JP2010217640A - Method of manufacturing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a toner by which the time required for emulsification or dispersion when manufacturing toner which has a narrow particle size distribution and is deformed, can be shortened. <P>SOLUTION: The method of manufacturing toner comprises: a process of preparing a first liquid by dissolving or dispersing toner material containing a polymer and/or a binder resin, the polymer having a functional group which can react with an active hydrogen group; and a process of preparing a second liquid by emulsifying or dispersing the first liquid into an aqueous medium, wherein, when the average roundness of particles giving the minimum volume-average particle diameter is presented by (A), the particles being produced by feeding the liquid prepared by emulsifying or dispersing the first liquid into an aqueous medium into water, and average roundness and volume-average particle diameter of particles produced by feeding the liquid prepared by emulsifying or dispersing the first liquid into the aqueous medium for t[min], into water are respectively presented by A(t) and Dv(t)[μm], the following relationships are satisfied: 0.01<A-A(t)<0.075(0.98≤A≤1), ¾Dv(t)-Dv(t+1)¾<0.2, t<10. Therein, the second liquid is a liquid prepared by emulsifying or dispersing the first liquid into the aqueous medium for t+1[min]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner manufacturing method.

  In an example of electrophotography, an electrostatic latent image is formed on a photoreceptor by charging and exposure, and then the electrostatic latent image is developed using a developer containing toner to form a toner image. . Further, after the toner image is transferred to the recording material, the toner image is fixed. On the other hand, toner remaining on the photoreceptor without being transferred to the recording material is removed by a cleaning member such as a blade or a roller arranged in pressure contact with the surface of the photoreceptor.

  As a toner production method, an oil phase containing a monomer, a polymerization initiator and the like is added to an aqueous medium containing a dispersant to form oil droplets, and then polymerized by a suspension polymerization method, an emulsion polymerization method, etc. Polymerization methods are known.

  However, the toner thus obtained has a spherical shape due to the influence of surface tension and the like because the oil phase generally exhibits Newtonian viscosity. As a result, when the toner remaining on the photoreceptor is removed by the blade, a cleaning failure occurs.

  Therefore, when the toner remaining on the photosensitive member is removed by a blade, a deformed toner is used.

  Patent Document 1 discloses a toner manufacturing method in which an oil phase containing at least a binder resin and / or a binder resin precursor is emulsified or dispersed in an aqueous medium to granulate the toner. In this method, the difference ΔDv between the volume average particle diameter Dv1 that is the minimum of the toner being granulated during emulsification or dispersion and the volume average particle diameter Dv2 of the granulated toner after emulsification or dispersion is 0.5-3. 0.0 μm. Thus, a toner having an average circularity of 0.925 to 0.970 and a ratio Dv / Dn of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of 1.00 to 1.30. Is granulated.

  However, since the index for determining the end point of emulsification or dispersion is not clear, there is a problem that the toner must be emulsified or dispersed for a long time in order to stably produce the toner.

  SUMMARY OF THE INVENTION In view of the above-described problems of the prior art, the present invention provides a method for producing a toner capable of shortening the time for emulsification or dispersion when producing an irregularly shaped toner having a narrow particle size distribution. Objective.

The invention according to claim 1 is a method for producing a toner having host particles, wherein a toner material containing a polymer having a functional group capable of reacting with an active hydrogen group and / or a binder resin is organic. A step of preparing a first liquid by dissolving or dispersing in a solvent; and a step of preparing a second liquid by emulsifying or dispersing the first liquid in an aqueous medium. The average circularity when the volume average particle size of particles produced by introducing a liquid emulsified or dispersed in an aqueous medium into water is minimized, and the first liquid is t [ Min] When the average circularity and volume average particle diameter of particles produced by introducing an emulsified or dispersed liquid into water are A (t) and Dv (t) [μm], respectively, the formula 0.01 <A −A (t) <0.075 (0.98 ≦ A ≦ 1)
| Dv (t) −Dv (t + 1) | <0.2
t <10
And the second liquid is a liquid obtained by emulsifying or dispersing the first liquid in an aqueous medium for t + 1 [min].

  According to a second aspect of the present invention, in the toner production method according to the first or second aspect, the toner material further includes inorganic particles.

  According to a third aspect of the present invention, in the toner production method according to the second aspect, the inorganic particles are a modified layered inorganic mineral in which at least a part of metal cations are ion-exchanged with organic cations. And

  According to a fourth aspect of the present invention, in the toner production method according to the third aspect, the organic cation is a quaternary ammonium ion.

  According to a fifth aspect of the present invention, in the toner manufacturing method according to any one of the first to fourth aspects, the base particles have a content of particles having a circularity of 0.95 or less of 20% by number or more. 80% by number or less.

  According to a sixth aspect of the present invention, in the method for producing a toner according to any one of the first to fifth aspects, the base particle has a ratio of a volume average particle diameter to a number average particle diameter of 1.0 to 1. .3 or less.

  According to a seventh aspect of the present invention, in the toner manufacturing method according to any one of the first to sixth aspects, the base particle has a content of particles having a particle diameter of 2 μm or less of 1% by number or more and 20%. It is characterized by being no more than a number%.

  According to an eighth aspect of the present invention, in the toner production method according to any one of the first to seventh aspects, the binder resin contains polyester.

  The invention according to claim 9 is the toner manufacturing method according to any one of claims 1 to 8, wherein the polymer having a functional group capable of reacting with the active hydrogen group has an isocyanate group. It is the polyester which has.

  According to a tenth aspect of the present invention, in the toner manufacturing method according to any one of the first to ninth aspects, the active hydrogen group can be reacted in the step of preparing the second liquid. It is characterized by reacting a polymer having a functional group with a compound having an active hydrogen group.

  According to the present invention, it is possible to provide a toner production method capable of shortening the time for emulsification or dispersion when producing a toner having a narrow particle size distribution and an irregular shape.

  Next, the form for implementing this invention is demonstrated with drawing.

  The method for producing a toner of the present invention is a method for producing a toner having host particles, wherein a toner material containing a polymer having a functional group capable of reacting with an active hydrogen group and / or a binder resin is organically used. It has a step of preparing a first liquid by dissolving or dispersing in a solvent, and a step of preparing a second liquid by emulsifying or dispersing the first liquid in an aqueous medium.

  In general, when preparing the second liquid, it is necessary to apply a shearing force, and the particle size of the oil droplets changes with the application time of the shearing force. Primary particles with Dv1 are obtained. Thereafter, the primary particles aggregate to obtain base particles having a volume average particle diameter of Dv2. At this time, if the shearing force at the time of preparing the second liquid is large, Dv1 becomes small, so that the aggregation of primary particles proceeds too much, ΔDv (= Dv2−Dv1) becomes large, and the particle size distribution of the base particles Becomes wider. On the other hand, if the shearing force at the time of preparing the second liquid is small, Dv1 becomes large, so that the aggregation of primary particles becomes insufficient, ΔDv becomes small, and deformed base particles cannot be obtained. The particle size distribution becomes wider. For this reason, the shape and particle size distribution of the base particles can be controlled by adjusting the shear force when preparing the second liquid to control ΔDv.

In the present invention, the average circularity when the volume average particle diameter of particles produced by introducing a liquid obtained by emulsifying or dispersing the first liquid in an aqueous medium into water is A, The average circularity and volume average particle diameter of the particles produced by introducing a liquid obtained by emulsifying or dispersing the liquid in an aqueous medium for t [minutes] into water are A (t) and Dv (t) [μm], respectively. Then, the formula 0.01 <A−A (t) <0.075 (0.98 ≦ A ≦ 1)
| Dv (t) −Dv (t + 1) | <0.2
t <10
Meet. At this time, the second liquid is a liquid obtained by emulsifying or dispersing the first liquid in an aqueous medium for t + 1 [min]. As a result, an irregularly shaped toner having a narrow particle size distribution can be produced in a short time.

  When A is less than 0.98, aggregation of primary particles becomes insufficient, ΔDv becomes small, and the particle size distribution becomes wide.

  When AA (t) is 0.01 or less, the aggregation of primary particles becomes insufficient, ΔDv becomes small, deformed base particles cannot be obtained, and the particle size distribution becomes wide. On the other hand, when AA (t) is 0.075 or more, aggregation of primary particles proceeds too much, ΔDv increases, and the particle size distribution of the base particles becomes wider.

  When | Dv (t) −Dv (t + 1) | is 0.2 μm or more, primary particles are not sufficiently aggregated, ΔDv becomes small, deformed base particles cannot be obtained, and the particle size distribution becomes wide. .

  If t is 10 minutes or more, the toner cannot be produced in a short time.

  The volume average particle size can be measured using a particle size measuring device Multisizer III (Beckman Coulter, Inc.). The average circularity can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation). Here, when measuring the volume average particle diameter and the average circularity, the liquid in which the first liquid is emulsified or dispersed in the aqueous medium is poured into water because the solvent is instantaneously removed. is there.

  The organic solvent used for preparing the first liquid preferably has a boiling point of less than 150 ° C. in consideration of volatilization and removal. Examples of such organic solvents include, but are not limited to, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, chlorobenzene, dichloroethylidene, acetic acid. Examples thereof include methyl, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone, and two or more kinds may be used in combination. Of these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable, and ethyl acetate is particularly preferable.

  The amount of the organic solvent used is preferably 40 to 300 parts by weight, more preferably 60 to 140 parts by weight, and particularly preferably 80 to 120 parts by weight with respect to 100 parts by weight of the toner material. When the amount of the organic solvent used is less than 40 parts by mass, the viscosity of the first liquid is increased and Dv1 is increased. Therefore, aggregation of primary particles is insufficient, ΔDv is decreased, and the liquid is deformed. In some cases, the base particles cannot be obtained and the particle size distribution becomes wide. On the other hand, when the amount of the organic solvent used exceeds 300 parts by mass, the viscosity of the first liquid becomes small and Dv1 becomes small. Therefore, the aggregation of primary particles proceeds too much, and ΔDv becomes large. The particle size distribution may be broadened.

  Although it does not specifically limit as an aqueous medium used when preparing a 2nd liquid, Water, the solvent miscible with water, the mixed solvent of water, etc. are mentioned. Although it does not specifically limit as a solvent miscible with water, Alcohol, such as methanol, isopropanol, and ethylene glycol; Dimethylformamide; Tetrahydrofuran; Cellsolves, such as methyl cellsolve; Lower ketones, such as acetone and methyl ethyl ketone, etc. are mentioned.

  When emulsifying or dispersing the first liquid in an aqueous medium, a known disperser such as a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, or an ultrasonic disperser. However, a high-speed shearing disperser is preferable. When using a high-speed shearing disperser, the number of rotations is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is usually 0.1 to 5 minutes in the case of a batch method. Moreover, the temperature at the time of dispersion | distribution is 0-150 degreeC (under pressure) normally, and 40-98 degreeC is preferable. At this time, the higher the temperature during dispersion, the lower the viscosity of the second liquid and the easier the dispersion.

  The amount of the aqueous medium used relative to 100 parts by mass of the toner material is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass. When the amount of the aqueous medium used is less than 50 parts by mass, the dispersed state is deteriorated, and mother particles having a predetermined particle diameter may not be obtained. When the amount exceeds 2000 parts by mass, the deformed mother particles are It may not be obtained.

  Moreover, the aqueous medium may contain a dispersant as necessary. Thereby, the dispersion stability of the second liquid can be improved and the particle size distribution of the toner can be narrowed. As the dispersant, surfactants, inorganic particles, resin particles, polymeric protective colloids, and the like can be used.

  The surfactant is not particularly limited, but anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters; alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines and the like. Cationic surfactant of amine salt type; Cationic interface of quaternary ammonium salt type such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride Activating agents; nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives; alanine, dodecylbis (aminoethyl) glycine, bis (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammoni Amphoteric surfactants such as Mubetain like. Among these, a surfactant having a fluoroalkyl group is preferable because the addition amount can be very small.

  Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms and a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6 to C11) oxy. ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid and Metal salts, perfluoroalkyl carboxylic acids (C7 to C13) and their metal salts, perfluoroalkyl (C4 to C12) sulfonic acids and their metal salts, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2- Hydroxyethyl) perfluorooctane Examples include honamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like.

  Commercially available anionic surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129. (Manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon) Ink Corporation), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204, (Tochem Products), Footgent F-100, F150 (Neos) ) And the like.

  Although it does not specifically limit as a cationic surfactant which has a fluoroalkyl group, The aliphatic primary, secondary or tertiary amine acid which has a fluoroalkyl group, perfluoroalkyl (C6-C10) sulfonamide propyl trimethyl ammonium salt Aliphatic quaternary ammonium salts such as benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

  Commercially available cationic surfactants having a fluoroalkyl group include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Kogyo Co., Ltd.), Mega Fuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footent F-300 (Neos Co., Ltd.) and the like can be mentioned.

  Examples of the inorganic particles include, but are not limited to, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite. In addition, when tricalcium phosphate is used as the inorganic particles, tricalcium phosphate can be removed using a method of dissolving with hydrochloric acid or the like and then washing with water or a method of decomposing with an enzyme.

  Examples of the resin particles include, but are not limited to, vinyl resin, polyurethane, epoxy resin, polyester, polyamide, polyimide, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate, and the like. You may use together. Among these, vinyl resin, polyurethane, epoxy resin, or polyester is preferable because fine spherical resin particles can be easily obtained.

  In addition, as a vinyl resin, a styrene- (meth) acrylic acid ester copolymer, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride A copolymer, a styrene- (meth) acrylic acid copolymer, etc. are mentioned. In synthesizing a vinyl resin, a monomer having a plurality of vinyl groups can be copolymerized. Examples of the monomer having a plurality of vinyl groups include sodium salt eleminol RS-30 (manufactured by Sanyo Chemical Industries) of ethylene oxide adduct sulfate, divinylbenzene, 1,6-hexanediol diacrylate, and the like.

  The resin particles can be produced using a known method, but are preferably used as an aqueous dispersion of resin particles. As a method for preparing an aqueous dispersion of resin particles, in the case of a vinyl resin, an aqueous dispersion of resin particles is obtained by polymerizing a vinyl monomer using a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method. In the case of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, a precursor such as a monomer or oligomer or a solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant. After that, heating or adding a curing agent to cure, a method for producing an aqueous dispersion of resin particles, a precursor such as a monomer or oligomer, or an appropriate emulsifier is dissolved in the solution, and then water is added. Examples include a phase inversion emulsification method. As a method for preparing an aqueous dispersion of resin particles other than these, after obtaining resin particles by pulverizing and classifying the resin using a mechanical pulverizer such as a mechanical rotary type or a jet type, an appropriate dispersant is used. A method of dispersing in water in the presence of the resin, a method of dispersing the resin particles in water in the presence of a suitable dispersant after obtaining resin particles by spraying the resin solution in the form of a mist, a poor solvent in the resin solution Or by cooling the resin solution dissolved in the solvent by heating, the resin particles are precipitated, the solvent is removed to obtain the resin particles, and then the resin particles are dispersed in water in the presence of an appropriate dispersant. A method in which a resin solution is dispersed in an aqueous medium in the presence of a suitable dispersant, and then a solvent is removed by heating, decompression, etc., a suitable emulsifier is dissolved in the resin solution, Examples thereof include a method of phase inversion emulsification by adding water.

  The polymeric protective colloid is not particularly limited, but carboxyl groups such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, etc. Vinyl monomers having: β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylic acid 3-chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate (Meth) acrylic monomers having hydroxyl groups such as acid esters, N-methylol acrylamide, N-methylol methacrylamide; alkyl vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether; vinyl acetate, vinyl propionate, vinyl butyrate (Meth) acrylamide monomers such as acrylamide, methacrylamide and diacetone acrylamide; methylolated products of (meth) acrylamide monomers; (meth) acrylic acid chloride monomers such as acrylic acid chloride and methacrylic acid chloride Homopolymers or copolymers such as vinyl monomers having a nitrogen atom such as vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine or the heterocyclic ring thereof; Other polymeric protective colloids include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl. Polyoxyalkylene resins such as ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester; celluloses such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose; polyvinyl alcohol, etc. Is mentioned.

  In the present invention, it is preferable to wash and dry after removing the organic solvent from the second liquid to form the base particles. The method of removing the organic solvent from the second liquid is not particularly limited, but a method of gradually raising the temperature of the second liquid to volatilize the organic solvent, and spraying the second liquid into a dry atmosphere. And a method of volatilizing an organic solvent.

  In the present invention, the polymer having a functional group capable of reacting with an active hydrogen group is not particularly limited, and examples thereof include polyol resins, acrylic resins, polyesters, epoxy resins, and derivatives thereof, and two or more thereof. You may use together. Among these, polyester is preferable in terms of high fluidity and transparency during melting. The functional group capable of reacting with the active hydrogen group is not particularly limited, and examples thereof include an isocyanate group, an epoxy group, a carboxyl group, and a chlorocarbonyl group, and two or more kinds may be used in combination. Of these, an isocyanate group is preferable.

  As a polymer having a functional group capable of reacting with an active hydrogen group, it is easy to adjust the molecular weight of the high molecular weight component, and there is no oilless low-temperature fixing property, in particular, no release oil coating mechanism to a fixing heating medium. Even in such cases, a polyester having an isocyanate group capable of producing a urea-modified polyester (hereinafter referred to as a prepolymer (A)) is preferable because good releasability and fixing properties can be secured.

  An adhesive substrate is produced by reacting a polymer having a functional group capable of reacting with an active hydrogen group and a compound having an active hydrogen group. The active hydrogen group includes a hydroxyl group (alcoholic). Hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group and the like, and two or more kinds may be used in combination. Of these, an amino group capable of producing a urea-modified polyester is preferable.

  At this time, the first liquid may be prepared by dissolving or dispersing a toner material further containing a compound having an active hydrogen group in an organic solvent, or the first liquid may be contained in an aqueous medium containing a compound having an active hydrogen group. The second liquid may be prepared by emulsifying or dispersing the liquid. Thereby, in the step of preparing the second liquid, a compound having an active hydrogen group and a polymer having a functional group capable of reacting with the active hydrogen group can be reacted.

  The adhesive substrate may be a mixture of a reaction product of a polymer having a functional group capable of reacting with active hydrogen groups and a compound having active hydrogen groups and a binder resin, or a binder. Resin may be used.

  Hereinafter, the case where the prepolymer (A) is used as a polymer having a functional group capable of reacting with an active hydrogen group and the amine (B) is used as a compound having an active hydrogen group will be described.

  The prepolymer (A) can be obtained, for example, by reacting a polyester having an alcoholic hydroxyl group obtained by polycondensation of a polyol and a polycarboxylic acid with a polyisocyanate.

  Examples of the polyol include a diol, a trihydric or higher alcohol, and a mixture of a diol and a trihydric or higher alcohol, and a diol or a mixture of a diol and a trihydric or higher alcohol is preferable.

  The diol is not particularly limited, but alkylene glycol such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol; diethylene glycol, triethylene glycol, Condensates of alkylene glycols such as dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols, ethylene oxide, propylene Addition of alkylene oxide such as oxide and butylene oxide; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; bisphenols and ethylene Kishido, propylene oxide, such as those obtained by adding alkylene oxides such as butylene oxide. These may be used alone or in combination. Among them, alkylene glycols having 2 to 12 carbon atoms or alkylene oxide adducts of bisphenols are preferable, and alkylene oxide adducts of bisphenols or mixtures of alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms are preferred. Particularly preferred.

  Although it does not specifically limit as alcohol more than trivalence, Trivalent or more aliphatic alcohols, such as glycerol, a trimethylol ethane, a trimethylol propane, a pentaerythritol, sorbitol; Trivalents, such as a trisphenol PA, a phenol novolak, a cresol novolak Examples of the above polyphenols: trihydric or higher polyphenols to which an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide is added may be used, and two or more of them may be used in combination.

  When a mixture of a diol and a trihydric or higher alcohol is used as the polyol, the mass ratio of the trihydric or higher alcohol to the diol is preferably 0.01 to 10%, and more preferably 0.01 to 1%.

  Examples of the polycarboxylic acid include a dicarboxylic acid, a trivalent or higher carboxylic acid, and a mixture of a dicarboxylic acid and a trivalent or higher carboxylic acid, and a mixture of a dicarboxylic acid and a trivalent or higher polycarboxylic acid is preferable.

  The dicarboxylic acid is not particularly limited, but alkylene dicarboxylic acids such as succinic acid, adipic acid and sebacic acid; alkenylene dicarboxylic acids such as maleic acid and fumaric acid; aromatics such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid Group dicarboxylic acid and the like, and two or more of them may be used in combination. Among these, alkenylene dicarboxylic acids having 4 to 20 carbon atoms or aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.

  Although it does not specifically limit as carboxylic acid more than trivalence, Aromatic polycarboxylic acid, such as trimellitic acid and pyromellitic acid, etc. are mentioned, You may use 2 or more types together. Of these, aromatic polycarboxylic acids having 9 to 20 carbon atoms are preferred.

  When a mixture of a dicarboxylic acid and a trivalent or higher carboxylic acid is used as the polycarboxylic acid, the mass ratio of the trivalent or higher carboxylic acid to the dicarboxylic acid is preferably 0.01 to 10%, and 0.01 to 1 % Is more preferable.

  In place of polycarboxylic acid, polycarboxylic acid anhydride or lower alkyl ester such as methyl ester, ethyl ester, isopropyl ester may be used.

  When synthesizing a polyester having an alcoholic hydroxyl group, it is heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc. It is preferable to distill off. At this time, the equivalent ratio of the hydroxyl group to the carboxyl group is usually 1 to 2, preferably 1 to 1.5, and more preferably 1.02 to 1.3.

  Examples of polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, etc. Aliphatic diisocyanates such as isophorone diisocyanate and cyclohexylmethane diisocyanate; tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4'-diisocyanatodiphenyl, 4,4'- Diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-me Aromatic diisocyanates such as tildiphenylmethane, 4,4′-diisocyanato-diphenyl ether; aromatic aliphatic diisocyanates such as α, α, α ′, α′-tetramethylxylylene diisocyanate; tris (isocyanatoalkyl) isocyanurate, tris ( Isocyanurates such as isocyanatocycloalkyl) isocyanurate; those blocked with a phenol derivative, oxime, caprolactam, etc. may be used, and two or more may be used in combination.

  When the polyester having an alcoholic hydroxyl group is reacted with the polyisocyanate, it is preferably synthesized at 40 to 140 ° C. At this time, the equivalent ratio of the isocyanate group to the alcoholic hydroxyl group is usually 1 to 5, preferably 1.2 to 4, and more preferably 1.5 to 2.5. If this equivalent ratio exceeds 5, the molecular weight of the urea-modified polyester increases, and the low-temperature fixability may decrease. If it is less than 1, the molecular weight of the urea-modified polyester decreases and hot offset resistance is reduced. May decrease.

  Moreover, when synthesizing the prepolymer (A), a solvent inert to isocyanate may be added as necessary. Examples of the solvent include aromatic solvents such as toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate; amides such as dimethylformamide and dimethylacetamide; ethers such as tetrahydrofuran and the like. Two or more kinds may be used in combination.

The weight average molecular weight of the prepolymer (A) is preferably 3 × 10 ³ to 2 × 10 ⁴ . If the weight average molecular weight is less than 3 × 10 ³ , it may be difficult to control the reaction rate of the prepolymer (A) and the amines (B), and the urea-modified polyester may not be stably produced. When more than 10 ^4, the reaction of the prepolymer (a) and the amine (B) may not proceed sufficiently, offset resistance may be lowered.

  In the present invention, the number average molecular weight and the weight average molecular weight are molecular weights in terms of polystyrene measured using GPC (gel permeation chromatography).

  Content of the structural component derived from polyisocyanate in a prepolymer (A) is 0.5-40 mass% normally, 1-30 mass% is preferable, and 2-20 mass% is more preferable. When this content is less than 0.5% by mass, the offset resistance may be lowered, and when it exceeds 40% by mass, the low-temperature fixability may be lowered.

  The content (average value) of isocyanate groups per molecule of the prepolymer (A) is usually 1 or more, preferably 1.5 to 3 and more preferably 1.8 to 2.5. If this content is less than 1, the molecular weight of the urea-modified polyester becomes small, and the offset resistance may decrease.

  Examples of amines (B) include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and the like, and two or more of them may be used in combination. Among these, diamine or a mixture of diamine and trivalent or higher polyamine is preferable.

  Examples of diamines include aromatic diamines such as phenylenediamine, diethyltoluenediamine, and 4,4′-diaminodiphenylmethane; alicyclic groups such as 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Diamine; Aliphatic diamines such as ethylene diamine, tetramethylene diamine, hexamethylene diamine and the like may be mentioned, and two or more kinds may be used in combination.

  Examples of the trivalent or higher amine include diethylenetriamine, triethylenetetramine, and the like, and two or more amines may be used in combination.

  Examples of amino alcohols include ethanolamine and hydroxyethylaniline, and two or more kinds may be used in combination.

  Examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan, and two or more of them may be used in combination.

  Examples of amino acids include aminopropionic acid and aminocaproic acid, and two or more amino acids may be used in combination.

  In addition, you may use what blocked the amino group of amines (B) instead of amines (B). Examples of the blocked amino group of amines (B) include ketimine compounds and oxazolidine compounds obtained from amines (B) and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Also good.

  In the present invention, the equivalent ratio of the isocyanate group of the prepolymer (A) to the amino group of the amine (B) is usually 1/3 to 3, preferably 0.5 to 2, and 2/3 to 1. 5 is more preferable. When the equivalent ratio is less than 1/3 and exceeds 3, the molecular weight of the urea-modified polyester is decreased, and offset resistance may be deteriorated.

  Moreover, you may form a urethane bond by adding alcohol other than amines (B). The equivalent ratio of the urethane bond to the urea bond formed in this manner is usually 0 to 9, preferably 0.25 to 4, and more preferably 2/3 to 7/3. When this equivalent ratio exceeds 9, offset resistance may be lowered.

  In the present invention, a catalyst such as dibutyltin laurate or dioctyltin laurate can be used when the prepolymer (A) and the amines (B) are reacted. Moreover, although reaction time is suitably selected according to the combination of prepolymer (A) and amines (B), for example, it is 10 minutes-40 hours normally, and 2-24 hours are preferable. The reaction temperature is usually 0 to 150 ° C, preferably 40 to 98 ° C.

  If necessary, the molecular weight of the urea-modified polyester can be adjusted using a reaction terminator. Examples of the reaction terminator include monoamines such as diethylamine, dibutylamine, butylamine, and laurylamine. In addition, you may use what blocked the amino group of monoamine instead of monoamine.

  In the present invention, the binder resin preferably contains polyester. This makes it possible to achieve both heat resistant storage stability and low-temperature fixability of the toner.

  The polyester can be obtained by polycondensation of polyol and polycarboxylic acid in the same manner as described above.

The weight average molecular weight of the polyester is preferably 1 × 10 ^{3 to} 3 × 10 ⁴ . When the weight average molecular weight is less than 1 × 10 ³ , the heat-resistant storage stability may be lowered, and when it exceeds 3 × 10 ⁴ , the low-temperature fixability may be lowered.

  The glass transition point of polyester is usually 30 to 70 ° C, preferably 35 to 60 ° C, and more preferably 35 to 55 ° C. When the glass transition point is less than 30 ° C, the heat-resistant storage stability may be lowered, and when it exceeds 70 ° C, the low-temperature fixability may be lowered.

  In the present invention, the glass transition point can be measured using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation).

  The hydroxyl value of the polyester is usually 5 mgKOH / g or more, preferably 10 to 120 mgKOH / g, more preferably 20 to 80 mgKOH / g. When the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.

  The polyester preferably has an acid value of 1 to 50 KOHmg / g. Thereby, negatively charged toner is obtained.

  In this invention, a hydroxyl value and an acid value can be measured based on the measuring method as described in JIS K0070-1966 and JIS K0070-1992, respectively.

  In the present invention, the adhesive substrate preferably contains urea-modified polyester and polyester. Thereby, low temperature fixability and glossiness can be improved. At this time, the urea-modified polyester is preferably compatible with at least a part of the polyester in terms of low-temperature fixability and offset resistance. For this reason, the polyester component of the urea-modified polyester is preferably similar in composition to the polyester.

The weight average molecular weight of the adhesive substrate is usually 3 × 10 ³ or more, preferably 5 × 10 ³ to 1 × 10 ⁶ , and more preferably 7 × 10 ^{3 to} 5 × 10 ⁵ . When the weight average molecular weight is less than 3 × 10 ³ , the offset resistance may be lowered.

  The glass transition point of the adhesive substrate is preferably 30 to 70 ° C, and more preferably 40 to 65 ° C. When the glass transition point is less than 30 ° C, the heat-resistant storage stability may be lowered, and when it exceeds 70 ° C, the low-temperature fixability may be lowered.

  The mass ratio of the prepolymer (A) to the polyester is preferably 5/95 to 25/75, more preferably 10/90 to 25/75. When the mass ratio is less than 5/95, the offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the gloss may be lowered.

  Specific examples of the adhesive substrate include a urea-modified polyester obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-condensate and a polycondensate of isophthalic acid with isophorone diisocyanate and isophorone diamine, and bisphenol A ethylene oxide. A mixture of a 2-mol adduct and a polycondensate of isophthalic acid; a urea-modified polyester obtained by reacting a bisphenol A ethylene oxide 2-mol adduct and a polycondensate of isophthalic acid with isophorone diisocyanate and a prepolymer reacted with isophorone diamine; Bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate mixture; bisphenol A ethylene oxide 2 mol adduct and bisphenol A propylene oxide 2 mol adduct and terephthalic acid Polycondensation of urea-modified polyester obtained by reacting polycondensate of formic acid with isophorone diisocyanate and prepolymer with isophorone diamine, bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct and terephthalic acid A urea modified polyester obtained by reacting a prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate, with isophorone diamine, Mixture of bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate Mixture of urea-modified polyester obtained by reacting a prepolymer reacted with cyanate with hexamethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid; bisphenol A ethylene oxide 2 mol adduct and terephthalic acid A polycondensation product of urea-modified polyester obtained by reacting a polycondensate of bisphenol A with isophorone diisocyanate and hexamethylene diamine, bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 2-mole adduct, and terephthalic acid polycondensate A mixture of bisphenol A ethylene oxide 2 mol and a polycondensate of terephthalic acid with isophorone diisocyanate, and a urea-modified polymer obtained by reacting a prepolymer with ethylenediamine. A mixture of a reester and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid; a prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with diphenylmethane diisocyanate. Of urea-modified polyester reacted with bisphenol A ethylene oxide 2-mole adduct and polycondensate of isophthalic acid; bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 2-mole adduct, terephthalic acid and dodecenyl succinate A urea-modified polyester obtained by reacting a polycondensate of an acid anhydride with diphenylmethane diisocyanate and a hexamethylenediamine and bisphenol A ethylene; Mixture of a 2 mol adduct of xylene, a 2 mol adduct of bisphenol A propylene oxide and a polycondensate of terephthalic acid; a prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with toluene diisocyanate. Examples thereof include a mixture of a urea-modified polyester reacted with hexamethylenediamine, a 2-mol adduct of bisphenol A ethylene oxide and a polycondensate of isophthalic acid.

  In the present invention, the toner material preferably further contains inorganic particles as a viscosity modifier. Thereby, the first liquid has a non-Newtonian viscosity, and the toner can be deformed.

  The inorganic particles are not particularly limited, but silicon dioxide (silica), titanium dioxide (titania), aluminum oxide (alumina), iron oxide, copper oxide, zinc oxide, tin oxide, antimony trioxide, magnesium oxide, zirconium oxide, oxidation Oxides such as chromium and cerium oxide; titanates such as barium titanate, magnesium titanate, calcium titanate and strontium titanate; carbonates such as barium carbonate and calcium carbonate; nitrides such as silicon nitride; Examples include clay, mica, wollastonite, and diatomaceous earth. Two or more kinds may be used in combination. Among these, a modified layered inorganic mineral is preferable.

  The modified layered inorganic mineral is obtained by substituting at least part of metal cations present between layers of a layered inorganic mineral in which layers of inorganic minerals having a thickness of several nanometers are laminated (Japanese translations 2003-2003). No. 515795, Special Table 2006-500605, Special Table 2006-503313). Thereby, since the modified layered inorganic mineral has moderate hydrophobicity, the first liquid has a non-Newtonian viscosity, and the toner can be deformed.

  The layered inorganic mineral is not particularly limited, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, and sepiolite, and two or more kinds may be used in combination. Among these, montmorillonite or bentonite is preferable because the viscosity can be easily adjusted with a small addition amount that does not affect the properties of the toner.

  The organic cation that replaces at least a part of the metal cation is not particularly limited, and is a quaternary ammonium ion such as trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium; phosphonium ion And imidazolium ions, and quaternary ammonium ions are preferred.

  Moreover, an organic anion can be introduce | transduced by substituting a part of bivalent metal cation which exists between the layers of a layered inorganic mineral with a trivalent metal cation. Such an organic anion is not particularly limited, but linear, branched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide And sulfate ions, sulfonate ions, carboxylate ions, phosphate ions and the like having propylene oxide, and the like. Among these, carboxylate ions having an ethylene oxide skeleton are preferable.

  Commercially available modified layered inorganic minerals in which at least some of the metal cations present between the layers are replaced with organic cations are Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst) ), Clayton 34, Clayton 40, Clayton XL (above, manufactured by Southern Clay), etc., Quaterium 18 bentonite; And stearalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay), and the like. Of these, Clayton AF and Clayton APA are preferable.

Moreover, as a commercial item of the modified layered inorganic mineral in which at least a part of the metal cations existing between the layers is substituted with an organic anion, the general formula R ₁ (OR ₂ ) _n OSO ₃ ^—
(In the formula, R ₁ is an alkyl group having 13 carbon atoms, R ₂ is an alkylene group having 2 to 6 carbon atoms, and n is an integer of 2 to 10).
DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) substituted with an organic anion represented by As a commercially available product of such an organic anion, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.) can be mentioned.

  The content of the modified layered inorganic mineral in the toner material is preferably 0.05 to 2% by mass.

  In the present invention, the toner material may further contain a colorant, a release agent, a charge control agent, a cleaning improver, a magnetic material, and the like.

  Although it does not specifically limit as a coloring agent (dye or pigment), carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, Titanium Yellow, Polyazo Yellow, Oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tart Rajn Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise Red, Parachloro Ortho Nitroaniline Les , Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazole Chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine And anthraquinone green, titanium oxide, zinc white, lithobon and the like.

  The dispersed particle diameter of the pigment is preferably 1 μm or less. When the dispersed particle diameter exceeds 1 μm, the image quality may be deteriorated. The dispersed particle diameter of the pigment can be measured using a particle size distribution measuring apparatus Microtrac ultrafine particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.) using a laser Doppler method.

  The colorant may be added as a composite in which a pigment and a resin are combined, that is, as a master batch. The master batch is obtained by applying a high shear force to the mixture of pigment and resin, and mixing and kneading. At this time, an organic solvent may be used in order to enhance the interaction between the pigment and the binder resin. A three-roll mill or the like can be used as a high shearing dispersion device that applies a high shearing force when mixing and kneading.

  Moreover, you may manufacture a masterbatch using the flushing method. Specifically, an aqueous paste containing a pigment is mixed and kneaded with a resin and an organic solvent to transfer the pigment to the binder resin side, and then moisture and the organic solvent are removed. When the flushing method is used, since the wet pigment cake can be used as it is, it is not necessary to dry it.

  As the resin used for producing the masterbatch, in addition to the above-mentioned modified polyester and polyester, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene and the like, and polymers of substituted products thereof; styrene-p-chlorostyrene Copolymer, Styrene-propylene copolymer, Styrene-vinyltoluene copolymer, Styrene-vinylnaphthalene copolymer, Styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, Styrene-butyl acrylate Copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer Copolymerization, styrene-acrylonitrile copolymerization Styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Styrene copolymer of polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, Modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like may be used, and two or more kinds may be used in combination.

  Instead of using a toner material further containing a colorant, a solution obtained by dissolving or dispersing a colorant in an organic solvent may be emulsified or dispersed in an aqueous medium. At this time, when the pigment is dispersed in the organic solvent, a resin or the like may be added to adjust the viscosity in order to apply an appropriate shearing force.

  The content of the colorant in the base particles is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. If the content is less than 1% by mass, the coloring power may be reduced. If the content exceeds 15% by mass, poor dispersion of the pigment may occur, resulting in a reduction in coloring power or electrical characteristics. There are things to do.

  The release agent is not particularly limited, but carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18- An ester having a plurality of alkanoic acid residues such as octadecandiol diol stearate; an ester having a plurality of alkanol residues such as tristearyl trimellitic acid and distearyl maleate; a plurality of alkanoic acid residues such as dibehenyl amide An amide having a plurality of monoamine residues such as trimellitic acid tristearyl amide; a wax having a carbonyl group such as a dialkyl ketone such as distearyl ketone; a polyolefin wax such as polyethylene wax and polypropylene wax And long chain hydrocarbons such as paraffin wax and sazol wax, and two or more kinds may be used in combination. Of these, esters having a plurality of alkanoic acid residues are preferred.

  The melting point of the release agent is usually 40 to 160 ° C, preferably 50 to 120 ° C, and more preferably 60 to 90 ° C. When the melting point is less than 40 ° C., the heat-resistant storage stability may be lowered, and when it exceeds 160 ° C., the low-temperature fixability may be lowered.

  The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps at a temperature 20 ° C. higher than the melting point of the release agent. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving the offset resistance and the low-temperature fixability may not be obtained.

  The content of the release agent in the base particles is preferably 0 to 40% by mass, and more preferably 3 to 30% by mass. When this content exceeds 40% by mass, the fluidity of the toner may be lowered.

  The charge control agent is not particularly limited, but nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (fluorine-modified quaternary ammonium salt) Salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorosurfactants, salicylic acid metal salts, metal salts of salicylic acid derivatives, copper phthalocyanines, perylenes, quinacridones, azo pigments, etc. . Examples of the charge control agent other than these include polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium base.

  Commercially available charge control agents include Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal Complex E-84, phenol-based condensate E-89 (above, Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industry Co., Ltd.), 4 Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (from Hoechst), LRA-901, boron complex LR- 147 (made by Nippon Carlit Co., Ltd.).

  The charge control agent may be added as a composite with a resin, that is, as a master batch.

  The content of the charge control agent in the base particles is usually 0 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the resin component in the base particles. When this content exceeds 10 parts by mass, the chargeability of the toner is too great, the effect of the charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, the fluidity of the toner is decreased, The image density may decrease.

  The cleaning property improver is not particularly limited, but includes fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid; resin particles obtained by using soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles. 2 or more may be used in combination. The resin particles preferably have a volume average particle diameter of 0.01 to 1 μm.

  Although it does not specifically limit as a magnetic material, Iron powder, magnetite, a ferrite, etc. are mentioned, You may use 2 or more types together. Among them, a white magnetic material is preferable in terms of color tone.

  In the present invention, the average circularity of the base particles is preferably 0.925 to 0.970, and more preferably 0.945 to 0.965. If the average circularity is less than 0.925, the transferability may be deteriorated, and a cleaning failure may occur in the photoreceptor or the transfer belt.

  Further, the content of particles having a circularity of 0.95 or less in the base particles is preferably 20 to 80% by number. When the content of particles having a circularity of 0.95 or less is less than 20% by number, cleaning failure may occur in the photosensitive member or the transfer belt, and when it exceeds 80% by number, transferability is deteriorated. There is.

  The circularity can be measured using a flow particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

  In the present invention, the volume average particle diameter of the base particles is preferably 3 to 7 μm. When the volume average particle diameter is less than 3 μm, when used as a two-component developer, the toner may be fused to the surface of the carrier due to long-term stirring in the developing device, and the charging ability of the carrier may be reduced. When used as a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may occur. On the other hand, when the volume average particle size exceeds 7 μm, it becomes difficult to form a high-resolution and high-quality image, and when used as a two-component developer, the balance of the toner in the developer was performed. In some cases, the variation in the particle size of the toner may increase.

  The base particles preferably have a volume average particle size to number average particle size ratio of 1.0 to 1.3, more preferably 1.0 to 1.2. When this ratio exceeds 1.3, the toner behavior varies during development, and the reproducibility of the fine dots is reduced, and a high-quality image may not be obtained.

  In addition, the volume average particle diameter and the number average particle diameter of the base particles can be measured using a particle size measuring device Multisizer III (manufactured by Beckman Coulter, Inc.).

  In the present invention, the content of the particles having a particle size of 2 μm or less in the base particles is preferably 1 to 20% by number. When the content of the particles having a particle size of 2 μm or less is less than 1% by number, when used as a two-component developer, the toner is fused to the surface of the carrier by long-term stirring in the developing device, and the carrier The charging ability may be reduced. When used as a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may occur. On the other hand, when the content of particles having a particle size of 2 μm or less exceeds 20% by number, when used as a two-component developer, the toner is fused to the surface of the carrier by long-term stirring in the developing device, and the carrier The charging ability may be reduced.

  The content of particles having a base particle size of 2 μm or less can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

  The toner production method of the present invention preferably further includes a step of adding inorganic particles to the base particles. Thereby, it is possible to suppress a decrease in fluidity and chargeability of the toner.

  The inorganic particles are not particularly limited, but silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

The average primary particle size of the inorganic particles is preferably 5 nm to 2 μm, more preferably 5 to 500 nm. Further, BET specific surface area of the inorganic particles is preferably 20 to 500 m ² / g.

  In addition, the inorganic particles are obtained by using a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, modified silicone oil, or the like. It is preferable that it is surface-treated. Accordingly, it is possible to suppress a decrease in toner fluidity and chargeability even under high humidity.

  The content of inorganic particles in the toner is preferably 0.01 to 5% by mass, more preferably 0.01 to 2.0% by mass.

  The toner manufactured using the toner manufacturing method of the present invention can be used as a developer for developing an electrostatic latent image by electrophotography, electrostatic recording method, electrostatic printing method or the like. The toner may be used as a one-component developer, or may be mixed with a magnetic carrier and used as a two-component developer.

  Examples of the present invention will be described below, but the present invention is not limited to the examples. In addition, a part means a mass part in an Example.

[Synthesis of Polyester 1]
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propion oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and dibutyltin oxide 2 parts were added and reacted at 230 ° C. for 7 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 4 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to obtain polyester 1. Polyester 1 had a weight average molecular weight of 5040, a glass transition point of 43 ° C., and an acid value of 25 mgKOH / g.

[Prepolymer synthesis]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15mHg for 5 hours, and intermediate polyester was obtained. The intermediate polyester had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition point of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.

  Next, 410 parts of the intermediate polyester, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Was synthesized. Prepolymer 1 had a free isocyanate content of 1.53% by mass.

[Synthesis of ketimine]
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize ketimine 1. Ketimine 1 had an amine value of 418 mgKOH / g.

[Preparation of masterbatch]
Using Henschel mixer (Mitsui Mining Co., Ltd.), 1200 parts of ion-exchanged water, 540 parts of carbon black Printex 35 (made by Dexa) having a DBP oil absorption of 42 ml / 100 mg and a pH of 9.5 and 1200 parts of polyester 1 were mixed. did. The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized using a pulverizer (manufactured by Hosokawa Micron Corporation) to obtain a master batch 1.

[Preparation of Toner Material Liquid 1]
In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of polyester 1, 110 parts of carnauba wax and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and held at 80 ° C. for 5 hours. Cooled to 30 ° C. in 1 hour. Next, 500 parts of master batch and 500 parts of ethyl acetate were added and mixed for 1 hour to obtain a mixed solution.

  1324 parts of the obtained mixed solution was transferred to a reaction vessel, and filled with 80% by volume of zirconia beads having a particle size of 0.5 mm using an ultra visco mill (manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hour. Three passes were performed under the condition of a disk peripheral speed of 6 m / sec. Next, 1324 parts of a 65 mass% ethyl acetate solution of polyester 1 was added, and one pass was performed under the same conditions as described above.

  To 200 parts of the resulting dispersion, 2 parts of a modified layered inorganic mineral Kraton APA (manufactured by Southern Clay Products) are added. K. The mixture was stirred at 7000 rpm for 60 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co.).

  749 parts of the obtained dispersion, 40 parts of ethyl acetate, 115 parts of prepolymer 1 and 2.9 parts of ketimine 1 were charged, and mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika). Thus, a toner material liquid 1 was obtained.

[Preparation of Toner Material Liquid 2]
In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of polyester 1, 110 parts of carnauba wax and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and held at 80 ° C. for 5 hours. Cooled to 30 ° C. in 1 hour. Next, 500 parts of master batch and 500 parts of ethyl acetate were added and mixed for 1 hour to obtain a mixed solution.

  1324 parts of the obtained mixed solution was transferred to a reaction vessel, and filled with 80% by volume of zirconia beads having a particle size of 0.5 mm using an ultra visco mill (manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hour. Three passes were performed under the condition of a disk peripheral speed of 6 m / sec. Next, 1300 parts of a 65 mass% ethyl acetate solution of polyester 1 was added, and one pass was performed under the same conditions as described above.

  200 parts of the resulting dispersion were added to T.W. K. The mixture was stirred at 7000 rpm for 60 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co.).

  749 parts of the obtained dispersion, 40 parts of ethyl acetate, 115 parts of prepolymer 1 and 2.9 parts of ketimine 1 were charged, and mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika). Thus, a toner material liquid 2 was obtained.

[Preparation of Toner Material Liquid 3]
In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of polyester 1, 110 parts of carnauba wax and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and held at 80 ° C. for 5 hours. Cooled to 30 ° C. in 1 hour. Next, 500 parts of master batch and 500 parts of ethyl acetate were added and mixed for 1 hour to obtain a mixed solution.

  1324 parts of the obtained mixed solution was transferred to a reaction vessel, and filled with 80% by volume of zirconia beads having a particle size of 0.5 mm using an ultra visco mill (manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hour. Three passes were performed under the condition of a disk peripheral speed of 6 m / sec. Next, 1324 parts of a 65 mass% ethyl acetate solution of polyester 1 was added, and one pass was performed under the same conditions as described above.

  To 200 parts of the resulting dispersion, 2 parts of a modified layered inorganic mineral Kraton APA (manufactured by Southern Clay Products) are added. K. The mixture was stirred at 7000 rpm for 60 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

  749 parts of the obtained dispersion, 80 parts of ethyl acetate, 115 parts of prepolymer 1 and 2.9 parts of ketimine 1 were charged, and TK type homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used for 1 minute at 5000 rpm. The toner material liquid 3 was obtained by mixing.

[Preparation of Toner Material Liquid 4]
In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of polyester 1, 110 parts of carnauba wax and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and held at 80 ° C. for 5 hours. Cooled to 30 ° C. in 1 hour. Next, 500 parts of master batch and 500 parts of ethyl acetate were added and mixed for 1 hour to obtain a mixed solution.

  1324 parts of the obtained mixed solution was transferred to a reaction vessel, and filled with 80% by volume of zirconia beads having a particle size of 0.5 mm using an ultra visco mill (manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hour. Three passes were performed under the condition of a disk peripheral speed of 6 m / sec. Next, 1300 parts of a 65 mass% ethyl acetate solution of polyester 1 was added, and one pass was performed under the same conditions as described above.

  To 200 parts of the resulting dispersion, 35 parts of a viscosity modifier MEK-ST (manufactured by Nissan Chemical Industries, Ltd.) having a solid content of 20% by mass is added. K. The mixture was stirred at 7000 rpm for 60 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co.).

  749 parts of the obtained dispersion, 40 parts of ethyl acetate, 115 parts of prepolymer 1 and 2.9 parts of ketimine 1 were charged, and mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika). Thus, a toner material liquid 4 was obtained.

[Preparation of aqueous medium]
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of ion-exchanged water, 11 parts of reactive emulsifier (sodium salt of sulfuric acid ester of methacrylic acid ethylene oxide adduct), Eleminol RS-30 (manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes. Next, after heating up to 75 degreeC and making it react for 5 hours, 30 mass parts of 1 mass% ammonium persulfate aqueous solution was added, and it age | cure | ripened at 75 degreeC for 5 hours, and prepared the resin particle dispersion. It was 105 nm when the volume average particle diameter of the resin particles was measured using a particle size distribution measuring apparatus Microtrac Ultra Fine Particle Size Distribution Analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.) using a laser Doppler method. Further, a part of the resin particle dispersion was dried to isolate the solid content, and the glass transition point was measured. As a result, it was 59 ° C., and the weight average molecular weight was 1.5 × 10 ⁵ .

  990 parts of ion-exchanged water, 83 parts of resin particle dispersion, 37 parts of 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate, eleminol MON-7 (manufactured by Sanyo Kasei Kogyo Co., Ltd.), 1% by weight aqueous solution of sodium carboxymethylcellulose Serogen BS- An aqueous medium 1 was obtained by mixing and stirring 135 parts of H-3 (Daiichi Kogyo Seiyaku Co., Ltd.) and 90 parts of ethyl acetate.

[Example 1]
867 parts of the toner material liquid 1 was added to 1200 parts of an aqueous medium, and the mixture was mixed for 3 minutes at 13000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsified slurry. At this time, after adding the toner material liquid 1, oil droplets during emulsification were sampled every 30 seconds. The sampled oil droplets were put into 80 ml of ion-exchanged water placed in a glass 100 ml beaker, and after instantaneous solvent removal, the average circularity and volume average particle diameter were measured. The evaluation results are shown in Table 1.

次に、撹拌機及び温度計をセットした反応容器中に、乳化スラリーを仕込み、３０℃で８時間脱溶剤した後、４５℃で４時間熟成し、分散スラリーを得た。

Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, the mixture was aged at 45 ° C. for 4 hours to obtain a dispersed slurry.

  After filtering 100 parts of the obtained dispersion slurry under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed for 10 minutes at 12000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), followed by filtration. did. 10% by mass phosphoric acid was added to the obtained filter cake to adjust the pH to 3.7, and the mixture was mixed for 10 minutes at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and then filtered. . After adding 300 parts of ion-exchanged water to the obtained filter cake and mixing for 10 minutes at 12000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), the operation of filtering was performed twice to obtain a filter cake. Obtained.

  The obtained filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and sieved with a mesh having a mesh size of 75 μm to obtain base particles. Table 2 shows the characteristics of the base particles.

母体粒子１００部に、疎水化シリカ１．０部と、疎水化酸化チタン０．５部を添加し、ヘンシェルミキサー（三井鉱山社製）を用いて混合し、トナーを得た。

To 100 parts of base particles, 1.0 part of hydrophobized silica and 0.5 part of hydrophobized titanium oxide were added and mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain a toner.

[Example 2]
To 1200 parts of the aqueous medium, 867 parts of the toner material liquid 1 was added and mixed for 6 minutes at 13000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsified slurry.

  A toner was obtained in the same manner as in Example 1 except that the obtained emulsified slurry was used.

[Example 3]
867 parts of the toner material liquid 1 was added to 1200 parts of an aqueous medium, and mixed for 2 minutes at 13000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsified slurry.

  A toner was obtained in the same manner as in Example 1 except that the obtained emulsified slurry was used.

[Example 4]
867 parts of the toner material liquid 1 was added to 1200 parts of an aqueous medium, and the mixture was mixed for 2.5 minutes at 13000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsified slurry.

  A toner was obtained in the same manner as in Example 1 except that the obtained emulsified slurry was used.

[Example 5]
867 parts of the toner material liquid 1 was added to 1200 parts of an aqueous medium, and mixed for 4 minutes at 13,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsified slurry.

  A toner was obtained in the same manner as in Example 1 except that the obtained emulsified slurry was used.

[Comparative Example 1]
To 1200 parts of the aqueous medium, 867 parts of the toner material liquid 2 was added and mixed for 6 minutes at 13000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsified slurry.

  A toner was obtained in the same manner as in Example 1 except that the obtained emulsified slurry was used.

[Comparative Example 2]
To 1200 parts of the aqueous medium, 867 parts of the toner material liquid 3 was added and mixed for 9 minutes at 13000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsified slurry.

  A toner was obtained in the same manner as in Example 1 except that the obtained emulsified slurry was used.

[Comparative Example 3]
867 parts of the toner material liquid 4 was added to 1200 parts of the aqueous medium, and the mixture was mixed for 12 minutes at 13000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain an emulsified slurry.

  A toner was obtained in the same manner as in Example 1 except that the obtained emulsified slurry was used.

  Next, the measurement method used in this example will be described.

(Number average particle size and volume average particle size)
The number average particle size and the volume average particle size were measured using a particle size analyzer Multimizer III (manufactured by Beckman Coulter) and analysis software Beckman Coulter Multisizer 3 Version 3.51. Specifically, first, 0.5% of a 10% by weight surfactant (alkylbenzene sulfonate) Neogen SC-A (Daiichi Kogyo Seiyaku Co., Ltd.) and a sample of 0.5 mg were added, and the mixture was stirred with a micropartel. 80 ml of ion exchange water was added. The obtained dispersion liquid was dispersed for 1 minute using an ultrasonic disperser W-113MK-II (manufactured by Honda Electronics Co., Ltd.). When the obtained dispersion is mixed with Isoton III (manufactured by Coulter), the number average particle diameter and volume average particle diameter when the concentration indicated by Multimizer III is 8 ± 2% are measured at an aperture diameter of 100 μm. did.

(Content of particles whose circularity and particle size are 2 μm or less)
Using a flow particle image analyzer FPIA-2100 and analysis software FPIA-2100 Data Processing Program for FPIA version 00-10 (manufactured by Sysmex Corporation), the content of particles having a circularity and a particle size of 2 μm or less was measured. Specifically, first, 10% by mass of a surfactant (alkylbenzene sulfonate) Neogen SC-A (Daiichi Kogyo Seiyaku Co., Ltd.) 0.1 to 0.5 ml in 100 to 150 ml of ion-exchanged water from which impurities have been previously removed. And 0.1 to 0.5 g of sample was added. The degree of circularity and the particle size are 2 μm or less when the concentration obtained when the obtained dispersion is dispersed for 1 to 3 minutes using an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.) is 3000 to 10,000 / μl. The content of the particles was measured.

  Table 3 shows the evaluation results of the toners of Examples 1 to 5 and Comparative Examples 1 to 3.

次に、トナーの評価方法について説明する。

Next, a toner evaluation method will be described.

(Cleanability)
Using Imagio NEO C600PRO (manufactured by Ricoh Co., Ltd.), after the initial printing of 1,000 sheets and 100,000 sheets, the toner remaining on the photosensitive member that has passed the cleaning process is used using Scotch tape (manufactured by Sumitomo 3M Co.). Moved to blank paper. Next, the reflection density of the white paper on which the toner was transferred and the white paper on which the toner was not transferred were measured using a Macbeth reflection densitometer RD514 type. In addition, it judged as a thing with a difference of reflection density less than 0.01 being (circle), what is 0.01 or more and less than 0.1 (triangle | delta), and what is 0.1 or more as x.

(Filming)
After evaluating the cleaning property, that is, after printing 100,000 sheets using Imagio NEO C600PRO (manufactured by Ricoh Co., Ltd.), all solid images were output, and it was evaluated whether there was any omission in the image. At this time, if filming has occurred on the photoconductor, the image is missing. It was determined that the image clearly had omission, x, density unevenness, etc. occurred, but the image not significantly affecting the image was Δ, and the image had no omission was evaluated as o.

(Toner scattering)
After evaluating the cleaning performance and filming, 100 sheets of white paper were printed using Imagio NEO C600PRO (manufactured by Ricoh), and the white paper was evaluated and the scattering state of the toner in the machine was evaluated. In addition, the case where the toner is clearly present on the white-printed paper is X, the case where the toner is not present on the white-printed paper but the toner is found to be scattered in the machine is Δ, and the toner is not present on the white-printed paper. The case where no toner scattering was observed in the machine was evaluated as “◯”.

JP 2008-70710 A

Claims (10)

A method for producing a toner having base particles,
A step of preparing a first liquid by dissolving or dispersing a toner material containing a polymer having a functional group capable of reacting with an active hydrogen group and / or a binder resin in an organic solvent;
Having the step of preparing a second liquid by emulsifying or dispersing the first liquid in an aqueous medium;
The average circularity when the volume average particle size of particles produced by introducing or emulsifying or dispersing a liquid obtained by emulsifying or dispersing the first liquid in an aqueous medium is minimized, and the first liquid is an aqueous system. When the average circularity and volume average particle size of particles produced by introducing a liquid emulsified or dispersed in a medium into t [min] are put into water, A (t) and Dv (t) [μm] respectively, 0.01 <A-A (t) <0.075 (0.98 ≦ A ≦ 1)
| Dv (t) −Dv (t + 1) | <0.2
t <10
The filling,
The method for producing toner, wherein the second liquid is a liquid obtained by emulsifying or dispersing the first liquid in an aqueous medium for t + 1 [min].   The toner manufacturing method according to claim 1, wherein the toner material further includes inorganic particles.   The toner manufacturing method according to claim 2, wherein the inorganic particles are a modified layered inorganic mineral in which at least a part of a metal cation is ion-exchanged with an organic cation.   The method for producing a toner according to claim 3, wherein the organic cation is a quaternary ammonium ion.   5. The method for producing a toner according to claim 1, wherein the base particles have a content of particles having a circularity of 0.95 or less of 20% by number or more and 80% by number or less. .   6. The toner manufacturing method according to claim 1, wherein the base particles have a ratio of a volume average particle diameter to a number average particle diameter of 1.0 to 1.3.   7. The toner manufacturing method according to claim 1, wherein the base particles have a content of particles having a particle diameter of 2 μm or less in a range of 1% by number to 20% by number.   The toner manufacturing method according to claim 1, wherein the binder resin contains polyester.   The method for producing a toner according to claim 1, wherein the polymer having a functional group capable of reacting with an active hydrogen group is a polyester having an isocyanate group.   10. The method according to claim 1, wherein in the step of preparing the second liquid, a polymer having a functional group capable of reacting with the active hydrogen group is reacted with a compound having an active hydrogen group. A method for producing the toner according to claim 1.