# US 12,222,677 B2 · Fine particle, external additive for toner, toner, two-component developer, and method for manufacturing toner > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,222,677 B2 - Document ID: US12222677B2 - Status: Granted - Kind: B2 - Application number: 17/648,330 - Filed: 2022-01-19 - Published: 2022-07-28 - Granted: 2025-02-11 - Earliest claimed: 2021-01-25 - Assignees: Canon Kabushiki Kaisha - Applicants: Canon Kabushiki Kaisha - Inventors: Hiroki Watanabe; Ichiro Kanno; Masaharu Miura; Hayato Ida - Web page: https://patentgrep.com/patent/US12222677B2 ## CPC - G03G 9/09775: {containing atoms other than carbon, hydrogen or oxygen (G03G9/09741 - G03G9/09766 take precedence)} - G03G 9/0819: {characterised by the dimensions of the particles} - G03G 9/0821: {characterised by physical parameters (magnetic parameters G03G9/083)} - G03G: ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY ## Abstract A fine particle of a silicon polymer having a siloxane group and a silanol group, wherein a moisture adsorption amount of the fine particle at a temperature of 30° C. and a humidity of 80% RH is from 1.0 mg/g to 22.0 mg/g, an amount of the silanol group of the fine particle measured by a titration method using KOH is from 0.012 mmol/g to 0.120 mmol/g, and a number average particle diameter of primary particle of the fine particle is from 0.05 μm to 0.30 μm. ## Claims ### Claim 1 A fine particle, comprising: a silicon polymer having a siloxane group and a silanol group; the fine particle having a moisture adsorption amount of 1.0 to 22.0 mg/g at a temperature of 30° C. and a humidity of 80% RH, an amount of the silanol group of the fine particle measured by a titration method using KOH being 0.012 to 0.120 mmol/g; and a number average particle diameter of primary particle of the fine particle being 0.05 to 0.30 μm, wherein in a chart obtained by measurement of 29Si-NMR of the fine particle S3/A≤0.40 0.20≤S4/A≤0.50 and 0.40≤S2/A≤0.70 where a total peak area corresponding to the silicon polymer is denoted by A, a peak area corresponding to a structure represented by formula (a) is denoted by S3, a peak area corresponding to a structure represented by formula (b) is denoted by S4, and a peak area corresponding to a structure represented by formula (c) is denoted by S2, where R1 represents an alkyl group having 1 to 6 carbon atoms, and R2 and R3 independently represent an alkyl group having 1 to 6 carbon atoms. ### Claim 2 (depends on 1) The fine particle according to claim 1, wherein the fine particle has a BET specific surface area of 30 to 250 m2/g. ### Claim 3 (depends on 1) The fine particle according to claim 1, wherein the fine particle is surface-treated with at least one compound selected from the group consisting of an alkylsilazane, a cyclic dimethylpolysiloxane, a chlorosilane, a fluorosilane, and a silicone oil. ### Claim 4 (depends on 1) The fine particle according to claim 1, wherein the silicon polymer is a polycondensation polymer of at least one silicon compound selected from the group consisting of silicon compounds having a structure represented by formula (A): where R12, R13, R14 and R15 independently represent an alkyl group having 1 to 6 carbon atoms, a phenyl group or a reactive group, and the reactive group represents a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group having 1 to 6 carbon atoms; and at least one of R12, R13, R14 and R15 is the reactive group. ### Claim 5 An external additive for toner, comprising: a fine particle comprising a silicon polymer having a siloxane group and a silanol group; the fine particle having a moisture adsorption amount of 1.0 to 22.0 mg/g at a temperature of 30° C. and a humidity of 80% RH, an amount of the silanol group of the fine particle measured by a titration method using KOH being 0.012 to 0.120 mmol/g; and a number average particle diameter of primary particle of the fine particle being 0.05 to 0.30 μm, wherein in a chart obtained by measurement of 29Si-NMR of the fine particle S3/A≤0.40 0.20≤S4/A≤0.50 and 0.40≤S2/A≤0.70 where a total peak area corresponding to the silicon polymer is denoted by A, a peak area corresponding to a structure represented by formula (a) is denoted by S3, a peak area corresponding to a structure represented by formula (b) is denoted by S4, and a peak area corresponding to a structure represented by formula (c) is denoted by S2, where R1 represents an alkyl group having 1 to 6 carbon atoms, and R2 and R3 independently represent an alkyl group having 1 to 6 carbon atoms. ### Claim 6 (depends on 5) A toner comprising a toner particle and an external additive for toner, wherein the toner particle comprises a binder resin, and the external additive is the external additive for toner according to claim 5. ### Claim 7 (depends on 6) The toner according to claim 6, wherein an amount of the external additive in the toner is 0.1 to 20.0 parts by mass with respect to 100 parts by mass of the toner particle. ### Claim 8 (depends on 6) The toner according to claim 6, wherein a fixing ratio of the external additive to the toner particle is 20% or more, when the toner is dispersed in an aqueous medium including a surfactant and sucrose, shaken with a shaker, and then centrifuged. ### Claim 9 A two-component developer, comprising: a toner and a magnetic carrier; the toner comprising a toner particle and an external additive for toner; the toner particle comprising a binder resin; the external additive comprising a fine particle of a silicon polymer having a siloxane group and a silanol group; the fine particle having a moisture adsorption amount of 1.0 to 22.0 mg/g at a temperature of 30° C. and a humidity of 80% RH, an amount of the silanol group of the fine particle measured by a titration method using KOH being 0.012 to 0.120 mmol/g; and a number average particle diameter of primary particle of the fine particle being 0.05 to 0.30 μm, wherein in a chart obtained by measurement of 29Si-NMR of the fine particle S3/A≤0.40 0.20≤S4/A≤0.50 and 0.40≤S2/A≤0.70 where a total peak area corresponding to the silicon polymer is denoted by A, a peak area corresponding to a structure represented by formula (a) is denoted by S3, a peak area corresponding to a structure represented by formula (b) is denoted by S4, and a peak area corresponding to a structure represented by formula (c) is denoted by S2, where R1 represents an alkyl group having 1 to 6 carbon atoms, and R2 and R3 independently represent an alkyl group having 1 to 6 carbon atoms. ### Claim 10 (depends on 6) A method for manufacturing the toner according to claim 6, comprising the steps of: mixing the toner particle and the external additive for toner to obtain a toner particle mixture; and heat-treating the toner particle mixture.