JP4798202B2 - Method for producing toner for developing electrostatic latent image - Google Patents

Description

The present invention, electrophotography, a method of manufacturing a static latent image developing toner that is used to develop an electrostatic latent image in an electrostatic recording and electrostatic printing and the like.

  Conventionally, a toner for developing an electrostatic latent image (hereinafter also simply referred to as a toner) used for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, or the like is obtained by heating a pigment such as carbon black. It has been produced by a so-called pulverization method in which a uniform dispersion is obtained by mixing, melting and kneading in a plastic resin, and then pulverizing into a powder having a required particle size as a toner by an appropriate pulverization apparatus.

  However, in recent years, it is possible to obtain resin particles having a small particle size and a relatively uniform particle size in place of the pulverization method from the viewpoint of reduction in production cost and high image quality, suspension polymerization method, emulsion polymerization aggregation method, A wet manufacturing method (chemical toner) in which toner particles are granulated in a liquid typified by an emulsification dispersion method has attracted attention (see, for example, Patent Document 1).

  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 is a method of emulsifying a polymerization composition containing a polymerizable monomer, a polymerization initiator and the like in a dispersion medium, and polymerizing the fine resin particles granulated by coloring, an offset preventing agent. And the like in an emulsified state to perform desired granulation. In the emulsification dispersion method, a binder resin and a colorant are dissolved or dispersed in an appropriate organic solvent to form a colored resin solution, which is added to an aqueous dispersion and vigorously stirred to form droplets of the resin solution. Then, granulation is performed by heating to remove the organic solvent from the droplets (see, for example, Patent Document 2).

  According to the wet manufacturing method, it is easy to form toner particles having a small particle size 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 itself is synthesized simultaneously with the synthesis of the resin itself (see, for example, Patent Document 3).

  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.
JP-A-12-98653 JP 2001-255698 A JP 2003-330226 A

  An object of the present invention is to provide a toner that can obtain a stable charge amount, can reproduce a high-definition image, can be fixed at a low temperature while having heat-resistant storage property, and has excellent mechanical strength.

  The present invention can be achieved by adopting the following configuration.

Invention according to claim 1,
“At least for developing electrostatic latent images produced through the steps of agglomerating resin particles on the surface of mother particles obtained by suspension polymerization and containing a colorant to form an outer layer and then fusing them. In the toner manufacturing method,
Resin particles children for forming the outer layer,
A polyester resin synthesized from an aromatic dicarboxylic acid or a derivative thereof and an aliphatic dialcohol state, and are those containing acrylic resin,
Mixing the polyester resin and the acrylic resin in an organic solvent, adding a resin solution formed by dissolving in an aqueous medium, wherein after dispersing, the Der Rukoto those formed by removing the organic solvent A method for producing a toner for developing an electrostatic latent image. ].

The invention described in claim 2
2. The method for producing a toner for developing an electrostatic latent image according to claim 1 , wherein the aromatic dicarboxylic acid or a derivative thereof is terephthalic acid or a derivative thereof. ].
The invention according to claim 3
3. The method for producing a toner for developing an electrostatic latent image according to claim 1, wherein the acrylic resin is formed by synthesizing at least styrene, acrylic ester, and methacrylic acid. . ].

The invention according to claim 4
The method for producing a toner for developing an electrostatic latent image according to any one of claims 1 to 3 , wherein the toner for developing an electrostatic latent image contains an offset preventing agent. ].

The invention described in claim 5
"A volume average particle size of the electrostatic latent image developing toner is 3 to 7 [mu] m, according to claim 1 to 4, the volume average particle diameter / number average particle diameter is equal to or is 1.05 to 1.20 The method for producing a toner for developing an electrostatic latent image according to any one of the above. ].

  According to the present invention, an electrostatic latent image developing toner having excellent chargeability, capable of reproducing a high-definition image, capable of low-temperature fixing, having high mechanical strength, excellent durability, and excellent heat-resistant storage stability, and The manufacturing method can be provided.

  As a result of various investigations to achieve the above object, the present inventors have found that the performance can be greatly improved by mixing a specific polyester resin and an acrylic resin, and have reached the present invention.

  That is, the toner of the present invention contains at least a polyester resin synthesized from an aromatic dicarboxylic acid or a derivative thereof and an aliphatic dialcohol and an acrylic resin.

  Specifically, the toner of the first invention comprises at least a colorant and resin particles added to the surface of the mother particles obtained by suspension polymerization to agglomerate the mother particles to form an outer layer, In a wet process toner obtained by subsequent heat fusion, at least one of the mother particles and the resin particles for forming the outer layer is at least an aromatic dicarboxylic acid or a derivative thereof and an aliphatic dicarboxylic acid. It contains a polyester resin synthesized from alcohol and an acrylic resin.

  The toner of the second invention is a polyester resin synthesized from an aromatic dicarboxylic acid or a derivative thereof and an aliphatic dialcohol in a wet process toner containing at least an acrylic monomer and a colorant and obtained by suspension polymerization. It is characterized by containing.

  In the present invention, the toner produced by the wet method is agglomerated by adding a salting-out agent as an aggregating agent having a critical aggregation concentration or more in a dispersion in which at least resin particles and colorant particles are dispersed. Step 2, a resin particle dispersion in which resin particles are dispersed is added and mixed into the aggregated aggregated particle dispersion, and the second step in which the adhered particles are formed by adhering the resin particles to the aggregated particles. When manufactured through the third step, particularly good characteristics are exhibited.

  The polyester resin used in the present invention has a high charge amount due to its molecular structure. In addition, the polyester resin used in the present invention can be designed with a thermophysical property that increases the glass transition temperature (Tg) and lowers the softening temperature (Tm), and can be made into a sharp melt. Therefore, it is possible to achieve both heat-resistant storage properties and low-temperature fixability.

  Further, since the polyester resin used in the present invention is superior in mechanical strength compared to other resins such as acrylic resin due to its molecular structure, a toner having high mechanical strength can be produced.

  Further, the toner of the present invention can be produced by a wet polymerization method so that the particle size is small, the particle size distribution is sharp, and the chargeability is uniform. When a toner image is formed using this toner, high image quality is achieved. Images can be obtained.

  First, the physical property measuring method and preferred range of the toner and resin particles according to the present invention will be described.

<Average particle size and particle size distribution of toner particles>
The volume and number average particle diameter (μm) of the toner particles are determined by measuring with “Coulter Multisizer II” (manufactured by Coulter Counter). From the measurement results, the volume average particle diameter (Dv), the number average particle diameter (Dp), and the ratio (Dv / Dp) are calculated.

  The particle size distribution of the toner particles is evaluated by the ratio (Dv / Dp) of the volume average particle size (Dv) and the number average particle size (Dp). The smaller this value, the narrower the particle size distribution. The volume average particle size of the toner particles is preferably 3 to 7 μm, and the particle size distribution (Dv / Dp) of the toner particles is preferably 1.05 to 1.20.

<Average circularity of toner particles>
The average circularity of the toner particles is expressed by the circumference of the equivalent circle / the circumference of the particle projection image. The perimeter of the equivalent circle and the perimeter of the particle projection image are obtained by measuring toner particles in an aqueous dispersion using a flow type particle image analyzer “FPIA-2000” (manufactured by Sysmex Corporation). The average circularity of the toner particles is preferably 0.90 to 1.00.

<Volume average particle diameter of resin particles>
The volume average particle diameter of the resin particles is obtained by measuring with a dynamic light scattering particle size distribution measuring device “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.). A preferred range will be described later.

<Glass-transition temperature>
The glass transition temperature (Tg) is a physical property value measured according to JIS K7121, and means an intermediate glass transition temperature described in the standard.

  Specifically, the glass transition temperature (Tg) is determined by measuring using a differential scanning calorimeter “DSC-200” (manufactured by Seiko Denshi). A sample 10 mg to be measured was precisely weighed, put in an aluminum pan, and used as a reference in which alumina was put in an aluminum pan. After raising the temperature from room temperature to 200 ° C. at a heating rate of 30 ° C./min, This is cooled and measured at a rate of temperature increase of 10 ° C./min between 20 ° C. and 120 ° C., and the shoulder value of the main endothermic peak in the range of 30 ° C. to 90 ° C. is defined as the glass transition temperature during this temperature increase process.

<Softening temperature>
The softening temperature (Tm) is determined by measuring with a flow tester “CFT-500” (manufactured by Shimadzu Corporation). Specifically, 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, a heating rate of 3.0 ° C./min, a preheating time of 180 seconds, a load of 30 kg, and measurement. Measurement is performed under conditions of a temperature range of 60 to 180 ° C., and the temperature at which the above sample flows out by half is defined as the softening temperature. A preferable softening temperature will be described later.

<Weight average molecular weight>
The weight average molecular weight is determined by measuring with gel permeation chromatography “807-IT type” (manufactured by JASCO Corporation). Specifically, while maintaining the column temperature at 40 ° C., tetrahydrofuran as a carrier solvent was caused to flow at 1 kg / cm ² , 30 mg of a sample to be measured was dissolved in 20 ml of tetrahydrofuran, and 0.5 mg of this solution was mixed with the above-mentioned carrier solvent in the apparatus. And calculated by polystyrene conversion. A preferred weight average molecular weight will be described later.

<Acid value>
The acid value indicates the number of milligrams of potassium hydroxide necessary to neutralize the acid present in 1 g of the resin, and indicates the amount of acidic polar groups present in so-called molecular terminals. The acid value can be measured by a method defined in JIS K0070. In the present invention, a mixed solvent of toluene / methanol (2: 1) is used as a solvent for measurement.

  The acid value is preferably from 0.1 to 20, and more preferably from 1 to 10. The smaller the acid value, the better the stability to the environment, but it is preferable to have a certain acid value because the dispersion stability of the particles in water is maintained.

<Toner charge amount>
The toner charge amount can be measured by a blow-off method.

Specifically, 1.0 g of a sample (developer) in which a carrier and toner are mixed is taken, put into a cell with a stainless steel mesh, and blown for 6 sec at a nitrogen gas pressure of 2 N / cm ² . The charge amount of the toner is calculated by measuring the charge amount (Q) of the remaining carrier.

Charge amount of toner (μC / mg) = Q / (M−M ₀ )
M: Sample mass before blowing
M ₀ : Sample mass after blow The toner charge amount is preferably −40 to −55 μC / g, more preferably −42 to −55 μC / g. By setting the toner charge amount within this range, it is preferable that a high density image can be stably obtained without occurrence of fogging or deterioration with time.

  Next, resin particles containing a polyester resin and an acrylic resin used in the present invention will be described.

  The polyester resin used in the present invention is synthesized from an aromatic dicarboxylic acid or a derivative thereof and an aliphatic dialcohol.

  Specific examples of aromatic dicarboxylic acids or derivatives thereof include phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, terephthalic acid dichloride, terephthalic acid dibromide, diethyl terephthalate, dimethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate , Isophthalic acid dichloride, isophthalic acid dibromide, diethyl isophthalate, dimethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, naphthalene dicarboxylic acid, naphthalic anhydride, naphthalene dicarboxylic acid dichloride, naphthalene dicarboxylic acid dibromide, dimethyl naphthalenedicarboxylic acid , Diethyl naphthalenedicarboxylate, dipropyl naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, diphenyldicarboxylic acid, diphenic acid Things, diphenyl dicarboxylic acid dichloride, diphenyl dicarboxylic acid dibromide, diphenyl dicarboxylic acid dimethyl, diphenyl dicarboxylic acid diethyl, diphenyl dicarboxylic acid dipropyl, there may be mentioned the diphenyl dicarboxylic acid dibutyl, but the present invention is not particularly limited thereto.

  Among these, terephthalic acid having a small content of terminal carboxylic acid group or sulfonic acid group or a derivative thereof is preferable because a high toner can be obtained and a good toner can be obtained.

  Specific examples of the aliphatic dialcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, methylpentanediol, nonanediol, ethylbutylpropanediol, and dimethylpropanediol. , Cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, neopentylglycol, butylethylhexanediol, bis (4-hydroxycyclohexyl) propane, dimethylolheptane, hydroxypivalic acid neopentylglycol ester, etc. It is not limited.

  In the present invention, in addition to the above specific examples, a polyvalent carboxylic acid or a polyhydric alcohol may be added. Examples of the polyvalent carboxylic acid 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 their acids. Anhydrides, halides, lower alkyl esters and the like can be mentioned. 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.

  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. In this case, it is preferable to use a catalyst excluding a tin compound from the viewpoint of toxicity and the like.

  Examples of catalysts preferably used include titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, titanium tetrabutoxide, zirconium tetrabutoxide, hafnium tetrabutoxide, titanium tetraisopropoxide, zirconium tetrapropoxide, zirconium chloride oxide, chloride Hafnium oxide, trifluoromethanesulfonic acid, sodium trifluoromethanesulfonate, sulfuric acid and the like.

Maximum value of the weight average molecular weight of the polyester resin used in the present invention, in terms of styrene value obtained by gel permeation chromatography (GPC measurement), the range of 2 ^× 10 2 ~3 × 10 ⁴ are preferable, 3 × 10 ³ ~ 3 × 10 ⁴ is more preferable.

  By setting the maximum value of the weight average molecular weight within this range, heat resistant storage stability and powder flow characteristics are improved, melt viscosity is lowered, and low temperature fixability is improved.

  When the glass transition temperature (Tg) of the polyester resin used in the present invention is too low, the heat-resistant storage stability is lowered. Therefore, the glass transition temperature is preferably 50 ° C. or higher.

  The softening temperature (Tm) of the polyester resin used in the present invention is preferably 120 ° C. or lower from the viewpoint of low-temperature fixability. Moreover, 80 degreeC or more is preferable from a heat resistant storage viewpoint.

  The present invention may use resin particles in which the resin component is dissolved in an organic solvent and then mixed with water and phase-inverted and emulsified, or the polyester resin is dissolved in an acrylic monomer and suspension polymerization or mini-resin is used. Emulsion polymerization may be performed. Alternatively, polyester resin particles may be produced, and an acrylic resin may be formed on the particle surface by seed polymerization.

  In the present invention, when preparing resin particles by phase inversion emulsification, the corresponding polyester resin and acrylic resin are dissolved in an organic solvent, and the solution is added to water, or water is added to the dissolved solution. Can be obtained using a well-known dispersion method mechanically or surface-chemically. That is, a method of mechanically emulsifying an organic solvent solution of a polyester resin and an acrylic resin 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, those which dissolve polyester resin and acrylic resin well are good, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, tetrahydrofuran, dioxane, dioxolane, Diethyl ether, dichloromethane, dichloromethane and the like can be used, but water-insoluble solvents such as toluene and dichloromethane are particularly preferably used since the particle size distribution becomes sharp. In order to remove the solvent, a solvent having a low boiling point and easy to remove by azeotropy with water or the like is preferable.

  In the present invention, in the case of preparing resin particles by dissolving a polyester resin in an acrylic monomer and performing suspension polymerization or miniemulsion polymerization, the corresponding polyester resin is dissolved in the acrylic monomer and the solution is subjected to interfacial chemistry in water. It can be produced by polymerizing after suspending or emulsifying using a known dispersion method.

  In the present invention, when preparing polyester resin particles and forming resin particles by forming an acrylic resin on the particle surface by seed polymerization, the corresponding polyester resin is prepared by a phase inversion emulsification method or the like. It can be produced by adding an acrylic monomer to the aqueous dispersion solution and polymerizing the acrylic monomer on the surface using the polyester resin particles as seeds.

  The volume average particle size of the resin particles used in the present invention is preferably 0.01 to 10 μm, and more preferably 0.05 to 7 μm. In particular, when producing resin particles for forming an emulsion aggregation method or an outer layer of a base material, 0.1 to 0.5 μm is preferable.

  In the case of suspension polymerization, the volume average particle size of the resin particles is preferably 3 to 6 μm. The particle size can be controlled by conditions such as the organic solvent used during suspension and emulsification, the solid content concentration, the number of rotations, the temperature, the type of surfactant and the amount added.

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

  In the case of the suspension polymerization method, a polymerization initiator, a chain transfer agent, a colorant, an additive such as a charge control agent, magnetic powder, and an anti-offset agent that are added as necessary, and a polyester resin in a polymerizable amount Dissolved and dispersed in the body, suspended in an aqueous 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 aggregation method, a mixed monomer particle of an emulsion polymer particle obtained by emulsifying and dispersing a polymerizable monomer, a polymerization initiator, and a chain transfer agent, and a polyester resin and an acrylic resin, and a colorant, a charge Additives such as control agents, magnetic powder, and anti-offset agents may be emulsified and dispersed, and then agglomerated and fused together. After obtaining mixed resin particles of polyester resin and acrylic resin, agglomerate with colorant and magnetic powder. , You may merge.

  Alternatively, the polyester resin may be dissolved in a polymerizable monomer and emulsified and dispersed to obtain resin particles, and then additives such as a colorant, a charge control agent, magnetic powder, and an anti-offset agent may be aggregated and fused. Then, an additive such as an anti-offset agent or a charge control material may be added and polymerized to obtain resin particles, and then agglomerated together with the colorant to fuse them.

  Alternatively, the above resin particles may be mixed with emulsion-polymerized acrylic resin particles and agglomerated and fused together with additives such as a colorant, a charge control agent, magnetic powder, and an anti-offset agent.

  Further, as an acrylic polymerizable monomer used for a toner prepared by the suspension polymerization method and the emulsion aggregation method according to the present invention, used for dissolving a polyester resin or seed-polymerizing the surface of polyester resin particles. For example, styrene monomer such as styrene, methyl styrene, methoxy styrene, ethyl styrene, propyl styrene, butyl styrene, phenyl styrene, chloro styrene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid Pentyl, dodecyl acrylate, stearyl acrylate, ethyl hexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, dodecyl methacrylate, methacrylic acid Teariru, ethylhexyl methacrylate, acrylic acid ester or methacrylic acid ester monomer of lauryl methacrylate. Of these, styrene and butyl (meth) acrylate are particularly preferably used.

  In the synthesis of the acrylic resin, a third vinyl compound can be copolymerized. Examples of the third vinyl compound include acid monomers such as acrylic acid, methacrylic acid, maleic anhydride, vinyl acetate, acrylamide, methacrylamide, acrylonitrile, ethylene, propylene, butylene, vinyl chloride, N-vinylpyrrolidone, butadiene, and the like. .

  The copolymerization ratio of these monomers is selected so that the glass transition temperature of the resin is 80 ° C. or lower, preferably 40 to 80 ° C., more preferably 40 to 70 ° C.

  The copolymerization ratio of styrene and alkyl (meth) acrylate is usually selected from a range of mass ratios of 20/80 to 90/10. For example, in the case of styrene and butyl acrylate, the mass ratio is preferably 40/60 to 90/10, and more preferably 60/40 to 80/20. The copolymerization ratio with respect to the whole of the third vinyl compound is usually 20% by mass or less, preferably 10% by mass or less.

  The acrylic resin may further contain a polyfunctional vinyl compound as a copolymerization component. Examples of the polyfunctional vinyl compound include diacrylates such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol, dimethacrylates such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol, divinylbenzene, pentaerythritol, and triacrylate. Examples include diallylates of tertiary alcohols such as methylolpropane, triacrylates, pentaerythritol, dimethacrylates of trihydric alcohols such as trimethylolpropane, and trimethacrylates. The copolymerization ratio of the polyfunctional vinyl compound is usually 0.001 to 5% by mass, preferably 0.003 to 2% by mass, and more preferably 0.01 to 1% by mass. By setting the copolymerization ratio of the polyfunctional vinyl compound in the above range, the low-temperature fixability is good, and good transparency can be secured when used for OHP.

  Although a gel component insoluble in tetrahydrofuran is produced by copolymerization of the polyfunctional vinyl compound, the proportion of the gel component in the whole polymer is usually 40% by mass or less, preferably 20% by mass or less.

  The maximum peak molecular weight of the acrylic resin used in the present invention is usually 7,000 to 200,000, preferably 2 to 150,000, more preferably 3 to 100,000 as a polystyrene conversion value by gel permeation chromatography (GPC) measurement. It is. 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.

  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, tert-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. Although the addition amount of a chain transfer agent changes with desired molecular weights or molecular weight distribution, specifically, it is preferable to add in 0.1-5 mass% with respect to the mass of a polymerizable monomer.

  As the colorant, various organic or inorganic pigments and dyes as shown below can be used.

  Examples of black pigments 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 etc.

  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, various substances can be used as substances that can give positive or negative charges by frictional charging. Examples of charge control agents include quaternary ammoniums such as nigrosine-based dyes such as nigrosine base ES (manufactured by Orient Chemical Industries), P-51 (manufactured by Orient Chemical Industries), and copy charge PX VP435 (manufactured by Clariant). Examples thereof include salts, alkoxylated amines, alkylamides, molybdate chelate pigments, and imidazole compounds such as PLZ1001 (manufactured by Shikoku Kasei Kogyo Co., Ltd.).

  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 pigments, Bontron E-89 (Orient Chemical Co., Ltd.) and other 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 size of the form supplied as a commercial product exceeds the upper limit of the above range, it is desirable to adjust to an appropriate particle size by a known method such as pulverization with a jet mill or the like.

  As the magnetic powder, magnetite, γ-hematite, various ferrites, or the like can be used.

  As the offset preventing agent, any of known waxes can be used. Specifically, olefin wax such as low molecular weight polyethylene, low molecular weight polypropylene and copolymer polyethylene, paraffin wax; ester wax having a long chain aliphatic group such as behenate ester, montanate ester and stearate ester; water Plant waxes such as added castor oil and carnauba wax; ketones having long chain alkyl groups such as distearyl ketone; silicon having alkyl groups; higher fatty acids such as stearic acid; long chain aliphatic alcohols, pentaerythritol, trimethylolpropane, etc. (Partial) esters of polyhydric alcohols and long chain fatty acids; higher fatty acid amides such as oleic acid amide, stearic acid amide, palmitic acid amide, and the like.

  These offset inhibitors are generally 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 resin.

  Preferred embodiments of the toner production method according to the present invention include suspension polymerization, emulsion aggregation, and emulsion dispersion.

  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, 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. A known surfactant can be used as the dispersion stabilizer, and a dispersion stabilizer 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-sulfonate sodium, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfonate sodium, 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, stear) Potassium phosphate, calcium oleate, etc.) 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.

  In the suspension polymerization method, it is necessary to suppress the residual monomer in the polymer 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 the monomer residue, the first half of the reaction is performed at a low temperature (40 to 70 ° C.), and the second half of the reaction is performed at a high temperature (50 to 80 ° C.). It is desirable to use a prepolymer.

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

  Specific examples of the polymerization initiator used in suspension polymerization, emulsion polymerization, and miniemulsion polymerization include hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, peroxide. Benzoyl oxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl -1-hydroperoxide, pertriphenylacetic acid-tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, Excess n- ( -Toluyl) peroxides such as tert-butyl palmitate; 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo (methylethyl) Diacetate, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis- (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyl Amine, 2,2′-azobisisobutyronitrile, methyl 2,2′-azobis-2-methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2 -Methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) 2-methylmalonodinitrile, 4,4′-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalono Dinitrile, 2,2′-azobis-2-methylvaleronitrile, dimethyl 4,4′-azobis-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′-azo Biscyclohexanenitrile, 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, 4-nitrophenylazo Ethyl benzyl cyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis- Azo compounds such as 4-cyanopentanoate) and poly (tetraethylene glycol-2,2′-azobisisobutyrate); 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxy Carbonyl-1,4-diphenyl-2-tetrazene and the like. Among these, a water-soluble polymerization initiator is suitably used for the emulsion polymerization method.

  As the binder resin used in the emulsion aggregation method, a resin used in a general pulverized toner can be used. Specifically, styrene-acrylic resin, epoxy resin, polyester resin, etc. polymerized using styrene-acrylic monomer used in suspension polymerization or emulsion polymerization are used, but the balance between cost and performance To styrene-acrylic resin is preferably used.

  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 particle in the aggregation process and adjusting the aggregation force of the dispersed particles. In other words, since the nonionic surfactant has a markedly reduced dispersion stabilizing power at the cloud point or higher, an appropriate amount is allowed to coexist with the ionic surfactant when preparing the 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.

  In the emulsion aggregation method, the resin particle dispersion prepared by the emulsion polymerization method, the mixed resin particles of polyester resin and acrylic resin, and at least a separately prepared colorant dispersion are associated to form an associated particle dispersion. A liquid preparation step (hereinafter also referred to as an associating step) and a step of aggregating the associated particles and heating and fusing them to form toner particles (hereinafter also referred to as an aggregating and fusing step).

  In addition, polyester particles are obtained by heating and fusing together particles obtained by associating resin particle dispersion prepared by emulsion polymerization, mixed resin particles of polyester resin and acrylic resin, and at least separately prepared colorant dispersion. The toner particles may be formed by associating mixed resin particles of a resin and an acrylic resin to obtain associated particles, followed by heat fusion.

  Alternatively, the mixed resin particles of polyester and acrylic resin alone may be associated with at least the colorant dispersion, and the associated particles may be heated and fused.

  In the association step, the resin 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, homoaggregation or the like. At this time, for the purpose of stabilizing the associated particles and controlling the particle size / particle size distribution, one of ionic surfactants and metal salts having a polarity different from that of the associated particles is used. A compound having a charge higher than the value can be added.

  In the agglomeration and fusion process, the aggregation and fusion are performed 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; Metal salts of inorganic acids such as magnesium, 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, salicylic acid Aliphatic acids such as potassium, metal salts of aromatic acids; metal salts of phenols such as sodium phenolate, metal salts of amino acids, aliphatics such as triethanolamine hydrochloride and aniline hydrochloride, inorganics of aromatic amines Acid salts. 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. In the case of monovalent, 3% by mass or less, in the case of divalent 1% by mass or less, in the case of trivalent It is about 0.5% 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 / fusion step, an attachment step of adding other particle dispersions to the associated particle dispersion and mixing them uniformly on the surface of the associated particles to form attached particles can be provided. 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 particles, and agglomerated and melted to form aggregated fused particles.

  The toner particles in the dispersion formed by the suspension polymerization method or the emulsion aggregation method are solid-liquid separated from the dispersion to form a toner cake. The toner cake is washed to remove impurities mixed during the production and dried. Toner particles.

  In the solid-liquid separation / washing step, acidic and possibly basic water is added several times to the toner particles and stirred, and then solid-liquid separation is performed to obtain a toner cake. To this, pure water is added several times to the toner cake and stirred for cleaning. This operation is repeated several times, and the washing is finished when the pH of the filtrate after solid-liquid separation reaches about 7. In the drying step, the toner cake obtained by washing is 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.

  An external additive can be added to the toner particles produced by the above process.

  As the external additive, known inorganic fine particles used as a fluidity adjusting agent in the field of toner can be used. For example, silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, Various carbides such as tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, diamond carbon lactam, various nitrides such as boron nitride, titanium nitride, zirconium nitride, various borides such as zirconium boride, oxidation Various oxides such as titanium (titania), calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, silica, colloidal silica, various titanate compounds such as calcium titanate, magnesium titanate, strontium titanate, disulfide Sulfides such as molybdenum Use various fluorides such as magnesium fluoride and carbon fluoride, various metal soaps such as aluminum stearate, calcium stearate, zinc stearate and magnesium stearate, various nonmagnetic inorganic fine particles such as talc and bentonite, alone or in combination. Can do.

  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. It is preferable that the surface treatment is performed 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.

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

  The toner of the present invention 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.

  The toner of the present invention can also be used as a non-magnetic one-component developer or two-component developer toner.

  When mixed with a carrier and used as a toner for a two-component developer, a conventionally known material such as a metal such as iron, ferrite, or magnetite, or an alloy of such a metal with a metal such as aluminum or lead is used as the carrier. Of these, ferrite is preferred. The volume average particle diameter of the carrier is preferably 15 to 100 μm, and more preferably 25 to 80 μm.

  The volume average particle diameter of the carrier can be measured by a laser diffraction type particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

  The carrier is preferably a carrier in which magnetic particles are coated with a resin, or a so-called binder type carrier in which magnetic particles are dispersed in a resin. Known resins can be used as the coating resin, and examples thereof include olefin resins, styrene resins, styrene-acrylic resins, silicone resins, ester resins, and fluorine-containing polymer resins. Moreover, as a resin for constituting the binder type carrier, a known resin can be used, and examples thereof include a styrene-acrylic resin, a polyester resin, a fluorine resin, and a phenol resin.

The toner of the present invention may be used in an image forming apparatus having each type of fixing device. However, the toner of the type in which the amount of release oil applied to a fixing member such as a roller is reduced, that is, the releasing device is used. It is preferably used for an image forming apparatus having a fixing device in which the application amount of the mold oil is 4 mg / m ² or less, particularly a fixing device of a type that does not apply the release oil.

  FIG. 1 is a cross-sectional view showing an example of an image forming apparatus used in the present invention.

  In FIG. 1, reference numeral 50 denotes a photosensitive drum (photosensitive member) which is an image bearing member, and is a photosensitive member in which an organic photosensitive layer is coated on a drum and a resin layer is coated thereon. It is rotated. Reference numeral 52 denotes a scorotron charger (charging means) for uniformly charging the circumferential surface of the photosensitive drum 50 by corona discharge. Prior to the charging by the charger 52, the peripheral surface of the photosensitive member may be discharged by performing exposure by the pre-charging exposure unit 51 using a light emitting diode or the like in order to eliminate the history of the photosensitive member in the previous image formation.

  After uniform charging of the photoreceptor, image exposure based on the image signal is performed by an image exposure unit 53 as an image exposure unit. The image exposure unit 53 in this figure uses a laser diode (not shown) as an exposure light source. Scanning on the photosensitive drum is performed by the light whose optical path is bent by the reflection mirror 532 through the rotating polygon mirror 531 and the fθ lens, and an electrostatic latent image is formed.

  Here, the reversal development process employed in the image forming method of the present invention is a region where the surface of the photosensitive member is uniformly charged by the charger 52 and image exposure is performed, that is, the exposed portion potential (exposed portion region) of the photosensitive member. ) Is an image forming method in which the image is visualized by a developing step (means). On the other hand, the unexposed portion potential is not developed by the developing bias potential applied to the developing sleeve 541.

The electrostatic latent image is then developed by a developing device 54 as developing means. A developing device 54 containing a developer composed of toner and carrier is provided on the periphery of the photosensitive drum 50, and development is performed by a developing sleeve 541 that contains a magnet and rotates while holding the developer. The inside of the developing device 54 is composed of developer agitating / conveying members 544 and 543, a conveying amount regulating member 542, and the like, and the developer is agitated and conveyed and supplied to the developing sleeve. Controlled by members. The amount of the developer transported varies depending on the linear velocity of the applied organic electrophotographic photoreceptor and the developer specific gravity, but is generally in the range of ^{20 to} 200 mg / cm ² .

  The developer is transported to the development zone with the layer thickness regulated by the transport amount regulating member, and development is performed. At this time, usually, development is performed by applying a DC bias between the photosensitive drum 50 and the developing sleeve 541 and, if necessary, an AC bias voltage. The developer is developed in contact with or non-contact with the photoreceptor. The potential of the photosensitive member is measured by providing a potential sensor 547 above the development position as shown in FIG.

  The recording paper P is fed to the transfer area by the rotation operation of the paper feed roller 57 when the transfer timing is ready after the image formation.

  In the transfer area, a transfer electrode (transfer means: transfer device) 58 on the peripheral surface of the photosensitive drum 50 is operated in synchronization with the transfer timing, and the fed recording paper P is sandwiched and transferred.

  Next, the recording paper P is neutralized by a separation electrode (separator) 59 that is activated almost simultaneously with the transfer electrode, separated by the peripheral surface of the photosensitive drum 50, and conveyed to the fixing device 60. After the toner is welded by heating and pressurizing the pressure roller 602, the toner is discharged to the outside of the apparatus via the paper discharge roller 61. The transfer electrode 58 and the separation electrode 59 are retracted away from the peripheral surface of the photosensitive drum 50 after the recording paper P has passed to prepare for the next toner image formation. In FIG. 1, a transfer band electrode of corotron is used as the transfer electrode 58. The transfer electrode setting conditions vary depending on the process speed (peripheral speed) of the photosensitive member and cannot be specified. For example, the transfer current is set to +100 to +400 μA, and the transfer voltage is set to +500 to +2000 V. can do.

  On the other hand, the photosensitive drum 50 from which the recording paper P has been separated removes and cleans residual toner by the pressure contact of the blade 621 of the cleaning device (cleaning means) 62, and the charge removal by the pre-charge exposure unit 51 and the charging device 52 again. Upon receiving the charge, the next image forming process is started.

  Reference numeral 70 denotes a detachable process cartridge in which a photoconductor, a charger, a transfer device, a separator, and a cleaning device are integrated.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this. In addition, a part represents a mass part in a present Example.

(Synthesis of polyester resin 1: Formula 1)
A glass four-necked flask equipped with a stirrer, a distillation column, a thermometer, and a nitrogen inlet tube was charged with a ratio of neopentyl glycol 8 mol, ethylene glycol 4 mol, and terephthalic acid 8 mol. This was heated to 180 ° C. in a mantle heater under a nitrogen stream, and 0.14% by mass of a polymerization initiator (titanium tetrabutoxide) was added to the total charge of acid and alcohol components, and the mixture was stirred. The reaction was carried out by heating. The progress of the reaction was followed by measuring the acid value, and when the predetermined acid value was reached, the reaction was terminated and the weight average molecular weight was 6,700 (value measured by “807-IT type”), Glass transition temperature (Tg) is 56 ° C. (value measured by “DSC-200”), softening temperature (Tm) is 103 ° C. (value measured by “CFT-500”), and acid value is 3.2 (JIS K0070). The value of “polyester resin A” was obtained.

(Preparation of polyester resin particle dispersion 1)
Next, 20 parts of “Polyester Resin A”, 70 parts of ethyl acetate and 30 parts of methyl ethyl ketone are placed in a beaker and stirred at 10,000 rpm using “TK Homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.) to dissolve evenly. To prepare a polyester resin solution.

  On the other hand, an aqueous medium is prepared by dissolving 1% by mass of a dispersant (sodium polyoxylauryl sulfate) in 450 parts of ion exchange water, and the polyester resin solution is suspended in the aqueous medium using a “TK homomixer”. It was made turbid to form an O / W type emulsion. The emulsion was formed under the conditions of a “TK homomixer” rotating at 12000 rpm and a stirring time of 30 minutes. Thereafter, the number of revolutions of the “TK homomixer” was reduced to 200 rpm and heated with stirring to remove the mixed solvent to obtain “polyester resin particle dispersion A”. The volume average particle diameter of the obtained polyester resin particles was 120 nm (value measured by “ELS-800”).

<Preparation 1 of acrylic resin-containing polyester resin particle dispersion 1>
The “polyester resin particle dispersion 1” was charged into a reactor equipped with a stirrer, a cooling tube, and a temperature sensor, heated to 80 ° C. while stirring under a nitrogen stream, and then 1% by mass of potassium persulfate. 12 parts of an aqueous solution was added. Next, after adding “monomer mixture 1” having the following composition over 1 hour, 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 “dispersion of acrylic resin-containing polyester resin particles A”. In addition, the volume average particle diameter of the obtained acrylic resin-containing polyester resin particles was 130 nm.

[Monomer mixture 1]
Styrene 1.2 parts Butyl acrylate 0.4 parts Methacrylic acid 0.03 parts n-Octyl mercaptan 0.03 parts <Preparation 2 of polyester resin-containing acrylic resin particle dispersion 2>
A reactor equipped with a stirrer, a condenser, and a temperature sensor was charged with 450 parts of distilled water and 1.12 parts of sodium dodecyl sulfate, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. 120 parts of an aqueous potassium persulfate solution was added. Next, after adding “monomer mixture 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 milky white “styrene-acrylic resin particle dispersion A1”. The acrylic resin particles obtained had a weight average molecular weight of 11,000, Tg of 48 ° C., Tm of 87 ° C., and an average particle size of 58 nm.

[Monomer mixture 2]
Styrene 98 parts Butyl acrylate 52 parts Methacrylic acid 14 parts n-Octyl mercaptan 6 parts Next, 21 parts of styrene, n in a reaction flask equipped with a stirrer, heating / cooling device, concentrating device, and raw material / auxiliary charging device -14 parts of "Polyester Resin A" is added to a monomer mixture consisting of 6 parts of butyl acrylate, 1.3 parts of methacrylic acid, and 1.1 parts of n-octyl mercaptan, heated to 85 ° C and dissolved. A monomer solution was prepared. On the other hand, a solution prepared by dissolving 0.3 part of sodium dodecyl sulfonate in 540 parts of ion-exchanged water was heated to 80 ° C., and the above-mentioned “styrene-acrylic resin particle dispersion A1” was added to this solution at 5.6 in terms of solid content. Then, the monomer solution was mixed and dispersed with a homogenizer “TK homomixer” to prepare an emulsion. Next, a solution prepared by dissolving 1 part of potassium persulfate in 50 parts of ion-exchanged water and 150 parts of ion-exchanged water were added to this emulsion, and the temperature was adjusted to 80 ° C., followed by polymerization for 3 hours to obtain “polyester resin”. Dispersion liquid of contained acrylic resin particles B "was obtained. The average particle diameter of the obtained polyester resin-containing acrylic resin particles was 110 nm.

(Synthesis of polyester resin 2)
A glass four-necked flask equipped with a stirrer, distillation column, thermometer, and nitrogen inlet tube is charged with a ratio of 4 mol of neopentyl glycol, 4 mol of ethylene glycol, 2 mol of 1,2-propanediol, and 8 mol of terephthalic acid. It is. This was heated to 180 ° C. in a mantle heater under a nitrogen stream, and 0.14% by mass of a polymerization initiator (titanium tetrabutoxide) was added to the total charge of acid and alcohol components, and the mixture was 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 7,500, Tg is 49 ° C., Tm is 92 ° C., acid value 8.6 of “polyester resin B” was obtained.

(Preparation of polyester resin particle dispersion 2)
Next, 20 parts of “Polyester Resin A”, 70 parts of ethyl acetate and 30 parts of methyl ethyl ketone are placed in a beaker and stirred at 10,000 rpm using “TK Homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.) to dissolve evenly. To prepare a polyester resin solution.

  On the other hand, an aqueous medium is prepared by dissolving 1% by mass of a dispersant (sodium polyoxylauryl sulfate) in 450 parts of ion-exchanged water, and the polyester resin solution is suspended in the aqueous medium using a “TK homomixer”. It was made turbid to form an O / W type emulsion. At this time, the "TK homomixer" was stirred at 12000 rpm for 30 minutes. Thereafter, the mixed solvent was removed by heating while stirring at 200 rpm in a “TK homomixer” to obtain “Polyester resin particle dispersion B”. In addition, the average particle diameter of the obtained polyester resin particles was 110 nm.

<Preparation 3 of acrylic resin-containing polyester resin particle dispersion 3>
Next, the above-mentioned “polyester resin particle dispersion 2” was charged into a reactor equipped with a stirrer, a cooling tube, and a temperature sensor, heated to 80 ° C. while stirring under a nitrogen stream, and 1 mass% excess was added thereto. 12 parts of an aqueous potassium sulfate solution was added. Next, after adding “monomer mixture 3” having the following composition over 1 hour, the mixture was further maintained for 2 hours to complete the polymerization. After the completion of the polymerization reaction, the content was cooled to room temperature to obtain a milky white “dispersion of acrylic resin-containing polyester resin particles C”. The obtained resin particles had a volume average particle size of 120 nm.

[Monomer mixture 3]
Styrene 1.0 part butyl acrylate 0.6 part methacrylic acid 0.06 part n-octyl mercaptan 0.03 part <Preparation 4 of polyester resin-containing acrylic resin particle dispersion 4>
A reactor equipped with a stirrer, a condenser, and a temperature sensor was charged with 450 parts of distilled water and 1.12 parts of sodium dodecyl sulfate, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. 120 parts of an aqueous potassium persulfate solution was added. Next, after adding “monomer mixed solution 4” having the following composition over 1.5 hours, the mixture was further maintained for 2 hours to complete the polymerization. After the completion of the polymerization reaction, the contents were cooled to room temperature to obtain milky white “styrene-acrylic resin particle dispersion B1”. The obtained resin particles had a weight average molecular weight of 12,000, Tg of 53 ° C., Tm of 92 ° C., and a volume average particle size of 61 nm.

[Monomer mixture 4]
Styrene 100 parts butyl acrylate 57 parts methacrylic acid 7 parts n-octyl mercaptan 6 parts Next, 21 parts of styrene, n in a reaction flask equipped with a stirrer, heating / cooling device, concentrating device, and raw material / auxiliary charging device -30 parts of "Polyester resin B" is added to a monomer mixture composed of 6 parts of butyl acrylate, 1.3 parts of methacrylic acid, and 1.1 parts of n-octyl mercaptan, heated to 85 ° C and dissolved. A monomer solution was prepared. On the other hand, a solution prepared by dissolving 0.3 part of sodium dodecyl sulfonate in 540 parts of ion-exchanged water was heated to 80 ° C., and the above-mentioned “styrene-acrylic resin particle dispersion B1” was added to this solution at 5.6 in terms of solid content. Then, the monomer solution was mixed and dispersed with a homogenizer “TK homomixer” to prepare an emulsion. Next, a solution prepared by dissolving 1 part of potassium persulfate in 50 parts of ion-exchanged water and 150 parts of ion-exchanged water were added to this emulsion, and the temperature was adjusted to 80 ° C., followed by polymerization for 3 hours to obtain “polyester resin”. Dispersion liquid of contained acrylic resin particles D "was obtained. The obtained polyester resin-containing acrylic resin particles had a volume average particle size of 130 nm.

(Polyester resin synthesis 3: prescription 2)
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. The weight average molecular weight of the obtained polyester resin was 7,300, Tg was 61 ° C., Tm was 108 ° C., and the acid value was 10.2. In this way, “polyester resin C” was obtained.

(Preparation of polyester resin particle dispersion 3)
20 parts of “Polyester resin C”, 70 parts of toluene and 30 parts of methyl ethyl ketone were placed in a beaker, and stirred at 12000 rpm using a “TK homomixer” to uniformly dissolve the polyester resin solution.

  Meanwhile, an aqueous medium was prepared by dissolving 1% by mass of a dispersant (sodium dodecylbenzenesulfonate) in 450 parts of ion exchange water.

  The polyester resin solution was suspended in the aqueous medium using a “TK homomixer” to form an O / W type emulsion. At this time, the "TK homomixer" was stirred at 12000 rpm for 30 minutes. Thereafter, the “TK homomixer” was heated while being stirred at a rotation speed of 200 rpm to remove the mixed solvent to obtain “polyester resin particle dispersion C”. In addition, “polyester resin particle dispersion C” having a volume average particle diameter of 100 nm of the obtained polyester resin particles was obtained.

<Preparation 5 of acrylic resin-containing polyester resin particle dispersion 5>
The above-mentioned “polyester resin particle dispersion C” was charged into a reactor equipped with a stirrer, a condenser, and a temperature sensor, heated to 80 ° C. while stirring under a nitrogen stream, and then added with a 1 mass% potassium persulfate aqueous solution. 12 parts were added. Next, after adding “monomer mixed solution 5” having the following composition over 1 hour, 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 “dispersion of acrylic resin-containing polyester resin particles E”. In addition, the volume average particle diameter of the obtained acrylic resin-containing polyester resin particles was 110 nm.

[Monomer mixture 5]
Styrene 1.3 parts Butyl acrylate 0.3 part Methacrylic acid 0.06 part n-Octyl mercaptan 0.03 part <Preparation 6 of acrylic resin-containing polyester resin particle dispersion 6>
A reactor equipped with a stirrer, a condenser, and a temperature sensor was charged with 450 parts of distilled water and 1.12 parts of sodium dodecyl sulfate, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. 120 parts of an aqueous potassium persulfate solution was added. Next, after adding “monomer mixed solution 6” having the following composition over 1.5 hours, the mixture was further maintained for 2 hours to complete the polymerization. After the completion of the polymerization reaction, the contents were cooled to room temperature to obtain milky white “styrene-acrylic resin particle dispersion C1”. The obtained resin particles had a weight average molecular weight of 13,400, Tg of 57 ° C., Tm of 98 ° C., and a volume average particle size of 60 nm.

[Monomer mixture 6]
Styrene 120 parts Butyl acrylate 42 parts Methacrylic acid 8 parts n-Octyl mercaptan 6 parts Next, in a reaction flask equipped with a stirrer, heating / cooling device, concentrating device, and raw material / auxiliary charging device, 21 parts of styrene, n -35 parts of "Polyester resin C" is added to a monomer mixture composed of 6 parts of butyl acrylate, 1.3 parts of methacrylic acid, and 1.1 parts of n-octyl mercaptan, and heated to 85 ° C to dissolve. A monomer solution was prepared. On the other hand, a solution in which 0.3 part of sodium dodecyl sulfonate was dissolved in 540 parts of ion-exchanged water was heated to 80 ° C., and the above-mentioned “styrene-acrylic resin particle dispersion C1” was added to this solution in an amount of 5. After adding 6 parts, the monomer solution was mixed and dispersed with a “TK homomixer” to prepare an emulsion. Next, a solution prepared by dissolving 1 part of potassium persulfate in 50 parts of ion-exchanged water and 150 parts of ion-exchanged water were added to this emulsion, and the temperature was adjusted to 80 ° C., followed by polymerization for 3 hours to obtain “polyester resin”. A dispersion of contained acrylic resin particles F "was obtained. In addition, the volume average particle diameter of the obtained resin particles was 150 nm.

(Synthesis of acrylic resin 1)
A reactor equipped with a stirrer, a condenser, and a temperature sensor was charged with 450 parts of distilled water and 1.12 parts of sodium dodecyl sulfate, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. 120 parts of an aqueous potassium persulfate solution was added. Next, after adding “monomer mixed solution 7” having the following composition over 1.5 hours, the mixture was further maintained for 2 hours to complete the polymerization. After the completion of the polymerization reaction, the contents were cooled to room temperature to obtain milky white “styrene-acrylic resin particle dispersion D1”. The obtained resin particles had a weight average molecular weight of 10,800, Tg of 49 ° C., Tm of 90 ° C., and a volume average particle size of 60 nm.

[Monomer mixture 7]
Styrene 100 parts Butyl acrylate 54 parts Methacrylic acid 10 parts n-Octyl mercaptan 6 parts Particles are separated from this "styrene-acrylic resin particle dispersion D1", washed with water and dried to obtain "acrylic resin A" It was.

<Preparation 7 of acrylic resin-containing polyester resin particle dispersion>
Next, 15 parts of “Polyester Resin C”, 5 parts of “Acrylic Resin A”, 70 parts of toluene and 30 parts of methyl ethyl ketone are placed in a beaker and stirred at 10000 rpm using a “TK homomixer” to be uniformly dissolved. An acrylic resin-containing polyester resin solution was prepared.

  On the other hand, 1% by mass of a dispersant (sodium dodecylbenzenesulfonate) is dissolved in 450 parts of ion-exchanged water to prepare an aqueous medium, and the polyester resin solution is suspended in the aqueous medium using a “TK homomixer”. It was made turbid to form an O / W type 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 dispersion of acrylic resin-containing polyester resin particles G”. The obtained resin particles had a volume average particle size of 100 nm.

  Table 1 shows each physical property value of each resin particle.

(Preparation of anti-offset agent particles (1) dispersion)
680 parts of distilled water, 180 parts of carnauba wax (manufactured by Celarica Noda), 17 parts of sodium dodecylbenzenesulfonate “Neogen SC” (manufactured by Daiichi Kogyo Seiyaku) are mixed and emulsified and dispersed by applying high-pressure shearing. Particle (1) dispersion ”was obtained. The volume average particle diameter of the offset inhibitor particles was 110 nm (value measured by “ELS-800”).

(Preparation of offset inhibitor particles (2) dispersion)
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) are mixed and emulsified and dispersed by applying high-pressure shear. To obtain “offset inhibitor particles (2) dispersion”. The average particle size of the offset inhibitor particles was 130 nm (value measured with “ELS-800”).

(Colorant particles (1) dispersion)
Dissolve 10 parts of sodium dodecylbenzenesulfonate "Neogen SC" (Daiichi Kogyo Seiyaku) in 180 parts of distilled water and add 25 parts of carbon black "Regal 330R" (Cabot) as colorant particles. To obtain a “colorant particle (1) dispersion”. The volume average particle diameter of the dispersed carbon black was 106 nm (value measured by “ELS-800”).

(Colorant particles (2) dispersion)
10 parts of sodium dodecylbenzenesulfonate “Neogen SC” (Daiichi Kogyo Seiyaku Co., Ltd.) is dissolved in 180 parts of distilled water, and the cyan pigment “copper phthalocyanine B15: 3” (manufactured by Dainichi Seika Co., Ltd.) is used as a colorant particle. Part was added and dispersed to obtain a “colorant particle (2) dispersion”. The volume average particle diameter of the dispersed carbon black was 110 (value measured by “ELS-800”) nm.

(Polymer primary particle (1) Preparation of dispersion)
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 mixture A” 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 milky white “polymer primary particles (1) dispersion”. The polymer had a weight average molecular weight of 11,000, Tg of 34 ° C., Tm of 82 ° C., and a volume average particle size of 120 nm.

[Monomer mixture A]
Styrene 99 parts Butyl acrylate 52 parts Methacrylic acid 14 parts n-Octyl mercaptan 6 parts (Preparation of polymer primary particle (2) dispersion)
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 B” 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 “polymer primary particle (2) dispersion”. The weight average molecular weight of the polymer was 9,800, Tg was 30 ° C., Tm was 78 ° C., and the volume average particle size was 110 nm.

[Monomer mixture B]
Styrene 95 parts Butyl acrylate 58 parts Methacrylic acid 12 parts n-Octyl mercaptan 8 parts <Production of toner particles 1>
In a reactor equipped with a stirrer, a cooling tube, and a temperature sensor, 240 parts of “acrylic resin-containing polyester resin particle A dispersion”, 13.6 parts of “offset inhibitor particle (1) dispersion”, “colorant particles ( 1) Charge 24 parts of dispersion, 5 parts of anionic surfactant “Neogen SC” (Daiichi Kogyo Seiyaku Co., Ltd.), and 240 parts of distilled water, and add 2 mol / L sodium hydroxide aqueous solution while stirring. The pH of the mixed dispersion was adjusted 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 washing treatment such as filtration of the solution and resuspension treatment of the obtained solid content in distilled water is repeated several times, followed by drying to obtain a volume average particle size of 4.8 μm (“Coulter “Toner Particles 1” of “Multisizer II” (measured by Coulter Counter) was obtained.

<Manufacture of toner particles 2>
In a reactor equipped with a stirrer, a cooling pipe, and a temperature sensor, 120 parts of “acrylic resin-containing polyester resin particle B dispersion”, 120 parts of “polymer primary particle (1) dispersion”, “offset inhibitor particles (1 ) Dispersion "13.6 parts," Colored particles (2) Dispersion "24 parts, Anionic surfactant" Neogen SC "(Daiichi Kogyo Co., Ltd.) 5 parts, and distilled water 240 parts, While stirring, a 2 mol / L aqueous sodium hydroxide solution was added 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 particles 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 a washing treatment such as filtration of the solution and resuspension treatment of the obtained solid content in distilled water is repeated several times, followed by drying to obtain a “toner having a volume average particle diameter of 4.8 μm. Particle 2 "was obtained.

<Manufacture of toner particles 3>
In a reactor equipped with a stirrer, a cooling pipe, and a temperature sensor, 240 parts of “acrylic resin-containing polyester resin particle C dispersion”, 13.6 parts of “offset inhibitor particle (1) dispersion”, “colorant particles ( 1) Charge 24 parts of dispersion, 5 parts of anionic surfactant “Neogen SC” (Daiichi Kogyo Seiyaku Co., Ltd.), and 240 parts of distilled water, and add 2 mol / L sodium hydroxide aqueous solution while stirring. The pH of the mixed dispersion was adjusted 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. Warmed and held for another 0.5 hours. The average particle size of the toner particles in the mixed dispersion at this time was 4.5 μm. Next, after cooling the temperature to 50 ° C., 30 parts of “acrylic resin-containing polyester resin particle C dispersion” was added, the temperature was raised to 80 ° C. and held for 0.5 hour, and then 120 g of a 20% by mass sodium chloride aqueous solution was added. Was added for another 0.5 hours. Thereafter, the contents are cooled to room temperature, and a washing treatment such as filtration of the solution and resuspension treatment of the obtained solid content in distilled water is repeated several times, followed by drying to obtain a “toner having a volume average particle diameter of 4.8 μm. Particle 3 "was obtained.

<Manufacture of toner particles 4>
In a reactor equipped with a stirrer, a cooling tube, and a temperature sensor, 160 parts of “polymer primary particle (1) dispersion”, 80 parts of “polyester resin-containing acrylic resin particle D dispersion”, “offset inhibitor particles (2 ) Dispersion "13.6 parts," Colorant particles (2) Dispersion "24 parts, Anionic surfactant" Neogen SC "(Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts, and distilled water 240 parts While stirring, a 2 mol / L aqueous sodium hydroxide solution was added to adjust the pH of the mixed dispersion to 10.0. 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 . At this time, the average particle size of the toner particles in the mixed dispersion was 4.3 μm. Next, after cooling the temperature in the system to 60 ° C., 40 parts of “polyester resin-containing acrylic resin particle D dispersion” was added, the temperature was raised to 80 ° C. and held for 0.5 hour, and then 20% by mass. After adding 120 g of an aqueous sodium chloride solution, the mixture was held for another 0.5 hour. Thereafter, the contents are cooled to room temperature, and washing treatment such as filtration of the solution and resuspension treatment of the obtained solid content in distilled water is repeated several times, and then dried to obtain a “toner having a volume average particle size of 4.7 μm. Particle 4 "was obtained.

<Manufacture of toner particles 5>
In a reactor equipped with a stirrer, a cooling tube, and a temperature sensor, 200 parts of “polymer primary particle dispersion (2)”, 40 parts of “polyester resin-containing acrylic resin particle E dispersion”, “offset inhibitor particles (2 ) Dispersion "13.6 parts," Colorant particles (2) Dispersion "24 parts, Anionic surfactant" Neogen SC "(Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts, and distilled water 240 parts While stirring, a 2 mol / L aqueous sodium hydroxide solution was added to adjust the pH of the mixed dispersion to 10.0. 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 “acrylic resin-containing polyester resin particle E dispersion” was added, the temperature was raised to 80 ° C. and held for 0.5 hour, and then 20% by mass. After adding 120 g of an aqueous sodium chloride solution, the mixture was held for another 0.5 hour. Thereafter, the contents are cooled to room temperature, and a washing treatment such as filtration of the solution and resuspension treatment of the obtained solid in distilled water is repeated several times, followed by drying to obtain a “toner having a volume average particle diameter of 4.6 μm. Particle 5 "was obtained.

<Manufacture of toner particles 6>
In a reactor equipped with a stirrer, a cooling tube and a temperature sensor, 160 parts of “polymer primary particle (2) dispersion”, 80 parts of “acrylic resin-containing polyester resin particle F dispersion”, “offset inhibitor particles (2 ) Dispersion "13.6 parts," Colorant particles (2) Dispersion "24 parts, Anionic surfactant" Neogen SC "(Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts, and distilled water 240 parts While stirring, a 2 mol / L aqueous sodium hydroxide solution was added to adjust the pH of the mixed dispersion 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 particles 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 washing treatment such as filtration of the solution and resuspension treatment of the obtained solid content in distilled water is repeated several times, and then dried to obtain a “toner having a volume average particle size of 4.9 μm. Particle 6 "was obtained.

<Manufacture of toner particles 7>
In a reactor equipped with a stirrer, a cooling tube, and a temperature sensor, 160 parts of “polymer primary particle (2) dispersion”, 80 parts of “acrylic resin-containing polyester resin particle G dispersion”, “offset inhibitor particles (2 ) Dispersion "13.6 parts," Colorant particles (2) Dispersion "24 parts, Anionic surfactant" Neogen SC "(Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts, and distilled water 240 parts While stirring, a 2 mol / L aqueous sodium hydroxide solution was added 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. Warmed and held for another 0.5 hours. At this time, the average particle size of the toner particles in the mixed dispersion was 4.6 μm. Next, after cooling the temperature to 50 ° C., 30 parts of “acrylic resin-containing polyester resin particle F dispersion” was added, the temperature was raised to 80 ° C. and held for 0.5 hour, and then 120 g of a 20 mass% sodium chloride aqueous solution was added. Was added for another 0.5 hours. Thereafter, the contents are cooled to room temperature, and a washing treatment such as filtration of the solution and resuspension treatment of the obtained solid content in distilled water is repeated several times, followed by drying to obtain a “toner having a volume average particle diameter of 4.8 μm. Particle 7 "was obtained.

<Manufacture of toner particles 8>
In a reaction flask equipped with “TK Homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.), heating / cooling device, concentrating device, and raw material / auxiliary charging device, 325 parts of ion-exchanged water and anionic surfactant “New Coal 220L” A solution prepared by dissolving 10 parts (made by Nippon 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.) Then, a monomer mixture composed of 2 parts of Cr dye “TRH” (Hodogaya Chemical Co., Ltd.) and 6 parts of t-butylperoxy-2-ethylhexanoate was uniformly mixed.

  Next, the monomer mixture was poured into the aqueous continuous phase, heated at 80 ° C. under a nitrogen stream, and granulated with a “TK homomixer” rotating at 10,000 rpm and stirring time of 10 minutes. 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 “acrylic resin-containing polyester resin particle G 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 warming and holding for 0.5 hours, 120 g of a 20% by mass aqueous sodium chloride solution was added, and the mixture was further held for 0.5 hours. The produced suspension polymerization particles were filtered, then washed repeatedly with ion-exchanged water and filtered. Thereafter, it was dried with warm air of 40 ° C. to obtain “Toner Particles 8” having a volume average particle diameter of 5.1 μm.

<Manufacture of toner particles 9>
In a reactor equipped with a stirrer, a condenser, and a temperature sensor, 288 parts of “polymer primary particle (1) dispersion”, 13.6 parts of “offset inhibitor particle (1) dispersion”, “colorant particle ( 1) Dispersion "24 parts and 240 parts of distilled water were charged, and a 2 mol / L 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 a washing treatment such as filtration of the solution and resuspension treatment of the obtained solid content in distilled water is repeated several times, followed by drying to obtain a “toner having a volume average particle diameter of 4.8 μm. Particle 9 "was obtained.

<Manufacture of toner particles 10>
In a reactor equipped with a stirrer, a condenser, and a temperature sensor, 240 parts of “polymer primary particle (1) dispersion”, 13.6 parts of “offset inhibitor particle (1) dispersion”, “colorant particle ( 1) Charge 24 parts of dispersion, 5 parts of anionic surfactant “Neogen SC” (Daiichi Kogyo Seiyaku Co., Ltd.), and 240 parts of distilled water, and add 2 mol / L sodium hydroxide aqueous solution while stirring. The pH of the mixed dispersion was adjusted to 10.0. 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 particles 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 “polymer primary particle (2) dispersion” was added, the temperature was raised to 80 ° C. and held for 0.5 hour, and then 20% by mass. After adding 120 g of an aqueous sodium chloride solution, the mixture was held for another 0.5 hour. Thereafter, the contents are cooled to room temperature, and a washing treatment such as filtration of the solution and resuspension treatment of the obtained solid content in distilled water is repeated several times, followed by drying to obtain a “toner having a volume average particle diameter of 4.8 μm. Particle 10 "was obtained.

<Manufacture of toner particles 11>
The above-mentioned polyester resin, pigment masterbatch and polyester wax “WE-5” are prepared so that the cyan colorant “CI Pigment Blue 15: 3” becomes 7 parts per 100 parts of “Polyester Resin A”. One part (manufactured by Nippon Oil & Fats Co., Ltd.) was sufficiently mixed with a “Henschel mixer” (manufactured by Mitsui Miike Chemical Co., Ltd.) at a peripheral speed of 40 m / sec over 180 seconds.

  And this mixture was melt-kneaded with a biaxial extrusion kneader “PCM-30” (Ikegai Iron Works Co., Ltd.), this kneaded product was rolled to a thickness of 2 mm with a press roller, cooled by a cooling belt, Coarsely pulverized with a feather mill. After that, this is pulverized by a mechanical pulverizer “KTM” (manufactured by Kawasaki Heavy Industries, Ltd.) and further pulverized by a jet pulverizer “IDS” (manufactured by Nippon Pneumatic Kogyo Co., Ltd.). Classification was performed using a classifier 100ATP (manufactured by Hosokawa Micron Corporation) to obtain "Toner Particles 11" having a volume average particle size of 5.2 μm.

<Toner particle external additive treatment>
For each 100 parts of “toner particles 1 to 11” produced above, 0.5 part of hydrophobic silica “H-2000” (manufactured by Clariant) and titanium oxide “STT30A” (manufactured by Titanium Industry Co., Ltd.) 1 0.0 part, 1.0 part of strontium titanate (average particle size 0.2 μm) was added, and after using a “Henschel mixer” (manufactured by Mitsui Miike Chemical Co., Ltd.), a peripheral speed of 40 m / sec and a mixing treatment for 60 seconds, Sieve with a sieve having an opening of 90 μm, to obtain “Toners 1 to 11”. “Toners 1 to 7 ” are referred to as “ Reference Examples 1 to 7 ”, “Toner 8” is referred to as “Example 8”, and “Toners 9 to 11” are referred to as “Comparative Examples 1 to 3”.

  Table 2 shows the respective dispersions used for the production of the toner particles, the volume average particle diameter, the particle size distribution, and the average circularity.

<Preparation of developer>
In order to evaluate the toner obtained above as a two-component developer, a binder type carrier was manufactured.

  As the binder type carrier, 100 parts by mass of a polyester resin “NE-1110” (manufactured by Kao Corporation), 700 parts by mass of magnetic particles “magnetite EPT-1000” (manufactured by Toda Kogyo Co., Ltd.) and carbon black “Mogal L” (Cabot Corporation) 2 parts by mass were sufficiently mixed with a “Henschel mixer” (manufactured by Mitsui Miike Chemical Co., Ltd.), set to 180 ° C. in the cylinder part and 170 ° C. in the cylinder head part with 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 prepare a “binder type carrier” having a volume average particle diameter of 40 μm.

  The developer was prepared by mixing 6 parts by mass of “Toners 1 to 11” prepared above and 100 parts by mass of “Binder type carrier” using a “Henschel mixer” (manufactured by Mitsui Miike Chemical Co., Ltd.). These are designated as “Developers 1 to 11”.

<Evaluation of toner characteristics>
The toner characteristics were evaluated by the following method for the following items.

<Charge amount>
30 g of “Developers 1 to 11” prepared above were sequentially placed in a 50 ml polyethylene bottle and rotated at 1200 rpm for 90 minutes and stirred. Thereafter, the charge amount of the toner was determined by the blow-off method.

A: Charge amount is −42 to −53 and particularly preferable range ○: Charge amount is −40 to less than −42 and preferable range ×: Charge amount is less than −40 and there is a problem.

<image quality>
The image quality was evaluated by using a commercially available digital copying machine “DIALTA Di350” (manufactured by Konica Minolta Co., Ltd.) for the initial state and the state of image quality after continuous printing of 100,000 sheets.

◎: Image quality after initial printing and 100,000 sheets is very good ○: Image quality after initial printing and 100,000 sheets is good △: Partially gritty or noise is seen in images after 100,000 sheets printing ×: Roughness and noise occurred on the image after printing 100,000 sheets. XX: Image quality is inferior in both the initial image and the image after printing 100,000 sheets.

<Heat resistant storage>
The heat-resistant storage property was evaluated by putting 10 g of toner in a glass container and leaving it at a high temperature of 50 ° C. for 24 hours, and then visually observing the aggregation state of the toner.

A: No aggregates were observed. O: Less than 10 aggregates were present. X: 10 or more aggregates were present.

<Low temperature fixability>
The low-temperature fixability was comprehensively evaluated from the evaluation results of peel resistance and offset resistance.

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

<Peeling resistance>
The above-mentioned “toner 1-11” and “developer 1-11” are sequentially loaded into a digital copying machine “DIALTA Di350” (manufactured by Konica Minolta Co., Ltd.) equipped with an oilless fixing device, and the fixing temperature is in the range of 80 to 130 ° C. While printing at 2 ° C., a solid image of 1.5 cm × 1.5 cm (attachment amount 2.0 mg / cm ² ) was printed on high-quality paper, and each printed image was folded in half from the middle to obtain the image. It was visually evaluated whether or not the toner on the part was peeled off.

  The peel resistance was evaluated by setting a temperature between the fixing temperature when the toner in the image area is slightly peeled off and the lower fixing temperature at which the toner is not peeled at all as a 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>
To the digital copier “DIALTA Di350” (manufactured by Konica Minolta Co., Ltd.) equipped with an oilless fixing device, the above “Toner 1-11” and “Developer 1-11” are sequentially loaded, fixing speed is halved, and fixing is performed. Halftone images were printed on fine paper while the temperature was changed in increments of 5 ° C. in the range of 90-150 ° C.

  The offset resistance was evaluated by visually observing the state of occurrence of offset and the temperature at which 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.

<Mechanical strength>
The above-mentioned “Toner 1-11” and “Developer 1-11” are sequentially loaded into a digital copying machine “DIALTA Di350” (manufactured by Konica Minolta Co., Ltd.) equipped with an oil-less fixing device, and 100,000 sheets of high-quality paper are used. Printed out.

  The mechanical strength was evaluated based on a state in which the crushed or worn toner adhered to the surface of the photoreceptor after printing 100,000 sheets.

A: No toner adhesion was visible on the surface of the photoconductor. O: A small amount of toner was visible on the surface of the photoconductor, but was not visible on the printed image. X: No toner was visible on the surface of the photoconductor. And was visible as fog on the printed image.

  Table 3 shows the evaluation results of the toner charge amount, image quality, heat resistant storage stability, fixability, and mechanical strength.

As apparent from Table 3, "toner over 8" of the present invention compared to Comparative Example "Toner 9-11", the charge amount, quality, heat-resistant storage stability, low-temperature fixing property, excellent both in mechanical strength I know that.

It is sectional drawing which shows an example of the image forming apparatus used by this invention.

Explanation of symbols

50 Photosensitive drum (photosensitive member)
DESCRIPTION OF SYMBOLS 51 Pre-charge exposure part 52 Charging device 53 Image exposure device 54 Developing device 57 Paper feed roller 58 Transfer electrode 59 Separation electrode 60 Fixing device 70 Process cartridge P Recording paper

Claims (5)

At least, the surface of the base particles obtained by suspension polymerization containing a colorant, a resin particles by aggregating and forming an outer layer, an electrostatic latent image developing that is manufactured through a step of Ru is then fused In the toner manufacturing method ,
Resin particles children for forming the outer layer,
A polyester resin synthesized from an aromatic dicarboxylic acid or a derivative thereof and an aliphatic dialcohol state, and are those containing acrylic resin,
Mixing the polyester resin and the acrylic resin in an organic solvent, adding a resin solution formed by dissolving in an aqueous medium, wherein after dispersing, the Der Rukoto those formed by removing the organic solvent A method for producing a toner for developing an electrostatic latent image. The method for producing a toner for developing an electrostatic latent image according to claim 1, wherein the aromatic dicarboxylic acid or a derivative thereof is terephthalic acid or a derivative thereof . 3. The method for producing a toner for developing an electrostatic latent image according to claim 1 , wherein the acrylic resin is formed by synthesizing at least styrene, acrylic acid ester, and methacrylic acid . The method for producing a toner for developing an electrostatic latent image according to claim 1, wherein the toner for developing an electrostatic latent image contains an offset preventing agent. The volume average particle diameter of the electrostatic latent image developing toner is 3 to 7 μm, and the volume average particle diameter / number average particle diameter is 1.05 to 1.20 . The method for producing a toner for developing an electrostatic latent image according to claim 1.

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