# US 5,028,508 A · Metal salts of beta-diketones as charging adjuvants for electrostatic liquid developers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,028,508 A - Document ID: US5028508A - Status: Granted - Kind: A - Application number: 07/453,834 - Filed: 1989-12-20 - Granted: 1991-07-02 - Earliest claimed: 1989-12-20 - Assignees: DXImaging - Inventors: Gregg A. Lane; James R. Larson; Ronald L. Mueller - Web page: https://patentgrep.com/patent/US5028508A ## CPC - G03G 9/1355: {Ionic, organic compounds} - G03G 9/12: in liquid developer mixtures - G03G: ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY ## Abstract An electrostatic 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, less than 30 .mu.m average particle size, a nonpolar liquid soluble ionic or zwitterionic charge director compound (C), and (D) a metal salt of a .beta.-diketone as described. The process of preparation of the liquid electrostatic developer is also described. The liquid developers of the invention are useful in copying, color proofing, including digital color proofing, lithographic printing plates and resists. ## Claims ### Claim 1 An improved electrostatic liquid developer consisting essentially of (A) a nonpolar liquid having a Kauri-butanol value of less then 30, present in a major amount, (B) thermoplastic resin particles having an average by area particle size of less than 30 .mu.m, (C) a nonpolar liquid soluble ionic or zwitterionic charge director compound, and (D) a .beta.-diketone compound of the general formula: ##STR4## where M is a metal cation; R and R.sup.1 which can be the same or different are alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 30 carbon atoms, or substituted aryl of 6 to 30 carbon atoms; n is the valency of the metal; J is 0 to n-1; and X.sup.- is OH, Cl, F, sulphate, nitrate, chlorate, phosphate, acetate, alkyl carboxylate of 1 to 18 carbon atoms, or aryl carboxylate of 6 to 30 carbon atoms. ### Claim 2 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the metal salt of .beta.-diketone is calcium acetylacetonate. ### Claim 3 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the metal salt of .beta.-diketone is aluminium octadecanoylacetonate. ### Claim 4 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the metal salt of .beta.-diketone is aluminium benzoylacetonate. ### Claim 5 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the metal salt of .beta.-diketone is nickel acetylacetonate. ### Claim 6 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the metal salt of .beta.-diketone is chromium acetylacetonate. ### Claim 7 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the metal salt of .beta.-diketone is aluminum acetylacetonate. ### Claim 8 (depends on 1) 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 liquid developer, the total weight of developer solids is 0.1 to 15.0% by weight, and component (C) is present in an amount of 0.25 to 1500 mg/g developer solids. ### Claim 9 (depends on 8) An electrostatic liquid developer according to claim 8 wherein the metal salt of .beta.-diketone is present in 0.1 to 40% by weight based on the total weight of the developer solids. ### Claim 10 (depends on 1) 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. ### Claim 11 (depends on 10) An electrostatic liquid developer according to claim 10 wherein the colorant is a pigment. ### Claim 12 (depends on 10) An electrostatic liquid developer according to claim 10 wherein the colorant is a dye. ### Claim 13 (depends on 1) An electrostatic liquid developer according to claim 1 wherein a fine particle size inorganic oxide is present. ### Claim 14 (depends on 1) 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 compound, aminoalcohol, polybutylene succinimide, metallic soap, and an aromatic hydrocarbon. ### Claim 15 (depends on 10) An electrostatic liquid developer according to claim 10 wherein an additional compound is present which is an adjuvant selected from the group consisting of polyhydroxy compound, aminoalcohol, polybutylene succinimide, metallic soap, and an aromatic hydrocarbon. ### Claim 16 (depends on 14) An electrostatic liquid developer according to claim 14 wherein a polyhydroxy compound is present. ### Claim 17 (depends on 14) An electrostatic liquid developer according to claim 14 wherein an aminoalcohol compound is present. ### Claim 18 (depends on 14) An electrostatic liquid developer according to claim 14 wherein a polybutylene succinimide compound is present. ### Claim 19 (depends on 14) An electrostatic liquid developer according to claim 14 wherein a metallic soap compound is present dispersed in the resin particles. ### Claim 20 (depends on 14) An electrostatic liquid developer according to claim 14 wherein an aromatic hydrocarbon compound is present. ### Claim 21 (depends on 17) An electrostatic liquid developer according to claim 17 wherein the aminoalcohol compound is triisopropanolamine. ### Claim 22 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the thermoplastic resin is a copolymer of ethylene and an .alpha.,.beta.-ethylenically unsaturated acid selected from the group consisting of acrylic acid and methacrylic acid. ### Claim 23 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the thermoplastic resin is polystyrene. ### Claim 24 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the thermoplastic resin is a copolymer of ethylene (80 to 99.9%)/acrylic or methacrylic acid (20 to 0%)/alkyl ester of acrylic or methacrylic acid wherein alkyl is 1 to 5 carbon atoms (0 to 20%). ### Claim 25 (depends on 10) An electrostatic liquid developer according to claim 10 wherein the thermoplastic resin is a copolymer of ethylene (80 to 99.9%)/acrylic or methacrylic acid (20 to 0%)/alkyl ester of acrylic or methacrylic acid wherein alkyl is 1 to 5 carbon atoms (0 to 20%). ### Claim 26 (depends on 24) An electrostatic liquid developer according to claim 24 wherein the thermoplastic resin is a copolymer of ethylene (90%)/methacrylic acid (10%) having a melt index at 190.degree. C. of 500. ### Claim 27 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the particles have an average by area particle size of less than 5 .mu.m. ### Claim 28 (depends on 1) An electrostatic liquid toner according to claim 1 wherein component (C) is an oil-soluble petroleum sulfonate. ### Claim 29 (depends on 1) An electrostatic liquid toner according to claim 1 wherein component (C) is an anionic glyceride. ### Claim 30 A process for preparing electrostatic liquid developer for electrostatic imaging comprising (A) dispersing at an elevated temperature in a vessel a thermoplastic resin and a dispersant nonpolar liquid 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 liquify the resin and below that at which the dispersant nonpolar liquid degrades and the resin and/or colorant decomposes, (B) 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 with or without 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; (C) separating the dispersion of toner particles having an average particle size of less than 30 .mu.m from the particulate media; (D) adding to the dispersion a nonpolar liquid soluble ionic or zwitterionic charge director compound; and (E) adding during any of steps (A), (B), (C) or (D) a metal salt of the general formula: ##STR5## where M is a metal cation; R and R.sup.1 which can be the same or different are alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 30 carbon atoms, or substituted aryl of 6 to 30 carbon atoms; n is the valency of the metal; J is 0 to n-1; and X.sup.- is OH, Cl, F, sulphate, nitrate, chlorate, phosphate, acetate, alkyl carboxylate of 1 to 18 carbon atoms, or aryl carboxylate of 6 to 30 carbon atoms. ### Claim 31 (depends on 30) A process according to claim 30 wherein the metal salt of .beta.-diketone is calcium acetylacetonate. ### Claim 32 (depends on 30) A process according to claim 30 wherein the metal salt of .beta.-diketone is aluminum acetylacetonate. ### Claim 33 (depends on 30) A process according to claim 30 wherein the metal salt of .beta.-diketone is aluminium octadecanoylacetonate. ### Claim 34 (depends on 30) A process according to claim 30 wherein the metal salt of .beta.-diketone is aluminium benzoylacetonate. ### Claim 35 (depends on 30) A process according to claim 30 wherein the metal salt of .beta.-diketone is nickel acetylacetoneate. ### Claim 36 (depends on 30) A process according to claim 30 wherein the metal salt of .beta.-diketone is chromium acetylacetonate. ### Claim 37 (depends on 30) A process according to claim 30 wherein there is present in the vessel up to 100% by weight of a polar liquid having a Kauri-butanol value of at least 30, the percentage being based on the total weight of the developer liquid. ### Claim 38 (depends on 30) A process according to claim 30 wherein the particulate media are selected from the group consisting of stainless steel, carbon steel, ceramic, alumina, zirconia, silica, and sillimanite. ### Claim 39 (depends on 30) A process according to claim 30 wherein the thermoplastic resin is a copolymer of ethylene and an .alpha.,.beta.-ethylenically unsaturated acid selected from the group consisting of acrylic acid and methacrylic acid. ### Claim 40 (depends on 30) A process according to claim 30 wherein the thermoplastic resin is a copolymer of ethylene (80 to 99.9%)/acrylic or methacrylic acid (20 to 0%)/alkyl ester of acrylic or methacrylic acid wherein alkyl is 1 to 5 carbon atoms (0 to 20%). ### Claim 41 (depends on 40) A process according to claim 40 wherein the thermoplastic resin is a copolymer of ethylene (90%)/methacrylic acid (10%) having a melt index at 190.degree. C. of 500. ### Claim 42 (depends on 30) A process according to claim 30 wherein the charge director compound is an oil-soluble petroleum sulfonate. ### Claim 43 (depends on 30) A process according to claim 30 wherein the charge director is an anionic glyceride. ### Claim 44 (depends on 30) A process according to claim 30 wherein the additional nonpolar liquid, polar liquid, or combinations thereof is present to reduce the concentration of toner particles to between 0.1 to 15 percent by weight with respect to the liquid. ### Claim 45 (depends on 44) A process according to claim 44 wherein the concentration of toner particles is reduced by additional nonpolar liquid. ### Claim 46 (depends on 30) A process according to claim 30 wherein cooling the dispersion is accomplished 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. ### Claim 47 (depends on 30) A process according to claim 30 wherein cooling the dispersion is accomplished without stirring to form a gel or solid mass, followed by shredding the gel or solid mass and grinding by means of particulate media with or without the presence of additional liquid. ### Claim 48 (depends on 30) A process according to claim 30 wherein cooling the dispersion is accomplished with stirring to form a viscous mixture and grinding by means of particulate media with or without the presence of additional liquid. ### Claim 49 (depends on 30) A process according to claim 30 wherein an adjuvant compound selected from the group consisting of polyhydroxy compound, aminoalcohol, polybutylene succinimide, metallic soap, and aromatic hydrocarbon is added during the dispersing step (A). ### Claim 50 (depends on 49) A process according to claim 49 wherein the adjuvant compound is an aminoalcohol. ### Claim 51 (depends on 50) A process according to claim 50 wherein the aminoalcohol is triisopropanolamine. ### Claim 52 (depends on 44) A process according to claim 44 wherein an adjuvant compound selected from the group consisting of polyhydroxy compound, aminoalcohol, polybutylene succinimide, metallic soap, and an aromatic hydrocarbon is added to the liquid developer. ### Claim 53 (depends on 52) A process according to claim 52 wherein the adjuvant compound is a polyhydroxy compound. ### Claim 54 (depends on 53) A process according to claim 53 wherein the polyhydroxy compound is ethylene glycol. ### Claim 55 (depends on 52) A process according to claim 52 wherein the adjuvant compound is a metallic soap dispersed in the resin particles. ### Claim 56 (depends on 55) A process according to claim 55 wherein the adjuvant compound is aluminium tristearate. ### Claim 57 (depends on 1) A process for preparing electrostatic liquid developer comprising (A) dispersing a colorant in a thermoplastic resin in the absence of a dispersant 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 particle size of less than 30 .mu.m from the particulate media, (E) 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; (F) adding to the dispersion a liquid soluble ionic or zwitterionic charge director compound, and (G) adding during any of steps (A), (B), (C), (D), (E), or (F) a metal salt of a .beta.-diketone according to claim 1. ### Claim 58 (depends on 1) A process for preparing electrostatic liquid developer comprising (A) dispersing a colorant in a thermoplastic resin in the absence of a dispersant nonpolar liquid having a Kauri-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 dispersant nonpolar liquid having a Kauri-butanol value of less than 30, while maintaining the temperature in the vessel at a temperature sufficient to plasticize and liquify the resin and below that at which the dispersant 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 with or without 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 particle size of less than 30 .mu.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; (G) adding to the dispersion a liquid soluble ionic or zwitterionic charge director compound, and (H) adding during any of steps (A), (B), (C), (D), (E), (F) or (G) a metal salt of a .beta.-diketone according to claim 1.