# US 5,130,221 A · Salts of acid-containing AB diblock copolymers as charge directors for positive-working 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 5,130,221 A - Document ID: US5130221A - Status: Granted - Kind: A - Application number: 07/489,649 - Filed: 1990-03-07 - Granted: 1992-07-14 - Earliest claimed: 1990-03-07 - Assignees: DXImaging - Inventors: Lyla M. El-Sayed; Loretta A. G. Page - Web page: https://patentgrep.com/patent/US5130221A ## CPC - C08F 293/00: Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule (on to polymers modified by introduction of unsaturated end groups C08F290/02) - C08F 297/02: using a catalyst of the anionic type - G03G 9/133: {Graft-or block polymers} - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - G03G: ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY ## Abstract Positive-working electrostatic liquid developer consisting essentially of (A) nonpolar liquid having Kauri-butanol value less than 30, present in major amount, (B) thermoplastic resin particles having an average particle size by area of less than 10 .mu.m, and (C) an AB diblock copolymer charge director compound as defined. 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 A positive-working 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 (C) an AB diblock copolymer charge director 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 salt of a carboxylic acid-containing polymer having a number average molecular weight range of 200 to 10,000, the weight percent of the A block being 5 to 40% of the polymer. ### 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 X, (2) CH.sub.2 .dbd.CHCO.sub.2 X, (3) CH.sub.2 .dbd.COR--CO.sub.2 X, and (4) CH.sub.2 .dbd.CHR.sup.1 --CO.sub.2 X wherein R is alkyl of 1 to 200 carbon atoms, aryl of 6 to 30 carbon atoms, alkylaryl of 7 to 200 carbon atoms, R.sup.1 is an aromatic ring wherein the ring carbon atoms not substituted by the vinyl group may be substituted with R, and X is a Ca.sup.2+, Ba.sup.2+, Zr.sup.2+, Fe.sup.3+, Mn.sup.2+, NR.sup.4 +, wherein R is alkyl of 1 to 200 carbon atoms, aryl of 6 to 30 carbon atoms, alkylaryl of 7 to 200 carbon atoms. ### Claim 3 (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 salts of acrylic acid, methacrylic acid, 2-vinyl benzoic acid, 3-vinyl benzoic acid, and 4-vinyl benzoic acid. ### Claim 4 (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 5 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the AB diblock copolymer is selected from the group consisting of poly-(N,N-trimethyl-benzyl ammonium) methacrylate and polyethylhexyl methacrylate; poly-calcium methacrylate and polyethylhexyl methacrylate, poly-iron acrylate and polybutadiene, poly-barium-2-vinylbenzoic acid and polyisoprene, polymanganese-4-vinylbenzoic acid and polylauryl methacrylate, and polymethyltriethylammonium methacrylate and polystearylmethacrylate. ### Claim 6 (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, and component (C) is present in 0.1 to 10,000 milligrams per gram of developer solids. ### Claim 7 (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 8 (depends on 7) An electrostatic liquid developer according to claim 7 wherein the colorant is a pigment. ### Claim 9 (depends on 7) An electrostatic liquid developer according to claim 7 wherein the colorant is a dye. ### Claim 10 (depends on 1) An electrostatic liquid developer according to claim 1 wherein a fine particle size oxide is present. ### Claim 11 (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 12 (depends on 7) An electrostatic liquid developer according to claim 7 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 11) An electrostatic liquid developer according to claim 11 wherein a polyhydroxy adjuvant compound is present. ### Claim 14 (depends on 11) An electrostatic liquid developer according to claim 11 wherein an aminoalcohol adjuvant compound is present. ### Claim 15 (depends on 11) An electrostatic liquid developer according to claim 11 wherein a polybutylene succinimide adjuvant compound is present. ### Claim 16 (depends on 11) An electrostatic liquid developer according to claim 11 wherein a metallic soap adjuvant compound is present dispersed in the thermoplastic resin. ### Claim 17 (depends on 11) An electrostatic liquid developer according to claim 11 wherein an aromatic hydrocarbon adjuvant compound having a Kauri-butanol value of greater than 30 is present. ### Claim 18 (depends on 14) An electrostatic liquid developer according to claim 14 wherein the aminoalcohol adjuvant compound is triisopropanolamine. ### Claim 19 (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 20 (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 21 (depends on 7) An electrostatic liquid developer according to claim 7 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 20) An electrostatic liquid developer according to claim 20 wherein the thermoplastic resin is a copolymer of ethylene (89%)/methacrylic acid (11%) having a melt index at 190.degree. C. of 100. ### Claim 23 (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 24 (depends on 23) An electrostatic liquid developer according to claim 23 wherein the thermoplastic resin component is a copolymer of methyl methacrylate(50-90%)/methacrylic acid (0-20%)/ethylhexyl acrylate(10-50%). ### Claim 25 (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 26 A process for preparing a positive-working electrostatic liquid developer for electrostatic imaging comprising (A) dispersing at an elevated temperature in a vessel a thermoplastic resin, and a 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 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 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 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) an AB diblock copolymer charge director 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 salt of a carboxylic acid-containing polymer having a number average molecular weight range of 200 to 10,000, the weight percent of the A block being 5 to 40% of the polymer. ### Claim 27 (depends on 26) A process according to claim 26 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 X, (2) CH.sub.2 .dbd.CHCO.sub.2 X, (3) CH.sub.2 .dbd.COR--CO.sub.2 X, and (4) CH.sub.2 .dbd.CHR.sup.1 --CO.sub.2 X wherein R is alkyl of 1 to 200 carbon atoms, aryl of 6 to 30 carbon atoms, alkylaryl of 7 to 200 carbon atoms, R.sup.1 is an aromatic ring wherein the ring carbon atoms not substituted by the vinyl group may be substituted with R, and X is a Ca.sup.2+, Ba.sup.2+, Zr.sup.2+, Fe.sup.3+, Mn.sup.2+, NR.sub.4.sup.+, wherein R is alkyl of 1 to 200 carbon atoms, aryl of 6 to 30 carbon atoms, alkylaryl of 7 to 200 carbon atoms. ### Claim 28 (depends on 26) A process according to claim 26 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 29 (depends on 26) A process according to claim 26 wherein the AB diblock copolymer is selected from the group consisting of poly-(N,N-dimethyl-benzyl ammonium) methacrylate and polyethylhexyl methacrylate; poly-calcium methacrylate and polyethylhexyl methacrylate, poly-iron acrylate and polybutadiene, poly-barium-2-vinylbenzoic acid and polyisoprene, poly-manganese-4-vinylbenzoic acid and polylauryl methacrylate, and polymethyltriethylammonium methacrylate and polystearylmethacrylate. ### Claim 30 (depends on 26) A process according to claim 26 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 31 (depends on 26) A process according to claim 26 wherein the particulate media are selected from the group consisting of stainless steel, carbon steel, ceramic, alumina, zirconia, silica and sillimanite. ### Claim 32 (depends on 26) A process according to claim 26 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 33 (depends on 26) A process according to claim 26 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 34 (depends on 33) A process according to claim 33 wherein the thermoplastic resin is a copolymer of ethylene (89%)/methacrylic acid (11%) having a melt index at 190.degree. C. of 100. ### Claim 35 (depends on 26) A process according to claim 26 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 36 (depends on 35) A process according to claim 35 wherein the thermoplastic resin component is a copolymer of methyl methacrylate (50-90%)/methacrylic acid (0-20%)/ethylhexyl acrylate (10-50%). ### Claim 37 (depends on 26) A process according to claim 26 wherein 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 developer liquid. ### Claim 38 (depends on 37) A process according to claim 37 wherein the concentration of toner particles is reduced by additional nonpolar liquid. ### Claim 39 (depends on 26) A process according to claim 26 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 40 (depends on 26) A process according to claim 26 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 41 (depends on 26) A process according to claim 26 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 42 (depends on 26) A process according to claim 26 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 43 (depends on 42) A process according to claim 42 wherein the adjuvant compound is an aminoalcohol. ### Claim 44 (depends on 37) A process according to claim 37 wherein an adjuvant compound selected from the group consisting of polyhydroxy compound, aminoalcohol, polybutylene succinimide, metallic soap, and an aromatic hydrocarbon is added. ### Claim 45 (depends on 44) A process according to claim 44 wherein the adjuvant compound is a polyhydroxy compound. ### Claim 46 (depends on 44) A process according to claim 44 wherein the adjuvant compound is a metallic soap dispersed in the thermoplastic resin. ### Claim 47 (depends on 46) A process according to claim 46 wherein the metallic soap adjuvant compound is aluminium stearate. ### Claim 48 A process for preparing a positive-working electrostatic liquid developer comprising (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 .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 an AB diblock copolymer charge director 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 salt of a carboxylic acid-containing polymer having a number average molecular weight range of 200 to 10,000, the weight percent of the A block being 5 to 40% of the polymer. ### Claim 49 A process for preparing a positive-working 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) redispersing the shredded solid mass at an elevated temperature in a vessel in the presence of a 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 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, and (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 an AB diblock copolymer charge director 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 salt of a carboxylic acid-containing polymer having a number average molecular weight range of 200 to 10,000, the weight percent of the A block being 5 to 40% of the polymer.