Low gloss toner compositions and processes thereof

An encapsulated toner composition and process thereof, which toner is comprised of a core comprised of a polymer resin or resins, color pigment, dye, or mixtures thereof, and thereover an inner shell resin comprised, for example, of a polyurea, and thereover an outer shell coating comprised of an alkyl cellulose. The colored encapsulated toners are useful in reprographic processes wherein, for example, low gloss is desired.

BACKGROUND OF THE INVENTION 
The present invention is generally directed to toner compositions and 
processes thereof, and more specifically, to colored encapsulated toner 
compositions and processes thereof, and wherein toners can be directly 
generated without resorting to the conventional pulverization and 
classification methods. In one embodiment, the present invention relates 
to colored encapsulated toner compositions which display low gloss levels 
of, for example, from about 1 gloss unit to about 15 gloss units, and more 
preferably from about 3 gloss units to about 14 gloss units, as measured 
by the Gardner.TM. gloss unit apparatus. In another embodiment, the 
present invention relates to a process of preparing colored encapsulated 
toner of fine particle size of from about 0.5 micron to about 15 microns 
in diameter, and more preferably from about 2 microns to about 7 microns 
diameter, as measured by a Counter Counter. In another embodiment, the 
present invention relates to colored encapsulated toner compositions which 
display low fixing temperatures of from about 110.degree. C. to about 
150.degree. C., thereby reducing the energy consumption of an 
electrostatographic imaging or printing apparatus and prolonging the 
lifetime of the fuser contained therein. Furthermore, in another 
embodiment, the present invention relates to a colored encapsulated toner 
composition and process of generating an inner shell material surrounding 
a core material and wherein the resulting composite is surrounded by an 
outer shell or coating material. The colored encapsulated toners of this 
invention in embodiments are comprised of a core comprised of a polymer 
resin and colorants, including color pigments, dyes, or mixtures thereof, 
an inner shell material comprised of, for example, a polyurea, a 
polyurethane or a polyester and the like, and an outer coating layer 
comprised of a cellulose component, such as methyl cellulose, 
hydroxypropyl cellulose, hydroxyethylmethyl cellulose, and the like. The 
processes of the present invention in embodiments thereof are comprised of 
an initial dispersion step for forming a stabilized organic microdroplet 
suspension comprised of pigment, dyes or colorant, free-radical monomers, 
and an inner shell forming monomer such as a diisocyanate suspended in an 
aqueous medium containing an outer coating material, such as 
hydroxyethylmethyl cellulose; followed by addition of the second monomer 
forming the inner shell material by interfacial polymerization step, such 
as a diamine; and a final core resin formation step by free radical 
polymerization. The precipitation of the outer coating cellulose molecules 
is believed to begin at the initial dispersion-stabilization stage, and 
continues during the inner shell formation and core resin forming free 
radical polymerization step. In embodiments, the processes of the present 
invention can also utilize a mixture of cellulose polymers of from about 
0.1 percent to about 5 percent by weight of the toner, and ionic or 
inorganic surfactants of from about 0.01 percent to about 0.5 percent by 
weight of toner, such as potassium oleate, sodium dodecyl sulfate, and the 
like during the dispersion step. The cellulose-ionic or inorganic 
surfactant system facilitates efficient generation of very small sized 
microdroplets, particularly those with an average particle diameter of 
from about 0.5 micron to about 7 microns, together with a narrow particle 
size distribution of less than 1.35 , as measured by the Counter Counter. 
The primary function of the inner shell of the colored encapsulated toner 
of the present invention is to provide for the mechanical integrity of the 
toner, minimizing or eliminating the seepage of the inner core material, 
hence preventing toner aggregation or coalescing, as well as providing the 
low gloss properties to the toner image, highly desired in black and 
highlight reprographic technologies utilizing a VITON.RTM. roll fuser. The 
primary function of the outer cellulose shell for the colored encapsulated 
toner compositions prepared by the processes of the present invention is 
to provide additional low gloss or preferably a matte finish. In addition, 
this outer coating shell is selected to provide additional mechanical 
integrity to the toner compositions, and ensure effective protection with 
the inner shell material for the containment of the core components. In 
addition, the coatings also inhibit toner particles from coalescing and 
prevent, or minimize toner agglomeration during the dispersion step and 
interfacial polymerization step for generating the inner shell. The 
primary function of the outer shell coatings relates to the nullification, 
or passivation of the triboelectric charging effects of colorants present 
in the toner compositions, such that the triboelectric charging 
characteristics of the toner compositions are primarily controlled or 
dominated by the charging effects of the cellulose layer, and surface 
additives. Accordingly, the processes of the present invention are useful 
for the preparation of a wide variety of colored toners possessing similar 
or substantially similar triboelectric charging characteristics with a 
selected carrier, irrespective of the nature of the colorants present in 
the toners. For single component development where triboelectric charging 
is generally accomplished by a frictional charging blade, similar 
equilibrium triboelectric charge levels can also be obtained under 
substantially identical conditions with different colored toners of the 
present invention. The cellulose coating for the toner compositions 
obtained by the processes of the present invention are in general 
relatively thin in nature, its presence therefore does not substantially 
affect the toner's fusing characteristics. 
In color reprography, such as in full color or highlight color 
applications, colored toners with a wide variety of colors including black 
are usually employed. In color reprography, a heat-assisted transfix step 
or heat-roll fusing is applied to the toner image on paper. It is highly 
desirable to use VITON.RTM. fuser rollers rather than the conventional 
silicone roll fusers due to the drastically prolonged lifetime attained by 
a fuser roll containing VITON.RTM. surfaces. During the fixing step 
employing heated VITON.RTM. roll fusers, the toner is fixed on paper and 
the energy necessary to achieve this is related to the temperature applied 
by the rolls. Accordingly, toners which fix on paper with minimum amount 
of heat are highly desirable. The temperature necessary to properly fix a 
particular toner onto paper is known as the minimum fixing temperature 
(MFT). It is known that encapsulated toner compositions are highly 
desirable for low minimum fixing applications, such as from about 
110.degree. C. to about 150.degree. C., and preferably from about 
110.degree. C. to about 130.degree. C. The aforementioned encapsulated 
colored toners are comprised of an inner core with low glass transition 
temperature resin for fixing the toner onto paper at the low 
aforementioned minimum fixing temperatures, in that the core of the 
encapsulated toner is surrounded by a shell material thereby avoiding 
agglomeration of the core materials during, for example, storage or until 
its use in the final fixing step. Toner fusing onto paper is accomplished 
by the melting of the toner and its penetration into the paper fiber, and 
sticking or adherence of the resin onto the paper with colorants, dyes and 
additives. After this fixing step, the surface of the toner image on paper 
is usually smooth, and in addition, paper calendering results especially 
when excessive pressure is applied by the fuser, such that the toner image 
surface and paper is very smooth. This aforementioned fixing mechanism is 
responsible for high gloss properties to the toner image, such as from 
about 40 gloss units to about 80 gloss units, as measured by the 
GARDNER.TM. gloss unit. The gloss level is proportional to the smoothness 
of the toner image after fixing, and can easily be measured using a known 
GARDNER.TM. gloss unit. In color reprography, such as full or pictorial 
color applications, high gloss is highly desirable such as from about 40 
gloss units to about 80 gloss units and more preferably from about 45 to 
about 60 gloss units, as measured by the GARDNER.TM. gloss unit on toner 
image after fixing. When using colored conventional toners for full or 
pictorial colored applications, high gloss is easily achieved, and the use 
of colored encapsulated toners comprised of a core containing resin, 
pigment, dyes or colorant and optionally surrounded by a shell for full 
color or pictorial applications, high gloss can be achieved. For color 
reprography, wherein black or highlight color application is desired, low 
gloss is desired, and preferably low gloss of less than 14 gloss units and 
more preferably less than 11 gloss units as measured by the GARDNER.TM. 
gloss unit. Gloss values of from about 14 gloss units and below are 
usually known to those in the art as "matte finish". However, both the 
aforementioned conventional and prior art encapsulated colored toners do 
not exhibit low gloss values, and are inferior to black and highlight 
color reprographic technologies which utilizes VITON.RTM. roll fusers. The 
colored encapsulated toner compositions of this invention alleviate the 
problem of high gloss and provide low gloss black and highlight colored 
images, and more preferably of a matte finish when transfixed using 
VITON.RTM. fuser rolls. Furthermore, the colored encapsulated toners of 
this invention can be of a fine average particle size of from about 0.5 
micron to about 9 microns and more preferably from about 2 microns to 
about 7 microns in diameter, unattainable economically by conventional 
pulverization process. Additionally, the encapsulated toner compositions 
of this invention display low minimum fixing characteristics with 
excellent tribo characteristics such that the triboelectric properties of 
different colored toners be desirably controlled so that they all attain 
similar equilibrium triboelectric charging levels when utilized with a 
selected carrier. This is especially useful for custom colored toner 
packages since colored toners with a wide variety of custom colors can be 
obtained by simple blending of the primary colored toners. Another 
important aspect for two component development is the rate of charging of 
new toner to equilibrium charge levels when they are added to the toner 
depleted development housing. A fast rate of charging of fresh toner can 
be important in ensuring proper image development, particularly for high 
speed, greater than 70 copies per minute for example, reprographic 
systems. 
It is known that color pigments or dyes present in the toner have a 
dominant effect on the toner's triboelectric charging behavior, arising 
primarily because these colorants are often also present at or close to 
the surface of the toner, and are, therefore, exposed to their 
environments. As a consequence, when the toner particles are admixed with 
carriers, the interactions of the exposed pigments of the toners with the 
carrier particles drastically affect the charging behavior of the toner. 
Similar effects are obtained for a number of prior art encapsulated toners 
where the color pigment particles are not completely encapsulated within 
the toner shell. Thus, it is often observed that toners with identical 
components, except colorants, exhibit different charging behavior, even to 
the extent of having triboelectric charges of opposite polarity. To 
overcome this difficulty, it is usually necessary to utilize different 
charge control additives for different colorants, or to use high levels of 
charge control additives so as to nullify or overcome the different 
charging effects of different colorants, and exert a dominating influence 
on the charging characteristics of the toners. The toners and processes of 
the present invention eliminate or overcome this difficulty through 
complete or substantially complete encapsulation of core components with 
an inner shell, and in addition, by the precipitation of an outer coating 
on the inner shell. As a consequence, the need to rely on only one shell 
material is avoided by the use of an additional outer layer precipitated 
coating of this invention. It is believed that the inner shell and outer 
shell precipitated coating, especially when TYLOSE.RTM. is employed, 
avoids toner smoothness after the fixing step, and alleviates unwanted 
gloss properties for black and highlight color reprographic technologies 
employing VITON.RTM. roll fusers. Other advantages associated with the 
toner compositions obtained by the processes of the present invention 
include, for example, rapid triboelectric charging rates, small toner size 
and narrow size distribution for high resolution images, excellent color 
mixing properties and image color fidelity, low minimum fusing 
temperatures, acceptable powder flow, and nonblocking and nonagglomerating 
characteristics. The toner compositions of the present invention can be 
selected for a variety of known imaging processes including 
electrophotographic and ionographic processes. It is also known that 
colored, including black single component magnetic toners, as well as 
encapsulated single component magnetic toners for ionographic 
applications, exhibit undesired high gloss properties, such as from about 
40 gloss unit to about 80 gloss. This is primarily due to the high 
pressures exerted by the dielectric receivers on the toner image. The 
colored, including black, toners of this invention contain an additional 
outer coating not present in prior art toners, enabling the toner images 
with low gloss and preferably matte in finish. 
Encapsulated toners and processes containing two shells are known. For 
example, U.S. Pat. No. 4,565,764 discloses a colored microcapsule toner 
composition and process thereof comprised of a core comprised of a wax and 
colorant, a first shell resin wall having an affinity for both the core 
and a second shell wall; and note column 3, line 13, wherein the first 
wall is chemically bonded to at least the second wall and core material, 
and note column 7, line 65, to column 8, line 5, wherein the first resin 
wall is oppositely charged to those of the core material and second resin 
wall. Furthermore, the microcapsules are prepared by a coacervation or 
phase separation process. U.S. Pat. No. 4,797,339 discloses a toner 
comprising an inner layer comprising a resin ion complex having a colorant 
and ionically crosslinked with a resin of opposite charge, and containing 
an outer layer comprised of flowability imparting agent. Similarly, U.S. 
Pat. No. 4,996,127 teaches a process of producing microcapsule toner 
composed of associated particles of secondary particles comprising primary 
particles of a polymer having an acidic or basic polar group, coloring 
agent and charge controlling agent. With the present invention in 
embodiments, the inner shell and outer shell are not chemically or 
ionically bound, and contain an interfacial polymer resin, such as a 
polyurea, for low gloss attributes, and also the outer coating material, 
such as TYLOSE.RTM., is not believed to be disclosed in '497, '764 or 
'127, which TYLOSE.RTM. is selected for low gloss and triboelectricity 
control. Additionally, the microcapsule of this invention is prepared by a 
suspension free-radical process, followed by interfacial polymerization, 
and coating thereof. Encapsulated toners and processes containing one 
shell are also known, for example, both U.S. Pat. No. 4,626,489 and 
British Patent 1,538,787, as well as U.S. Pat. No. 4,766,051 disclose 
similar processes for colored encapsulated toners wherein both the core 
resin and shell material are prepared by suspension polymerization 
techniques. However, only one shell material is present in the toner 
compositions of the aforementioned prior art. Similarly, other prior art, 
such as U.S. Pat. No. 4,727,011, discloses a process for preparing 
encapsulated toners which involves a shell forming interfacial 
polycondensation and a core binder forming free radical polymerization; 
and U.S. Pat. No. 4,708,924 discloses the use of a mixture of two 
polymers, one having a glass transition temperature in the range of 
-90.degree. C. to 5.degree. C., and the other having a softening 
temperature in the range of 25.degree. C. to 180.degree. C., as the core 
binders for a pressure fixable encapsulated toner. Other representative 
U.S. Pat. Nos. are: 4,339,518, which relates to a process of electrostatic 
printing with fluorinated polymer toner additives where suitable materials 
for the dielectric toner are thermoplastic silicone resins and fluorine 
containing resins having low surface energy; U.S. Pat. No. 4,016,099, 
which discloses methods of forming encapsulated toner particles and 
wherein there are selected organic polymers including homopolymers and 
copolymers, such as vinylidene fluoride, tetrafluoroethylene, 
chlorotrifluoroethylene, and the like; U.S. Pat. No. 4,497,885, which 
discloses a pressure fixable microcapsule toner comprising a pressure 
fixable component, a magnetic material, and other optional components, and 
wherein the core material can contain a soft material, typical examples of 
which include polyvinylidene fluoride, polybutadiene, and the like; U.S. 
Pat. No. 4,520,091, which discloses an encapsulated toner with a core 
which comprises a colorant, a dissolving solvent, a nondissolving liquid 
and a polymer, and may include additives such as a fluorine containing 
resin; and U.S. Pat. No. 4,590,142 relating to capsule toners wherein 
additives such as polytetrafluoroethylenes are selected as lubricating 
components. Furthermore, there are disclosed in the prior art encapsulated 
toner compositions containing costly pigments and dyes, reference for 
example the color photocapsule toners of U.S. Pat. Nos. 4,399,209; 
4,482,624; 4,483,912 and 4,397,483. 
In a U.S. Pat. No. 5,175,071 (D/90516), the disclosure of which is totally 
incorporated herein by reference, a colored encapsulated toner comprised 
of a core resin and colorant, coated with a cellulose shell material is 
disclosed, and wherein no inner shell material is present and low gloss 
properties are not disclosed. Furthermore, the gloss properties with the 
colored encapsulated toner compositions of this patent, containing only 
one shell are not attained generally as illustrated herein. 
The following U.S. patents located in a patentability search report for 
encapsulated toners are mentioned: U.S. Pat. No. 4,967,962, which 
discloses a toner composition comprising a finely divided mixture 
comprising a colorant and a polymeric material which is a block or graft 
copolymer, including apparently copolymers of polyurethane and a polyether 
(column 6), reference for example the Abstract of the Disclosure, and also 
note the disclosure in columns 2, 3, 6 and 7, particularly lines 13 and 
35; however, it does not appear that encapsulated toners are disclosed in 
this patent; 4,626,490 contains a similar teaching as the '764 patent, and 
more specifically, discloses an encapsulated toner comprising a binder of 
a mixture of a long chain organic compound and an ester of a higher 
alcohol and a higher carboxylic acid encapsulated within a thin shell, 
reference the Abstract of the Disclosure, for example, and note 
specifically examples of shell materials in column 8, beginning at line 
64, and continuing on to column 9, line 17, which shells can be comprised, 
for example, of polyurethanes, polyurea, epoxy resin, polyether resins 
such as polyphenylene oxide or thioether resin, or mixtures thereof; U.S. 
Pat. Nos. 4,442,194 and 4,465,755, mentioned herein; and U.S. Pat. Nos. of 
background interest including 4,520,091; 4,590,142; 4,610,945; 4,642,281; 
4,740,443 and 4,803,144. 
Furthermore, other prior art, primarily of background interest, includes 
U.S. Pat. Nos. 4,254,201; 4,465,755 and Japanese Patent Publication 
58-100857. The Japanese publication discloses a capsule toner with high 
mechanical strength, which is comprised of a core material including a 
display recording material, a binder, and a shell, which shell is 
preferably comprised of a polyurea resin. In the U.S. Pat. No. '201 there 
are disclosed encapsulated electrostatographic toners wherein the shell 
material comprises at least one resin selected from polyurethane resins, a 
polyurea resin, or a polyamide resin. In addition, the U.S. Pat. No. '755 
discloses a pressure fixable toner comprising encapsulated particles 
containing a curing agent, and wherein the shell is comprised of a 
polyurethane, a polyurea, or a polythiourethane. Moreover, in the U.S. 
Pat. No. '201 there are illustrated pressure sensitive adhesive toners 
comprised of clustered encapsulated porous particles, which toners are 
prepared by spray drying an aqueous dispersion of the granules containing 
an encapsulated material. 
Also, in U.S. Pat. No. 4,599,271, the disclosure of which is totally 
incorporated herein by reference, there are illustrated microcapsules 
obtained by mixing organic materials in water emulsions at reaction 
parameters that permit the emulsified organic droplets of each emulsion to 
collide with one another, reference the disclosure in column 4, lines 5 to 
35. Examples of polymeric shells are illustrated, for example, in column 
5, beginning at line 40, and include isocyanate compounds such as toluene 
diisocyanate, and polymethylene polyphenyl isocyanates. Further, in column 
6, at line 54, it is indicated that the microcapsules disclosed are not 
limited to use on carbonless copying systems; rather, the film material 
could comprise other components including xerographic toners, see column 
6, line 54. 
Illustrated in U.S. Pat. No. 4,758,506, the disclosure of which is totally 
incorporated herein by reference, are single component cold pressure 
fixable toner compositions, wherein the shell selected can be prepared by 
an interfacial polymerization process. In U.S. Pat. No. 5,043,240, the 
disclosure of which is totally incorporated herein by reference, there are 
illustrated encapsulated toners with a core comprised of a polymer binder, 
pigment or dye, and thereover a polymeric shell, which contains a soft and 
flexible component, permitting, for example, proper packing of shell 
materials resulting in the formation of a high density shell structure, 
which can effectively contain the core binder and prevent its loss through 
diffusion and leaching process. The soft and flexible component in one 
embodiment is comprised of a polyether function. Specifically, in one 
embodiment there are disclosed in the aforementioned patent encapsulated 
toners comprised of a core containing a polymer binder, pigment or dye 
particles, and thereover a shell preferably obtained by interfacial 
polymerization, which shell has incorporated therein a polyether 
structural moiety. Another specific embodiment of the patent is directed 
to encapsulated toners comprised of a core of polymer binder, pigment, dye 
or mixtures thereof, and a polymeric shell of a polyether-incorporated 
polymer, such as a poly(ether urea), a poly(ether amide), a poly(ether 
ester), a poly(ether urethane), mixtures thereof, and the like. 
Many of the prior art encapsulated toner compositions, in particular 
colored toner compositions, suffer from a number of deficiencies as 
indicated herein. For example, these toners do not possess, it is 
believed, desirable low gloss of from about 14 gloss units and below and 
more preferably less than 11 gloss units or a matte finish in color 
reprography utilizing VITON.RTM. fusers. The prior art encapsulated toner 
compositions contain only one shell material, or do not contain an inner 
shell material and outer shell material to enable low gloss applications, 
such as from about 1 gloss unit to about 14 gloss units. The gloss 
property of some of the prior art colored encapsulated toner compositions 
containing only one shell are reported in the Comparative Examples, and 
wherein the desired low gloss properties of from about 1 gloss unit to 
about 14 gloss units are not attained. Also, many of the prior art 
encapsulated toners do not display fusing properties such as being able to 
be fused at a reasonably low temperature of, for example, less than 
160.degree. C.; they usually require different or excessive amounts of 
charge control agents for different colored toners; and their rates of 
triboelectric charging are poor. In addition, some prior art colored 
encapsulated toners cannot be obtained in smaller toner size of, for 
example, less than 7 or 8 microns in diameter with a narrow size 
distribution of less than about 1.35, and more preferably of from about 2 
to about 7 microns with a narrow size distribution of less than about 1.35 
in a cost effective manner. Also, toner blocking or agglomeration may be a 
problem with several of the prior art encapsulated toners because of the 
porosity of the shell structure, especially when they are exposed to 
conditions of elevated temperatures. Further, some of the prior art 
colored encapsulated toners are comprised of colored pigment particles 
that may not completely be encapsulated by the shell, and the 
triboelectric charging effects of such pigments are, therefore, not fully 
passivated, and this would adversely affect and degrade the toner 
triboelectric characteristics, thereby causing image quality to 
deteriorate. In addition, many of the prior art toner compositions do not 
possess the necessary long-term physical and environmental stability. 
These and other disadvantages are eliminated or substantially eliminated 
with the process and toner compositions of the present invention. 
There is a need for colored toners which display low gloss values and are 
preferably matte finish, especially with color reprographic systems 
employing VITON.RTM. fuser rolls. Additionally, there is a need for color 
toners with low minimum fusing temperatures, wide fusing latitude, of fine 
particle size, of nonblocking tendencies, and of stable triboelectricity 
properties including complete passivation. These and other needs are 
accomplished with the colored encapsulated toners and process thereof of 
the present invention. More specifically, thus with the toners of the 
present invention, the toner properties can in many instances be tailored 
to certain specifications. Specifically, with the toners of the present 
invention in embodiments, low gloss images of matte finish are attainable 
with reprographic technologies employing VITON.RTM. fuser rolls. 
Additionally, complete or substantial passivation of the triboelectric 
charging effects of the colorants is accomplished, and smaller toner 
particle size with narrow size distribution can be achieved without 
conventional classification techniques. Also, the toners of the present 
invention do not block or agglomerate over an extended period of time, for 
example up to six months, in embodiments. 
SUMMARY OF THE INVENTION 
It is a feature of the present invention to provide toner compositions with 
many of the advantages illustrated herein. 
It is also a feature of the present invention to provide colored 
encapsulated toner compositions, including black, with desirable low gloss 
and matte finish prints. 
Additionally, it is a feature of the present invention to provide desirable 
properties as excellent toner powder flow, and nonblocking 
characteristics, excellent color fidelity, resistance to vinyl offset, and 
excellent image permanence characteristics. 
In another feature of the present invention, there are provided toner 
compositions comprised of a core of polymer resin, colorants such as 
pigments, dyes, or mixtures thereof, and thereover an inner shell 
comprised of polyurea, polyurethane, polyesters and the like, and 
thereover an outer shell coating comprised of TYLOSE.RTM., a 
hydroxyethylmethyl cellulose, a methyl cellulose, or the derivatives 
thereof. 
An additional feature of the present invention is the provision of toner 
compositions whose low gloss properties are predominantly controlled by 
the inner shell and outer cellulose layer. 
Another feature of the present invention is the provision of toner 
compositions whose triboelectric properties are predominantly controlled 
by the outer cellulose layer, and the optionally added surface additives. 
Further, in another feature of the present invention, there are provided 
color toners which exhibit similar equilibrium triboelectric properties 
against a selected carrier irrespective of the colorants present. 
A related feature of the present invention is the provision of colored 
toner compositions whose triboelectric charging polarity can be desirably 
controlled or adjusted. 
A still further related feature of the present invention is to provide 
colored toners which possess rapid rates of triboelectric charging when 
admixed with carrier particles. 
Moreover, another feature of the present invention is the provision of 
colored toners exhibiting low temperature fusing properties. 
A further feature of the present invention is to provide a simple process 
for the generation of small sized black and colored toners with narrow 
size distribution without the need to resort to conventional pulverization 
and classification techniques. 
In a further feature of the present invention, there are provided 
preparative processes for directly generating toner compositions comprised 
of a polymer resin or resins and colorants, encapsulated by an inner shell 
condensation resin and an outer overcoated layer of a cellulose polymer, 
and wherein the gloss level of the toner image after fixing is of matte 
finish. 
Another related feature of the present invention is the provision of a 
simple chemical preparation process for toner compositions wherein no 
toxic reagents are utilized. 
These and other features of the present invention can be accomplished by 
the provision of toners, and more specifically, toners with an inner shell 
and certain coating thereover. In one embodiment of the present invention, 
there are provided toners with a core comprised of a polymer resin, 
colorants, such as pigment or dye, and thereover an inner shell comprised 
of a polyurea, a polyurethane, a polyether, a polyamide, or a polyester, 
and thereover an outer shell coating comprised of a cellulose polymer, 
such as methyl cellulose, a mixture of methyl cellulose and methyl 
ethylcellulose, available as TYLOSE.RTM. from Fluka Biochemica Company, 
and the like. The aforementioned inner and outer shells are believed to 
yield low gloss or matte finish prints of from about one gloss unit to 
about 14 gloss units, especially when reprographic technologies employing 
VITON.RTM. fusers are utilized. The aforementioned outer coatings can also 
passivate or nullify the triboelectric charging effects of the colorants 
present in the toner compositions, thereby providing for the achievement 
of similar triboelectric properties for different colored toners. 
Specifically, in one embodiment there are provided in accordance with the 
present invention toners whose gloss level and triboelectric charging 
properties are primarily controlled by the inner and outer coating, and 
the added surface additives. The toner compositions of the present 
invention in embodiments are comprised of a core containing a polymer 
resin, color pigment particles or dye components, and thereover an inner 
shell comprised of condensation polymer, such as a polyurea, with 
effective thickness of, for example, from between about 0.1 to 2 microns 
as measured by Tunnelling Electron Microscopy (TEM), and thereover an 
outer shell coating comprised of cellulose polymer, such as 
hydroxyethylmethyl cellulose, with an effective thickness of, for example, 
from between about 0.0001 to about 0.5 micron as measured by TEM. Another 
specific embodiment of the present invention is directed to color toners 
whose outer cellulose coatings have been removed or substantially removed 
or chemically modified so as to provide other specific properties. 
The toner compositions of the present invention can be prepared by a simple 
one-pot process involving formation of stabilized particle suspension, 
followed by an interfacial inner shell polymerization, and by a core resin 
forming free radical polymerization within the particles. The outer shell 
coating is believed to be initially formed during the stabilized particle 
suspension, and continues to be formed by precipitation during the inner 
shell and core free-radical steps. The process is comprised of, for 
example, (1) thoroughly mixing or blending a mixture of core resin 
monomers, optional preformed core resins, free radical initiators, 
colorants, and an inner shell forming monomer such as a diisocyante 
(DESMODUR W.TM.); (2) dispersing the aforementioned well blended mixture 
by high shear blending to form stabilized microdroplets of specific 
droplet size and size distribution in an aqueous medium containing a 
suitable outer shell coating cellulose polymer, such as TYLOSE.RTM., and 
an optional ionic or inorganic surfactant, such as sodium dodecyl sulfate, 
to control the desired particle size, and wherein the volume average 
microdroplet diameter can be desirably adjusted to be from about 2 microns 
to about 15 microns with the volume average droplet size dispersity being 
less than 1.35; (3) adding the second inner shell monomer such as a 
diamine (DYTEK A.TM.) which diffuse through the outer coating and 
condenses with the diamine inner shell forming monomer via an interfacial 
polymerization mechanism resulting in a polyurea inner shell material; (4) 
effecting the free radical polymerization to form the core resin by 
heating; and (5) processing the resulting particles by washing, drying and 
treating with known surface additives. The formation of stabilized 
particle suspension is generally conducted at ambient, about 25.degree. C. 
in embodiments, temperature, while the free radical polymerization can be 
accomplished at a temperature of from about 35.degree. C. to about 
120.degree. C., and preferably from about 45.degree. C. to about 
90.degree. C., for a period of time of from about 1 to about 24 hours 
depending primarily on the monomers and free radical initiators used. The 
core resin obtained via free radical polymerization, together with the 
optional preformed polymer resin, comprises from about 60 to about 95 
percent, and preferably of from about 75 to about 95 percent by weight of 
toner, the colorant comprises from about 1 to about 15 percent by weight 
of the toner, the inner shell material comprises from about 5 to about 30 
percent by weight and more preferably from about 10 to about 20 percent by 
weight, the outer shell cellulose coating comprises from about 0.001 to 
about 5 percent by weight of the toner, while the surface additives like 
flow aids, surface release agents, and charge control chemicals can 
comprise from about 0.1 to about 5 percent of toner in embodiments 
thereof. 
The volume average particle size of the colored encapsulated toners of this 
invention in embodiments can be controlled by appropriately adjusting the 
concentration of the outer coating material and ionic or inorganic 
surfactant. For example, in an embodiment, the colored encapsulated toner 
process of this invention can be controlled such that the volume average 
toner particle size is 7 microns in diameter by adjusting the outer 
coating cellulose material, such as TYLOSE.RTM., of from about 0.75 to 
about 1 percent by weight of water, and utilizing an ionic surfactant such 
as sodium dodecylsulfate of from about 0 to about 0.005 percent by weight 
of water. In another embodiment, the volume average particle size of the 
colored encapsulated toner can be controlled to about 5 microns in 
diameter by adjusting the outer coating cellulose material, such as 
TYLOSE.RTM., of from about 0.75 to about 1 percent by weight of water, and 
the ionic surfactant, such as sodium dodecyl sulfate, of from about 0.01 
to about 0.02 percent by weight of water. In yet another embodiment, the 
volume average particle size of the colored encapsulated toner can be 
controlled to about 3 microns in diameter by adjusting the outer coating 
cellulose material, such as TYLOSE.RTM., of from about 0.75 to about 1 
percent by weight of water, and the ionic surfactant, such as sodium 
dodecyl sulfate, of from about 0.02 to about 0.04 percent by weight of 
water. Additionally, in another embodiment, the volume average particle 
size of the colored encapsulated toner can be controlled to about 0.5 
micron in diameter by adjusting the outer coating cellulose material, such 
as TYLOSE.RTM., of from about 0.5 to about 1.25 percent by weight of 
water, and the ionic surfactant, such as sodium dodecyl sulfate, of from 
about 0.1 to about 0.5 percent by weight of water. Generally, higher 
concentration of outer coating material and ionic or inorganic surfactant 
tends to decrease the average particle size diameter of the colored 
encapsulated toner. 
In an embodiment, the colored encapsulated toner composition can be 
prepared by (i) mixing a core resin forming monomer, such as styrene, from 
about 0.6 mole to 0.8 mole, stearyl methacrylate from about 0.06 mole to 
about 0.08 mole, a colorant, such as HELIOGEN BLUE.TM., from about 0.01 
mole to about 0.015 mole, an inner shell forming diisocyanate monomer, 
such as DESMODUR W.TM., of from about 0.03 mole to about 0.05 mole and 
free-radical iniators, such as VAZO 67.TM., from about 0.001 mole to about 
0.003 mole; (ii) dispersing this mixture using a high shearing device, 
such as a Brinkman 45G probe, at from about 8,000 to about 10,000 rpm for 
a duration of from about 30 to about 120 seconds, in a vessel containing 
from about a 0.5 liter to about 0.75 liter of water, dissolved therein an 
outer coating cellulose surfactant, such as TYLOSE.RTM., of from about 
0.75 to about 1 percent by weight of water, and an ionic surfactant such 
as sodium dodecyl sulfate of from about 0 to 0.04 percent by weight of 
water; (iii) adding the second inner shell diamine monomer, such as DYTEK 
A.TM., of from about 0.03 mole to about 0.05 mole; and (iv) heating the 
mixture to effect free-radical core polymer formation, from about 
60.degree. C. to about 95.degree. C., and for a duration of from about 360 
minutes to about 720 minutes. The toner product is then washed by 
centrifugation from about four to about six times, and dried using 
preferably a fluidized bed operated of from about 30.degree. C. to about 
60.degree. C. for a duration of from about 240 minutes to about 480 
minutes, known flow additives to improve flow characteristics may then 
optionally be employed such as AEROSIL R-200.RTM. and the like. 
Illustrative examples of core monomers, which are subsequently polymerized, 
include a number of known components such as acrylates, methacrylates, 
olefins including styrene and its derivatives such as methyl styrene, and 
the like. Specific examples of core monomers include methyl acrylate, 
methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, 
propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, 
pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, 
heptyl methacrylate, octyl acrylate, octyl methacrylate, cyclohexyl 
acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, 
stearyl acrylate, stearyl methacrylate, benzyl acrylate, benzyl 
methacrylate, ethoxypropyl acrylate, ethoxypropyl methacrylate, 
methylbutyl acrylate, methylbutyl methacrylate, ethylhexyl acrylate, 
ethylhexyl methacrylate, methoxybutyl acrylate, methoxybutyl methacrylate, 
cyanobutyl acrylate, cyanobutyl methacrylate, tolyl acrylate, tolyl 
methacrylate, styrene, substituted styrenes, other substantially 
equivalent addition monomers, and known addition monomers, reference for 
example U.S. Pat. No. 4,298,672, the disclosure of which is totally 
incorporated herein by reference, and mixtures thereof. Illustrative 
examples of optional preformed core resins include styrene polymers, such 
as styrene-butadiene copolymers, PLIOLITES.RTM., PLIOTONES.RTM., 
polyesters, acrylate and methacrylate polymers, and the like. 
Various known colorants may be selected for the toner compositions of the 
present invention providing, for example, that they do not substantially 
interfere with the free radical polymerization. Typical examples of 
specific colorants, preferably present in an effective amount of, for 
example, from about 3 to about 10 weight percent of toner include IOGEN 
VIOLET 5100.TM. and 5890.TM. (BASF), NORMANDY MAGENTA RD-2400.TM. (Paul 
Uhlich), PERMANENT VIOLET VT2645.TM. (Paul Uhlich), HELIOGEN GREEN 
L8730.RTM. (BASF), ARGYLE GREEN XP-111-S.TM. (Paul Uhlich), BRILLIANT 
GREEN TONER GR 0991.RTM. (Paul Uhlich), LITHOL SCARLET D3700.RTM. (BASF), 
TOLUIDINE RED.TM. (Aldrich), SCARLET FOR THERMOPLAST NSD RED.TM. 
(Aldrich), LITHOL RUBINE TONER.TM. (Paul Uhlich), LITHOL SCARLET 4440.TM., 
NBD 3700.TM. (BASF), BON RED C.TM. (Dominion Color), ROYAL BRILLIANT RED 
RD-8192.TM. (Paul Uhlich), ORACET PINK RF.TM. (Ciba Geigy), IOGEN RED 
3340.TM. and 3871K.TM. (BASF), LITHOL FAST SCARLET L4300.TM. (BASF), 
HELIOGEN BLUE D6840.TM., D7080.TM., K7090.TM. , K6902.TM., K6910.TM. and 
L7020.TM. (BASF), SUDAN BLUE OS.TM. (BASF), NEOPEN BLUE FF4012.TM. (BASF), 
PV FAST BLUE B2G01.TM. (American Hoechst), IRGALITE BLUE BCA.TM. (Ciba 
Geigy), IOGEN BLUE.TM. 6470 (BASF), SUDAN II.TM., III.TM. and IV.TM. 
(Matheson, Coleman, Bell), SUDAN ORANGE.TM. (Aldrich), SUDAN ORANGE 
220.TM. (BASF), IOGEN ORANGE 3040.TM. (BASF), ORTHO ORANGE OR 2673.TM. 
(Paul Uhlich), IOGEN YELLOW 152.TM. and 1560.TM. (BASF), LITHOL FAST 
YELLOW 0991K.TM. (BASF), IOTOL YELLOW 1840.TM. (BASF), NOVAPERM YELLOW 
FGL.TM. (Hoechst), PERMANENT YELLOW YE 0305.TM. (Paul Uhlich), LUMOGEN 
YELLOW D0790.TM. (BASF), SUCO-GELB L1250.TM. (BASF), SUCO-YELLOW D1355.TM. 
(BASF), SICO FAST YELLOW D1165.TM., D1355.TM. and D1351.TM. (BASF), 
HOSTAPERM PINK E.TM. (Hoechst), FANAL PINK D4830.TM. (BASF), CINQUASIA 
MAGENTA.TM. (DuPont), IOGEN BLACK L0084.TM. (BASF), PIGMENT BLACK K801 
(BASF) and carbon blacks such as REGAL 330.RTM. (Cabot), CARBON BLACK 
5250.RTM. and 5750.RTM. (Columbian Chemicals), and the like. 
Examples of the outer shell coating polymers selected for the toners and 
processes of the present invention include alkyl celluloses with the alkyl 
groups containing, for example, from 1 to about 10 carbon atoms; and more 
specifically methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, 
hydroxypropyl cellulose, hydroxyethylmethyl cellulose, TYLOSE.RTM. and the 
like. The effective concentration of the cellulose polymer in the aqueous 
phase at the dispersion or microdroplet formation step is, for example, 
from about 0.1 percent by weight to about 5 percent by weight, with the 
preferred amount being determined primarily by the nature of the toner 
precursor materials and the desired toner particle size. In embodiments, 
inorganic surfactants are also utilized in combination with the cellulose 
polymer for achieving a smaller microdroplet size. Illustrative examples 
of suitable inorganic surfactants include alkali salts, such as potassium 
oleate, potassium caprate, potassium stearate, sodium laurate, sodium 
dodecyl sulfate, sodium oleate, sodium laurate, and the like. The 
effective concentration of inorganic surfactant that is generally employed 
is, for example, from about 0.005 to about 0.5 percent by weight, and 
preferably from about 0.01 to about 0.10 percent by weight. Known surface 
additives, such as silicas like AEROSIL R972.RTM., metal oxides, such as 
tin oxide, in effective amounts such as about 0.5 to about 1 weight 
percent, and effective mixtures of the aforementioned additives can also 
be selected for the toners of the present invention. 
Examples of preferred inner shell polymers include polyureas, polyamides, 
polyethers, polyurethanes, mixtures thereof, and the like, and which 
shells may contain within their structures certain soft, flexible moieties 
such as polyether functions which, for example, assist in the molecular 
packing of the shell materials as well as imparting the desirable low 
surface energy characteristics to the shell structure. The shell amounts 
are generally from about 5 to about 30 percent by weight of the toner, and 
have a thickness generally, for example, of less than about 5 microns as 
indicated herein. In one embodiment of the present invention, the 
encapsulant inner shells are formed by interfacial polycondensation of one 
or more diisocyanates with one or more diamines. Examples of diisocyanates 
include Uniroyal Chemical's diphenylmethane diisocyanate-based liquid 
polyether VIBRATHANES.RTM. such as B-635, B-843, and the like, toluene 
diisocyanate-based liquid polyether VIBRATHANES.RTM. such as B-604, B-614, 
and the like, and Mobay's Chemical Corporation's liquid polyether 
isocyanate prepolymers, E-21.TM. or E-21A.TM. (product code number D-716), 
743 (product code numbers D-301), 744 (product code number D-302), and the 
like. Other diisocyanates that can be selected for the formation of shell 
material are those available commercially including, for example, benzene 
diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 
1,6-hexamethylene diisocyanate, DESMODUR W.TM., 
bis(4-isocyanatocyclohexyl)methane, MODUR CB-60.TM., MONDUR CB-75.TM., 
MONDUR MR.TM., MONDUR MRS 10.TM., PAPI 27.TM., PAPI 135.TM., ISONATE 
143L.TM., ISONATE 181.TM., ISONATE 125M.TM., ISONATE 191.TM., and ISONATE 
240.TM.. Illustrative examples of diamines suitable for the interfacial 
polycondensation shell formation include, for example, ethylenediamine, 
tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 
p-phenylenediamine, m-phenylenediamine, 2-hydroxy trimethylenediamine, 
diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, 
1,8-diaminooctane, xylylene diamine, bis(hexamethylene)triamine, 
tris(2-aminoethyl)amine, 4,4'-methylene bis(cyclohexylamine), 
bis(3-aminopropyl)ethylene diamine, 1,3-bis(aminomethyl)cyclohexane, 
1,5-diamino-2-methylpentane, piperazine, 2-methylpiperazine, 
2,5-dimethylpiperazine, 1,4-bis(3-aminopropyl)-piperazine, and 
2,5-dimethylpentamethylene diamine. Generally, the shell polymer comprises 
from about 5 to about 30 percent by weight of the total toner composition, 
and preferably comprises from about 10 percent by weight to about 20 
percent by weight of the toner composition. During the aforementioned 
interfacial polycondensation to form the inner shell, the temperature is 
maintained at from about 15.degree. C. to about 55.degree. C., and 
preferably from about 20.degree. C. to about 30.degree. C. Also, generally 
the reaction time is from about 5 minutes to about 5 hours, and preferably 
from about 20 minutes to about 90 minutes. Other temperatures and times 
can be selected, and further polyisocyanates and polyamines not 
specifically illustrated may be selected. 
Illustrative examples of known free radical initiators that can be selected 
for the preparation of the toners include azo-type initiators such as 
2,2'-azobis(dimethylvaleronitrile), azobis(isobutyronitrile), 
azobis(cyclohexanenitrile), azobis(methylbutyronitrile), mixtures thereof, 
and the like, peroxide initiators such as benzoyl peroxide, lauroyl 
peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, 
2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, di-tert-butyl peroxide, 
cumene hydroperoxide, dichlorobenzoyl peroxide, and mixtures thereof, with 
the effective quantity of initiator being, for example, from about 0.1 
percent to about 10 percent by weight of that of core monomer. 
For two component developers, carrier particles including steel ferrites, 
copper zinc ferrites, and the like, with or without coatings, can be 
admixed, from about 1 to about 3 parts of toner for each 100 parts of 
carrier for example, with the encapsulated toners of the present 
invention, reference for example the carriers illustrated in U.S. Pat. 
Nos. 4,937,166; 4,935,326; 4,560,635; 4,298,672; 3,839,029; 3,847,604; 
3,849,182; 3,914,181; 3,929,657 and 4,042,518, the disclosures of which 
are totally incorporated herein by reference. 
The following examples are being submitted to further define various 
species of the present invention. These examples are intended to be 
illustrative only and are not intended to limit the scope of the present 
invention. Comparative Examples are also provided. 
COMATIVE EXAMPLE I 
A 6.8 micron (volume average particle diameter) cellulose-coated cyan 
toner, as disclosed in Example I of copending patent application U.S. Ser. 
No. 720,300 (D/90516), which comprises a core coated with an alkyl 
cellulose shell material, was prepared as follows: 
A mixture of 185.0 grams of isobutyl methacrylate, and 4.0 grams of 
HELIOGEN BLUE K7090 (BASF) pigment was ball milled for 24 hours. To this 
mixture were added 3.0 grams each of two free radical initiators, 
2,2'-azobis-(2,4-dimethylvaleronitrile) and 2,2'-azobis(isobutyronitrile), 
and the mixture was roll blended until all the free radical initiators 
were dissolved. One hundred and fifty (150) grams of the resulting mixture 
were then transferred to a 2-liter reaction vessel containing 700 
milliliters of a 1.0 percent aqueous TYLOSE.RTM. solution, and the 
resulting mixture was homogenized for 2 minutes using a Brinkmann polytron 
operating at 10,000 rpm. Thereafter, the mixture was mechanically stirred 
at room temperature, 25.degree. C., for 30 minutes before heating to 
80.degree. C. over a period of 1 hour, and maintained at this temperature 
for another 10 hours. After cooling down to room temperature, the reaction 
product was washed repeatedly with water until the aqueous phase was 
clear, and the product was then freeze dried for 24 hours. The resulting 
toner particle product evidenced a volume average particle diameter of 6.8 
microns, and a particle size distribution of 1.31 according to Coulter 
Counter measurements. 
Fifty (50.0) grams of the above prepared dried toner particles were dry 
blended with a mixture of 0.75 gram of AEROSIL R812.RTM. and 0.80 gram of 
conductive tin oxide powder for 10 minutes using a Grey blender with its 
blending impeller operating at 2,500 rpm. A negatively charged developer 
was prepared by blending 2 parts by weight of the above toner particles 
with 98 parts by weight of carrier particles comprised of a ferrite core 
coated with a terpolymer of methyl methacrylate, styrene, and vinyl 
triethoxysilane polymer, 0.7 weight percent of coating, reference U.S. 
Pat. Nos. 3,467,634 and 3,526,533, the disclosures of which are totally 
incorporated herein by reference. Latent images were then formed in a 
xerographic experimental imaging device similar to the Xerox Corporation 
9200, and subsequent to the development of images with the aforementioned 
prepared toner, the images was transferred to a paper substrate and fixed 
with heat, about 160.degree. C., with a VITON.RTM. fuser roll. The toner 
image thereafter was measured using a GARDNER.TM. gloss unit and displayed 
a gloss value of 55 gloss units. 
COMATIVE EXAMPLE II 
A colored encapsulated yellow toner, as disclosed in Example I of U.S. Pat. 
No. 4,766,051, the disclosure of which is totally incorporated herein by 
reference, which comprises a core of polybutadiene resin and yellow 
pigment, and a polyurea shell material, was prepared as follows: 
NOVAPERM YELLOW FGL.TM. (Hoechst), 5 grams; VISTANEX LMMH.TM., 12 grams; 
cyclohexane ACS (Caledon) 50 grams; and 5 millimeters diameter ball 
bearings (1/3 of the total volume) were placed in a 250 milliliter plastic 
bottle and ball milled for 16 hours. Thereafter, TDI-80, a mixture of 2,4 
and 2,6 toluene diisocyanate, 9 grams, and DESMODUR RF.TM. 
(tris(p-isocyanato-phenyl)thiophosphate), 5 grams, in dichloromethane, 20 
milliliters, were added to the pigment mixture. The mixture was then 
homogenized with a Brinkman homogenizer PT 10-35 set at speed 9for 90 
seconds (generator PT-20). Thereafter, the mixture was then dispersed in a 
1 percent poly(vinyl alcohol) solution, 500 milliliters and 2-decanol, 0.5 
milliliter with a Brinkman homogenizer PT 10-35 set at speed 7 to 15 
seconds (generator PT-35/4). Subsequently, this mixture was transferred to 
a 2 liter beaker equipped with a mechanical stirrer, and an oil bath under 
the beaker. Diethylene triamine, 5 milliliters in water, 22 milliliters, 
was added to the aforementioned mixture over a period of 2 minutes, and 
the mixture was kept at room temperature overnight. During this period, an 
interfacial polymerization reaction ensued enabling the polyurea polymer 
shell to formulate. The next day, about 18 hours later, the temperature 
was increased to 65.degree. C. for 8 hours to permit the reaction to 
proceed to completion and to remove volatiles, such as the residual 
solvents, cyclohexane and dichloromethane. The reaction mixture was then 
allowed to stabilize at room temperature, and the yellow toner resulting 
was comprised of polyisobutylene core polymer, about 37 percent by weight, 
the yellow pigment, 16 percent by weight, and a polyurea shell, 47 percent 
by weight. 
Fifty (50.0) grams of the above prepared dried toner particles were dry 
blended with a mixture of 0.75 gram of AEROSIL R812.RTM. and 0.80 grams of 
conductive tin oxide powder for 10 minutes using a Grey blender with its 
blending impeller operating at 2,500 rpm. A negatively charged developer 
was prepared by blending 2 parts by weight of the above toner particles 
with 98 parts by weight of carrier particles comprised of a ferrite core 
coated with a terpolymer of methyl methacrylate, styrene, and vinyl 
triethoxysilane polymer, 0.7 weight percent of coating, reference U.S. 
Pat. Nos. 3,467,634 and 3,526,533, the disclosures of which are totally 
incorporated herein by reference. The toner latent images were then formed 
in a xerographic experimental imaging device similar to the Xerox 
Corporation 9200, and subsequent to the development of images with the 
aforementioned prepared toner, the images were then transferred to a paper 
substrate and fixed with heat, about 160.degree. C., with a VITON.RTM. 
fuser roll. The toner image thereafter was measured using a GARDNER.TM. 
gloss unit and displayed a gloss value of 35 gloss units.

EXAMPLE I 
A 7.1 micron (volume average particle diameter) encapsulated cyan toner was 
prepared as follows. 
A mixture of 103.9 grams of styrene, 69.3 grams of stearyl methacrylate, 
11.9 grams of HELIOGEN BLUE K7090.TM. (BASF) pigment flushed in 42 percent 
by weight of poly(styrene-butylmethacrylate), 3.0 grams each of two free 
radical initiators, 2,2'-azobis-(2,4-dimethylvaleronitrile) and 
2,2'-azobis-(isobutyronitrile), and 34.5 grams of bis 
(p-isocyanatocyclohexyl)-methane (DESMODUR W.TM.) was formed. The mixture 
was shaken in a polyethylene closed polyethylene container (250 
milliliters) until all the free radical initiators were dissolved. One 
hundred and fifty (150) grams of the resulting mixture was then 
transferred to a 2-liter reaction vessel containing 700 milliliters of a 
1.0 percent aqueous methyl cellulose (TYLOSE.RTM.) solution and 0.005 
percent of sodium dodecyl sulfate, and the resulting mixture was 
homogenized for 2 minutes using a Brinkmann polytron operating at 10,000 
rpm. Thereafter, 15.9 grams of 2,5-pentamethylene diamine (DYTEK A.TM.) 
was added and the mixture was mechanically stirred at room temperature, 
25.degree. C., for 30 minutes before heating to 80.degree. C. over a 
period of 1 hour, and maintained at this temperature for another 10 hours. 
After cooling down to room temperature, about 25.degree. C., the reaction 
product was washed repeatedly with water until the aqueous phase was 
clear, and the product was then freeze dried for 48 hours. The resulting 
toner was comprised of 76 percent by toner weight of styrene-methacrylate 
core resin, 3 percent by toner weight of pigment, 21 percent by toner 
weight of inner shell polyurea, and less than one percent by toner weight 
of outer shell alkyl cellulose coating. The dry product evidenced a volume 
average particle diameter of 7.1 microns, and a particle size distribution 
of 1.33 according to Coulter Counter measurements. 
Fifty (50.0) grams of the above prepared dried toner particles were then 
dry blended with a mixture of 0.25 gram of AEROSIL R812.RTM. and 0.40 gram 
of conductive tin oxide powder for 15 minutes using a Grey blender with 
its blending impeller operating at 2,500 rpm. A negatively charged 
developer was prepared by blending 2 parts by weight of the above toner 
particles with 98 parts by weight of carrier particles comprised of a 
ferrite core coated with a terpolymer of methyl methacrylate, styrene, and 
vinyl triethoxysilane polymer, 0.7 weight percent of coating, reference 
U.S. Pat. Nos. 3,467,634 and 3,526,533, the disclosures of which are 
totally incorporated herein by reference. The toner displayed a 
triboelectric value of -22 microcoulombs per gram as determined in the 
known Faraday Cage apparatus. The toner latent images were then formed in 
a xerographic experimental imaging device similar to the Xerox Corporation 
9200, and subsequent to the development of images with the aforementioned 
prepared toner, the images were then transferred to a paper substrate and 
fixed with heat, about 120.degree. C., with a VITON.RTM. fuser roll. The 
toner images thereafter were measured using a GARDNER.TM. gloss unit and 
displayed a gloss value of a 14 gloss units. The gloss values were about 
41 gloss units lower than comparative Example I, and about 21 gloss units 
lower than that of Eaxmple II. 
EXAMPLE II 
A 5 micron (volume average particle diameter) encapsulated cyan toner was 
prepared as follows. 
A mixture of 103.9 grams of styrene, 69.3 grams of stearyl methacrylate, 
11.9 grams of HELIOGEN BLUE K7090.TM. (BASF) pigment flushed in 42 percent 
by weight of poly(styrene-butylmethacrylate), 3.0 grams each of two free 
radical initiators, 2,2'-azobis-(2,4-dimethylvaleronitrile) and 
2,2'-azobis-(isobutyronitrile), and 34.5 grams of 
bis(p-isocyanatocyclohexyl)-methane (DESMODUR W.TM.). The mixture was 
shaken in a closed polyethylene container (250 milliliters) until all the 
free radical initiators were dissolved. One hundred and fifty (150) grams 
of the resulting mixture were then transferred to a 2-liter reaction 
vessel containing 700 milliliters of a 1.0 percent aqueous methyl 
cellulose (TYLOSE.RTM.) solution and 0.01 percent of sodium 
dodecylsulfate, and the resulting mixture was homogenized for 2 minutes 
using a Brinkmann polytron operating at 10,000 rpm. Thereafter, 15.9 grams 
of 2,5-pentamethylene diamine (DYTEK A.TM.) was added and the mixture was 
mechanically stirred at room temperature, 25.degree. C., for 30 minutes 
before heating to 80.degree. C. over a period of 1 hour, and maintained 
at this temperature for another 10 hours. After cooling down to room 
temperature, about 25.degree. C., the reaction product was washed 
repeatedly with water until the aqueous phase was clear, and the product 
was then freeze dried for 48 hours. The resulting toner was comprised of 
76 percent by toner weight of styrene-methacrylate core resin, 3 percent 
by toner weight of pigment, 21 percent by toner weight of inner shell 
polyurea, and about one percent by toner weight of outer shell alkyl 
cellulose coating. The dry toner product evidenced a volume average 
particle diameter of 5 microns, and a particle size distribution of 1.33 
according to Coulter Counter measurements. 
A negatively charged developer was prepared similarly to that decribed in 
Example I. The toner displayed a triboelectric value of -17 microcoulombs 
per gram as determined in the known Faraday Cage apparatus. The toner 
latent images were then formed in a xerographic experimental imaging 
device similar to the Xerox Corporation 9200, and subsequent to the 
development of images with the aforementioned prepared toner, the images 
were then transferred to a paper substrate and fixed with heat, about 
160.degree. C., with a VITON.RTM. fuser roll. The toner image thereafter 
were measured using a GARDNER.TM. gloss unit and displayed a gloss value 
of 14 gloss units. 
EXAMPLE III 
A 3 micron (volume average particle diameter) encapsulated cyan toner was 
prepared as follows. 
There was formed a mixture of 103.9 grams of styrene, 69.3 grams of stearyl 
methacrylate, 11.9 grams of HELIOGEN BLUE K7090.TM. (BASF) pigment flushed 
in 42 percent by weight of poly(styrenebutylmethacrylate), 3.0 grams each 
of two free radical intiators, 2,2'-azobis-(2,4-dimethylvaleronitrile) and 
2,2'-azobis-(isobutyronitrile), and 34.5 grams of 
bis(p-isocyanatocyclohexyl)-methane (DESMODUR W.TM.). The mixture was 
shaken in a closed polyethylene container (250 milliliters) until all the 
free radical initiators were dissolved. One hundred and fifty (150) grams 
of the resulting mixture were then transferred to a 2-liter reaction 
vessel containing 700 milliliters of a 1.0 percent aqueous methyl 
cellulose (TYLOSE.RTM.) solution and 0.03 percent of sodium 
dodecylsulfate, and the resulting mixture was homogenized for 2 minutes 
using a Brinkmann polytron operating at 10,000 rpm. Thereafter, 15.9 grams 
of 2,5-pentamethylene diamine (DYTEK A.TM.) were added and the mixture was 
mechanically stirred at room temperature, 25.degree. C., for 30 minutes 
before heating to 80.degree. C. over a period of 1 hour, and maintained at 
this temperature for another 10 hours. After cooling down to room 
temperature, about 25.degree. C., the reaction product was washed 
repeatedly with water until the aqueous phase was clear, and the product 
was then freeze dried for 48 hours. The resulting toner was comprised of 
76 percent by toner weight of a styrene-methacrylate core resin, 3 percent 
by toner weight of pigment, 21 percent by toner weight of inner shell 
polyurea, and about 1 percent by toner weight of outer shell alkyl 
cellulose coating. The dry product evidenced a volume average particle 
diameter of 5 microns, and a particle size distribution of 1.33 according 
to Coulter Counter measurements. 
A negatively charged developer was prepared similarly to that described in 
Example I. The toner displayed a triboelectric value of -11 microcoulombs 
per gram as determined in the known Faraday Cage apparatus. Latent images 
were then formed in a xerographic experimental imaging device similar to 
the Xerox Corporation 9200, and subsequent to the development of images 
with the aforementioned prepared toner, the images were then transferred 
to a paper substrate and fixed with heat, about 160.degree. C., with a 
VITON.RTM. fuser roll. The images were measured using a GARDNER.TM. gloss 
unit and displayed a gloss value of 10 gloss units. 
EXAMPLE IV 
A 0.5 micron (volume average particle diameter) encapsulated cyan toner was 
prepared as follows. 
There was prepared a mixture of 103.9 grams of styrene, 69.3 grams of 
stearyl methacrylate, 11.9 grams of HELIOGEN BLUE K7090.TM. (BASF) pigment 
flushed in 42 percent by weight of poly(styrene-butylmethacrylate), 3.0 
grams each of two free radical initiators, 
2,2'-azobis-(2,4-dimethylvaleronitrile) and 
2,2'-azobis-(isobutyronitrile), and 34.5 grams of 
bis(p-isocyanatocyclohexyl)-methane (DESMODUR W.TM.). The mixture was 
shaken in a closed polyethylene container (250 milliliters) until all the 
free radical initiators were dissolved. One hundred and fifty (150) grams 
of the resulting mixture were then transferred to a 2-liter reaction 
vessel containing 700 milliliters of a 1.0 percent aqueous methyl 
cellulose (TYLOSE.RTM.) solution and 0.5 percent of sodium dodecylsulfate, 
and the resulting mixture was homogenized for 2 minutes using a Brinkmann 
polytron operating at 10,000 rpm. Thereafter, 15.9 grams of 
2,5-pentamethylene diamine (DYTEK A.TM.) was added and the mixture was 
mechanically stirred at room temperature, 25.degree. C., for 30 minutes 
before heating to 80.degree. C. over a period of 1 hour, and maintained at 
this temperature for another 10 hours. After cooling down to room 
temperature, about 25.degree. C., the reaction product was washed 
repeatedly with water until the aqueous phase was clear, and the product 
was then freeze dried for 48 hours. The resulting toner was comprised of 
76 percent by toner weight of styrene-methacrylate core resin, 3 percent 
by toner weight of pigment, 21 percent by toner weight of inner shell 
polyurea, and about 1 percent by toner weight of outer shell alkyl 
cellulose coating. The dry product evidenced a volume average particle 
diameter of 0.5 micron, and a particle size distribution of 1.43 according 
to Coulter Counter measurements. 
EXAMPLE V 
A 5.3 micron (volume average particle diameter) encapsulated cyan toner was 
prepared as follows. 
There was prepared a mixture of 103.9 grams of styrene, 69.3 grams of 
lauryl methacrylate, 11.9 grams of HELIOGEN BLUE K7090.TM. (BASF) pigment 
flushed in 42 percent by weight of poly(styrene-butylmethacrylate), 3.0 
grams each of two free radical initiators, 
2,2'azobis-(2,4-dimethylvaleronitrile) and 2,2'-azobis-(isobutyronitrile), 
and 34.5 grams of bis(p-isocyanatocyclohexyl)-methane (DESMODUR W.TM.). 
The mixture was shaken in a polyethylene closed polyethylene container 
(250 milliliters) until all the free radical initiators were dissolved. 
One hundred and fifty (150) grams of the resulting mixture were then 
transferred to a 2-liter reaction vessel containing 700 milliliters of a 
1.0 percent aqueous methyl cellulose (TYLOSE.RTM.) solution and 0.01 
percent of sodium dodecylsulfate, and the resulting mixture was 
homogenized for 2 minutes using a Brinkmann polytron operating at 10,000 
rpm. Thereafter, 15.9 grams of 2,5-pentamethylene diamine (DYTEK A.TM.) 
was added and the mixture was mechanically stirred at room temperature, 
25.degree. C., for 30 minutes before heating to 80.degree. C. over a 
period of 1 hour, and maintained at this temperature for another 10 hours. 
After cooling down to room temperature, about 25.degree. C., the reaction 
product was washed repeatedly with water until the aqueous phase was 
clear, and the product was then freeze dried for 48 hours. The resulting 
toner was comprised of 76 percent by toner weight of styrene-methacrylate 
core resin, 3 percent by toner weight of pigment, 21 percent by toner 
weight of inner shell polyurea, and about 1 percent by toner weight of 
outer shell alkyl cellulose coating. The dry product evidenced a volume 
average particle diameter of 5.3 microns, and a particle size distribution 
of 1.38 according to Coulter Counter measurements. 
A negatively charged developer was prepared similarly to that described in 
Example I. The toner displayed a triboelectric value of -25 microcoulombs 
per gram as determined in the known Faraday Cage apparatus. Latent images 
were then formed in a xerographic experimental imaging device similar to 
the Xerox Corporation 9200, and subsequent to the development of images 
with the aforementioned prepared toner, the images were then transferred 
to a paper substrate and fixed with heat, about 160.degree. C., with a 
VITON.RTM. fuser roll. The toner images thereafter were measured using a 
GARDNER.TM. gloss unit and displayed a gloss value of 7 gloss units. 
EXAMPLE VI 
A 6.0 micron (volume average particle diameter) encapsulated cyan toner was 
prepared as follows. 
There was prepared a mixture of 103.9 grams of styrene, 34.7 grams of 
lauryl methacrylate, 34.7 grams of stearyl methacrylate, 11.9 grams of 
HELIOGEN BLUE K7090.TM. (BASF) pigment flushed in 42 percent by weight of 
poly(styrene-butylmethacrylate), 3.0 grams each of two free radical 
initiators, 2,2'-azobis-(2,4-dimethylvaleronitrile) and 
2,2'-azobis-(isobutyronitrile), and 34.5 grams of 
bis(p-isocyanatocyclohexyl)-methane (DESMODUR W.TM.). The mixture was 
shaken in a polyethylene closed polyethylene container (250 milliliters) 
until all the free radical initiators were dissolved. One hundred and 
fifty (150) grams of the resulting mixture were then transferred to a 
2-liter reaction vessel containing 700 milliliters of a 1.0 percent 
aqueous methyl cellulose (TYLOSE.TM.) solution and 0.01 percent of sodium 
dodecyl sulfate, and the resulting mixture was homogenized for 2 minutes 
using a Brinkmann polytron operating at 10,000 rpm. Thereafter, 15.9 grams 
of 2,5-pentamethylene diamine (DYTEK A.TM.) was added and the mixture was 
mechanically stirred at room temperature, 25.degree. C., for 30 minutes 
before heating to 80.degree. C. over a period of 1 hour, and maintained at 
this temperature for another 10 hours. After cooling down to room 
temperature, about 25.degree. C., the reaction product was washed 
repeatedly with water until the aqueous phase was clear, and the product 
was then freeze dried for 48 hours. The resulting toner was comprised of 
76 percent by toner weight of styrene-methacrylate core resin, 3 percent 
by toner weight of pigment, 21 percent by toner weight of inner shell 
polyurea, and about 1 percent by toner weight of outer shell alkyl 
cellulose coating. The dry product evidenced a volume average particle 
diameter of 6.0 microns, and a particle size distribution of 1.39 
according to Coulter Counter measurements. 
A negatively charged developer was prepared similarly to that described in 
Example I. The toner displayed a triboelectric value of -23 microcoulombs 
per gram as determined in the known Faraday Cage apparatus. Latent images 
were then formed in a xerographic experimental imaging device similar to 
the Xerox Corporation 9200, and subsequent to the development of images 
with the aforementioned prepared toner, the images were then transferred 
to a paper substrate and fixed with heat, about 160.degree. C., with a 
VITON.RTM. fuser roll. The toner images thereafter were measured using a 
GARDNER.TM. gloss unit and displayed a gloss value of 3 gloss units. 
EXAMPLE VII 
A 2.0 micron (volume average particle diameter) encapsulated cyan toner was 
prepared as follows. 
There was formed a mixture of 103.9 grams of styrene, 34.7 grams of lauryl 
methacrylate, 34.7 grams of stearyl methacrylate, 11.9 grams of HELIOGEN 
BLUE K7090.TM. (BASF) pigment flushed in 42 percent by weight of 
poly(styrene-butylmethacrylate), 3.0 grams each of two free radical 
initiators, 2,2'-azobis-(2,4-dimethylvaleronitrile) and 
2,2'-azobis-(isobutyronitrile), and 34.5 grams of 
bis(p-isocyanatocyclohexyl)-methane (DESMODUR W.TM.). The mixture was 
shaken in a polyethylene closed polyethylene container (250 milliliters) 
until all the free radical initiators were dissolved. One hundred and 
fifty (150) grams of the resulting mixture were then transferred to a 
2-liter reaction vessel containing 700 milliliters of a 1.0 percent 
aqueous methyl cellulose (TYLOSE.RTM.) solution and 0.04 percent of sodium 
dodecyl sulfate, and the resulting mixture was homogenized for 2 minutes 
using a Brinkmann polytron operating at 10,000 rpm. Thereafter, 15.9 grams 
of 2,5-pentamethylene diamine (DYTEK A.TM.) was added and the mixture was 
mechanically stirred at room temperature, 25.degree. C., for 30 minutes 
before heating to 80.degree. C. over a period of 1 hour, and maintained at 
this temperature for another 10 hours. After cooling down to room 
temperature, about 25.degree. C., the reaction product was washed 
repeatedly with water until the aqueous phase was clear, and the product 
was then freeze dried for 48 hours. The resulting toner was comprised of 
76 percent by toner weight of styrene-methacrylate core resin, 3 percent 
by toner weight of pigment, 21 percent by toner weight of inner shell 
polyurea, and about 1 percent by toner weight of outer shell alkyl 
cellulose coating. The dry product evidenced a volume average particle 
diameter of 2.0 microns, and a particle size distribution of 1.44 
according to Coulter Counter measurements. 
Other embodiments and modifications of the present invention may occur to 
those skilled in the art subsequent to a review of the present 
application; these embodiments and modifications, as well as equivalents 
thereof, are also included within the scope of this invention.