thereof. In embodiments of the present invention, there are 
provided processes for the economical direct preparation of fluorescent 
toner compositions by a flocculation or heterocoagulation, and coalescence 
processes. 
In embodiments, the present invention is directed to processes for the 
preparation of toner compositions, which comprise initially attaining or 
generating an ionic pigment dispersion by, for example, dispersing an 
aqueous mixture of an invisible dye, pigment or pigments wherein the 
pigment, pigments, or dye are excitable by ultraviolet light in the 
frequency range of from about 254 to about 366 nanometers and fluoresce in 
the visible spectrum of from about 400 to about 700 nanometers, such as 
quinacridone type components with a cationic surfactant, such as 
benzalkonium chloride, by utilizing a high shearing device, such as a 
Brinkman Polytron, thereafter shearing this mixture by utilizing a high 
shearing device such as a Brinkman Polytron, or sonicator or 
microfluidizer with a suspended resin mixture comprised of polymer 
particles such as styrene butadiene or styrene butylacrylate 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 a 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 with the oppositely charged anionic surfactant absorbed on the 
resin particles; and further stirring the mixture using a mechanical 
stirrer at 250 to 500 rpm and allowing the formation of electrostatically 
stabilized aggregates ranging from about 0.5 micron to about 10 microns in 
volume average diameter; and heating 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 volume average particle diameter as measured by the Coulter 
Counter. 
In embodiments of the present invention, there are also provided emulsion 
aggregation coalescent processes wherein the surfactant selected for the 
preparation of the pigment dispersion is an anionic surfactant, and the 
counterionic surfactant present in the latex mixture is a cationic 
surfactant; the dispersion of step (i) is accomplished by homogenizing at 
from about 1,000 revolutions per minute to about 10,000 revolutions per 
minute at a temperature of from about 25.degree. C. to about 35.degree. C. 
and for a duration of from about 1 minute to about 120 minutes; the 
dispersion of step (i) is accomplished by an ultrasonic probe at from 
about 300 watts to about 900 watts of energy, at from about 5 to about 50 
megahertz of amplitude, at a temperature of from about 25.degree. C. to 
about 55.degree. C., and for a duration of from about 1 minute to about 
120 minutes, or wherein the dispersion of step (i) is accomplished by 
microfluidization in a microfluidizer or in a nanojet for a duration of 
from about 1 minute to about 120 minutes; the homogenization of step (ii) 
is accomplished by homogenizing at from about 1,000 revolutions per minute 
to about 10,000 revolutions per minute, and for a duration of from about 1 
minute to about 120 minutes; the heating of the statically bound aggregate 
particles forms toner size composite particles comprised of pigment, resin 
particles and optional charge control agent is accomplished at a 
temperature of from about 60.degree. C. to about 95.degree. C. for a 
duration of from about 1 hour to about 8 hours; the resin particles are 
selected from the group consisting of poly(styrene-butadiene-acrylic 
acid), poly(styrene-butadiene-methacrylic acid), poly(styrene-butyl 
methacrylate-acrylic acid), or poly(styrene-butyl acrylate-acrylic acid); 
PLIOTONE.TM., a styrene butadiene, polyethyleneterephthalate, 
polypropylene-terephthalate, polybutylene-terephthalate, 
polypentylene-terephthalate, polyhexalene-terephthalate, 
polyheptadeneterephthalate, and polyoctalene-terephthalate; the cationic 
surfactant is a quaternary ammonium salt; the fluorescent pigment is 
initially invisible, and subsequently rendered visible by subjecting it to 
ultraviolet light, and has a volume average diameter from about 0.01 to 
about 3 microns; the toner particles isolated are from about 3 to about 15 
microns in volume average diameter, and the geometric size distribution is 
from about 1.15 to about, 1.35; the statically bound aggregate particles 
formed in step (iii) are from about 1 to about 10 microns in volume 
average diameter; the nonionic surfactant concentration is about 0.1 to 
about 5 weight percent of the toner component; the toner is washed with 
warm water and the surfactants are removed from the toner surface, 
followed by drying; the solvent is water; a process for the preparation of 
fluorescent toner compositions comprising: 
(i) preparing a pigment dispersion, which dispersion is comprised of a 
pigment or dye, 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 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 the Tg of the resin and wherein 
the pigment or dye is excitable by ultraviolet light in the frequency 
range of from about 254 to about 366 nanometers, and fluoresces in the 
visible spectrum of from about 400 to about 700 nanometers; the 
temperature below the resin Tg of (iii) enables the size of the aggregated 
particles to be in the range of from about 2.5 to about 10 microns in 
volume average diameter; the size of said aggregates can be increased to 
from about 2.5 to about 10 microns by increasing the temperature of 
heating in (iii) to from about room temperature to about 50.degree. C.; a 
process for the preparation of fluorescent toner compositions with 
controlled particle size comprising: 
(i) preparing a pigment dispersion in water, which dispersion is comprised 
of a pigment or dye of a diameter of from about 0.01 to about 1 micron, 
and an ionic surfactant; 
(ii) shearing the pigment dispersion with a latex blend comprised of resin 
of submicron size of from about 0.01 to about 1 micron, 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 and resin to form a 
uniform dispersion of solids in the water and surfactant; 
(iii) heating the above sheared blend at a temperature of from about 
5.degree. to about 20.degree. C. below the Tg of the resin to form 
electrostatically bound toner size aggregates with a narrow particle size 
distribution; 
(iv) heating the statically bound aggregated particles at a temperature of 
from about 5.degree. to about 50.degree. C. above the Tg of the resin to 
provide a mechanically stable toner composition comprised of polymeric 
resin and pigment; and optionally 
(v) separating the toner particles; and 
(vi) drying the toner particles, and wherein the pigment or dye is 
excitable by ultraviolet light in the frequency range of from about 254 to 
about 366 nanometers and fluoresces in the visible spectrum of from about 
400 to about 700 nanometers; a process for the preparation of fluorescent 
toner compositions comprising: 
(i) preparing a pigment dispersion in water, which dispersion is comprised 
of a pigment or dye and an ionic surfactant; 
(ii) shearing the pigment dispersion with a latex blend comprised of resin 
of submicron size, a counterionic surfactant with a charge polarity of 
opposite sign to that of the ionic surfactant and a nonionic surfactant 
thereby causing a flocculation or heterocoagulation of the formed 
particles of pigment, resin and charge control agent to form a uniform 
dispersion of solids in the water and surfactant; 
(iii) heating the above sheared blend below or about equal to the glass 
transition temperature (Tg) of the resin to form electrostatically bound 
toner size aggregates with a narrow particle size distribution; 
(iv) heating the statically bound aggregated particles above or about equal 
to the Tg of the resin particles to provide a toner composition comprised 
of resin; followed by optionally 
(v) separating the toner particles from said water by filtration; and 
(vi) drying the toner particles, and wherein the pigment or dye is 
excitable by ultraviolet light in the frequency range of 254 to 366 
nanometers, and fluoresces in the visible spectrum of 400 to 700 
nanometers; the resin Tg is 54.degree. C. and heating in (iv) is from 
about 59.degree. C. to about 104.degree. C.; the resin Tg in (iii) is from 
about 52.degree. to about 65.degree. C.; and the resin Tg in (iv) is from 
about 52.degree. C. to about 65.degree. C.; the heating in (iii) is equal 
to or slightly above the resin Tg; and the heating in (iv) is equal to or 
slightly above the resin Tg. 
Embodiments of the present invention include a process for the preparation 
of toner compositions or toner particles comprising 
(i) preparing a dye or pigment dispersion in a solvent, which dispersion is 
comprised of a pigment, an ionic surfactant and optionally a charge 
control agent; and wherein the pigment or dye emits light in response to 
excitation by ultraviolet radiation in the wavelength range of from about 
256 to about 366 nanometers, and fluoresces in the visible region of the 
light spectrum, that is at wavelengths of from about 400 to about 700 
nanometers; 
(ii) shearing the pigment dispersion with a latex mixture comprised of a 
counterionic surfactant with a charge polarity of opposite sign to that of 
ionic surfactant of (i), 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 or bounded toner size aggregates; 
(iii) heating the statically bound aggregated particles to form a toner 
composition comprised of polymeric resin, pigment and optionally a charge 
control agent; and thereafter optionally cooling the toner particles 
formed. 
Also, in embodiments the present invention is directed to processes for the 
preparation of toner compositions which comprise (i) preparing an ionic 
pigment mixture by dispersing a pigment or dye excitable by ultraviolet 
light, such as 4,4'-bis(styryl)biphenyl, 
2-(4-phenylstilben-4-yl)-6-t-butylbenzoxazole, .beta.-methylumbelliferone, 
4-methyl-7-dimethylaminocoumarin, 4-methyl-7-aminocoumarin, 
N-methyl-4-methoxy-1,8-naphthalimide, 9, 10-bis(phenethynyl)anthracene, 
5,12-bis(phenethynyl)naphthacene, or DAYGLO INVISIBLE BLUE.TM. A-594-5, of 
from about 2 to about 10 percent by weight of the toner in an aqueous 
mixture containing a cationic surfactant, such as dialkylbenzene 
dialkylammonium chloride like SANIZOL B-50.TM. available from Kao 
Chemicals 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 Brinkman 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, styrene methacrylate, PLIOTONE.TM. or 
styrene butadiene 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 such as sodium dodecylsulfate, dodecylbenzenesulfonate 
or NEOGEN R.TM., of from about 0.5 to about 2 percent by weight of water, 
a nonionic surfactant, such as polyethylene glycol or polyoxyethytene 
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) homogenizing the resulting flocculent 
mixture with a high shearing device such as a Brinkman 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 from about 250 to 
500 rpm to form electrostatically stable aggregates of from about 0.5 
micron to about 5 microns in volume average diameter; (iv) diluting the 
aggregate particle mixture with water from about 50 percent solids to 
about 15 percent solids; (v) heating the statically bound aggregate 
composite particles at from about 60.degree. C. to about 95.degree. C. and 
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) cooling and 
isolating the toner sized particles by washing, filtering and drying 
thereby providing a composite toner composition. Flow additives to improve 
flow characteristics and charge additives to improve charging 
characteristics may then optionally be adding 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. 
One preferred method of obtaining a pigment dispersion depends on the form 
of the pigment utilized. In some instances, pigments are available in the 
wet cake or concentrated form containing water; they can be easily 
dispersed utilizing a homogenizer or stirring. In other instances, 
pigments are available in a dry form, whereby dispersion in water is 
effected by microfluidizing using, for example, a M-110 microfluidizer and 
passing the pigment dispersion from 1 to 10 times through the 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. 
Illustrative examples of resin or resin particles selected for the process 
of the present invention include known polymers such as 
poly(styrene-butadiene), poly(para-methyl styrene-butadiene), 
poly(metamethyl styrene-butadiene), poly(alpha-methyl styrene-butadiene), 
poly(methylmethacrylate-butadiene), poly(ethylmethacrylate-butadiene), 
poly(propylmethacrylate-butadiene), poly(butytmethacrylate-butadiene), 
poly(methylacrylate-butadiene), poly(ethylacrylate-butadiene), 
poly(propylacrylate-butadiene), poly(butylacrylate-butadiene), 
poly(styrene-isoprene), poly(para-methyl styrene-isoprene), 
poly(metamethyl 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., a 
styrene/butadiene copolymer, available from Goodyear, 
polyethylene-terephthalate, polypropylene-terephthalate, 
polybutyleneterephthalate, polypentylene-terephthalate, 
polyhexalene-terephthalate, polyheptadene-terephthalate, 
polyoctalene-terephthalate, POLYLITE.TM., a polyester resin (Reichhold 
Chemical Inc), PLASTHALL.TM., a polyester, (Rohm & Hass), CYGLAS.TM., a 
polyester molding compound (American Cyanamide), ARMCO.TM., a polyester 
(Armco Composites), ARPOL.TM. (Ashland Chemical), CELANEX.TM., a glass 
reinforced thermoplastic polyester, (Celanese Eng), RYNITE.TM., a 
thermoplastic polyester, (DuPont), and STYPOL.TM., a polyester with 
styrene monomer, (Freeman Chemical Corporation). 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 70 weight percent to about 98 weight 
percent of the toner, and can be of small average particle size, such as 
from about 0.01 micron to about 1 micron in volume average diameter as 
measured by the Brookhaven nanosize particle analyzer. Other effective 
amounts of resin can be selected. 
The resin particles selected for the process of the present invention are 
preferably prepared from 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 carbontetrachloride, can also be selected when preparing resin 
particles by emulsion polymerization. Other processes 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. 
Various known second nonfluorescing colorants or pigments can also be 
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, including 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 PIGMENT RED 48.TM., E.D. TOLUIDINE RED.TM. and BON RED C.TM. 
available from Dominion Color Corporation, Ltd., Toronto, Ontario, 
HOSTAPERM PINK E.TM., FANAL PINK.TM. from Hoechst, and CINQUASIA 
MAGENTA.TM. available from E. I. DuPont de Nemours & Company, QUINDO 
MAGENTA.TM., LITHOL RED.TM., RHODOMINE YS.TM. from Sun Chemicals, and the 
like. Generally, second colored pigments that can be selected are magenta, 
and highlight color of the magnets and the red such as those of the LITHOL 
SCARLET.TM. and Hostafine Red family. 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 Cl 
60710, Cl Dispersed Red 15, diazo dye identified in the Color Index as Cl 
26050, Cl Solvent Red 19, and the like. 
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 effective 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, 
polyoxyethytene octyl ether, polyoxyethytene 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 used to prepare the copolymer resin. 
Examples of anionic surfactants selected include, for example, sodium 
dodecylsulfate (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 used to prepare the copolymer resin. 
Examples of the cationic surfactants selected for the toners and processes 
of the present invention are, for example, dialkyl benzenealkyl ammonium 
chloride, lauryl trimethyl ammonium chloride, alkytbenzyl 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 triethyt 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. The 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 latex preparation is in 
range of 0.5 to 4, preferably from 0.5 to 2. 
Surface additives that can be added to the toner compositions after washing 
or drying include, for example, metal salts, metal salts of fatty acids, 
colloidal silicas, 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 1 percent toner concentration. 
Percentage amounts of components are based on the total toner components 
unless otherwise indicated.

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. 
GENERAL EXAMPLE 
Preparation of the Toner Resin: 
Emulsion (latex) or microsuspension particles selected for the preparation 
of toner particles in embodiments of the aggregation process of the 
present invention were prepared as follows: 
Latex A: 
328 Grams of styrene, 72 grams of butyl acrylate, 8 grams of acrylic acid, 
and 12 grams of dodecane thiol were mixed with 500 milliliters of 
deionized water in which 9 grams of sodium dodecyl benzene sulfonate 
anionic surfactant (NEOGEN R.TM. which contains 60 percent of active 
component), and 8.5 grams of polyoxyethylene nonyl phenyl ether nonionic 
surfactant (ANTAROX 897.TM.--70 percent active) were added. 4 Grams of 
ammonium persulfate initiator were dissolved in 100 milliliters. The 
emulsion was then polymerized at 80.degree. C. for 6 hours. A latex 
containing 40 percent solids of styrene/butylacrylate/acrylic acid in the 
ratio of 82:18:2 pph (parts per hundred) with a particle size of 225 
nanometers, as measured on a Brookhaven nanosizer, was obtained. 
Tg=52.degree. C., as measured on DuPont DSC; M.sub.w =22,000 and M.sub.n 
=7,000 as determined on Hewlett Packard GPC. 
Latex B: 
328 Grams of styrene, 72 grams of butyl acrylate, 8 grams of acrylic acid, 
and 12 grams of dodecane thiol were mixed with 500 milliliters of 
deionized water to which were added 9 grams of sodium dodecyl benzene 
sulfonate anionic surfactant (NEOGEN R.TM. which contains 60 percent of 
active component), and 8.5 grams of polyoxyethylene nonyl phenyl ether 
nonionic surfactant (ANTAROX 897.TM.--70 percent active). 4 Grams of 
ammonium persulfate initiator were dissolved in 100 milliliters. The 
emulsion was then polymerized at 70.degree. C. for 6 hours. A latex 
containing 40 percent solids of styrene/butylacrylate/acrylic acid in the 
ratio of 82:18:2 pph with a particle size of 225 nanometers, as measured 
on a Brookhaven nanosizer, was obtained. Tg=55.degree. C., as measured on 
DuPont DSC; M.sub.w =31,000 and M.sub.n =5,800 as determined on Hewlett 
Packard GPC. 
Latex C: 
350 Grams of styrene, 8 grams of acrylic acid, and 12 grams of dodecane 
thiol were mixed and charged in a pressure container, to which 50 grams of 
butadiene was introduced into. This organic phase was then charged (under 
pressure of approximately 300 Kpa)into a reactor containing the aqueous 
surfactant phase comprised of 600 milliliters of deionized water, 9 grams 
of sodium dodecyl benzene sulfonate anionic surfactant (NEOGEN R.TM. which 
contains 60 percent of active component), 8.5 grams of polyoxyethylene 
nonyl phenyl ether nonionic surfactant (ANTAROX 897.TM.--70 percent 
active) and 4 grams of ammonium persulfate initiator. The emulsion was 
then polymerized at 80.degree. C. for 6 hours. A latex containing 40 
percent solids of styrene/butadiene/acrylic acid in the ratio of 
87.5:12.5:2 pph (parts per hundred) with a particle size of 225 
nanometers, as measured on Brookhaven nanosizer, was obtained. 
Tg=54.degree. C., as measured on DuPont DSC; M.sub.w =32,000 and M.sub.n 
=9,000 as determined on Hewlett Packard GPC. 
PREATION OF TONER TICLES: 
EXAMPLE I 
6.7 Grams of dry INVISIBLE BLUE.TM. pigment, A-595-5 obtained from Dayglo 
Corporation, and excitable by ultraviolet light in the frequency range of 
from about 254 to about 366 nanometers and fluoresces in the visible 
spectrum of from about 400 to about 700 nanometers was dispersed in 200 
milliliters of deionized water containing 1.46 gram of alkylbenzyldimethyl 
ammonium chloride cationic surfactant (SANIZOL B.TM.) using an ultrasonic 
probe for 2 minutes. The pigment solution was then added to 300 grams of 
water containing 1.46 grams of cationic surfactant and stirred. This 
cationic dispersion of the pigment was then simultaneously added with 325 
grams of Latex A to 300 grams of water while being homogenized with an IKA 
G45M probe for 3 minutes at 7,000 rpm. This mixture then was transferred 
into a reaction kettle and its temperature increased to 45.degree. C. for 
a period of 1 hour. The particle size of the aggregate obtained was 5.3 
microns with a GSD of 1.20 as measured by Coulter Counter. 60 Milliliters 
of 20 percent (WAN) anionic surfactant solution was then added to the 
aggregates, after which the reactor temperature was raised to 80.degree. 
C. for 5 hours to complete the coalescence of the aggregates. The final 
particle size obtained was 5.3 microns with a GSD of 1.22. The particles 
were then washed with deionized water and freeze dried. The dry particles 
were then illuminated under ultraviolet light at 254 nanometers and 
luminescence was observed. 
EXAMPLE II 
5.2 Grams of dry INVISIBLE BLUE.TM. pigment, and 16 grams (40 percent 
solids) of QUINDO MAGENTA.TM. wet dispersion were added to 240 milliliters 
of deionized water containing 2.8 grams of alkylbenzyldimethyl ammonium 
chloride cationic surfactant (SANIZOL B.TM.) and roll milled for 20 
minutes. This cationic dispersion of the pigment was then simultaneously 
added with 260 grams of Latex B to 400 grams of water while being 
homogenized with an IKA G45M probe for 3 minutes at 7,000 rpm. This 
mixture then was transferred into a reaction kettle and its temperature 
raised to 45.degree. C. for a period of 1 hour. The particle size of the 
aggregate obtained was 4.8 microns with a GSD of 1.20 as measured by 
Coulter Counter. 60 Milliliters of 20 percent (W/W) anionic surfactant 
solution were added to the aggregates, after which the reactor temperature 
was raised to 85.degree. C. for 5 hours to complete the coalescence of the 
aggregates. The toner particle size obtained was 5.0 microns with a GSD of 
1.21. The particles were then washed with deionized water and freeze 
dried. The dry particles were then illuminated at 254 nanometers under 
ultraviolet light and luminescence was observed. 
EXAMPLE III 
A toner was prepared by the process of Example II with the exception that 
there was selected as the latex, Latex C, and similar results were 
observed. 
EXAMPLE IV 
5.2 Grams of dry INVISIBLE BLUE.TM. pigment obtained from Dayglo 
Corporation, and 15 grams (44 percent solids) of LITHOL RUBIN.TM. wet 
dispersion obtained from Sun Chemicals were added to 240 milliliters of 
deionized water containing 2.8 grams of alkylbenzyldimethyl ammonium 
chloride cationic surfactant (SANIZOL B.TM.) and rolled milled for 20 
minutes. This cationic dispersion of the pigment was then simultaneously 
added with 260 grams of Latex A to 400 grams of water while being 
homogenized with an IKA G45M probe for 3 minutes at 7,000 rpm. This 
mixture then was transferred into a reaction kettle and its temperature 
raised to 45.degree. C. for a period of 1.5 hour. The particle size of the 
aggregate obtained was 5.5 microns with a GSD of 1.22 as measured by 
Coulter Counter. 60 Milliliters of 20 percent (W/W) anionic surfactant 
solution were added to the aggregates, after which the reactor temperature 
was raised to 90.degree. C. for 4 hours to complete the coalescence of the 
aggregates. The final particle size obtained was 5.8 microns with a GSD of 
1.22. The particles were then washed with deionized water and freeze 
dried. The dry particles were then illuminated under ultraviolet light at 
254 nanometers and luminescence was observed. 
EXAMPLE V 
5.2 Grams of dry INVISIBLE BLUE.TM. pigment, and 14.6 grams (46 percent 
solids) of RHODAMINE YS.TM. wet dispersion obtained from Sun Chemicals 
were added to 240 milliliters of deionized water containing 2.8 grams of 
alkylbenzyldimethyl ammonium chloride cationic surfactant (SANIZOL B.TM.) 
and rolled milled for 20 minutes. This cationic dispersion of the pigment 
was then simultaneously added with 260 grams of Latex 13 to 400 grams of 
water while being homogenized with an IKA G45M probe for 3 minutes at 
7,000 rpm. This mixture then was transferred into a reaction kettle and 
its temperature raised to 45.degree. C. for a period of 1.5 hour. The 
particle size of the aggregate obtained was 4.9 microns with a GSD of 1.19 
as measured by Coulter Counter. 60 Milliliters of 20 percent (W/W) anionic 
surfactant solution were added to the aggregates, after which the reactor 
temperature was raised to 90.degree. C. for 4 hours to complete the 
coalescence of the aggregates. The final particle size obtained was 5.1 
microns with a GSD of 1.20. The particles were then washed with deionized 
water and freeze dried. The dry particles were then illuminated under 
ultraviolet light at 254 nanometers and luminescence was observed. 
EXAMPLE VI 
5.2 Grams of dry INVISIBLE BLUE.TM. pigment, and 8 grams of dry FANAL 
PINK.TM. pigment were added to 240 milliliters of deionized water 
containing 2.8 grams of alkylbenzyldimethyl ammonium chloride cationic 
surfactant (SANIZOL B.TM.) and sonified for 2 minutes. This cationic 
dispersion of the pigment was then simultaneously added with 260 grams of 
Latex C to 400 grams of water while being homogenized with an IKA G45M 
probe for 3 minutes at 7,000 rpm. This mixture then was transferred into a 
reaction kettle and its temperature raised to 45.degree. C. for a period 
of 90 minutes. The particle size of the aggregate obtained was 4.5 microns 
with a GSD of 1.18 as measured by Coulter Counter. 60 Milliliters of 20 
percent (W/W) anionic surfactant solution were added to the aggregates, 
after which the reactor temperature was raised to 90.degree. C. for 4 
hours to complete the coalescence of the aggregates. The final particle 
size obtained was 4.8 microns with a GSD of 1.20. The particles were then 
washed with deionized water and freeze dried. The dry particles were then 
illuminated under ultraviolet light at 254 nanometers and luminescence was 
observed. 
EXAMPLE VIII 
5.2 Grams of dry INVISIBLE BLUE.TM. pigment, and 14 grams (53 percent 
solids)of wet cake of HOSTAPERM PINK.TM. pigment obtained from BASF 
Chemicals were added to 240 milliliters of deionized water containing 2.8 
grams of alkylbenzyldimethyl ammonium chloride cationic surfactant 
(SANIZOL B.TM.) and sonified for 2 minutes. This cationic dispersion of 
the pigment was then simultaneously added with 260 grams of Latex A to 400 
grams of water while being homogenized with an IKA G45M probe for 3 
minutes at 7,000 rpm. This mixture then was transferred into a reaction 
kettle and its temperature raised to 45.degree. C. for a period of 90 
minutes. The particle size of the aggregate obtained was 4.9 microns with 
a GSD of 1.23 as measured by Coulter Counter. 60 Milliliters of 20 percent 
(W/W) anionic surfactant solution were added to the aggregates, after 
which the reactor temperature was raised to 90.degree. C. for 4 hours to 
complete the coalescence of the aggregates. The final particle size 
obtained was 5.3 microns with a GSD of 1.25. The particles were then 
washed with deionized water and freeze dried. The dry particles were then 
illuminated under ultraviolet light at 254 nanometers and luminescence was 
observed. 
EXAMPLE VIII 
6.5 Grams of a wet cake of HOSTAPERM PINK.TM. pigment obtained from Sun 
Chemicals were dispersed in 60 milliliters of water by an ultrasonic probe 
for 1 minute. This dispersion was homogenized using a Brinkman probe (20 
millimeters), while 60 milliliters of emulsion A (anionic) were added. 
After 10 minutes of polytroning, 0.2 gram of cationic surfactant was added 
while still shearing. The resulting "whipped cream" was then diluted with 
120 milliliters of water. After 24 hours stirring at room temperature, the 
kettle contents were heated up to 75.degree. C. for two hours to coalesce 
the particles. Toner sized particles of 5.1 with GSD=1.39 (as measured on 
the Coulter Counter) were obtained. Those particles comprised of styrene 
(88 parts), butyl acrylate (12 parts), acrylic acid (2 parts), and 
quinacridone magenta pigment (10 percent by weight of toner) had a 
Tg=73.degree. C. (DSC measurement), a M.sub.w =43,000 and a M.sub.n 
=12,500 (measured on GPC). The yield of toner particles was 96 percent. 
Toner yields with the prior art processes were 60 percent or less, 
reference for example U.S. Pat. Nos. 4,996,127 and 4,797,339; and with 
these processes classification was needed to obtain, for example, 
desirable GSD. 
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.