US20060087052A1 - Microtoner formulations having blended copolymers of a first and second resin and method of producing same - Google Patents
Microtoner formulations having blended copolymers of a first and second resin and method of producing same Download PDFInfo
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- US20060087052A1 US20060087052A1 US10/887,967 US88796704A US2006087052A1 US 20060087052 A1 US20060087052 A1 US 20060087052A1 US 88796704 A US88796704 A US 88796704A US 2006087052 A1 US2006087052 A1 US 2006087052A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
- G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
Definitions
- the present invention relates to toner for use in electrophotographic processes and/or printing machines, and a method for producing such toner particles.
- the toner used in electrophotographic printing machines is a blend of materials, including plastic binder resins, coloring pigments, such as, for example, carbon black, magnetic iron oxides, waxes, and charge control agents and other ingredients. Most toners are produced in bulk using a melt mixing or hot compounding process. The plastic binder resins, coloring pigments and other ingredients are blended together while in a molten state to thereby form a hot paste having a consistency similar to cake mix. This mixture is then cooled, typically, by forming it into slabs on a cooling belt or by pelletizing the mixture and cooling the pellets. The raw toner is then ground or pulverized into a toner powder by, for example, jet mills or air-swept hammer mills.
- plastic binder resins coloring pigments
- coloring pigments such as, for example, carbon black, magnetic iron oxides, waxes, and charge control agents and other ingredients.
- Most toners are produced in bulk using a melt mixing or hot compounding process.
- This process produces a toner powder having a wide range or distribution of particle sizes.
- toner having a narrow distribution of relatively small or fine particle sizes is preferable in that such toner produces higher-quality images. Therefore, the toner powder is sifted or classified to remove over-size and under-size toner particles. A toner powder having a relatively narrow distribution around a desired particle size is thus produced.
- the toner powder is then blended with additives to adjust various properties, such as, for example, flow, and electrostatic properties, and packaged for use.
- the fracture mechanics of the binder resin is the limiting factor in reducing toner particle size.
- the fracture mechanics of the binder resin also limits the rate at which a given particle size is obtained. Further, as the particle size of the binder resin decreases the rate at which particle size reduction occurs also decreases.
- Toner binders are typically mechanically reduced (i.e., by non-chemical methods, such as, for example, by grinding, milling, or pulverizing) to a volume median particle size of from approximately 6 to approximately 12 microns ( ⁇ ), and the particles are then classified to produce a toner having a desired particle-size distribution.
- Mechanically reducing toner binder resin particles to a size of less than approximately 5 ⁇ is relatively inefficient due to the reduced rate at which particle-size-reduction occurs in such small-size particles.
- the present invention provides a particulate microtoner and method for producing same.
- the invention comprises, in one form thereof, a microtoner including a blend of at least one polymer and at least one thermoplastic polymer.
- the method of producing the microtoner includes blending the at least one polymer with the at least one thermoplastic polymer and with one or more pigments to thereby form a toner formulation.
- the toner formulation is pulverized by mechanical means into an unclassified particulate microtoner. The unclassified particulate microtoner is then classified.
- An advantage of the present invention is that a microtoner having a volume-median particle size approximately equal to the particle sizes achieved by chemical particle size reduction methods is produced using conventional mechanical non-chemical particle size reduction means and/or methods.
- a further advantage of the present invention is that the microtoner has a particle size distribution that is desirably smaller or tighter than the particle size distribution of conventional microtoner produced by conventional means.
- FIG. 1 shows one embodiment of a method for producing toner of the present invention
- FIG. 2 shows one embodiment of an apparatus for producing toner of the present invention
- FIG. 3 is a plot of the volume median particle size distribution of the two blended-polymer binders
- FIG. 4 is a plot of the particle size dispersity index of the blended-polymer binders of FIG. 3 ;
- FIG. 5 is a plot of the particle size distribution for a conventional toner and for one embodiment of a toner of the present invention.
- Method 10 includes the processes of dry blending 12 , melt mixing 14 , extruding 16 , particle size reduction 18 and classifying 20 .
- Dry blending process 12 includes the blending together of more than one polymer binder resin P 1 , P 2 , . . . and P N , at least one of which is a thermoplastic binder resin, with other ingredients generally designated A that are conventionally used in toner, such as, for example, colorants, charge control agents, waxes, and other additives to produce a dry blend toner formulation or dry mix T.
- the polymer binders P 1 , P 2 , . . . and P N and the other ingredients/additives A are mixed or blended together using a blender 22 ( FIG. 2 ), such as, for example, a high-speed blender manufactured by Henschel Industrietechnik GmbH.
- Polymer binder resins P 1 , P 2 , . . . and P N include polyesters, polyamides, polyolefins, acrylic polymers and copolymers, methacrylic polymers and copolymers, styrenic polymers and copolymers, vinyl polymers and copolymers, and polyurethanes. If two polymer binder resins P 1 and P 2 of the same chemical composition are blended together to form blended-polymer dry mix T, it is not necessary to have a difference in the physical composition of the polymer resin binders. However, it is preferable that the polymer binder resins P 1 and P 2 have different physico-chemical compositions.
- the blend of polymer binder resins suitable for use in blended-polymer dry mix T may also be achieved by multi-block copolymer polymerization.
- Dry mix toner formulation T is approximately 1 to approximately 30 percent by weight of one or more colorants, and approximately 70 to approximately 99 percent by weight of the combined polymer binder resins P 1 , P 2 , . . . and P N .
- dry mix T is approximately 4 to approximately 20 percent by weight of one or more colorants, and approximately 80 to approximately 96 percent by weight of combined polymer binder resins P 1 , P 2 , . . . and P N .
- dry mix T is approximately 6 to approximately 10 percent by weight of one or more colorants, and approximately 90 to approximately 94 percent by weight of combined polymer binder resins P 1 , P 2 , . . . and P N .
- Dry mix T may also include ingredients, such as, for example, a charge agent, waxy-like release agent, or other additives.
- Dry mix T when made with two polymer binder resins, is approximately 5 to approximately 95 percent by weight of first thermoplastic polymer P 1 and approximately 95 to approximately 5 percent by weight of second thermoplastic polymer P 2 .
- dry mix T is approximately 20 to approximately 40 percent by weight of first thermoplastic polymer P 1 and approximately 80 to approximately 60 percent by weight of second thermoplastic polymer P 2 .
- Melt mixing process 14 is carried out by processing blended-polymer dry mix T through a conventional melt mixing apparatus 24 , such as, for example, an extruder, roll mill or kneading mill, at conventional melt mixing temperatures of approximately 60° C. to approximately 160° C. and preferably approximately 120° C. Thereafter, extruding process 16 is similarly carried out by conventional methods/means thereby producing toner extrudate E.
- a conventional melt mixing apparatus 24 such as, for example, an extruder, roll mill or kneading mill
- Particle size reduction process 18 is then conducted upon extrudate E.
- Particle size reduction process 18 utilizes conventional particle size reduction apparatus 26 , such as, for example, a jet mill, air mill, pulverizer, or grinder, and conventional particle size reduction process parameters to reduce the particle size of toner extrudate E.
- particle size reduction apparatus 26 is accomplished by processing extrudate E with a jet mill pulverizer operating with a pressure of less than 200 pounds per square inch (psi.) and preferably below approximately 115 psi.
- Raw and unclassified toner U produced by particle size reduction process 18 is then provided to classifying process 20 .
- Classifying process 20 is also carried out using a conventional cyclone apparatus 28 and/or classifying apparatus 30 as required or preferred.
- the undesirably fine and/or dust particles, often referred to collectively as super-fine particles, contained within unclassified toner U are carried by a pressurized flow of air or gas from cyclone 28 into a dust collector 32 .
- the classifier 30 receives the remainder of the unclassified toner U from cyclone 28 , sorts or classifies the unclassified toner U based on particle size, and delivers classified toner powder C having a desired range of particle sizes (i.e., classified product) to other processing equipment, such as, for example, a bulk container or bulk container-filling apparatus (not shown).
- the volume median particle size achieved is significantly less than the volume median particle size that is achieved by a substantially-identical particle size reduction process performed on a conventional toner extrudate having a single polymer binder resin. Further, a tighter particle size distribution is obtained along with a desirable and significant reduction in fine and super fine particles.
- a first plurality of blended-polymer toner batches, collectively referred to hereinafter as B 1 , absent any pigment was prepared by melt blending two resins and a charge control agent at approximately 115-120° C. on a two roll mill.
- the first polyester being a Binder W-85 very similar to a propoxylated bisphenol A-terephthalic acid based polyester
- the second polyester being a Binder C very similar to a propoxylated bisphenol A, a fumaric/maleic acid based polyester, both marketed as toner binder resins and available from Kao Corporation of Tokyo, Japan.
- the charge control agent, Bontron E-84 available from Orient Chemical Corporation of Japan was present at the same concentration, i.e., approximately 3 parts per hundred (pph).
- a second plurality of blended-polymer toner batches, collectively referred to hereinafter as B 2 , of clear toner was similarly prepared by melt blending two resins and a charge control agent at approximately 115-120 ° C. on a two roll mill.
- the first polyester in this second batch of toner was also Binder W-85, as described above, and the second Binder TF-90, very similar to a terpolymer of propoxylated bisphenol A-terephthalic acid and fumaric acid based polyester, also available from Kao Corporation of Tokyo, Japan.
- the ratio of the first binder to the second binder in each batch of the plurality of blended-polymer toner batches B 1 and B 2 is varied from 100:0, 80:20, 60:40, 40:60, 20:80, and 0:100.
- FIG. 3 the volume median particle sizes for the first and second blended-polymer toner batches B 1 and B 2 are plotted against the percentage of the second binder type present in each toner batch.
- FIG. 3 it is seen that when either toner batch contains none of the second binder type (i.e., containing zero percent of the second binder type which corresponds to the vertical axis of the FIG. 3 plot) that toner batch is ground to a substantially smaller particle size than a toner batch containing none of the first binder type (i.e., containing one-hundred percent of the second toner which corresponds to the extreme right-hand side of the FIG. 3 plot).
- FIG. 3 it is seen that when either toner batch contains none of the second binder type (i.e., containing zero percent of the second binder type which corresponds to the vertical axis of the FIG. 3 plot) that toner batch is ground to a substantially smaller particle size than a toner batch containing none of the first binder type (i.e., containing one
- the first binder type and/or a toner containing substantially only the first binder type is reduced or ground to a significantly smaller particle size than the second binder type and/or a toner containing only the second binder type. Further, adding relatively small amounts, such as, for example, less than approximately fifty percent, of the second binder type to a toner batch does not significantly adversely affect (i.e., does not significantly increase) the particle sizes to which the toner batches are reduced or ground.
- toner batches that have a certain percentage or range of percentages of the second binder type exhibit a desirably reduced (i.e., narrower) particle size dispersity index (PSDI).
- PSDI is defined as the ratio of the volume median particle size of toner particles to the number median particle size thereof.
- toner that includes a certain concentration, such as, for example, from approximately ten to approximately sixty percent, of a second binder type has a significantly and desirably reduced (i.e., narrowed) particle size distribution and a more desirably PSDI.
- a conventional, single polymer toner extrudate was prepared by melt blending in a 30 millimeter (mm) twin-screw extruder Regal 330 carbon black pigment, obtained from by Cabot Corporation, Billerica, Mass., USA, with Binder C polyester, obtained from Kao Corporation of Tokyo, Japan, and with 2 parts per hundred (pph) Bontron E-84 charge agent such that the final pigment concentration was 4.5 parts of pigment per 100 parts resin by weight.
- the pigment concentration was chosen for specific calorimetric properties not pertinent to the invention.
- the toner extrudate was cooled out of the extruder using a chill-belt and granulated in a Wiley-type mill into granules of approximately 500 microns in size.
- the above described granulated black toner extrudate was then pulverized using a Hosokawa-Alpine 200 AFG jet mill pulverizer at a nozzle pressure of approximately 80 pounds per square inch and an average rotor speed of approximately 11,500 revolutions per minute to produce an unclassified toner.
- the unclassified toner had a volume-median particle size of approximately 5.26 microns and a number-median particle size of approximately 3.44 microns as measured on a Coulter Mutlisizer with a 70 ⁇ aperture.
- PSDI particle size dispersity index
- model number of the mill is specific to the size of the mill, and is independent of the experimental data presented herein.
- a second conventional single-polymer toner extrudate was prepared by melt blending in a 30 mm twin-screw extruder Regal 330 carbon black pigment, obtained from Cabot Corporation, Billerica, Mass. USA, with Binder W-85 polyester, obtained from Kao Corporation of Tokyo, Japan, and with 2 pph Bontron E-84 charge agent such that the final pigment concentration was 6.0 parts of pigment per 100 parts resin by weight.
- the pigment concentration was chosen for specific colorimetric properties not pertinent to the invention.
- the toner extrudate was cooled out of the extruder through a chill-belt and granulated in a Wiley-type mill into granules of approximately 500 microns in size.
- the above-described granulated black toner extrudate was then pulverized using a Hosokawa-Alpine 200 AFG jet mill pulverizer at a nozzle pressure of approximately 80 psi with an average rotor speed of approximately 10,500 revolutions per minute.
- An unclassified toner was produced having a volume-median particle size of approximately 3.77 microns ( ⁇ ) and a 2.46 number-median particle size as measured on a Coulter Multisizer with a 30 ⁇ aperture.
- a particle size dispersity index of 1.53 was also obtained.
- Example 2 Comparing the above examples shows that substantially identical pulverization processes were applied to the conventional single-polymer toner extrudates of Examples 1 and 2, and yet the unclassified toner produced in Example 2 had a smaller volume-median particle size (approximately 3.46 ⁇ ) than the unclassified toner produced in Example 1. It should be particularly noted, however, that the unclassified toner produced in Example 2 had a significantly higher amount of super-fine particulates (i.e., particles of less than approximately 2 microns) than the unclassified toner produced in Example 1. The higher amount of super-fine particulates makes classification of the unclassified toner produced in Example 2 a more difficult, time consuming and costly process. Thus, although a desirably smaller volume-median particle size was achieved in Example 2, a less desirable particle size distribution resulted.
- super-fine particulates i.e., particles of less than approximately 2 microns
- the pulverization rates of both batches of granulated black toner extrudate were approximately 3 kilograms per hour.
- the pulverization rate in general, was limited by the practical limit of the rotor speed, which, in turn, limits the particle size.
- the pulverization rate is indicative of the lower limit of fracture size for the toner formulation/extrudate.
- the method of the present invention processes blended-polymer dry mix T through the same or substantially the same conventional non-chemical pulverizing methods and/or processes, and yet produces an unclassified toner U desirably having a smaller volume-median particle size, a tighter distribution of particle sizes, and a significantly smaller amount of super-fine particles.
- extrudate E was prepared by melt blending in a 30 mm twin-screw extruder Regal 330 carbon black pigment, obtained from Cabot Corporation of Billerica, Mass., U.S.A., with 2 pph Bontron E-84 charge agent, and with a blend of two polyesters.
- the polyesters in this exemplary embodiment were Binder C and binder W-85, both of which were obtained from Kao Corporation of Tokyo, Japan.
- the ratio of the two polyesters was 20 percent to 80 percent of the 100 parts total resin.
- the final pigment concentration was 6.0 parts of pigment per 100 parts resin by weight.
- the pigment concentration was chosen for specific colorimetric properties not pertinent to the invention.
- the toner extrudate E was cooled out of the extruder through a chill-belt, and granulated in a Wiley-type mill into granules of approximately 500 micron in size.
- the above-described granulated black toner extrudate E was then pulverized on a Hosokawa-Alpine 200 AFG jet mill pulverizer, using a nozzle pressure of approximately 80 psi, an average rotor speed of approximately 11,500 revolutions per minute, and a bed level indicted by the rotor current of 2.6 amps.
- An unclassified toner powder U was thereby produced having a volume-median particle size of approximately 3.72 microns and a 2.61 number-median particle size as measured on a Coulter Multisizer using a 30 micron aperture. Thus, a particle size dispersity index of 1.42 was also obtained.
- FIG. 5 the volume and number particle size distributions for the unclassified toner powder U of inventive example 1 are plotted. More particularly, the volume distribution for the unclassified blended-polymer toner powder U of inventive example 1 is shown by curve V 1 and the number particle size distribution for the unclassified blended-polymer toner powder U of inventive example 1 is shown by curve N 1 . Similarly, FIG. 5 also plots as curves V 2 and N 2 , respectively, the volume particle size distribution and the number particle size distribution for the conventional (unclassified) toner described above in Example 2.
- the volume distribution curve V 1 for the unclassified blended-polymer toner powder U of inventive example 1 has a peak at a smaller volume average particle size than the peak of the volume distribution curve V 2 for the conventional (unclassified) toner described above in Example 2.
- the number particle size distribution curve N 1 for the unclassified blended-polymer toner powder U of inventive example 1 lies above the number particle size distribution curve N 2 for the conventional toner of Example 2. Since the area under each of curves N 1 and N 2 indicates the number of particles of a given size, and since for particle sizes of less than approximately 2 ⁇ the area under curve N 1 is less than the area under curve N 2 , it is shown that the toner of inventive Example 1 has a substantially reduced number of fine or super fine particles.
- curves N 1 and N 2 of FIG. 5 represent and generally correspond to extrapolations of a “best case” condition in terms of the quantity of particles having a particle size of less than approximately 1 micron for curve N 1 .
- curve N 1 is likely to become more horizontal in nature, and may even reverse its slope to a positive value and at least temporarily trend upward.
- inventive example 1 is likely to be significantly more advantageous than illustrated therein.
- the unclassified blended-polymer toner powder U of inventive example 1 has a desirably smaller volume median particle size and desirably has significantly fewer fine and super fine particles than conventional single-polymer toners.
- the unclassified blended-polymer toner powder U of inventive example 1 is therefore more readily and less expensively classified than conventional single-polymer toners.
- the lower limit of volume-median particle size that can be achieved from conventional pulverizing and microtoner processing equipment and methods is reduced by using a blended-polymer dry mix T that has a lower limit of fracture size.
- two polymer binder resins are combined to produce a dry mix T having a reduced particle size, tighter particle size distribution, and fewer fine and super fine particles relative to conventional single-polymer toners.
- the binders are generally described as being present from approximately 5 to approximately 95 percent by weight for the first thermoplastic polymer and approximately 95 to approximately 5 percent by weight of the second thermoplastic polymer.
- similar benefits can be achieved by adding or mixing as little as one percent of a second polymer to a first polymer or by adding/synthesizing a multi-block copolymer for use in and/or addition to the mix.
- the particular proportions of the mix and the benefits obtained are dependent upon the specific polymers involved and their respective physical properties and fracture mechanics.
- the process of producing the toner of the present invention blends the polymers prior to the melt mixing operation/process.
- the process can be alternately configured, such as, for example, blending the polymers before or during the melt mix and extruding processes, and/or before the pulverization process.
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Abstract
Description
- The present invention relates to toner for use in electrophotographic processes and/or printing machines, and a method for producing such toner particles.
- The toner used in electrophotographic printing machines is a blend of materials, including plastic binder resins, coloring pigments, such as, for example, carbon black, magnetic iron oxides, waxes, and charge control agents and other ingredients. Most toners are produced in bulk using a melt mixing or hot compounding process. The plastic binder resins, coloring pigments and other ingredients are blended together while in a molten state to thereby form a hot paste having a consistency similar to cake mix. This mixture is then cooled, typically, by forming it into slabs on a cooling belt or by pelletizing the mixture and cooling the pellets. The raw toner is then ground or pulverized into a toner powder by, for example, jet mills or air-swept hammer mills.
- This process produces a toner powder having a wide range or distribution of particle sizes. Generally, toner having a narrow distribution of relatively small or fine particle sizes is preferable in that such toner produces higher-quality images. Therefore, the toner powder is sifted or classified to remove over-size and under-size toner particles. A toner powder having a relatively narrow distribution around a desired particle size is thus produced. The toner powder is then blended with additives to adjust various properties, such as, for example, flow, and electrostatic properties, and packaged for use.
- Since the binder resin is the dominant component of toner formulations, typically constituting greater than eighty percent and often greater than ninety percent by weight of the toner formulation, the fracture mechanics of the binder resin is the limiting factor in reducing toner particle size. The fracture mechanics of the binder resin also limits the rate at which a given particle size is obtained. Further, as the particle size of the binder resin decreases the rate at which particle size reduction occurs also decreases.
- Toner binders are typically mechanically reduced (i.e., by non-chemical methods, such as, for example, by grinding, milling, or pulverizing) to a volume median particle size of from approximately 6 to approximately 12 microns (μ), and the particles are then classified to produce a toner having a desired particle-size distribution. Mechanically reducing toner binder resin particles to a size of less than approximately 5μ is relatively inefficient due to the reduced rate at which particle-size-reduction occurs in such small-size particles. Thus, in general, it is not economically feasible to produce a toner powder with toner binder resin particles that have been mechanically reduced to particle sizes of approximately 5μ or less. Further, the relatively wide particle-size distribution that results from mechanically reducing toner binder resin particles to particle sizes of approximately 5μ or less makes classification of the particles into a narrow distribution of particle sizes difficult. Certain chemical processing methods are capable of producing such small binder resin particle sizes and narrow particle size distributions. However, the chemical methods require the purchase, storage, handling, and disposal of chemicals that may be hazardous or toxic. Further, the chemical methods must be closely controlled and monitored, and are not as environmentally friendly as the mechanical methods.
- Therefore, what is needed in the art is a toner formulation that enables the production by mechanical particle size reduction methods of a toner having a volume-average particle size of the same order of magnitude as the volume-average particle size produced by chemical particle size reduction processes.
- Furthermore, what is needed in the art is a method of producing a toner using mechanical particle size reduction processes and achieving a volume-average particle size of the same order of magnitude as the volume-average particle size produced by chemical particle size reduction processes.
- The present invention provides a particulate microtoner and method for producing same.
- The invention comprises, in one form thereof, a microtoner including a blend of at least one polymer and at least one thermoplastic polymer. The method of producing the microtoner includes blending the at least one polymer with the at least one thermoplastic polymer and with one or more pigments to thereby form a toner formulation. The toner formulation is pulverized by mechanical means into an unclassified particulate microtoner. The unclassified particulate microtoner is then classified.
- An advantage of the present invention is that a microtoner having a volume-median particle size approximately equal to the particle sizes achieved by chemical particle size reduction methods is produced using conventional mechanical non-chemical particle size reduction means and/or methods.
- A further advantage of the present invention is that the microtoner has a particle size distribution that is desirably smaller or tighter than the particle size distribution of conventional microtoner produced by conventional means.
- The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become apparent and be better understood by reference to the following description of one embodiment of the invention in conjunction with the accompanying drawings, wherein:
-
FIG. 1 shows one embodiment of a method for producing toner of the present invention; -
FIG. 2 shows one embodiment of an apparatus for producing toner of the present invention; -
FIG. 3 is a plot of the volume median particle size distribution of the two blended-polymer binders; -
FIG. 4 is a plot of the particle size dispersity index of the blended-polymer binders ofFIG. 3 ; and -
FIG. 5 is a plot of the particle size distribution for a conventional toner and for one embodiment of a toner of the present invention. - Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate one preferred embodiment of the invention, in one form, and such exemplifications are not to be construed as limiting the scope of the invention in any manner.
- Referring now to
FIGS. 1 and 2 , there is respectively shown one embodiment of a method and one embodiment of an apparatus for producing toner of the present invention.Method 10 includes the processes ofdry blending 12, melt mixing 14, extruding 16,particle size reduction 18 and classifying 20. -
Dry blending process 12 includes the blending together of more than one polymer binder resin P1, P2, . . . and PN, at least one of which is a thermoplastic binder resin, with other ingredients generally designated A that are conventionally used in toner, such as, for example, colorants, charge control agents, waxes, and other additives to produce a dry blend toner formulation or dry mix T. The polymer binders P1, P2, . . . and PN and the other ingredients/additives A are mixed or blended together using a blender 22 (FIG. 2 ), such as, for example, a high-speed blender manufactured by Henschel Industrietechnik GmbH. - Polymer binder resins P1, P2, . . . and PN include polyesters, polyamides, polyolefins, acrylic polymers and copolymers, methacrylic polymers and copolymers, styrenic polymers and copolymers, vinyl polymers and copolymers, and polyurethanes. If two polymer binder resins P1 and P2 of the same chemical composition are blended together to form blended-polymer dry mix T, it is not necessary to have a difference in the physical composition of the polymer resin binders. However, it is preferable that the polymer binder resins P1 and P2 have different physico-chemical compositions. The blend of polymer binder resins suitable for use in blended-polymer dry mix T may also be achieved by multi-block copolymer polymerization.
- Dry mix toner formulation T is approximately 1 to approximately 30 percent by weight of one or more colorants, and approximately 70 to approximately 99 percent by weight of the combined polymer binder resins P1, P2, . . . and PN. Preferably, dry mix T is approximately 4 to approximately 20 percent by weight of one or more colorants, and approximately 80 to approximately 96 percent by weight of combined polymer binder resins P1, P2, . . . and PN. Most preferably, dry mix T is approximately 6 to approximately 10 percent by weight of one or more colorants, and approximately 90 to approximately 94 percent by weight of combined polymer binder resins P1, P2, . . . and PN. Dry mix T may also include ingredients, such as, for example, a charge agent, waxy-like release agent, or other additives.
- Dry mix T, when made with two polymer binder resins, is approximately 5 to approximately 95 percent by weight of first thermoplastic polymer P1 and approximately 95 to approximately 5 percent by weight of second thermoplastic polymer P2. Preferably, dry mix T is approximately 20 to approximately 40 percent by weight of first thermoplastic polymer P1 and approximately 80 to approximately 60 percent by weight of second thermoplastic polymer P2.
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Melt mixing process 14 is carried out by processing blended-polymer dry mix T through a conventionalmelt mixing apparatus 24, such as, for example, an extruder, roll mill or kneading mill, at conventional melt mixing temperatures of approximately 60° C. to approximately 160° C. and preferably approximately 120° C. Thereafter,extruding process 16 is similarly carried out by conventional methods/means thereby producing toner extrudate E. - Particle
size reduction process 18 is then conducted upon extrudate E. Particlesize reduction process 18 utilizes conventional particlesize reduction apparatus 26, such as, for example, a jet mill, air mill, pulverizer, or grinder, and conventional particle size reduction process parameters to reduce the particle size of toner extrudate E. For example, particlesize reduction apparatus 26 is accomplished by processing extrudate E with a jet mill pulverizer operating with a pressure of less than 200 pounds per square inch (psi.) and preferably below approximately 115 psi. Raw and unclassified toner U produced by particlesize reduction process 18 is then provided to classifyingprocess 20. - Classifying
process 20 is also carried out using aconventional cyclone apparatus 28 and/or classifyingapparatus 30 as required or preferred. The undesirably fine and/or dust particles, often referred to collectively as super-fine particles, contained within unclassified toner U are carried by a pressurized flow of air or gas fromcyclone 28 into adust collector 32. Theclassifier 30 receives the remainder of the unclassified toner U fromcyclone 28, sorts or classifies the unclassified toner U based on particle size, and delivers classified toner powder C having a desired range of particle sizes (i.e., classified product) to other processing equipment, such as, for example, a bulk container or bulk container-filling apparatus (not shown). - As illustrated in the following Examples, by performing
method 10 generally, and particlesize reduction process 18 particularly, upon toner extrudate E formed from the blended-polymer dry mix toner formulation T of the present invention the volume median particle size achieved is significantly less than the volume median particle size that is achieved by a substantially-identical particle size reduction process performed on a conventional toner extrudate having a single polymer binder resin. Further, a tighter particle size distribution is obtained along with a desirable and significant reduction in fine and super fine particles. - General Blended Polymer Example
- A first plurality of blended-polymer toner batches, collectively referred to hereinafter as B1, absent any pigment was prepared by melt blending two resins and a charge control agent at approximately 115-120° C. on a two roll mill. The first polyester being a Binder W-85 very similar to a propoxylated bisphenol A-terephthalic acid based polyester, and the second polyester being a Binder C very similar to a propoxylated bisphenol A, a fumaric/maleic acid based polyester, both marketed as toner binder resins and available from Kao Corporation of Tokyo, Japan. The charge control agent, Bontron E-84 available from Orient Chemical Corporation of Japan, was present at the same concentration, i.e., approximately 3 parts per hundred (pph).
- A second plurality of blended-polymer toner batches, collectively referred to hereinafter as B2, of clear toner was similarly prepared by melt blending two resins and a charge control agent at approximately 115-120 ° C. on a two roll mill. The first polyester in this second batch of toner was also Binder W-85, as described above, and the second Binder TF-90, very similar to a terpolymer of propoxylated bisphenol A-terephthalic acid and fumaric acid based polyester, also available from Kao Corporation of Tokyo, Japan. The charge control agent, Bontron E-84 available from Orient Chemical Corporation of Japan, was present at a concentration of approximately 3 parts per hundred (pph).
- The ratio of the first binder to the second binder in each batch of the plurality of blended-polymer toner batches B1 and B2 is varied from 100:0, 80:20, 60:40, 40:60, 20:80, and 0:100.
- Referring now to
FIG. 3 , the volume median particle sizes for the first and second blended-polymer toner batches B1 and B2 are plotted against the percentage of the second binder type present in each toner batch. As shown inFIG. 3 , it is seen that when either toner batch contains none of the second binder type (i.e., containing zero percent of the second binder type which corresponds to the vertical axis of theFIG. 3 plot) that toner batch is ground to a substantially smaller particle size than a toner batch containing none of the first binder type (i.e., containing one-hundred percent of the second toner which corresponds to the extreme right-hand side of theFIG. 3 plot). Thus,FIG. 3 shows that the first binder type and/or a toner containing substantially only the first binder type is reduced or ground to a significantly smaller particle size than the second binder type and/or a toner containing only the second binder type. Further, adding relatively small amounts, such as, for example, less than approximately fifty percent, of the second binder type to a toner batch does not significantly adversely affect (i.e., does not significantly increase) the particle sizes to which the toner batches are reduced or ground. - Moreover, and as best shown in
FIG. 4 , toner batches that have a certain percentage or range of percentages of the second binder type exhibit a desirably reduced (i.e., narrower) particle size dispersity index (PSDI). PSDI is defined as the ratio of the volume median particle size of toner particles to the number median particle size thereof. AsFIG. 4 shows, toner that includes a certain concentration, such as, for example, from approximately ten to approximately sixty percent, of a second binder type has a significantly and desirably reduced (i.e., narrowed) particle size distribution and a more desirably PSDI. - Thus, it is shown that a desirable reduction in volume median particle size and a desirable reduction in particle size distribution are achieved when mechanically reducing or grinding a toner formed from a blend of more than one polymer.
- A conventional, single polymer toner extrudate was prepared by melt blending in a 30 millimeter (mm) twin-screw extruder Regal 330 carbon black pigment, obtained from by Cabot Corporation, Billerica, Mass., USA, with Binder C polyester, obtained from Kao Corporation of Tokyo, Japan, and with 2 parts per hundred (pph) Bontron E-84 charge agent such that the final pigment concentration was 4.5 parts of pigment per 100 parts resin by weight. The pigment concentration was chosen for specific calorimetric properties not pertinent to the invention. The toner extrudate was cooled out of the extruder using a chill-belt and granulated in a Wiley-type mill into granules of approximately 500 microns in size.
- The above described granulated black toner extrudate was then pulverized using a Hosokawa-Alpine 200 AFG jet mill pulverizer at a nozzle pressure of approximately 80 pounds per square inch and an average rotor speed of approximately 11,500 revolutions per minute to produce an unclassified toner.
- The unclassified toner had a volume-median particle size of approximately 5.26 microns and a number-median particle size of approximately 3.44 microns as measured on a Coulter Mutlisizer with a 70μ aperture. Thus, a particle size dispersity index (PSDI), which is the ratio of the volume-median particle size to the number-median particle size, of 1.53 was obtained.
- It is to be understood that the model number of the mill is specific to the size of the mill, and is independent of the experimental data presented herein.
- A second conventional single-polymer toner extrudate was prepared by melt blending in a 30 mm twin-screw extruder Regal 330 carbon black pigment, obtained from Cabot Corporation, Billerica, Mass. USA, with Binder W-85 polyester, obtained from Kao Corporation of Tokyo, Japan, and with 2 pph Bontron E-84 charge agent such that the final pigment concentration was 6.0 parts of pigment per 100 parts resin by weight. The pigment concentration was chosen for specific colorimetric properties not pertinent to the invention. The toner extrudate was cooled out of the extruder through a chill-belt and granulated in a Wiley-type mill into granules of approximately 500 microns in size.
- The above-described granulated black toner extrudate was then pulverized using a Hosokawa-Alpine 200 AFG jet mill pulverizer at a nozzle pressure of approximately 80 psi with an average rotor speed of approximately 10,500 revolutions per minute. An unclassified toner was produced having a volume-median particle size of approximately 3.77 microns (μ) and a 2.46 number-median particle size as measured on a Coulter Multisizer with a 30μ aperture. Thus, a particle size dispersity index of 1.53 was also obtained.
- Comparing the above examples shows that substantially identical pulverization processes were applied to the conventional single-polymer toner extrudates of Examples 1 and 2, and yet the unclassified toner produced in Example 2 had a smaller volume-median particle size (approximately 3.46μ) than the unclassified toner produced in Example 1. It should be particularly noted, however, that the unclassified toner produced in Example 2 had a significantly higher amount of super-fine particulates (i.e., particles of less than approximately 2 microns) than the unclassified toner produced in Example 1. The higher amount of super-fine particulates makes classification of the unclassified toner produced in Example 2 a more difficult, time consuming and costly process. Thus, although a desirably smaller volume-median particle size was achieved in Example 2, a less desirable particle size distribution resulted.
- The pulverization rates of both batches of granulated black toner extrudate were approximately 3 kilograms per hour. The pulverization rate, in general, was limited by the practical limit of the rotor speed, which, in turn, limits the particle size. Thus, the pulverization rate is indicative of the lower limit of fracture size for the toner formulation/extrudate.
- In contrast to the above examples, the method of the present invention processes blended-polymer dry mix T through the same or substantially the same conventional non-chemical pulverizing methods and/or processes, and yet produces an unclassified toner U desirably having a smaller volume-median particle size, a tighter distribution of particle sizes, and a significantly smaller amount of super-fine particles.
- More particularly, extrudate E was prepared by melt blending in a 30 mm twin-screw extruder Regal 330 carbon black pigment, obtained from Cabot Corporation of Billerica, Mass., U.S.A., with 2 pph Bontron E-84 charge agent, and with a blend of two polyesters. The polyesters in this exemplary embodiment were Binder C and binder W-85, both of which were obtained from Kao Corporation of Tokyo, Japan. The ratio of the two polyesters was 20 percent to 80 percent of the 100 parts total resin. The final pigment concentration was 6.0 parts of pigment per 100 parts resin by weight. The pigment concentration was chosen for specific colorimetric properties not pertinent to the invention. The toner extrudate E was cooled out of the extruder through a chill-belt, and granulated in a Wiley-type mill into granules of approximately 500 micron in size.
- The above-described granulated black toner extrudate E was then pulverized on a Hosokawa-Alpine 200 AFG jet mill pulverizer, using a nozzle pressure of approximately 80 psi, an average rotor speed of approximately 11,500 revolutions per minute, and a bed level indicted by the rotor current of 2.6 amps. An unclassified toner powder U was thereby produced having a volume-median particle size of approximately 3.72 microns and a 2.61 number-median particle size as measured on a Coulter Multisizer using a 30 micron aperture. Thus, a particle size dispersity index of 1.42 was also obtained.
- Discussion
- Referring now to
FIG. 5 , the volume and number particle size distributions for the unclassified toner powder U of inventive example 1 are plotted. More particularly, the volume distribution for the unclassified blended-polymer toner powder U of inventive example 1 is shown by curve V1 and the number particle size distribution for the unclassified blended-polymer toner powder U of inventive example 1 is shown by curve N1. Similarly,FIG. 5 also plots as curves V2 and N2, respectively, the volume particle size distribution and the number particle size distribution for the conventional (unclassified) toner described above in Example 2. Comparing the plots, it is seen that the volume distribution curve V1 for the unclassified blended-polymer toner powder U of inventive example 1 has a peak at a smaller volume average particle size than the peak of the volume distribution curve V2 for the conventional (unclassified) toner described above in Example 2. - Further, as
FIG. 5 shows, for particle size values of less than approximately two microns the number particle size distribution curve N1 for the unclassified blended-polymer toner powder U of inventive example 1 lies above the number particle size distribution curve N2 for the conventional toner of Example 2. Since the area under each of curves N1 and N2 indicates the number of particles of a given size, and since for particle sizes of less than approximately 2μ the area under curve N1 is less than the area under curve N2, it is shown that the toner of inventive Example 1 has a substantially reduced number of fine or super fine particles. - It should be particularly noted that the dashed-line extensions of curves N1 and N2 of
FIG. 5 represent and generally correspond to extrapolations of a “best case” condition in terms of the quantity of particles having a particle size of less than approximately 1 micron for curve N1. In practice, curve N1 is likely to become more horizontal in nature, and may even reverse its slope to a positive value and at least temporarily trend upward. Thus, it is likely that the toner of Example 1 will undesirably contain a significantly greater number of fine and super fine particles than is shown byFIG. 5 , and therefore inventive example 1 is likely to be significantly more advantageous than illustrated therein. - In summary, the unclassified blended-polymer toner powder U of inventive example 1 has a desirably smaller volume median particle size and desirably has significantly fewer fine and super fine particles than conventional single-polymer toners. The unclassified blended-polymer toner powder U of inventive example 1 is therefore more readily and less expensively classified than conventional single-polymer toners. Furthermore, it is seen that the lower limit of volume-median particle size that can be achieved from conventional pulverizing and microtoner processing equipment and methods is reduced by using a blended-polymer dry mix T that has a lower limit of fracture size.
- Table 1 summarizes the above results:
TABLE 1 Volume median Number Median Particle size Particle Size Toner (μ) (μ) PSDI Example 1 5.26 3.44 1.53 Example 2 3.77 2.46 1.53 Inventive 3.72 2.61 1.42 Example 1 - In the embodiments shown and described, two polymer binder resins are combined to produce a dry mix T having a reduced particle size, tighter particle size distribution, and fewer fine and super fine particles relative to conventional single-polymer toners. The binders are generally described as being present from approximately 5 to approximately 95 percent by weight for the first thermoplastic polymer and approximately 95 to approximately 5 percent by weight of the second thermoplastic polymer. However, it is to be understood that similar benefits can be achieved by adding or mixing as little as one percent of a second polymer to a first polymer or by adding/synthesizing a multi-block copolymer for use in and/or addition to the mix. The particular proportions of the mix and the benefits obtained are dependent upon the specific polymers involved and their respective physical properties and fracture mechanics.
- In the embodiments shown, the process of producing the toner of the present invention blends the polymers prior to the melt mixing operation/process. However, it is to be understood that the process can be alternately configured, such as, for example, blending the polymers before or during the melt mix and extruding processes, and/or before the pulverization process.
- While this invention has been described as having a preferred design, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the present invention using the general principles disclosed herein. Further, this application is intended to cover such departures from the present disclosure as come within the known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
-
- 10. Process
- 12. Dry Blend Process
- 14. Melt mixing process
- 16. Extruding process
- 18. Pulverizing process
- 20. Classifying
- 22. Blender
- 24. Melt Mixer
- 26. Particle size reducing apparatus
- P1, P2, P3 . . . PN—Polymer Binder Resins
- B1 B2—Toner batches
- T—Dry Mix Toner Formulation
- A—Additives
- E—Extrudate
- U—Unclassified Toner
- C—Classified Toner
Claims (34)
Priority Applications (1)
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US10/887,967 US20060087052A1 (en) | 2004-07-09 | 2004-07-09 | Microtoner formulations having blended copolymers of a first and second resin and method of producing same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US10/887,967 US20060087052A1 (en) | 2004-07-09 | 2004-07-09 | Microtoner formulations having blended copolymers of a first and second resin and method of producing same |
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US20060087052A1 true US20060087052A1 (en) | 2006-04-27 |
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US10/887,967 Abandoned US20060087052A1 (en) | 2004-07-09 | 2004-07-09 | Microtoner formulations having blended copolymers of a first and second resin and method of producing same |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060127791A1 (en) * | 2003-08-13 | 2006-06-15 | Eastman Kodak Company | Creation of different gloss values in print |
US20100304142A1 (en) * | 2009-05-27 | 2010-12-02 | Toshiba Tec Kabushiki Kaisha | Color erasable recording material and method for producing the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5571655A (en) * | 1995-04-17 | 1996-11-05 | Xerox Corporation | Toner reactive melt mixing process |
US20030064313A1 (en) * | 2001-03-28 | 2003-04-03 | Fuji Photo Film Co., Ltd. | Process for forming image |
US20030124446A1 (en) * | 2001-12-28 | 2003-07-03 | Toyo Ink Manufacturing Co., Ltd. | Electrostatic image developing toner and image-forming method using the same |
US20030190543A1 (en) * | 2001-12-14 | 2003-10-09 | Hideki Sugiura | External additives for electrophotographic toner, electrophotographic toner, electrophotographic developer, image forming method and image forming apparatus |
-
2004
- 2004-07-09 US US10/887,967 patent/US20060087052A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5571655A (en) * | 1995-04-17 | 1996-11-05 | Xerox Corporation | Toner reactive melt mixing process |
US20030064313A1 (en) * | 2001-03-28 | 2003-04-03 | Fuji Photo Film Co., Ltd. | Process for forming image |
US20030190543A1 (en) * | 2001-12-14 | 2003-10-09 | Hideki Sugiura | External additives for electrophotographic toner, electrophotographic toner, electrophotographic developer, image forming method and image forming apparatus |
US20030124446A1 (en) * | 2001-12-28 | 2003-07-03 | Toyo Ink Manufacturing Co., Ltd. | Electrostatic image developing toner and image-forming method using the same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060127791A1 (en) * | 2003-08-13 | 2006-06-15 | Eastman Kodak Company | Creation of different gloss values in print |
US20100304142A1 (en) * | 2009-05-27 | 2010-12-02 | Toshiba Tec Kabushiki Kaisha | Color erasable recording material and method for producing the same |
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