Classifications

• • 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
  • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G9/08706—Polymers of alkenyl-aromatic compounds
  • G03G9/08708—Copolymers of styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/02—Hydrogenation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/04—Reduction, e.g. hydrogenation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/10—Copolymers of styrene with conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/06—Copolymers with vinyl aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
  • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D135/06—Copolymers with vinyl aromatic monomers
• • 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
• • 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
  • G03G9/08775—Natural macromolecular compounds or derivatives thereof
  • G03G9/08782—Waxes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2391/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
  • C08J2391/06—Waxes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes

Definitions

• the present invention relates waxes and, more particularly how to incorporate waxes in electrophotographic toners to improve toner performance.
• Waxes are incorporated into electrophotographic toners to aid release from the fuser roller surfaces, without the need to use silicone oil.
• the domain sizes of these materials affect the many properties of the toner, including the powder flow, tribocharging, release and glossing.
• the domain sizes can be effectively controlled by a separate step of milling the waxes to form a dispersion. For this purpose, it is beneficial to mill the wax in a volatile organic solvent that can be removed after the wax is added to the toner. While the wax domain size can be reduced in milling without an aid, it is usually desirable to have milling aid that can act as a colloidal stabilizer for the wax particles. The stabilizer prevents the agglomeration of the wax particles thereby increasing the efficiency of milling and also reduces the viscosity of the dispersion, thereby allowing a higher wax yield and consequently lower milling costs.
• Another method of controlling a domain size of the wax is to mill the wax within a solvent medium.
• U.S. Patent Numbers 6,682,866; 6,800,412; and 6,824,945; and U.S. Patent Application No. 2004/01 15551 disclose combining a polyester binder, pigment, charge control agent and wax and milling it in the presence of zirconia beads. The organic phase is then dispersed, with controlled shearing, in an aqueous phase containing hydroxylapatite and sodium dodecyl benzene sulfonate as dispersants. The solvent is then removed by evaporation.
• polyester binder do not adsorb well on to waxes, particularly polyolefin and polyester waxes which results in high degree of flocculation and difficulty in milling.
• Other methods of incorporating wax via chemical toner processes are by emulsion aggregation technology. In these cases aqueous dispersions of wax, latex, pigment and charge control agent are mixed in a reactor and aggregated to form toner sized particles.
• Aqueous dispersions of wax can be prepared by several methods.
• Patent Numbers 6,849,371 and 6,210,853 disclose the preparation of wax dispersions by using a sulfonated polyester as a dispersant, which is also the toner binder, raising the aqueous dispersion temperature to above the melting point of the wax, using a high pressure reactor and then emulsifying the wax.
• U.S. Patent No. 6,808,851 discloses a similar preparation method with an anionic surfactant as the stabilizer.
• U.S. Patent Application No. 2004/0044108 Al describes the details of preparing the wax dispersions. While aqueous dispersions of waxes are environmentally more benign than solvent based dispersions, the cost of carrying out high pressure homogenizations is relatively high. Furthermore it is substantially more difficult to carry out the emulsion aggregation process and incorporate the wax, than by using a solvent to dissolve and disperse the toner components.
• dispersions of waxes in solvents are prepared, for incorporating into toners prepared by certain chemical processes.
• the dispersions are prepared by breaking down the wax particles into sub micron particles using milling media.
• the cost of preparing these dispersions is proportional to time required to reach the final particle size. Therefore it is beneficial to have a high solid loading in these dispersions, for the reasons of reducing the cost.
• the choice of dispersant determines the rate of milling.
• dispersants that enable fast milling are good stabilizers. That is, they adsorb strongly to the wax particles, and provide a good barrier to particle flocculation. While flocculated dispersions can be milled, they are typically higher in viscosity and hard to handle in the process. Consequently, the particle concentrations in flocculated dispersions cannot be high.
• the desired stabilizer should be able to produce fast milled dispersions with small particle size and low viscosity.
• a dispersant comprised of a copoloymer of styrene and butadiene, where the butadiene is partially or completely hydrogenated.
• the present invention is method of manufacturing a wax dispersion.
• the method includes forming a solution of a solvent and a dispersant, the dispersant being a polymer of partially or fully hydrogenated styrene butadiene wherein the styrene mole fraction of the polymer is from 20 to 90.
• Wax is added to the solution to form a slurry.
• the particle size of the wax is reduced through communition of the slurry.
• the wax dispersion can be used for the manufacture of toner particles.
• the wax dispersion of the instant invention is preferably made with a polar solvent where the dispersant is completely or partially soluble in the solvent.
• the dispersant is a copolymer of styrene and butadiene, where the styrene mole ratio varies from 20% to 90%.
• the choice of solvent will partially specify the actual styrene mole fraction, because of solubility considerations.
• the preferred mole fraction in the preferred solvents of ethyl acetate, propyl acetate and dichloromethane is between 50 and 75%.
• the molecular weight of the polymer can be from 4Kdaltons to 500 K Daltons.
• the polymer may not provide adequate stability to the wax particles to prevent flocculation. If the molecular weight is too high it will increase the viscosity of the dispersion and may also cause flocculation via "bridging.” Furthermore it is desired that the butadiene portion of the dispersant be partially or totally hydrogenated.
• the mole fraction of the butadiene that is to be hydrogenated is from 2 to 100% and preferably from 30 to 100%.
• the wax can be dispersed in a single solvent or a mixture of solvents.
• the wax dispersion is used in the preparation of electrophotographic toner prepared with the aid of a solvent as described in U.S. Patent No. 4,833,060. It is highly preferred that the solvent used for the preparation of the wax dispersion of the current invention, be the same as the one being used to prepare the toner. Solvents that are useful for the preparation of toner as per U.S. Patent No.
• waxes examples include polyolefins such as polyethylene wax and polypropylene wax. Long chain hydrocarbon wax such as paraffin wax.
• Another class of waxes are carbonyl group-containing wax which include polyalkanoic acid ester waxes such as montan wax, trimethylolpropane tribehenate, glycerin tribehenate; polyalkanol ester waxes such as tristearyl trimellilate and distearyl maleate; polyalkanoic acid amide waxes such as trimellitic acid tristearyl amide.
• Examples of useful aliphatic amides and aliphatic acids include oleamide, eucamide, stearamide, behenamide, ethylene bis(oleamide), ethylene bis(stearamide), ethylene bis(behenamide) and long chain acids including stearic, lauric, montanic, behenic, oleic and tall oil acids.
• Particularly preferred aliphatic amides and acids include stearamide, erucamide, ethylene bis- stearamide and stearic acid.
• the aliphatic amide or aliphatic acid is present in an amount from 0.5 to 30 percent by weight, preferably from 0.5 to 10 percent by weight.
• aliphatic amides and aliphatic acids can also be used.
• One useful stearamide is commercially available from Witco Corporation as Kemamide STM.
• a useful stearic acid is available from Witco Corporation as Hysterene 9718TM.
• Naturally occurring polyalkanoic acid ester waxes include Carnauba wax.
• a particularly useful class of ester waxes are made from long chain fatty acids and alcohol. Examples of this class are Licowax series made by Clariant Corp. derived from montanic acid.
• Another example useful in toner applications are the WE series made by NOF which is a highly purified narrow melting solid ester wax.
• Fluorinated waxes such as polyfluo 190, Polyflo 200, Polyfluo 523XF, Aqua Polyfluo 41 1- -all polyethylene/PTFE functionalized waxes, Aqua Polysilk 19, Polysilk 14,— all polethylene/PTFE/amide functionalized waxes available from Micro Powders INC are also useful. In some applications it may be useful to use more than one of the above waxes together to prepare the dispersion, particularly if the combination of waxes in the final application is useful. Although the wax used in the present invention can have a broad range of applications, it is generally desired for toner applications that the wax have a melting point of 40-160 0 C, preferably 50-120 0 C, more preferably 60- 90°C.
• a melting point of wax below 40 0 C may adversely affect the heat resistance and preservability of the toner, while too high a melting point, i.e. in excess of 160 0 C is apt to cause cold offset of toner when the fixation is performed at a low temperature.
• the melting peak of wax as obtained by methods such as differential scanning calorimetry and it is preferred that the onset of melting to the peak melting temperature be less than 10 0 C.
• the wax has a melt viscosity of 5-1000 cps, more preferably 10-100 cps, at a temperature higher by 20°C than the melting point thereof. When the viscosity is greater than 1000 cps, the anti-hot offset properties and low fixation properties of the toner are adversely affected.
• the amount of the wax in the toner is generally 1 -40% by weight, preferably 3-10% by weight, based on the weight of the toner.
• the wax dispersion of the instant invention can be prepared by any one of several comminution processes. These include high shear dispersers like the IKA mill, Kady mill or a Gaulin. Equipment used to homogenize emulsions may also be used, particularly where the wax particles are brittle. Media milling techniques are particularly useful for comminution of solid particles. Media milling can be accomplished by an attriter, a ball mill, a sand mill or a vibration mill using media made of silica, silicon nitride, sand, zirconium oxide, alumina, titanium, glass, etc. The bead sizes typically range from 0.25 to 3.0 mm in diameter.
• the volume of the media can be from 5 to 200% of the volume of the solution containing the wax particles.
• the slurry that is being milled contains one or more solvents described earlier, one or more types of waxes described above and at least one dispersant comprising a hydrogenated styrene-butadiene copolymer.
• the amount of wax particles in the slurry can be from 0.1% to 50%. If the wax dispersion is further used to make electrophotographic toner, the time involved in processing a given amount of wax is directly proportional to the cost of making the toner. In order to maximize productivity and minimize the cost, it is desired that the wax content in the slurry be high as possible.
• the rheological profile of the solid particle dispersion is typically shear thinning — i.e. its viscosity decreases as the rate of shear imparted increases.
• a partially stabilized or unstable dispersion will typically exhibit an extreme case of shear thinning where the viscosity at low shear rates ( ⁇ 0.5 s ⁇ ') is high.
• an unstable, flocculated dispersion may exhibit a yield stress and may not flow at the low shear rates.
• the proper choice of dispersant such as the one described in the instant invention, will stabilize the particles and reduce the viscosity at low shear rates.
• the low shear viscosity of the milled dispersion measured at 0.5 s "1 , be lower than 500 cp when the wax level is at 10%.
• the dispersant comprising the partially or totally hydrogenated styrene-butadiene polymer should be present at a level from between 2 to 50% based on the amount of wax present. The preferred amount is from 5 to 20%. If the level is too low, there will not be enough dispersant to stabilize the wax particles when the size is reduced. If the level is too high, then polymer will comprise a significant portion of the toner when the dispersion is used to prepare the toner.
• the dispersion of the instant invention be used in the preparation of toner. It is well known in the art that in order for the wax to perform well as a release agent upon fusing that the wax blooms to the surface of the toner. However, prior to the fusing step it is also desired that the wax be encapsulated by the toner binder. In order for this to happen, the wax particle size should be substantially smaller than the final desired size of the toner particle.
• the predispersed wax can be added to the extrusion step that is the first step of a conventional melt pulverized toner (MPT method). In this step all the components of the toner are extruded and mixed at elevated temperatures.
• MPT method melt pulverized toner
• the extrusion step cannot disperse or break down large particles of wax. Therefore, it is advantageous to comminute the particles as described above and add them to the extrusion step. Furthermore, it is more advantageous to disperse the wax in an organic solvent, instead of an aqueous medium, because dispersants used in aqueous dispersion processes can cause the toner to become sensitive to the relative humidity from the tribo- charging perspective.
• the wax dispersion of the instant invention can be used to make toner in by the MPT method mentioned above.
• Ingredients of the toner such as a binder including a modified polyester resin, a coloring agent, the wax dispersion and a charge control agent are mechanically mixed with each other using a mixer such as a rotary blade mixer to obtain a mixture.
• the mixture is then kneaded using a suitable kneader.
• a single axis type (or single cylinder type) kneader, a two axis type (or two cylinder type) continuous extruder or a roll mill may be suitably used as the kneader.
• the kneading should be performed at a temperature near the softening point of the binder resin so as not to cause breakage of the molecular chain of the binder resin. Too high a temperature above the softening point will cause breakage of the molecular chain of the binder resin.
• the dispersion of the coloring agent, etc. in the binder resin will not sufficiently proceed when the temperature is excessively lower than the softening point.
• the kneaded mixture is then solidified and the solidified mixture is ground, preferably in two stages, coarsely grinding and finely grinding.
• the coarsely grinding stage may be carried out by impinging the solidified mixture to an impact plate under a jet stream, while the finely grinding stage may be performed using a combination of a rotor and a stator with a small gap.
• the ground mixture is classified in a jet flow utilizing tangential force to obtain a toner having an average size of, for example, 5-20 ⁇ m.
• the obtained toner is, if desired, mixed with an external additive such as a fluidizing agent to improve the fluidity, preservability, developing efficiency and transfer efficiency.
• the mixing with the external additive may be carried out using a conventional mixer preferably capable of controlling the mixing temperature.
• the external additive may be added gradually or at once.
• the rotational speed, mixing time and mixing temperature may be varied in any suitable manner.
• suitable mixers are V-type mixers, rocking mixers, Ledige mixers, nauter mixers and Henschel mixers.
• a preferred method of using the wax dispersions to make toner is via chemical means.
• the dispersion of the instant invention is mainly useful in processes that dissolve/disperse the toner components in a solvent phase. Such methods are disclosed in U.S. Patent Numbers 4,833,060; 4,965,131; 6,682,866; 6,800,412; and 6,544,705; and U.S. Patent Application No. 20040161687 Al .
• the toner is prepared by dissolving/dispersing the binder, optionally one or more pigments, one or more charge control agents in one or more of the preferred solvents.
• the wax dispersion of the instant invention is added to this mixture and mixed well. The order of adding the dispersion is not important.
• aqueous phase containing a stabilizer is prepared.
• the preferred stabilizer is a particulate dispersing agent and a promoter which drives the particulate dispersing agent to the interface between the water layer and the polymer solvent droplets formed by the agitation on the system.
• Suitable colloidal stabilizing agents known in the art of forming polymeric particles by the addition reaction of ethylenically unsaturated monomers by the limited coalescence technique can be employed such as, for example, inorganic materials such as, metal salt or hydroxides or oxides or clays, organic materials such as starches, sulfonated crosslinked organic homopolymers and resinous polymers as described, for example, in U.S. Patent No. 2,932,629; silica as described in U.S.
• Silica is the preferred suspension stabilizing agent for use in accordance with this invention.
• the SiO 2 dispersing agent generally should have dimensions such that they are from 0.001 ⁇ m to 1 ⁇ m preferably from 5 to 150 nanometers and most preferably from 5-75 nanometers. The size and concentration of these particles controls and predetermines the size of the final toner particle.
• colloidal silica dispersing agents are sold under the brand names of Ludox, Nalcoag and Snowtex among others. Colloidal silicas are naturally charged negatively at ph greater than 2 and these are the preferred stabilizers. However, silica modified with alumina are positively charged and are also suitable as a stabilizer.
• Suitable promoters to drive the suspension stabilizing agent to the interface of the lubricant droplets and the aqueous phase include sulfonated polystyrenes, alginates, carboxymethyl cellulose, tetramethyl ammonium hydroxide or chloride, triethylphenyl ammonium hydroxide, triethylphenyl ammonium hydroxide, triethylphenyl ammonium chloride, diethylaminoethylmethacrylate, gelatin, glue, casein, albumin, gluten, methoxycellulose, and the like.
• a particularly suited promoter is a water-soluble soluble condensation product of diethanol amine and adipic acid, such as poly(adipic acid-co-methylaminoethanol), water soluble condensation products of ethylene oxide, urea, and formaldehyde and polyethyleneimine.
• adipic acid such as poly(adipic acid-co-methylaminoethanol), water soluble condensation products of ethylene oxide, urea, and formaldehyde and polyethyleneimine.
• colloidal silica as stabilizer, it is generally desired to control the pH of the system at a value of from 2 to 7, preferably from 3 to 6 and most preferably 4.
• the promoter should be present in an amount of 1 to 50 percent based on the amount of silica.
• the dispersion of the solvent drops containing the binder and the dispersant in the aqueous medium is then vigorously mixed by any suitable device including high speed agitation, ultrasonic devices, homogenizers, and the like in order to reduce the particle size of the lubricant droplets to less than that ultimately desired.
• any suitable device including high speed agitation, ultrasonic devices, homogenizers, and the like in order to reduce the particle size of the lubricant droplets to less than that ultimately desired.
• the presence of the particulate suspension stabilizer then controls the level of coalescence that takes place until an equilibrium is reached and the particle size does not grow any farther.
• the solvent is next removed from the droplets by any suitable technique, such as, for example, heating the entire system to vaporize the solvent and thus remove it from the discontinuous phase droplets remaining in the aqueous solution surrounded by the SiO 2 particles.
• the solvent can also be removed by purging the stirred dispersion with air or an inert gas like nitrogen.
• U.S. Patent No. 5,580,692 discloses a method by which excess water is added to the dispersion that extracts the solvent. The particles are separated from the water/solvent mixture by filtration.
• the SiO 2 dispersing agent may be removed from the surface of the polymer particles by any suitable technique such as dissolving in HF or other fluoride ion or by adding an alkaline agent such as potassium hydroxide to the aqueous phase containing the polymer particles to thereby raise the pH to at least 12 while stirring. This method is preferred. Subsequently to raising the pH and dissolving the silica, the polymer particles can be recovered by filtration and finally washed with water or other agents to remove any desired impurities from the surface thereof. The toner particles thus produced can be dried and surface treated to produce usable toner for electrophotographic engines.
• any suitable technique such as dissolving in HF or other fluoride ion or by adding an alkaline agent such as potassium hydroxide to the aqueous phase containing the polymer particles to thereby raise the pH to at least 12 while stirring. This method is preferred.
• the polymer particles can be recovered by filtration and finally washed with water or other agents to remove any desired impurities from
• charge-control agent refers to a toner addendum used to modify the triboelectric charging properties of the resulting toner.
• charge control agents for positive and negative charging toners are available. Suitable charge control agents are disclosed, for example, in U.S. Patent Numbers 3,893,935; 4,079,014; 4,323,634; and 4,394,430; and British Patent Numbers. 1 ,501 ,065 and 1 ,420,839. Additional charge control agents which are useful are described in U.S. Patent Numbers 4,624,907; 4,814,250; 4,840,864; 4,834,920; 4,683,188; and 4,780,553. Mixtures of charge control agents can also be used.
• charge control agents include chromium salicylate organo-complex salts, and azo-iron complex-salts, an azo- iron complex-salt, particularly ferrate (1-), bis[4-[(5-chloro-2- hydroxyphenyl)azo]-3-hydroxy-N-phenyl-2-naphthalenecarb oxamidato(2-)], ammonium, sodium, and hydrogen (Organoiron available from Hodogaya Chemical Company Ltd.).
• the polymeric dispersant is first dissolved in the solvent of choice.
• the solvent in this instance is ethyl acetate.
• Three dispersants were used: a) Tuftec P2000 (made by AKA elastomer) which is a partially hydrogenated styrene butadiene polymer. The styrene amount is 61%. 60% of the butadiene is hydrogenated; b) Piccotoner 1221 (made by Hercules) which is a styrene butylacrylate polymer where the styrene mole % is 80; and c) Brij93 (polyoxyethylene (2) oleyl ether, made by ICI).
• each dispersant was separately dissolved in 45gms of solvent. The solution was transferred to a 4oz glass jar, to which 35 ml of 2mm zirconia beads were added. To each jar, 5gms of Polywax 500 (polyethylene wax of MW 500, from Baker Huges) T-60 (60 ⁇ m powder) grade was added. The wax level in the dispersion was 10%. Each jar was rolled for 4 days at 30 rpm. At the end of the period the contents of the jar were poured into a funnel with a mesh screen to separate out the beads. The dispersions made with the Piccotoner 1221 and the Brij93 were pasty and did not flow well, whereas the dispersion made with the Tuftec P2000 flowed relatively easily and separated from the media.
• Polywax 500 polyethylene wax of MW 500, from Baker Huges
• T-60 60 ⁇ m powder
• LicowaxF which a montanic acid ester wax (made by Clariant) comes as millimeter sized flakes, which was used instead of the Polywax 500.
• the dispersions made with the Piccotoner 1221 and the Brij 93 as the dispersants were viscous and the dispersion made with Tuftec P2000 was fluid.
• Tuftec P2000 a) Tuftec P2000; b) Tuftec H 1043 (Styrene-butadiene polymer where the styrene level is at 61 mol% and where all the butadiene has been hydrogenated, made by AKA Elastomer); and c) Sartomer EF40 (Styrene-maleic anhydride polymer with 80mol% styrene, made by Sartomer).
• the milling media used for the Licowax and the WE-3 waxes was 5mm stainless steel balls.
• the milling media used for the smaller sized PW500 was the 2mm zirconia beads.
• the volume of the milling media was fixed at 35ml for all experiments. After 24 hours of rolling at 30 rpm, the contents of the jars were drained. The fluidity of the dispersions were observed and the appearance of the wax particles under the microscope.
• the dispersions prepared with the dispersants of the instant invention have low viscosity and well behaved with respect to the particle flocculation.
• the styrenic polymer by comparison does not give high quality dispersions.
• the dispersants of the instant invention had some degree of hydrogenation to the butadiene segment of the polymer.
• the properties of the polymers tested are given below:
• Example 2 The experimental procedure described in Example 1 was followed for each of the dispersants listed above. After the dispersion was separated from the milling media, the wax percent in the dispersion was adjusted to 10%, by adding the appropriate amount of solvent. The viscosity of the dispersion was measured in a Haake rheometer, using the double gap geometry. In each case the dispersion was sheared at 3000 s "1 at which point any aggregates were broken up and the viscosity was steady with time. The shear rate was ramped down to 0.5s " . The shear rate was then held for 5 min at 0.5 s " ' and the change in viscosity with time was recorded.
• the viscosities of the dispersion are reported at the high shear rate (3000 s "1 ) and the low shear rate (0.5 s "1 ), obtained from the shear rate ramp. Furthermore, the change in viscosity over the 5 minute period of low shear is also reported.
• the first two measurements reveal the fluidity of the dispersions under extremes of shear which can be experienced in the manufacturing process.
• the change in viscosity at constant shear rate reveals the rate of aggregation of the wax particles due to intrinsic colloidal instabilities.
• the table below shows the measured viscosities under the different conditions.
• Two dispersants (Tuftec P2000 and Tuftec H 1043) were used in this example.
• the total percent solids (dispersant+wax) was kept constant in these experiments at 20%.
• the dispersant levels variations were at 5, 10 and 15% based on the amount of wax, for each dispersant.
• lOgms solids Polywax500 + dispersant
• 35ml of 2mm zirconia beads was added to the jar and the jar was put on to a Sweco mill which was vibrated for 24 hours. After the milling period, the dispersions were separated from the media.
• Example 2 The dispersions made with the three waxes and the dispersants of the instant invention in Example 2 (i.e. Polywax 500/Tuftec P2000, Polywax 500/Tuftec H 1043, Licowax F/Tuftec P2000, LicowaxF/Tuftec Hl 043, WE3/Tuftec P2000 and WE3/Tuftec H 1043) were used to prepare toner particles.
• the solvent phase included mixing 2.9 gms of a cyan flush of copper phthalocyanine (40/60 in a polyester binder), 19.3 gms of polyester binder — tuftone NE303 made by Kao Corporation, a total of 102 gms of wax dispersion and solvent, ethyl acetate.
• the actual amount of wax dispersion added was calculated to have exactly 2.5 gms of wax, which corresponds to 10 parts of wax per hundred parts of total solids in the solvent phase.
• the aqueous phase was prepared by first dissolving 1.5 gms of potassium hydrogen phthalate buffer in 237.5 gms of water. 10 gms of Nalco
• Dispersion Preparation of Dispersion
• the solvent phase was added to the aqueous phase with intense mixing using a Lab Silverson mixer at 2000 rpm. After approximately 1 min of mixing, the entire dispersion was passed through a Microfluidics Microfluidizer H-1 10, as a homogenizer. After homogeinizing , the dispersion was evaporated under 25in Hg vacuum and 50C to remove the ethyl acetate solvent. The resulting dispersion, containing toner particles were isolated as follows:
• the dispersion was first filtered through a fine fritted glass funnel.
• the wet cake of particles was transferred to a beaker along with 400ml of 0. IN KOH, and stirred for two hours, after which it was filtered once more and the cake was treated with the above amount of alkali solution for one hour.
• the final mixture was filtered and then washed with DI water till the conductivity of the filtrate was below 1 O ⁇ S/cm.
• the cake was dried in a vacuum oven overnight under full vacuum and 4OC.
• the particles were sieved to deagglomerate the clumps, resulting in toner particles.
• the particle size distribution was measured using a Coulter Multisizer II. The median volume size is reported along with two parameters - a fineness index is defined as the ratio of the diameters at 50% vs
• a coarseness index is defined as the ratio of the diameters at 84% vs 50% from the volume weighted cumulative distribution curve
• the fineness index is a measure of the undersize particles in the distribution, while the coarseness index is a measure of oversized particles in the distribution.
• the table below shows the particle size data for the toner particles containing 1 Opph of wax, prepared with dispersions containing the dispersant of the instant invention.

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