# US 5,346,798 A · Suspension polymerization method and toner for electrophotography obtained therewith > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,346,798 A - Document ID: US5346798A - Status: Granted - Kind: A - Application number: 08/030,652 - Filed: 1993-03-12 - Granted: 1994-09-13 - Earliest claimed: 1992-03-18 - Assignees: Tomoegawa Paper Co., Ltd. - Inventors: Masafumi Kamiyama; Masahiro Maeda; Hiroki Totsuka; Akihiro Sano; Toshiya Matsushita - Web page: https://patentgrep.com/patent/US5346798A ## CPC - C08F 2/18: Suspension polymerisation - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract The present invention provides a suspension polymerization method which provides polymerized particles exhibiting excellent charging properties and a toner composed of the polymerized particles obtained with the method. The method includes the steps of: placing a continuous phase component of an aqueous medium in a continuous phase vessel, and placing a dispersed phase component composed of a monomer composition and at least one solid compound having a specific structure in a dispersed phase vessel; continuously and simultaneously supplying each of the dispersed phase component and the continuous phase component to an apparatus for providing a shear force; exerting a shear force on the dispersed phase component and the continuous component to form a suspension material including polymerizable liquid-drops of a desired size; leading the suspension material to a polymerization vessel; subjecting the suspension material in the polymerization vessel to a polymerization reaction to form a polymerized material; and drying the polymerized material to obtain the polymerized particle. ## Claims ### Claim 1 A suspension polymerization method for producing a negatively or positively charged polymerized particle comprising the steps of: preparing a continuous phase component of an aqueous medium; preparing a dispersed phase component comprising a monomer composition and at least one solid compound which acts as a charge control agent for maintaining a negative or positive charge on said polymerized particle; preparing suspension polymerization means comprising a continuous phase vessel for holding a continuous phase component, a dispersed phase vessel for holding a dispersed phase component, shearing means for providing a shear force, and a polymerization vessel for polymerization reaction; and in turn placing the continuous phase component in the continuous phase vessel and the dispersed phase component in the dispersed phase vessel; continuously and simultaneously supplying each of the dispersed phase component and the continuous phase component, separately, to the shearing means for providing a shear force; exerting a shear force on the dispersed phase component and the continuous component in the shearing means to form a suspension material comprising polymerizable liquid drops of a desired size; leading the suspension material to the polymerization vessel; and subsequently subjecting the suspension material in the polymerization vessel to a polymerization reaction to form said negatively or positively charged polymerized particle. ### Claim 2 (depends on 1) A suspension polymerization method as recited in claim 1, wherein said solid compound is selected from the group consisting of compounds represented by formulae (A) to (F): ##STR24## wherein R.sub.1 and R.sub.2 each represents independently a hydrogen atom, nitro group, halogen group, alkyl group, amino group, or carboxyl group; R.sub.3 and R.sub.4 each represents independently a hydrogen atom, alkyl group, carboxyl group, or nitro group; R.sub.5 and R.sub.6 each represents independently a hydrogen atom, alkyl group, carboxyl group, amino group, or nitro group; M.sub.1 represents Fe, Ni, Co, or Cr; M.sub.2 represents H, Na, K, or an organic 920 ammonium salt; and n is an integer of 1 to 4, ##STR25## wherein R.sub.1, R.sub.2, M.sub.1, M.sub.2, and n are as defined above, ##STR26## wherein R.sub.1, R.sub.2, M.sub.1, M.sub.2, and n are as defined above, ##STR27## wherein R.sub.1, R.sub.3, R.sub.5, M.sub.1, M.sub.2, and n are as defined above, ##STR28## wherein R.sub.1 and R.sub.2 are as defined above, and ##STR29## wherein R.sub.7, R.sub.8, and R.sub.9 each represents independently an alkyl group, phenyl group, phenylamino group, naphthyl group, or the derivative of the same; R.sub.10 represents a hydrogen atom, hydroxy group, carboxyl group, amino group, nitro group, or halogen group; and X represents a sulfonyl anion group, phenylsulfonyl anion group, or the derivative of the same. ### Claim 3 (depends on 1) A suspension polymerization method as recited in claim 1, wherein the monomer composition in the dispersed phase component comprises at least one monomer selected from the group consisting of a styrene, a styrene derivative, an ethylene unsaturated mono-olefin, a halogenated vinyl compound, an organoacidic vinyl ester, a methacrylic acid, a methacrylic acid derivative, an acrylic acid, an acrylic acid derivative, a vinyl ester, a vinyl ketone, an N-vinyl compound, a vinyl naphthalene, an acrylonitrile, a methacrylonitrile, and an acrylamido. ### Claim 4 (depends on 1) A suspension polymerization method as recited in claim 1, wherein the dispersed phase component further comprises at least one supplementary material selected from the group consisting of an organic pigment, an inorganic pigment, a dye, a resin additive, and an organic compound. ### Claim 5 (depends on 1) A suspension polymerization method as recited in claim 1, wherein the continuous phase component further comprises a suspension stabilizer having at least one hydrophilic group and at least one hydrophobic group in a molecule of the stabilizer. ### Claim 6 (depends on 5) A suspension polymerization method as recited in claim 5, wherein the suspension stabilizer is a material selected from the group consisting of a polyvinyl alcohol, a casein, a gelatin, a cellulose derivative, a starch, a starch derivative, a polymethacrylic acid, a salt of the polymethacrylic acid, a calcium phosphate, and a finegrained silica. ### Claim 7 (depends on 1) A suspension polymerization method as recited in claim 1, wherein said negatively or positively charged polymerized particle is a toner particle for use in electrophotography. ### Claim 8 A toner for use in electrophotography comprising negatively or positively charged polymerized particles, produced by the steps of: preparing for a continuous phase component of an aqueous medium; preparing a dispersed phase component comprising a monomer composition and at least one solid compound which acts as a charge control agent for maintaining a negative or positive charge on said polymerized particle; preparing suspension polymerization means including a continuous phase vessel for holding a continuous phase component, a dispersed phase vessel for holding a dispersed phase component, shearing means for providing a shear force, and a polymerization vessel for a polymerization reaction; and in turn placing the continuous phase component in the continuous phase vessel and the dispersed phase component in the dispersed phase vessel; continuously and simultaneously supplying each of the dispersed phase component and the continuous phase component in the shearing means to form a suspension material including polymerizable liquid-drops of a desired size; leading the suspension material to the polymerization vessel; and subsequently subjecting the suspension material in the polymerization vessel to a polymerization reaction to form a polymerized material to obtain said negatively or positively charged polymerized particle. ### Claim 9 (depends on 8) A toner for use in electrophotography as recited in claim 8, wherein said solid compound is selected from the group consisting of compounds represented by formulae (A) to (F): ##STR30## wherein R.sub.1 and R.sub.2 each represents independently a hydrogen atom, nitro group, halogen group, alkyl group, amino group, or carboxyl group; R.sub.3 and R.sub.4 each represents independently a hydrogen atom, alkyl group, carboxyl group, or nitro group; R.sub.5 and R.sub.6 each represents independently a hydrogen atom, alkyl group, carboxyl group, amino group, or nitro group; M.sub.1 represents Zn, Fe, Ni, Co, or Cr; M.sub.2 represents H, Na, K, or an organic ammonium salt; and n is an integer of 1 to 4, ##STR31## wherein R.sub.1, R.sub.2, M.sub.1, M.sub.2 and n are as defined above, ##STR32## wherein R.sub.1, R.sub.2, M.sub.1, M.sub.2, and n are as defined above, ##STR33## wherein R.sub.1, R.sub.3, R.sub.3, R.sub.5, M.sub.1, M.sub.2, and n are as defined above, ##STR34## wherein R.sub.1 and R.sub.2 are as defined above, and ##STR35## wherein R.sub.7, R.sub.8, and R.sub.9 each represents independently an alkyl group, phenyl group, phenylamino group, naphthyl group, or the derivative of the same; R.sub.10 represents a hydrogen atom, hydroxy group, carboxyl group, amino group, nitro group, or halogen group; and X represents a sulfonyl anion group, phenylsulfonyl anion group, or the derivative of the same. ### Claim 10 (depends on 9) A toner for use in electrophotography as recited in claim 9, wherein said toner carries a negative charge and wherein said solid compound is selected from the group consisting of compounds represented by formulae (A) to (D). ### Claim 11 (depends on 9) A toner for use in electrophotography as recited in claim 9, wherein said toner carries a positive charge and wherein said solid compound is selected from the group consisting of compounds represented by formulae (E) and (F). ### Claim 12 (depends on 9) A toner for use in electrophotography as recited in claim 9, wherein the monomer composition in the dispersed phase component comprises at least one monomer selected from the group consisting of a styrene, a styrene derivative, an ethylene unsaturated mono-olefin, a halogenated vinyl compound, an organoacidic vinyl ester, a methacrylic acid, a methacrylic acid derivative, an acrylic acid, an acrylic acid derivative, a vinyl ether, a vinyl ketone, an N-vinyl compound, a vinyl napthalene; acrylonitrile, a methacrylonitrile, and an acrylamido. ### Claim 13 (depends on 10) A toner for use in electrophotography as recited in claim 10, wherein said solid compound is incorporated into the polymerized particles. ### Claim 14 (depends on 11) A toner for use in electrophotography as recited in claim 11, wherein said solid compound is incorporated into the polymerized particles. ### Claim 15 A method for producing a toner for use in electrophotography which includes toner particles comprising the steps of: preparing a continuous phase component of an aqueous medium; preparing a dispersed phase component comprising a monomer composition and at least one solid compound which acts as a charge control agent for maintaining a negative or positive charge on said polyermized particle; preparing suspension polyermization means including a continuous phase vessel for holding a continuous phase component, a dispersed phase vessel for holding a dispersed phase component, shearing means for providing a shear force, and a polymerization vessel for polymerization reaction; and in turn placing the continuous phase component in the continuous phase vessel and the dispersed phase component in the dispersed phase vessel; continuously and simultaneously supplying each of the dispersed phase component and the continuous phase component, separately, to the shearing means for providing a shear force; exerting a shear force on the dispersed phase component and the continuous component in the shearing means to form a suspension material including polymerizable liquid drops of a desired size; leading the suspension material to the polymerization vessel; and subsequently subjecting the suspension material in the polymerization vessel to a polymerization reaction to form the negatively or positively charged polymerized particle. ### Claim 16 (depends on 15) A method for producing a toner for use in electrophotography as recited in claim 15, wherein said solid compound is selected from the group consisting of compounds represented by formulae (A) to (F): ##STR36## wherein R.sub.1 and R.sub.2 each represents independently a hydrogen atom, nitro group, halogen group, alkyl group, amino group, or carboxyl group; R.sub.3 and R.sub.4 each represents independently a hydrogen atom, alkyl group, carboxyl group, or nitro group; R.sub.5 and R.sub.6 each represents independently a hydrogen atom, alkyl group, carboxyl group, amino group, or nitro group; M.sub.1 represents Zn, Fe, Ni, Co, or Cr; M.sub.2 represents H, Na, K, or an organic ammonium salt; and n is an integer of 1 to 4, ##STR37## wherein R.sub.1, R.sub.2, M.sub.1, M.sub.2, and n are as defined above, ##STR38## wherein R.sub.1, R.sub.2, M.sub.1, M.sub.2, and n are as defined above, ##STR39## wherein R.sub.1, R.sub.3, R.sub.5, M.sub.1, M.sub.2, and n are as defined above, ##STR40## wherein R.sub.1 and R.sub.2 are as defined above, and ##STR41## wherein R.sub.7, R.sub.8, and R.sub.9 each represents independently an alkyl group, phenyl group, phenylamino group, napthyl group, or the derivative of the same; R.sub.10 represents a hydrogen atom, hydroxy group, carboxyl group, amino group, nitro group, or halogen group; and X represents a sulfonyl anion group, phenylsulfonyl anion group, or the derivative of the same. ### Claim 17 (depends on 15) A method for producing a toner for use in electrophotography as recited in claim 15, wherein the monomer composition in the dispersed phase component comprises at least one monomer selected from the group consisting of a styrene, a styrene derivative, an ethylene unsaturated mono-olefin, a halogenated vinyl compound, an organoacidic vinyl ester, a methacrylic acid, a m ethacrylic acid derivative, an acrylic acid, an acrylic acid derivative, a vinyl ether, a vinyl ketone, an N-vinyl compound, a vinyl naphthalene, a acrylonitrile, a methacrylonitrile, and an acrylamido. ### Claim 18 (depends on 15) A method for producing a toner for use in electrophotography as recited in claim 15, wherein said dispersed phase component further comprises at least one supplementary material selected from the group consisting of an organic pigment, an inorganic pigment, a dye, a resin additive, and an organic compound. ### Claim 19 (depends on 15) A method for producing a toner for use in electrophotography as recited in claim 15, wherein said continuous phase component further comprises a suspension stabilizer having at least one hydrophilic group and at least one hydrophobic group in a molecule of the stabilizer. ### Claim 20 (depends on 15) A method for producing a toner for use in electrophotography as recited in claim 15, wherein the suspension stabilizer is a material selected from the group consisting of a polyvinyl alcohol, a casein, a gelatin, a cellulose derivative, a starch, a starch derivative, a polymethacrylic acid, a salt of the polymethacrylic acid, calcium phosphate, and a fine-grained silicia. ### Claim 21 (depends on 16) A method for producing a toner for use in electrophotography as recited in claim 16, wherein said toner carries a negative charge and wherein said solid compound is selected from the group consisting of compounds represented by formulae (A) to (D). ### Claim 22 (depends on 16) A method for producing a toner for use in electrophotography as recited in claim 16, wherein said toner carries a positive charge and wherein said solid compound is selected from the group consisting of compounds represented by formulae (E) and (F).