Organic sulfate and sulfonate compositions

This invention is generally directed to new organic sulfate and organic sulfonate compositions and processes for the preparation of such compositions. These compositions are of the following formula ##STR1## wherein R.sub.1 is an alkyl group containing from about 12 carbon atoms to about 22 carbon atoms, R.sub.2 and R.sub.3 are independently selected from alkyl groups containing from about 1 carbon atom to about 5 carbon atoms, R.sub.4 is an alkylene group containing from about 1 carbon atom to about 5 carbon atoms, R.sub.5 is a para substituted phenyl group wherein the substituent is an alkyl group containing from about 1 carbon atom to about 6 carbon atoms, or an alkyl group containing from about 1 carbon atom to about 3 carbon atoms, and n is the number 3 or 4.

BACKGROUND OF THE INVENTION 
This invention is generally directed to new organic sulfate and sulfonate 
compositions and process for the preparation of such compositions. More 
specifically the present invention is directed to certain toluene 
sulfonate and sulfate compositions which are useful as charge enhancing 
additives for electrostatographic developer compositions comprised of 
toner particles and carrier particles. Thus, for example, toner 
compositions containing the sulfates and sulfonates of the present 
invention are useful in electrostatographic imaging systems wherein the 
imaging member is charged negatively, and further such compositions are 
useful in imaging systems containing a Viton fuser roll as more 
specifically detailed hereinafter. 
Described in a copending application U.S. Ser. No. 212,969, filed Dec. 4, 
1980, are toner compositions containing the organic sulfate and sulfonate 
compounds of the present invention. The disclosure of the copending 
application is totally incorporated herein by reference. 
Various sulfate and sulfonate compositions are known including, for 
example, ammonium lauryl sulfate, sodium xylene sulfonate, sodium dodecyl 
benzene sulfonate, triethanol amine dodecyl benzene sulfonate, cetyl 
trimethyl ammonium para-toluene sulfonate, sodium tetradecyl sulfate, and 
the like. These materials are, for example, useful as surfactants, 
anti-static additives for toiletry preparations, and the like. There 
continues to remain a need, however, for new sulfates and sulfonates, 
particularly those which are useful as charge enhancing additives. The 
need for these additive, especially those which impart a positive charge 
to the toner resin has experienced a recent growth in view of the desire 
to use negatively charged photoresponsive imaging devices in electrostatic 
imaging systems. 
Various charge control additives are disclosed in the prior art, thus for 
example, there is disclosed in U.S. Pat. No. 3,893,935 the use of certain 
quaternary ammonium compounds as charge control agents for electrostatic 
toner compositions. According to the disclosure of this patent, certain 
quaternary ammonium compounds when incorporated into toner materials were 
found to provide a toner composition which exhibited relatively high 
uniform and stable net toner charge when mixed with a suitable carrier 
vehicle. A similar teaching is contained in U.S. Pat. No. 4,079,014 
wherein a diazo toner charge control additive is described. Further, there 
is disclosed in U.S. Pat. No. 4,298,672 as charge enhancing additives 
alkyl pyridinium compositions including cetyl pyridinium chloride. 
Many of the above disclosed charge control materials interact with certain 
fuser rolls, such as Viton fuser rolls, used in electrostatographic 
systems. This interaction causes these fuser rolls to be adversely 
affected, resulting ultimately in a deterioration of image quality. For 
example, the Viton fuser rolls discolor and turn black, as well as develop 
multiple surface cracks when certain charge control additive compounds are 
employed in the toner mixture. 
One Viton fuser roll selected for electrostatographic devices, particularly 
xerographic imaging systems, is comprised of a soft roll fabricated from 
lead oxide and duPont Viton E-430 resin (a vinylidene fluoride, 
hexafluoropropylene copolymer). This roll can be prepared by blending 
together, and curing at elevated temperatures approximately 15 parts of 
lead oxide, and 100 parts of Viton E-430. Apparently the function of the 
lead oxide is to generate unsaturation by dehydrofluorination for 
cross-linking, and to provide release mechanisms for the toner 
compositions. Excellent image quality has been obtained with the use of 
Viton fuser rolls, however, in some instances, there is a toner-fuser 
compatibility problem when charge control substances are contained in the 
toner mixture. It appears that certain charge control additive, such as 
quaternary ammonium compounds, and alkyl pyridinium compounds react with 
the Viton fuser roll. For example, cetyl pyridinium chloride when part of 
the toner mixture appears to be catalytically decomposed by the lead oxide 
in the fuser roll, resulting in a highly unsaturated compound, which 
polymerizes and condenses with the unsaturated Viton. As a result, the 
Viton fuser turns black and develops multiple surface cracks, thereby 
resulting in image quality deterioration. 
SUMMARY OF THE INVENTION 
It is an object of the present invention to provide novel organic sulfate 
and organic sulfonate compositions and processes for the preparation of 
such compositions. 
A further object of the present invention is to provide organic sulfonate 
compositions containing a nitrogen atom therein. 
In yet another object of the present invention there is provided organic 
sulfate compositions containing a nitrogen atom therein. 
In a further object of the present invention there is provided certain 
organic sulfonates and sulfate compositions which contain a positively 
charged portion and a negatively charged portion. 
These and other objects of the present invention are accomplished by the 
provision of organic sulfates and sulfonates of the following formula: 
##STR2## 
wherein R.sub.1 is an alkyl group containing from about 12 carbon atoms to 
about 22 carbon atoms, and preferably from about 14 carbon atoms to about 
18 carbon atoms, R.sub.2 and R.sub.3 are independently selected from alkyl 
groups containing from about 1 carbon atom to about 5 carbon atoms, 
R.sub.4 is an alkylene group containing from about 1 carbon atom to about 
5 carbon atoms, R.sub.5 is a para substituted phenyl group wherein the 
substituent is an alkyl group containing from about 1 to about 5 carbon 
atoms, such as a tolyl group, or an alkyl group containing from about 1 
carbon atom to about 3 carbon atoms, and n is the number 3, sulfonate, or 
4, sulfate. 
With further reference to the above formula, illustrative examples of alkyl 
groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, 
decyl, myristyl, cetyl, olely, pentadecyl, heptadecyl, stearyl and the 
like. Preferred alkyl groups for R.sub.1 include myristyl, stearyl, and 
cetyl, while the preferred alkyl groups for R.sub.2, R.sub.3, and R.sub.5 
include methyl, ethyl and propyl. The preferred alkylene groups for 
R.sub.4 are methylene and ethylene. Examples of other alkylene groups 
include propylene, butylene, pentylene and the like. 
Illustrative examples of organic sulfate, and sulfonate materials of the 
present invention include stearyl dimethyl benzyl ammonium para-toluene 
sulfonate, stearyl dimethyl benzyl ammonium methyl sulfate, stearyl 
dimethyl phenethyl ammonium methyl sulfate, stearyl dimethyl phenethyl 
ammonium para-toluene sulfonate, phenethyl dodecyl dimethyl ammonium 
para-toluene sulfonate, benzyl hexadecyl ammonium para-toluene sulfonate, 
phenethyl stearyl dimethyl ammonium4-propyl phenyl sulfonate, cetyl 
diethyl benzyl ammonium methyl sulfate, myristyl dimethyl phenethyl 
ammonium para-toluene sulfonate, cetyl dimethyl benzyl ammonium 
methylsulfate, and the like. 
The compositions of the present invention are prepared by, for example, 
reacting under suitable reaction conditions, the appropriate alkyl 
tosylate when the sulfonate compound is desired, or the appropriate 
sulfate, when the sulfate compound is desired with a suitable amine. The 
reaction conditions are generally similar for obtaining either the sulfate 
or the sulfonate. Further, generally, the reactions are accomplished in 
the presence of suitable solvents, such as ethyl acetate, methyl ethyl 
ketone, and the like. 
The organic sulfonates can thus be prepared by reacting the appropriate 
organic sulfur containing compound with a tertiary amine in accordance 
with the following equation, wherein the substiuents R.sub.1, R.sub.2, 
R.sub.3 and R.sub.4 are as defined herein, and R.sub.5 is a para 
substituted phenyl group, wherein the substiuent is an alkyl group 
containing from about 1 carbon atom to about 6 carbon atoms, such as a 
tolyl group: 
##STR3## 
Illustrative examples of organic sulfur compound reactants selected for the 
preparation of the sulfonates include phenethyl tosylate, benzyl tosylate, 
other known tosylates, and the like, while examples of tertiary amine 
reactants include stearyl dimethyl amine, dodecyl dimethyl amine, and the 
like. 
The organic sulfates are prepared in a similar manner wherein the 
appropriate sulfate is reacted with a tertiary amine. Thus, for example, 
stearyl dimethyl phenethyl ammonium methyl sulfate is prepared by reacting 
dimethyl sulfate with phenethyl stearyl methyl amine in the presence of a 
solvent, and heat. 
Generally, the reactants are mixed together in equimolar ratios in the 
presence of from about 800 milliliters to about 1,500 milliliters of 
solvent, such as ethyl acetate, methyl ethyl ketone or similar solvents. 
Other solvent amounts can be selected provided the objectives of the 
present invention are achieved, thus, less than 800 milliliters, or more 
than 1,500 milliliters of solvent can be used. The reaction is generally 
accomplished at elevated temperatures, that is a temperature exceeding 
65.degree. C., and generally at a temperature of from 80.degree. C. to 
90.degree. C., until the reaction has been completed as evidenced by the 
disappearance of the tertiary amine. Subsequently, the reaction mixture is 
cooled to room temperature, subjected to filtration and washing with a 
solvent used in the initial reaction. The washed product is then allowed 
to dry at room temperature, and the desired product is obtained, which 
product is identified by analyzing for the presence of the cation with 
sodium tetraphenyl boron, and/or elemental carbon, hydrogen, oxygen, 
nitrogen, sulfur analysis. 
Numerous known methods may be selected for preparing toner compositions and 
developer compositions containing the sulfate, or sulfonate compositions 
of the present invention. These materials when present in the toner or 
developer compositions, function as charge enhancing additives in that 
they impart a positive charge to the toner resin. One method for preparing 
the toner composition involves melt blending resin particles, and pigment 
particles coated with the organic sulfate or organic sulfonate of the 
present invention, followed by mechanical attrition. Other methods include 
those well known in the art such as spray drying, melt dispersion, 
dispersion polymerization and suspension polymerization. In dispersion 
polymerization a solvent dispersion of a resin pigment in the organic 
sulfate or sulfonate composition of the present invention are spray dried 
under controlled conditions, thereby resulting in the desired toner 
composition, which product contains a positively charged toner in 
relationship to the carrier materials. 
While any suitable resin may be selected for the toner composition, typical 
of such resins are polyamides, epoxies, polyurethanes, vinyl resins, and 
polyesters, especially those prepared from dicarboxylic acids and diols 
comprising diphenols. Any suitable vinyl resin may be selected including 
homopolymers or copolymers of two or more vinyl monomers. Typical of such 
vinyl monomeric units include: styrene, p-chlorostyrene, vinyl 
naphthalene, ethylenically unsaturated mono-olefins such as ethylene, 
propylene, butylene, isobutylene and the like; vinyl halides such as vinyl 
chloride, vinyl bromide, vinyl fluoride, vinyl esters such as vinyl 
acetate, vinyl propionate, vinyl benzoate, vinyl butyrate and the like; 
esters of alphamethylene aliphatic monocarboxylic acids such as methyl 
acrylate, ethyl acrylate, n-butylacrylate, isobutyl acrylate, dodecyl 
acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, 
methylalpha-chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl 
methacrylate and the like; acrylonitrile, methacrylonitrile, acrylamide, 
vinyl ethers such as vinyl methyl ether, vinyl isobutyl ether, vinyl ethyl 
ether, and the like; vinyl ketones such as vinyl methyl ketone, vinyl 
hexyl ketone, methyl isopropenyl ketone and the like; vinylidene halides 
such as vinylidene chloride, vinylidene chlorofluoride and the like; and 
N-vinyl indole, N-vinyl pyrrolidene and the like; and mixtures thereof. 
Generally, toner resins containing a relatively high percentage of styrene 
are preferred. The styrene resin employed may be a homopolymer of styrene 
or styrene homologs of copolymers of styrene with other monomeric groups. 
Any of the above typical monomeric units may be copolymerized with styrene 
by addition polymerization. Styrene resins may also be formed by the 
polymerization of mixtures of two or more unsaturated monomeric materials 
with a styrene monomer. The addition polymerization technique employed 
embraces known polymerization techniques such as free radical, anionic, 
and cationic polymerization processes. Any of these vinyl resins may be 
blended with one or more resins if desired, preferably other vinyl resins, 
which insure good triboelectric properties and uniform resistance against 
physical degradation. However, non-vinyl type thermoplastic resins may 
also be employed including resin modified phenol formaldehyde resins, oil 
modified epoxy resins, polyurethane resins, cellulosic resins, polyether 
resins, and mixtures thereof. 
Also esterification products of a dicarboxylic acid, and a diol comprising 
a diphenol may be used as a preferred resin material for the toner 
composition. These materials are illustrated in U.S. Pat. No. 3,655,374, 
the disclosure of which is totally incorporated herein by reference, the 
diphenol reactant being of the formula as shown in Column 4, beginning at 
line 5 of this patent, and the dicarboxylic acid being of the formula as 
shown in Column 6 of the above patent. 
The toner resin is present in an amount in order that the total of all 
toner ingredients is equal to about 100 percent, thus when 5 percent by 
weight of the sulfonate or sulfate charge enhancing compound is present, 
and 10 percent by weight of a pigment or colorant, such as carbon black is 
present, about 85 percent by weight of resin material is present. 
Any suitable pigment or dye may be selected as the colorant for the toner 
particles, such materials being well known and including for example, 
carbon black, magnetite, iron oxides, nigrosine dye, chrome yellow, 
ultramarine blue, duPont oil red, methylene blue chloride, phthalocyanine 
blue, and mixtures thereof. The pigment or dye should be present in the 
toner in sufficient quantity to render it highly colored, thus allowing 
the toner to form a clearly visible image on the recording member. For 
example, where conventional xerographic copies of documents are desired, 
the toner may comprise a black pigment, such as carbon black, or a black 
dye such as Amaplast black dye available from National Aniline Products, 
Inc. Preferably, the pigment is employed in amounts of from about 3 
percent to about 50 percent by weight based on the total weight of the 
toner composition (toner resin, pigment, charge enhancing additive), 
however, if the pigment employed is a dye, substantially smaller 
quantities, for example, less than 10 percent by weight, may be used. 
Various suitable carrier materials can be selected in formulating the 
developing compositions (toner plus carrier), as long as such carrier 
particles are capable of triboelectrically obtaining a charge of opposite 
polarity to that of the toner particles. In one embodiment, that would be 
a negative polarity, causing the toner particles to adhere to, and 
surround the carrier particles. Thus, the carrier particles are selected 
so that the toner particles acquire a charge of a positive polarity, and 
include materials such as sodium chloride, ammonium chloride, ammonium 
potassium chloride, Rochelle salt, sodium nitrate, aluminum nitrate, 
potassium chlorate, granular zircon, granular silicon, methylmethacrylate, 
glass, steel, nickel, iron ferrites, silicon dioxide and the like, with 
metallic carriers especially magnetic carriers being preferred. The 
carriers can be used with or without a coating. The coatings generally 
contain polyvinyl fluoride resins, but other resins especially those which 
charge negatively, such as polystyrene, halogen containing ethylenes and 
the like can be used. Many of the typical carriers that may be used are 
described in U.S. Pat. Nos. 2,638,552; 3,618,522; 3,533,835; and 
3,526,533. Also nickel berry carriers as described in U.S. Pat. Nos. 
3,847,604 and 3,767,598 can be employed, these carriers being nodular 
carrier beads of nickel characterized by surface of reoccurring recesses 
and protrusions providing particles with a relatively large external area. 
The diameter of the coated carrier particle is from about 50 to about 
1,000 microns, thus allowing the carrier to possess sufficient density and 
inertia to avoid adherence to the electrostatic images during the 
development process. 
The carrier may be employed with the toner composition in any suitable 
combination, however, best results are obtained when about 1 part of toner 
composition is used to about 10 to about 200 parts by weight of carrier. 
Toner compositions containing the sulfate, or sulfonate materials of the 
present invention are useful for causing the development of electrostatic 
latent images on most suitable electrostatic imaging surfaces capable of 
retaining charge, including conventional photoconductors, however, the 
toners of the present invention are best utilized in electrostatic systems 
wherein a negative charge resides on the photoreceptor surface, and this 
usually occurs with organic photoreceptors. Illustrative examples of such 
photoreceptors are polyvinyl carbazole, 4-dimethylaminobenzylidene, 
benzyhydrazide; 2-benzylidene-amino-carbazole, 4-dimethylaminobenzylidene, 
polyvinylcarbazole; (2-nitro-benzylidene)p-bromoaniline; 
2,4-diphenyl-quinazoline; 1,2,4-triazine; 1,5-diphenyl-3-methyl pyrazoline 
2-(4'dimethylamino phenyl)-benzoxazole; 3-amino-carbazole; 
polyvinylcarbazole-trinitrofluorenone charge transfer complex; 
phthalocyainines, layered photoresponsive devices as disclosed in U.S. 
Pat. No. 4,265,990, the disclosure of which is totally incorporated herein 
by reference, and the like. 
In these imaging systems, the organic sulfate and sulfonate compositions of 
the present invention function as charge enhancing additives as indicated 
herein. Accordingly, the organic sulfonate and sulfates of the present 
invention impart a high positive charge to the toner resin. Generally, 
this is accomplished by incorporating the sulfate and sulfonate compounds 
in the toner composition in an amount of from about 0.1 percent by weight 
to about 10 percent by weight of the toner particles, and preferably from 
about 0.5 weight percent to about 5 weight percent. In one preferred 
embodiment, the organic sulfonate and sulfate compounds of the present 
invention are present in the toner composition in an amount of from 0.75 
weight percent to about 3.0 weight percent. The sulfonate and sulfate 
materials of the present invention can either be blended into the toner 
resin or coated on the colorant or pigment used therein such as carbon 
black. When employed as a coating the materials of the present invention 
are present in an amount of from about 2 weight percent to about 20 weight 
percent, and preferably from about 5 weight percent to about 10 weight 
percent based on the weight of the pigment. 
The following examples are being supplied to further define the species of 
the present invention, it being noted that these examples are intended to 
illustrate and not limit the scope of the present invention. Parts and 
percentages are by weight unless otherwise indicated.

EXAMPLE I 
There was prepared the organic sulfonate stearyl dimethyl phenethyl 
ammonium para-toluene sulfonate by mixing in a 2 liter autoclave, 276 
grams (1 gram mole) of phenethyl tosylate, 300 grams (1.01 gram moles) of 
stearyl dimethyl amine, and 1,000 milliliters of methylethyl ketone. The 
reaction mixture was then heated to a temperature of 86.degree. C., and 
maintained at this temperature for 48 hours. Subsequently, the reaction 
mixture was cooled to a temperature of about 18.degree.-20.degree. C., and 
subjected to a filtration wherein the desired product was separated. This 
product was washed with 1,000 milliliters of methylethyl ketone and dried. 
The product was identified by elemental carbon, hydrogen, oxygen, nitrogen, 
sulfur analysis, and by analyzing for the presence of the cation with 
sodium tetraphenyl boron, as stearyl dimethyl phenethyl ammonium 
para-toluene sulfonate of the following formula: 
##STR4## 
This compound had a melting point of about 75.degree. C., and was 
non-hygroscopic. 
EXAMPLE II 
The procedure of Example I was repeated with the exception that 215 grams 
(1.01 gram moles) of dodecyl dimethyl amine was used in place of the 
stearyl dimethyl amine of Example I, and there resulted the sulfonate 
phenethyl dodecyl dimethyl ammonium para-toluene sulfonate. 
EXAMPLE III 
There was prepared benzyl stearyl dimethyl ammonium para-toluene sulfonate 
by mixing in a 2 liter flask 262 grams (1 gram mole) of a benzyl tosylate, 
300 grams (1.01 gram moles) of stearyl dimethyl amine, and 1,000 
milliliters of methylethyl ketone. The reaction was maintained at reflux 
under a nitrogen blanket for 16-20 hours. Subsequent to cooling the 
reaction mixture to room temperature, filtration was accomplished, and the 
resulting product was washed with methylethyl ketone and dried. 
The isolated product was identified as benzyl stearyl dimethyl ammonium 
para-toluene sulfonate of the following formula: 
##STR5## 
EXAMPLE IV 
The procedure of Example III was repeated with the exception that 215 grams 
(1.01 gram moles) of dodecyl dimethyl amine was used in place of the 300 
grams of the stearyl dimethyl amine of Example III and there was isolated 
hexadecyl dimethyl benzyl ammonium para-toluene sulfonate. 
EXAMPLE V 
There was prepared phenethyl stearyl dimethyl ammonium 4-propyl phenyl 
sulfonate by mixing in a 2 liter autoclave 304 grams (1.01 gram moles) of 
phenethyl 4-propyl benzene sulfonate, 300 grams of stearyl dimethyl amine, 
and 1,000 milliliters of methylethyl ketone. The reaction was then 
accomplished in accordance with Example I, and there was isolated after 
washing and filtration phenethyl stearyl dimethyl ammonium 4-propyl phenyl 
sulfonate. 
The following examples relate to the preparation of toner compositions and 
developer compositions containing the organic sulfate and sulfonate 
compounds of the present invention. 
EXAMPLE VI 
A toner comprising 2 percent by weight of stearyl dimethyl benzyl ammonium 
para-toluene sulfonate, prepared in accordance with Example III, 6 percent 
of Regal.RTM. 330, a carbon black, commercially available from Cabot 
Corporation, and 92 percent of a styrene/n-butylmethacrylate copolymer 
resin, 65/35, (65 percent by weight styrene and 35 percent by weight of 
n-butylmethacrylate), was prepared by melt blending followed by mechanical 
attrition. The resulting toner was classified in order to remove particles 
smaller than 5 microns in diameter. 
The triboelectric charge of this toner was measured against a Hoeganese 
steel carrier coated with 0.15 percent Kynar 30, a vinylidene fluoride 
resin commercially available from Pennwalt Company, at 3 percent toner 
concentration with the following results: 
______________________________________ 
Toner Tribo 
Time uc/g (microcoulombs per gram) 
______________________________________ 
10 minutes +59 
1 hour +49 
4 hours +36 
24 hours +19 
______________________________________ 
Charge distribution measurements showed that the above developer had a 
narrow charge distribution, with a minimum insignificant number, less than 
1 percent of toner particles, containing a low charge, less than +15 uc/g, 
and minimum wrong sign negatively charged toner particles. Admix 
experiments showed that the toner had fast charging properties when fresh 
uncharged toner was added to the developer, that is, the fresh toner 
became positively charged in less than 1 minutes. 
The above developer was also exposed to an atmosphere at 10 percent, 42 
percent, and 80 percent relative humidity for 48 hours, and the 
triboelectric properties measured. 
The triboelectric properties after 4 hours of roll milling varied only 
slightly at high and low relative humidity indicating the humidity 
insensitivity of this developer. The measurements were as follows: 
______________________________________ 
Relative 
Humidity Toner Tribo at 4 hours 
Percentage uc/g (microcoulombs per gram) 
______________________________________ 
10 +39 
42 +36 
80 +34 
______________________________________ 
The above developer was used in a xerographic imaging device, containing an 
organic polyvinyl carbazole photoreceptor, charged negatively, which 
device also contained a Viton fuser roll. Not only were excellent high 
quality images obtained, but no damage occurred to the Viton fuser roll 
after 50,000 imaging cycles. 
A sample of the stearyl dimethyl benzyl ammonium para-toluene sulfonate was 
placed on a part of a Viton fuser roll, lead oxide, duPont Viton E-430 
resin, and heated to 205.degree. C. for 30 minutes. The Viton fuser roll 
was then washed with alcohol to remove the compound and examined for 
discoloration and cracks. The Viton fuser roll did not discolor, nor turn 
black, nor were any surface cracks observed, indicating that this compound 
was compatible with the Viton fuser. 
EXAMPLE VII 
A toner composition comprised of 2 percent by weight of stearyl dimethyl 
benzyl ammonium para-toluene sulfonate prepared in accordance with Example 
III, 6 percent Regal.RTM. 330 carbon black, and 92 percent of a 
styrene/butadiene copolymer resin (91/9), was prepared by melt blending 
followed by mechanical attrition. The resulting toner was classified to 
remove particles smaller than 5 microns in diameter. The classified toner 
was blended with the carrier described in Example VI, at 2.7 percent toner 
concentration. The triboelectric charge of the toner was measured with the 
following results: 
______________________________________ 
Toner tribo uc/g 
Time (microcoulombs per gram) 
______________________________________ 
10 minutes +83 
1 hour +53 
3 hours +43 
5 hours +35 
24 hours +15 
______________________________________ 
EXAMPLE VIII 
A toner comprising 2 percent by weight of stearyl dimethyl phenethyl 
ammonium para-toluene sulfonate prepared in accordance with Example I, 6 
percent of Regal.RTM. 330, a carbon black, and 92 percent by weight of a 
styrene/n-butadiene copolymer resin, 91/9, was prepared by melt blending 
followed by mechanical attrition. The resulting toner was classified to 
remove particles smaller than 5 microns in diameter. The classified toner 
was blended with the carrier of Example VI at 2.7 percent toner 
concentration. The triboelectric charge of this toner was measured with 
the following results: 
______________________________________ 
Toner Tribo uc/g 
Time (microcoulombs per gram) 
______________________________________ 
10 minutes +35 
1 hour +42 
3 hours +32 
5 hours +20 
24 hours +6 
______________________________________ 
Charge distribution measurements showed that the above developer had a 
narrower charge distribution, with a minimum insignificant number, less 
than 1 percent of the toner particles, containing a low charge, less than 
+15 uc/g, and minimum wrong sign negatively charged toner particles. Admix 
experiments showed that the toner had fast charging properties when fresh 
uncharged toner was added to the developer, that is, the fresh toner 
became positively charged in less than 1 minute. 
The above developer was tested in a device using an organic photoreceptor 
containing a trigonal selenium photogenerating layer, and coated thereover 
a charge transport lever of N,N'-diphenyl-N,N'-bis(3-methyl 
phenyl)-1,1'-biphenyl-4,4'-diamine, reference U.S. Pat. No. 4,265,990, 
which was negatively charged, and the Viton fuser of Example VI. Good 
quality prints with high solid area density and low background density 
were obtained. The Viton fuser was not noticeably affected. 
The stearyl dimethyl phenethyl ammonium para-toluene sulfonate prepared in 
accordance with Example I, was placed on a part of a Viton fuser roll, 
lead oxide, duPont Viton E-430 and heated to 205.degree. C. for 30 
minutes. The Viton fuser roll was then washed with alcohol to remove the 
compound and the roll was examined for discoloration and cracks. The Viton 
fuser roll did not discolor, nor turn black, nor were any surface cracks 
observed, indicating that stearyl dimethyl phenethyl ammonium para-toluene 
sulfonate was compatible with the Viton fuser. 
EXAMPLE IX 
A toner comprising 2 percent by weight of the stearyl dimethyl phenethyl 
ammonium para-toluene sulfonate prepared in accordance with Example I, 20 
percent of Mapico Black magnetite pigment commercially available from 
Cites Services Co., and 78 percent by weight of a 
styrene/n-butylmethacrylate resin 58/42, 58 weight percent styrene, 42 
percent n-butylmethacrylate, was fabricated by melt blending followed by 
mechanical attrition. The toner was further classified to remove particles 
smaller than 5 microns. The triboelectric charge of this toner against the 
carrier described in Example VI at 3 percent toner concentration are given 
below: 
______________________________________ 
Toner Tribo uc/g 
Time (microcoulombs per gram) 
______________________________________ 
10 minutes +31 
1 hour +24 
4 hours +21 
24 hours +15 
______________________________________ 
Charge distribution measurements showed that the above developer had a 
narrow charge distribution, with a minimum insignificant number, less than 
1 percent of toner particles, containing a low charge, less than +15 uc/g, 
and minimum wrong sign negatively charged toner particles. Admix 
experiments showed that the toner had fast charging properties when fresh 
uncharged toner was added to the developer, that is, the fresh toner 
became positively charged in less than 1 minute. 
The toners and developers of the present invention are useful for causing 
the development of images in electrophotographic systems as indicated 
herein. In one imaging method there is form a negative electrostatic 
latent image on the photoreceptor surface, followed by containing the 
image with the dry positively charged developing compositions of the 
present invention. Subsequently, the developed latent image can be 
transferred to a substrate, such as paper, and optionally permanently 
fixed thereto by heat. 
The triboelectric charges shown were determined by the known Faraday Cage 
technique. 
Other modifications of the present invention may occur to those skilled in 
the art based upon a reading of the disclosure of the present application 
and these modifications are intended to be included within the scope of 
the present invention.