CA2042097A1 - Hydrocarbon soluble sulfonic or sulfamic acids as charge adjuvants for positive electrostatic liquid developers - Google Patents

Abstract

HYDROCARBON SOLUBLE SULFONIC OR SULFAMIC ACIDS AS CHARGE
ADJUVANTS FOR POSITIVE ELECTROSTATIC LIQUID DEVELOPERS
ABSTRACT OF THE INVENTION
A positive charged electrostatic liquid developer consisting essentially of (A) a nonpolar liquid having a Kauri-butanol value of less than 30, present in a major amount, (B) thermoplastic resin particles having an average by area particle size of less than 10 µm, (C) a charge director compound, and (D) at least one sulfonic or sulfamic acid compound of the 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, or substituted aryl of 6 to 30 carbon atoms which is soluble in an amount of at least 0.5% based on the weight of component (C) in a mixture of components (A) and (C).

The liquid developer is useful in copying, color proofing, digital color proofing, making lithographic printing plates, and resists.

Description

20~2097 TITL~
HYDROC~RBON SOLUBLE SULFONIC OR SVLFAMIC ACIDS AS CHARGE
ADJUVANTS FOR POSITIVE ELECTROSTATIC LIQUID DEVELOPERS
5~ESCRIPTION
TECHNICAL FIELn 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.
RACKGR~U~D OF THE INVE~ION
15It is known that 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 discharglng 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 109 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 20~2~g7 Sizer described below. After the latent electrostatic image has been formed, the image is developed by the colored toner particles dispersed in said nonpolar liquid and the image may subsequently be transferred to a carrier sheet.
Since the formatlon of proper images depends on the differences of the charge between the liquid developer and the latent electrostatic image to be developed, it has been found desirable to add a charge director compound and preferably adjuvants, e.g., polyhydroxy compounds, polybutylene succinimide, an aromatic hydrocarbon, etc., to the liquid developer comprising the thermoplastic resin, nonpolar liquid, and preferably a colorant. 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.
It has been found that the above disadvantages can be overcome and improved positive-charged developers prepared containing a nonpolar liquid, charge director compound, a thermoplastic resin, and preferably a colorant and a hydrocarbon soluble sulfonic acid or sulfamic acid adjuvant as described below. The 3 0 electrostatic l'quid developer when used to develop an electrostatic image results in improved lmage quality, reduced squash, lmproved solid area coverage independent of the pigment and charge director compound present.

2~20~7 SuMM~y OF T~ TNVFNTTON
In accordance with this invention there is provided an electrostatic liquid developer hav~ng positive charging characteristics consisting essentially of:
(A) a non~polar liquid having a Kauri-butanol value of less than 30, present in a ma~or amount, (B) thermoplastic resin particles having an average by area partlcle size of less than 10 ~m, (C) a charge director compound, and (D) 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 df said nonpolar liquid and charge director compound and being represented by the following 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 earbon atoms, or substituted aryl of 6 to 30 carbon atoms.
Throughout the specification the below-listed terms have the following meanings:
In the claims appended hereto "consisting essentially of" means the composition of the electrostatic liquid developer does not exclude unspecified components which do not prevent the advantages of the deveIoper from being realized. For example, in addition to the primary components, there can be present 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, ~, , . ' ' ' ' -.: .
.: . ' ' ' 2~20~7 Isopar~9-G, Isopar~ , Isopar~9-K, Isopar~-L, Isopar~)-M
and Isopar~-V. These hydrocarbon liquids are narrow cuts of iso-paraffini_ hydrocarbon fractions with extremely high levels of purity. For example~ the boiling range of Isopar~9-G is between 157C and 176C, Isopar~-H between 17 6C and 191C, Isopar~9-K between 177C and 197C, Isoparg)-L between 188C and 206C and Isopar(19-M between 207C and 254C and Isopar~)-V between 254.4C and 329.4C. Isopar~-L has a mid-boiling point 1 O of approximately 194C. Isopar~-M has a flash point of 80C and an auto-ignition temperature of 338C.
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 odvr. 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 2 0 have the following flash points and auto-ignition temperatures:
Auto-Ignition T~ uidE1 ash Po;nt (Cl Temp ( C) Norpart~12 69 204 2 5 Norpar~913 93 210 Norpart~15 118 210 All of the nonpolar liquids have an electrical volume resistivity in excess of 109 ohm centimeters and 3 0 a dielectric constant below 3Ø The vapor pressures at 25C are less than 10 Torr. Isopar~g)-G has a flash point, determined by the tag closed cup method, of 40C, Isopar/~9-H has a flash point of 53C determined by ASTM D
56. Isopar~9-L and Isopar~9-M have flash points of 61C, 3 5 and 80C, respectively, determined by the same method.

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2~42~

While these are the preferred nonpolar liquids, the essential characteristics of all suitable nonpolar liquids are the electrical volume resistivity and the dielectric constant. In addition, a feature of the nonpolar liqulds is a low Kaurl-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 wei~ht, 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.
Useful thermoplastic resins or polymers tB~
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 Cs) 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
68~2 Natural 7 also sold by Union Carbide Corp.; Surlyn~
ionomer resin by E. I. du Pont de Nemours and Company, Wilmington, DE, etc., or blends thereof, polyesters, polyvinyl toluene, polyamides, styrene/butadiene 2~2~7 copolymers and epoxy resins. The synthesis of copolymers of ethylene and an ~,~-ethylenically unsaturated acid of either acrylic acid or methacrylic acid is described in Rees U.S. Patent 3,264,272, the disclosure of which is incorporated herein by reference.
For the purposes of preparing the preferred copolymers, the reaction of the acid contalning copolymer with the ionizable metal compound, as described in the Rees patent, is omitted. The ethylene constituent is present in about 80 to 99.9~ by weight of the copolymer and the acid component in about 20 to 0.1% 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 1 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 190C, respectively.
Other 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 acld 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. 1. 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 hereln.
In addition, the resins have the following preferred characteristics:
1. Be able to disperse the colorant, e.g., pigment, etc.

20~20~7 2. Be substantially insoluble in the dispersant liquid at temperatures below 40C, so that the resin will not dissolve or solvate in storage, 3. Be able to solvate at temperatures above 50C, 4. Be able to be ground to form particles between 0.1 ~m and 5 ~m, ln diameter (preferred size), e.g., determined by Horiba CAPA-500 centrifugal particle analyzer; and between 1 ~m and 15 ~m in diameter, e.g., determined by Malvern 3600E described below, 1 0 5. Be able to form a particle ~average by area) of less than 10 ~m, e.g., determined by Horiba CAPA-500 centrifugal automatic particle analyzer, manufactured by Horiba Instruments, Inc., Irvine, CA: solvent viscosity of 1.29 cps, solvent density of 0.76 g/cc, sample density of 1.32 using a centrifugal rotation of 1,000 rpm, a particle size range of 0.01 to less than 10 ~m, and a particle size cut of 1.0 ~m, and about 30 ~m average particle size, e.g., determined by Malvern 3600E
Particle Sizer, and 6. Be able to fu'se at temperatures in excess of 70C.
By solvation in 3. above, the resins forming the toner particles will become swollen, or gelatinous, or softened.
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 3 0 particle size the readings differ. The following correlation of the average size of toner particles in micrometers (~m) for the two instruments is:

20~2~7 Value Determined By Expected Range For 9.9 + 3 9 6.4 + 1.9 515 4.6 + 1.3 2.8 + 0.8 ~ 1.0 + 0.5 3 0.2 + 0.6 0 This correlation is obtained by statistical analysis of average particle sizes for 67 liquid electrostatic developer samples (not of this invention) obtained on both instruments. The expected range of Horiba values was determined using a linear regression at a confidence level of 95%. In the claims appended to this specification the particle size values are as measured using the Horiba instrument.
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~, Calclum 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 palmitate; calcium, cobalt, manganese, iron, lead ':
.~ .

:

2~2~7 and zinc naphthenates; calcium, cobalt, manganese, lead and zinc resinates, etc.
Hydrocarbon soluble sulfonic and sulfamic acids (D) of the invention are represented by the general formulae:
(1) R-S03H, and (2) R-NH-S03H
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.
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, ~-chlorGbenzenesulfonic 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 acid, 1-dodecylsulfamic acid, etc.
Preferred acids include: p-toluenesulfonic acid, dinonylnaphthalenesulfonic acid, butylsulfonic acid, butylsulfamic acid, ethyl benzenesulfonic acid, n-cyclohexylsulfamic acid, and 10-camphorsulfonic acid.
3 0 The 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.
As indicated above, additional components that can be present in the electrostatic liquid developer are : .

.
:
:

. : :
., ~ .

2842~7 colorants, such as pigments or dyes and combinatlons 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, may be present in the amount of up to about 60 percent by weight based on the total weight of developer solids, preferably 0.01 to 30% by weight based on the total weight of developer solids. The amount of colorant may vary depending on the use of the developer. Examples of 0 pigments include:
pigment List Colour Index e~t Rrand ~ame ~anufacturer Pi~ment Permanent Yellow DHG Hoechst Yellow 12 15 Permanent Yellow GR Hoechst Yellow 13 ~ermanent Yellow G Hoechst Yellow 14 Permanent Yellow NCG-71 Hoechst Yellow 16 Permanent Yellow GG Hoechst Yellow 17 Hansa Yellow RA Hoechst Yellow 73 Hansa Brilliant Yellow 5GX-02 Hoechst Yellow 74 Dalamar~ Yellow YT-858-D Heubach Yellow 74 Hansa Yellow X Hoechst Yellow 75 Novoperm~ Yellow HR Hoechst Yellow 83 Chromophtal~ Yellow 3G Clba-Geigy Yellow 93 25 Chromophtal~ Yellow GR Ciba-Geigy Yellow 95 Novoperm~ Yellow FGL Hoechst Yellow 97 Hansa Brilliant Yellow lOGX Hoechst Yellow 98 Lumogen~ Light Yellow BASF Yellow 110 Permanent Yellow G3R-01 Hoechst Yellow 114 30 Chromophtal~ Yellow 8G Ciba-Geigy Yellow 128 Irgazin~ Yellow 5GT Ciba-Geigy Yellow 129 Hostaperm~ Yellow H4G Hoechst Yellow 151 Hostaperm~ Yellow H3G Hoechst Yellow 154 L74-1357 Yellow Sun Chem. Yellow 14 L75-1331 Yellow Sun Chem. Yellow 17 L75-2337 Yellow Sun Chem. Yellow 83 2~42~97 Hostaperm~ Orange GR Hoechst Orange 43 Paliogen~ Orange BASF Orange 51 Irqalite~ Rubine 4BL Ciba-Geigy Red 57:1 Quindo~ Magenta Mobay Red 122 Indofast~ Brilliant Scarlet Mobay Red 123 ~ostaperm~ Scarlet GO Hoechst Red 168 Permanent Rubine F6B Hoechst Red 184 Monastral~ Magenta Ciba-Geigy Red 202 Monastral~ Scarlet Ciba-Geigy Red 207 10 Heliogen~ Blue L 6901F BASF Blue 15:2 Heliogen~ Blue NBD 7010 BASF Blue:3 Heliogen~ Blue K 7090 BASF Blue 15:3 Heliogen~ Blue L 7101F BASF Blue 15:4 Paliogen~ Blue L 6470 BASF Blue 60 15 Heliogen~ Green K 8683 BASF Green 7 Heliogen~ Green L 9140 BASF Green 36 Monastral~ Violet R Ciba-Geigy Violet 19 Monastral~ Red B Ciba-Geigy Violet 19 Quindo~ Red R6700 Mobay Violet 19 20 Quindo~ Red R6713 Mobay Indofast~ Violet Mobay Violet 23 Monastral~ Violet Maroon B Ciba-Geigy Violet 42 Sterling~ NS Black Cabot Black 7 Sterling~ NSX 76 Cabot Tipure~ R-101 Du Pont White 6 Other 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 wlth the colorant. Metal particles can also be added.
Another additional component of the electrostatic liquid developer is an adjuvant which can be selected 2~2~7 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 S 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 ad~uvants include:
~ LI~.D5~U~ 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. Patent 3,900,412, column 20, lines 5 to 13, incorporated herein by reference; Amoco 575 having a number average molecular weight of about 600 ~vapor pressure osmometry) made by reacting maleic anhydride with polybutene to give an alkenylsuccinlc anhydride which in turn is reacted with a polyamine. Amoco 575 is 40 to 45% surfactant, 36% aromatic hydrocarbon, and the remainder oil, etc. These ad~uvants are described in El-Sayed and Taggi U.S. Patent 4,702,984; and ~ L~ac~s~: benzene, toluene, naphthalene, substituted benzene and naphthalene compounds, e.g., trimethylbenzene, xylene, dimethylethylbenzene, ethylmethylbenzene, propylbenzene, Aromatic 100 which is a mixture of Cg and C1o alkyl-substituted benzenes manufactured by Exxon Corp., etc., as described in Mitchell U.S. Patent 4,631,244.
The disclosures of the above-listed United States patents describing the adjuvants are incorporated herein by reference.

2~2a~7 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 plurallty of fibers integrally extending therefrom although the formation of fibers extending from the toner particles is preferred. The term "fibers" as used herein means pigmented toner particles formed with fibers, t~ndrils, 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). For example, into 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, equlpped 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. Generally the resin, nonpolar liquid and optional colorant are placed in the vessel prior to starting the dispersing step. Optionally the colorant 3 0 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 .
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2~2a~

temperature, i.e., the temperature of ingredien~s 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 ls 80 to 120C. Other temperatures outside this range may be suitable, however, depending on the particular ingredients used. The presence of the irregularly moving particulate media in the vessel is preferred to prepare the dispersion of toner particles.
Other stirring means can be used as well, however, to prepare dispersed toner particles of proper si~e, configuration and morphology. Useful 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 ~1.0 to approx. 13 mm).
After dispersing the ingredients in the vessel, with or without a polar additive present, until the desired dispersion is achieved, typically 1 hour with the mixture being fluid, the dispersion is cooled, e.g., in the range of 0C to 50C. 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 3 0 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 grlnding by means of particulate media. Additional liquid may be added at any step during the preparation of the liquid 1~

- 2~42~97 electrostatic toners to facilitate grinding or to di~ute the toner to the appropriate % solids needed for toning.
Additional liquid means nonpolar liquid, polar liquid or combinations thereof. Cooling is accomplished by means 5 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 ~acket 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.
lS After cooling and separating the dispersion of toner particles from the particulate media, if present, by means known to those skilled in the art, it is possible to reduce the concentration of the toner particles in the dispersion, impart an electrostatic charge of predetermined polarity to the toner particles, or a combination of these variations. 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 0.1 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 3 0 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., a$ter 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 : . .

2~ll23~7 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 5 can be added prior to, concurrently with, or subsequent thereto. If an additional ad~uvant 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.
Other process embodiments for preparing the electrostatic liquid developer include:
(A) dispersing a thermoplastic resin and optionally a colorant and/or adjuvant in the absence of a nonpolar liquid having a Kauri-butanol value of less than 30 to form a solid mass.
(B) shredding the solid mass, (C) grinding the shredded solid mass by means of particulate media in the presence of a liquid selected from the group consisting of a polar liquid having a Kauri-butanol value of at least 30, a nonpolar liquid having a Kauri-butanol value of less than 30, and combinations thereof, (D) separating the dispersion of toner particles having an average by area particle size of less than 10 ~m from the particulate media, and (E) adding additional nonpolar liquid, polar liquid or combinations thereof to reduce the 3 0 concentration of toner particles to between 0.1 to 15.0 percent by weight with respect to the liquid; and (F) adding to the dlspersion a nonpolar soluble ionic or zwitterionic charge director compound and at least one sulfonic or sulfamic acid as described above, and 2~2~97 (A) dispersing a thermoplastic resin and optionally a colorant and/or adjuvant in the absence of a nonpolar liquid having a Xauri-butanol value of less than 30 to form a solid mass.
(B) shredding the solid mass, (C) redispersing the shredded solid mass at an elevated temperature in a vessel in the presence of a nonpolar llquid having a Kauri~butanol value of less than 30, and optionally a colorant while maintaining the temperature in the vessel at a temperature sufficient to plasticize and iiquify the resin and below that at which the nonpolar liquid degrades and the resin and/or colorant decomposes, (D) cooling the dispersion, either (1) without stirring to form a gel or solid mass, followed by shredding the gel or solid mass and grinding by means of particulate media in the presence of additional liquid;
(2) with stirring to form a viscous mixture and grinding by means of particulate media with or without the presence of additional liquid; or (3) while grinding by means of particulate media to prevent the formation of a gel or solid mass with or without the presence of additional liquid;
(E) separating the dispersion of toner particles having an average by area particle size of less than 10 ~m from the particulate media, and (F) adding additional nonpolar liquid, polar liquid or combinations thereof to reduce the concentration of toner particles to between 0.1 to 15.0 percent by weight with respect to the liquid; and (G) adding to the dispersion a nonpolar soluble ionic or ~witterionic charqe director compound and at least one soluble sulfonic or sulfamic acid as described above.

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20~20~7 TN~Us~RI~ AP~LIGA~ILIT~
The positive charged liquid electrostatic developers of this invention demonstrate improved image quality, resolution, solid area coverage (density), and S 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 0 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. In copying and proofing 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, 0 llthographic printing plateQ, and resists.
MPLT;'.~
The following controls and examples wherein the parts and percentages are by weight illustrate but do not limit the invention. In the examples the 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. Thls device conslsts 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 decreaslnq the 2~20~7 diameter of the roll spacers to maintain the same gap between the roll and photoconductor.
Electrical modifications include:
~1) disconnecting the image density feedback loop from the development electrode and connecting the electrode to a Keithly high voltage supply (model 247), (Keithly, Cleveland, OH), (2) connecting a Keithly high voltage supply~model 297) to the modified reverse roll, and ~3) disconnecting the transfer corona and connectinq same to a Trek (model 610) high voltage supply, ITrek~ Medina, NY).
The modified Savin 870 was then used to evaluate both positive and negative developers depending on the voltages and biasses used. To evaluate positive developers the copier was run in a positive mode:
reversed image target was used with negative transfer corona voltages and positive development bias. The reversed image target consists of white characters and lines, etc., on a black background.
The principal of operation is described below. 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 increaslng discharge-black areas and white areas). 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.

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2Q~20~7 Actual voltages and biases used can be found in the examples.
~ONT~I~l In a Union Process lS attritor, Union Process Compa~y, Akron, Ohio were placed the following ingredients:
I~RE~ NTs a~OUNT
Copolymer of ethylene ~91%) and256.8 methacrylic acid (9~), melt index at 10 190C is 500, acid number 54 NBD 7010 cyan pigment 64.2 (BASF, Holland, MI) Isopar~-L (Exxon Corporation)1284.0 The ingredients were heated to 100C 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 wlth 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.
In addition, Neutral Barium Petronate~ and butyl alcohol were added to a fourth sample. After equilibration, the conductivity and mobility of the samples were measured. The mobility was measured on an Electrokinetic Sonic Amplitude instrument, Matec, Inc., Hopkinton, MA. Samples were equllibrated 3 days before measurement, unless otherwise noted. Results are given in Table 1 below.

2~42~7 ~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.

Charging additives were prepared as follows:

1. 0.086 gram of butanesulfonic acid (Pfaltz and 1 0 Bauer, Inc., Waterbury, CT) was added to 19.92 grams of 10% Emphos~ D70-30C in Isopar~-L and sonicated for 15 minutes.
2. 0.086 gram of butanesulfonic acid (Pfaltz and Bauer, Inc.) was added to 19.99 grams of 10%
Neutral Barium Petronate~ ~NBP) in Isopar~-L
and sonicated for 15 minutes.
3. 0.55 gram of 1-R-(-)-10-camphorsulfonic acid (Aldrich, Milwaukee, WI) was added to 110 grams of 10% Neutral Barium Petronate~ in Isopar~-L
and ground for 4 hours on a ball mill.
4. 0.55 gram of 1-butylsulfamic acid (Aldrich) was added to 110 grams of 10% Neutral Barlum Petronate~ in Isopar~-L and ground for 4 hours on a ball mill.
5. 0.55 gram of 1-butylsulfamic acid (Aldrich) was added to 110 grams of 10% Emphos~ D70-30C in Isopar~-L and ground for 4 hours on a ball mill.

6. A 10% solution of alkylbenzenesulfonic acid (Alfa, Danvers, MA) was made in Isopar~-L.

7. 0.5 g of n-cyclohexylsulfamic acid ~Fluka, Ronkonkoma, NY) was dissolved in 5 g of butyl alcohol. This solution was then added to 50 g of 10% Neutral Barium Petronate~.
The charging additives in Table 1 below were added to 30 g samples of the cyan develop~r and the ' ' , :
, 20420~7 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.

`^" 20~2097 T~B~.E 1 Conductivity Mobility Additive (~mhos/cm) (XlO1Om2/Vs) 120 mg/g Emphos~ 30 3.7 (control) 120 mg/g BsP 62 1.4 1 0 (control)1 120 mg/g NBP 27 2.3 (control) 150 mg/g NBP 22 2.0 (control) 150 mg/g NBP + 17 1.2 150 mg/g butyl alcohol (control)2 120 mg/g Emphos~ 35 5~3 D70-30C + 6 mg/g butanesulfonic acid 120 mg/g NBP+ 135 5.2 6 mg/g butane-; sulfonic acid 120 mg/g NBP + 47 3.6 6 mg/g camphor-su1fonic acid 2~2097 ~ABLE 1 (continuedL
Conductivity Mobility Additive (Pmhos/cm) (XlO1Om2/Vs) 120 mg/g NBP + 31 3.4 6 mg/g butyl-sulfamic acid 120 mg/g Emphos~ 33 5.7 10 D70-30C + 6 mg/g butylsulfamic acid 120 mg/g Emphos~ 90 4.3 15 D70-30C + 42 mg/g alkylbenzene-sulfonic acidl 120 mg/g BBP+ 52 2.5 42 mg/q alkylbenzene-sulfonic acid1 120 mg/g NBP+ 129 4.2 20 mg/g alkylbenzene-sulfonic acid 150 mg NBP + 23 4.8 15 mg/g N-cyclohexyl-sulfamic acid 2 1 Equilibrated 24 hours.
2 Equilibrated 2 weeks.

2~20:~7 Control 2 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%
5 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 0 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.

~xample 2 The procedure of Control 2 was followed with the following exceptions: two developer soluble additives 2~ 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 gi-~en in Table 2 below.

2~'~2~97 ~2 - TRANSF.
COND. MOBILITY DEN- RES. EFF. UNIFO~M-ADDITIVE ~Pn~ho~/cm) (X1010m2/V~) SITY (lp/nun~ ~%) ITY

None 6 3 . 9 0 . 77 5 37 POOR
( cont rol ) Butyl- 28 9 . 0 0 . 70 4 ~2 GOOD
~ulfonic 1 0 acid Butyl- 9 5. 5 0 . 90 7 56 FAIR
sulfamic acid Control 3 A black toner was prepared in a Union Process lS
Attritor, Union Process Company, Akron, O~ with the following ingredients:
AMOUNT ( Sr ) Terpolymer of methyl methacrylate ~67%), 256.8 methacrylic acid (3%) and ethylhexylacrylate (30%), acid No. 13 Sterling NS black pigment, 64.2 Cabot Corporation, Boston, MA
Isopar~-L, Exxon Corp. 1284.0 The mixture was milled at 100C 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 s~ze 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~ D70-2 ~ 9 7 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 S 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 0 Amplitude instrument. Results are given in Table 3 below.

~xam~le 3 Two toners were prepared as described in Control 3 except that developer soluble additives dinonyl-naphthalenesulfonic acid (Alfa), 50 mg/g toner solids, and ethylbenzenesulfonic acid (Aldrich), 70 mg/g toner solids were added to the developer. The image quality was evaluated on a Savin 870 and the results are given in Table 3 below.
~RT.~ 3 TRANSF.
COND. MOBILITY DEN- RES. EFF. VNIFORM-ADDITIVE ~pmhos/cm) (X1010m2/V~) SITY ~lD/mm) (~) ITY
25 None 14 -1.4 UNMEARSVREABLE
(control) Dinonyl-10 4.8 0.22 5 23 GOOD
naphtha-lene~ul-3 0 fonic acid Ethylbenzene 8 7.4 0.24 - 33 GOOD
qulfonic acid

Claims (26)

1. An electrostatic liquid developer having positive charging characteristics consisting essentially of (A) a nonpolar liquid having a Kauri-butanol value of less than 30, present in a major amount, (B) thermoplastic resin particles having an average by area particle size of less than 10 µm, (C) a charge director compound, and (D) 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 said nonpolar liquid and charge director compound and being represented by the following 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, or substituted aryl of 6 to 30 carbon atoms.

2. An electrostatic liquid developer according to claim 1 wherein the acid compound is of the formula:

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, or substituted aryl of 6 to 30 carbon atoms.

3. An electrostatic liquid developer according to claim 1 wherein the acid compound is of the formula:

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, or substituted aryl of 6 to 30 carbon atoms.

4. An electrostatic liquid developer according to claim 1 wherein the sulfur-containing acid compound is selected from the group consisting of 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 acid, and 1-dodecylsulfamic acid.

5. An electrostatic liquid developer according to claim 2 wherein the acid compound is butylsulfonic acid.

6. An electrostatic liquid developer according to claim 2 wherein the acid compound is dinonylnaphthalenesulfonic acid.

7. An electrostatic liquid developer according to claim 2 wherein the acid compound is ethylbenzenesulfonic acid.

8. An electrostatic liquid developer according to claim 1 wherein component (A) is present in 85 to 99.9%
by weight, based on the total weight of the liquid developer, the total weight of developer solids is 0.1 to 15% by weight, component (C) is present in an amount of 0.25 to 1,500 mg/g developer solids, and the sulfonic or sulfamic acid compound (D) is present in an amount of at least 0.5 percent based on the weight of charge director compound in a mixture of nonpolar liquid and charge director compound.

9. An electrostatic liquid developer according to claim 1 containing up to about 60% by weight of a colorant based on the total weight of developer solids.

10. An electrostatic liquid developer according to claim 9 wherein the colorant is a pigment.

11. An electrostatic liquid developer according to claim 9 wherein the colorant is a dye.

12. An electrostatic liquid developer according to claim 1 wherein a fine particle size oxide is present.

13. An electrostatic liquid developer according to claim 1 wherein an additional compound is present which is an adjuvant selected from the group consisting of polyhydroxy compounds, polybutylene succinimide, and an aromatic hydrocarbon.

14. An electrostatic liquid developer according to claim 9 wherein an additional compound is present which is an adjuvant selected from the group consisting of polyhydroxy compounds, polybutylene succinimide, and an aromatic hydrocarbon.

15. An electrostatic liquid developer according to claim 13 wherein a polyhydroxy adjuvant compound is present.

16. An electrostatic liquid developer according to claim 13 wherein a polybutylene succinimide adjuvant compound is present.

17. An electrostatic liquid developer according to claim 13 wherein an aromatic hydrocarbon adjuvant compound having a Kauri-butanol value of greater than 30 is present.

18. An electrostatic liquid developer according to claim 1 wherein the thermoplastic resin component (B) is a copolymer of at least one alkyl ester of acrylic or methacrylic acid wherein alkyl is 1 to 20 carbon atoms and acrylic or methacrylic acid.

19. An electrostatic liquid developer according to claim 1 wherein the thermoplastic resin component is a copolymer of methyl methacrylate (50-90%)/methacrylic acid (0-20%)/ethylhexyl acrylate (10-50%).

20. An electrostatic liquid developer according to claim 19 wherein the thermoplastic resin component is a copolymer of methyl methacrylate (67%)/methacrylic acid (3%)/ethylhexyl acrylate (30%).

21. An electrostatic liquid developer according to claim 1 wherein the thermoplastic resin component is a copolymer of ethylene (89%)/methacrylic acid (11%) having a melt index at 190°C of 100.

22. An electrostatic liquid developer according to claim 1 wherein the particles have an average particle size by area of less than 5 µm.

23. An electrostatic liquid developer according to claim 1 wherein component (C) is a salt of phosphated mono- and diglycerides with unsaturated or saturated acid substituents.

24. An electrostatic liquid developer according to claim 1 wherein component (C) is an oil-soluble petroleum sulfonate.

25. An electrostatic liquid developer according to claim 1 wherein component (C) is a metallic soap.

26. An electrostatic liquid developer according to claim 1 wherein the resin particles have a plurality of fibers integrally extending therefrom.