# US 4,957,844 A · Liquid electrostatic developer containing multiblock polymers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,957,844 A - Document ID: US4957844A - Status: Granted - Kind: A - Application number: 07/331,306 - Filed: 1989-03-31 - Granted: 1990-09-18 - Earliest claimed: 1989-03-31 - Assignees: DXImaging - Inventors: Loretta A. G. Page - Web page: https://patentgrep.com/patent/US4957844A ## CPC - G03G 9/132: {obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds} - C08L 53/02: of vinyl-aromatic monomers and conjugated dienes - G03G 9/131: {obtained by reactions only involving carbon-to-carbon unsaturated bonds} - G03G: ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Liquid electrostatic developer consisting essentially of A. nonpolar liquid having Kauri-butanol value less than 30, present in major amount, B. thermoplastic resin particles, average by area particle size less than 10 .mu.m, consisting essentially of mixture (1) 80-95% by weight thermoplastic resin and (2) 20 to 5% by weight multiblock copolymer compound as defined, and C. charge director compound. The process of preparation is also defined. The said developer is useful in copying, making proofs, including digital color proofs, lithographic printing plates, and resists. ## Claims ### Claim 1 A liquid electrostatic developer consisting essentially of 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 consisting essentially of a mixture of (1) 80 to 95% by weight of a thermoplastic resin and (2) 20 to 5% by weight of a multiblock copolymer compound of the general formula: X-Y-(Z)n wherein X is a polymerized vinyl aromatic Y is a polymerized diene, and Z is a polymerized vinyl aromatic when n is 1 and a block copolymer of a polymerized vinyl aromatic and a polymerized diene when n is 2 to 10, the weight percentages based on the total weight of resin particles, and C. a charge director compound. ### Claim 2 (depends on 1) An electrostatic liquid developer according to claim 1 wherein n in the formula is 1 to 5. ### Claim 3 (depends on 1) An electrostatic liquid developer according to claim 1 wherein n in the formula is 1. ### Claim 4 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the ratio of polymerized vinyl aromatic component to diene polymer of the multiblock copolymer compound is 10/90 to 50/50. ### Claim 5 (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 6 (depends on 5) An electrostatic liquid developer according to claim 5 wherein the thermoplastic resin component is a copolymer of methyl methacrylate (50-90%)/methacrylic acid (0-20%)/ethyl hexyl acrylate (10-50%). ### Claim 7 (depends on 6) An electrostatic liquid developer according to claim 6 wherein the thermoplastic resin component is a copolymer of methyl methacrylate (67%)/methacrylic acid (3%)/ethyl hexyl acrylate (30%). ### Claim 8 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the thermoplastic resin component is a styrene/butadiene random copolymer. ### Claim 9 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the thermoplastic resin component is polyethylene. ### Claim 10 (depends on 5) An electrostatic liquid developer according to claim 5 wherein the multiblock copolymer component is a styrene/butadiene/styrene triblock copolymer. ### Claim 11 (depends on 6) An electrostatic liquid developer according to claim 6 wherein the multiblock copolymer is a styrene/butadiene/styrene triblock copolymer. ### Claim 12 (depends on 8) An electrostatic liquid developer according to claim 8 wherein the multiblock copolymer is a styrene/butadiene/styrene triblock copolymer. ### Claim 13 (depends on 9) An electrostatic liquid developer according to claim 9 wherein the multiblock copolymer is a styrene/butadiene/styrene triblock copolymer. ### Claim 14 (depends on 5) An electrostatic liquid developer according to claim 5 wherein the multiblock copolymer component is a styrene/isoprene/styrene triblock copolymer ### Claim 15 (depends on 6) An electrostatic liquid developer according to claim 6 wherein the multiblock copolymer component is a styrene/isoprene/styrene triblock copolymer. ### Claim 16 (depends on 5) An electrostatic liquid developer according to claim 5 wherein the multiblock copolymer is styrene/butadiene/(styrene/butadiene)n wherein n is 1-10. ### Claim 17 (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 18 (depends on 17) An electrostatic liquid developer according to claim 17 wherein the colorant is a pigment. ### Claim 19 (depends on 1) An electrostatic liquid developer according to claim 1 wherein a fine particle size oxide is present. ### Claim 20 (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, aromatic hydrocarbon, metallic soap and inorganic metal salt, the metallic soap and inorganic metal salt being dispersed in the resin particles. ### Claim 21 (depends on 20) An electrostatic liquid developer according to claim 20 wherein the resin particles have dispersed therein a metallic soap adjuvant. ### Claim 22 (depends on 17) An electrostatic liquid developer according to claim 17 wherein the thermoplastic resin component is a copolymer of acrylic acid or methacrylic acid and at least one alkyl ester of acrylic or methacrylic acid wherein alkyl is 1 to 20 carbon atoms. ### Claim 23 (depends on 22) An electrostatic liquid developer according to claim 22 wherein the thermoplastic resin component is a copolymer of methyl methacrylate (50-90%)/methacrylic acid (0-20%)/ethyl hexyl acrylate (10-50%). ### Claim 24 (depends on 23) An electrostatic liquid developer according to claim 23 wherein the multiblock copolymer is a styrene/butadiene/styrene triblock copolymer. ### Claim 25 (depends on 23) An electrostatic liquid developer according to claim 23 wherein the multiblock copolymer is a styrene/isoprene/styrene triblock copolymer. ### Claim 26 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the resin particles have an average by area particle size of less than 5 .mu.m. ### Claim 27 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the charge director is lecithin. ### Claim 28 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the charge director is an oilsoluble petroleum sulfonate. ### Claim 29 (depends on 1) An electrostatic liquid developer according to claim 1 wherein the charge director is a compound selected from the group consisting of iron naphthenate, manganese octoate, calcium naphthenate, calcium alkanoate, iron alkanoate and manganese alkanoate. ### Claim 30 Process for preparing liquid electrostatic developer for electrostatic imaging comprising (A) dispersing at an elevated temperature in a vessel (1) 80 to 95% by weight of a thermoplastic resin and (2) 20 to 5% by weight of a multiblock copolymer compound of the general formula: X-Y-(Z)n wherein X is a polymerized vinyl aromatic Y is a polymerized diene, and Z is a polymerized vinyl aromatic when n is 1 and a block copolymer of a polymerized vinyl aromatic and a polymerized diene when n is 2 to 10, the weight percentages based on the total weight of components (1) and (2), and (3) 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 components (1) and (2) and below that at which the nonpolar liquid degrades and components (1) and (2) decompose, (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; and 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 charge director compound. ### Claim 31 (depends on 30) A process according to claim 30 wherein n in the formula is 1 to 5. ### Claim 32 (depends on 30) A process according to claim 30 wherein n in the formula is 1. ### Claim 33 (depends on 30) A process according to claim 30 wherein the ratio of polymerized vinyl aromatic component to diene polymer of the multiblock copolymer compound is 10/90 to 50/50. ### Claim 34 (depends on 30) A process according to claim 30 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 35 (depends on 34) A process according to claim 34 wherein the thermoplastic resin component is a copolymer of methyl methacrylate (50-90%)/methacrylic acid (0-20%) ethyl hexyl acrylate (10-50%). ### Claim 36 (depends on 35) A process according to claim 35 wherein the thermoplastic resin component is a copolymer of methyl methacrylate (67%)/methacrylic acid (3%)/ethyl hexyl acrylate (30%). ### Claim 37 (depends on 30) A process according to claim 30 wherein the thermoplastic resin component is a styrene/butadiene random copolymer. ### Claim 38 (depends on 30) A process according to claim 30 wherein the thermoplastic resin component is polyethylene. ### Claim 39 (depends on 34) A process according to claim 34 wherein the multiblock copolymer component is a styrene/butadiene/styrene triblock copolymers ### Claim 40 (depends on 35) A process according to claim 35 wherein the multiblock copolymer is a styrene/butadiene/styrene triblock copolymer. ### Claim 41 (depends on 37) A process according to claim 37 wherein the multiblock copolymer is a styrene/butadiene/styrene triblock copolymer. ### Claim 42 (depends on 38) A process according to claim 38 wherein the multiblock copolymer is a styrene/butadiene/styrene triblock copolymer. ### Claim 43 (depends on 34) A process according to claim 34 wherein the multiblock copolymer component is a styrene/isoprene/styrene triblock copolymer. ### Claim 44 (depends on 35) A process according to claim 35 wherein the multiblock copolymer component is a styrene/isoprene/styrene triblock copolymer. ### Claim 45 (depends on 34) A process according to claim 34 wherein the multiblock copolymer is styrene/butadiene/(styrene/butadiene)n wherein n is 1 to 10. ### Claim 46 (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 based on the total weight of developer liquid. ### Claim 47 (depends on 30) A process according to claim 30 wherein the charge director is lecithin. ### Claim 48 (depends on 30) A process according to claim 30 wherein the charge director is an oil-soluble petroleum sulfonate. ### Claim 49 (depends on 30) A process according to claim 30 wherein the charge director is a compound selected from the group consisting of iron naphthenate, manganese octoate, calcium naphthenate, calcium alkanoate, iron alkanoate and manganese alkanoate. ### Claim 50 (depends on 30) A process according to claim 30 wherein the concentration of toner particles is reduced to between 0.02 to 15% by weight with respect to the liquid by adding additional nonpolar liquid, polar liquid, or combinations thereof. ### Claim 51 (depends on 50) A process according to claim 50 wherein the concentration of toner particles is reduced by additional nonpolar liquid. ### Claim 52 (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 53 (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 54 (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 55 (depends on 30) A process according to claim 30 wherein during dispersing step (A) is added an adjuvant compound selected from the group consisting of polyhydroxy compound, aminoalochol, polybutylene succinimide, aromatic hydrocarbon, metallic soap and inorganic metal salt, the metallic soap and inorganic metal salt being dispersed in the resin particles. ### Claim 56 (depends on 55) A process according to claim 55 wherein the adjuvant compound is a metallic soap. ### Claim 57 A process for preparing electrostatic liquid developer for electrostatic imaging comprising (A) mixing in a vessel (1) a thermoplastic resin and (2) multiblock copolymer of the general formula: X-Y-(Z)n wherein X is a polymerized vinyl aromatic Y is a polymerized diene, and Z is a polymerized vinyl aromatic when n is 1 and a block copolymer of a polymerized vinyl aromatic and a polymerized diene when n is 2 to 10, 80 to 95% by weight (1) and 20 to 5% by weight (2), respectively, based on the total weight of components (1) and (2); (3) a colorant and/or (4) adjuvant in the absence of a liquid 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 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, to form a dispersion of toner particles in the liquid, (D) separating the particulate media from the dispersion of toner particles having an average by area particle size of less than 10 .mu.m, (E) adding to the dispersion during or subsequent to step (C) a charge director compound. ### Claim 58 (depends on 57) A process according to claim 57 wherein during at least one of steps (C) to (E) is added additional liquid selected from the group consisting of nonpolar liquid, polar liquid, and combinations thereof. ### Claim 59 (depends on 30) A process according to claim 30 wherein the thermoplastic resin component is a copolymer of ethylene (89%)/methacrylic acid (11%) having a melt index at 190.degree. C. of 100. ### Claim 60 (depends on 1) 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.degree. C. of 100. ### Claim 61 (depends on 17) An electrostatic liquid developer according to claim 17 wherein the thermoplastic resin component is a copolymer of ethylene (89%)/methacrylic acid (11%) having a melt index at 190.degree. C. of 100.