# Patent

## Title
Dry toners comprising amphipathic copolymeric binder having non-sorptive components in the shell portion thereof

## Abstract

The invention provides dry electrographic toner compositions comprising toner particles. The toner particles comprise polymeric binder comprising at least one amphipathic copolymer comprising one or more S material portions and one or more D material portions prepared from an organosol reaction process utilizing a liquid carrier reaction medium having a Kauri-Butanol number less than about 30 mL. The S material portion comprises at least one soluble component and at least one non-sorptive component, wherein the non-sorptive component is the reaction product of monomers having an absolute difference in Hildebrand solubility parameter from the liquid carrier of about 3.0 MPa1/2 or greater. Additionally, dry electrographic toner compositions are provided wherein the toner particles comprise polymeric binder comprising at least one amphipathic copolymer comprising one or more S material portions and one or more D material portions. The S material portion of the amphipathic copolymer has an average Hildebrand solubility parameter of from about from about 16 MPa1/2 to about 17.3 MPa1/2, and comprises at least one non-sorptive component having an average Hildebrand solubility parameter that is at least about 0.4 MPa1/2 greater than the average Hildebrand solubility parameter of the S material portion.
The resulting dry toner composition can exhibit excellent final image durability characteristics, and can also provide excellent images at low fusion temperatures on a final image receptor.

## Background
FIELD OF THE INVENTION
The present invention relates to dry toner compositions having utility in electrography. More particularly, the invention relates to dry toner compositions comprising an amphipathic copolymer binder having a non-sorptive component in the shell portion of the copolymer.
BACKGROUND OF THE INVENTION
In electrophotographic and electrostatic printing processes (collectively electrographic processes), an electrostatic image is formed on the surface of a photoreceptive element or dielectric element, respectively. The photoreceptive element or dielectric element can be an intermediate transfer drum or belt or the substrate for the final toned image itself, as described by Schmidt, S. P. and Larson, J. R. in Handbook of Imaging Materials Diamond, A. S., Ed: Marcel Dekker: New York; Chapter 6, pp 227-252, and U.S. Pat. Nos. 4,728,983, 4,321,404, and 4,268,598.
Electrophotography forms the technical basis for various well-known imaging processes, including photocopying and some forms of laser printing. Other imaging processes use electrostatic or ionographic printing. Electrostatic printing is printing where a dielectric receptor or substrate is “written” upon imagewise by a charged stylus, leaving a latent electrostatic image on the surface of the dielectric receptor. This dielectric receptor is not photosensitive and is generally not re-useable. Once the image pattern has been “written” onto the dielectric receptor in the form of an electrostatic charge pattern of positive or negative polarity, oppositely charged toner particles are applied to the dielectric receptor in order to develop the latent image. An exemplary electrostatic imaging process is described in U.S. Pat. No. 5,176,974.
In contrast, electrophotographic imaging processes typically involve the use of a reusable, light sensitive, temporary image receptor, known as a photoreceptor, in the process of producing an electrophotographic image on a final, permanent image receptor. A representative electrophotographic process involves a series of steps to produce an image on a receptor, including charging, exposure, development, transfer, fusing, cleaning, and erasure.
In the charging step, a photoreceptor is covered with charge of a desired polarity, either negative or positive, typically with a corona or charging roller. In the exposure step, an optical system, typically a laser scanner or diode array, forms a latent image by selectively exposing the photoreceptor to electromagnetic radiation, thereby discharging the charged surface of the photoreceptor in an imagewise manner corresponding to the desired image to be formed on the final image receptor. The electromagnetic radiation, which can also be referred to as “light,” can include infrared radiation, visible light, and ultraviolet radiation, for example.
In the development step, toner particles of the appropriate polarity are generally brought into contact with the latent image on the photoreceptor, typically using a developer electrically-biased to a potential having the same polarity as the toner polarity. The toner particles migrate to the photoreceptor and selectively adhere to the latent image via electrostatic forces, forming a toned image on the photoreceptor.
In the transfer step, the toned image is transferred from the photoreceptor to the desired final image receptor; an intermediate transfer element is sometimes used to effect transfer of the toned image from the photoreceptor with subsequent transfer of the toned image to a final image receptor.
In the fusing step, the toned image on the final image receptor is heated to soften or melt the toner particles, thereby fusing the toned image to the final receptor. An alternative fusing method involves fixing the toner to the final receptor under high pressure with or without heat. In the cleaning step, residual toner remaining on the photoreceptor is removed. Finally, in the erasing step, the photoreceptor charge is reduced to a substantially uniformly low value by exposure to light of a particular wavelength band, thereby removing remnants of the original latent image and preparing the photoreceptor for the next imaging cycle.
Electrophotographic imaging processes can also be distinguished as being either multi-color or monochrome printing processes. Multi-color printing processes are commonly used for printing graphic art or photographic images, while monochrome printing is used primarily for printing text. Some multi-color electrophotographic printing processes use a multi-pass process to apply multiple colors as needed on the photoreceptor to create the composite image that will be transferred to the final image receptor, either by via an intermediate transfer member or directly. One example of such a process is described in U.S. Pat. No. 5,432,591.
A single-pass electrophotographic process for developing multiple color images is also known and can be referred to as a tandem process. A tandem color imaging process is discussed, for example in U.S. Pat. No. 5,916,718 and U.S. Pat. No. 5,420,676. In a tandem process, the photoreceptor accepts color from developer stations that are spaced from each other in such a way that only a single pass of the photoreceptor results in application of all of the desired colors thereon.
Alternatively, electrophotographic imaging processes can be purely monochromatic. In these systems, there is typically only one pass per page because there is no need to overlay colors on the photoreceptor. Monochromatic processes may, however, include multiple passes where necessary to achieve higher image density or a drier image on the final image receptor, for example.
Two types of toner are in widespread, commercial use: liquid toner and dry toner. The term “dry” does not mean that the dry toner is totally free of any liquid constituents, but connotes that the toner particles do not contain any significant amount of solvent, e.g., typically less than 10 weight percent solvent (generally, dry toner is as dry as is reasonably practical in terms of solvent content), and are capable of carrying a triboelectric charge. This distinguishes dry toner particles from liquid toner particles.
The art continually searches for improved dry toner compositions that produce high quality, durable images at low fusion temperatures on a final image receptor.
SUMMARY OF THE INVENTION
The present invention relates to dry electrographic toner compositions comprising toner particles. The toner particles comprise polymeric binder comprising at least one amphipathic copolymer comprising one or more S material portions and one or more D material portions. In prior amphipathic copolymer systems, the S material portion has been carefully selected to assure that the resulting toner particle would be readily dispersed in a liquid reaction solvent, also called a liquid carrier herein, in the formation of particles using an organosol process. To achieve this effect, the S material portion has been prepared from monomeric materials that are soluble in the liquid carrier. The present invention, in contrast, provides amphipathic copolymers wherein the S material portion comprises at least one soluble component and at least one non-sorptive component. This non-sorptive component is the reaction product of monomers having an absolute difference in Hildebrand solubility parameter from the liquid carrier of about 3.0 MPa1/2 or greater. Preferably, the non-sorptive component is the reaction product of monomers having an absolute difference in Hildebrand solubility parameter from the liquid carrier of about 3.15 MPa1/2 or greater, more preferably of about 3.30 MPa1/2 or greater or of about 3.40 MPa1/2 or greater.
The present invention additionally provides a dry electrographic toner composition that comprises a plurality of toner particles, wherein the toner particles comprise polymeric binder comprising at least one amphipathic copolymer comprising one or more S material portions and one or more D material portions. The S material portion of the amphipathic copolymer has an average Hildebrand solubility parameter of from about from about 16 MPa1/2 to about 17.3 MPa1/2. The S material portion comprises at least one non-sorptive component having an average Hildebrand solubility parameter that is at least about 0.4 MPa1/2 greater than the average Hildebrand solubility parameter of the S material portion. Preferably, the non-sorptive component has an average Hildebrand solubility parameter that is at least about 0.7 MPa1/2 greater than the average Hildebrand solubility parameter of the S material portion. In a particularly preferred embodiment, the S material portion has an average Hildebrand solubility parameter of from about from about 16 MPa1/2 to about 17.0 MPa1/2, and the non-sorptive component has an average Hildebrand solubility parameter that is greater than about 17.5 MPa1/2.
Surprisingly, the formulations of amphipathic copolymer as described herein provide dry toners that can exhibit excellent final image durability characteristics, and can also provide a toner composition that provides excellent images at low fusion temperatures on a final image receptor. The images that are formed from toner compositions of the present invention can exhibit excellent durability and erasure resistance properties. While not being bound by theory, it is believed that the non-sorptive component of the S material portion of the amphipathic copolymer provides superior interaction between the S material portion and the D material portion of the copolymer, thereby resulting in better overall fusion of the toner particle.


DETAILED DESCRIPTION OF PRESENTLY PREFERRED EMBODIMENTS
The embodiments of the present invention described below are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather, the embodiments are chosen and described so that others skilled in the art can appreciate and understand the principles and practices of the present invention.
The toner particles of the dry toner composition comprise a polymeric binder that comprises an amphipathic copolymer. The term “amphipathic” refers to a copolymer having a combination of portions having distinct solubility and dispersibility characteristics in a desired liquid carrier that is used to make the organosol and/or used in the course of preparing the dry toner particles. Preferably, the liquid carrier is selected such that at least one portion (also referred to herein as S material or portion(s)) of the copolymer is more solvated by the carrier while at least one other portion (also referred to herein as D material or portion(s)) of the copolymer constitutes more of a dispersed phase in the carrier.
Preferably, the nonaqueous liquid carrier of the organosol is selected such that at least one portion (also referred to herein as the S material or portion) of the amphipathic copolymer is more solvated by the carrier while at least one other portion (also referred to herein as the D material or portion) of the copolymer constitutes more of a dispersed phase in the carrier. In other words, preferred copolymers of the present invention comprise S and D material having respective solubilities in the desired liquid carrier that are sufficiently different from each other such that the S blocks tend to be more solvated by the carrier while the D blocks tend to be more dispersed in the carrier. More preferably, the S blocks are soluble in the liquid carrier while the D blocks are insoluble. In particularly preferred embodiments, the D material phase separates from the liquid carrier, forming dispersed particles.
From one perspective, the polymer particles when dispersed in the liquid carrier can be viewed as having a core/shell structure in which the D material tends to be in the core, while the S material tends to be in the shell. The S material thus functions as a dispersing aid, steric stabilizer or graft copolymer stabilizer, to help stabilize dispersions of the copolymer particles in the liquid carrier. Consequently, the S material can also be referred to herein as a “graft stabilizer.” The core/shell structure of the binder particles tends to be retained when the particles are dried when incorporated into dry toner particles.
The solubility of a material, or a portion of a material such as a copolymeric portion, can be qualitatively and quantitatively characterized in terms of its Hildebrand solubility parameter. The Hildebrand solubility parameter refers to a solubility parameter represented by the square root of the cohesive energy density of a material, having units of (pressure)1/2, and being equal to (ΔH/RT)1/2/V1/2, where ΔH is the molar vaporization enthalpy of the material, R is the universal gas constant, T is the absolute temperature, and V is the molar volume of the solvent. Hildebrand solubility parameters are tabulated for solvents in Barton, A. F. M., Handbook of Solubility and Other Cohesion Parameters, 2d Ed. CRC Press, Boca Raton, Fla., (1991), for monomers and representative polymers in Polymer Handbook, 3rd Ed., J. Brandrup & E. H. Immergut, Eds. John Wiley, N.Y., pp 519-557 (1989), and for many commercially available polymers in Barton, A. F. M., Handbook of Polymer-Liquid Interaction Parameters and Solubility Parameters, CRC Press, Boca Raton, Fla., (1990).
The degree of solubility of a material, or portion thereof, in a liquid carrier can be predicted from the absolute difference in Hildebrand solubility parameters between the material, or portion thereof, and the liquid carrier. A material, or portion thereof, will be fully soluble or at least in a highly solvated state when the absolute difference in Hildebrand solubility parameter between the material, or portion thereof, and the liquid carrier is less than approximately 1.5 MPa1/2. On the other hand, when the absolute difference between the Hildebrand solubility parameters exceeds approximately 3.0 MPa1/2, the material, or portion thereof, will tend to phase separate from the liquid carrier, forming a dispersion. When the absolute difference in Hildebrand solubility parameters is between 1.5 MPa1/2 and 3.0 MPa1/2, the material, or portion thereof, is considered to be weakly solvatable or marginally insoluble in the liquid carrier.
Consequently, in preferred embodiments, the absolute difference between the respective Hildebrand solubility parameters of the S material portion(s) of the copolymer and the liquid carrier is less than 3.0 MPa1/2. In a preferred embodiment of the present invention, the absolute difference between the respective Hildebrand solubility parameters of the S material portion(s) of the copolymer and the liquid carrier is from about 2 to about 3.0 MPa1/2. In a particularly preferred embodiment of the present invention, the absolute difference between the respective Hildebrand solubility parameters of the S material portion(s) of the copolymer and the liquid carrier is from about 2.5 to about 3.0 MPa1/2. Additionally, it is also preferred that the absolute difference between the respective Hildebrand solubility parameters of the D material portion(s) of the copolymer and the liquid carrier is greater than 2.3 MPa1/2, preferably greater than about 2.5 MPa1/2, more preferably greater than about 3.0 MPa1/2, with the proviso that the difference between the respective Hildebrand solubility parameters of the S and D material portion(s) is at least about 0.4 MPa1/2, more preferably at least about 1.0 MPa1/2. Because the Hildebrand solubility of a material can vary with changes in temperature, such solubility parameters are preferably determined at a desired reference temperature such as at 25° C.
As noted above, the S material portion comprises a non-sorptive component that is the reaction product of monomers having an absolute difference in Hildebrand solubility parameter from the liquid carrier of about 3.0 MPa1/2 or greater. The S material portion, notwithstanding the presence of the non-sorptive component, must have an overall solubility characteristic to be soluble in the carrier liquid. Thus, the S material portion as a whole preferably meets the specified and preferred ranges of solubility parameter as discussed above, notwithstanding the presence of the non-sorptive component. When identifying the average Hildebrand solubility parameter of the S material portion of the amphipathic copolymer (e.g. when determining that the average is from about 16 MPa1/2 to about 17.3 MPa1/2), one must include all components, including the non-sorptive component, in the calculation. The average Hildebrand solubility parameter of the non-sorptive component that is a part of the S material portion can be separately determined by identifying all components that make up the S material portion and determining if there are one or more components present in the S material portion having a Hildebrand solubility parameter exceeding the defined value greater than the average Hildebrand solubility parameter of the S material portion.
The S material portion may be prepared by incorporation of a single type of monomer that exhibits the desired solubility parameter as the non-sorptive component, or may be prepared by incorporation of a plurality of monomers, each of which exhibits the desired solubility parameter as the non-sorptive component. In a preferred embodiment of the present invention, the non-sorptive component is present in an amount of from about 1% to about 40% of the S material portion (not counting the anchoring group functionality if present in the graft copolymer). In another preferred embodiment, the non-sorptive component is present in an amount of from about 1% to about 20% or from about 1% to about 5% of the S material portion
Those skilled in the art understand that the Hildebrand solubility parameter for a copolymer, or portion thereof, can be calculated using a volume fraction weighting of the individual Hildebrand solubility parameters for each monomer comprising the copolymer, or portion thereof, as described for binary copolymers in Barton A. F. M., Handbook of Solubility Parameters and Other Cohesion Parameters, CRC Press, Boca Raton, p 12 (1990). The magnitude of the Hildebrand solubility parameter for polymeric materials is also known to be weakly dependent upon the weight average molecular weight of the polymer, as noted in Barton, pp 446-448. Thus, there will be a preferred molecular weight range for a given polymer or portion thereof in order to achieve desired solvating or dispersing characteristics. Similarly, the Hildebrand solubility parameter for a mixture can be calculated using a volume fraction weighting of the individual Hildebrand solubility parameters for each component of the mixture.
In addition, we have defined our invention in terms of the calculated solubility parameters of the monomers and solvents obtained using the group contribution method developed by Small, P. A., J. Appl. Chem., 3, 71 (1953) using Small's group contribution values listed in Table 2.2 on page VII/525 in the Polymer Handbook, 3rd Ed., J. Brandrup & E. H. Immergut, Eds. John Wiley, New York, (1989). We have chosen this method for defining our invention to avoid ambiguities which could result from using solubility parameter values obtained with different experimental methods. In addition, Small's group contribution values will generate solubility parameters that are consistent with data derived from measurements of the enthalpy of vaporization, and therefore are completely consistent with the defining expression for the Hildebrand solubility parameter. Since it is not practical to measure the heat of vaporization for polymers, monomers are a reasonable substitution.
For purposes of illustration, Table I lists Hildebrand solubility parameters for some common solvents used in an electrographic toner and the Hildebrand solubility parameters and glass transition temperatures (based on their high molecular weight homopolymers) for some common monomers used in synthesizing organosols.







TABLE I







Hildebrand Solubility Parameters


Solvent Values at 25° C.












Kauri-Butanol





Number by ASTM




Method D1133-
Hildebrand Solubility



Solvent Name
54T (ml)
Parameter (MPa1/2)







Norpar TM 15
18
13.99



Norpar TM 13
22
14.24



Norpar TM 12
23
14.30



Isopar TM V
25
14.42



Isopar TM G
28
14.60



Exxsol TM D80
28
14.60







Source: Calculated from equation #31 of Polymer Handbook, 3rd Ed., J. Brandrup E. H. Immergut, Eds. John Wiley, NY, p. VII/522 (1989).







Monomer Values at 25° C.










Hildebrand




Solubility
Glass Transition


Monomer Name
Parameter (MPa1/2)
Temperature (° C.)*





3,3,5-Trimethyl
16.73
125


Cyclohexyl Methacrylate


Isobornyl Methacrylate
16.90
110


Isobornyl Acrylate
16.01
94


n-Behenyl acrylate
16.74
<−55 (58 m.p.)**


n-Octadecyl Methacrylate
16.77
−100 (28 m.p.)**


n-Octadecyl Acrylate
16.82
−55 (42 m.p.)**


Lauryl Methacrylate
16.84
−65


Lauryl Acrylate
16.95
−30


2-Ethylhexyl Methacrylate
16.97
−10


2-Ethylhexyl Acrylate
17.03
−55


n-Hexyl Methacrylate
17.13
−5


t-Butyl Methacrylate
17.16
107


n-Butyl Methacrylate
17.22
20


n-Hexyl Acrylate
17.30
−60


n-Butyl Acrylate
17.45
−55


Ethyl Methacrylate
17.62
65


Ethyl Acrylate
18.04
−24


Methyl Methacrylate
18.17
105


Styrene
18.05
100





Calculated using Small's Group Contribution Method, Small, P. A. Journal of Applied Chemistry 3 p. 71 (1953). Using Group Contributions from Polymer Handbook, 3rd Ed., J. Brandrup E. H. Immergut, Eds., John Wiley, NY, p. VII/525 (1989).


*Polymer Handbook, 3rd Ed., J. Brandrup E. H. Immergut, Eds., John Wiley, NY, pp. VII/209-277 (1989). The Tg listed is for the homopolymer of the respective monomer.


**m.p. refers to melting point for selected Polymerizable Crystallizable Compounds.






The liquid carrier is a substantially nonaqueous solvent or solvent blend. In other words, only a minor component (generally less than 25 weight percent) of the liquid carrier comprises water. Preferably, the substantially nonaqueous liquid carrier comprises less than 20 weight percent water, more preferably less than 10 weight percent water, even more preferably less than 3 weight percent water, most preferably less than one weight percent water.
The substantially nonaqueous liquid carrier can be selected from a wide variety of materials, or combination of materials, which are known in the art, but preferably has a Kauri-butanol number less than 30 ml. The liquid is preferably oleophilic, chemically stable under a variety of conditions, and electrically insulating. Electrically insulating refers to a dispersant liquid having a low dielectric constant and a high electrical resistivity. Preferably, the liquid dispersant has a dielectric constant of less than 5; more preferably less than 3. Electrical resistivities of carrier liquids are typically greater than 109 Ohm-cm; more preferably greater than 1010 Ohm-cm. In addition, the liquid carrier desirably is chemically inert in most embodiments with respect to the ingredients used to formulate the toner particles.
Examples of suitable liquid carriers include aliphatic hydrocarbons (n-pentane, hexane, heptane and the like), cycloaliphatic hydrocarbons (cyclopentane, cyclohexane and the like), aromatic hydrocarbons (benzene, toluene, xylene and the like), halogenated hydrocarbon solvents (chlorinated alkanes, fluorinated alkanes, chlorofluorocarbons and the like) silicone oils and blends of these solvents. Preferred liquid carriers include branched paraffinic solvent blends such as IsoparTM G, IsoparTM H, IsoparTM K, IsoparTM L, IsoparTM M and IsoparTM V (available from Exxon Corporation, NJ), and most preferred carriers are the aliphatic hydrocarbon solvent blends such as NorparTM 12, NorparTM 13 and NorparTM 15 (available from Exxon Corporation, NJ). Particularly preferred liquid carriers have a Hildebrand solubility parameter of from about 13 to about 15 MPa1/2.
As used herein, the term “copolymer” encompasses both oligomeric and polymeric materials, and encompasses polymers incorporating two or more monomers. As used herein, the term “monomer” means a relatively low molecular weight material (i.e., generally having a molecular weight less than about 500 Daltons) having one or more polymerizable groups. “Oligomer” means a relatively intermediate sized molecule incorporating two or more monomers and generally having a molecular weight of from about 500 up to about 10,000 Daltons. “Polymer” means a relatively large material comprising a substructure formed two or more monomeric, oligomeric, and/or polymeric constituents and generally having a molecular weight greater than about 10,000 Daltons.
The weight average molecular weight of the amphipathic copolymer of the present invention can vary over a wide range, and can impact imaging performance. The polydispersity of the copolymer also can impact imaging and transfer performance of the resultant dry toner material. Because of the difficulty of measuring molecular weight for an amphipathic copolymer, the particle size of the dispersed copolymer (organosol) can instead be correlated to imaging and transfer performance of the resultant dry toner material. Generally, the volume mean particle diameter (Dv) of the toner particles, determined by laser diffraction particle size measurement, preferably should be in the range of about 0.1 to about 100.0 microns, more preferably in the range of about 1 to about 20 microns, most preferably in the range of about 5 to about 10 microns.
In addition, a correlation exists between the molecular weight of the solvatable or soluble S material portion of the graft copolymer, and the imaging and transfer performance of the resultant toner. Generally, the S material portion of the copolymer has a weight average molecular weight in the range of 1000 to about 1,000,000 Daltons, preferably 5000 to 400,000 Daltons, more preferably 50,000 to 300,000 Daltons. It is also generally desirable to maintain the polydispersity (the ratio of the weight-average molecular weight to the number average molecular weight) of the S material portion of the copolymer below 15, more preferably below 5, most preferably below 2.5. It is a distinct advantage of the present invention that copolymer particles with such lower polydispersity characteristics for the S material portion are easily made in accordance with the practices described herein, particularly those embodiments in which the copolymer is formed in the liquid carrier in situ.
The relative amounts of S and D material portions in a copolymer can impact the solvating and dispersability characteristics of these portions. For instance, if too little of the S material portion(s) are present, the copolymer can have too little stabilizing effect to sterically-stabilize the organosol with respect to aggregation as might be desired. If too little of the D material portion(s) are present, the small amount of D material can be too soluble in the liquid carrier such that there can be insufficient driving force to form a distinct particulate, dispersed phase in the liquid carrier. The presence of both a solvated and dispersed phase helps the ingredients of particles self assemble in situ with exceptional uniformity among separate particles. Balancing these concerns, the preferred weight ratio of D material to S material is in the range of 1/20 to 20/1, preferably 1/1 to 15/1, more preferably 2/1 to 10/1, and most preferably 4/1 to 8/1.
Glass transition temperature, Tg, refers to the temperature at which a (co)polymer, or portion thereof, changes from a hard, glassy material to a rubbery, or viscous, material, corresponding to a dramatic increase in free volume as the (co)polymer is heated. The Tg can be calculated for a (co)polymer, or portion thereof, using known Tg values for the high molecular weight homopolymers (see, e.g., Table I herein) and the Fox equation expressed below:

1/Tg=w1/Tg1+w2/Tg2+ . . . wi/Tgi

wherein each wn is the weight fraction of monomer “n” and each Tgn is the absolute glass transition temperature (in degrees Kelvin) of the high molecular weight homopolymer of monomer “n” as described in Wicks, A. W., F. N. Jones & S. P. Pappas, Organic Coatings 1, John Wiley, NY, pp 54-55 (1992).

In the practice of the present invention, values of Tg for the D or S material portion of the copolymer or of the soluble polymer were determined either using the Fox equation above or experimentally, using e.g., differential scanning calorimetry. The glass transition temperatures (Tg's) of the S and D material portions can vary over a wide range and can be independently selected to enhance manufacturability and/or performance of the resulting dry toner particles. The Tg's of the S and D material portions will depend to a large degree upon the type of monomers constituting such portions. Consequently, to provide a copolymer material with higher Tg, one can select one or more higher Tg monomers with the appropriate solubility characteristics for the type of copolymer portion (D or S) in which the monomer(s) will be used. Conversely, to provide a copolymer material with lower Tg, one can select one or more lower Tg monomers with the appropriate solubility characteristics for the type of portion in which the monomer(s) will be used.
Polymeric binder materials suitable for use in dry toner particles typically have a high glass transition temperature (Tg) of at least about 50-65° C. in order to obtain good blocking resistance after fusing, yet typically require high fusing temperatures of about 200-250° C. in order to soften or melt the toner particles and thereby adequately fuse the toner to the final image receptor. High fusing temperatures are a disadvantage for dry toner because of the long warm-up time and higher energy consumption associated with high temperature fusing and because of the risk of fire associated with fusing toner to paper at temperatures approaching the autoignition temperature of paper (233° C.).
In addition, some dry toners using high Tg polymeric binders are known to exhibit undesirable partial transfer (offset) of the toned image from the final image receptor to the fuser surface at temperatures above or below the optimal fusing temperature, requiring the use of low surface energy materials in the fuser surface or the application of fuser oils to prevent offset. Alternatively, various lubricants or waxes have been physically blended into the dry toner particles during fabrication to act as release or slip agents; however, because these waxes are not chemically bonded to the polymeric binder, they may adversely affect triboelectric charging of the toner particle or may migrate from the toner particle and contaminate the photoreceptor, an intermediate transfer element, the fuser element, or other surfaces critical to the electrophotographic process.
A wide variety of one or more different monomeric, oligomeric and/or polymeric materials can be independently incorporated into the S and D material portions, as desired. Representative examples of suitable materials include free radically polymerized material (also referred to as vinyl copolymers or (meth)acrylic copolymers in some embodiments), polyurethanes, polyester, epoxy, polyamide, polyimide, polysiloxane, fluoropolymer, polysulfone, combinations of these, and the like. Preferred S and D material portions are derived from free radically polymerizable material. In the practice of the present invention, “free radically polymerizable” refers to monomers, oligomers, and/or polymers having functionality directly or indirectly pendant from a monomer, oligomer, or polymer backbone (as the case can be) that participate in polymerization reactions via a free radical mechanism. Representative examples of such functionality includes (meth)acrylate groups, olefinic carbon-carbon double bonds, allyloxy groups, alpha-methyl styrene groups, (meth)acrylamide groups, cyanate ester groups, vinyl ether groups, combinations of these, and the like. The term “(meth)acryl”, as used herein, encompasses acryl and/or methacryl.
Free radically polymerizable monomers, oligomers, and/or polymers are advantageously used to form the copolymer in that so many different types are commercially available and can be selected with a wide variety of desired characteristics that help provide one or more desired performance characteristics. Free radically polymerizable monomers, oligomers, and/or monomers suitable in the practice of the present invention can include one or more free radically polymerizable moieties.
Representative examples of monofunctional, free radically polymerizable monomers include styrene, alpha-methylstyrene, substituted styrene, vinyl esters, vinyl ethers, N-vinyl-2-pyrrolidone, (meth)acrylamide, vinyl naphthalene, alkylated vinyl naphthalenes, alkoxy vinyl naphthalenes, N-substituted (meth)acrylamide, octyl(meth)acrylate, nonylphenol ethoxylate(meth)acrylate, N-vinyl pyrrolidone, isononyl(meth)acrylate, isobornyl(meth)acrylate, 2-(2-ethoxyethoxy)ethyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, beta-carboxyethyl(meth)acrylate, isobutyl(meth)acrylate, cycloaliphatic epoxide, alpha-epoxide, 2-hydroxyethyl(meth)acrylate, (meth)acrylonitrile, maleic anhydride, itaconic acid, isodecyl(meth)acrylate, lauryl(dodecyl)(meth)acrylate, stearyl(octadecyl)(meth)acrylate, behenyl(meth)acrylate, n-butyl(meth)acrylate, methyl(meth)acrylate, ethyl(meth)acrylate, hexyl(meth)acrylate, (meth)acrylic acid, N-vinylcaprolactam, stearyl(meth)acrylate, hydroxy functional caprolactone ester(meth)acrylate, isooctyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxymethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxyisopropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxyisobutyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, isobornyl(meth)acrylate, glycidyl(meth)acrylate vinyl acetate, combinations of these, and the like.
The monomeric components that are reacted to form the S material portions are, in one embodiment of the present invention, selected to provide the desired Tg of the S material portion by selection of monomers having Tgs within a given range, matched with solubility parameter characteristics. Advantageously, the fusion characteristics and durability property characteristics of the toner and the resulting image formed therefrom can be manipulated by selection of relative Tg s of components of S material portions of the amphipathic copolymer. In this manner, performance characteristics of toner compositions can be readily tailored and/or optimized for use in desired imaging systems. For example, in one embodiment, the average Tg of the non-sorptive component is lower than the average Tg of the soluble components of the S material portion. In a preferred aspect of this embodiment, the average Tg of the non-sorptive component is less than about 70° C., and the average Tg of the soluble components of the S material portion is greater than about 90° C. In another preferred embodiment, the non-sorptive component has an average Tg of less than about 0° C., and is from about 1 to about 15% by weight of the S material portion; the soluble component has an average Tg of greater than about 90° C., and is from about 85 to about 99% by weight of the S material portion.
In another preferred embodiment, the average Tg of the non-sorptive component is higher than the average Tg of the soluble components of the S material portion. In a preferred aspect of this embodiment, the average Tg of the non-sorptive component is greater than about 50° C., and the average Tg of the soluble components of the S material portion is less than about 0° C. In another preferred embodiment, the non-sorptive component has an average Tg of is greater than about 50° C., and is from about 1 to about 50% by weight of the S material portion; the soluble component has an average Tg of less than about 0° C., and is from about 50 to about 99% by weight of the S material portion.
The S material portion is preferably made from (meth)acrylate based monomers and comprises the reaction products of soluble monomers selected from the group consisting of trimethyl cyclohexyl methacrylate; t-butyl methacrylate; n-butyl methacrylate; isobornyl(meth)acrylate; 1,6-Hexanediol di(meth)acrylate; 2-hydroxyethyl methacrylate; lauryl methacrylate; and combinations thereof; and further comprises non-sorptive components that are the reaction products of monomers selected from the group consisting of ethyl acrylate and ethyl methacrylate.
Preferred copolymers of the present invention can be formulated with one or more radiation curable monomers or combinations thereof that help the free radically polymerizable compositions and/or resultant cured compositions to satisfy one or more desirable performance criteria.
An exemplary class of radiation curable monomers that tend to have relatively high Tg characteristics suitable for incorporation into the high Tg component generally comprise at least one radiation curable (meth)acrylate monomer and at least one nonaromatic, alicyclic and/or nonaromatic heterocyclic monomer. Isobornyl(meth)acrylate is a specific example of one such monomer. A cured, homopolymer film formed from isobornyl acrylate, for instance, has a Tg of 110° C. The monomer itself has a molecular weight of 222 g/mole, exists as a clear liquid at room temperature, has a viscosity of 9 centipoise at 25° C., and has a surface tension of 31.7 dynes/cm at 25° C. Additionally, 1,6-Hexanediol di(meth)acrylate is another example of a monomer with high Tg characteristics. Other examples of preferred high Tg components include trimethyl cyclohexyl methacrylate; t-butyl methacrylate; n-butyl methacrylate. Combinations of high Tg components for use in both the S material portion and the soluble polymer are specifically contemplated, together with anchor grafting groups such as provided by use of HEMA subsequently reacted with TMI.
Examples of graft amphipathic copolymers that may be further formulated to further incorporate non-sorptive components in the S material portion for use in the present binder particles are described in Qian et al, U.S. Ser. No. 10/612,243, filed on Jun. 30, 2003, entitled ORGANOSOL INCLUDING AMPHIPATHIC COPOLYMERIC BINDER AND USE OF THE ORGANOSOL TO MAKE DRY TONERS FOR ELECTROGRAPHIC APPLICATIONS and Qian et al., U.S. Ser. No. 10/612,535, filed on Jun. 30, 2003, entitled ORGANOSOL INCLUDING AMPHIPATHIC COPOLYMERIC BINDER HAVING CRYSTALLINE MATERIAL, AND USE OF THE ORGANOSOL TO MAKE DRY TONER FOR ELECTROGRAPHIC APPLICATIONS for dry toner compositions.
Copolymers of the present invention can be prepared by free-radical polymerization methods known in the art, including but not limited to bulk, solution, and dispersion polymerization methods. The resultant copolymers can have a variety of structures including linear, branched, three dimensionally networked, graft-structured, combinations thereof, and the like. A preferred embodiment is a graft copolymer comprising one or more oligomeric and/or polymeric arms attached to an oligomeric or polymeric backbone. In graft copolymer embodiments, the S material portion or D material portion materials, as the case can be, can be incorporated into the arms and/or the backbone.
Any number of reactions known to those skilled in the art can be used to prepare a free radically polymerized copolymer having a graft structure. Common grafting methods include random grafting of polyfunctional free radicals; copolymerization of monomers with macromonomers; ring-opening polymerizations of cyclic ethers, esters, amides or acetals; epoxidations; reactions of hydroxyl or amino chain transfer agents with terminally-unsaturated end groups; esterification reactions (i.e., glycidyl methacrylate undergoes tertiary-amine catalyzed esterification with methacrylic acid); and condensation polymerization.
Representative methods of forming graft copolymers are described in U.S. Pat. Nos. 6,255,363; 6,136,490; and 5,384,226; and Japanese Published Patent Document No. 05-119529, incorporated herein by reference. Representative examples of grafting methods are also described in sections 3.7 and 3.8 of Dispersion Polymerization in Organic Media, K. E. J. Barrett, ed., (John Wiley; New York, 1975) pp. 79-106, also incorporated herein by reference.
In preferred embodiments, the copolymer is polymerized in situ in the desired liquid carrier, as this yields substantially monodisperse copolymeric particles suitable for use in toner compositions. The resulting organosol is then preferably mixed with at least one visual enhancement additive and optionally one or more other desired ingredients to form a desired toner particle. During such combination, ingredients comprising the visual enhancement particles and the copolymer will tend to self-assemble into composite particles having solvated (S) portions and dispersed (D) portions. Specifically, it is believed that the D material of the copolymer will tend to physically and/or chemically interact with the surface of the visual enhancement additive, while the S material helps promote dispersion in the carrier.
Representative examples of grafting methods also can use an anchoring group. The function of the anchoring group is to provide a covalently bonded link between the core part of the copolymer (the D material) and the soluble shell component (the S material). Preferred amphipathic copolymers are prepared by first preparing an intermediate S material portion comprising reactive functionality by a polymerization process, and subsequently reacting the available reactive functionalities with a graft anchoring compound. The graft anchoring compound comprises a first functionality that can be reacted with the reactive functionality on the intermediate S material portion, and a second functionality that is a polymerizably reactive functionality that can take part in a polymerization reaction. After reaction of the intermediate S material portion with the graft anchoring compound, a polymerization reaction with selected monomers can be carried out in the presence of the S material portion to form a D material portion having one or more S material portions grafted thereto.
Suitable monomers containing anchoring groups include: adducts of alkenylazlactone comonomers with an unsaturated nucleophile containing hydroxy, amino, or mercaptan groups, such as 2-hydroxyethylmethacrylate, 3-hydroxypropylmethacrylate, 2-hydroxyethylacrylate, pentaerythritol triacrylate, 4-hydroxybutylvinylether, 9-octadecen-1-ol, cinnamyl alcohol, allyl mercaptan, methallylamine; and azlactones, such as 2-alkenyl-4,4-dialkylazlactone.
The preferred methodology described above accomplishes grafting via attaching an ethylenically-unsaturated isocyanate (e.g., dimethyl-m-isopropenyl benzylisocyanate, TMI, available from CYTEC Industries, West Paterson, N.J.; or isocyanatoethyl methacrylate, IEM) to hydroxyl groups in order to provide free radically reactive anchoring groups.
A preferred method of forming a graft copolymer of the present invention involves three reaction steps that are carried out in a suitable substantially nonaqueous liquid carrier in which resultant S material is soluble while D material is dispersed or insoluble.
In a first preferred step, a hydroxyl functional, free radically polymerized oligomer or polymer is formed from one or more monomers, wherein at least one of the monomers has pendant hydroxyl functionality. Preferably, the hydroxyl functional monomer constitutes about 1 to about 30, preferably about 2 to about 10 percent, most preferably 3 to about 5 percent by weight of the monomers used to form the oligomer or polymer of this first step. This first step is preferably carried out via solution polymerization in a substantially nonaqueous solvent in which the monomers and the resultant polymer are soluble. For instance, using the Hildebrand solubility data in Table 1, monomers such as octadecyl methacrylate, octadecyl acrylate, lauryl acrylate, and lauryl methacrylate are suitable for this first reaction step when using an oleophilic solvent such as heptane or the like.
In a second reaction step, all or a portion of the hydroxyl groups of the soluble polymer are catalytically reacted with an ethylenically unsaturated aliphatic isocyanate (e.g. meta-isopropenyldimethylbenzyl isocyanate commonly known as TMI or isocyanatoethyl methacrylate, commonly known as IEM) to form pendant free radically polymerizable functionality which is attached to the oligomer or polymer via a polyurethane linkage. This reaction can be carried out in the same solvent, and hence the same reaction vessel, as the first step. The resultant double-bond functionalized polymer generally remains soluble in the reaction solvent and constitutes the S material portion material of the resultant copolymer, which ultimately will constitute at least a portion of the solvatable portion of the resultant triboelectrically charged particles.
The resultant free radically reactive functionality provides grafting sites for attaching D material and optionally additional S material to the polymer. In a third step, these grafting site(s) are used to covalently graft such material to the polymer via reaction with one or more free radically reactive monomers, oligomers, and or polymers that are initially soluble in the solvent, but then become insoluble as the molecular weight of the graft copolymer. For instance, using the Hildebrand solubility parameters in Table 1, monomers such as e.g. methyl(meth)acrylate, ethyl(meth)acrylate, t-butyl methacrylate and styrene are suitable for this third reaction step when using an oleophilic solvent such as heptane or the like.
The product of the third reaction step is generally an organosol comprising the resultant copolymer dispersed in the reaction solvent, which constitutes a substantially nonaqueous liquid carrier for the organosol. At this stage, it is believed that the copolymer tends to exist in the liquid carrier as discrete, monodisperse particles having dispersed (e.g., substantially insoluble, phase separated) portion(s) and solvated (e.g., substantially soluble) portion(s). As such, the solvated portion(s) help to sterically-stabilize the dispersion of the particles in the liquid carrier. It can be appreciated that the copolymer is thus advantageously formed in the liquid carrier in situ.
Before further processing, the copolymer particles can remain in the reaction solvent. Alternatively, the particles can be transferred in any suitable way into fresh solvent that is the same or different so long as the copolymer has solvated and dispersed phases in the fresh solvent. In either case, the resulting organosol is then converted into toner particles by mixing the organosol with at least one visual enhancement additive. Optionally, one or more other desired ingredients also can be mixed into the organosol before and/or after combination with the visual enhancement particles. During such combination, it is believed that ingredients comprising the visual enhancement additive and the copolymer will tend to self-assemble into composite particles having a structure wherein the dispersed phase portions generally tend to associate with the visual enhancement additive particles (for example, by physically and/or chemically interacting with the surface of the particles), while the solvated phase portions help promote dispersion in the carrier.
The visual enhancement additive(s) generally may include any one or more fluid and/or particulate materials that provide a desired visual effect when toner particles incorporating such materials are printed onto a receptor. Examples include one or more colorants, fluorescent materials, pearlescent materials, iridescent materials, metallic materials, flip-flop pigments, silica, polymeric beads, reflective and non-reflective glass beads, mica, combinations of these, and the like. The amount of visual enhancement additive coated on binder particles may vary over a wide range. In representative embodiments, a suitable weight ratio of copolymer to visual enhancement additive is from 1/1 to 20/1, preferably from 2/1 to 10/1 and most preferably from 4/1 to 8/1.
Useful colorants are well known in the art and include materials listed in the Colour Index, as published by the Society of Dyers and Colourists (Bradford, England), including dyes, stains, and pigments. Preferred colorants are pigments which may be combined with ingredients comprising the binder polymer to form dry toner particles with structure as described herein, are at least nominally insoluble in and nonreactive with the carrier liquid, and are useful and effective in making visible the latent electrostatic image. It is understood that the visual enhancement additive(s) may also interact with each other physically and/or chemically, forming aggregations and/or agglomerates of visual enhancement additives that also interact with the binder polymer. Examples of suitable colorants include: phthalocyanine blue (C.I. Pigment Blue 15:1, 15:2, 15:3 and 15:4), monoarylide yellow (C.I. Pigment Yellow 1, 3, 65, 73 and 74), diarylide yellow (C.I. Pigment Yellow 12, 13, 14, 17 and 83), arylamide (Hansa) yellow (C.I. Pigment Yellow 10, 97, 105 and 111), isoindoline yellow (C.I. Pigment Yellow138), azo red (C.I. Pigment Red 3, 17, 22, 23, 38, 48:1, 48:2, 52:1, and 52:179), quinacridone magenta (C.I. Pigment Red 122, 202 and 209), laked rhodamine magenta (C.I. Pigment Red 81:1, 81:2, 81:3, and 81:4), and black pigments such as finely divided carbon (Cabot Monarch 120, Cabot Regal 300R, Cabot Regal 350R, Vulcan X72, and Aztech EK 8200), and the like.
The toner particles of the present invention may additionally comprise one or more additives as desired. Additional additives include, for example, UV stabilizers, mold inhibitors, bactericides, fungicides, antistatic agents, anticaking agents, gloss modifying agents, other polymer or oligomer material, antioxidants, and the like.
The additives may be incorporated in the binder particle in any appropriate manner, such as combining the binder particle with the desired additive and subjecting the resulting composition to one or more mixing processes. Examples of such mixing processes include homogenization, microfluidization, ball-milling, attritor milling, high energy bead (sand) milling, basket milling or other techniques known in the art to reduce particle size in a dispersion. The mixing process acts to break down aggregated additive particles, when present, into primary particles (preferably having a diameter of from about 0.005 to about 5 microns, more preferably having a diameter of from about 0.05 to about 3 microns, and most preferably having a diameter of from about 0.1 to about 1 microns) and may also partially shred the binder into fragments that can associate with the additive. According to this embodiment, the copolymer or fragments derived from the copolymer then associate with the additives. Optionally, one or more visual enhancement agents may be incorporated within the binder particle, as well as coated on the outside of the binder particle.
One or more charge control agents can be added before or after this mixing process, if desired. Charge control agents are often used in dry toner when the other ingredients, by themselves, do not provide the desired triboelectric charging or charge retention properties. The amount of the charge control agent, based on 100 parts by weight of the toner solids, is generally 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight.
Examples of positive charge control agents for the toner include nigrosine; modified products based on metal salts of fatty acids; quaternary-ammonium-salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonic acid or tetrabutylammonium tetrafluoroborate; alkyl pyridinium halides, including cetyl pyridinium chloride and others as disclosed in U.S. Pat. No. 4,298,672; sulfates and bisulfates, including distearyl dimethyl ammonium methyl sulfate as disclosed in U.S. Pat. No. 4,560,635; distearyl dimethyl ammonium bisulfate as disclosed in U.S. Pat. No. 4,937,157, U.S. Pat. No. 4,560,635; onium salts analogous to the quaternary-ammonium-salts such as phosphonium salts, and lake pigments of these; triphenylmethane dyes, and lake pigments of these; metal salts of higher fatty acids; diorgano tin oxides such as dibutyl tin oxide, dioctyl tin oxide, and dicyclohexyl tin oxide; and diorgano tin borates such as dibutyl tin borate, dioctyl tin borate, and dicyclohexyl tin borate.
Further, homopolymers of monomers having the following general formula (1) or copolymers with the foregoing polymerizable monomers such as styrene, acrylic acid esters, and methacrylic acid esters may be used as the positive charge control agent. In that case, those charge control agents have functions also as (all or a part of) binder resins.




    R1 is H or CH3;
    X is a linking group, such as a —(CH2)m— group, where m is an integer between 1 and 20, inclusive, and one or more of the methylene groups is optionally replaced by —O—, —(O)C—, —O—C(O)—, —(O)C—O—. Preferably, X is selected from alkyl,






     and alkyl-O-alkyl, where the alkyl group has from 1 to 4 carbons.
    R2 and R3 are independently a substituted or unsubstituted alkyl group having (preferably 1 to 4 carbons).


Examples of commercially available positive charge control agents include azine compounds such as BONTRON N-01, N-04 and N-21; and quaternary ammonium salts such as BONTRON P-51 from Orient Chemical Company and P-12 from Esprix Technologies; and ammonium salts such as “Copy Charge PSY” from Clariant.
Examples of negative charge control agents for the toner include organometal complexes and chelate compounds. Representative complexes include monoazo metal complexes, acetylacetone metal complexes, and metal complexes of aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids. Additional negative charge control agents include aromatic hydroxyl carboxylic acids, aromatic mono- and poly-carboxylic acids, and their metal salts, anhydrides, esters, and phenolic derivatives such as bisphenol. Other negative charge control agents include zinc compounds as disclosed in U.S. Pat. No. 4,656,112 and aluminum compounds as disclosed in U.S. Pat. No. 4,845,003.
Examples of commercially available negatively charged charge control agents include zinc 3,5-di-tert-butyl salicylate compounds, such as BONTRON E-84, available from Orient Chemical Company of Japan; zinc salicylate compounds available as N-24 and N-24HD from Esprix Technologies; aluminum 3,5-di-tert-butyl salicylate compounds, such as BONTRON E-88, available from Orient Chemical Company of Japan; aluminum salicylate compounds available as N-23 from Esprix Technologies; calcium salicylate compounds available as N-25 from Esprix Technologies; zirconium salicylate compounds available as N-28 from Esprix Technologies; boron salicylate compounds available as N-29 from Esprix Technologies; boron acetyl compounds available as N-31 from Esprix Technologies; calixarenes, such as such as BONTRON E-89, available from Orient Chemical Company of Japan; azo-metal complex Cr (III) such as BONTRON S-34, available from Orient Chemical Company of Japan; chrome azo complexes available as N-32A, N-32B and N-32C from Esprix Technologies; chromium compounds available as N-22 from Esprix Technologies and PRO-TONER CCA 7 from Avecia Limited; modified inorganic polymeric compounds such as Copy Charge N4P from Clariant; and iron azo complexes available as N-33 from Esprix Technologies.
Preferably, the charge control agent is colorless, so that the charge control agent does not interfere with the presentation of the desired color of the toner. In another embodiment, the charge control agent exhibits a color that can act as an adjunct to a separately provided colorant, such as a pigment. Alternatively, the charge control agent may be the sole colorant in the toner. In yet another alternative, a pigment may be treated in a manner to provide the pigment with a positive charge.
Examples of positive charge control agents having a color or positively charged pigments include Copy Blue PR, a triphenylmethane from Clariant. Examples of negative charge control agents having a color or negatively charged pigments include Copy Charge NY VP 2351, an Al-azo complex from Clariant; Hostacoply N4P-N101 VP 2624 and Hostacoply N4P-N203 VP 2655, which are modified inorganic polymeric compounds from Clariant.
The preferred amount of charge control agent for a given toner formulation will depend upon a number of factors, including the composition of the polymer binder. The preferred amount of charge control agent further depends on the composition of the S portion of the graft copolymer, the composition of the organosol, the molecular weight of the organosol, the particle size of the organosol, the core/shell ratio of the graft copolymer, the pigment used in making the toner, and the ratio of organosol to pigment. In addition, preferred amounts of charge control agent will also depend upon the nature of the electrophotographic imaging process, particularly the design of the developing hardware and photoreceptive element. It is understood, however, that the level of charge control agent may be adjusted based on a variety of parameters to achieve the desired results for a particular application.
Dry electrophotographic toner compositions of the present invention may be prepared by techniques as generally described above, including the steps of forming an amphipathic copolymer that incorporates a non-sorptive component in the S material portion and/or D material portion of the amphipathic copolymer; and formulating the resulting amphipathic copolymer into a dry electrophotographic toner composition. As noted above, the amphipathic copolymer is prepared in a liquid carrier to provide a copolymer having portions with the indicated solubility characteristics. Addition of components of the ultimate toner composition, such as charge control agents or visual enhancement additives, can optionally be accomplished during the formation of the amphipathic copolymer. The step of formulating the resulting amphipathic copolymer into a dry electrophotographic toner composition comprises removing the carrier liquid from the composition to the desired level so that the composition behaves as a dry toner composition, and also optionally incorporating other desired additives such as charge control agents, visual enhancement additives, or other desired additives such as described herein to provide the desired toner composition. Surprisingly, it has been found that toner compositions of the present invention may comprise up to about 30% of carrier liquid by weight, while exhibiting performance properties of a dry toner composition. Preferably, the toner composition comprises less than about 20%, and more preferably less than about 10% of carrier liquid by weight.
The resulting toner particle may optionally be further processed by additional coating processes or surface treatment such as spheroidizing, flame treating, and flash lamp treating. If desired, the toner particle may be additionally milled by conventional techniques, such as using a planetary mill, to break apart any undesired particle aggregates.
The toner particles may then be provided as a toner composition, ready for use, or blended with additional components to form a toner composition.
Toners of the present invention are in a preferred embodiment used to form images in electrophotographic processes. While the electrostatic charge of either the toner particles or photoreceptive element may be either positive or negative, electrophotography as employed in the present invention is preferably carried out by dissipating charge on a positively charged photoreceptive element. A positively-charged toner is then applied to the regions in which the positive charge was dissipated using a toner development technique.
The invention will further be described by reference to the following nonlimiting examples.
EXAMPLES
Percent Solids/volatiles Measurement
In the following toner composition examples, percent solids of the graft stabilizer solutions and the organosol and liquid toner dispersions as well as percent volatiles in the dry toners were determined thermo-gravimetrically by drying in an aluminum weighing pan an originally-weighed sample at 160° C. for at least two hours for graft stabilizer, liquid toner dispersions, or dry toners, and three hours for organosol, weighing the dried sample, and calculating the percentage ratio of the dried sample weight to the original sample weight, after accounting for the weight of the aluminum weighing pan.
Molecular Weight
In the practice of the invention, molecular weight is normally expressed in terms of the weight average molecular weight, while molecular weight polydispersity is given by the ratio of the weight average molecular weight to the number average molecular weight. Molecular weight parameters were determined with gel permeation chromatography (GPC) using a Hewlett Packard Series II 1190 Liquid Chromatograph made by Agilent Industries (formerly Hewlett Packard, Palo Alto, Calif.) (using software HPLC Chemstation Rev A.02.02 1991-1993 395). Tetrahydrofuran was used as the carrier solvent. The three columns used in the Liquid Chromatograph were Jordi Gel Columns (DVB 1000A, and DVB10000A and DVB100000A; Jordi Associates, Inc., Bellingham, Mass.). Absolute weight average molecular weight were determined using a Dawn DSP-F light scattering detector (software by Astra v.4.73.04 1994-1999) (Wyatt Technology Corp., Santa Barbara, Calif.), while polydispersity was evaluated by ratioing the measured weight average molecular weight to a value of number average molecular weight determined with an Optilab DSP Interferometric refractometer detector (Wyatt Technology Corp., Santa Barbara, Calif.).
Particle Size
The organosol and liquid toner particle size distributions were determined using a Horiba LA-920 laser diffraction particle size analyzer (commercially obtained from Horiba Instruments, Inc, Irvine, Calif.) using NorparTM12 fluid that contains 0.1% (w/w) Aerosol OT (dioctyl sodium sulfosuccinate, sodium salt, Fisher Scientific, Fairlawn, N.J.) surfactant.
The dry toner particle size distributions were determined using a Horiba LA-900 laser diffraction particle size analyzer (commercially obtained from Horiba Instruments, Inc, Irvine, Calif.) using de-ionized water that contains 0.1% (w/w) Triton X-100 surfactant (available from Union Carbide Chemicals and Plastics, Inc., Danbury, Conn.).
Prior to the measurements, samples were pre-diluted to approximately 1% (w/w) by the solvent (i.e., NorparTM12 or water) and were sonicated for 6 minutes in a Direct Tip Probe VirSonic sonicator (Model-550 by The VirTis Company, Inc., Gardiner, N.Y.). In both procedures, the samples were diluted by approximately 1/500 by volume and sonicated for one minute prior to the data collections. Sonication on the Horiba LA-920 was operated at 150 watts and 20 kHz. The particle size was expressed on a volume-average basis (i.e., volume mean particle size) in order to provide an indication of dominance of the coalesced primary particle aggregate size of the particles.
Glass Transition Temperature
For the glass transition temperature (Tg) measurement, a graft stabilizer sample was prepared by washing the polymer mixture with acetone and/or methanol followed by drying at 100° C. for 2 hours while an organosol sample was prepared by drying the polymer mixture in an oven at 160° C. for 3 hours. The glass transition temperatures of the dried polymers were measured by using a Differential Scanning Calorimeter (DSC Model 2929 by TA Instruments, New Castle, Del.) equipped with a DSC refrigerated cooling system (−60° C. minimum temperature limit), and dry helium and nitrogen exchange gases. The calorimeter ran on a Thermal Analyst 2100 workstation with version 8.10B software. An empty aluminium pan was used as the reference. The samples were prepared by placing 6.0 to 12.0 mg of the dried polymer into an aluminum sample pan and crimping the upper lid to produce a hermetically sealed sample for DSC testing. The results were normalized on a per mass basis. Each sample was evaluated using 10° C./min heating and cooling rates with a 5-10 min isothermal bath at the end of each heating or cooling ramp. Each sample was heated three to five times and the values for Tg were reported from either the third or fourth heat ramp.
Conductivity for Liquid Toner
The liquid toner bulk conductivity was determined at approximately 18 Hz using a Scientifica Model 627 conductivity meter (Scientifica Instruments, Inc., Princeton, N.J.).
Q/M for Dry Toners
One important characteristic of xerographic toners is the toner's electrostatic charging performance (or specific charge), given in units of Coulombs per gram. To measure the specific charge of each toner, a 0.5 g toner sample was first electrostatically charged by combining it with 9.5 g of MgCuZn ferrite carrier beads (Steward Corporation, Chattanooga, Tenn.) to form the developer in a plastic container. This developer was gently agitated using a U.S. Stoneware mill mixer for 5 min, 15 min, and 30 min intervals before 0.2 g of the toner/carrier developer was analyzed using a Toshiba Blow-off tester (Toshiba Model TB200 Blow-Off Powder Charge measuring apparatus with size #400 mesh stainless steel screens pre-washed in tetrahydrofuran and dried over nitrogen, (Toshiba Chemical Co., Tokyo, Japan). Specific charge measurements were repeated at least three times for each toner to obtain a mean value and a standard deviation. The data was monitored for quality, namely, a visual observation that nearly all of the toner was blown-off of the carrier during the measurement. Tests were considered valid if nearly all of toner mass was blown-off from the carrier beads. Tests with low mass loss were rejected.
Dry Toner Fusing Test
A mask is placed on a sheet of white printing paper covering the entire page except an area 2 inches by 2 inches square. An amount of dry toner powder sufficient to completely cover the exposed area is placed in this square and is spread around gently with a bristle artist's brush having natural fibers. After about one minute of gentle brushing, the paper and the toner particles become tribocharged and the toner particles are attracted to the paper. This is continued until an even distribution of toner particles over the entire exposed area is achieved.
Next, the sheet of paper (including the mask) with the two-inch square patch of toner on it is placed on a six-inch audio loudspeaker in direct contact with the speaker cone and vibrated at 120 Hertz to achieve a very even distribution of toner in the square. Excess toner may be removed by tilting the paper slightly so that gravity acts on the vibrating particles. Those particles not held in place electrostatically will migrate away from the two-inch square dry toner patch where they can be discarded. After the square has been developed to a smooth and even toner image, the mask is removed and the paper, with the square toner image facing upward, is then passed twice between two heated, rubber fusing rollers at the speed of 1.5 inches per second. The top roller is heated to 240° C. and the bottom roller is heated to 180° C. The pneumatic force engaging the two rollers is 20 pounds per square inch.
Optical Density
Optical density on the fused image was measured by using a GRETAG SPM 50 LT meter (Gretag Limited, CH-8105 Regensdort, Switzerland). The meter has several different functions through different modes of operations, selected through different buttons and switches. When a function (optical density, for example) is selected, the measuring orifice of the meter is placed on a background, or non-imaged portion of the imaged substrate in order to “zero” it. It is then placed on the designated color patch and the measurement button is activated. The optical densities of the various color components of the color patch will then displayed on the screen of the meter (i.e., Db, Dc, Dm, and Dy for black, cyan, magenta, and yellow, respectively). For instance, where a color patch is magenta, the optical density reading may be listed as the value on the screen for Dm.
Fused Image Erasure Resistance
This test is used to determine image durability when a fused image is subjected to abrasion from materials such as other paper, linen cloth, and pencil erasers.
In order to quantify the resistance of the fused toner to erasure forces, an erasure test has been defined. This erasure test consists of using a device called a Crockmeter to abrade the areas that were covered with fused dry toner with a linen cloth loaded under a known and controlled force. A standard test procedure followed generally by the inventors is defined in ASTM #F 1319-94 (American Standard Test Methods). The Crockmeter used in this testing was an AATCC Crockmeter Model CM1 manufactured by Atlas Electric Devices Company, Chicago, Ill.
A piece of linen cloth (WW-3009 Super Clean Wiper made by WOOJIN Act Corp., Korea) is affixed to the Crockmeter probe; the probe is placed onto the fused image surface with a controlled force and caused to slew back and forth on the printed surface a prescribed number of times (in this case, 10 times by the turning of a small crank with 5 full turns at two slews per turn).
For this Crockmeter, the head weight was 934 grams, which is the weight placed on the fused image during the 10-slew test, and the area of contact of the linen-covered probe head with the fused image was 1.76 cm2. The results of this test are obtained as described in the standard test method, by determining the optical density of the fused image before the abrasion measured on paper and the optical density after the abrasion measured on the linen cloth. The difference between the two numbers divided by the original optical density was determined as the fused image erasure resistance (%).
MATERIALS GLOSSARY OF CHEMICAL ABBREVIATIONS
The following abbreviations are used in the examples:

    EA: Ethyl acrylate (available from Aldrich Chemical Co., Milwaukee, Wis.)
    EMA: Ethyl methacrylate (available from Aldrich Chemical Co., Milwaukee, Wis.)
    HEMA: 2-Hydroxyethyl methacrylate (available from Aldrich Chemical Co., Milwaukee, Wis.)
    LMA: Lauryl methacrylate (available from Aldrich Chemical Co., Milwaukee, Wis.)
    TCHMA: Trimethyl cyclohexyl methacrylate (available from Ciba Specialty Chemical Co., Suffolk, Va.)
    TMI: Dimethyl-m-isopropenyl benzyl isocyanate (available from CYTEC Industries, West Paterson, N.J.)
    V-601: Dimethyl 2,2′-azobisisobutyrate (an initiator available as V-601 from WAKO Chemicals U.S.A., Richmond, Va.)
    V-64: 2,2′-azobisisobutyronitrile (an initiator available as V-64 from WAKO Chemicals U.S.A., Richmond, Va.)
    DBTDL: Dibutyl tin dilaurate (a catalyst available from Aldrich Chemical Co., Milwaukee, Wis.)
    Zirconium HEX—CEM: (metal soap, zirconium tetraoctoate, available from OMG Chemical Company, Cleveland, Ohio)


NOMENCLATURE
In the following examples, the compositional details of each copolymer will be summarized by ratioing the weight percentages of monomers used to create the copolymer. The grafting site composition is expressed as a weight percentage of the monomers comprising the copolymer or copolymer precursor, as the case may be. For example, a graft stabilizer (precursor to the S portion of the copolymer) designated TCHMA/HEMA-TMI (97/3-4.7% w/w) is made by copolymerizing, on a relative basis, 97 parts by weight TCHMA and 3 parts by weight HEMA, and this hydroxy functional polymer was reacted with 4.7 parts by weight of TMI.
Similarly, a graft copolymer organosol designated TCHMA/HEMA-TMI//EMA (97/3-4.7//100% w/w) is made by copolymerizing the designated graft stabilizer (TCHMA/HEMA-TMI (97/3-4.7% w/w)) (S portion or shell) with the designated core monomer EMA (D portion or core, 100% by weight of EMA) at a specified ratio of D/S (core/shell) determined by the relative weights reported in the examples.
EXAMPLE 1 (COMPARATIVE)
A clean 50 gallon reactor was equipped with a condenser, a thermocouple connected to a digital temperature controller, a nitrogen inlet tube connected to a source of dry nitrogen and a mixer. 194 lbs of NorparTM12 was charged to the reactor by vacuum. The vacuum was then broken and a flow of 1 CFH of nitrogen applied and the agitation was started at 70 RPM. 66.4 lbs of LMA was added and the container rinsed with 2.5 lbs of NorparTM12. 2.10 lbs of 98% (w/w) HEMA was added and the container rinsed with 1.37 lbs of NorparTM12. Finally 0.52 lb of V-64 was added and the container rinsed with 0.2 lb of NorparTM12. A full vacuum was then applied for 10 minutes, and then broken by a nitrogen blanket. A second vacuum was pulled for 10 minutes, and then agitation stopped to verify that no bubbles were coming out of the solution. The vacuum was then broken with a nitrogen blanket and a light flow of nitrogen of 1 CFH (cubic foot per hour) was applied. Agitation was resumed at 75 RPM and the mixture was heated to 70° C. and held for 16 hours. The conversion was quantitative.
The mixture was heated to 90° C. and held at that temperature for 1 hour to destroy any residual V-64, and then was cooled back to 70° C. The nitrogen inlet tube was then removed, and 1.06 lbs of 95% (w/w) DBTDL was added to the mixture using 1.37 lbs of NorparTM12 to rinse container, followed by 3.23 lbs of TMI. The TMI was added drop wise over the course of approximately 5 minutes while stirring the reaction mixture and the container was rinsed with 1.4 lbs of NorparTM12. The mixture was allowed to react at 70° C. for 6 hours, at which time the conversion was quantitative.
The cooled mixture was a viscous, transparent liquid containing no visible insoluble matter. The percent solids of the liquid mixture was determined to be 26.6% (w/w) using the thermo-gravimetric method described above. Subsequent determination of molecular weight was made using the GPC method described above; the copolymer had a Mw of 261,950 Da and Mw/Mn of 2.4 based upon two independent measurements. The calculated glass transition temperature of the polymer was −63° C., as described earlier according to the Fox equation. The product was a copolymer of LMA and HEMA containing random side chains of TMI and was designated herein as LMA/HEMA-TMI (97/3-4.7% w/w). It can be used to make an organosol.
EXAMPLE 2 (COMPARATIVE)
Using the method and apparatus of Example 1, the reactor was charged with 195 lbs of NorparTM12 by vacuum. The vacuum was then broken and a flow of 1 CFH of nitrogen applied and the agitation was started at 70 RPM. 66.4 lbs of TCHMA was added and the container rinsed with 2.7 lbs of NorparTM12. 2.10 lbs of 98% (w/w) HEMA was added and the container rinsed with 1.37 lbs of NorparTM12. Finally 0.86 lb of V-601 was added and the container rinsed with 0.2 lb of NorparTM12. A full vacuum was then applied for 10 minutes, and then broken by a nitrogen blanket. A second vacuum was pulled for 10 minutes, and then agitation stopped to verify that no bubbles were coming out of the solution. The vacuum was then broken with a nitrogen blanket and a light flow of nitrogen of 1 CFH (cubic foot per hour) was applied. Agitation was resumed at 75 RPM and the mixture was heated to 75° C. and held for 4 hours. The conversion was quantitative.
The mixture was heated to 100° C. and held at that temperature for 1 hour to destroy any residual V-601, and then was cooled back to 70° C. The nitrogen inlet tube was then removed, and 0.11 lb of 95% (w/w) DBTDL was added to the mixture using 1.37 lbs of NorparTM12 to rinse container, followed by 3.23 lbs of TMI. The TMI was added drop wise over the course of approximately 5 minutes while stirring the reaction mixture and the container was rinsed with 1.4 lbs of NorparTM12. The mixture was allowed to react at 70° C. for 2 hours, at which time the conversion was quantitative.
The cooled mixture was a viscous, transparent liquid containing no visible insoluble matter. The percent solids of the liquid mixture was determined to be 26.2% (w/w) using the thermo-gravimetric method described above. Subsequent determination of molecular weight was made using the GPC method described above; the copolymer had a Mw of 251,300 Da and Mw/Mn of 2.8 based on two independent measurements. The measured glass transition temperature of the polymer was 123.0° C., as determined by DSC using the method described above. The product was a copolymer of TCHMA and HEMA containing random side chains of TMI and was designated herein as TCHMA/HEMA-TMI (97/3-4.7% w/w). It can be used to make an organosol.
EXAMPLE 3 
A 32 ounce (0.72 liter), narrow-mouthed glass bottle was charged with 478 g of NorparTM12, 108.9 g of LMA, 48.7 g of EMA, 5.0 g of 98% (w/w) HEMA and 1.6 g of V-601. The bottle was then sealed with a screw cap fitted with a Teflon liner and the cap was secured in place using electrical tape. The sealed bottle was inserted into a metal cage assembly and installed on the agitator assembly of an Atlas Launder-Ometer (Atlas Electric Devices Company, Chicago, Ill.). The Launder-Ometer was operated at its fixed agitation speed of 42 RPM with a water bath temperature of 75° C. The mixture in the sealed bottle was allowed to react for 4 hours at which time the conversion of monomer to polymer was quantitative. The mixture was heated to 100° C. for 1 hour to destroy any residual V-601, and then was cooled to room temperature.
The bottle was then opened and 0.25 g of 95% (w/w) DBTDL and 7.6 g of TMI were added to the mixture. The bottle was sealed again and returned to the Atlas Launder-Ometer as described above. The Launder-Ometer was operated at its fixed agitation speed of 42 RPM with a water bath temperature of 70° C. The mixture was allowed to react for 2 hours, at which time the conversion was quantitative.
The cooled mixture was a viscous, transparent liquid containing no visible insoluble matter. The percent solids of the liquid mixture was determined to be 23.4% (w/w) using the thermo-gravimetric method described above. Subsequent determination of molecular weight was made using the GPC method described above; the copolymer had a Mw of 104,750 Da and Mw/Mn of 2.2 based on two independent measurements. The measured glass transition temperature of the polymer was −5.3° C., as determined by DSC using the method described above. The product was a copolymer of LMA, EMA and HEMA containing random side chains of TMI and was designated herein as LMA/EMA/HEMA-TMI (67/30/3-4.7% w/w). It can be used to make an organosol.
EXAMPLE 4 
Example 4 was prepared similarly to Example 3, except that at the beginning of the reactions, a mixture of 478 g of NorparTM12, 92.6 g of LMA, 65.0 g of EMA, 5.0 g of 98% (w/w) HEMA and 1.63 g of V-601 was charged to the narrow-mouthed glass bottle.
The cooled mixture was a viscous, transparent liquid containing no visible insoluble matter. The percent solids of the liquid mixture was determined to be 23.5% (w/w) using the thermo-gravimetric method described above. Subsequent determination of molecular weight was made using the GPC method described above; the copolymer had a Mw of 102,950 Da and Mw/Mn of 2.4 based on two independent measurements. The measured glass transition temperature of the polymer was 1.1° C., as determined by DSC using the method described above. The product was a copolymer of LMA, EMA and HEMA containing random side chains of TMI and was designated herein as LMA/EMA/HEMA-TMI (57/40/3-4.7% w/w). It can be used to make an organosol.
EXAMPLE 5 (COMPARATIVE)
Example 5 was prepared similarly to Example 3, except that at the beginning of the reactions, a mixture of 478 g of NorparTM12, 84.5 g of LMA, 73.1 g of EMA, 5.0 g of 98% (w/w) HEMA and 1.63 g of V-601 was charged to the narrow-mouthed glass bottle.
The cooled mixture was a viscous, hazy liquid with phase separation. The product was a copolymer of LMA, EMA and HEMA containing random side chains of TMI and was designated herein as LMA/EMA/HEMA-TMI (52/45/3-4.7% w/w). It was not used to make an organosol due to the phase separation of the polymer in NorparTM12.
EXAMPLE 6 
Example 6 was prepared similarly to Example 3, except that at the beginning of the reactions, a mixture of 478 g of NorparTM12, 149.5 g of TCHMA, 8.1 g of EA, 5.0 g of 98% (w/w) HEMA and 1.6 g of V-601 was charged to the narrow-mouthed glass bottle.
The cooled mixture was a viscous, transparent liquid containing no visible insoluble matter. The percent solids of the liquid mixture was determined to be 25.8% (w/w) using the thermo-gravimetric method described above. Subsequent determination of molecular weight was made using the GPC method described above; the copolymer had a Mw of 221,900 Da and Mw/Mn of 2.9 based on two independent measurements. The measured glass transition temperature of the polymer was 119.6° C., as determined by DSC using the method described above. The product was a copolymer of TCHMA, EA and HEMA containing random side chains of TMI and was designated herein as TCHMA/EA/HEMA-TMI (92/5/3-4.7% w/w). It can be used to make an organosol.
EXAMPLE 7 
Example 7 was prepared similarly to Example 3, except that at the beginning of the reactions, a mixture of 478 g of NorparTM12, 133.2 g of TCHMA, 24.4 g of EA, 5.0 g of 98% (w/w) HEMA and 1.63 g of V-601 was charged to the narrow-mouthed glass bottle.
The cooled mixture was a viscous, transparent liquid containing no visible insoluble matter. The percent solids of the liquid mixture was determined to be 25.8% (w/w) using the thermo-gravimetric method described above. Subsequent determination of molecular weight was made using the GPC method described above; the copolymer had a Mw of 208,000 Da and Mw/Mn of 2.6 based on two independent measurements. The measured glass transition temperature of the polymer was 91.4° C., as determined by DSC using the method described above. The product was a copolymer of TCHMA, EA and HEMA containing random side chains of TMI and was designated herein as TCHMA/EA/HEMA-TMI (82/15/3-4.7% w/w). It can be used to make an organosol.
EXAMPLE 8 (COMPARATIVE)
Example 8 was prepared similarly to Example 3, except that at the beginning of the reactions, a mixture of 478 g of NorparTM12, 125.1 g of TCHMA, 32.5 g of EA, 5.0 g of 98% (w/w) HEMA and 1.63 g of V-601 was charged to the narrow-mouthed glass bottle.
The cooled mixture was a viscous, hazy liquid with phase separation. The product was a copolymer of TCHMA, EMA and HEMA containing random side chains of TMI and was designated herein as TCHMA/EMA/HEMA-TMI (77/20/3-4.7% w/w). It was not used to make an organosol due to the phase separation of the polymer in NorparTM12.
EXAMPLE 9 
A 5000 ml 3-neck round flask equipped with a mechanic stirrer, a condenser, a thermocouple connected to a digital temperature controller, and a nitrogen inlet tube connected to a source of either vacuum or dry nitrogen, was charged with a mixture of 2573 g of NorparTM12, 828 g of TCHMA, 21 g of EMA, 26.8 g of 98% (w/w) HEMA and 8.75 g of V601. While stirring the mixture, the reaction flask was purged with vacuum at 40 torr for 10 min., followed by nitrogen to break down the vacuum, and was purged with vacuum again at 40 torr for 10 min., followed by nitrogen to break down the vacuum. The nitrogen flow rate was then reduced to approximately 0.5 liters/minute. The mixture was heated to 75° C. for 4 hours. The conversion was quantitative.
The mixture was then heated to 100° C. and held at that temperature for 1 hour to destroy any residual V-601, and then was cooled down to 70° C. The nitrogen inlet tube was then removed, and 1.36 g of 95% (w/w) DBTDL were added to the mixture, followed by 41.1 g of TMI. The TMI was pulled slowly into the mixture over the course of approximately 2 minutes while stirring the reaction mixture. The nitrogen inlet tube was replaced and the mixture was allowed to react at 70° C. for 2 hours, at which time the conversion was quantitative.
The cooled mixture was a viscous, transparent liquid containing no visible insoluble matter. The percent solids of the liquid mixture was determined to be 25.7% (w/w) using the thermo-gravimetric method described above. Subsequent determination of molecular weight was made using the GPC method described above; the copolymer had a Mw of 216,500 Da and Mw/Mn of 2.4 based on two independent measurements. The measured glass transition temperature of the polymer was 123.9° C., as determined by DSC using the method described above. The product was a copolymer of TCHMA, EMA and HEMA containing random side chains of TMI and was designated herein as TCHMA/EMA/HEMA-TMI (94.5/2.5/3-4.7% w/w). It can be used to make an organosol.
EXAMPLE 10 
Example 10 was prepared similarly to Example 9, except that at the beginning of the reactions, a mixture of 2573 g of NorparTM12, 785 g of TCHMA, 64 g EMA, 26.8 g of 98% (w/w) HEMA and 8.75g of V-601 was charged to the reactor.
The cooled mixture was a viscous, transparent liquid containing no visible insoluble matter. The percent solids of the liquid mixture was determined to be 25.4% (w/w) using the thermo-gravimetric method described above. Subsequent determination of molecular weight was made using the GPC method described above; the copolymer had a Mw of 240,400 Da and Mw/Mn of 2.4 based on two independent measurements. The measured glass transition temperature of the polymer was 119.2° C., as determined by DSC using the method described above. The product was a copolymer of TCHMA, EMA and HEMA containing random side chains of TMI and was designated herein as TCHMA/EMA/HEMA-TMI (89.5/7.5/3-4.7% w/w). It can be used to make an organosol.
EXAMPLE 11 (COMPARATIVE)
Example 11 was prepared similarly to Example 9, except that at the beginning of the reactions, a mixture of 2573 g of NorparTM12, 764 g of TCHMA, 85 g EMA, 26.8 g of 98% (w/w) HEMA and 8.75g of V-601 was charged to the reactor.
The cooled mixture was a viscous liquid with slight phase separation. The product was a copolymer of TCHMA, EMA and HEMA containing random side chains of TMI and was designated herein as TCHMA/EMA/HEMA-TMI (87/10/3-4.7% w/w). It was not used to make an organosol due to the phase separation of the polymer in NorparTM12.
The compositions of the graft stabilizers of Example 1 to 11 are summarized in the following Table 1.







TABLE 1







Graft Stabilizers Containing Non-Sorptive Segments













Non-Sorptive
Tg of the



Examples
Compositions
Segments, % (w/w)
Polymers, ° C.
Polymer in NP-12














1, Comp.
LMA/HEMA-TMI (97/3-4.7)
None
−63
Soluble


2, Comp.
TCHMA/HEMA-TMI (97/3-4.7)
None
123.0
Soluble


3
LMA/EMA/HEMA-TMI (67/30/3-4.7)
EMA, 30%
−5.3
Soluble


4
LMA/EMA/HEMA-TMI (57/40/3-4.7)
EMA, 40%
1.1
Soluble


5, Comp.
LMA/EMA/HEMA-TMI (52/45/3-4.7)
EMA, 45%
N/A
Phase sep.


6
TCHMA/EA/HEMA-TMI (92/5/3-4.7)
EA, 5%
119.6
Soluble


7
TCHMA/EA/HEMA-TMI (82/15/3-4.7)
EA, 15%
91.4
Soluble


8, Comp.
TCHMA/EA/HEMA-TMI (77/20/3-4.7)
EA, 20%
N/A
Phase sep.


9
TCHMA/EMA/HEMA-TMI (94.5/2.5/3-4.7)
EMA, 2.5%
123.9
Soluble


10 
TCHMA/EMA/HEMA-TMI (89.5/7.5/3-4.7)
EMA, 7.5%
119.2
Soluble


11, Comp. 
TCHMA/EMA/HEMA-TMI (87/10/3-4.7)
EMA, 10%
N/A
Slightly Phase sep.









EXAMPLES 12-19
Preparations of Organosols
EXAMPLE 12 (COMPARATIVE)
This is a comparative example using the graft stabilizer in Example 1 to prepare an organosol with a core/shell ratio of 8/1. To a clean 60 gallon reactor, equipped with a condenser, a thermocouple connected to a digital temperature controller, a nitrogen inlet tube connected to a source of dry nitrogen and a mixer, was charged with a mixture of 146.5 lbs of NorparTM12 and 13.4 lbs of the graft stabilizer mixture from Example 1 along with an additional 1 lb of NorparTM12 to rinse the pump. Agitation was then turned on at a rate of 60 RPM, and temperature was check to ensure maintenance at ambient. Next 0.48 lb of V-64 was added, along with 1 lb of NorparTM12 to rinse the container. Finally 28.4 lbs of EMA was added along with 28.4 lbs NorparTM12 for rinsing the pump. A vacuum was then applied at 16 torr for 10 minutes, and then broken by a nitrogen blanket. A second vacuum was pulled at 22 torr for 10 minutes, and then agitation stopped to verify that no bubbles were coming out of the solution. The vacuum was then broken with a nitrogen blanket and a light flow of nitrogen of 0.5 CFH (cubic foot per hour) was applied. Agitation of 85 RPM was resumed and the temperature of the reactor was heated to 70° C. and maintained for 16 hours. The conversion was quantitative.
The resulting mixture was stripped of residual monomer by adding 40 lbs of n-heptane and agitation was held at 90 RPM with the batch heated to 95° C. The nitrogen flow was stopped and a vacuum of 165 torr was pulled and held for 10 minutes. The vacuum was then increased to 105, 66, and 40 torr, being held at each level for 10 minutes. Finally, the vacuum was increased to 26 torr and held for 30 minutes. The vacuum was then broken, and the stripped organosol was cooled to room temperature, yielding an opaque white dispersion.
This organosol was designated LMA/HEMA-TMI//EMA (97/3-4.7//100% w/w) and can be used to make ink formulations. The percent solids of the organosol dispersion after stripping was determined to be 18.6% (w/w) using the thermo-gravimetric method described above. Subsequent determination of average particles size was made using the laser diffraction method described above; the organosol had a volume average diameter 8.9 μm. The measured glass transition temperature of the polymer was 64.3° C., as determined by DSC using the method described above.
EXAMPLE 13 (COMPARATIVE)
This is a comparative example using the graft stabilizer in Example 2 to prepare an organosol with a core/shell ratio of 6/1. A 5000 ml open head reactor equipped with a condenser, a thermocouple connected to a digital temperature controller, a nitrogen inlet tube connected to a source of dry nitrogen and a mechanical stirrer with anchor blade, was charged with a mixture of 2899.0 g of NorparTM12, 360.0 g of EMA, and 237.2 g of the graft stabilizer mixture from Example 2, and 4.2 g of V-601. While stirring the mixture, the reaction flask was purged with dry nitrogen for 30 minutes at flow rate of approximately 2 liters/minute and was then reduced to approximately 0.5 liters/minute. The mixture was heated to 75° C. for 5 hours. The conversion was quantitative.
Approximately 500 g of n-heptane were added to the cooled organosol, and the resulting mixture was stripped of residual monomer using a rotary evaporator equipped with a dry ice/acetone condenser and operating at a temperature of 90° C. and a vacuum of approximately 15 mm Hg. The stripped organosol was cooled to room temperature, yielding an opaque white dispersion.
This organosol was designated TCHMA/HEMA-TMI//EMA (97/3-4.7//100% w/w) and can be used to make ink formulations. The percent solids of the organosol dispersion after stripping was determined to be 13.3% (w/w) using the thermo-gravimetric method described above. Subsequent determination of average particles size was made using the laser diffraction method described above; the organosol had a volume average diameter 30.6 μm. The measured glass transition temperature of the polymer was 66.7° C., as determined by DSC using the method described above.
EXAMPLE 14 
Example 14 was prepared similarly to Example 13, except that at the beginning of the reactions, a mixture of 2879 g of NorparTM12, 360 g of EMA, 256.4 g of the graft stabilizer mixture from Example 3, and 4.2 g of V-601 were charged to the reactor.
This organosol was designated LMA/EMA/HEMA-TMI//EMA (67/30/3-4.7//100% w/w) and can be used to make ink formulations. The percent solids of the organosol dispersion after stripping was determined to be 12.3% (w/w) using the thermo-gravimetric method described above. Subsequent determination of average particles size was made using the laser diffraction method described above; the organosol had a volume average diameter 19.6 μm. The measured glass transition temperature of the polymer was 63.7° C., as determined by DSC using the method described above.
EXAMPLE 15 
Example 15 was prepared similarly to Example 13, except that at the beginning of the reactions, a mixture of 2880 g of NorparTM12, 360 g of EMA, 255.3 g of the graft stabilizer mixture from Example 4, and 4.2 g of V-601 were charged to the reactor.
This organosol was designated LMA/EMA/HEMA-TMI//EMA (57/40/3-4.7//100% w/w) and can be used to make ink formulations. The percent solids of the organosol dispersion after stripping was determined to be 11.6% (w/w) using the thermo-gravimetric method described above. Subsequent determination of average particles size was made using the laser diffraction method described above; the organosol had a volume average diameter 24.8 μm. The measured glass transition temperature of the polymer was 65.9° C., as determined by DSC using the method described above.
EXAMPLE 16 
Example 16 was prepared similarly to Example 13, except that at the beginning of the reactions, a mixture of 2903 g of NorparTM12, 360 g of EMA, 232.6 g of the graft stabilizer mixture from Example 6, and 4.2 g of V-601 were charged to the reactor.
This organosol was designated TCHMA/EA/HEMA-TMI//EMA (92/5/3-4.7//100% w/w) and can be used to make ink formulations. The percent solids of the organosol dispersion after stripping was determined to be 11.1% (w/w) using the thermo-gravimetric method described above. Subsequent determination of average particles size was made using the laser diffraction method described above; the organosol had a volume average diameter 38.1 μm. The measured glass transition temperature of the polymer was 68.5° C., as determined by DSC using the method described above.
EXAMPLE 17 
Example 17 was prepared similarly to Example 13, except that at the beginning of the reactions, a mixture of 2903 g of NorparTM12, 360 g of EMA, 232.6 g of the graft stabilizer mixture from Example 7, and 4.2 g of V-601 were charged to the reactor.
This organosol was designated TCHMA/EA/HEMA-TMI//EMA (82/15/3-4.7//100% w/w) and can be used to make ink formulations. The percent solids of the organosol dispersion after stripping was determined to be 12.6% (w/w) using the thermo-gravimetric method described above. Subsequent determination of average particles size was made using the laser diffraction method described above; the organosol had a volume average diameter 44.3 μm. The measured glass transition temperature of the polymer was 71.3° C., as determined by DSC using the method described above.
EXAMPLE 18 
Example 18 was prepared similarly to Example 13, except that at the beginning of the reactions, a mixture of 2902 g of NorparTM12, 360 g of EMA, 233.5 g of the graft stabilizer mixture from Example 9, and 4.2 g of V-601 were charged to the reactor.
This organosol was designated TCHMA/EMA/HEMA-TMI//EMA (94.5/2.5/3-4.7//100% w/w) and can be used to make ink formulations. The percent solids of the organosol dispersion after stripping was determined to be 13.1% (w/w) using the thermo-gravimetric method described above. Subsequent determination of average particles size was made using the laser diffraction method described above; the organosol had a volume average diameter 26.7 μm. The measured glass transition temperature of the polymer was 65.6° C., as determined by DSC using the method described above.
EXAMPLE 19 
Example 19 was prepared similarly to Example 13, except that at the beginning of the reactions, a mixture of 2900 g of NorparTM12, 360 g of EMA, 236.2 g of the graft stabilizer mixture from Example 10, and 4.2 g of V-601 were charged to the reactor.
This organosol was designated TCHMA/EMA/HEMA-TMI//EMA (89.5/7.5/3-4.7//100% w/w) and can be used to make ink formulations. The percent solids of the organosol dispersion after stripping was determined to be 12.0% (w/w) using the thermo-gravimetric method described above. Subsequent determination of average particles size was made using the laser diffraction method described above; the organosol had a volume average diameter 33.1 μm. The measured glass transition temperature of the polymer was 66.2° C., as determined by DSC using the method described above.
The compositions of the organosol copolymers formed in Examples 12 to 19 are summarized in the following Table-2:







TABLE 2







Organosols Containing Non-Sorptive Segments in the Shells











Organosol Compositions
Tg of the
Non-Sorptive


Examples
% (w/w)
Polymers, ° C.
Segments, % (w/w)





12, Comp.
LMA/HEMA-TMI//EMA (97/3-4.7//100)
64.3
None


13, Comp.
TCHMA/HEMA-TMI//EMA (97/3-4.7//100)
66.7
None


14
LMA/EMA/HEMA-TMI//EMA (67/30/3-4.7//100)
63.7
EMA, 30%


15
LMA/EMA/HEMA-TMI//EMA (57/40/3-4.7//100)
65.9
EMA, 40%


16
TCHMA/EA/HEMA-TMI//EMA (92/5/3-4.7//100)
68.5
EA, 5%


17
TCHMA/EA/HEMA-TMI//EMA (82/15/3-4.7//100)
71.3
EA, 15%


18
TCHMA/EMA/HEMA-TMI//EMA (94.5/2.5/3-4.7//100)
65.6
EMA, 2.5%


19
TCHMA/EMA/HEMA-TMI//EMA (89.5/7.5/3-4.7//100)
66.2
EMA, 7.5%









EXAMPLES 20-27
Preparation of Chemical Toners
For characterization of the prepared chemical toners in these Examples, the following were measured: size-related properties (particle size) for both liquid inks and dry toners; charge-related properties in liquid inks (bulk conductivity); percent of volatiles in dry toners; Q/M in dry toners; reflectance optical density (Z/ROD) in fused images from dry toners, and fused image erasure resistance.
EXAMPLE 20 (COMPARATIVE)
This is a comparative example of preparing a magenta dry toner at an organosol to pigment ratio of 6 using the organosol prepared in example 12.
First, 175.2 g of the organosol example 12 were combined with 117.0 g of NorparTM12, 3.9 g of Pigment Red 146 (DIC Japan, FR4580), 1.3 g Pigment Red 81:4 (Magruder Color Company, Inc., Elizabeth, N.J.), 1.3 g of Pigment Red 269 (Magruder Color Company, Inc., Elizabeth, N.J.), and 1.3 g of 5.0% (w/w) Zirconium HEX—CEM solution (OMG Chemical Company, Cleveland, Ohio) in a 16 ounce glass jar. This mixture was then milled in a 0.5 liter vertical bead mill (Model 6TSG-1/4, Aimex Co., Ltd., Tokyo, Japan) charged with 390 g of 1.3 mm diameter Potters glass beads (Potters Industries, Inc., Parsippany, N.J.). The mill was operated at 2,000 RPM for 30 min. with a water-bath circulating at 55° C. through the heating jacket of the milling chamber. At the end of the milling, 187.5 g of NorparTM12 was used to rinse the milling chamber and the resulting liquid toner were left on a mechanic shaker till it was ready for testing. The measured volume mean particle size in the liquid ink was 6.4 micron and the measured bulk conductivity for the liquid ink was 54 picoMhos/cm.
Second, the liquid toner was washed with 15 ̃20 times in volume with heptanes, filtered through a Whatman® Grade 50 filter paper (Aldrich Chemical Co., Milwaukee, Wis.), and air-dried overnight. About 3 ̃5 g of the dried toner sample was then milled by using a planetary mono mill (Model LC-106A, manufactured by Fritsch GMBH of Idar-Oberstien, Germany) with thirty-five grinding balls made of silicon-nitride (Si3N4) and having a 10 mm diameter in an 80 ml grinding bowl also made of Si3N4. The planetary mill was run at 600 RPM for three milling cycles each lasting 3 minutes, 20 seconds with 5 minutes of intervals in order to minimize temperature increase within the grinding bowl. After the third milling cycle, the grinding bowl was removed from the planetary mill and the grinding balls were separated by pouring the contents onto a # 35 sieve. The milled toner powder was passed through the sieve onto a collection sheet and subsequently sealed in an airtight glass jar. Measured properties for the dry toner were listed below:
Percent of volatiles: 3.3% (w/w)
Volume mean particle size: 27.8 microns
Q/m=24.7 μC/g
OD on fused images: 1.7
Image erasure resistances: 81.5%
EXAMPLE 21 (COMPARATIVE)
This is a comparative example of preparing a magenta dry toner. It was prepared and analyzed similarly to example 20, except that 244.4 g of the organosol example 13 was combined with 47.8.0 g of NorparTM12 and the rest of the materials that were used in example 20 when preparing for the milling of magenta liquid ink. The liquid ink had a measured volume mean particle size of 6.4 micron and a measured bulk conductivity of 54 picoMhos/cm. Measured properties for the dry toner were listed below:
Percent of volatiles: 1.9% (w/w)
Volume mean particle size: 46.7 microns
Q/m=31.3 μC/g
OD on fused images: 1.7
Image erasure resistances: 69.9%
EXAMPLE 22 
This is an example of preparing a magenta dry toner. It was prepared and analyzed similarly to example 20, except that 264.2 g of the organosol example 14 was combined with 28.1.0 g of NorparTM12 and the rest of the materials that were used in example 20 when preparing for the milling of magenta liquid ink and that after 30 min. of milling at 55° C., it was milled for an additional 96 min. at 45° C. The liquid ink had a measured volume mean particle size of 4.1 micron and a measured bulk conductivity of 73 picoMhos/cm. Measured properties for the dry toner were listed below:
Percent of volatiles: 3.8% (w/w)
Volume mean particle size: 43.7 microns
Q/m=30.1 μC/g
OD on fused images: 1.7
Image erasure resistances: 94.3%
EXAMPLE 23 
This is an example of preparing a magenta dry toner. It was prepared and analyzed similarly to example 20, except that 280.2 g of the organosol example 15 was combined with 12.2 g of NorparTM12 and the rest of the materials that were listed in example 20 when preparing for the milling of magenta liquid ink and that after 30 min. of milling at 55° C., the liquid ink was milled for an additional 96 min. at 45° C. The liquid ink had a measured volume mean particle size of 4.5 micron and a measured bulk conductivity of 78 picoMhos/cm. Measured properties for the dry toner were listed below:
Percent of volatiles: 5.3% (w/w)
Volume mean particle size: 37.6 microns
Q/m=32.9 μC/g
OD on fused images: 1.7
Image erasure resistances: 96.9%
EXAMPLE 24 
This is an example of preparing a magenta dry toner. It was prepared and analyzed similarly to example 20, except that 283.6 g of the organosol example 16 was combined with 9.7 g of NorparTM12, and the rest of the materials that were used in example 20 when preparing for the milling of magenta liquid ink and that after 30 min. of milling at 55° C., it was milled for an additional 45 min. at 45° C. The liquid ink had a measured volume mean particle size of 4.1 micron and a measured bulk conductivity of 131 picoMhos/cm. Measured properties for the dry toner were listed below:
Percent of volatiles: 4.8% (w/w)
Volume mean particle size: 43.2 microns
Q/m=31.9 μC/g
OD on fused images: 1.7
Image erasure resistances: 83.5%
EXAMPLE 25 
This is an example of preparing a magenta dry toner. It was prepared and analyzed similarly to example 20, except that 257.9 g of the organosol example 17 was combined with 34.4 g of NorparTM12, and the rest of the materials that were used in example 20 when preparing for the milling of magenta liquid ink and that after 30 min. of milling at 55° C., it was milled for an additional 80 min. at 45° C. The liquid ink had a measured volume mean particle size of 4.6 micron and a measured bulk conductivity of 118 picoMhos/cm. Measured properties for the dry toner were listed below:
Percent of volatiles: 4.6% (w/w)
Volume mean particle size: 59.1 microns
Q/m=31.5 μC/g
OD on fused images: 1.7
Image erasure resistances: 91.0%
EXAMPLE 26 
This is an example of preparing a magenta dry toner. It was prepared and analyzed similarly to example 20, except that 248.1 g of the organosol example 18 was combined with 44.3 g of NorparTM12, and the rest of the materials that were used in example 20 when preparing for the milling of magenta liquid ink and that after 30 min. of milling at 55° C., it was milled for an additional 5 min. 45° C. The liquid ink had a measured volume mean particle size of 4.6 micron and a measured bulk conductivity of 157 picoMhos/cm. Measured properties for the dry toner were listed below:
Percent of volatiles: 4.1% (w/w)
Volume mean particle size: 30.0 microns
Q/m=34.4 μC/g
OD on fused images: 1.7
Image erasure resistances: 87.2%
EXAMPLE 27 
This is an example of preparing a magenta dry toner. It was prepared and analyzed similarly to example 20, except that 270.8 g of the organosol example 19 was combined with 21.5 g of NorparTM12, and the rest of the materials that were used in example 20 when preparing for the milling of magenta liquid ink and that after 30 min. of milling at 55° C., it was milled for an additional 5 min. at 45° C. The liquid ink had a measured volume mean particle size of 4.6 micron and a measured bulk conductivity of 157 picoMhos/cm. Measured properties for the dry toner were listed below:
Percent of volatiles: 5.5% (w/w)
Volume mean particle size: 31.6 microns
Q/m=33.7 μC/g
OD on fused images: 1.7
Image erasure resistances: 67.9%
The fused image erasure resistances for Examples 21 to 27 are summarized in the Table 3 below:







TABLE 3







Image Erasure Resistance for Examples 20-27











Main Chains in
Non-Sorptive Segments in
Image Erasure


Examples
Graft Stabilizer
Graft Stabilizer
Resistance, %





20, Comp.
LMA
None
81.5%


21, Comp.
TCHMA
None
69.9%


22
LMA
EMA, 30%
94.3%


23
LMA
EMA, 40%
96.9%


24
TCHMA
EA, 5%
83.5%


25
TCHMA
EA, 15%
91.0%


26
TCHMA
EMA, 2.5%
87.2%


27
TCHMA
EMA, 7.5%
67.9%









Other embodiments of this invention will be apparent to those skilled in the art upon consideration of this specification or from practice of the invention disclosed herein. All patents, patent documents, and publications cited herein are incorporated by reference as if individually incorporated. Various omissions, modifications, and changes to the principles and embodiments described herein can be made by one skilled in the art without departing from the true scope and spirit of the invention which is indicated by the following claims.

## Claims

1. A dry electrographic toner composition comprising:
a plurality of toner particles, wherein the toner particles comprise polymeric binder comprising at least one amphipathic copolymer comprising one or more S material portions and one or more D material portions prepared from an organosol reaction process utilizing a liquid carrier reaction medium having a Kauri-Butanol number less than about 30 mL; and
wherein the S material portion comprises at least one soluble component and at least one non-sorptive component, wherein the non-sorptive component is the reaction product of monomers having an absolute difference in Hildebrand solubility parameter from the liquid carrier of about 3.0 MPa1/2 or greater.

2. The dry electrographic toner composition of claim 1, wherein the non-sorptive component is the reaction product of monomers having an absolute difference in Hildebrand solubility parameter from the liquid carrier of about 3.15 MPa1/2 or greater.

3. The dry electrographic toner composition of claim 1, wherein the non-sorptive component is the reaction product of monomers having an absolute difference in Hildebrand solubility parameter from the liquid carrier of about 3.30 MPa1/2 or greater.

4. The dry electrographic toner composition of claim 1, wherein the non-sorptive component is the reaction product of monomers having an absolute difference in Hildebrand solubility parameter from the liquid carrier of about 3.40 MPa1/2 or greater.

5. The dry electrographic toner composition of claim 1, wherein the non-sorptive component is present in an amount of from about 1% to about 40% of the S material portion.

6. The dry electrographic toner composition of claim 1, wherein the non-sorptive component is present in an amount of from about 1% to about 20% of the S material portion.

7. The dry electrographic toner composition of claim 1, wherein the non-sorptive component is present in an amount of from about 1% to about 5% of the S material portion.

8. The dry electrographic toner composition of claim 1, wherein the absolute difference in Hildebrand solubility parameters between the S material portion(s) and the liquid carrier is from about 2 to about 3.0 MPa1/2.

9. The dry electrographic toner composition of claim 1, wherein the non-sorptive component is randomly arranged within the S material portion of the amphipathic copolymer.

10. The dry electrographic toner composition of claim 1, wherein the non-sorptive component is prepared by incorporation of a single type of monomer that exhibits the desired solubility parameter as the non-sorptive component of the S material portion of the amphipathic copolymer.

11. The dry electrographic toner composition of claim 1, wherein the non-sorptive component is prepared by incorporation a plurality of monomers, each of which exhibits the desired solubility parameter as the non-sorptive component of the S material portion of the amphipathic copolymer.

12. The dry electrographic toner composition of claim 1, wherein the average Tg of the non-sorptive component is lower than the average Tg of the soluble components of the S material portion.

13. The dry electrographic toner composition of claim 1, wherein the average Tg of the non-sorptive component is less than about 70° C., and the average Tg of the soluble components of the S material portion is greater than about 90° C.

14. The dry electrographic toner composition of claim 1, wherein the non-sorptive component has an average Tg of less than about 0° C., and is from about 1 to about 15% by weight of the S material portion and the soluble component has an average Tg of greater than about 90° C., and is from about 85 to about 99% by weight of the S material portion.

15. The dry electrographic toner composition of claim 1, wherein the average Tg of the non-sorptive component is higher than the average Tg of the soluble components of the S material portion.

16. The dry electrographic toner composition of claim 1, wherein the average Tg of the non-sorptive component is greater than about 50° C., and the average Tg of the soluble components of the S material portion is less than about 0° C.

17. The dry electrographic toner composition of claim 1, wherein the non-sorptive component has an average Tg of greater than about 50° C., and is from about 1 to about 50% by weight of the S material portion and wherein the soluble component has an average Tg of less than about 0° C., and is from about 50 to about 99% by weight of the S material portion.

18. The dry electrographic toner composition of claim 1, wherein S material portion comprises the reaction products of soluble monomers selected from the group consisting of trimethyl cyclohexyl methacrylate; t-butyl methacrylate; n-butyl methacrylate; isobornyl(meth)acrylate; 1,6-Hexanediol di(meth)acrylate; 2-hydroxyethyl methacrylate; lauryl methacrylate; and combinations thereof; and further comprises non-sorptive components that are the reaction products of monomers selected from the group consisting of ethyl acrylate and ethyl methacrylate.

19. A dry electrographic toner composition comprising a plurality of toner particles, wherein the toner particles comprise polymeric binder comprising at least one amphipathic copolymer comprising one or more S material portions and one or more D material portions;
wherein the S material portion has an average Hildebrand solubility parameter of from about from about 16 MPa1/2 to about 17.3 MPa1/2, and the S material portion comprises at least one non-sorptive component having an average Hildebrand solubility parameter that is at least about 0.4 MPa1/2 greater than the average Hildebrand solubility parameter of the S material portion.

20. The dry electrographic toner composition of claim 19, wherein the S material portion comprises at least one non-sorptive component having an average Hildebrand solubility parameter that is at least about 0.7 MPa1/2 greater than the average Hildebrand solubility parameter of the S material portion.

21. The dry electrographic toner composition of claim 19, wherein the S material portion has an average Hildebrand solubility parameter of from about from about 16 MPa1/2 to about 17.0 MPa1/2, and the non-sorptive component has an average Hildebrand solubility parameter that is greater than about 17.5 MPa1/2.

22. A process of preparing a dry toner composition, comprising
a) preparing polymeric binder comprising at least one amphipathic copolymer comprising one or more S material portions and one or more D material portions, wherein the S material portion comprises at least one soluble component and at least one non-sorptive component, wherein the non-sorptive component is the reaction product of monomers having an absolute difference in Hildebrand solubility parameter from the liquid carrier of about 3.0 MPa1/2 or greater; and
b) formulating a plurality of toner particles of desired size using the amphipathic copolymer of step a) to provide a dry toner composition.