# US 5,106,717 A · AB diblock copolymers as toner particle dispersants 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 5,106,717 A - Document ID: US5106717A - Status: Granted - Kind: A - Application number: 07/518,034 - Filed: 1990-05-02 - Granted: 1992-04-21 - Earliest claimed: 1990-05-02 - Assignees: DXImaging - Inventors: William A. Houle; Loretta A. Grezzo Page - Web page: https://patentgrep.com/patent/US5106717A ## CPC - G03G 9/133: {Graft-or block polymers} - G03G 9/12: in liquid developer mixtures - G03G: ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY ## Abstract 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 .mu.m, and coated with (C), (C) an AB diblock copolymer toner particle dispersant as defined, and (D) a nonpolar liquid soluble ionic or zwitterionic compound. Optionally a colorant and charge adjuvant are present. The process of making the electrostatic liquid developer is described. The electrostatic liquid developer is useful in copying, making proofs including digital color proofs, 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 than 30, present in a major amount, (B) thermoplastic resin particles having an average by area particle size of less than 10 .mu.m and coated with (C), (C) an AB diblock copolymer toner particle dispersant substantially soluble in component (A), wherein the B block is a polymer substantially soluble in component (A) having a number average molecular weight range of 2,000 to 50,000, and the A block is a trialkyl amino polymer having a number average molecular weight range of 200 to 10,000, the number average degree of polymerization (DP) ratio of the B block to the A block being in the range of 10 to 2 to 100 to 20, and (D) a nonpolar liquid soluble ionic or zwitterionic compound. ### Claim 2 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the A block of the AB diblock copolymer is a polymer prepared from at least one monomer selected from the group consisting of (1) CH.sub.2 .dbd.CCH.sub.3 CO.sub.2 R, (2) CH.sub.2 .dbd.CHCO.sub.2 R wherein R in (1) and (2) is alkyl of 1 to 20 carbon atoms where the terminal end of R is of the general formula N(R.sup.1).sub.3, where N is nitrogen and R.sup.1 is alkyl of 1 to 200 carbon atoms, aryl of 6 to 30 carbon atoms, and alkylaryl of 7 to 200 carbon atoms, and (3) 2-, 3-, or 4-vinyl pyridine wherein the ring carbon atoms not substituted by the vinyl group may be substituted with R.sup.1 and the pyridine nitrogen atom is substituted with R.sup.1 wherein R.sup.1 is alkyl of 1-200 carbon atoms. ### Claim 3 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the B block of the AB diblock copolymer is a polymer prepared from at least one monomer selected from the group consisting of butadiene, isoprene, and compounds of the general formulas: CH.sub.2 .dbd.CCH.sub.3 CO.sub.2 R.sup.2 and CH.sub.2 .dbd.CHCO.sub.2 R.sup.2 wherein R.sup.2 is alkyl of 8 to 30 carbon atoms. ### Claim 4 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the AB diblock copolymer toner particle dispersant is selected from the group consisting of poly-2-(N,N-dimethylamino)ethyl methacrylate/polyethylhexyl methacrylate; poly-2-(N,N-diethylamino)ethyl methacrylate/polylauryl methacrylate; poly-2-vinyl pyridine/polyethylhexyl acrylate; poly-4-vinyl pyridine/polybutadiene, poly-2-(N,N-dimethylamino)ethyl methacrylate/polylauryl methacrylate and poly-2-(N,N-diethylamino)ethyl methacrylate/polyethylhexyl methacrylate. ### Claim 5 (depends on 4) An electrostatic liquid developer according to claim 4 wherein the poly-2-(N,N-dimethylamino)ethyl methacrylate/polyethylhexyl methacrylate AB diblock copolymer has a number average degree of polymerization ratio of the B block to the A block of 30 to 8. ### Claim 6 (depends on 4) An electrostatic liquid developer according to claim 4 wherein the poly-2-(N,N-diethylamino)ethyl methacrylate/polyethylhexyl methacrylate AB diblock copolymer has a number average degree of polymerization ratio of the B block to the A block of 30 to 8. ### Claim 7 (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 the liquid developer, the total weight of solids is 0.1 to 15% by weight, component (C) is present in 0.1 to 10,000 milligrams per gram of developer solids and component (D) is present in 0.25 to 1,500 milligrams per gram of developer solids. ### Claim 8 (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 9 (depends on 8) An electrostatic liquid developer according to claim 8 wherein the colorant is a pigment. ### Claim 10 (depends on 8) An electrostatic liquid developer according to claim 8 wherein the colorant is a dye. ### Claim 11 (depends on 1) An electrostatic liquid developer according to claim 1 wherein a fine particle size oxide is present. ### Claim 12 (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 13 (depends on 8) An electrostatic liquid developer according to claim 8 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 14 (depends on 12) An electrostatic liquid developer according to claim 12 wherein a polyhydroxy adjuvant compound is present. ### Claim 15 (depends on 12) An electrostatic liquid developer according to claim 12 wherein an aminoalcohol adjuvant compound is present. ### Claim 16 (depends on 12) An electrostatic liquid developer according to claim 12 wherein a polybutylene succinimide adjuvant compound is present. ### Claim 17 (depends on 12) An electrostatic liquid developer according to claim 12 wherein a metallic soap adjuvant compound is present dispersed in the thermoplastic resin. ### Claim 18 (depends on 12) An electrostatic liquid developer according to claim 12 wherein an aromatic hydrocarbon adjuvant compound having a Kauri-butanol value of greater than 30 is present. ### Claim 19 (depends on 15) An electrostatic liquid developer according to claim 15 wherein the aminoalcohol adjuvant compound is triisopropanolamine. ### Claim 20 (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 21 (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 22 (depends on 8) An electrostatic liquid developer according to claim 8 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 23 (depends on 21) An electrostatic liquid developer according to claim 21 wherein the thermoplastic resin is a copolymer of ethylene (89%)/methacrylic acid (11%) having a melt index at 190.degree. C. of 100. ### Claim 24 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the thermoplastic resin component is a copolymer of acrylic or methacrylic acid and at least one alkyl ester of acrylic or methacrylic acid wherein alkyl is 1 to 20 carbon atoms. ### Claim 25 (depends on 24) An electrostatic liquid developer according to claim 24 wherein the thermoplastic resin component is a copolymer of methyl methacrylate (50-90%)/methacrylic acid (0-20%)/ethylhexyl acrylate (10-50%). ### Claim 26 (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 27 A process for preparing a 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, 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 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; (2) with stirring to form a viscous mixture and grinding by means of particulate media; or (3) while grinding by means of particulate media to prevent the formation of a gel or solid mass; (C) separating the dispersion of toner particles having an average by area particle size of less than 10 .mu.m from the particulate media, and (D) adding to the dispersion during or subsequent to Step (A) a nonpolar liquid soluble ionic or zwitterionic charge director compound and an AB diblock copolymer substantially soluble in component (A), wherein the B block is a polymer substantially soluble in component (A) having a number average molecular weight in the range of about 2,000 to 50,000, and the A block is a trialkyl amino polymer having a number average molecular weight in the range of about 200 to 10,000, the number average degree of polymerization ratio of the B block to the A block being in the range of 10 to 2 to 100 to 20. ### Claim 28 (depends on 27) A process according to claim 27 wherein the A block of the AB diblock copolymer is a polymer prepared from at least one monomer selected from the group consisting of (1) CH.sub.2 .dbd.CCH.sub.3 CO.sub.2 R, (2) CH.sub.2 .dbd.CHCO.sub.2 R wherein R in (1) and (2) is alkyl of 1 to 20 carbon atoms where the terminal end of R is of the general formula N(R.sup.1).sub.3, where N is nitrogen, and R.sup.1 is alkyl of 1 to 200 carbon atoms, aryl of 6 to 30 carbon atoms, alkylaryl of 7 to 200 carbon atoms, and (3) 2-, 3-, or 4-vinyl pyridine wherein the ring carbon atoms not substituted by the vinyl group may be substituted with R.sup.1 and the pyridine nitrogen atom is substituted with R.sup.1 wherein R.sup.1 is alkyl of 1-200 carbon atoms. ### Claim 29 (depends on 27) A process according to claim 27 wherein the B block of the AB diblock copolymer is a polymer prepared from at least one monomer selected from the group consisting of butadiene, isoprene and compounds of the general formulas: CH.sub.2 .dbd.CCH.sub.3 CO.sub.2 R.sup.2 and CH.sub.2 .dbd.CHCO.sub.2 R.sup.2 wherein R.sup.2 is alkyl of 8 to 30 carbon atoms. ### Claim 30 (depends on 27) A process according to claim 27 wherein the AB diblock copolymer toner particle dispersants are selected from the group consisting of poly-2-(N,N-dimethylamino)ethyl methacrylate/polyethylhexyl methacrylate; poly-2-(N,N-diethylamino)ethyl methacrylate/polylauryl methacrylate; poly-2-vinyl pyridine/polyethylhexyl acrylate; poly-4-vinyl pyridine/polybutadiene, poly-2-(N,N-dimethylamino)ethyl methacrylate/polylauryl methacrylate and poly-2-(N,N-diethylamino)ethyl methacrylate/polyethylhexyl methacrylate. ### Claim 31 (depends on 27) A process according to claim 27 wherein the poly-2-(N,N-dimethylamino)ethyl methacrylate/polyethylhexyl methacrylate AB diblock copolymer has a number average degree of polymerization ratio of the B block to the A block of 30 to 8. ### Claim 32 (depends on 27) A process according to claim 27 wherein the poly-2-(N,N-diethylamino)ethyl methacrylate/polyethylhexyl methacrylate AB diblock copolymer has a number average degree of polymerization ratio of the B block to the A block of 30 to 8. ### Claim 33 (depends on 27) A process according to claim 27 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 based on the total weight of the developer liquid. ### Claim 34 (depends on 27) A process according to claim 27 wherein the particulate media are selected from the group consisting of stainless steel, carbon steel, ceramic, alumina, zirconia, silica and sillimanite. ### Claim 35 (depends on 27) A process according to claim 27 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 36 (depends on 27) A process according to claim 27 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 37 (depends on 36) A process according to claim 36 wherein the thermoplastic resin is a copolymer of ethylene (89%)/methacrylic acid (11%) having a melt index at 190.degree. C. of 100. ### Claim 38 (depends on 27) A process according to claim 27 wherein the thermoplastic resin component is a copolymer of acrylic or methacrylic acid and at least one alkyl ester of acrylic or methacrylic acid wherein alkyl is 1 to 20 carbon atoms. ### Claim 39 (depends on 38) A process according to claim 38 wherein the thermoplastic resin component is a copolymer of methyl methacrylate (50-90%)/methacrylic acid (0-20%)/ethylhexyl acrylate (10-50%). ### Claim 40 (depends on 27) A process according to claim 27 wherein additional dispersant 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 developer liquid. ### Claim 41 (depends on 40) A process according to claim 40 wherein the concentration of toner particles is reduced by additional dispersant nonpolar liquid. ### Claim 42 (depends on 27) A process according to claim 27 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 43 (depends on 27) A process according to claim 27 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 44 (depends on 27) A process according to claim 27 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 45 (depends on 27) A process according to claim 27 wherein an adjuvant compound selected from the group consisting of polyhydroxy compound aminoalcohol, polybutylene succinimide, metallic soap, and an aromatic hydrocarbon is added during the dispersing step (A). ### Claim 46 (depends on 45) A process according to claim 45 wherein the adjuvant compound is an aminoalcohol. ### Claim 47 (depends on 40) A process according to claim 40 wherein an adjuvant compound selected from the group consisting of polyhydroxy compound, aminoalcohol, polybutylene succinimide, metallic soap, and an aromatic hydrocarbon is added. ### Claim 48 (depends on 47) A process according to claim 47 wherein the adjuvant compound is a polyhydroxy compound. ### Claim 49 (depends on 47) A process according to claim 47 wherein the adjuvant compound is a metallic soap dispersed in the thermoplastic resin. ### Claim 50 (depends on 49) A process according to claim 49 wherein the metallic soap adjuvant compound is aluminium stearate dispersed in the thermoplastic resin. ### Claim 51 A process for preparing electrostatic liquid developer comprising (A) dispersing a thermoplastic resin and optionally a colorant and/or adjuvant 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 by area particle size of less than 10 .mu.m from the particulate media, and (E) adding additional nonpolar liquid, polar liquid or combinations thereof to reduce the concentration of toner particles to between 0.1 to 15 percent by weight with respect to the liquid; and (F) adding to the dispersion a nonpolar liquid soluble ionic or zwitterionic charge director compound and an AB diblock copolymer substantially soluble in component (A), wherein the B block is a polymer substantially soluble in Component (A) having a number average molecular weight in the range of about 2,000 to 50,000, and the A block is a trialkyl amino polymer having a number average molecular weight in the range of about 200 to 10,000, the number average degree of polymerization ratio of the B block to the A block being in the range of 10 to 2 to 100 to 20. ### Claim 52 A process for preparing electrostatic liquid developer comprising (A) dispersing a thermoplastic resin and a colorant and/or adjuvant 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 by area particle size of less than 10 .mu.m from the particulate media, (F) adding additional nonpolar liquid, polar liquid or combinations thereof to reduce the concentration of toner particles to between 0.1 to 15 percent by weight with respect to the liquid; and (G) adding to the dispersion a nonpolar liquid soluble ionic or zwitterionic charge director compound and an AB diblock copolymer substantially soluble in component (A), wherein the B block is a polymer substantially soluble in component (A) having a number average molecular weight in the range of about 2,000 to 50,000, and the A block is a trialkyl amino polymer having a number average molecular weight in the range of about 200 to 10,000, the number average degree of polymerization ratio of the B block to the A block being in the range of 10 to 2 to 100 to 20.