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Elektrophotographischer Flüssigentwickler mit Ladungssteuerungsmittel - Dokument EP0568369

Dokumentenidentifikation EP0568369 03.09.1998
EP-Veröffentlichungsnummer 0568369
Titel Elektrophotographischer Flüssigentwickler mit Ladungssteuerungsmittel
Anmelder Lexmark International Inc., Greenwich, Conn., US
Erfinder Beach, Bradley L., Lexington, Kentucky 40505, US;
Murthy, Ashok, Lexington, Kentucky 40515, US;
Butler, Carla M., Lexington, Kentucky 40523, US;
Pramod, Sharma K., Lexington, Kentucky 40514, US;
Franey, Terence E., Lexington, Kentucky 40515, US;
Suthar, Ajay K., Lexington, Kentucky 40514, US
Vertreter Abitz & Partner, 81679 München
DE-Aktenzeichen 69319957
Vertragsstaaten DE, FR, GB
Sprache des Dokument En
EP-Anmeldetag 29.04.1993
EP-Aktenzeichen 933033615
EP-Offenlegungsdatum 03.11.1993
EP date of grant 29.07.1998
Veröffentlichungstag im Patentblatt 03.09.1998
IPC-Hauptklasse G03G 9/13

Technical Field

This invention relates to electrophotographic imaging with liquid developers, and more specifically to the composition of a liquid developer having a charge director mixture.

Background of the Invention

Liquid developers are known having a pigment-containing resin or resin mixture, an inert organic liquid vehicle, and a charge director. This invention comprises a selection of materials to provide optimum results and is believed applicable with any inert pigment or coloring matter. The vehicle of this invention is mineral oil, which is known for use as such a vehicle. The resin is a mixture of two resins which have been employed or mentioned in prior art as resins for such a liquid toner, but not in combination. The toner charge director is a combination including materials which have been employed or mentioned in prior art as charge directors, but not in the combination of this invention.

U.S. Patent No. 5,047,307 to Landa et al at column 7 discloses mineral oil as a vehicle for such liquid toners. Similarly, U.S. Patent No. 4,886,729 to Grushkin et al at column 4 is illustrative of other teachings of such use of mineral oil.

U.S. Patent No. 4,925,763 to Tsubuko et al teaches ionomeric resins to toner with some blends, and with a separately added lauryl acrylate-acrylic acid resin in liquid toners. U.S. Patent No. 5,034,299 to Houle et al at column 3 mentions Surlyn (trademark) ionomer resin and blends including that resin as the resin in such a liquid toner. U.S. Patent No. 4,772,528 to Larson teaches blends of resins and mentions Surlyn in a list of suitable resins. Similarly, U.S. Patent No. 4,923,778 to Blair et al at column 4 and U.S. Patent No. 4,707,429 to Trout at column 4 are illustrative of other teachings of such use of Surlyn resin. This invention employs a Surlyn resin blended with a Nucrel (trademark) resin, a similar, but non-ionic resin. Nucrel resin, not combined with Surlyn resin, appears prominently in the liquid toner compositions disclosed in U.S. 5,019,477 to Felder. Similarly, Nucrel resin alone is disclosed in the Example of U.S. Patent No. 4,891,286 to Gibson. The added acrylate-acrylic acid resin of the foregoing patent 4,925,763 has an acid component but in this patent the ionomeric component is mixed with the pigment and finely devided before being kneaded with the acrylate-acrylic acid resin.

The foregoing U.S. Patent No. 4,707,429 to Trout teaches the Surlyn resin, lecithin as a charge control agent, calcium Petronate (trademark) as a charge control agent, and aluminum tristearate as an additive to such liquid toner compositions. The foregoing patent 4,772,528 discloses lecithin and calcium petronate and barium petronate as charge control agents. Lecithin is widely taught as a charge control agent. U.S. Patent No. 4,897,332 to Gibson teaches the combination of lecithin and alkylated N-vinyl pyrrolidone in combination as a charge control agent. Further illustrative teachings of lecithin, calcium Petronate, and aluminum tristearate appear in U.S. Patent No. 5,066,821 to Houle et al at column 6. The foregoing U.S. Patent No. 5,047,307 to Landa et al at column 19 is further illustrative of a use of calcium Petronate. The subject invention employs lecithin, aluminum tristearate (optional), and calcium Petronate in combination with other material not included in the foregoing patents.

Disclosure of the Invention

The liquid toner of the present invention comprises mineral oil as a vehicle, fine particles of a thorough blend of ionomeric resin and a resin which is an acid form of an ionomeric resin, pigment, aluminum tristearate (optional), and a separate charge control mixture added to the final mixture of the final materials. The charge control mixture is lecithin, N-methyl-2-pyrrolidone, and calcium Petronate as a 10% - 30% solution in mineral oil. This charge control mixture is selected to optimize speed of recovery of charge properties during continual use.

Best Mode for Carrying Out the Invention

Sixty-four and eight-tenths (64.8) parts by weight Surlyn 9020, an ionomeric resin, a trademarked product of Du Pont Co., is mixed with forty-one and one-tenth (41.1) parts by weight Nucrel 599 resin, a trademarked product of Du Pont Co., an acid form of resin of otherwise the same structure as the Surlyn resins. Surlyn 9020 is a sodium ionomer having melt flow index of 1.0 and nominal density of 0.95. Thirty-five parts by weight of this combination of solids mixture is mixed with 65 parts by weight of Peneteck (trademark) mineral oil. Alternatively, Surlyn 7940, closely similar to Surlyn 9020, is employed as above described with Nucrel 699. Surlyn 7940 is a lithium ionomer having melt flow index of 2.6 and nominal density of 0.94. This produces a somewhat harder toner.

Peneteck mineral oil is described by the manufacturer as a food grade white mineral oil. It is highly purified to remove all aromatics and odor producing impurities. Analysis shows it consists of a mixture of straight chained and branched alkanes. The straight chain portion consists of about 25% of the total and is predominantly a mixture of C-14 to C-18 alkanes. The remaining 75% is a mixture of branched alkanes ranging predominantly from C-16 to C-19 has low volatility.

This mixture is mixed thoroughly as by double planetary mixing or screw extrusion at elevated temperatures (140-160°C) to a mixture in which the resins are thoroughly mixed and plasticized with mineral oil, and all of the mineral oil is completely incorporated into the resulting solid. Where extrusion is employed, the resulting solid may be extruded into cold water with chopping at the nozzle of the extruder. This product from the extruder is pellets having the general appearance of grains of rice. The solid is 21.6% Surlyn resin 14.4% Nucrel resin and 64% mineral oil. This may be termed the "plasticized product."

This product is ground one step further, if needed, in a high speed blender. This added step is needed in the case of the double planetary mixer. In the case of the extruder, the resulting product is in pellets that can go directly into an attritor.

To this product is added pigments, aluminum tristearate, and additional of the mineral oil in an amount to bring the total mineral oil content to 80 to 90% by weight. This is size reduced in an attritor for 6 to 14 hours until the final mixture has volume averaged particle diameter measured using a Shimadzu centrifugal particle size analyzer of about 1 to 3 µm (microns). Preferred attrition is by Union Process model 1S attritor. (The attritor has a one gallon (3,78 l) fluid capacity.) For that attritor, attritor speed may be 200 to 400 rpm. Attritor temperature is 20 to 70°C. Attritor temperature affects morphology and attritor speed affects the time to achieve desired particle size. Preferred temperature is 50°C. The resulting product remains ten to twenty percent solids.

Total solids from the foregoing in each of black and three substractive colors for color imaging are as follows: Black Solids by Weight % Plasticized Product 74.2 Mogul-L (trademark) Carbon Black 22.3 NBS6157 violet dye 2.3 Alum.TriStearate 1.2 Cyan Plasticized Product 81.7 Toyo FG7341 cyan pigment 16.8 Alum.TriStearate 1.5 Magenta Plasticized Product 78.0 Mobay ER8616 magenta dye 20.0 Alum.TriStearate 2.0 Yellow Plasticized Product 84.6 Toyo FG1310 yellow dye 15.7

After the attrition is completed, the mixture is diluted with the mineral oil to two percent solids with stirring. To each of the foregoing color formulas is added a mixture of lecithin, 2-methyl-N-pyrrolidone, and calcium Petronate in a 10-30% solution with the mineral oil until conductivity of approximately 50 picomhos/cm is reached.

This mixture is for charge control. It is formulated as follows: 20 grams of lecithin is dissolved in 500 ml of the mineral oil by stirring at room temperature, after the lecithin is dissolved, 15 ml of N-methyl-2-pyrrolidone is added with continued stirring. This causes an obvious turbidity in the solution. Then 20 grams of calcium petronate is added and dissolved with stirring. Finally, the mixture is centrifuged sufficiently to result in a clear, stable solution which can be decanted from any residue.

Roughly 2 ml of this charge director is required to charge 100 ml of the foregoing resin mixture to the 50 picomhos/cm.

The resulting toner is a negative liquid toner providing good-resolution printing and fixing at relatively moderate temperatures. The mineral oil vehicle does not vaporize well and is readily condensed, thus permitting use as a toner without significant environmental disturbance.

Important parameters to selected are transfer efficiency, fuse grade and optical density. Transfer efficiency is the movement of images from surface to surface since this is done to move an image from a photoconductor surface to an intermediate roller where three colors and black are accumulated in registration, and then to a print roller. Transfer efficiency is measured by direct observation of extent of transfer in typical operation.

Fuse grade is a measure of permanence of final printing. It is determined by measuring the resistance of print in a typical operation to rubbing and scratching.

Optical density is measured on a colored block using a standard OD meter with different filters for different colors.

The foregoing formulas result from a selection balancing good results for the foregoing properties, as well as the necessary properties for liquid toning.

The charge control agent is selected to maximize recovery speed of electrical properties as toner is continually circulated is active imaging system. Since mineral oil is a heavy vehicle, maximization of edge definition may be a more dominated design objective, and the charge control agent would then differ.

An important property of the charge director is termed "percent recovery." That is the percent of the original current generator after a high voltage spike is applied at 90 second intervals. The percent recover is obtained using the following procedure:

The sample is placed in a cell with electrode diameters of 25 mm and a spacing of 1 mm. The voltage applied is 2000 volts for 7 seconds. The current vs time graph is displayed on an oscilloscope and the current maximum is recorded. The sample is allowed to "relax" for 1.5 minutes whereupon a second voltage of 2000 volts is applied. The current maximum is again recorded. The ratio of the second current to the first is the measure of "% recovery."

The electrodes must be cleaned with IPA and allowed to totally dry in-between samples.

The following table illustrates the importance of the presence of N-methyl-2-pyrrolidone (NM2P) to the % recovery. To a stock solution of 4% lecithin and 4% calcium Petronate, NM2P was added. The resulting charge director is used to charge the toner to a 50pmhos/cm level and percent recovery was measured. % NM2P Added % Recovery 0 52 0.8 68 1.5 75 3 90

Some of the data might lead one to speculate that the role of the NM2P may be nothing more than to select the correct solubility fraction of lecithin since the addition of NM2P does cause the solution to go cloudy and some lecithin is centrifuged out. To test that hypothesis a charge director was made up with Isopar-H (trademark isoparaffin) instead of the mineral oil so that after the centrifuge step the Isopar paraffin and the NM2P could be removed with evaporation. Then mineral oil can be added back, which results in a charge director containing the proper fraction of lecithin but without the presence of NM2P.

The following procedure was followed: 2 grams lecithin was dissolved with heat in Isopar-H paraffin. 2 grams of calcium Petronate and 1.5 ml NM2P were added. Stirring was continued in an ice bath to complete the precipitation of the lecithin. The sample was centrifuged and tested to show the initial percent recovery. Then the isopar and NM2P were evaporated off and 50 ml mineral oil was replaced. This sample was tested.

Also, to 25 ml of the mineral oil sample, 0.75 ml of NM2P was added back therefore the right solubility fraction of lecithin was confirmed.

The surprising result was that the sample which had the NM2P removed by evaporation did not have a stable conductivity. That is, a significant drop was observed over the first few hours of the dilution. The following table illustrates this property. 2 ml of each charge director was added to 100 ml the mineral oil and the conductivity was monitored with time. CONDUCTIVITY (pmhos/cm) Time W/ NM2P W/O NM2P Initial 59 160 15 min. 55 67 1 hour 52 60 1.5 hours 52 56 4 hours 52 53 overnight 52 53

This data suggests that the NM2P may play a role in micelle stabilization.

The following table contains the results from the % recovery testing of these samples. CD TO T=1:30 (current) %Recovery Initial sample in Isopar-H 1.74 1.54 88% Sample with mineral oil replacement w/o NM2P 2.5 1.44 57% Sample with mineral 1.66 oil replacement + NM2P (remained clear) 1.66 1.52 91%

The solubility of lecithin may contribute to the variation seen between 80 and 90% recovery BUT the presence of the NM2P does more than just select this solubility fraction. In addition to the % recovery being low for the sample without the NM2P, a surprising result of conductivity instability was observed. This suggests that the NM2P plays a role in stabilizing the micelles, that's why the conductivity drops so drastically without it.

Variations within the scope of the claims of this invention will be apparent.

  1. Flüssigtoner, umfassend Mineralöl, das eine Mischung aus geradkettigen und verzweigten Alkanen ist, als Vehikel, Harzteilchen, die eine innige Mischung aus einem ionomeren Harz und der Säureform eines Harzes, das ansonsten die gleiche Strukturform wie das ionomere Harz hat, umfassen, wenigstens ein Pigment und, als Ladungssteuermaterialien, eine Mischung aus Lecithin, N-Methyl-2-pyrrolidon und Calcium-Petronate.
  2. Toner nach Anspruch 1, bei welchem das genannte ionomere Harz Surlyn-7940-Harz ist und das genannte Säureform-Harz Nucrel-699-Harz ist.
  3. Toner nach Anspruch 1, bei welchem das genannte ionomere Harz Surlyn-9020-Harz ist und das genannte Säureform-Harz Nucrel-599-Harz ist.
  4. Toner nach Anspruch 2 oder Anspruch 3, bei welchem die genannten Harze in einem Verhältnis von etwa 6 Gewichtsteilen Surlyn-Harz zu 4 Gewichtsteilen Nucrel-Harz vorliegen.
  5. Toner nach irgendeinem vorhergehenden Anspruch, der auch Aluminiumtristearat umfaßt.
  6. Toner nach irgendeinem vorhergehenden Anspruch, bei welchem das genannte Lecithin, das genannte Pyrrolidon und das genannte Petronate in einer Menge von 20 Gramm Lecithin, 15 ml Pyrrolidon und 20 Gramm Petronate vorliegen.
  1. A liquid toner comprising mineral oil which is a mixture of straight chained and branched alkanes as a vehicle, resin particles comprising a thorough mixture of an ionomeric resin and the acid form of a resin otherwise of the same structural form of said ionomeric resin, at least one pigment, and as charge control materials, a mixture of lecithin, N-methyl-2-pyrrolidone and calcium Petronate.
  2. A toner as in claim 1 in which said ionomeric resin is Surlyn 7940 resin and said acid-form resin is Nucrel 699 resin.
  3. A toner as in claim 1 in which said ionomeric resin is Surlyn 9020 resin and said acid-form resin is Nucrel 599 resin.
  4. A toner as in claim 2 or claim 3 in which said resins are in a ratio of about 6 parts by weight Surlyn resin to 4 parts by weight Nucrel resin.
  5. The toner as claimed in any preceding claim also comprising aluminum tristearate.
  6. The toner as in any preceding claim in which said lecithin, said pyrrolidone and said Petronate are in proportion of 20 grams lecithin, 15 ml pyrrolidone and 20 grams Petronate.
  1. Toner liquide comprenant une huile minérale qui est un mélange d'alcanes à chaîne droite et à chaîne ramifiée en tant que véhicule, des particules de résine comprenant un mélange complet d'une résine ionomère et de la forme acide d'une résine ayant par ailleurs la même forme structurale que cette résine ionomère, au moins un pigment et en tant que matières de contrôle de charge un mélange de lécithine, de N-méthyl-2-pyrrolidone et de Petronate de calcium.
  2. Toner suivant la revendication 1, dans lequel ladite résine ionomère est la résine Surlyn 7940 et ladite résine sous forme acide est la résine Nucrel 699.
  3. Toner suivant la revendication 1, dans lequel ladite résine ionomère est la résine Surlyn 9020 et ladite résine sous forme acide est la résine Nucrel 599.
  4. Toner suivant les revendications 1 ou 3, dans lequel lesdites résines sont présentes selon un rapport d'environ 6 parties en poids de résine Surlyn à 4 parties en poids de résine Nucrel.
  5. Toner suivant l'une quelconque des revendications précédentes, comprenant aussi du tristéarate d'aluminium.
  6. Toner suivant l'une quelconque des revendications précédentes, dans lequel ladite lécithine et ledit Petronate sont présents à raison de 20 g de lécithine, 15 ml de pyrrolidone et 20 g de Petronate.

A Täglicher Lebensbedarf
B Arbeitsverfahren; Transportieren
C Chemie; Hüttenwesen
D Textilien; Papier
E Bauwesen; Erdbohren; Bergbau
F Maschinenbau; Beleuchtung; Heizung; Waffen; Sprengen
G Physik
H Elektrotechnik



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