JP2009168930A - Developer for electrostatic charge image development, and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer for electrostatic charge image development which is excellent in charging performance (in particular, suppressing reduction in a charge amount after left unattended in a high temperature and high humidity environment) and fixing property. <P>SOLUTION: The developer for electrostatic charge image development includes a toner containing a crystalline polyester resin and a release agent, and a carrier coated with a resin having a siloxane structure. In a cross section of the toner dyed with ruthenium, a structure of the crystalline polyester resin in contact with the release agent is present; the cross-sectional area A of the above structure, a cross-sectional area B of the release agent in a single state, and a cross-sectional area C of the crystalline polyester resin in a single state satisfy 5≤100×A/(A+B+C)≤35; and the toner particles contain a residual alcohol component by 0.01 ppm to 10 ppm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a developer for electrostatic charge development and a method for producing the same.

  In order to reduce the amount of energy used in image forming apparatuses such as copiers and printers, a technology for fixing toner with lower energy is desired, and there is a demand for toner for electrophotography that can be fixed at a lower temperature. strong.

  As a means for lowering the toner fixing temperature, a technique for lowering the glass transition temperature of a toner resin (binder) is generally performed. In view of the aggregation of powder (blocking) and the storage stability of the toner on the fixed image, in the resin for toner, 50 ° C. is practically the lower limit of the glass transition temperature, and preferably a glass transition temperature of about 60 ° C. is necessary.

  As a means for achieving both blocking prevention, image storability up to 60 ° C., and low-temperature fixability, a technique using a crystalline resin as a binder constituting the toner is considered (for example, Patent Document 1).

  In addition, a technique using a crystalline resin is widely known for the purpose of preventing offset (for example, Patent Document 2 and the like), pressure fixing (for example, Patent Document 3 and the like), and the like.

  Further, a technique using a crystalline resin having a melting point of 110 ° C. or less and a mixture of an amorphous resin (for example, Patent Document 4) has been proposed.

  On the other hand, in order to realize low-temperature fixability, it has been proposed to use a crystalline polyester resin alone for hot roll fixing as much as possible. As a technique using a crystalline polyester resin, techniques described in Patent Documents 5, 6, 7 and the like can be mentioned.

  Further, in Patent Document 8, there is a description that a toner containing a crystalline polyester resin having a crosslinked structure as a main component is excellent in antiblocking property and image storage and can realize low-temperature fixing.

  Further, Patent Document 9 proposes a manufacturing method using a phase inversion phenomenon as a method of manufacturing a small diameter toner having a uniform particle diameter. In this method, an aqueous dispersion is added to a polymer solution obtained by dissolving a polymer in a water-insoluble organic solvent to cause phase inversion and emulsified to form an O / W type emulsion. This is performed by applying heat to the W-type emulsion to evaporate the organic solvent and depositing polymer particles. According to this phase inversion emulsification method, polymer fine particles having a uniform particle diameter can be obtained by a relatively simple operation, and the production efficiency can be improved and the cost can be reduced. In addition, compared to pulverization methods and suspension polymerization methods, there are many types of resins that can be used, and the use of the resulting polymer particles is expanded.

  Further, Patent Document 10 proposes a technique (phase-inversion emulsification using an inorganic dispersant) in which a specific inorganic salt is added to an aqueous medium to obtain shape controllability.

Japanese Patent Publication No. 56-13943 Japanese Examined Patent Publication No.62-39428 Japanese Patent Publication No. 63-25335 Japanese Patent Publication No. 4-30014 Japanese Patent Laid-Open No. 4-120554 JP-A-4-239021 JP-A-5-165252 JP 2001-117268 A Japanese Patent Laid-Open No. 4-303849 JP 2001-255698 A

  To properly dry toner particles produced by a wet process such as phase inversion emulsification, not only adjustment of drying temperature, time, and pressure, but also how liquid components such as moisture and alcohol can be removed from the toner surface. It is important to move to. In general, a coarse toner having a relatively large volume of one particle has a large distance from the inside of the particle to the surface and tends to take a long time to dry. Therefore, toner particles having a certain particle size distribution are similarly dried. Then, the toner of the coarse powder becomes insufficiently dried, and the liquid component tends to remain.

  The alcohol component remaining inside the toner oozes out to the outside due to its small molecule. For example, if a large amount of alcohol component remains in the toner, even if the toner surface is appropriately charged, the alcohol component remaining in the toner thereafter leaks charge, making it difficult to secure the charge amount. This influence tends to increase as the volume of coarse powder toner increases.

  The alcohol component on the toner surface can be removed by drying or the like, but the alcohol component tends to remain in the resin after phase inversion / aggregation, and is particularly difficult to remove due to hydrogen bonds with ester groups in the polyester. In particular, moisture tends to escape the developer charge amount in a high-temperature and high-humidity environment, so the charge amount decreases if left untreated, and the toner adheres to the white paper portion without being able to maintain the toner charge when several sheets are output after being left. Fogging occurs. In particular, in a coarse toner having a relatively large volume of one particle, the distance from the inside of the particle to the surface is large, and the alcohol component tends to remain.

  The present invention is a developer for electrostatic charge development excellent in charging performance (particularly, suppression of decrease in charge amount after standing in a high-temperature and high-humidity environment) and fixability, and a method for producing the same.

  The present invention has the following features.

  (1) A toner containing a crystalline polyester resin and a release agent, wherein a structure in which the crystalline resin polyester resin is in contact with the release agent is present on the cross section of the toner particle, and the cross-sectional area of the structure is A, where B is the sectional area of the release agent alone and C is the sectional area of the crystalline resin polyester resin alone, 5 ≦ 100 × A / (A + B + C) ≦ 35, and residual alcohol in the toner particles An electrostatic charge developing developer comprising a toner having a component of 0.01 ppm to 10 ppm and a carrier coated with a resin having a siloxane structure.

  (2) The electrostatic charge developing developer according to (1) above, wherein the resin having a siloxane structure includes an aminosilane coupling agent.

  (3) A neutralizing agent and an aqueous medium are added to a resin solution in which each of an amorphous polyester resin and a crystalline polyester resin is dissolved in an organic solvent to cause phase inversion, and O / W type resin emulsified particles, respectively. In addition, the non-crystalline polyester resin particle dispersion obtained by removing the organic solvent from both O / W type resin emulsified particle dispersions and the crystalline resin particle dispersion are aggregated and united to form toner particles. And a step of producing a carrier coated with a resin having a siloxane structure. The method for producing a developer for developing an electrostatic charge according to the above (1) or (2).

  The present invention specifies the amount of residual alcohol component of resin particles produced by a phase inversion emulsification method, etc., constitutes a structure of a crystalline polyester resin and a release agent in the toner, and further combines with a specific carrier This solves the problem. Here, the “structure” means a structure having a state in which the crystalline polyester resin is in contact with or embedded in the release agent as described later.

  According to the first aspect of the invention, the toner has a structure in which the crystalline polyester resin and the release agent are in contact within a predetermined range, and the concentration of the alcohol component remaining inside the toner particles is controlled within the predetermined range. In addition, by using a predetermined resin-coated carrier, stable charging characteristics can be maintained, and as a result, fogging after leaving under high temperature and high humidity can be suppressed.

  According to the invention of claim 2, by using a carrier coated with a resin having a siloxane structure containing an aminosilane coupling agent, it becomes possible to reduce the modification of the carrier surface over time, which is stable over a long period of time. Chargeability can be controlled. Here, the “denaturation” may include physical or chemical changes to the carrier surface, such as adhesion, dissolution, and peeling over time.

  According to the third aspect of the invention, there is provided a developer including a toner in which a structure in which a crystalline polyester resin and a release agent are in contact is formed inside toner particles, and a resin-coated carrier having a specific structure. By using this, it is possible to suppress the occurrence of fog after being left under high temperature and high humidity.

  Hereinafter, the developer for electrostatic charge development of the present invention and the production method thereof will be described in detail.

[Developer for electrostatic charge development]
The developer for developing an electrostatic charge according to the present embodiment is a two-component developer including a toner and a carrier. Hereinafter, the “developer for electrostatic charge development” in this exemplary embodiment may be abbreviated as “developer”.

[toner]
The toner according to the embodiment of the present invention is a toner containing a crystalline polyester resin and a release agent, and there is a structure in which the crystalline polyester resin is in contact with the release agent in a cross section of the toner particle. When the sectional area of the structure is A, the sectional area of the release agent alone is B, and the sectional area of the crystalline polyester resin alone is C, 5 ≦ 100 × A / (A + B + C) ≦ 35, and toner The residual alcohol component in the particles is 0.01 ppm to 10 ppm. Here, the “structure” refers to a structure 100 having a structure in which the crystalline polyester 12 is in contact with or recessed into the release agent 10 even at one point, as shown in FIG. In addition, the amorphous polyester resin mentioned later exists in the circumference | surroundings of the said structure, the circumference | surroundings of a mold release agent alone, and the circumference | surroundings of crystalline polyester resin alone.

-Crystalline polyester resin-
Here, the “crystalline polyester resin” refers to a resin having a clear endothermic peak rather than a stepwise endothermic amount change in differential scanning weight measurement (DSC). Here, “crystallinity” used in the electrostatic charge developing toner means that it has a clear endothermic peak in differential scanning calorimetry (DSC). Specifically, the temperature rising rate is 10 ° C. / It means that the half-value width of the endothermic peak when measured in min is within 6 ° C.

  As the crystalline polyester resin, specifically, an aliphatic crystalline polyester resin having an appropriate melting point and an alkyl group having 6 or more carbon atoms is more preferable. The polyester resin having an alkyl group having 6 or more carbon atoms can be obtained by using a polymerizable monomer having an alkyl group having 6 or more carbon atoms in the above polyvalent carboxylic acid or polyhydric alcohol. For example, dodecenyl succinate Although an acid etc. can be used, it is not restricted to this.

  The crystalline polyester resin is obtained mainly by condensation polymerization of polyvalent carboxylic acids and polyhydric alcohols. In the present embodiment, a copolymer obtained by copolymerizing other components with a proportion of 50% by mass or less with respect to the crystalline polyester main chain is also a crystalline polyester.

  Examples of the polyvalent carboxylic acids used in the production of the polyester resin used in the embodiment of the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Aromatic dicarboxylic acids such as diphenic acid, aromatic oxycarboxylic acids such as p-oxybenzoic acid and p- (hydroxyethoxy) benzoic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, adipic acid, azelaic acid, sebacic acid , Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, trimer acid, hydrogenated dimer acid, cyclohexane dicarboxylic acid, Unsaturated aliphatic such as cyclohexene dicarboxylic acid Fine alicyclic dicarboxylic acids, etc., and can be used other trimellitic acid as a polycarboxylic acid, trimesic acid, and the like trivalent or higher polyvalent carboxylic acids such as pyromellitic acid.

  Examples of the polyhydric alcohol used in the production of the polyester resin include aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, aromatic polyhydric alcohols and the like. Aliphatic polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Ring opening of lactones such as neopentyl glycol, diethylene glycol, dipropylene glycol, dimethylol heptane, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ε-caprolactone Examples include aliphatic diols such as lactone-based polyester polyols obtained by polymerization, triols such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol, and tetraols.

  Alicyclic polyhydric alcohols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, spiroglycol, hydrogenated bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, tricyclodecane Examples include diol, tricyclodecane dimethanol, dimer diol, hydrogenated dimer diol and the like.

  As aromatic polyhydric alcohols, para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, bisphenol A, ethylene oxide adduct of bisphenol A and Examples thereof include propylene oxide adducts.

  A monofunctional monomer may be introduced into the polyester resin for the purpose of blocking the polar group at the end of the polyester resin and improving the environmental stability of toner charging characteristics. Monofunctional monomers include benzoic acid, chlorobenzoic acid, bromobenzoic acid, parahydroxybenzoic acid, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, n-dodecylaminocarbonylbenzoic acid Acid, tertiary butylbenzoic acid, naphthalenecarboxylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenylacetic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, octanecarboxylic acid, lauric acid, stearyl Monocarboxylic acids such as acids and lower alkyl esters thereof, or monoalcohols such as aliphatic alcohols, aromatic alcohols, and alicyclic alcohols can be used.

  In the present embodiment, it is desirable to use polyvalent carboxylic acids containing 5 mol% or more of cyclohexanedicarboxylic acid. Furthermore, the amount of cyclohexanedicarboxylic acid used is preferably 10 to 70 mol% in the polyvalent carboxylic acid, 15 -50 mol% is more preferable, and the use of 20-40 mol% is still more preferable. As the cyclohexanedicarboxylic acid, one or more of 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid can be used. Moreover, you may combine what substituted some hydrogen of the cyclohexane ring by the alkyl group etc. If the content of cyclohexanedicarboxylic acid is less than this range, the fixing characteristics are not exhibited. If the content is too large, the unit price of the resin increases, which may cause a problem in cost.

  The method for producing the crystalline polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. They are manufactured using different types of monomers.

  The production of the crystalline polyester resin can be carried out at a polymerization temperature of 180 to 230 ° C., and the reaction is carried out while reducing the pressure in the reaction system as necessary to remove water and alcohol generated during condensation. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. In the case where a monomer having poor compatibility exists in the copolymerization reaction, it is preferable that the monomer having poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component.

  Catalysts that can be used in the production of the crystalline polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metals such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium Compounds: Phosphorous acid compounds, phosphoric acid compounds, amine compounds, and the like, and specific examples include the following compounds.

  For example, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium Tetrapropoxide, titanium tetraisoproxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, naphthenic acid Zirconium, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenyl Sufaito, tris (2, 4-t-butylphenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine. The amount of such a catalyst added is preferably 0.01 to 1.00% by mass relative to the total amount of raw materials.

  As melting | fusing point of crystalline resin, Preferably it is 50-120 degreeC, More preferably, it is 60-110 degreeC. If the melting point of the crystalline resin is lower than 50 ° C., the toner storage stability and the storage stability of the toner image after fixing may become a problem. It may not be obtained.

  Here, the measurement of the melting point of the crystalline resin is shown in ASTM D3418-8 when a differential scanning calorimeter (DSC) is used and the temperature is measured from room temperature to 150 ° C. at a heating rate of 10 ° C. per minute. It can be determined as the melting peak temperature of differential scanning calorimetry. The measurement of the glass transition temperature of the non-crystalline polyester resin described later can be similarly measured.

  A crystalline resin may show a plurality of melting peaks, but in the embodiment of the present invention, the melting point is the maximum peak.

  Furthermore, for example, DSC-7 manufactured by Perkin Elmer can be used for measurement of the melting point of the resin in the present embodiment. The temperature correction of the detection part of this apparatus uses the melting point of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan is used, an empty pan is set as a control, and the measurement is performed at a heating rate of 10 ° C./min. The measurement of the softening temperature of the non-crystalline polyester resin described later can be similarly measured.

  The crystalline polyester resin used in the toner according to the embodiment of the present invention has a weight average molecular weight (Mw) of 10,000 by molecular weight measurement by gel permeation chromatography (GPC) method of tetrahydrofuran (THF) soluble content. ˜25,000, preferably 20,000 to 25,000. When the weight average molecular weight is less than 10,000, the compatibility with the amorphous resin or the release agent proceeds, and plasticity may be generated. On the other hand, if the weight average molecular weight exceeds 25,000, the viscosity at the time of melting the toner increases, and the fixability and image glossiness may be impaired. Here, the molecular weight of the resin was measured with a THF solvent using a TSO gel GPC / HLC-9120, a Tosoh column “TSKgel SuperHM-M” (15 cm), and a monodisperse polystyrene standard sample. The molecular weight was calculated using the prepared molecular weight calibration curve. The same measurement was performed for the non-crystalline polyester resin described later.

  As the toner according to the embodiment of the present invention, a crystalline polyester resin having a melting point (mp) measured in accordance with ASTM D3418-8 of 65 to 75 ° C. is preferably used. When the melting point is less than 65 ° C., the thermal stability of the toner is lowered, and when it exceeds 75 ° C., the image glossiness at the time of toner fixing may be lowered.

  The acid value of the crystalline polyester resin (number of mg of KOH required to neutralize 1 g of resin) can be controlled to, for example, 5 to 10 mgKOH / g. When the acid value is less than 5 mgKOH / g, the crystalline resin particles form aggregates, which makes it difficult to form a structure with the release agent, and the crystalline resin particles exist independently in the toner. Alternatively, it may grow large and be exposed on the toner surface, which is not preferable from the viewpoint of toner fluidity and chargeability. On the other hand, when the acid value exceeds 10 mgKOH / g, it may be difficult to encapsulate the toner, and a stable structure may not be constructed.

-Amorphous polyester resin-
As an amorphous polyester resin, the above-mentioned catalyst is used, and it is mainly obtained by polycondensation of the above-described polyvalent carboxylic acids and polyhydric alcohols.

  The amorphous polyester resin can be produced by subjecting the polyhydric alcohol and polyvalent carboxylic acid to a condensation reaction according to a conventional method. For example, the above polyhydric alcohol and polyvalent carboxylic acid, if necessary, a catalyst, and blended in a reaction vessel equipped with a thermometer, a stirrer, a flow-down condenser, and in the presence of an inert gas (such as nitrogen gas), Heat at 150 to 250 ° C. to continuously remove by-product low-molecular compounds out of the reaction system, stop the reaction when a predetermined acid value is reached, cool, and obtain the desired reactant Can be manufactured.

  The glass transition temperature of the amorphous polyester resin used in the embodiment of the present invention is required to be 50 ° C. or higher when calculated in accordance with ASTM D3418-8, and more preferably 55 ° C. or higher. Further, it is preferably 60 ° C. or higher, more preferably 65 ° C. or higher and lower than 90 ° C. When the glass transition temperature is less than 50 ° C., there is a tendency to aggregate during handling or storage, which may cause a problem in storage stability. On the other hand, when the glass transition temperature is 90 ° C. or higher, not only the fixability is lowered but also the speed dependency is increased, which is not preferable.

  Moreover, it is preferable that the softening temperature of the amorphous polyester resin used for this Embodiment is the range of 60-90 degreeC. In the toner in which the softening temperature of the resin is suppressed to less than 60 ° C., the toner tends to aggregate during handling or storage, and the fluidity may be greatly deteriorated particularly during long-time storage. When the softening temperature exceeds 90 ° C., the fixability may be hindered. In addition, since the fixing roll needs to be heated to a high temperature, the material of the fixing roll and the material of the base material to be copied may be limited.

  The amorphous polyester resin used in the toner according to the embodiment of the present invention has a weight average molecular weight (Mw) of 20, as determined by a molecular weight measurement by a gel permeation chromatography (GPC) method in which tetrahydrofuran (THF) is soluble. 000 to 50,000, preferably 25,000 to 50,000. When the weight average molecular weight is less than 20,000, not only the heat storage property of the toner is lowered, but also the strength of the fixed image may be lowered. On the other hand, if it exceeds 50,000, the fixability may deteriorate and the image gloss may also decrease.

  The acid value of the amorphous polyester resin can be controlled to, for example, 10 to 15 mgKOH / g. If the acid value is less than 10 mg KOH / g, the particle size growth of the aggregates during the production of the toner is accelerated, and there is a problem that the particle size distribution of the resulting toner is expanded. In addition, when the acid value exceeds 15 mgKOH / g, the difference between the acid value of the crystalline polyester resin and the release agent increases, so that only the aggregation with the crystalline polyester resin and the release agent may proceed. As a result, there is a problem that the abundance ratio of the structures exceeds the range of the present embodiment. The acid value of the non-crystalline polyester resin can be adjusted by controlling the carboxyl group at the end of the polyester by the blending ratio and reaction rate of the raw polyhydric carboxylic acid and polyhydric alcohol. Or what has a carboxyl group in the principal chain of polyester is obtained by using trimellitic anhydride as a polyvalent carboxylic acid component.

  In the toner according to the embodiment of the present invention, a preferred weight ratio between the crystalline polyester resin and the amorphous resin is 5/95 to 40/60. If the proportion of the amorphous polyester resin is less than 60%, good fixing characteristics can be obtained, but the phase separation structure in the fixed image becomes non-uniform, and the strength of the fixed image, particularly the scratch strength, decreases, and is easily scratched. May present problems. On the other hand, if it exceeds 95%, the sharp melt property derived from the crystalline polyester resin cannot be obtained, and plasticity may simply occur. To ensure good low-temperature fixability, toner blocking resistance, image storage I can't keep sex.

  The resin particle dispersion of crystalline polyester resin and amorphous polyester can be prepared by adjusting the acid value of the resin or emulsifying and dispersing using an ionic surfactant.

  In addition, in the case of resins prepared by other methods, if the resin is soluble in an oily solvent with relatively low solubility in water, the resin is dissolved in those solvents to dissolve the ionic surfactant or polymer electrolyte in water. At the same time, the particles are dispersed in water by a disperser such as a homogenizer, and then heated or decompressed to evaporate the solvent, whereby a resin particle dispersion can be prepared. Alternatively, a resin particle dispersion may be prepared by adding a surfactant to the resin and emulsifying and dispersing in water with a disperser such as a homogenizer or by a phase inversion emulsification method.

  The particle size of the resin particle dispersion thus obtained can be measured, for example, with a laser diffraction particle size distribution measuring device (LA-700, manufactured by Horiba, Ltd.).

-Release agent-
Specific examples of the release agent used in the embodiment of the present invention include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene, silicones which show a softening point by heating; oleic acid amide, erucic acid amide, ricinoleic acid amide , Fatty acid amides such as stearamide; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, micro Mineral and petroleum waxes such as crystallin wax, Fischer-Tropsch wax, ester waxes of higher fatty acids and higher alcohols such as stearyl stearate and behenyl behenate; butyl stearate, propyl oleate, monostearin Ester waxes of higher fatty acids such as glycerides, glyceryl distearate, pentaerythritol tetrabehenate and unit or polyhydric lower alcohols; diethylene glycol monostearate, dipropylene glycol distearate, distearic acid diglyceride, tetrastearic acid triglyceride, etc. Ester waxes composed of higher fatty acids and polyhydric alcohol multimers; sorbitan higher fatty acid ester waxes such as sorbitan monostearate; cholesterol higher fatty acid ester waxes such as cholesteryl stearate. In this Embodiment, these mold release agents may be used individually by 1 type, and may use 2 or more types together. Further, in the present embodiment, those having a melting point of 40 ° C. to 120 ° C. are used, but in order to meet the recent demand for low temperature fixability as energy saving measures, in particular, 50 ° C. to 100 ° C. The thing of 50 degreeC is preferable, More preferably, the thing of 50-80 degreeC is used.

  The addition amount of these release agents is preferably in the range of 0.5 to 50% by weight, more preferably in the range of 1 to 30% by weight, and still more preferably in the range of 5 to 15% by weight with respect to the total amount of toner. % Range. If the addition amount is less than 0.5% by weight, the effect of adding the release agent is not sufficient, and if it exceeds 50% by weight, the chargeability is likely to be affected, or the toner is easily destroyed inside the developing device. In addition to the effect that the release agent becomes spent on the carrier and the charge tends to decrease, for example, when color toner is used, the image surface is not sufficiently oozed out during fixing. This is not preferable because the release agent tends to stay in the image and transparency may be deteriorated.

  The volume average particle size of the wax particles in the release agent dispersion is preferably in the range of 0.1 to 0.5 μm, particularly preferably 0.1 to 0.3 μm. When the volume average particle size exceeds 0.5 μm, the toner is easily exposed to the toner surface, and the powder fluidity of the toner is deteriorated and filming on the photosensitive member and the developing member is facilitated. In addition, there may be a problem that the release agent particles are not included in the coalescing process and fall off in the coalescing process. In particular, in the case of obtaining a color toner, if the release agent particles are large, OHP permeability may be lowered due to irregular reflection, and color reproducibility may be lowered. In addition, the said volume average particle diameter can be measured using the laser diffraction type particle size distribution measuring instrument etc. which were mentioned above, for example. If the volume average particle size is 0.1 μm or less, it may not be possible to impart sufficient releasability to the toner, which is not preferable.

  The dispersion medium in the release agent dispersion is preferably an aqueous medium, and water, pure water, or ion exchange water is used. A surfactant is used as the dispersant. Preparation of the wax dispersion used in the toner of the present embodiment is well-known, for example, a media type dispersing machine such as a ball mill, a sand mill, an attritor, a high pressure type dispersing machine such as a nanomizer, a microfluidizer, an optimizer, and a gorin. As long as the particle diameter and content described above can be satisfied by using the dispersing means, any method and conditions may be used.

-Colorant-
The colorant is usually present in an effective amount in the toner, for example from about 1 to about 15% by weight of the toner, desirably from about 3 to about 10% by weight. It does not specifically limit as a coloring agent used with the manufacturing method of embodiment of this invention, A well-known coloring agent can be used and it can select suitably according to the objective. One type of pigment may be used alone, or two or more types of pigments of the same type may be mixed and used. Two or more different types of pigments may be mixed and used. Specific examples of the colorant include carbon blacks such as furnace black, channel black, acetylene black, and thermal black; inorganic pigments such as bengara, aniline black, bitumen, titanium oxide, and magnetic powder; fast yellow, monoazo Azo pigments such as yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine (3B, 6B, etc.), para brown, etc .; phthalocyanine pigments such as copper phthalocyanine, metal-free phthalocyanine; flavantron yellow, dibromoanthrone orange, perylene red, quinacridone And condensed polycyclic pigments such as red and dioxazine violet.

  Chrome Yellow, Hansa Yellow, Benzidine Yellow, Slen Yellow, Quinoline Yellow, Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Watch Young Red, Permanent Red, Dupont Oil Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Various pigments such as Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, Para Brown; Acridine, Xanthene, Azo, Benzoquinone, Azine, Anthraquinone, dioxazine, thiazine, azomethine, indigo, thioindigo, phthalocyanine, aniline black , Polymethine dyes, triphenylmethane dyes, diphenylmethane dyes, thiazole type, various dyes such as xanthene; and the like. You may mix black pigments, such as carbon black, and dye to such an extent that transparency is not reduced to these colorants. Moreover, a disperse dye, an oil-soluble dye, etc. are mentioned.

  The dispersion medium for dispersing the colorant is preferably an aqueous medium, and water, pure water, and deionized water are used. A surfactant is used as the dispersant. Production of the colorant dispersion used for the toner of the embodiment of the present invention is, for example, a media type dispersing machine such as a ball mill, a sand mill, an attritor, a high pressure type dispersing machine such as a nanomizer, a microfluidizer, an optimizer, a gorin, Any known method and condition may be used as long as the particle size and content as described can be satisfied using known dispersing means such as.

<Other ingredients>
In the embodiment of the present invention, other components that can be used in the electrostatic charge developing toner are not particularly limited and may be appropriately selected depending on the purpose. For example, inorganic particles, organic particles, charge control agents, release agents Examples include various known additives such as an agent.

  The inorganic particles are generally used for the purpose of improving toner fluidity. Examples of the inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride. , Bengara, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, silicon nitride and the like. Among these, silica particles are preferable, and silica particles that have been hydrophobized are particularly preferable.

  The average primary particle diameter (number average particle diameter) of the inorganic particles is preferably in the range of 1 to 1000 nm, and the addition amount (external addition) is 0.01 to 20 parts by weight with respect to 100 parts by weight of the toner. A range is preferred.

  Organic particles are generally used for the purpose of improving cleaning properties, transfer properties, and sometimes charging properties. Examples of the organic particles include particles such as polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and polystyrene-acrylic copolymer.

  The charge control agent is generally used for the purpose of improving the chargeability. Examples of the charge control agent include salicylic acid metal salts, metal-containing azo compounds, nigrosine and quaternary ammonium salts.

<Toner structure>
The toner according to the embodiment of the present invention includes a crystalline polyester resin and a release agent, and a cross section of the ruthenium-dyed toner is observed with a transmission electron microscope, and the obtained image is analyzed. There is a structure in contact with the release agent.

  The ruthenium dyeing of the toner of the present embodiment is carried out by a usual method, and specifically, it was measured by the following method. Toner or toner particles were embedded in an epoxy resin and sectioned to a thickness of 100 nm by a microtome. The cross section of the toner was observed with a scanning electron microscope (TEM), and a structure in which the crystalline polyester resin was in contact with the release agent was confirmed. For dyeing, a 0.5% aqueous solution of ruthenium tetroxide was used. In the toner, the crystalline polyester resin and the release agent were judged from the contrast and shape. As shown in FIG. 2, the release agent 10 is present in the form of a rod or lump, and the linear crystals scattered around the release agent and in the toner non-crystalline polyester resin 14 are crystalline polyester resin. 12 was judged. In contrast, the whiter contrast portion was determined as the release agent 10. Since the binder resin other than the release agent has many double bond portions and is dyed with ruthenium tetroxide, the release agent portion can be distinguished from the resin portion other than the release agent. That is, as shown in FIG. 2, the release agent 10 is dyed lightest by ruthenium dyeing, then the crystalline polyester resin 12 is dyed, and the non-crystalline polyester resin 14 is dyed darkest. In addition, it adjusted so that the cross section of about 50 toner or a toner particle might be included in one section.

  Thereby, the structure 100 in which the crystalline resin polyester resin 12 is in contact with the release agent 10 via the non-crystalline polyester resin 14, the release agent 10 alone, and the crystalline polyester resin 12 alone are arranged on the cross section of the toner. The existence of is confirmed. The toner of this embodiment has a cross-sectional structure of 5 when the cross-sectional area of the structure is A, the cross-sectional area of the release agent alone is B, and the cross-sectional area of the crystalline resin polyester resin alone is C. ≦ 100 × A / (A + B + C) ≦ 35. In addition, as a specific method of setting 100 × A / (A + B + C) to 5 to 35, a crystalline polyester resin and another resin (for example, non-crystalline polyester) are sufficiently mixed and then contacted with a release agent. Thus, it can be adjusted by the difference in compatibility between the materials of the crystalline polyester resin, the other resins, and the release agent, and the ease of movement between the materials during toner preparation, that is, the ease of orientation. As a preferred method, a solution in which a crystalline polyester resin and other resins are simultaneously dissolved is prepared, and this is emulsified to prepare a state in which the crystalline polyester resin and other resins are mixed in the same particle. It is possible to produce a structure in which a part of the crystalline polyester resin is brought into contact with the releasing agent by heating or the like after being mixed with the releasing agent particles.

  By using particles in which the crystalline polyester resin and the non-crystalline polyester resin are compatible as described above, the release agent particles have a lower acid value, and the resin particle parts and the agglomeration are likely to occur. A toner having a structure in the form can be obtained.

  In the present embodiment, if the structure is less than 5%, the exudation of the residual alcohol component may not be suppressed, and if it exceeds 35%, the decrease in the charge amount after being left as described above can be suppressed. Further, phase dissolution and mixing of the release agent and the crystalline polyester occur, and the viscosity of the release agent increases, so that the peelability at the time of oilless fixing may be deteriorated.

<Toner characteristics>
In the toner of the present embodiment, it is preferable that the residual alcohol component is present in an amount of 0.01 ppm to 10 ppm with respect to the total amount of toner particles. If the residual alcohol component exceeds 10 ppm, it is difficult to control the alcohol component in the structure. Also, if the residual alcohol component is removed to less than 0.01 ppm, there is no problem with low-temperature fixability, but problems such as an increase in production equipment, agglomeration due to an increase in processing time, and a coarsening of toner particles occur. There is a case.

  Spilling out the alcohol component from the inside is suppressed by forming a structure in which the hydrophobic portion of the residual alcohol component is retained in the release agent component having a higher hydrophobicity than the resin and coated with crystalline polyester. It is considered possible.

  The toner particles of the present embodiment preferably have a volume average particle diameter of 1 to 12 μm, more preferably 3 to 9 μm, and even more preferably 3 to 8 μm. Further, the number average particle diameter of the toner particles of the exemplary embodiment is preferably 1 to 10 μm, and more preferably 2 to 8 μm. If the particle size of the toner particles is too small, not only will the manufacturability become unstable, but it will be difficult to control the inclusion structure, the chargeability will be insufficient, and the developability may be reduced. The image quality may be reduced.

  The toner particles of the present embodiment preferably have a volume average particle size distribution index GSDv of 1.30 or less. Further, the ratio (GSDv / GSDp) of the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp is preferably 0.95 or more. When the volume distribution index GSDv exceeds 1.30, the resolution of the image may decrease, and the ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp (GSDv / GSDp) is If it is less than 0.95, the toner chargeability may be reduced, the toner may be scattered, fogging, etc. may occur, leading to image defects.

  In the present embodiment, the particle size of the toner particles and the values of the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp are measured and calculated as follows. First, with respect to the particle size range (channel) obtained by dividing the particle size distribution of the toner particles measured using a Coulter Multisizer II (manufactured by Beckman-Coulter), the volume and number of individual toner particles from the small diameter side. A cumulative distribution is drawn, and the particle size that is 16% cumulative is defined as the volume average particle size D16v and the number average particle size D16p, and the particle size that is 50% cumulative is the volume average particle size D50v and the number average. The particle size is defined as D50p. Similarly, particle diameters that are 84% cumulative are defined as volume average particle diameter D84v and number average particle diameter D84p. At this time, the volume average particle size distribution index (GSDv) is defined as D84v / D16v, and the number average particle size index (GSDp) is defined as D84p / D16p. Using these relational expressions, a volume average particle size distribution index (GSDv) and a number average particle size index (GSDp) can be calculated.

  The charge amount of the toner of the present embodiment is an absolute value, preferably 15 to 60 μC / g, and more preferably 20 to 50 μC / g. If the charge amount is less than 15 μC / g, background stains (fogging) are likely to occur, and if it exceeds 60 μC / g, the image density tends to decrease. The ratio of the charge amount in summer (high temperature and humidity) and the charge amount in winter (low temperature and low humidity) of the toner of the present invention is preferably 0.5 to 1.5, more preferably 0.7 to 1.3. When the ratio is outside these ranges, the charging property is highly dependent on the environment, and the charging stability is poor, which is not preferable for practical use.

  The shape factor SF1 of the toner particles of the present embodiment is preferably 110 ≦ SF1 ≦ 140 from the viewpoint of image forming property. For the shape factor SF1, the average value of the shape factor (the square of the perimeter / projection area) is calculated by the following method, for example. That is, an optical microscopic image of toner particles dispersed on a slide glass is taken into a Luzex image analyzer through a video camera, and from 100 toner particles, (maximum squared) × π × 100 / (projected area × 4). ) And calculating the average value.

  In the toner particles of the present embodiment, the maximum endothermic value obtained by suggestive thermal analysis is preferably 70 to 120 ° C. from the viewpoint of fixability, more preferably 70 to 90 ° C., and still more preferably 85. ~ 90 ° C.

  The melting point of the toner particles can be obtained as the melting peak temperature of the input compensation differential scanning calorimetry shown in JIS K-7121-87. In addition, the toner particles may contain a crystalline resin that may show a plurality of melting peaks as a main component, or may contain a release agent, so may show a plurality of melting peaks, In the present embodiment, the maximum peak is regarded as the melting point.

[Toner Production Method]
Next, a toner manufacturing method in the embodiment of the present invention will be described.

  In an embodiment of the present invention, toner particles are prepared by dissolving a crystalline polyester resin and / or an amorphous polyester resin in an organic solvent, adding a neutralizing agent thereto, adding an aqueous medium, and performing phase inversion. It is obtained by forming O / W type resin emulsified particles and then distilling off the organic solvent from the emulsified resin particles dispersed in the aqueous medium. The phase inversion emulsification and the solvent distillation are performed in separate tanks. In the phase inversion emulsification, the solution viscosity in the step of dissolving the resin in the organic solvent and the step of phase inversion of the resin are greatly different, and particularly in the phase inversion emulsification step, extremely large power is required. On the other hand, in the solvent distillation step, the solution viscosity is relatively low, and it is necessary to secure the evaporation area of the solvent, that is, to renew the solution surface for the solvent distillation. For this reason, although it is possible to perform the said process with the same reactor, it becomes disadvantageous at the point of productivity or apparatus cost. Therefore, in the present embodiment, the emulsification step is performed as follows.

-Emulsification process-
In the emulsification step of the embodiment of the present invention, one or more types of crystalline polyester resin and one or more types of amorphous polyester resin are used at a temperature higher than the melting point or softening temperature of the resin, or the glass transition temperature. By heating and dissolving to a temperature below the boiling point of the organic solvent to make a uniform solution, adding a basic aqueous solution as a neutralizing agent, and then adding pure water to maintain pH 7-9 and applying stirring shear The phase is reversed to obtain an O / W emulsion (emulsion) of the resin. Next, the obtained emulsion is distilled under reduced pressure to remove the solvent, thereby obtaining a resin particle emulsion.

  In the operation of removing the organic solvent when preparing the resin particle dispersion in the emulsification step of the present embodiment, the inner wall temperature of the reaction tank is preferably maintained at 45 to 65 ° C. If the inner wall temperature of the reaction vessel is less than 45 ° C., it is difficult to evaporate the organic solvent even under reduced pressure, and it is difficult to remove the organic solvent. On the other hand, when the inner wall temperature of the reaction tank exceeds 65 ° C., the resin particle dispersion becomes a temperature higher than the glass transition temperature, and coarse particles are formed by aggregation and coalescence of the particles.

  In the operation of removing the organic solvent in the emulsification step of the present embodiment, the internal pressure of the reaction vessel is preferably 5 to 50 kPa [abs] under reduced pressure. If the internal pressure of the reaction tank is less than 5 kPa, water evaporation increases and the organic solvent may disappear under conditions where it evaporates preferentially, which may be disadvantageous in terms of production such as the amount of waste water and processing time. Further, if the internal pressure of the reaction tank exceeds 50 kPa, it is not preferable because evaporation of the organic solvent is difficult to be accelerated even at a high temperature, and it may be difficult to remove the organic solvent.

  In the operation of removing the organic solvent in the emulsification step of the present embodiment, it is preferable to distill until the total amount of residual solvent in the resin particle dispersion becomes 30 ppm to 1000 ppm. This is because if the total amount of the residual solvent is less than 30 ppm, shape control may be difficult in the formation and coalescence of aggregate particles during toner production. Further, if the total amount of residual solvent exceeds 1000 ppm, the storage stability as a resin particle dispersion is poor, and coarse particles may be formed by fusing and coalescing of resin particles.

  In the operation of removing the organic solvent in the emulsification step of the present embodiment, it is preferable to distill until the remaining amount of the alcohol component in the resin particle dispersion becomes 1 ppm to 200 ppm. If the alcohol component is less than 1 ppm, it becomes difficult to suppress foaming by stirring in the reaction tank in which pre-aggregates are formed and toner particles are formed at the time of toner production, and a stable toner structure is obtained due to an increase in the internal void area of the toner. This is because it is impossible to build. On the other hand, if the alcohol component exceeds 200 ppm, the ionized stability of the water-based dispersed particles tends to be lost in the formation of aggregate particles during toner production, and the particle size distribution may be deteriorated. May occur. By removing the solvent so that the remaining amount of the alcohol component in the resin particle dispersion is about 20 ppm to 200 ppm, the residual alcohol component in the obtained toner can be generally controlled to 0.01 ppm to 10 ppm. Become.

  In the emulsification step of the present embodiment, the pH after neutralization with a basic aqueous solution is 7 to 9, preferably pH 8. Examples of the basic aqueous solution include an aqueous ammonium solution, sodium hydroxide, and potassium hydroxide. Alkali metal hydroxides such as may be used. When the pH is less than 7, the dispersion of the finished resin particle dispersion may be unstable. When the pH exceeds 9, the particle size of the aggregated particles in the subsequent aggregation process is difficult to control. Problems may occur.

<Emulsified dispersion>
As an average particle diameter of the said resin particle, it is 1 micrometer or less normally, and it is preferable that it is 0.01-1 micrometer. When the average particle size exceeds 1 μm, the particle size distribution of the finally obtained electrostatic image developing toner is broadened or free particles are generated, which tends to deteriorate performance and reliability. On the other hand, when the average particle size is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toners is improved, and the variation in performance and reliability is advantageous. In addition, the said average particle diameter can be measured using a Coulter multisizer, a laser scattering particle size measuring apparatus, etc., for example.

  Examples of the dispersion medium in the dispersion include an aqueous medium and an organic solvent.

  Examples of the aqueous medium include water such as distilled water and deionized water, alcohols, acetate esters, ketones, and mixtures thereof. These may be used alone or in combination of two or more.

  In the embodiment of the present invention, a surfactant may be added to and mixed with the aqueous medium. Although it does not specifically limit as surfactant, For example, anionic surfactants, such as sulfate ester type, sulfonate type, phosphate ester type, soap type; amine salt type, quaternary ammonium salt type, etc. Nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based, and the like. Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

  Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like. Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. Among these, ionic surfactants such as anionic surfactants and cationic surfactants are preferable.

  As the organic solvent, for example, an alcohol such as ethyl acetate, methyl ethyl ketone, acetone, toluene and isopropyl alcohol can be used, and can be appropriately selected and used according to the binder resin.

  When the resin particles are a crystalline polyester resin and an amorphous polyester resin, the resin particles have a self-water dispersibility containing a functional group that can be anionic by neutralization, and a part or all of the functional group that can be hydrophilic A stable aqueous dispersion can be formed under the action of an aqueous medium neutralized with a base. The functional groups that can be converted into hydrophilic groups by neutralization in crystalline polyester resins and non-crystalline polyester resins are acidic groups such as carboxyl groups and sulfone groups, and examples of neutralizing agents include sodium hydroxide and potassium hydroxide. And inorganic bases such as lithium hydroxide, calcium hydroxide, sodium carbonate and ammonia, and organic bases such as diethylamine, triethylamine and isopropylamine.

  In addition, when a polyester resin that does not disperse in water, that is, does not have self-water dispersibility, is used as the binder resin, the resin solution and / or an aqueous medium mixed therewith are ionic as in the later-described release agent. Disperse with a polymer electrolyte such as surfactant, polymer acid, polymer base, etc., heat above the melting point, and process with a homogenizer or pressure discharge type disperser that can apply a strong shear force. The particle size can be 1 μm or less. When this ionic surfactant or polymer electrolyte is used, the concentration in the aqueous medium may be about 0.5 to 5% by weight.

  The non-crystalline polyester resin and the crystalline polyester resin will be described in detail in the production of the toner described later, but may be blended with a colorant or a release agent, or may be blended after being dissolved in an appropriate solvent. Alternatively, after making each other into an emulsion, they may be mixed and aggregated and then blended together. In the case of this melt-mixed blend, the toner is preferably prepared by a pulverization method. When blended after dissolving in a solvent, a toner production method in which wet granulation is performed together with a solvent and a dispersion stabilizer is preferable. When they are mixed together as an emulsion, there is no particular limitation. A wet manufacturing method for producing toner particles in water, such as a turbidity method, is preferable because it can control the shape of the developer so as not to cause toner destruction. In particular, it is desirable to prepare a toner by an aggregation and coalescence method of an emulsion that allows easy shape control and resin coating layer formation. In order to control the particle diameter and form the surface coating layer, it is desirable to prepare a toner by an aggregation and coalescence method of emulsions.

  Examples of the emulsifier used when forming the emulsified particles include a homogenizer, a homomixer, a cavitron, a clear mix, a pressure kneader, an extruder, and a media disperser.

  The above-mentioned agglomeration method is a mixing step of mixing a resin particle dispersion in which resin particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a release agent particle dispersion in which a release agent is dispersed; An agglomeration step of forming an agglomerated particle dispersion of the resin particles, the colorant particles, and the release agent particles; and a fusion / union step of fusing and coalescing the aggregated particles generated in the aggregation step by heating. It has a manufacturing method. Here, the resin particle dispersion is a mixture of both a crystalline polyester resin particle dispersion and an amorphous polyester resin particle dispersion, and the release agent dispersion is a crystalline polyester resin particle dispersion and an amorphous resin. The toner particles are produced through the agglomeration step and the coalescence / union step.

  Specifically, a resin particle dispersion containing an ionic surfactant is generally prepared by an emulsion polymerization method or the like, and the colorant particle dispersion and the release agent particle dispersion are mixed, and the ionic surfactant and Forms agglomerated particles having a toner particle size by causing heteroaggregation with an aggregating agent having the opposite polarity, and then heating to a temperature equal to or higher than the glass transition temperature of the resin particles to fuse and coalesce the agglomerated particles. The toner particles can be obtained by washing and drying.

  In the above release agent dispersion, the release agent is dispersed in the toner particles as particles having a volume average particle diameter in the range of 150 to 1500 nm, and contained in the range of 5 to 25% by weight. The releasability of the fixed image in the less fixing method can be improved. A preferable range is a volume average particle diameter of 160 to 1400 nm and an addition amount of 1 to 20% by weight.

  The release agent is dispersed in water together with ionic surfactants, polymer electrolytes such as polymer acids and polymer bases, and given strong shear using a homogenizer or pressure discharge type disperser while heating above the melting point. Thus, a dispersion liquid of release agent particles having a volume average particle diameter of 1 μm or less can be produced.

  The concentration of the surfactant used in the release agent dispersion is preferably 4% by weight or less with respect to the release agent. When the content is 4% by weight or more, the aggregation rate of particle formation becomes slow, the heating time becomes long, and the aggregates increase, which is not preferable.

  In the colorant dispersion, the colorant is dispersed in the toner particles as particles having a volume average particle diameter in the range of 100 to 330 nm, and contained in the range of 4 to 15% by weight, whereby the color developability is improved. Of course, OHP permeability is also excellent. The preferred volume average particle size of the colorant particles is in the range of 120 to 310 nm, and the preferred addition amount is in the range of 5 to 14% by weight.

  The colorant is dispersed by a known method, for example, a rotary shear type homogenizer, a ball mill, a sand mill, an attritor, a media disperser such as a coball mill, a roll mill such as a three roll mill, a cavitation mill such as a nanomizer, a colloid mill, A high-pressure opposed collision type disperser or the like is preferably used.

  In the toner production method according to the embodiment of the present invention, it is used for the purpose of emulsion polymerization of resin particles, dispersion of colorants, addition dispersion of resin particles, dispersion of release agents, aggregation thereof, or stabilization thereof. Examples of surfactants include sulfate surfactants, sulfonates, phosphates, soaps and other anionic surfactants, and amine surfactants, quaternary ammonium salt types and other cationic surfactants. Can be used. It is also effective to use a nonionic surfactant such as polyethylene glycol, alkylphenol ethylene oxide adduct, and polyhydric alcohol. As these dispersing means, general means such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill and the like can be used.

  When using colorant particles coated with polar resin particles, the resin and colorant are dissolved and dispersed in a solvent (water, surfactant, alcohol, etc.), and then the appropriate dispersant (activator as described above) is used. In addition, the colorant particles are fixed to the surface of the resin particles prepared by emulsion polymerization using mechanical shearing force or electrical adsorption force. It is possible to adopt a method of making it. These methods are effective for suppressing the release of the colorant added to the aggregated particles and improving the dependency of the chargeable colorant.

  In addition, after completion of the fusion / unification, desired toner particles can be obtained through a washing process, a solid-liquid separation process, and a drying process that are optionally performed as necessary. In the washing step, it is preferable to sufficiently perform substitution washing with deionized water in order to develop and maintain chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, centrifugal filtration, decanter and the like are preferably used from the viewpoint of productivity. Further, the drying process is not particularly limited, but from the viewpoint of productivity, aeration drying apparatus, spray drying apparatus, rotary drying apparatus, air flow drying apparatus, fluidized bed drying apparatus, heat transfer heating type drying apparatus, freeze drying apparatus, etc. are preferably used. It is done.

  Furthermore, for the purpose of imparting fluidity and improving cleaning properties, as in normal toner production, metal salts such as calcium carbonate, silica, alumina, titania, barium titanate, strontium titanate, calcium titanate, cerium oxide, Surface of toner particles by applying shearing force to inorganic particles such as metal oxide compounds such as zirconium oxide and magnesium oxide, ceramics, carbon black, etc., and resin particles such as vinyl resin, polyester resin, and silicone resin in a dry state Can be added.

  These inorganic particles are preferably surface-treated with a coupling agent or the like in order to control conductivity, chargeability, and the like. Specific examples of the coupling agent include methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, and trimethyl. Chlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane , Diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, hexamethylsilazane, N, N- (bistrimethylsilyl) acetamide, N, N- (Trimethylsilyl) urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3.4 epoxycyclohexyl) ethyltrimethoxysilane, γ Silane coupling agents such as glycidoxy propyl trimethoxysilane, γ-glycidoxy propylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, titanium coupling agents, etc. Can be mentioned.

  As a method for adding particles, after the toner particles are dried, they may be adhered to the toner particle surface in a dry manner using a mixer such as a V blender or a Henschel mixer, or the particles may be water or an aqueous liquid such as water / alcohol. After being dispersed in the toner particles, they may be added to the toner particles in a slurry state and dried to allow external additives to adhere to the toner particle surfaces. Moreover, you may dry, spraying a slurry on dry powder.

[Career]
Next, the carrier according to the embodiment of the present invention will be described.

  Examples of the carrier according to the embodiment of the present invention include a resin-coated carrier in which core particles are coated with a resin having a siloxane structure. Examples of the core particle of the carrier include normal iron powder, ferrite, magnetite molding, and the like, and the volume average particle size is in the range of about 30 to 200 μm.

  Examples of the resin having a siloxane structure include polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, polyorganosiloxane, and a mixture thereof. Resin having a siloxane structure has high water repellency, and the amount of charge is not easily lowered in a high temperature and high humidity environment. In addition, the resin has a strong alcohol resistance. be able to.

  Moreover, it is more preferable that the resin having a siloxane structure that covers the core particles further contains an aminosilane coupling agent. By improving the adhesion between the core material (nuclear particles) and the resin layer in the carrier by a coupling process, the peeling from the interface is suppressed, the carrier coating agent fog is prevented, the charging ability is maintained, and the toner particles Even when the residual alcohol component in the toner oozes out on the toner surface, the coupling agent component can improve the concealing effect of the OH group on the coat surface and further adhesion at the coat interface. (Induces a dehydration reaction of the coupling agent.)

  In the present embodiment, examples of aminosilane coupling agents include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, N-β- (N- Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-aminopropyltrimethoxysilane, octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride, γ-dibutylaminopropyltrimethoxysilane, γ -Diallylaminopropyltrimethoxysilane etc. can be mentioned.

  Examples of the method for forming the resin coating layer on the surface of the carrier core material include an immersion method in which a powder of the carrier core material is immersed in the solution for forming the coating layer, and a solution for forming the coating layer on the surface of the carrier core material. Spray method for spraying, fluidized bed method for spraying the solution for forming the coating layer in a state where the carrier core material is floated by the flowing air, and a kneader for mixing the carrier core material and the solution for forming the coating layer in a kneader coater to remove the solvent. Examples of the coater method include a powder coat method in which a coating resin is finely divided and mixed in a carrier core material and a kneader coater at a temperature equal to or higher than the melting point of the coating resin and then cooled to form a coating. The kneader coater method and the powder coating method are particularly preferably used.

  In the carrier of the present embodiment, the coating amount of the coating resin is preferably in the range of about 0.2 to 6 parts by weight, for example, 0.5 to 5 parts by weight with respect to 100 parts by weight of the core particles. A range is more preferred. If the coating amount of the coating resin is less than 0.2 parts by weight with respect to 100 parts by weight of the core particles, a uniform coating may not be formed on the surface of the composite magnetic particles. In some cases, the layer becomes too thick, granulation of carriers occurs, and uniform particles cannot be obtained.

  In the carrier of the present embodiment, the amount of the aminosilane coupling agent with respect to the coating resin is preferably, for example, in the range of about 5 to 40 parts by weight with respect to 100 parts by weight of the coating resin, A range is more preferred. If the compounding amount of the aminosilane coupling agent is less than 5 parts by weight with respect to 100 parts by weight of the coating resin, the effect of improving the adhesion between the core particles and the addition of the aminosilane coupling agent may not be sufficiently exhibited. On the other hand, when the amount exceeds 40 parts by weight, the degree of crosslinking of the resin coating layer becomes too high, and the charge-up phenomenon is likely to occur, which may cause image defects such as insufficient developability.

  A heating kneader, a heating Henschel mixer, a UM mixer, or the like can be used for manufacturing the carrier according to the present embodiment. Depending on the amount of the coating resin, a heating fluidized bed, a heating kiln, or the like can be used. Can be used.

  The particle size distribution of the carrier of the present embodiment is preferably 1.3 or less. A method for measuring the particle size distribution will be described later. If the particle size distribution of the carrier exceeds 1.3, the developer fluidity tends to deteriorate, so the developer agglomerates due to stirring in the developing machine, and streaks are generated due to clogging of the developer. There is a case.

The particle size distribution of the carrier is indicated by a weight distribution, and specifically, it can be indicated by a residual amount on the sieve when 100 g of the carrier is passed through several kinds of sieves having different openings. In the present embodiment, a sieve having an opening that gradually spreads from 10 μm to 100 μm, a small sieve having openings are arranged from the bottom, and a sieve having an opening of 100 μm is placed on top. After placing the carrier and applying sonic vibration, the weight of the carrier remaining on each sieve was measured. When the carrier passing weight is 100, the particle diameter of 16% from the bottom is D16, the particle diameter of 84% is D84, and the particle size distribution is (D84 / D16) ^0.5 . D16 and D84 do not always have a weight of 16% and a weight of 84% due to the opening of the sieve. In that case, D16 was calculated by the following calculation.

The sieve containing 1.16% is A μm, and the cumulative carrier amount counted from the bottom including the carrier remaining on the sieve is a.
2. Let B be the sieve that is one lower than the sieve containing the 16th mesh, and b be the cumulative amount of carrier counted from the bottom including the carrier remaining on this sieve.
3. D16 = {(16−b) / (ab)} × (A−B) + B
D84 was obtained by calculation as follows.
The sieve containing the 4.84% eye is C μm, and the cumulative carrier amount counted from the bottom including the carrier remaining on the sieve is c.
Let D be the sieve that is one lower than the sieve containing the 5.84% mesh, and d be the cumulative carrier amount counted from the bottom including the carrier remaining on the sieve.
6). D16 = {(84−d) / (cd)} × (CD) + D
According to the above method, D16 and D84 can be obtained even if the mesh openings of the sieves are different.

As a more specific example, if the opening is 20 μm, the opening is 12%, the opening is 25 μm, the opening is 30%, the opening is 75 μm, the opening is 70%, the opening is 100 μm, and the opening is 90%.
D16 = {(16-12) / (30-12)} × (25-20) + 20 = 21.1 μm
D84 = {(84-70) / (90-70)} × (100-75) + 75 = 92.5 μm
It becomes.

  In addition, the sieve used in this Embodiment and its opening are as follows. HD10 (10 μm), HC-15 (15 μm), P-25 (25 μm), NY31-HC (31 μm), DIN120-45 (45 μm), NY50-HD (50 μm), HC-60 (60 μm), DIN80-75 (75 μm), NY100-HC (100 μm) (both manufactured by Sanjiro Tanaka Shoten)

  In addition, as a method of setting the particle size distribution of the carrier to 1.3 or less, after preparing a carrier having a wide particle size distribution, for example, by sieving with a sieve having openings around the average particle size, smaller particle size, larger particle size There are a method of removing particles of a small particle size and a method of separating particles having a large particle size by a method such as air classification.

<Image forming apparatus>
Next, an image forming apparatus according to an embodiment of the present invention will be described.

  FIG. 1 is a schematic diagram illustrating a configuration example of an image forming apparatus for forming an image by the image forming method according to the embodiment of the present invention. In the illustrated image forming apparatus 200, four electrophotographic photosensitive members 401 a to 401 d are disposed in parallel in the housing 400 along the intermediate transfer belt 409. The electrophotographic photoreceptors 401a to 401d form, for example, images in which the electrophotographic photoreceptor 401a is yellow, the electrophotographic photoreceptor 401b is magenta, the electrophotographic photoreceptor 401c is cyan, and the electrophotographic photoreceptor 401d is black. Is possible.

  Each of the electrophotographic photosensitive members 401a to 401d can be rotated in a predetermined direction (counterclockwise on the paper surface), and the charging rolls 402a to 402d, the developing devices 404a to 404d, and the primary transfer roll 410a along the rotation direction. To 410d and cleaning blades 415a to 415d are arranged. Each of the developing devices 404a to 404d can be supplied with toner of four colors of black, yellow, magenta and cyan accommodated in the toner cartridges 405a to 405d, and the primary transfer rolls 410a to 410d are respectively intermediate transfer belts. 409 is in contact with the electrophotographic photoreceptors 401a to 401d.

  Further, an exposure device 403 is disposed at a predetermined position in the housing 400, and it becomes possible to irradiate the surfaces of the charged electrophotographic photoreceptors 401a to 401d with a light beam emitted from the exposure device 403. ing. Accordingly, charging, exposure, development, primary transfer, and cleaning are sequentially performed in the rotation process of the electrophotographic photosensitive members 401a to 401d, and the toner images of the respective colors are transferred onto the intermediate transfer belt 409 in an overlapping manner.

  Here, the charging rolls 402a to 402d contact the surface of the electrophotographic photoreceptors 401a to 401d with a conductive member (charging roll), and apply a voltage uniformly to the photoreceptor to charge the photoreceptor surface to a predetermined potential. (Charging process). In addition to the charging roll shown in this embodiment, charging by a contact charging method may be performed using a charging brush, a charging film, a charging tube, or the like. Moreover, you may charge by the non-contact system using a corotron or a scorotron.

  As the exposure apparatus 403, an optical system apparatus or the like that can expose a light source such as a semiconductor laser, an LED (light emitting diode), a liquid crystal shutter, or the like on the surfaces of the electrophotographic photosensitive members 401a to 401d can be used. Among these, when an exposure apparatus capable of exposing non-interference light is used, interference fringes between the electroconductive substrates of the electrophotographic photoreceptors 401a to 401d and the photosensitive layer can be prevented.

  As the developing devices 404a to 404d, a general developing device that develops the two-component electrostatic image developer in contact or non-contact with the developer can be used (developing step). Such a developing device is not particularly limited as long as a two-component electrostatic image developing developer is used, and a known one can be appropriately selected according to the purpose. In the primary transfer process, a primary transfer bias having a polarity opposite to that of the toner carried on the image carrier is applied to the primary transfer rolls 410a to 410d, so that each color toner is transferred from the image carrier to the intermediate transfer belt 409. The primary transfer is performed sequentially.

  The cleaning blades 415a to 415d are for removing residual toner adhering to the surface of the electrophotographic photosensitive member after the transfer process, and the electrophotographic photosensitive member cleaned by this cleaning process is repeatedly used in the above-described image forming process. Is done. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber.

  The intermediate transfer belt 409 is supported with a predetermined tension by a drive roll 406, a backup roll 408, and a tension roll 407, and can rotate without causing deflection due to the rotation of these rolls. Further, the secondary transfer roll 413 is disposed so as to contact the backup roll 408 via the intermediate transfer belt 409.

  By applying a secondary transfer bias having a reverse polarity to the toner on the intermediate transfer member to the secondary transfer roll 413, the toner is secondarily transferred from the intermediate transfer belt to the recording medium. The intermediate transfer belt 409 that has passed between the backup roll 408 and the secondary transfer roll 413 is cleaned by, for example, a cleaning blade 416 disposed near the drive roll 406 or a static eliminator (not shown). It is repeatedly used for the next image forming process. A tray (transfer medium tray) 411 is provided at a predetermined position in the housing 400, and the transfer medium 500 such as paper in the tray 411 is transferred to the intermediate transfer belt 409 and the secondary transfer roll by the transfer roll 412. Then, the paper is sequentially transferred between the two fixing rolls 414 that are in contact with each other and the two fixing rolls 414 that are in contact with each other.

  An image forming method according to an embodiment of the present invention uses a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member and a developer carried on the developer carrying member, and the latent image holding member surface A developing step for developing the electrostatic latent image formed on the surface to form a toner image, a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and the surface of the transfer target And a fixing step of thermally fixing the toner image transferred to the toner image, wherein the developer is at least a developer containing the electrostatic charge developing toner of the present invention. The developer may be either a one-component system or a two-component system.

  As each of the above steps, a known step in the image forming method can be used.

  As the latent image holding member, for example, an electrophotographic photosensitive member and a dielectric recording member can be used. In the case of an electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is uniformly charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic latent image (latent image forming step). Next, the toner particles are adhered to the electrostatic latent image in contact with or in proximity to a developing roll having a developer layer formed on the surface, thereby forming a toner image on the electrophotographic photosensitive member (developing step). The formed toner image is transferred onto the surface of a transfer medium such as paper using a corotron charger or the like (transfer process). Further, the toner image transferred to the surface of the transfer target is heat-fixed by a fixing device, and a final toner image is formed.

  In the heat fixing by the fixing device, a release agent is usually supplied to a fixing member in the fixing device in order to prevent offset and the like.

  The method for supplying the release agent to the surface of the roller or belt, which is a fixing member used for heat fixing, is not particularly limited. For example, a pad method using a pad impregnated with a liquid release agent, a web method, a roller method. Non-contact shower method (spray method) and the like, and the web method and the roller method are particularly preferable. These methods are advantageous in that the release agent can be supplied uniformly and it is easy to control the supply amount. In order to supply the release agent uniformly to the entire fixing member by a shower method, it is necessary to use a separate blade or the like.

  In the image forming apparatus according to the embodiment of the present invention, the contact time with the fixing member, that is, between the two fixing rolls 414 shown in FIG. 1, is 0.01 seconds or more and 0.1 seconds or less. If the contact time with the fixing member is less than 0.01 seconds, a sufficient amount of heat necessary for fixing may not be obtained, and adhesiveness with the recording medium may not be obtained. Exceeds 0.1 seconds, the release agent and the crystalline polyester resin ooze out of the toner of the present embodiment, the oozed crystalline polyester resin soaks into the recording medium, and then forms crystals by cooling. Sometimes the adhesiveness with the recording medium is lowered, and the folding resistance of the image tends to be lowered. The fixing member is a member that is in contact with the recording medium with a heated member such as a fixing roll, and the contact time with the fixing member is the time that the fixing member is in contact with the recording medium. For example, in the case of a fixing machine configuration in which the fixing roll and the recording medium come into contact with each other by passing the recording medium between the fixing roll and the roll in contact with the fixing roll, the fixing roll and the roll in contact with the fixing roll The contact width (nip width) divided by the passing speed when the recording medium passes is called the contact time with the fixing member. Specifically, if the nip width is 5 mm and the time for the recording medium to pass is 100 mm / s, the contact time with the fixing member is 5/100 = 0.05 seconds. The nip width was determined by the following method. First, a solid image is prepared using DocuCenter Color 400CP manufactured by Fuji Xerox Co., Ltd. and using R paper manufactured by Fuji Xerox Co., Ltd. However, if the entire surface is a solid image and the 75-degree specular gloss according to JIS Z8741-1997 is 20% or less, there is no problem other than this copying apparatus and paper. Next, the obtained solid image is put into the apparatus, the solid image is output, the apparatus is turned off while passing through the fixing device, and left as it is for 10 seconds. Thereafter, the solid image in contact with the fixing roll is taken out. Since the gloss of the solid image that has been in contact with the fixing roll is changed after being left for 10 seconds, the width thereof is measured, and this is defined as the nip width. The size of the paper used is A4, and the nip width is the width of the central portion.

  Examples of the transfer target (recording material) to which the toner image is transferred include plain paper and OHP sheet used for electrophotographic copying machines, printers, and the like.

[Preferred embodiment]
An electrostatic charge developing developer containing 0.01 to 1% by weight of toner having a toner particle diameter of 20 μm or more.

  Stable charging characteristics can be maintained by controlling the amount of coarse powder toner, which tends to be deteriorated in chargeability due to the remaining alcohol component, to an appropriate value.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.

  First, in this example, each measurement was performed as follows.

-Particle size and particle size distribution measurement method-
The particle size (also referred to as “particle size” or “particle size”) and particle size distribution measurement (also referred to as “particle size distribution measurement”) will be described.

  When the particle diameter to be measured was 2 μm or more, Coulter Multisizer-II type (manufactured by Beckman-Coulter) was used as the measuring apparatus, and ISOTON-II (manufactured by Beckman-Coulter) was used as the electrolyte.

  As a measurement method, 0.5 to 50 mg of a measurement sample is added to 2 mL of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, as a dispersant. This was added to 100 mL of the electrolyte solution.

  The electrolyte in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the particle size distribution of particles of 2 to 60 μm is measured using the Coulter Multisizer-II type with an aperture diameter of 100 μm. Volume average distribution and number average distribution were determined. The number of particles to be measured was 50,000.

  The particle size distribution of the toner was determined by the following method. For the particle size range (channel) obtained by dividing the measured particle size distribution, draw the volume cumulative distribution from the smaller particle size, define the cumulative number particle size to be 16% cumulative as D16p, and the cumulative volume to be 50% cumulative. The particle size is defined as D50v. Furthermore, the cumulative number particle size that is 84% cumulative is defined as D84p.

In the embodiment of the present invention, the volume average particle size is D50v, and the small diameter side number average particle size index GSDp is calculated by the following equation.
Formula: Lower GSDp = {(D84p) / (D16p)} ^0.5

  Moreover, when the particle diameter to measure was less than 2 micrometers, it measured using the laser diffraction type particle size distribution measuring apparatus (LA-700: made by Horiba, Ltd.). As a measuring method, the sample in the state of dispersion is adjusted so as to have a solid content of about 2 g, and deionized water is added thereto to make about 40 mL. This is put into the cell until an appropriate concentration is reached, waits for about 2 minutes, and is measured when the concentration in the cell becomes almost stable. The obtained volume average particle diameter for each channel was accumulated from the smaller volume average particle diameter, and the volume average particle diameter was determined to be 50%.

  When measuring powders such as external additives, 2 g of a measurement sample is added to 50 mL of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, and 2 with an ultrasonic disperser (1,000 Hz). A sample was prepared by dispersing for a minute, and the measurement was performed in the same manner as the above dispersion.

-Method of measuring toner particle shape factor SF1-
The toner particle shape factor SF1 is a shape factor SF indicating the degree of unevenness on the toner particle surface, and was calculated by the following equation.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the formula, ML represents the maximum length of toner particles, and A represents the projected area of the particles. The shape factor SF1 is measured by first taking an optical microscope image of toner or toner particles dispersed on a slide glass into an image analyzer through a video camera, calculating SF for 50 or more toners or toner particles, and obtaining an average value. It was.

-Measurement method of molecular weight and molecular weight distribution of toner and resin particles-
The molecular weight distribution is performed under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)” apparatus, and two columns use “TSKgel, SuperHM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15 cm)”. , THF (tetrahydrofuran) was used as an eluent. As experimental conditions, an experiment was performed using a sample concentration of 0.5%, a flow rate of 0.6 mL / min, a sample injection amount of 10 μL, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

-Measuring method of melting point and glass transition temperature-
The melting point and the glass transition temperature of the toner were determined by a DSC (Differential Scanning Calorimeter) measurement method, and were determined from the main maximum peak measured according to ASTM D3418-8.

  DSC-7 manufactured by Perkin Elmer Co. can be used for measurement of the main maximum peak. The temperature correction of the detection part of this apparatus uses the melting point of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan was used, an empty pan was set as a control, and the measurement was performed at a heating rate of 10 ° C./min.

-Method of measuring acid value-
About 1 g of resin is precisely weighed and dissolved in 80 mL of tetrahydrofuran. Phenolphthalein was added as an indicator, titrated with a 0.1N KOH ethanol solution, and the end point was when the color lasted for 30 seconds. From the amount of 0.1N KOH ethanol solution used, the acid value (contained in 1 g of resin) The number of mg of KOH necessary to neutralize free fatty acids was calculated according to JIS K0070: 92).

-Measurement of crystalline resin in toner and endothermic peak derived from release agent by differential scanning calorimetry-
The endothermic peak and endothermic amount derived from the crystalline resin and the release agent in the toner were measured using a thermal analyzer of a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-60A) (hereinafter abbreviated as “DSC”). . In the first temperature raising step, the temperature is raised from room temperature to 150 ° C. at a rate of 10 ° C./minute, held at 150 ° C. for 5 minutes, and then cooled to 0 ° C. at a rate of 10 ° C./minute using liquefied nitrogen. After holding at 0 ° C. for 5 minutes, as the second temperature raising step, the temperature was raised again from 0 ° C. to 150 ° C. at a rate of 10 ° C. per minute for measurement.

-Determination of residual alcohol components-
Method for quantitative analysis of isopropyl alcohol (IPA):
A sample (1 g of resin particle dispersion or 1 g of toner particles) was precisely weighed, 10 mL of carbon disulfide was added for extraction, and 1 microliter of this extract was injected into a gas chromatograph for analysis. The gas chromatograph was manufactured under the following conditions using GC-17A manufactured by Shimadzu Corporation.
Column: TC-1 60m
Inlet temperature: 200 ° C
Temperature rising condition: 5 minutes at 40 ° C, 140 ° C at 4 ° C / min Detector: FID

  The peak area values corresponding to the measured isopropyl alcohol of the chromatograph are 0.1, 1.0, 2.0, 4.0, 6.0, 8.0, 10.0, 12.0, 15.0, respectively. The isopropyl alcohol was quantified using the calibration curve data of isopropyl alcohol prepared in advance from a sample containing 20.0 ppm.

  Next, embodiments of the present invention will be described in detail with reference to examples. However, the present invention is not limited to the embodiments. In the embodiment of the present invention, the toner is obtained by the following method.

  That is, the following resin particle dispersion, colorant particle dispersion, and release agent particle dispersion are prepared. Next, while a predetermined amount of them are mixed and stirred, polyaluminum chloride is added thereto and ionically neutralized to form aggregates of the above particles. Resin particles are additionally added before reaching the desired toner particle size to obtain the desired toner particle size. Then, after adjusting the pH of the system from weakly acidic to alkaline using an inorganic hydroxide as an alkali agent, it is heated above the main maximum endothermic peak temperature obtained from the differential thermal analysis of the resin particles. Fusing together to obtain a toner suspension. After completion of the reaction, the suspension is rapidly cooled, and then desired toner particles are obtained through sufficient washing, solid-liquid separation, and drying processes.

  Below, the example of the preparation method of each material and the preparation method of an aggregated particle is described.

[Synthesis of resin materials]
-Synthesis of crystalline polyester resin-
In a heat-dried three-necked flask, 120.0 parts by weight of 1,10-decanediol, 75.0 parts by weight of dimethyl sebacate, 5.0 parts by weight of sodium dimethyl 5-sulfoisophthalate, and 4 parts by weight of dimethyl sulfoxide Then, 0.02 part by weight of dibutyltin oxide was added as a catalyst, the air in the container was evacuated by a depressurization operation, and the atmosphere was replaced with nitrogen gas to form an inert atmosphere, and mechanical stirring was performed at 180 ° C. for 3 hours. Stirring was performed. Dimethyl sulfoxide was distilled off under reduced pressure, 23.0 parts by weight of dimethyl dodecanedioic acid was added under a nitrogen stream, and the mixture was stirred at 180 ° C. for 1 hour.

-Synthesis of non-crystalline polyester resin-
In a heat-dried three-necked flask,
Dimethyl naphthalenedicarboxylate 112 parts by weight Dimethyl terephthalate 97 parts by weight Bisphenol A-ethylene oxide 2 mol adduct 221 parts by weight Ethylene glycol 80 parts by weight Tetrabutoxy titanate 0.07 parts by weight were charged and heated at 170-220 ° C. for 180 minutes. A transesterification reaction was performed. Subsequently, as a result of continuing reaction for 60 minutes at 220 degreeC and the system pressure of 1-10 mmHg, the amorphous polyester resin was obtained. The polyester resin had a glass transition temperature of 65 ° C. and Mw of 21,000.

-Preparation of resin particle dispersion (1)-
A resin particle dispersion was prepared using a coarsely pulverized resin obtained by synthesizing a crystalline polyester resin and an amorphous polyester resin with a hammer mill.

Methyl ethyl ketone (180 parts by weight) and IPA (60 parts by weight) were added to a ₂ L flask equipped with anchor blades for giving stirring power, N ₂ was supplied, and the air in the system was replaced with N ₂ . Next, 9 parts by weight of the crystalline polyester resin and 291 parts by weight of the non-crystalline polyester resin were slowly added while heating to 60 ° C. by an in-system oil bath apparatus, and dissolved while stirring. Next, 20 parts by weight of 10% ammonia water was added thereto, and 1500 parts by weight of deionized water was added thereto at a rate of 6.7 g / min while stirring using a metering pump. Emulsification was completed when the emulsification system was milky white and the stirring viscosity was reduced.

  Next, the resin particle dispersion is pumped up by a differential pressure based on centrifugal force, and the resin particles are dispersed in a 3 L separable flask equipped with a stirring blade that forms a wetting wall on the inner wall of the reaction tank, a reflux device, and a decompression device using a vacuum pump. The liquid was transferred, and the reaction vessel inner wall temperature was 58 ° C., and the reaction vessel internal pressure was 8 kPa [abs] under reduced pressure. When the reflux amount reached 650 parts by weight, this was taken as the end point, the internal pressure of the reaction vessel was set to normal pressure, and the mixture was cooled to room temperature while stirring. The particle size of the resin particles dispersed in the obtained resin particle dispersion (1) was measured using a laser diffraction / scattering particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.). The average particle size of the obtained emulsified resin particles was 162 nm.

-Preparation of resin particle dispersion (2)-
The same procedure as in the preparation of the resin particle dispersion (1) was performed except that 37.5 parts by weight of IPA and 13 parts by weight of 10% aqueous ammonia were used, and the end point of the decompression operation was changed to 622 parts by weight of reflux. A resin particle dispersion (2) having 201 nm resin particles was obtained.

-Preparation of resin particle dispersion (3)-
The same procedure as in the preparation of the resin particle dispersion (1) was performed except that 45 parts by weight of IPA and 15 parts by weight of 10% aqueous ammonia were used, and the end point of the decompression operation was changed to 632 parts by weight of reflux. A resin particle dispersion (3) having resin particles was obtained.

-Preparation of resin particle dispersion (4)-
The same procedure as in the preparation of the resin particle dispersion (1) was performed except that 67.5 parts by weight of IPA and 21 parts by weight of 10% aqueous ammonia were used, and the end point of the decompression operation was changed to 660 parts by weight. A resin particle dispersion (4) having 160 nm resin particles was obtained.

-Preparation of resin particle dispersion (5)-
The same procedure as in the preparation of the resin particle dispersion (1) was performed except that 82.5 parts by weight of IPA and 25 parts by weight of 10% aqueous ammonia were used, and the end point of the decompression operation was changed to 676 parts by weight of the reflux. A resin particle dispersion (5) having 183 nm resin particles was obtained.

-Preparation of resin particle dispersion (6)-
A resin particle dispersion (6) having resin particles with an average particle size of 133 nm was obtained by performing the same operation as in the preparation of the resin particle dispersion (1) except that the end point of the decompression operation was 1000 parts by weight of reflux.

-Preparation of resin particle dispersion (7)-
The same operation as in the preparation of the resin particle dispersion (1) was performed except that the end point of the decompression operation was changed to a reflux amount of 630 parts by weight to obtain a resin particle dispersion (7) having resin particles with an average particle size of 81 nm.

-Preparation of resin particle dispersion (8)-
The same operation as in the preparation of the resin particle dispersion (1) was carried out except that the end point of the depressurization operation was changed to 600 parts by weight to obtain a resin particle dispersion (8) having resin particles with an average particle size of 125 nm.

-Preparation of resin particle dispersion (9)-
The same procedure as in the preparation of the resin particle dispersion (1) was performed except that 30 parts by weight of IPA and 13 parts by weight of 10% aqueous ammonia were used, and the end point of the decompression operation was changed to 612 parts by weight. A resin particle dispersion (9) having resin particles was obtained.

-Preparation of resin particle dispersion (10)-
The same procedure as in the preparation of the resin particle dispersion (1) was performed except that 90 parts by weight of IPA and 26 parts by weight of 10% aqueous ammonia were used, and the end point of the decompression operation was changed to 686 parts by weight of reflux. A resin particle dispersion (10) having resin particles was obtained.

-Preparation of resin particle dispersion (11)-
A resin particle dispersion (11) having resin particles with an average particle size of 163 nm was obtained by performing the same operation as in the preparation of the resin particle dispersion (1) except that the end point of the decompression operation was 1200 parts by weight.

-Preparation of resin particle dispersion (12)-
A resin particle dispersion (12) having resin particles with an average particle size of 136 nm was obtained by performing the same operation as in the preparation of the resin particle dispersion (1) except that the end point of the decompression operation was changed to 590 parts by weight of the reflux amount.

-Preparation of resin particle dispersion (13)-
The same operation as in the preparation of the resin particle dispersion (1) was performed except that the end point of the depressurization operation was changed to a reflux amount of 540 parts by weight to obtain a resin particle dispersion (13) having resin particles with an average particle size of 152 nm.

-Preparation of magenta colorant dispersion-
C. I. Pigment Red 122: (manufactured by Clariant) 50 parts by weight ionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 5 parts by weight deionized water 195 parts by weight Dispersion was carried out for minutes to obtain a magenta colorant dispersion having a center particle size of 185 nm and a solid content of 20% by weight.

-Preparation of release agent dispersion-
Paraffin wax FNP92 (melting point 91 ° C., Nippon Seiwa Co., Ltd.) 50 parts by weight Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight Deionized water 195 parts by weight And then dispersed with a pressure discharge type gorin homogenizer to obtain a wax dispersion having a center diameter of 170 nm and a solid content of 20% by weight.

  Using the material prepared above, toner particles were produced by an aggregation coalescence method.

-Toner particle production example 1-
Resin Particle Dispersion (1) 1000 parts by weight Magenta colorant dispersion 60 parts by weight release agent dispersion 60 parts by weight The above was sufficiently mixed and dispersed in a round stainless steel flask using Ultra Turrax T50. Next, 0.41 part by weight of polyaluminum chloride (manufactured by Asada Chemical Co., Ltd.) was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 47 ° C. with stirring in an oil bath for heating. After maintaining at 47 ° C. for 60 minutes, 350 parts by weight of the resin particle dispersion (1) was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 90 ° C. while continuing to stir using a magnetic seal for 3 hours. Retained.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with deionized water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 L of deionized water at 40 ° C. and stirred and washed at 300 rpm for 15 minutes.

  This was further repeated 5 times. When the pH of the filtrate was 7.01, the electric conductivity was 9.8 μS / cm, and the surface tension was 71.1 Nm, No. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued at 40 ° C. for 12 hours to obtain toner particles 1.

  When the volume average particle diameter of the obtained toner particles 1 was measured, the volume average diameter D50 was 6.3 μm, the particle size distribution coefficient GSDv was 1.21, and the ratio of toner having a particle size distribution of 20 μm or more was 0.42%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 128.1.

-Toner particle production example 2-
Toner particles 2 were obtained in the same manner as in the toner particle production example 1 except that the resin particle dispersion (2) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 2 was measured, the volume average diameter D50 was 6.6 μm, the particle size distribution coefficient GSDv was 1.26, and the proportion of toner having a particle size distribution of 20 μm or more was 0.11%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 133.9.

-Toner particle production example 3-
Toner particles 3 were obtained in the same manner as in Toner Particle Production Example 1 except that the resin particle dispersion (3) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 3 was measured, the volume average diameter D50 was 5.8 μm, the particle size distribution coefficient GSDv was 1.22, and the proportion of toner having a particle size distribution of 20 μm or more was 0.79%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 130.3.

-Toner particle production example 4
Toner particles 4 were obtained in the same manner as in the toner particle production example 1 except that the resin particle dispersion (4) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 4 was measured, the volume average diameter D50 was 6.4 μm, the particle size distribution coefficient GSDv was 1.23, and the ratio of toner having a particle size of 20 μm or more was 0.06%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 131.5.

-Toner particle production example 5-
Toner particles 5 were obtained in the same manner as in Toner Particle Production Example 1 except that the resin particle dispersion (5) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 5 was measured, the volume average diameter D50 was 5.7 μm, the particle size distribution coefficient GSDv was 1.21, and the proportion of toner having a particle size distribution of 20 μm or more was 0.26%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 120.3.

-Toner particle production example 6
Toner particles 6 were obtained in the same manner as in Toner Particle Production Example 1 except that the resin particle dispersion (6) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 6 was measured, the volume average diameter D50 was 6.1 μm, the particle size distribution coefficient GSDv was 1.23, and the ratio of toner having a particle size distribution of 20 μm or more was 0.62%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 132.8.

-Toner particle production example 7-
Toner particles 7 were obtained in the same manner as in Toner Particle Production Example 1 except that the resin particle dispersion (7) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 7 was measured, the volume average diameter D50 was 6.4 μm, the particle size distribution coefficient GSDv was 1.20, and the proportion of toner having a particle size distribution of 20 μm or more was 0.02%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 126.6.

-Toner particle production example 8-
Toner particles 8 were obtained in the same manner as in Toner Particle Production Example 1 except that the resin particle dispersion (8) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 8 is measured, the volume average diameter D50 is 6.1 μm, the particle size distribution coefficient GSDv is 1.21, and the ratio of toner having a particle size distribution of 20 μm or more is 0.39%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 130.7.

-Toner particle production example 9-
Toner particles 9 were obtained in the same manner as in Toner Particle Production Example 1 except that the resin particle dispersion (9) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 9 was measured, the volume average diameter D50 was 6.5 μm, the particle size distribution coefficient GSDv was 1.25, and the proportion of toner having a particle size distribution of 20 μm or more was 0.21%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 129.6.

-Toner particle production example 10-
Toner particles 10 were obtained in the same manner as in the toner particle production example 1 except that the resin particle dispersion (10) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 10 is measured, the volume average diameter D50 is 5.9 μm, the particle size distribution coefficient GSDv is 1.22, and the ratio of toner having a particle size of 20 μm or more is 0.07%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 128.1.

-Toner particle production example 11-
Toner particles 11 were obtained in the same manner as in Toner Particle Production Example 1 except that the resin particle dispersion (11) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 11 was measured, the volume average diameter D50 was 6.3 μm, the particle size distribution coefficient GSDv was 1.22, and the proportion of toner having a particle size distribution of 20 μm or more was 0.15%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 129.1.

-Toner particle production example 12-
Toner particles 12 were obtained in the same manner as in Toner Particle Production Example 1 except that the resin particle dispersion (12) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 12 was measured, the volume average diameter D50 was 6.2 μm, the particle size distribution coefficient GSDv was 1.21, and the proportion of toner having a particle size distribution of 20 μm or more was 0.32%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 131.1.

-Toner particle production example 13-
Toner particles 13 were obtained in the same manner as in Toner Particle Production Example 1 except that the resin particle dispersion (13) was used instead of the resin particle dispersion (1).

  When the volume average particle diameter of the obtained toner particles 13 was measured, the volume average diameter D50 was 6.4 μm, the particle size distribution coefficient GSDv was 1.24, and the proportion of toner having a particle size distribution of 20 μm or more was 0.53%. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 130.5.

<Manufacture of carrier 1>
1,000 parts by weight of Mn—Mg ferrite (average particle size 50 μm: manufactured by Powder Tech) was added to a kneader, and a compound having a dimethylsiloxane structure (manufactured by Toray Dow Corning Silicone: SR 2411, solid content 20%) 90 A solution obtained by dissolving 1 part by weight of a silane coupling agent (γ-dibutylaminopropyltrimethoxysilane: AX43-034 manufactured by Toray Dow Corning Silicone Co., Ltd .: AX43-034) in 500 parts by weight of toluene is added at room temperature for 20 minutes at 50 rpm. Then, the mixture was heated to 70 ° C. and dried under reduced pressure, and further heated to 150 ° C. and allowed to stand for 2 hours to be cured to form a resin having a dimethylsiloxane structure. Thereafter, it was cooled to obtain a coat carrier. Further, the obtained coated carrier was sieved with a mesh having an opening of 75 μm, and coarse powder was removed to obtain a carrier 1.

<Manufacture of carrier 2>
1,000 parts of Mn—Mg ferrite (average particle size 50 μm: manufactured by Powder Tech) were added to a kneader, and a styrene-methyl methacrylate copolymer (polymerization ratio 40:60, glass transition temperature 102 ° C., weight average molecular weight 72, (000: manufactured by Soken Chemical Co., Ltd.) 150 parts by weight of toluene in 700 parts by weight of toluene was added, mixed at room temperature for 20 minutes at 50 rpm, heated to 70 ° C., dried under reduced pressure, then taken out and coated Got a career. Furthermore, the obtained coated carrier was sieved with a mesh having an opening of 75 μm, and coarse powder was removed to obtain a carrier 2.

<Manufacture of carrier 3>
A carrier 3 was obtained in the same manner as in the production of the carrier 1 except that no silane coupling agent was added.

  The structure of the toner particles 1 produced in Toner Particle Production Example 1 was evaluated. Observation of the toner particle cross section by TEM shows that the crystalline polyester resin contains the amorphous polyester resin, the crystalline polyester resin, and the release agent, and the release agent in the transmission electron microscope image of the ruthenium-dyed toner cross section. And a part of the complex is exposed, each of which has a single domain, a cross-sectional area A of the structure, a cross-sectional area B of the release agent alone, and the crystallinity. Assuming that the cross-sectional area C of the polyester resin alone was 100 × A / (A + B + C) = 20.

  The alcohol content in the toner particles 1 using a gas chromatograph was 6.5 ppm. These results are shown in Table 1.

  The structure of the toner particles 2 to 13 produced in the toner particle production examples 2 to 13 and the amount of the alcohol component in the toner particles were evaluated in the same manner as the toner particles 1. The results are shown in Table 1.

<Manufacture and evaluation of developer>
To 98.5 parts by weight of the toner particles produced in Toner Particle Production Examples 1 to 13, 1.5 parts by weight of colloidal silica (manufactured by Nippon Aerosil Co., Ltd .: R972) was added, and 30 m / s, 5 The mixture was mixed for minutes to obtain externally added toners (toners 1 to 13). Each of the externally added toner and the carrier is placed in a V blender at a weight ratio of 5:95 and stirred for 20 minutes, and each of the obtained electrophotographic developers is manufactured by DocuCenter Color 400CP (Fuji Xerox Co., Ltd.). ) It was put in a developing machine of a modified machine and left in an environment of temperature 30 ° C. and humidity 85% for 24 hours.

Thereafter, 1,000 full-tone images were output so that the applied amount of toner was 1 g / m ² . After outputting 1,000 sheets, the sheet was allowed to stand for 12 hours under the above environmental conditions, and then a blank paper image was copied to evaluate fog derived from coarse powder (coarse powder) of the output image. The fog derived from the coarse powder was evaluated by counting the toner coarse powder on the paper surface with a loupe, 0 to 1 as ◎, 2 to 3 as ○, 4 to 8 as Δ, and 8 or more as ×. The paper used was A4 size of J paper manufactured by Fuji Xerox.

As for the fixability, a patch of 5 cm × 5 cm was prepared so that the applied toner amount was 10 g / m ² , and images were fixed every 5 ° C. from 200 ° C. to 220 ° C., and the temperature at which no high temperature offset occurred was confirmed. . Needless to say, the allowable range should be not generated at 200 ° C. and should not be generated at a higher temperature. In the evaluation results summarized in Table 2, those in which high temperature offset did not occur at 220 ° C. were described as “> 220 ° C.”, and evaluation at temperatures exceeding 220 ° C. was not performed. On the other hand, the case where the high temperature offset occurred at 200 ° C. was described as “≦ 200 ° C.” and the evaluation below 200 ° C. was not performed. The carrier used for image output was carrier 1. What did not generate | occur | produce at 200 degreeC was made into good. The results are shown in Table 2.

  The results of Examples and Comparative Examples are summarized in Table 2. As shown in Table 2, fogging after being left under high temperature and high humidity can be suppressed by using the developers of Examples 1 to 9.

  The electrostatic charge developing toner of the present invention is particularly useful for uses such as electrophotography and electrostatic recording.

1 is a schematic diagram illustrating a configuration example of an image forming apparatus used in the present embodiment. FIG. 3 is a schematic diagram illustrating a structure in toner particles of the present embodiment.

Explanation of symbols

  200 Image forming apparatus, 400 housing, 401a to 401d electrophotographic photosensitive member, 402a to 402d charging roll, 403 exposure apparatus, 404a to 404d developing apparatus, 405a to 405d toner cartridge, 409 intermediate transfer belt, 410a to 410d primary transfer roll 411 Tray (transfer medium tray), 413 Secondary transfer roll, 414 Fixing roll, 415a to 415d, 416 Cleaning blade, 500 Transfer medium.

Claims (3)

A toner comprising a crystalline polyester resin and a release agent,
There is a structure in which the crystalline polyester resin is in contact with the release agent on the cross-section of the toner particles, the cross-sectional area of the structure is A, the cross-sectional area of the release agent alone is B, and the crystalline polyester resin alone A toner in which 5 ≦ 100 × A / (A + B + C) ≦ 35 and the residual alcohol component in the toner particles is 0.01 ppm to 10 ppm, where C is the cross-sectional area;
A carrier coated with a resin having a siloxane structure;
A developer for developing an electrostatic charge, comprising:   The developer for electrostatic charge development according to claim 1, wherein the resin having a siloxane structure contains an aminosilane coupling agent. A neutralizer and an aqueous medium are added to a resin solution in which each of an amorphous polyester resin and a crystalline polyester resin is dissolved in an organic solvent to cause phase inversion, thereby forming O / W type resin emulsified particles, respectively. Further, toner particles are prepared by agglomerating and combining the non-crystalline polyester resin particle dispersion obtained by removing the organic solvent from both O / W type resin emulsified particle dispersions and the crystalline resin particle dispersion. Process,
Producing a carrier coated with a resin having a siloxane structure;
The method for producing a developer for developing an electrostatic charge according to claim 1, wherein