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
  • G03G9/12—Developers with toner particles in liquid developer mixtures
  • G03G9/135—Developers with toner particles in liquid developer mixtures characterised by stabiliser or charge-controlling agents

Definitions

• This invention relates to electrostatic liquid developers. More particularly this invention relates to a positive-charged liquid electrostatic developer containing at least one sulfonic or sulfamic acid compound having a solubility of at least 0.5% based on the weight of charge director compound in a mixture of nonpolar liquid and charge director compound.
• a latent electrostatic image can be developed with toner particles dispersed in an insulating nonpolar liquid.
• Such dispersed materials are known as liquid toners or liquid developers.
• a latent electrostatic image may be produced by providing a photoconductive layer with a uniform electrostatic charge and subsequently discharging the electrostatic charge by exposing it to a modulated beam of radiant energy.
• Other methods are known for forming latent electrostatic images. For example, one method is providing a carrier with a dielectric surface and transferring a preformed electrostatic charge to the surface.
• Useful liquid developers comprise a thermoplastic resin and nonpolar liquid. Generally a suitable colorant is present such as a dye or pigment.
• the colored toner particles are dispersed in the nonpolar liquid which generally has a high-volume resistivity in excess of l09 ohm centimeters, a low dielectric constant below 3.0, and a high vapor pressure.
• the toner particles are less than 30 ⁇ m average size as determined using the Malvern Particle Sizer described below.
• a charge director compound and preferably adjuvants e.g., polyhydroxy compounds, polybutylene succinimide, an aromatic hydrocarbon, etc.
• Such liquid developers provide images of good resolution, but it has been found that charging and image quality are particularly pigment dependent. Some formulations, suffer from poor image quality manifested by low resolution, poor solid area coverage (density), and/or image squash. Some formulations result in wrong sign (negative) developers. In order to overcome such problems much research effort has been expended to develop new type charge directors and/or charging adjuvants for electrostatic liquid developers.
• composition of the electrostatic liquid developer does not exclude unspecified components which do not prevent the advantages of the developer from being realized.
• additional components such as a colorant, fine particle size oxides, adjuvant, e.g., polyhydroxy compound, polybutylene succinimide, aromatic hydrocarbon, etc.
• Conductivity is the conductivity of the developer measured in pmhos/cm at 5 hertz and 5 volts.
• the nonpolar liquids (A) are, preferably, branched-chain aliphatic hydrocarbons and more particularly, Isopar®-G, Isopar®-H, Isopar®-K, Isopar®-L, Isopar®-M and Isopar®-V. These hydrocarbon liquids are narrow cuts of iso-paraffinic hydrocarbon fractions with extremely high levels of purity.
• the boiling range of Isopar®-G is between 157°C and 176°C, Isopar®-H between 176°C and 191°C, Isopar®-K between 177°C and 197°C, Isopar®-L between 188°C and 206°C and Isopar®-M between 207°C and 254°C and Isopar®-V between 254.4°C and 329.4°C.
• Isopar®-L has a mid-boiling point of approximately 194°C.
• Isopar®-M has a flash point of 80°C and an auto-ignition temperature of 338°C.
• Stringent manufacturing specifications such as sulfur, acids, carboxyl, and chlorides are limited to a few parts per million. They are substantially odorless, possessing only a very mild paraffinic odor. They have excellent odor stability and are all manufactured by the Exxon Corporation. High-purity normal paraffinic liquids, Norpar®12, Norpar®13 and Norpar®15, Exxon Corporation, may be used. These hydrocarbon liquids have the following flash points and auto-ignition temperatures:
• All of the nonpolar liquids have an electrical volume resistivity in excess of l09 ohm centimeters and a dielectric constant below 3.0.
• the vapor pressures at 25°C are less than 10 Torr.
• Isopar®-G has a flash point, determined by the tag closed cup method, of 40°C
• Isopar®-H has a flash point of 53°C determined by ASTM D 56.
• Isopar®-L and Isopar®-M have flash points of 61°C, and 80°C, respectively, determined by the same method. While these are the preferred nonpolar liquids, the essential characteristics of all suitable nonpolar liquids are the electrical volume resistivity and the dielectric constant.
• a feature of the nonpolar liquids is a low Kauri-butanol value less than 30, preferably in the vicinity of 27 or 28, determined by ASTM D 1133.
• the ratio of thermoplastic resin to nonpolar liquid is such that the combination of ingredients becomes fluid at the working temperature.
• the nonpolar liquid is present in an amount of 85 to 99.9% by weight, preferably 97 to 99.5% by weight, based on the total weight of liquid developer.
• the total weight of solids in the liquid developer is 0.1 to 15%, preferably 0.5 to 3.0% by weight.
• the total weight of solids in the liquid developer is solely based on the resin, including any components dispersed therein, and any pigment component present.
• thermoplastic resins or polymers (B) include: ethylene vinyl acetate (EVA) copolymers (Elvax® resins, E. I. du Pont de Nemours and Company, Wilmington, DE), copolymers of ethylene and an ⁇ , ⁇ -ethylenically unsaturated acid selected from the group consisting of acrylic acid and methacrylic acid, copolymers of ethylene (80 to 99.9%)/acrylic or methacrylic acid (20 to 0%)/alkyl (C1 to C5) ester of methacrylic or acrylic acid (0 to 20%), polyethylene, polystyrene, isotactic polypropylene (crystalline), ethylene ethyl acrylate series sold under the trademark Bakelite® DPD 6169, DPDA 6182 Natural and DTDA 9169 Natural by Union Carbide Corp., Stamford, CN; ethylene vinyl acetate resins, e.g., DQDA 6479 Natural and DQDA 6832 Natural 7 also sold by Union Car
• the ethylene constituent is present in about 80 to 99.9% by weight of the copolymer and the acid component in about 20 to 0.l% by weight of the copolymer.
• a preferred copolymer is ethylene (89% by weight)/methacrylic acid (11% by weight).
• the acid numbers of the copolymers range from l to 120, preferably 54 to 90. Acid No. is milligrams potassium hydroxide required to neutralize l gram of polymer.
• the melt index (g/10 min) of 10 to 500 is determined by ASTM D 1238, Procedure A.
• Preferred copolymers of this type have an acid number of 66 and 54 and a melt index of 100 and 500 determined at 190°C, respectively.
• acrylic resins include acrylic resins, such as a copolymer of acrylic or methacrylic acid (optional but preferred) and at least one alkyl ester of acrylic or methacrylic acid wherein alkyl is 1-20 carbon atoms, e.g., methyl acrylate (50-90%)/methacrylic acid (0-20%)/ethylhexyl methacrylate (10-50%); and other acrylic resins including Elvacite® acrylic resins, E. I. du Pont de Nemours and Company, Wilmington, DE or blends of resins, polystyrene; polyethylene; and modified resins disclosed in El-Sayed et al. U.S. Patent 4,798,778, the disclosure of which is incorporated herein.
• acrylic resins such as a copolymer of acrylic or methacrylic acid (optional but preferred) and at least one alkyl ester of acrylic or methacrylic acid wherein alkyl is 1-20 carbon atoms, e.g., methyl acrylate
• the resins have the following preferred characteristics:
• the Malvern 3600E Particle Sizer manufactured by Malvern, Southborough, MA uses laser diffraction light scattering of stirred samples to determine average particle sizes. Since the Horiba and Malvern instruments use different techniques to measure average particle size the readings differ. The following correlation of the average size of toner particles in micrometers ( ⁇ m) for the two instruments is:
• Suitable nonpolar liquid soluble ionic or zwitterionic charge director compounds (C) which are used in an amount of 0.25 to 1,500 mg/g, preferably 2.5 to 400 mg/g developer solids, include: anionic glyceride such as Emphos® D70-30C and Emphos® F27-85, two commercial products sold by Witco Corp., New York, NY; which are sodium salts of phosphated mono- and diglycerides with unsaturated and saturated acid substituents respectively, lecithin, Basic Barium Petronate®, Neutral Barium Petronate®, Calcium Petronate®, Neutral Calcium Petronate®, oil-soluble petroleum sulfonates, Witco Corp., New York, NY; and metallic soaps such as aluminum tristearate, aluminum distearate; barium, calcium, lead and zinc stearates; cobalt, manganese, lead and zinc linoleates, aluminum, calcium and cobalt octoates; calcium and cobalt oleates; zinc palm
• Hydrocarbon soluble sulfonic and sulfamic acids (D) of the invention are represented by the general formulae: (1) R-SO3H, and (2) R-NH-SO3H wherein R is alkyl of 1 to 30 carbon atoms, aryl of 6 to 30 carbon atoms, substituted alkyl of 1 to 30 carbon atoms, e.g., halide, e.g., F, Cl, Br, I; hydroxy, nitro, carbonyl, carboxyl, alkyl, aryl, cyano, etc., or substituted aryl of 6 to 30 carbon atoms, e.g., substituents as described above for alkyl.
• R-SO3H and (2) R-NH-SO3H wherein R is alkyl of 1 to 30 carbon atoms, aryl of 6 to 30 carbon atoms, substituted alkyl of 1 to 30 carbon atoms, e.g., halide, e.g., F, Cl, Br,
• Useful such acids include: butanesulfonic acid, toluenesulfonic acid, dinonylnaphthalenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, benzenesulfonic acid, 4-ethylbenzenesulfonic acid, 1-butylsulfonic acid, 1-dodecylsulfonic acid, 1-octadecylsulfonic acid, 10-camphorsulfonic acid, 4-chlorobenzenesulfonic acid, dodecylbenzenesulfonic, 1-pyrenesulfonic acid, 5-sulfosalicylic acid, 2,5-xylenesulfonic acid, 1-butylsulfamic acid, cyclohexylsulfamic acid, 1-hexylsulfamic acid, 1-octylsulfamic acid, 1-decylsulfamic
• Preferred acids include: p-toluenesulfonic acid, dinonylnaphthalenesulfonic acid, butylsulfonic acid, butylsulfamic acid, ethyl benzenesulfonic acid, n-cyclohexylsulfamic acid, and 10-camphorsulfonic acid.
• hydrocarbon soluble sulfonic and sulfamic acids are soluble in the amount of at least 0.5% based on the weight of charge director compound in a mixture of nonpolar liquid and charge director compound.
• colorants such as pigments or dyes and combinations thereof, which are preferably present to render the latent image visible, though this need not be done in some applications.
• the colorant e.g., a pigment
• the amount of colorant may vary depending on the use of the developer.
• pigments include:
• ingredients may be added to the electrostatic liquid developer, such as fine particle size oxides, e.g., silica, alumina, titania, etc.; preferably in the order of 0.5 ⁇ m or less can be dispersed into the liquefied resin. These oxides can be used alone or in combination with the colorant. Metal particles can also be added.
• fine particle size oxides e.g., silica, alumina, titania, etc.
• These oxides can be used alone or in combination with the colorant.
• Metal particles can also be added.
• an adjuvant which can be selected from the group consisting of polyhydroxy compound which contains at least 2 hydroxy groups, polybutylene succinimide, and aromatic hydrocarbon having a Kauri-butanol value of greater than 30.
• the adjuvants are generally used in an amount of 1 to 1000 mg/g, preferably 1 to 200 mg/g developer solids.
• Examples of the various above-described adjuvants include: polyhydroxy compounds : ethylene glycol, 2,4,7, 9-tetramethyl-5-decyn-4,7-diol, poly(propylene glycol), pentaethylene glycol, tripropylene glycol, triethylene glycol, glycerol, pentaerythritol, glycerol-tri-12 hydroxystearate, ethylene glycol monohydroxystearate, propylene glycerol monohydroxy-stearate, etc., as described in Mitchell U.S. Patent 4,734,352; polybutylene/succinimide : OLOA®-1200 sold by Chevron Corp., analysis information appears in Kosel U.S.
• Amoco 575 having a number average molecular weight of about 600 (vapor pressure osmometry) made by reacting maleic anhydride with polybutene to give an alkenylsuccinic anhydride which in turn is reacted with a polyamine.
• Amoco 575 is 40 to 45% surfactant, 36% aromatic hydrocarbon, and the remainder oil, etc.
• Patent 4,702,984 and aromatic hydrocarbon : benzene, toluene, naphthalene, substituted benzene and naphthalene compounds, e.g., trimethylbenzene, xylene, dimethylethylbenzene, ethylmethylbenzene, propylbenzene, Aromatic 100 which is a mixture of C9 and C10 alkyl-substituted benzenes manufactured by Exxon Corp., etc., as described in Mitchell U.S. Patent 4,631,244.
• the particles in the electrostatic liquid developer have an average by area particle size of 10 ⁇ m or less (Horiba instrument).
• the average particle size determined by the Malvern 3600E Particle Sizer can vary depending on the use of the liquid developer.
• the resin particles of the developer may or may not be formed having a plurality of fibers integrally extending therefrom although the formation of fibers extending from the toner particles is preferred.
• fibers as used herein means pigmented toner particles formed with fibers, tendrils, tentacles, threadlets, fibrils, ligaments, hairs, bristles, or the like.
• the positively charged electrostatic liquid developer can be prepared by a variety of processes as described in copending application Serial No. , filed concurrently herewith entitled "Process for Preparing Positive Electrostatic Liquid Developers with Acidified Charge Directors” (DX-0015).
• a suitable mixing or blending vessel e.g., attritor, heated ball mill, heated vibratory mill such as a Sweco Mill manufactured by Sweco Co., Los Angeles, CA, equipped with particulate media, for dispersing and grinding, Ross double planetary mixer manufactured by Charles Ross and Son, Hauppauge, NY, etc., or a two roll heated mill (no particulate media necessary) are placed at least one of thermoplastic resin, and nonpolar liquid described above.
• the resin, nonpolar liquid and optional colorant are placed in the vessel prior to starting the dispersing step.
• the colorant can be added after homogenizing the resin and the nonpolar liquid.
• Polar additive similar to that described in Mitchell, U.S. Patent 4,631,244, can also be present in the vessel, e.g., up to 100% based on the weight of polar additive and nonpolar liquid.
• the dispersing step is generally accomplished at elevated temperature, i.e., the temperature of ingredients in the vessel being sufficient to plasticize and liquefy the resin but being below that at which the nonpolar liquid or polar additive, if present, degrades and the resin and/or colorant decomposes.
• a preferred temperature range is 80 to 120°C.
• particulate media are particulate materials, e.g., spherical, cylindrical, etc., selected from the group consisting of stainless steel, carbon steel, alumina, ceramic, zirconia, silica, and sillimanite. Carbon steel particulate media are particularly useful when colorants other than black are used.
• a typical diameter range for the particulate media is in the range of 0.04 to 0.5 inch (l.0 to approx. 13 mm).
• the dispersion is cooled, e.g., in the range of 0°C to 50°C. Cooling may be accomplished, for example, in the same vessel, such as the attritor, while simultaneously grinding with particulate media to prevent the formation of a gel or solid mass; without stirring to form a gel or solid mass, followed by shredding the gel or solid mass and grinding, e.g., by means of particulate media; or with stirring to form a viscous mixture and grinding by means of particulate media.
• Additional liquid may be added at any step during the preparation of the liquid electrostatic toners to facilitate grinding or to dilute the toner to the appropriate % solids needed for toning.
• Additional liquid means nonpolar liquid, polar liquid or combinations thereof. Cooling is accomplished by means known to those skilled in the art and is not limited to cooling by circulating cold water or a cooling material through an external cooling jacket adjacent the dispersing apparatus or permitting the dispersion to cool to ambient temperature. The resin precipitates out of the dispersant during the cooling. Toner particles of average particle size (by area) of less than 10 ⁇ m, as determined by a Horiba centrifugal particle size analyzer or other comparable apparatus, are formed by grinding for a relatively short period of time.
• the concentration of the toner particles in the dispersion is reduced by the addition of additional nonpolar liquid as described previously above.
• the dilution is normally conducted to reduce the concentration of toner particles to between 0.l to 15 percent by weight, preferably 0.3 to 3.0, and more preferably 0.5 to 2 weight percent with respect to the nonpolar liquid.
• One or more ionic or zwitterionic charge director compounds (C), of the type set out above, can be added to impart a positive charge.
• the addition may occur at any time during the process; preferably at the end of the process, e.g., after the particulate media, if used, are removed and the concentration of toner particles is accomplished.
• the sulfonic or sulfamic acid adjuvant may also be added at any stage of the process subsequent to Step (A), and preferably along with the charge director compound. If a diluting nonpolar liquid is also added, the charge director compound and sulfonic or sulfamic acid compound can be added prior to, concurrently with, or subsequent thereto. If an additional adjuvant compound of a type described above has not been previously added in the preparation of the developer, it can be added prior to or subsequent to the developer being charged. Preferably the adjuvant compound is added after the dispersing step.
• the positive charged liquid electrostatic developers of this invention demonstrate improved image quality, resolution, solid area coverage (density), and toning of fine details, evenness of toning, and reduced squash independent of charge director or pigment present.
• the particles are exclusively charged positive.
• the developers of the invention are useful in copying, e.g., making office copies of black and white as well as various colors; or color proofing, e.g., a reproduction of an image using the standard colors: yellow, cyan, magenta together with black as desired; highlight color copying, e.g., copying of two colors, usually black and a highlight color for letterheads, underlining, etc.
• highlight color copying e.g., copying of two colors, usually black and a highlight color for letterheads, underlining, etc.
• the toner particles are applied to a latent electrostatic image and can be transferred, if desired.
• Other uses envisioned for the positive liquid electrostatic developers include: digital color proofing, lithographic printing plates, and resists.
• melt indices are determined by ASTM D 1238, Procedure A; and the average particle sizes by area were determined by a Malvern 3600 Particle Sizer, or the Horiba CAPA 500 centrifugal particle analyzer.
• Image quality of the developers of the invention was determined on a modified Savin 870 copier unless specifically noted.
• This device consists of a Savin 870 copier with the modifications described below.
• Mechanical modifications include addition of a pretransfer corona and removing the anodized layer from the surface of the reverse roll while decreasing the diameter of the roll spacers to maintain the same gap between the roll and photoconductor.
• the modified Savin 870 was then used to evaluate both positive and negative developers depending on the voltages and biasses used.
• the reversed image target consists of white characters and lines, etc., on a black background.
• the photoconductor is charged positive (near 1000V) by means of the charging corona.
• the copy is imaged onto the photoconductor inducing the latter to discharge to lower voltages (in order of increasing discharge-black areas and white areas).
• the photoconductor When adjacent to the toner electrode the photoconductor has fields at its surface such that positively charged toner will deposit at the white imaged areas, negatively charged toner at the black imaged areas. If necessary toner background is removed by the biased reverse roll.
• the toner is then transferred to paper by the transfer corona (the transfer force due to the negative charge sprayed on the back of the paper).
• the toner is then thermally fused. Actual voltages and biases used can be found in the examples.
• the ingredients were heated to 100°C and milled for 1 hour with 0.1875 inch (4.76 mm) carbon steel balls.
• the mixture was cooled to ambient temperature, 535 grams of Isopar®-L were added, and the mixture was milled for 2 hours.
• the average particle size was 7.8 ⁇ m as measured with a Malvern 3700E Particle Sizer.
• the toner was diluted to 1.5% solids with additional Isopar®-L.
• To three 30 gram samples of the developer were added a 10% solution of Neutral Barium Petronate® (NBP), Witco Corporation, New York, NY; Emphos® D70-30C, Witco Corp.; or Basic Barium Petronate® (BBP), Witco Corp. in the amounts indicated in Table 1 below.
• NBP Neutral Barium Petronate®
• BBP Basic Barium Petronate®
• Control 1 The procedure of Control 1 was followed with the following exception: Charging additives indicated in Table 1 and prepared as described below were added to the developer.
• the charging additives in Table 1 below were added to 30 g samples of the cyan developer and the conductivity and mobility of the samples was measured. The mobility was measured on an Electrokinetic Sonic Amplitude instrument. Samples were equilibrated 3 days before measurement, unless otherwise noted. Mobility of the toner particles of the liquid electrostatic developers was found to be higher than control. Increased mobility is one of the primary factors in improving developer performance.
• the uncharged toner concentrate described in Control 1 was diluted and charged as follows: 1500 grams of 1.0% solids were charged with 9.0 grams of 10% Neutral Barium Petronate® (60 mg/g toner solids). Image quality was determined using Savin 870 under positive toner test conditions: charging corona set at +6.8 Kv, development bias set at +650 volts, and transfer corona set at -6.6 Kv, reversal image target (black areas on target image with negative toner, white areas on target image with positive toner, gray areas are background.) Image quality was determined on Xerox 4024 paper. The mobility was measured on an Electrokinetic Sonic Amplitude instrument, Matec, Inc., Hopkinton, MA. Results are given in Table 2 below.
• Control 2 The procedure of Control 2 was followed with the following exceptions: two developer soluble additives butylsulfonic acid (Aldrich) and butylsulfamic acid (Aldrich) were used at a 3 mg/g toner solid level. The image quality was determined on a Savin 870 as described in Control 2. Both additives gave developer which produced images with better transfer efficiency and uniformity. Results are given in Table 2 below.
• a black toner was prepared in a Union Process 1S Attritor, Union Process Company, Akron, OH with the following ingredients:
• the mixture was milled at 100°C for 1.25 hours with 0.1875 inch (4.76 mm) diameter carbon steel balls. The mixture was then cooled to ambient temperature, 535 grams of Isopar®-L were added, and the mixture was milled for 2 hours. The particle size was 7.5 ⁇ m measured with a Malvern Particle Sizer.
• the developer was diluted and charged as follows: 1500 grams of 1.0% solids were charged with 15.0 grams of 10% Emphos® D70-30C (100 mg/g toner solids).
• Image quality was determined using Savin 870 under positive toner test conditions: charging corona set at +6.8 Kv, development bias set at +650 volts, and transfer corona set at -6.6 Kv, reversal image target (black areas on target image with negative toner, white areas on target image with positive toner, gray areas are background). Image quality determined on Xerox 4024 paper. The mobility was measured on a Matec, Inc. Electrokinetic Sonic Amplitude instrument. Results are given in Table 3 below.

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Citations (4)

• 1991
  • 1991-05-07 EP EP91107386A patent/EP0456177A1/de not_active Withdrawn
  • 1991-05-08 CA CA002042097A patent/CA2042097A1/en not_active Abandoned
  • 1991-05-10 JP JP3133261A patent/JPH04229875A/ja active Pending
  • 1991-05-10 IL IL98103A patent/IL98103A0/xx unknown
  • 1991-05-10 AU AU76487/91A patent/AU7648791A/en not_active Abandoned
  • 1991-05-11 CN CN91103017.4A patent/CN1056587A/zh active Pending

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