JP2005336222A - Resin fine particle, method for producing the same, toner for electrostatic image development and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a toner for electrostatic image development, which has excellent chargeability, low-temperature fixability, image quality and heat-resistant preservability, to provide a method for producing the same, to obtain a resin fine particle useful for the toner for electrostatic image development and to provide a method for producing the same. <P>SOLUTION: The method for producing a resin fine particle comprises mixing a resin solution synthesized from solution polymerization in an organic solvent with water containing a surfactant and subjecting the mixture to inverse emulsification. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a toner for developing an electrostatic image used for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, and the like, a method for producing the same, and a resin used for the toner for developing an electrostatic image. The present invention relates to fine particles and a method for producing the same.

  Conventionally, a toner for developing an electrostatic charge image used for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, and the like is obtained by mixing, melting and kneading a pigment such as carbon black in a thermoplastic resin. It has been produced by a so-called pulverization method in which a uniform dispersion is pulverized into a powder having a required particle size as a toner by an appropriate pulverizer.

  However, in recent years, in place of the pulverization method from the viewpoint of reducing the production cost and improving the image quality, it is possible to obtain resin fine particles having a small particle size and a relatively uniform particle size, a suspension polymerization method, an emulsion polymerization aggregation method, A wet granulation method such as an emulsification dispersion method has attracted attention.

  In the suspension polymerization method, granulation is performed by suspending a polymerization composition containing a polymerizable monomer, a polymerization initiator, a colorant, and the like in a dispersion medium and polymerizing the suspension. In addition, the emulsion polymerization aggregation method emulsifies a polymer composition containing a polymerizable monomer, a polymerization initiator and the like in a dispersion medium and emulsifies the fine resin particles granulated by polymerization with a colorant, wax, and the like. It is agglomerated in a state to perform desired granulation. In the emulsification dispersion method, a binder resin and a colorant are dissolved or dispersed in a suitable organic solvent to obtain a colored resin solution, which is added to an aqueous dispersion and vigorously stirred to form droplets of the resin solution. And granulation is performed by removing the organic solvent from the droplets by heating.

  According to the wet granulation method, it is easy to form toner particles having a small particle diameter in general, so that it is possible to sufficiently cope with high image quality. The yield is also good.

  In particular, the suspension polymerization method and the emulsion polymerization aggregation method are advantageous in terms of energy compared to the emulsion dispersion method because the toner is formed at the same time as the resin itself is synthesized.

  However, since the toner produced by the above wet method is produced in water, the amount of charge is inevitably low, and there is a problem that the charge stability against the environment is deteriorated. Further, if the fixing temperature is lowered for energy saving, there is a problem that the glass transition temperature of the toner is lowered and the heat resistant storage property is deteriorated.

In contrast, an aqueous dispersion of polyester resin fine particles comprising a polymer from a polyester resin and a monomer having an ethylenically unsaturated bond is produced in an excellent recording agent (for example, see Patent Document 1) or in an aqueous medium. An electrophotographic toner (for example, see Patent Document 2) made of resin particles containing a colorant is known, but does not solve the above problem.
Japanese Patent Laid-Open No. 9-157508 JP-A-14-351141

  An object of the present invention is to provide a toner for developing an electrostatic image having excellent chargeability, low-temperature fixability, image quality, and heat storage stability, and a method for producing the same, and further, the toner for developing an electrostatic image is used. The object is to provide resin fine particles and a method for producing the same.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
A method for producing resin fine particles, which is obtained by mixing a resin solution synthesized by solution polymerization in an organic solvent with water containing a surfactant and subjecting it to phase inversion emulsification.

(Claim 2)
A resin fine particle produced by the method for producing a resin fine particle according to claim 1.

(Claim 3)
It is obtained by adding a solution containing a release agent to a resin solution synthesized by solution polymerization in an organic solvent and mixing the resulting solution with water containing a surfactant to phase-emulsify. A method for producing resin fine particles.

(Claim 4)
A resin fine particle produced by the method for producing a resin fine particle according to claim 3.

(Claim 5)
A solution obtained after adding a solution containing a colorant to a resin solution synthesized by solution polymerization in an organic solvent is obtained by mixing with water containing a surfactant and phase-emulsifying the solution. For producing resin fine particles.

(Claim 6)
A resin fine particle produced by the method for producing a resin fine particle according to claim 5.

(Claim 7)
An electrostatic charge image development obtained by adding a flocculant to an aqueous dispersion containing at least resin fine particles and colorant particles to agglomerate the resin fine particles and the colorant particles to form agglomerated particles, followed by heat fusion. 7. A method for producing a toner for developing an electrostatic image, wherein the resin fine particles according to claim 2, 4 or 6 are used as the resin fine particles for forming the aggregated particles.

(Claim 8)
An electrostatic image developing toner produced by the method for producing an electrostatic image developing toner according to claim 7.

(Claim 9)
After adding an aggregating agent to an aqueous dispersion containing at least resin fine particles and colorant particles to aggregate the resin fine particles and the colorant particles to form mother particles, an outer layer is formed, and then heat fusion is performed. In the method for producing a toner for developing an electrostatic image obtained, the resin fine particles according to claim 2, 4 or 6 are used as resin fine particles for forming at least one of the base particles and the outer layer. A method for producing a toner for developing an electrostatic image.

(Claim 10)
An electrostatic image developing toner produced by the method for producing an electrostatic image developing toner according to claim 9.

  According to the present invention, it is possible to provide a toner for developing an electrostatic image that is excellent in chargeability, low-temperature fixability, image quality, and heat-resistant storage stability.

  Hereinafter, the present invention will be described in detail.

  In order to achieve the above object, as a result of various studies, the present inventors have found that the performance can be greatly improved by agglomeration and fusion of specific resin fine particles, leading to the present invention. That is, the resin fine particles of the present invention and the method for producing the same are obtained by adding a resin solution synthesized by solution polymerization in an organic solvent to water containing a surfactant as it is and subjecting it to phase inversion emulsification. To do. The resin solution synthesized by solution polymerization in the organic solvent according to the present invention may be emulsified by mixing with water containing a surfactant after appropriately performing treatment such as concentration.

  The toner for developing an electrostatic charge image of the present invention and a method for producing the same include a resin fine particle obtained by adding a resin solution synthesized by solution polymerization in an organic solvent to water containing a surfactant and subjecting it to phase inversion emulsification. The resin composition is obtained by adding a flocculant to an aqueous dispersion containing colorant particles to agglomerate the resin particles and the colorant particles and then heat-sealing them.

  The toner for developing an electrostatic charge image of the present invention and the method for producing the same are formed by adding a flocculant to an aqueous dispersion containing at least resin fine particles and colorant particles to aggregate the resin particles and colorant particles. Thereafter, the resin fine particles are added to the base particles to aggregate them to form an outer layer, and then heat-fused to form the mother particles and / or the outer layer in a toner for developing electrostatic images. As the resin fine particles, resin fine particles obtained by adding a resin solution synthesized by solution polymerization in at least an organic solvent to water containing a surfactant and performing phase inversion emulsification are used.

  In the present invention, in a toner for developing an electrostatic charge image produced by a wet method, a salting-out agent is added as a coagulant having a critical coagulation concentration or higher in a dispersion obtained by dispersing at least resin fine particles and colorant particles. A first step of agglomerating, a second step of forming adhering particles by adding and mixing a fine particle dispersion in which resin fine particles are dispersed in the agglomerated aggregated particle dispersion, and adhering the fine particles to the agglomerated particles. And a toner including a third step of fusing the adhering particles by heating to exhibit particularly good characteristics.

  In addition, since the present invention is manufactured by a wet polymerization method, it is easy to reduce the particle size, and it is possible to manufacture a toner for developing an electrostatic image that obtains a high-definition image.

  The present invention reduces the cost by directly producing fine particles from a synthetic solution, and also has a small particle size, a sharp particle size distribution, and electrostatic image development with good moisture resistance even when applied to a wet polymerization method. Toner can be manufactured.

  For the resin fine particles of the present invention, resins synthesized by general solution polymerization can be used. Specifically, polyester resins, urethane-modified polyester resins, urea-modified polyester resins, epoxy resins, styrene-acrylic resins, alkyd resins. Phenoxy resin or the like is used. Of these, polyester resins, urethane-modified polyester resins, epoxy resins, and styrene-acrylic resins are particularly useful for toners.

  For example, as monomers used for polyester resins, urethane-modified, urea-modified polyesters, general aromatic dicarboxylic acids, aliphatic dicarboxylic acids or derivatives thereof, and alkylene oxide adducts such as aliphatic dialcohols and bisphenol A are used. However, in particular, when the content of the terminal carboxylic acid group or sulfonic acid group is small, a good toner with high chargeability can be produced.

  As monomers used in the polyester resin fine particles, urethane-modified polyester resin fine particles, and urea-modified polyester resin fine particles used in the present invention, as aromatic dicarboxylic acid and derivatives thereof, phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, Terephthalic acid dichloride, terephthalic acid dibromide, diethyl terephthalate, dimethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, diphthalate isophthalate, dibromide isophthalate, diethyl isophthalate, dimethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, 5-sodium sulfoisophthalic acid, naphthalene dicarboxylic acid, naphthalic anhydride, naphthalene dicarboxylic dichloride, naphthalene dicarboxylic dibromide, na Dimethyl diene dicarboxylate, diethyl naphthalene dicarboxylate, dipropyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, diphenyl dicarboxylic acid, diphenic anhydride, diphenyl dicarboxylic acid dichloride, diphenyl dicarboxylic acid dibromide, dimethyl diphenyl dicarboxylic acid, diethyl diphenyl dicarboxylate, Examples thereof include dipropyl diphenyl dicarboxylate and dibutyl diphenyl dicarboxylate, but are not particularly limited thereto.

  Aliphatic dicarboxylic acids include oxalic acid, fumaric acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, cyclohexanedicarboxylic anhydride, maleic acid, itaconic acid, citraconic acid However, it is not particularly limited to these.

  Aliphatic dialcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, methylpentanediol, nonanediol, ethylbutylpropanediol, dimethylpropanediol, cyclohexanediol , Cyclohexanedimethanol, tricyclodecane dimethanol, neopentyl glycol, butylethyl hexanediol, bis (4-hydroxycyclohexyl) propane, dimethylol heptane, hydroxypivalic acid neopentyl glycol ester, and the like, but are not limited thereto. .

  Further, glycols obtained by adding 1 to several moles of ethylene oxide and propylene oxide to two phenolic hydroxyl groups of bisphenols, for example, 2,2-bis (4-hydroxyethoxyphenyl) propane, etc. it can.

  In addition to these monomers, a polycarboxylic acid or a polyhydric alcohol may be added. Other polyvalent carboxylic acids used include succinic acid, adipic acid, sebacic acid, azelaic acid, octyl succinic acid, benzenetricarboxylic acid, cyclohexanetricarboxylic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, trimesic acid And acid anhydrides, halides, and lower alkyl esters thereof. Examples of the polyhydric alcohol include, but are not limited to, polyethylene glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, polypropylene glycol, polytetramethylene glycol and the like.

  Further, the urethane-modified polyester resin used in the present invention can be urethane-modified by reacting it with an organic diisocyanate compound with both ends as hydroxyl groups as a polyester polyol. Organic diisocyanate compounds used include hexamethylene diisocyanate, tetramethylene diisocyanate, dimethoxybiphenylene diisocyanate, xylylene diisocyanate, diisocyanate methylcyclohexane, diisocyanate dicyclohexane, diisocyanate cyclohexylmethane, isophorone diisocyanate, tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate. , Phenylene diisocyanate, naphthalene diisocyanate, dimethylbiphenylene diisocyanate, diisocyanate diphenyl ether, and the like.

  The polyester polyol used for the urethane-modified polyester resin uses the above-mentioned compound as a polycarboxylic acid and a polyol, and the ratio of the polyol and the polycarboxylic acid is an equivalent ratio [OH] / hydroxyl group [OH] to carboxyl group [COOH] / [COOH] is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.2 / 1 to 1.02 / 1.

  The urea-modified polyester resin used in the present invention can be urea-modified by reacting the above-obtained prepolymer having an isocyanate group with an amine compound. Examples of amine compounds used include phenylenediamine, aromatic diamines such as 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, diaminecyclohexane, isophoronediamine, ethylenediamine, and tetramethylene. Examples include, but are not limited to, aliphatic diamines such as diamine and hexamethylenediamine, polyvalent amines such as diethylenetriamine and triethylenetetramine, ethanolamine, and hydroxyethylaniline.

  The method for synthesizing the polyester resin used in the present invention is not particularly limited. For example, the polyester resin can be obtained by a polyester polycondensation reaction according to a conventional method. Examples of preferably used catalysts include dibutyltin oxide, tin distearate, tin dioctanoate, tin chloride, tin oxide, titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, titanium tetrabutoxide, zirconium tetrabutoxide, hafnium tetrabutoxide Titanium tetraisopropoxide, zirconium tetrapropoxide, zirconium chloride oxide, hafnium chloride oxide, trifluoromethanesulfonic acid, sodium trifluoromethanesulfonate, sulfuric acid and the like.

  The epoxy resin used in the present invention may be a novolac type epoxy resin or an epi-bis type epoxy resin. The novolac type epoxy resin is a resin obtained by a reaction of epichlorohydrin and a phenol novolak resin or a cresol novolac resin, and the epi-bis type epoxy resin is a resin obtained by a reaction of epichlorohydrin and bisphenols. Examples of bisphenols include glycols obtained by adding 1 to several moles of ethylene oxide and propylene oxide to two phenolic hydroxyl groups of bisphenols, such as 2,2-bis (4-hydroxyethoxyphenyl) propane. It can also be mentioned. Also, it is better to react the terminal epoxy group of epoxy resin with amine, alcohol, phenol, Grignard reagent, organic acid sodium acetylide, alkyl chloride, etc., or react with monovalent active hydrogen-containing compound to eliminate epoxy activity. This is advantageous in preventing skin irritation and hydrophilicity.

  As the styrene-acrylic resin used in the present invention, styrene alone or a copolymer obtained by copolymerizing styrene with an acrylic acid monomer or a methacrylic acid monomer, or a copolymer obtained by copolymerizing an acrylic acid monomer or a methacrylic acid monomer is used.

  Examples of the monomer used include styrene monomers such as styrene, methyl styrene, methoxy styrene, ethyl styrene, propyl styrene, butyl styrene, phenyl styrene, chloro styrene, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic Butyl acrylate, pentyl acrylate, dodecyl acrylate, stearyl acrylate, ethyl hexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, dodecyl methacrylate, stearyl methacrylate And acrylic acid ester or methacrylic acid ester monomers such as ethylhexyl methacrylate and lauryl methacrylate. Of these, styrene and butyl (meth) acrylate are particularly preferably used.

  In the synthesis of the polymerizable monomer, a third vinyl compound can be copolymerized. Examples of the third vinyl compound include acrylic acid, methacrylic acid, maleic anhydride, vinyl acetate and other acid monomers, acrylamide, methacrylamide, acrylonitrile, ethylene, propylene, butylene, vinyl chloride, N-vinylpyrrolidone, butadiene and the like. It is done. These monomers are synthesized by dissolving them in an organic solvent and adding a polymerization initiator for polymerization.

  As the polymerization initiator to be added, those dissolved in an organic solvent are used. Specifically, hydrogen peroxide, acetyl peroxide, cumyl peroxide, t-butyl peroxide, propionyl peroxide, benzoyl peroxide, Chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, t-butyl perphenylacetate Hydroperoxide, t-butyl formate, t-butyl peracetate, t-butyl perbenzoate, t-butyl perphenyl acetate, t-butyl permethoxyacetate, t-butyl per-N- (3-toluyl) palmitate, etc. 2,2'-azobispropane, 2,2'-dichloro-2,2 ' Azobispropane, 1,1'-azo (methylethyl) diacetate, 2,2'-azobisisobutane, 2,2'-azobisisobutylamine, 2,2'-azobisisobutyronitrile, 2, Methyl 2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, , 1'-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 3,5-dihydroxymethylphenylazo-2-methylmalono Dinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-a Dimethyl bis-4-cyanovalerate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1, 1'-azobis-1-chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1 '-Azobis-1-chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanecarbonitrile, 1,1'-azobis-1-phenylethane, 1, 1'-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenol Nylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis-4-cyanopentanoate), poly Azo compounds such as (tetraethylene glycol-2,2'-azobisisobutyrate); 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1,4-diphenyl-2 -Examples include, but are not limited to, tetrazen.

  In the present invention, a chain transfer agent is added to control the molecular weight distribution of the polymer during polymerization together with the polymerizable monomer. Examples of the chain transfer agent used include alkyl mercaptans such as octyl mercaptan, dodecyl mercaptan, t-dodecyl mercaptan, stearyl mercaptan, n-octyl mercaptopropionate, n-dodecyl mercaptopropionate, n-hexyl mercapto. Mercaptopropionate such as propionate, n-stearyl mercaptopropionate, n-octylmercaptoglycolate, n-decylmercaptoglycolate, n-dodecylmercaptoglycolate, 2-ethylhexylmercaptoglycolate Mercaptoglycolic acid esters such as esters, disulfide compounds and the like are used. As these chain transfer agents, commercially available products or synthesized products can be used. The addition amount of the chain transfer agent varies depending on the desired molecular weight and molecular weight distribution, but specifically, it is preferably added in the range of 0.1 to 5% by mass with respect to the mass of the polymerizable monomer.

In the case of a polycondensation resin such as a polyester resin or an epoxy resin, the weight average molecular weight of the resin fine particles of the present invention has a maximum value in the range of 2 × 10 ^{2 to} 3 × 10 ⁴ in terms of styrene by GPC measurement. The maximum value of the molecular weight is preferably 3 × 10 ^{3 to} 3 × 10 ⁴ . By setting the maximum value to 3 × 10 ³ or more, the heat-resistant storage property and the powder flow property are improved, and by setting the maximum value to 3 × 10 ⁴ or less, the melt viscosity is lowered and the fixing property is improved.

In addition, in the case of an addition polymerization resin such as a styrene-acrylic resin, it is usually 7 × 10 ³ to 2 × 10 ⁵ , preferably 2 × 10 ⁴ to 15 × 10 ⁴ , more preferably 3 × 10 ⁴ to 1 ×. 10 ⁵ . There may be two or more molecular weight peaks, but a single peak is preferred. The peak of the molecular weight distribution may have a shoulder, and may tail on the high molecular weight side. By setting the maximum value to 7 × 10 ³ or more, the heat-resistant storage property and powder flow characteristics are improved, and by setting the maximum value to 2 × 10 ⁵ or less, the melt viscosity is lowered and the fixability is improved.

  The glass transition temperature of the resin fine particles of the present invention is selected to be 80 ° C. or lower, preferably 45 to 80 ° C., more preferably 50 to 70 ° C. When it is too low, the storage stability is lowered, so that the glass transition temperature is preferably 45 ° C. or higher. In addition, the said glass transition temperature is a physical-property value measured based on JISK7121, and means the midpoint glass transition temperature described in this specification.

  The softening point (Tm) of the resin fine particles of the present invention is preferably 140 ° C. or lower from the viewpoint of fixability for use as an electrostatic charge image developing toner. Moreover, 80 degreeC or more is preferable from a heat resistant storage viewpoint. In addition, the softening point uses a flow tester (CFT-500: manufactured by Shimadzu Corporation), weighs 1.0 g of a sample to be measured, uses a h1.0 mm × φ1.0 mm die, and heats up at a rate of 3.0 ° C. / Min, preheating time of 180 seconds, load of 30 kg, measurement temperature range of 60 to 160 ° C., the temperature at which the above sample flowed out 1/2 was defined as the softening point (Tm).

  The present invention is resin fine particles obtained by mixing a resin solution synthesized by solution polymerization in an organic solvent with water containing a surfactant as it is and phase-inverting and emulsifying it. The method for producing resin fine particles in the present invention is to synthesize a corresponding resin using an organic solvent and add the solution to water containing a surfactant, or to add water containing a surfactant to the synthesized solution. After the addition, it can be obtained using a known dispersion method mechanically or surface-chemically. That is, a method of mechanically emulsifying a resin synthesis solution with a high-speed stirrer such as a homogenizer in the presence of an emulsifier such as a surfactant and removing the solvent can be used.

  As the organic solvent used in the present invention, a monomer (monomer) used at the time of synthesis or a resin that dissolves the synthesized resin is good, and toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, Propyl acetate, butyl acetate, tetrahydrofuran, dioxane, dioxolane, diethyl ether, diisopropyl ether, dichloromethane, dichloromethane, chloroform, dimethylformamide, etc. can be used, but water-insoluble solvents such as toluene and dichloromethane are particularly sharp in particle size distribution. From this point, it is preferably used. Moreover, in order to remove a solvent, the thing with a low boiling point and easy to remove by azeotropy with water etc. is preferable.

  In the dispersion medium, a surfactant is added to prevent aggregation of the dispersed droplets. As the surfactant, a known surfactant can be used, and a surfactant selected from a cationic surfactant, an anionic surfactant, a nonionic surfactant and the like can be used. Two or more of these surfactants may be used in combination.

  Specific examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like.

  Specific examples of anionic surfactants include sulfonates (sodium dodecylbenzene sulfonate, sodium arylalkyl polyether sulfonate, 3,3-disulfone diphenylurea-4,4-diazo-bis-amino-8-naphthol). -6 sodium sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, etc. ), Sulfate esters (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, Potassium Alin acid, calcium oleate), and the like.

  Nonionic surfactants include polyethylene oxide, polypropylene oxide, combinations of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, esters of higher fatty acids and polypropylene oxide. And sorbitan esters.

  Of these, anionic surfactants and / or nonionic surfactants are preferred.

  The particle diameter of the resin fine particles of the present invention can be set in a wide range having a volume average particle diameter of about 0.01 to 10 μm, but is particularly 0.05 for use in toner for developing electrostatic images. A range of ˜1 μm is preferred. A more preferable range is 0.1 to 0.5 μm. The particle size can be controlled by the emulsification conditions such as the organic solvent used in emulsification, the solid content concentration, the number of rotations, the temperature, and the amount of surfactant added.

  The present invention can be applied to a toner granulation method including a granulation process in a wet state, and is used for a suspension polymerization method, an emulsion polymerization aggregation method, an emulsion dispersion aggregation method, and the like.

  When the resin fine particles of the present invention are used for an electrostatic charge image developing toner, it is preferable that the resin fine particles have a low acid value or OH value. Specifically, the acid value is 20 or less and the OH value is 20 or less. More preferably, the acid value is 10 or less and the OH value is 15 or less. If the acid value or OH value is 20 or more, the hydrophilicity becomes too high, causing a reduction in the charge amount of the toner and deteriorating environmental stability.

  In the case of the suspension polymerization method, polymerization comprising a polymerizable monomer, a polymerization initiator, a chain transfer agent, a colorant, and additives such as a charge control agent, magnetic powder, and an anti-offset agent added as necessary. The composition and the resin fine particles of the present invention are suspended in a dispersion medium with a homogenizer to form oil droplet dispersed particles. And the method of superposing | polymerizing by heating is employ | adopted.

  In the case of the emulsion polymerization aggregation method, an emulsion polymer obtained by emulsifying and dispersing a polymerizable monomer, a polymerization initiator, and a chain transfer agent, and the resin fine particles and colorant of the present invention, a charge control agent, a magnetic powder, and an offset Additives such as inhibitors may be emulsified and dispersed, and coagulated and fused together, or the polymerizable monomer is seed emulsion polymerized in the presence of the emulsified charge control agent, offset inhibitor and other additives. Thus, resin fine particles may be obtained and agglomerated and fused together with the resin fine particles of the present invention, the colorant and the magnetic powder.

  In the case of the emulsification dispersion aggregation method, an emulsion heavy dispersion is prepared by phase inversion emulsification of a solution in which a binder resin is dissolved in an organic solvent, and the resin fine particles and colorant of the present invention, charge control agent, magnetic powder, offset Additives such as inhibitors may be agglomerated and fused, or a solution obtained by dissolving a binder resin with additives such as a colorant, charge control agent and offset inhibitor dissolved in an organic solvent is transferred. The binder resin fine particles obtained by phase emulsification may be aggregated and fused together with the resin fine particles of the present invention.

Further, only the resin fine particles of the present invention may be aggregated and fused together with additives such as a colorant, a charge control agent, magnetic powder, and an anti-offset agent. The colorant contained in the toner is as shown below. Various organic and inorganic pigments and dyes of various colors can be used.

  That is, examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, magnetic ferrite, and magnetite.

  Yellow pigments include yellow lead, zinc yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, Permanent Yellow NCG, Tartragin Lake and others.

  Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.

  Red pigments include Bengala, Pangdan, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red, Calcium Salt, Lake Red C, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B etc.

  Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.

  Examples of blue pigments include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue derivatives, first sky blue, and induslen blue BC.

  Examples of the green pigment include chrome green, chromium oxide, pigment green B, malachite green lake, final yellow green G, and phthalocyanine green.

  Examples of white pigments include zinc oxide, titanium oxide, zirconium oxide, aluminum oxide, calcium oxide, calcium carbonate, and tin oxide.

  Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white, and kaolin.

  Examples of the dye include rose bengal, triphenylmethane dye, monoazo dye, disazo dye, rhodamine dye, condensed azo dye, and phthalocyanine dye.

  These colorants can be used alone or in combination. The colorant is used in an amount of 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the polymer contained in the toner. When the amount of the colorant is more than 20 parts by mass, the toner fixing property is lowered, and when the amount is less than 1 part by mass, a desired image density cannot be obtained.

  As the charge control agent, there are various types of substances that can give positive or negative charge by triboelectric charging. As the positive charge control agent, for example, a two-glossin dye such as Nigrosine Base ES (manufactured by Orient Chemical Industries). , Quaternary ammonium salts such as P-51 (manufactured by Orient Chemical Co., Ltd.), copy charge PX VP435 (manufactured by Clariant), alkoxylated amines, alkylamides, molybdate chelate pigments, and PLZ1001 (manufactured by Shikoku Kasei Kogyo Co., Ltd.) And imidazole compounds.

  As the negative charge control agent, for example, Bontron S-22 (manufactured by Orient Chemical Industries), Bontron S-34 (manufactured by Orient Chemical Industries), Bontron E-81 (manufactured by Orient Chemical Industries), Bontron E-84 ( (Orient Chemical Co., Ltd.), Spiron Black TRH (Hodogaya Chemical Co., Ltd.) and other metal complexes, Thioindio pigment, Bontron E-89 (Orient Chemical Industries Co., Ltd.), Calex Allen compounds, Copy Charge NX VP434 ( Quaternary ammonium salts such as Clariant), and fluorine compounds such as magnesium fluoride and carbon fluoride. In addition to the above-mentioned metal complexes serving as negative charge control agents, oxycarboxylic acid metal complexes, dicarboxylic acid metal complexes, amino acid metal complexes, diketone acid metal complexes, diamine metal complexes, azo group-containing benzene- It may have various structures such as a benzene derivative skeleton metal complex and an azo group-containing benzene-naphthalene derivative skeleton metal complex.

  These charge control agents desirably have a particle size of about 10 to 100 nm from the viewpoint of obtaining uniform dispersion. When the particle diameter exceeds the upper limit of the above range in a form supplied as a commercial product, it is desirable to adjust to an appropriate particle diameter by a known method such as pulverization with a jet mill or the like.

  Examples of the magnetic powder include magnetite, γ-hematite, and various ferrites.

  As the anti-offset agent, any of known waxes can be used. Specifically, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene and copolymer polyethylene, paraffin wax; behenic acid ester, Ester waxes having a long chain aliphatic group such as montanate ester and stearate ester; plant waxes such as hydrogenated castor oil and carnauba wax; ketones having a long chain alkyl group such as distearyl ketone; silicon having an alkyl group Higher fatty acids such as stearic acid; (partial) ester of polyhydric alcohol such as long chain fatty alcohol, pentaerythritol, trimethylolpropane and long chain fatty acid; higher fatty acid such as oleic acid amide, stearic acid amide, palmitic acid amide Examples include fatty acid amides That.

  These offset inhibitors are usually used in an amount of 1 to 25 parts by mass, preferably 3 to 20 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the polymer.

  As described above, preferred embodiments of the method for producing a toner for electrostatic charge development according to the present invention include suspension polymerization and emulsion polymerization aggregation.

  Examples of the polymerization initiator used in the suspension polymerization method include peroxide initiators such as benzoyl-oxide, lauryl peroxide, stearyl peroxide, 2,2′-azobisisobutyronitrile, 2, Examples include azobis-based initiators such as 2'-azobis (2,4-dimethylvaleronitrile).

  In order to suspend the polymerization composition in the dispersion medium to form the oil droplet dispersed particles, vigorous stirring may be performed using a high-speed stirring type dispersing machine such as a homomixer or a homogenizer.

  In order to carry out the polymerization, the solution system in which the polymerization composition is dispersed may be set to an arbitrary temperature equal to or higher than the decomposition temperature of the polymerization initiator, but it is usually preferably 40 ° C to 150 ° C.

  A dispersion stabilizer is added to the dispersion medium in order to prevent aggregation of the dispersed droplets. As the dispersion stabilizer, a known surfactant as described above can be used, and a dispersion stabilizer selected from a cationic surfactant, an anionic surfactant, a nonionic surfactant and the like can be used. it can. Two or more of these surfactants may be used in combination.

  In the suspension polymerization method, it is necessary to suppress the residual monomer in the polymer fine particles as much as possible. When the residual amount of the monomer is large, it causes aggregation when removing the dispersion stabilizer by washing, odor after becoming a toner, destabilization of chargeability, variation in softening temperature, and the like. In order to suppress monomer residue, the first half of the reaction is polymerized at a low temperature (40 to 80 ° C.), and the second half of the reaction is conducted at a high temperature (80 to 150 ° C.). It is desirable to use a polymer.

  Further, a dispersion stabilizer may be added during or after the polymerization. Such re-addition of the dispersion stabilizer is effective for preventing droplet aggregation and aggregation of the granulated resin fine particles.

  As the polymerization initiator used in the emulsion polymerization method or miniemulsion polymerization method, a water-soluble polymerization initiator is preferably used in the emulsion polymerization method. Specifically, hydrogen peroxide, acetyl peroxide, hydrogen peroxide, Peroxides such as ammonium sulfate, sodium persulfate and potassium persulfate; azo compounds such as 2,2′-azobis (2-amidinopropane) hydrochloride and 2,2′-azobis (2-amidinopropane) nitrate; Etc.

  As the emulsifier and dispersion stabilizer used for emulsion polymerization or for preparing an emulsion dispersion, those used in the above-mentioned suspension polymerization can be used in the same manner.

  In the present invention, the nonionic surfactant is used not only as an emulsifier during emulsion polymerization, but also for the purpose of stabilizing the dispersion of each fine particle in the aggregation step and adjusting the cohesive force of the dispersed fine particle. That is, since the nonionic surfactant has a markedly reduced dispersion stabilizing power at the cloud point or higher, an appropriate amount of the nonionic surfactant is allowed to coexist with the ionic surfactant when preparing the fine particle dispersion. By adding an appropriate amount in advance, it becomes possible to adjust the cohesive force between particles based on the control of the coagulation temperature, and it is possible to realize the uniformity and efficiency of cohesion of particles.

  The emulsion polymerization aggregation method is a preparation of an associated particle dispersion that associates the resin fine particle dispersion prepared by the emulsion polymerization method with the resin fine particles of the present invention and at least a separately prepared colorant dispersion to form associated particles. A step (hereinafter referred to as an association step) and a step of forming toner particles by heat-fusion of the associated particles (hereinafter referred to as an aggregation and fusion step).

  In addition, the resin fine particles of the present invention are combined with the fine particles obtained by heat-merging the resin fine particle dispersion prepared by an emulsion polymerization method, the resin fine particles of the present invention, and at least a separately prepared colorant dispersion with associated particles. The toner particles may be formed by associating to obtain associating particles and heat-fusion.

  In the association step, the resin fine particle dispersion, the colorant dispersion, and, if necessary, the offset inhibitor dispersion are mixed with each other, and the resin particles are associated to form associated particles. The associated particles are formed by heteroaggregation or the like. At this time, for the purpose of stabilizing the associated particles and controlling the particle size / size distribution, the ionic surfactants or metal salts having a polarity different from those of the associated particles are used. Charged compounds can be added. In the agglomeration and fusion step, the resin is aggregated and melted by heating to a temperature equal to or higher than the glass transition temperature of the resin in the associated particles.

  Specific examples of the flocculant to be added include water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants; acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and oxalic acid; magnesium chloride Metal salts of inorganic acids such as calcium chloride, sodium chloride, aluminum chloride, aluminum sulfate, calcium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate; sodium acetate, potassium formate, sodium oxalate, sodium phthalate, potassium salicylate Aliphatic acids such as aliphatic acids, metal salts of aromatic acids; metal salts of phenols such as sodium phenolate, metal salts of amino acids, aliphatic acids such as triethanolamine hydrochloride, aniline hydrochloride, and inorganic acids of aromatic amines Salt. When considering the stability of the aggregated particles, the stability of the aggregating agent with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable in terms of performance and use.

  The amount of these flocculants to be added varies depending on the valence of the charge, but any of them may be small. About 5% by mass or less. A smaller amount of the flocculant is preferable, and a compound having a higher valence is preferable because the amount added can be reduced.

  Before the agglomeration and fusion step, there can be provided an attachment step in which other fine particle dispersion is added to and mixed with the associated particle dispersion to uniformly attach the fine particles to the surface of the associated particles to form attached particles. The adhered particles are formed by heteroaggregation or the like. Similarly to the above, this adhering particle dispersion is heated to a temperature equal to or higher than the glass transition temperature of the resin fine particles, and is aggregated and melted to form aggregated fused particles.

  In the suspension polymerization method or the emulsion polymerization aggregation method, the fine particles are taken out from the fine particle dispersion medium, the impurities mixed during the manufacturing process are removed in the washing step, and dried to obtain a toner for developing an electrostatic charge image.

  In the washing step, acidic and possibly basic water is added several times with respect to the fine particles and stirred, followed by filtration to obtain a solid content. The pure water is added several times to the solid content and stirred, followed by filtration. This operation is repeated several times, and is terminated when the pH of the filtrate after filtration reaches about 7, and colored toner particles are obtained. In the drying step, the toner particles obtained in the washing step are dried at a temperature not higher than the glass transition temperature. At this time, it is preferable to circulate dry air according to the required temperature, or to heat under vacuum conditions.

  In the drying step, an arbitrary method such as a normal vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be adopted.

  As an external additive used when externally treating the toner particles produced in the above-described steps, known inorganic fine particles used as a fluidity adjusting agent in the field of electrostatic image developing toners are used. For example, silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, diamond carbon lactam, etc. Various nitrides such as carbide, boron nitride, titanium nitride, zirconium nitride, various borides such as zirconium boride, titanium oxide (titania), calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, silica, colloidal silica Various oxides such as calcium titanate, magnesium titanate Various titanate compounds such as strontium, strontium titanate, sulfides such as molybdenum disulfide, various fluorides such as magnesium fluoride and carbon fluoride, various types such as aluminum stearate, calcium stearate, zinc stearate, magnesium stearate Various nonmagnetic inorganic fine particles such as metal soap, talc and bentonite can be used alone or in combination.

  Inorganic fine particles, especially silica, titanium oxide, alumina, zinc oxide, etc. are conventionally used hydrophobizing agents such as silane coupling agents, titanate coupling agents, silicone oils, silicone varnishes, and fluorine-based silanes. The surface treatment is preferably carried out by a known method using a coupling agent or a fluorine-based silicone oil, a coupling agent having an amino group or a quaternary ammonium base, or a modified silicone oil.

  The average primary particle size of the inorganic fine particles used as the external additive is 5 to 100 nm, preferably 10 to 50 nm, and more preferably 20 to 40 nm.

  Organic fine particles are granulated by emulsion polymerization, soap-free emulsion polymerization, wet polymerization such as non-aqueous dispersion polymerization, gas phase method, etc. for the purpose of cleaning aids, styrene, (meth) acrylic Fine particles such as benzoguanamine, melamine, Teflon (registered trademark), silicon, polyethylene, and polypropylene can be used.

  The toner of this embodiment may be used as a full color toner used in a full color image forming apparatus, or may be used as a monochrome toner used in a monochrome image forming apparatus.

In addition, the toner of this embodiment may be used in an image forming apparatus having any type of fixing device, but the type of fixing device in which the amount of release oil applied to a fixing member such as a roller is reduced. That is, it is preferably used for a fixing device having a release oil application amount of 4 mg / m ² or less, particularly an image forming apparatus having a fixing device of a type that does not apply release oil.

  Hereinafter, the present invention will be described more specifically with reference to examples. The following parts are parts by mass.

(Synthesis of polyester resin)
A glass four-necked flask equipped with a stirrer, a distillation column, a thermometer, and a nitrogen introduction tube was charged with 4 moles of neopentyl glycol, 4 moles of ethylene glycol, and 8 moles of terephthalic acid and dissolved in xylene. This was heated to 140 ° C. in a mantle heater under a nitrogen stream, and 0.14% of a polymerization initiator (trifluoromethanesulfonic acid) was added to the total charge of acid and alcohol components, and stirred. The reaction was carried out by heating. The progress of the reaction is monitored by measuring the acid value. When the predetermined acid value is reached, the reaction is terminated, and the weight average molecular weight is 6,700, Tg is 56 ° C., Tm is 103 ° C., and the acid value is A xylene solution of polyester resin 1 in 3.2 was obtained.

  Similarly, a xylene solution of polyester resins 2 to 8 was obtained.

(Synthesis of urethane-modified polyester resin)
In a reaction flask equipped with a stirrer, heating / cooling device, concentrating device, and raw material / auxiliary charging device, 4.9 mol of dimethyl terephthalate, 3.8 mol of neopentyl glycol, 7.4 mol of ethylene glycol and titanium tetrabutoxide 0.52 parts was charged, and the ester exchange reaction was carried out from 160 ° C. to 220 ° C. over 4 hours while stirring at a stirring speed of 200 rpm under a nitrogen stream. Subsequently, 0.2 mol of fumaric acid was added, and esterification reaction was performed from 200 ° C. to 220 ° C. over 1 hour. When the resin obtained by NMR or the like was measured, it was 48 mol% terephthalic acid, 2 mol% fumaric acid, 25 mol% neopentyl glycol, and 25 mol% ethylene glycol. Next, 108.7 parts of the obtained polyester polyol, 2.4 parts of propylene glycol, and 9 parts of diphenylmethane diisocyanate were dissolved in toluene and reacted at 60 ° C. in a nitrogen stream. The obtained urethane-modified polyester resin had a weight average molecular weight of 12,300, Tg of 59 ° C., and Tm of 114 ° C. In this way, a toluene solution of the urethane-modified polyester resin 9 was obtained.

  Similarly, a toluene solution of urethane-modified polyester resin 10 was obtained.

[Measurement of physical properties of resin]
(Glass transition temperature Tg)
Using a differential scanning calorimeter (DSC-200: manufactured by Seiko Electronics Co., Ltd.), 10 mg of a sample to be measured was accurately weighed, put in an aluminum pan, and heated as a reference using alumina in an aluminum pan. After the temperature was raised from room temperature to 200 ° C. at a rate of 30 ° C./min, this was cooled, measured at 20 to 120 ° C. at a rate of temperature rise of 10 ° C./min, and 30 to 90 ° C. during this temperature rise process. The shoulder value of the main endothermic peak in this range was taken as the glass transition point.

(Softening point Tm)
Using a flow tester (CFT-500: manufactured by Shimadzu Corporation), 1.0 g of a sample to be measured is weighed, a die having a diameter of 1.0 mm × a length of 1.0 mm is used, and a temperature rising rate is 3.0 ° C./min. The measurement was performed under the conditions of a preheating time of 180 seconds, a load of 30 kg, and a measurement temperature range of 60 to 180 ° C., and the temperature at which the above sample flowed out 1/2 was taken as the softening point.

(Weight average molecular weight)
The measurement was performed using gel permeation chromatography (807-IT type: manufactured by JASCO Corporation). While maintaining the column temperature at 40 ° C., tetrahydrofuran as a carrier solvent was flowed at 1 kg / cm ² , 30 mg of a sample to be measured was dissolved in 20 ml of tetrahydrofuran, 0.5 mg of this solution was introduced into the apparatus together with the carrier solvent, It calculated | required by polystyrene conversion.

  In addition, the numerical value in Table 1 represents a molar ratio.

  In the table, numbers such as 1 and 2 represent the diol bonding position, BPA-PO represents a propylene oxide adduct of bisphenol A, and DPMDI represents diphenylmethane diisocyanate.

(Preparation of polyester resin fine particle dispersion)
In 450 parts of ion-exchanged water, 0.9% by mass of a surfactant (sodium dodecylbenzenesulfonate) was dissolved to prepare an aqueous medium, and the xylene solution of the polyester resin 1 was added to the aqueous medium using a TK homomixer. To form an O / W emulsion. At this time, the TK homomixer was stirred at 12000 rpm for 30 minutes. Thereafter, the mixed solvent was removed by heating with stirring at 200 rpm in a TK homomixer to obtain a polyester resin fine particle 1 dispersion having a volume average particle size of 120 nm.

  In the same manner, polyester resin fine particles 2 to 8 dispersion were obtained from polyester resins 2 to 8, and urethane modified polyester resin fine particles 9 and 10 dispersion were obtained from urethane modified polyester resins 9 and 10.

(Preparation of wax dispersion (1))
680 parts of distilled water, 180 parts of carnauba wax (manufactured by Celerica Noda) and 17 parts of sodium dodecylbenzenesulfonate (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are mixed and emulsified and dispersed by high-pressure shearing to obtain a wax fine particle dispersion. Got. When the particle size of the wax fine particles was measured using a dynamic light scattering particle size distribution analyzer, ELS-800 (manufactured by Otsuka Electronics Co., Ltd.), the average particle size was 110 nm.

(Preparation of wax dispersion (2))
680 parts of distilled water, 180 parts of pentaerythritol ester (Unistar H476, manufactured by NOF Corporation) and 17 parts of sodium dodecylbenzenesulfonate (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are mixed, emulsified and dispersed by applying high-pressure shear, and wax. A fine particle dispersion was obtained. When the particle size of the wax fine particles was measured using a dynamic light scattering particle size distribution analyzer, ELS-800 (manufactured by Otsuka Electronics Co., Ltd.), the average particle size was 130 nm.

(Colorant fine particle dispersion (1))
10 parts of sodium dodecylbenzenesulfonate (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is dissolved in 180 parts of distilled water, and 25 parts of carbon black (Regal 330R; manufactured by Cabot Corporation) is added and dispersed therein as fine colorant particles. A colorant fine particle dispersion (1) was obtained. When the particle size of the dispersed carbon black was measured using a dynamic light scattering particle size distribution analyzer, ELS-800 (manufactured by Otsuka Electronics Co., Ltd.), the average particle size was 106 nm.

(Colorant fine particle dispersion (2))
10 parts of sodium dodecylbenzenesulfonate (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is dissolved in 180 parts of distilled water, and 25 parts of cyan pigment (copper phthalocyanine B15: 3; manufactured by Dainichi Seika Co., Ltd.) is added as fine colorant particles. In addition, it was dispersed to obtain a colorant fine particle dispersion (2). When the particle size of the dispersed carbon black was measured using a dynamic light scattering particle size distribution analyzer, ELS-800 (manufactured by Otsuka Electronics Co., Ltd.), the average particle size was 110 nm.

(Preparation of polymer primary fine particle dispersion (1))
A reactor equipped with a stirrer, a condenser, and a temperature sensor was charged with 450 parts of distilled water and 0.56 part of sodium dodecyl sulfate, heated to 80 ° C. with stirring under a nitrogen stream, and then 1% by mass. 120 parts of an aqueous potassium persulfate solution was added. Next, after adding monomer mixed solution 1 having the following composition over 1.5 hours, the mixture was further maintained for 2 hours to complete the polymerization. After completion of the polymerization reaction, the contents were cooled to room temperature to obtain a milky white primary polymer fine particle dispersion. The weight average molecular weight of the polymer was 11,000, Tg was 34 ° C., Tm was 82 ° C., and the average particle size measured with a dynamic light scattering particle size distribution analyzer (ELS-800; manufactured by Otsuka Electronics Co., Ltd.) was 120 nm. It was.

[Monomer mixture 1]
Styrene 99 parts Butyl acrylate 52 parts Methacrylic acid 14 parts n-Octyl mercaptan 6 parts (Preparation of polymer primary fine particle dispersion (2))
A reactor equipped with a stirrer, a condenser, and a temperature sensor was charged with 450 parts of distilled water and 0.56 part of sodium dodecyl sulfate, heated to 80 ° C. with stirring under a nitrogen stream, and then 1% by mass. 120 parts of an aqueous potassium persulfate solution was added. Next, after adding monomer mixed solution 2 having the following composition over 1.5 hours, the mixture was further maintained for 2 hours to complete the polymerization. After completion of the polymerization reaction, the contents were cooled to room temperature to obtain a milky white primary polymer fine particle dispersion. The weight average molecular weight of the polymer was 9,800, Tg was 30 ° C., Tm was 78 ° C., and the average particle size measured with a dynamic light scattering particle size distribution analyzer (ELS-800; manufactured by Otsuka Electronics Co., Ltd.) was 110 nm. It was.

[Monomer mixture 2]
Styrene 95 parts Butyl acrylate 58 parts Methacrylic acid 12 parts n-Octyl mercaptan 8 parts Example 1
In a reactor equipped with a stirrer, a condenser, and a temperature sensor, 240 parts of polyester resin fine particle 1 dispersion, 13.6 parts of wax dispersion (1), 24 parts of colorant fine particle dispersion (1), anionic surface activity 5 parts of an agent (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 240 parts of distilled water were added, and a 2M aqueous sodium hydroxide solution was added with stirring to adjust the pH of the mixed dispersion to 10.0. The temperature was raised to 50 ° C. while stirring, and then 40 parts of a 50% by weight magnesium chloride aqueous solution was added thereto. Then, the temperature was raised to 60 ° C. with stirring and held for 0.5 hour, and then raised to 80 ° C. Warmed and held for another 0.5 hours. At this time, the average particle size of the toner in the mixed dispersion was 4.8 μm. Next, 120 g of a 20 mass% sodium chloride aqueous solution was added, and the mixture was further held for 0.5 hour. Thereafter, the contents are cooled to room temperature, and the toner particles having a volume average particle diameter of 4.8 μm are dried by repeating several times of washing treatment such as filtration of the solution and resuspension treatment of the obtained solid in distilled water. 1 was obtained. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A; manufactured by Titanium Industry), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, mixed with a Henschel mixer (peripheral speed 40 m / sec, 60 seconds), and then sieved with a sieve having an opening of 90 μm to obtain toner 1.

Example 2
In Example 1, instead of using the polyester resin fine particle 1 dispersion, toner particles 2 having a volume average particle size of 4.8 μm were obtained by the same operation using the polyester resin fine particle 2 dispersion. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A; manufactured by Titanium Industry), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, and after mixing with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds), the mixture was sieved with a sieve having an opening of 90 μm to obtain toner 2.

Example 3
In a reactor equipped with a stirrer, a condenser, and a temperature sensor, 240 parts of polyester resin fine particle 3 dispersion, 13.6 parts of wax dispersion (1), 24 parts of colorant fine particle dispersion (1), anionic surface activity 5 parts of an agent (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 240 parts of distilled water were added, and a 2M aqueous sodium hydroxide solution was added with stirring to adjust the pH of the mixed dispersion to 10.0. The temperature was raised to 50 ° C. with stirring, and then 40 parts of a 50% by weight magnesium chloride aqueous solution was added thereto. Then, the temperature was raised to 60 ° C. with stirring and held for 0.5 hour, and then raised to 70 ° C. Warmed and held for another 0.5 hours. The average particle size of the toner in the mixed dispersion at this time was 4.5 μm. Next, after cooling the temperature to 50 ° C., 30 parts of polyester resin fine particle 4 dispersion was added, heated to 80 ° C. and held for 0.5 hours, and then added with 120 g of 20% by mass aqueous sodium chloride solution. Hold for another 0.5 hour. Thereafter, the contents are cooled to room temperature, and the toner particles having a volume average particle diameter of 4.8 μm are dried by repeating the washing process such as filtration of the solution and resuspension treatment of the obtained solid in distilled water several times. 3 was obtained. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A; manufactured by Titanium Industry), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, mixed with a Henschel mixer (peripheral speed 40 m / sec, 60 seconds), and then sieved with a sieve having an opening of 90 μm to obtain toner 3.

Example 4
In a reactor equipped with a stirrer, a condenser, and a temperature sensor, 240 parts of polymer primary particle dispersion (2), 13.6 parts of wax dispersion (2), 24 parts of colorant fine particle dispersion (2), anion Active surfactant (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 240 parts of distilled water were added, and 2M sodium hydroxide aqueous solution was added with stirring to adjust the pH of the mixed dispersion to 10.0. did. Next, after adding 40 parts of 50 mass% magnesium chloride aqueous solution to this, it heated up at 70 degreeC, stirring for 0.5 hour, then heated up to 75 degreeC and hold | maintained for further 0.5 hour . The average particle size of the toner in the mixed dispersion at this time was 4.3 μm. Next, after cooling the temperature in the system to 60 ° C., 40 parts of polyester resin fine particle 7 dispersion was added, heated to 80 ° C. and held for 0.5 hour, and then 120 g of 20% by mass sodium chloride aqueous solution was added. After the addition, it was held for another 0.5 hours. Thereafter, the contents are cooled to room temperature, and the toner particles having a volume average particle diameter of 4.7 μm are dried by repeating the washing process such as filtration of the solution and resuspension treatment of the obtained solid in distilled water several times. 4 was obtained. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A; manufactured by Titanium Industry), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, mixed with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds), and then sieved with a sieve having an opening of 90 μm to obtain toner 4.

Example 5
In a reactor equipped with a stirrer, a condenser, and a temperature sensor, 240 parts of polymer primary particle dispersion (1), 13.6 parts of wax dispersion (2), 24 parts of colorant fine particle dispersion (2), anion Active surfactant (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 240 parts of distilled water were added, and 2M sodium hydroxide aqueous solution was added with stirring to adjust the pH of the mixed dispersion to 10.0. did. Next, after adding 40 parts of 50 mass% magnesium chloride aqueous solution to this, it heated up at 70 degreeC, stirring for 0.5 hour, then heated up to 75 degreeC and hold | maintained for further 0.5 hour . The average particle size of the toner in the mixed dispersion at this time was 4.2 μm. Next, after cooling the temperature in the system to 60 ° C., 40 parts of polyester resin fine particle 8 dispersion was added, and the temperature was raised to 80 ° C. and held for 0.5 hours. After the addition, it was held for another 0.5 hours. Thereafter, the contents are cooled to room temperature, and the toner particles having a volume average particle diameter of 4.6 μm are dried by repeating the washing process such as filtration of the solution and resuspension treatment of the obtained solid content in distilled water several times. 5 was obtained. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, mixed with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds), and then sieved with a sieve having an opening of 90 μm to obtain toner 5.

Example 6
In a reactor equipped with a stirrer, a condenser, and a temperature sensor, 160 parts of polymer primary particle dispersion (2), 80 parts of polyester resin fine particle 5 dispersion, 13.6 parts of wax dispersion (2), colorant fine particles 24 parts of dispersion (2), 5 parts of an anionic surfactant (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 240 parts of distilled water were added, and 2M sodium hydroxide aqueous solution was added and mixed with stirring. The pH of the liquid was adjusted to 10.0. Next, after adding 40 parts of 50 mass% magnesium chloride aqueous solution to this, it heated up at 60 degreeC, stirring for 0.5 hour, and then heated up to 80 degreeC and hold | maintained for further 0.5 hour . At this time, the average particle size of the toner in the mixed dispersion was 4.9 μm. Next, 120 g of a 20 mass% sodium chloride aqueous solution was added, and the mixture was further held for 0.5 hour. Thereafter, the contents are cooled to room temperature, and the toner particles having a volume average particle diameter of 4.9 μm are dried by repeating several times of washing treatment such as filtration of the solution and resuspension treatment of the obtained solid in distilled water. 6 was obtained. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, mixed with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds), and then sieved with a sieve having an opening of 90 μm to obtain toner 6.

Example 7
In a reactor equipped with a stirrer, a cooling tube and a temperature sensor, 160 parts of polymer primary particle dispersion (2), 80 parts of polyester resin fine particle 6 dispersion, 13.6 parts of wax dispersion (2), fine colorant particles 24 parts of dispersion (2), 5 parts of an anionic surfactant (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 240 parts of distilled water were added, and 2M sodium hydroxide aqueous solution was added and mixed with stirring. The pH of the liquid was adjusted to 10.0. The temperature was raised to 50 ° C. with stirring, and then 40 parts of a 50% by weight magnesium chloride aqueous solution was added thereto. Then, the temperature was raised to 60 ° C. with stirring and held for 0.5 hour, and then raised to 70 ° C. Warmed and held for another 0.5 hours. The average particle size of the toner in the mixed dispersion at this time was 4.6 μm. Next, after cooling the temperature to 50 ° C., 30 parts of the urethane-modified polyester resin fine particle 10 dispersion liquid was added, heated to 80 ° C. and held for 0.5 hour, and then added with 120 g of a 20 mass% sodium chloride aqueous solution. After that, it was kept for another 0.5 hours. Thereafter, the contents are cooled to room temperature, and the toner particles having a volume average particle diameter of 4.8 μm are dried by repeating the washing process such as filtration of the solution and resuspension treatment of the obtained solid in distilled water several times. 7 was obtained. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, mixed with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds), and then sieved with a sieve having an opening of 90 μm to obtain toner 7.

Example 8
In a reaction flask equipped with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device, 325 parts of ion-exchanged water and an anionic surfactant (Newcol 220L: Japan) A solution prepared by dissolving 10 parts of Emulsifier Co., Ltd. in 500 parts of ion-exchanged water was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 12000 rpm.

  Next, 83 parts of styrene, 17 parts of n-butyl acrylate, 0.1 part of divinylbenzene, 3 parts of 2-mercaptoethyl octanoic acid ester, 5 parts of carbon black, 5 parts of paraffin wax (NHP0190: manufactured by Nippon Seiwa Co., Ltd.) A monomer mixture composed of 2 parts of a Cr dye (TRH: manufactured by Hodogaya Chemical Co., Ltd.) and 6 parts of t-butylperoxy-2-ethylhexanoate was uniformly mixed.

  Next, the monomer mixture was introduced into the aqueous continuous phase, and granulated by stirring at 10000 rpm for 10 minutes with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 80 ° C. in a nitrogen stream. Thereafter, while stirring with a paddle stirring blade, the reaction was carried out at 80 ° C. for 5 hours. After adding 4 parts of anhydrous sodium carbonate into the system, the reaction was continued for another 2 hours. After completion of the reaction, the mixture was cooled to 50 ° C., 10 parts of a polyester resin fine particle 7 dispersion was added, and then 1 part of a 50 mass% magnesium chloride aqueous solution was added thereto, and the temperature was raised to 80 ° C. After maintaining for 5 hours, 120 g of a 20% by mass aqueous sodium chloride solution was added, and the mixture was further maintained for 0.5 hours. The produced suspension polymerization particles were filtered, then washed repeatedly with ion-exchanged water and filtered. Thereafter, toner particles 8 having a volume average particle diameter of 5.1 μm were obtained by drying with warm air of 40 ° C. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, mixed with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds), and then sieved with a sieve having an opening of 90 μm to obtain toner 8.

Comparative Example 1
In a reactor equipped with a stirrer, a condenser, and a temperature sensor, 288 parts of polymer primary particle dispersion (1), 13.6 parts of wax dispersion (1), 24 parts of colorant fine particle dispersion (1), and 240 parts of distilled water was added, and a 2M aqueous sodium hydroxide solution was added with stirring to adjust the pH of the mixed dispersion to 10.0. Next, 40 parts of a 50 mass% magnesium chloride aqueous solution was added thereto, and then the temperature was raised to 70 ° C. with stirring and held for 1.5 hours. The average particle size of the mixed dispersion at this time was 4.8 μm. Next, 120 parts of a 20 mass% sodium chloride aqueous solution was added, and then the temperature was raised to 75 ° C. and held for 1 hour. Thereafter, the contents are cooled to room temperature, and the toner particles having a volume average particle diameter of 4.8 μm are dried by repeating several times of washing treatment such as filtration of the solution and resuspension treatment of the obtained solid in distilled water. Nine obtained. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A; manufactured by Titanium Industry), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, mixed with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds), and then sieved with a sieve having an opening of 90 μm to obtain toner 9.

Comparative Example 2
In a reactor equipped with a stirrer, a condenser, and a temperature sensor, 240 parts of polymer primary particle dispersion (1), 13.6 parts of wax dispersion (1), 24 parts of colorant fine particle dispersion (1), anion Active surfactant (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 240 parts of distilled water were added, and 2M sodium hydroxide aqueous solution was added with stirring to adjust the pH of the mixed dispersion to 10.0. did. Next, after adding 40 parts of 50 mass% magnesium chloride aqueous solution to this, it heated up at 70 degreeC, stirring for 0.5 hour, then heated up to 75 degreeC and hold | maintained for further 0.5 hour . The average particle size of the toner in the mixed dispersion at this time was 4.5 μm. Next, after cooling the temperature in the system to 70 ° C., 30 parts of the polymer primary particle dispersion (2) was added, the temperature was raised to 80 ° C. and held for 0.5 hour, and then 20 mass% sodium chloride. After adding 120 g of the aqueous solution, the solution was kept for another 0.5 hours. Thereafter, the contents are cooled to room temperature, and the toner particles having a volume average particle diameter of 4.8 μm are dried by repeating the washing process such as filtration of the solution and resuspension treatment of the obtained solid in distilled water several times. 10 was obtained. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A; manufactured by Titanium Industry), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, mixed with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds), and then sieved with a sieve having an opening of 90 μm to obtain toner 10.

Comparative Example 3
Cyan colorant C.I. per 100 parts of polyester resin I. Pigment Blue 15-3 is 7 parts, and 1 part of the above polyester-based resin, pigment masterbatch and polyester wax (WE-5: manufactured by Nippon Oil & Fats Co., Ltd.) is 180 with a Henschel mixer at a peripheral speed of 40 m / sec. Mix well over a second.

  And this mixture was melt-kneaded with a biaxial extrusion kneader (Ikegai Iron Works Co., Ltd .: PCM-30), this kneaded product was rolled to a thickness of 2 mm with a press roller, cooled with a cooling belt, and then feathered. Coarsely pulverized by a mill. After that, this was pulverized by a mechanical pulverizer (manufactured by Kawasaki Heavy Industries, Ltd .: KTM), and further pulverized by a jet pulverizer (manufactured by Nippon Pneumatic Kogyo Co., Ltd .: IDS), and then a rotor type classifier (manufactured by Hosokawa Micron: tee The toner particles 11 having a volume average particle diameter of 5.2 μm were obtained by classification using a plex type classifier 100ATP. To 100 parts of the toner particles, 0.5 part of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part of titanium oxide (STT30A; manufactured by Titanium Industry), strontium titanate (average particle size 0) .2 μm) 1.0 part was added, mixed with a Henschel mixer (peripheral speed 40 m / sec, 60 seconds), and then sieved with a sieve having an opening of 90 μm to obtain toner 11.

(Manufacture of binder type carrier)
In order to use the toners obtained in the above Examples and Comparative Examples as a two-component developer for evaluation, a binder type carrier was manufactured.

  100 parts of a polyester resin (Kao Corporation: NE-1110), 700 parts of magnetic particles (magnetite; EPT-1000: manufactured by Toda Kogyo Co., Ltd.) and 2 parts of carbon black (Mogal L; manufactured by Cabot Corporation) are sufficiently mixed with a Henschel mixer. Then, the cylinder part was set at 180 ° C. and the cylinder head part at 170 ° C. by a twin screw extrusion kneader, and melt kneaded. The kneaded product was cooled, then coarsely pulverized with a hammer mill, finely pulverized with a jet pulverizer, and classified to obtain a binder-type carrier having a volume average particle size of 40 μm.

[Physical properties and characteristics evaluation of toner]
(Heat resistant storage)
After 10 g of the toner was left at a high temperature of 50 ° C. for 24 hours, the toner was visually observed and evaluated.

○: No aggregate was found Δ: Less than 10 aggregates were present ×: 10 or more aggregates were present

  In the following evaluation, a developer obtained by mixing toner and carrier so that the toner concentration becomes 6% by mass was used.

(Fixability)
Fixability was comprehensively evaluated from the evaluation results of peel resistance and offset resistance.

◎: The result of all items was “◎” ○: “○” was included in addition to “◎” △: “△” was included in addition to “◎” or “○” X: At least one “x” was included.

Peeling resistance While changing the fixing temperature in the range of 80-130 ° C in increments of 2 ° C, using a digital copying machine equipped with an oilless fixing device (DIALTA Di350; manufactured by Konica Minolta Business Technologies, Inc.), 1.5 cm A solid image of × 1.5 cm (attachment amount 2.0 mg / cm ² ) was taken, each image was folded in half from the middle, and the peel resistance of the image was visually evaluated. The temperature between the fixing temperature when the image was slightly peeled off and the lower fixing temperature at which the image was not peeled at all was defined as the fixing lower limit temperature.

A: The fixing lower limit temperature was less than 105 ° C. ○: The fixing lower limit temperature was 105 ° C. or more and less than 110 ° C. Δ: The fixing lower limit temperature was 110 ° C. or more and less than 115 ° C. ×: The fixing lower limit temperature was It was 115 ° C or higher.

Offset resistance Halftone image while changing the fixing temperature of digital copier (DIALTA Di350; manufactured by Konica Minolta Business Technologies, Inc.) to 1/2 and changing the fixing temperature in the range of 90 to 150 ° C in 5 ° C increments. The offset state was visually observed to evaluate the temperature at which the high temperature offset occurs (offset temperature).

A: Offset temperature was 140 ° C. or higher. ○: Offset temperature was 130 ° C. or higher and lower than 140 ° C. Δ: Offset temperature was 120 ° C. or higher and lower than 130 ° C. ×: Offset temperature was lower than 120 ° C. there were.

(Stress resistance)
The stress resistance was evaluated based on the presence or absence of a phenomenon in which crushed or worn toner particles adhere to the surface of the organic photoconductor in a thin layer due to continuous use of the toner.

○: Adhesion of toner particles was not visually recognized. ×: Adhesion of toner particles was visually recognized.

(Volume average particle size)
The volume average particle size (Dv50) was measured using a Coulter Multisizer II (manufactured by Coulter Counter) using an aperture tube of 50 μm.

(Particle size distribution)
The particle size distribution takes a ratio between the volume average particle size (Dv50) and the number average particle size (Dp50). The smaller this ratio (Dv50 / Dp50), the sharper the particle size distribution.

○: 1.30 or less △: 1.31-1.50
X: 1.51 or more (average circularity)
The circularity is expressed as “perimeter of equivalent circle / perimeter of particle projection image”. The average circularity was measured in a water dispersion system using a flow type particle image analyzer (FPIA-2000: manufactured by Sysmex Corporation).

(Charge amount)
A developer for evaluation was prepared by mixing the toner (toner subjected to post-treatment) and the carrier at a mass ratio of 5:95. 30 g of this developer was placed in a 50 ml polyethylene bottle and the developer was stirred by rotating at 1200 rpm for 90 minutes. Then, the charge amount of the toner was determined by the blow-off method. The charge amount is preferably in the range of −40 to −55 in units of μC / mg. If the charge amount is low, toner scattering, fogging, and deterioration with time will be caused. The impact will increase.

(image quality)
The image quality was evaluated in the following manner based on the state of the image quality after initial printing and after A4100 continuous printing by placing it in a developing unit of a commercially available digital copying machine (DIALTA Di350; manufactured by Konica Minolta Technologies, Inc.) in the same manner as described above. .

◎: Very clean ○: Good △: Partially gritty or noise was observed x: Overall gritty or noise was generated.

(Moisture resistance)
The charge amount was measured in an environment of 30 ° C. and 80%, and the difference from the measured value from the normal temperature and normal humidity environment was evaluated as follows.

A: Difference is within 5 μC / mg. O: Difference is within 10 μC / mg. Δ: Difference is within 15 μC / mg. X: Difference is 15 μC / mg or more.

  From Table 4, it can be seen that the toners 1 to 8 of the present invention are superior in chargeability, image quality, heat-resistant storage property, and low-temperature fixability to the comparative toners 9 to 11.

Claims (10)

A method for producing resin fine particles, which is obtained by mixing a resin solution synthesized by solution polymerization in an organic solvent with water containing a surfactant and subjecting it to phase inversion emulsification. A resin fine particle produced by the method for producing a resin fine particle according to claim 1. It is obtained by adding a solution containing a release agent to a resin solution synthesized by solution polymerization in an organic solvent and mixing the resulting solution with water containing a surfactant to phase-emulsify. A method for producing resin fine particles. A resin fine particle produced by the method for producing a resin fine particle according to claim 3. A solution obtained after adding a solution containing a colorant to a resin solution synthesized by solution polymerization in an organic solvent is obtained by mixing with water containing a surfactant and phase-emulsifying the solution. For producing resin fine particles. A resin fine particle produced by the method for producing a resin fine particle according to claim 5. An electrostatic charge image development obtained by adding a flocculant to an aqueous dispersion containing at least resin fine particles and colorant particles to agglomerate the resin fine particles and the colorant particles to form agglomerated particles, followed by heat fusion. 7. A method for producing a toner for developing an electrostatic image, wherein the resin fine particles according to claim 2, 4 or 6 are used as the resin fine particles for forming the aggregated particles. An electrostatic image developing toner produced by the method for producing an electrostatic image developing toner according to claim 7. After adding an aggregating agent to an aqueous dispersion containing at least resin fine particles and colorant particles to aggregate the resin fine particles and the colorant particles to form mother particles, an outer layer is formed, and then heat fusion is performed. In the method for producing a toner for developing an electrostatic image obtained, the resin fine particles according to claim 2, 4 or 6 are used as resin fine particles for forming at least one of the base particles and the outer layer. A method for producing a toner for developing an electrostatic image. An electrostatic image developing toner produced by the method for producing an electrostatic image developing toner according to claim 9.