JP2008116568A - Toner for electrostatic charge development and method for manufacturing the same, developer for electrostatic charge development, cartridge, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge development excellent in charging performance (particularly suppression of reduction in charge amount after allowed to stand in a high temperature and high humidity environment) and fixability, a method for manufacturing the same, a developer for electrostatic charge development, a cartridge and an image forming apparatus. <P>SOLUTION: The toner includes a crystalline polyester resin and a release agent, wherein a structure in which the crystalline polyester resin is in contact with the release agent is present in a ruthenium dyed cross section of the toner, and the relationship of 40≤100×A/(A+B+C)≤70 is satisfied, when A is a cross-sectional area of the structure; B is a cross-sectional area of the release agent; and C is the cross-sectional area of the crystalline polyester resin, and an amount of a residual alcohol component in the toner is 0.1-80 ppm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic charge and a developer for developing an electrostatic charge that can be used in an electrophotographic apparatus utilizing an electrophotographic process such as a copying machine, a printer, and a facsimile, a method for producing the toner for developing an electrostatic charge, a cartridge, The present invention relates to an image forming apparatus.

  In image forming apparatuses such as copiers and printers, in order to reduce energy consumption during image output and standby, a technology for fixing toner with lower energy is desired, and for this purpose, an electronic that can be fixed at a lower temperature. There is a strong demand for photographic toner.

  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. The glass transition temperature is practically 50 ° C. as the lower limit of the glass transition temperature in the resin for toner because of the aggregation (blocking) of the toner or developer and the maintenance of the storage stability of the toner on the fixed image. Preferably, a glass transition temperature of about 60 ° C. is necessary.

  As a means for providing both blocking resistance, image storage stability up to 60 ° C., and low-temperature fixability, a technique using a crystalline resin as a binder constituting the toner can be considered. For the purpose of both blocking prevention and low-temperature fixing, a method using a crystalline resin as a toner is widely known (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.

  However, the disclosed technique, for example, the disclosed technique of Patent Document 1 applies a polymer having an alkyl group having 14 or more carbon atoms in the side chain to the toner, and has a melting point of 62 to 66 ° C. and a low temperature. Since the cohesion is strong, there is a problem in the reliability of powder and images. Further, the crystalline resins described in Patent Document 2 and Patent Document 3 have a problem that the fixing performance to paper is not sufficient.

  A polyester resin is an example of a crystalline resin that is expected to improve the fixability to paper. For example, Patent Document 2 discloses a technique for using a crystalline polyester resin in a toner. This is a technique in which an amorphous polyester resin having a glass transition temperature of 40 ° C. or higher and a crystalline polyester resin having a melting point of 130 to 200 ° C. are mixed and used. However, this technique has a problem that although it has blocking resistance and excellent fine pulverization property, the crystalline polyester resin has a high melting point, so that the low-temperature fixability cannot be achieved.

  In order to solve the above problem, a technique (for example, Patent Document 4) using a toner in which a crystalline resin having a melting point of 110 ° C. or less and a non-crystalline resin is mixed has been proposed. However, when the amorphous resin is mixed with the crystalline resin, the melting point of the toner is lowered, which causes practical problems such as occurrence of toner blocking and deterioration of image storage stability. In addition, when the amount of the amorphous resin component is large, the characteristics of the amorphous resin component are largely reflected, so that it is difficult to lower the fixing temperature than the conventional one. For this reason, if a crystalline resin is used alone as a resin for toner, or if a non-crystalline resin is mixed, it is difficult to put it into practical use.

  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. Examples of the technique using the crystalline polyester resin include the techniques described in Patent Documents 5, 6, 7, and the like. In these techniques, the crystalline polyester resin is a resin using alkylene glycol or alicyclic alcohol having a small number of carbon atoms with respect to the carboxylic acid component of terephthalic acid. Although these polyester resins are described as crystalline polyester resins in the above document, they are substantially partially crystalline polyester resins, so the viscosity change with respect to the temperature of the toner (resin) is not steep, and the blocking property / Although there is no problem in image storability, low temperature fixing could not be realized in heat roll fixing.

  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. There is a problem that the peeling stability in oilless fixing is unstable. Further, when the crystalline resin is used alone, although the low temperature fixing, the heat storage property of the toner and the document storage property are improved, the strength of the fixed image is low, and the image defect is easily caused by scratching. There was a problem. Although these toners certainly improve the low-temperature fixability and toner storage stability to some extent, the fixability changes greatly depending on the process speed of copying and printers. there were.

  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.

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

  However, the shape of the polymer particles obtained by the phase inversion emulsification method described in Patent Document 9 is spherical, the particle diameter is as small as nanometer order, and the surface is smooth. If the solvent is not sufficiently removed, the solvent remains relatively large as it is, which may be disadvantageous in terms of odor and total VOC (volatile organic compound). Such polymer particles are used as they are as electrophotographic toners. It is difficult.

  As a solution to this problem, for example, as in Patent Document 10 (phase-inversion emulsification using an inorganic dispersant), a technique has been proposed in which a specific inorganic salt is added to an aqueous medium to obtain shape controllability. With this method, shape controllability can be obtained, but it is difficult to obtain toner melt fluidity for obtaining fixability in a high-speed process.

  In general, in a toner containing a crystalline substance, although compatibility occurs in the toner manufacturing process, crystal growth proceeds from the viewpoint of thermodynamic stability, and the compatibility state is relaxed. For this reason, among the fixing characteristics, in particular, the bending resistance of the fixed image may deteriorate.

  The present invention is an electrostatic charge developing toner excellent in charging performance (especially, suppression of decrease in charge amount after standing in a high temperature and high humidity environment) and excellent in fixability, a method for producing the same, an electrostatic charge developing developer, It is an object to provide a cartridge and an image forming apparatus.

  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 polyester resin is in contact with the release agent is present on the cross section of the ruthenium-dyed toner. When the area is A, the sectional area of the release agent alone is B, and the sectional area of the crystalline polyester resin alone is C, 40 ≦ 100 × A / (A + B + C) ≦ 70 and residual alcohol in the toner It is an electrostatic charge developing toner having a component of 0.1 ppm to 80 ppm.

  (2) A neutralizer and an aqueous medium are added to a resin solution in which an amorphous polyester resin and a crystalline polyester resin are dissolved in an organic solvent to cause phase inversion. The electrostatic charge developing toner according to (1) above, wherein W-type resin emulsified particles are formed and the resin particle dispersion obtained by removing the organic solvent from both resin emulsified particle dispersions is aggregated and united. Is a method for producing an electrostatic charge developing toner.

  (3) A toner including a crystalline polyester resin and a release agent, wherein a structure in which the crystalline polyester resin is in contact with the release agent is present on the cross section of the ruthenium-dyed toner. When the area is A, the sectional area of the release agent alone is B, and the sectional area of the crystalline polyester resin alone is C, 40 ≦ 100 × A / (A + B + C) ≦ 70 and residual alcohol in the toner An electrostatic charge developing developer comprising a toner having a component of 0.1 ppm to 80 ppm and a carrier containing a resin having a polysiloxane structure.

  (4) A cartridge that includes a toner storage unit that stores the replenishment toner, and the replenishment toner is the electrostatic charge developing toner described in (1) above.

  (5) A latent image forming unit that forms a latent image on the latent image holding member, a developing unit that develops the latent image using electrostatic charge developing toner, and a transfer of the developed toner image onto the transfer target. And a fixing unit for fixing the toner image on the transfer object, wherein the electrostatic charge developing toner is the electrostatic charge developing toner described in (1) above. An image forming apparatus.

  The present invention specifies the amount of residual alcohol component of resin particles produced by a phase inversion emulsification method and the like, and constitutes a structure of a crystalline polyester resin and a release agent in the toner, so that a high temperature and high humidity can be obtained. This suppresses a decrease in charge amount under the environment.

  According to the first aspect of the present invention, the residual alcohol component amount of the resin particles produced by the phase inversion emulsification method or the like is specified, and the structure of the crystalline polyester resin and the release agent is in contact with the toner The problem is solved by configuring the body and setting the cross-sectional area ratio to a certain degree. 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.

  More specifically, in a toner having an aggregation step, the smaller the particle size distribution of the aggregated particles, the narrower the particle size distribution of the aggregated particles. By mixing with a solvent containing an alcohol component, the solubility of the mixed solvent in the resin decreases. For this reason, phase inversion can be promptly generated during phase inversion emulsification, and the particle size distribution of the resulting resin particles can be narrowed.

  On the other hand, the alcohol component tends to remain in the resin after phase inversion, and is difficult to remove, particularly due to hydrogen bonds with ester groups in the polyester, and the alcohol component leaks developer charge, particularly in a high temperature and high humidity environment. Therefore, if left unattended, the amount of charge is reduced, and after being left unattended, toner charge cannot be maintained when several sheets are output, and so-called fogging occurs in which toner adheres to the non-image area.

  The alcohol component on the toner surface can be removed by drying or the like, but the alcohol component oozes out from the inside due to its small molecule. Therefore, the hydrophobic part of the alcohol component is retained in the release agent component having a higher hydrophobicity than the resin, and a structure that covers with the crystalline polyester is configured to suppress the exudation of the alcohol component from the inside. And fogging after being left under high temperature and high humidity can be suppressed.

  In the invention according to claim 1, by setting the concentration of the alcohol component remaining in the interior to at least a predetermined amount or less, the extent of the alcohol exudation from the interior can be reduced. Furthermore, by forming the structure in which the crystalline polyester resin and the release agent are in contact with each other, the formation of the crystalline structure of the crystalline polyester resin can be suppressed, and the leakage of the residual alcohol component can be suppressed. Therefore, stable charging characteristics can be maintained, and as a result, fogging after being left under high temperature and high humidity can be suppressed.

  According to the invention of claim 2, the toner having the toner cross-sectional characteristics of claim 1 described above can be manufactured, whereby the structure in which the crystalline polyester resin and the release agent are in contact with each other has a crystal structure. The formation of the crystalline structure of the conductive polyester resin can be suppressed, and the bleeding of the alcohol component from the inside of the toner can be suppressed. Therefore, it is possible to suppress the occurrence of fog due to a decrease in the charge amount after being left under high temperature and high humidity.

  According to the invention of claim 3, by using a carrier containing a resin having a polysiloxane structure, it becomes possible to reduce the modification of the carrier surface over time, and stable charging control over a long period of time can be achieved. It becomes possible. Here, the “denaturation” may include physical or chemical changes to the carrier surface, such as adhesion, dissolution, and peeling over time.

  Hereinafter, the electrostatic charge developing toner and the production method thereof, the electrostatic charge developing developer, the cartridge, and the image forming apparatus of the present invention will be described in detail.

[Toner for electrostatic charge development]
The electrostatic charge developing toner of the present embodiment (hereinafter also referred to as “toner”) is a toner containing a crystalline polyester resin and a release agent, and the crystalline polyester resin is present on the cross section of the ruthenium-dyed toner. There is a structure in contact with the release agent, where A is the cross-sectional area of the structure, B is the cross-sectional area of the release agent alone, and C is the cross-sectional area of the crystalline polyester resin alone. XA / (A + B + C) ≦ 70 and the residual alcohol component in the toner is 0.1 ppm to 80 ppm. Here, the “structure” refers to a structure 100 having a structure in which the crystalline polyester resin 12 is in contact with or embedded in 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). A clear endothermic peak is a peak in which the DSC curve returns from the previous baseline and then returns to the baseline as described in JIS K 7121-1987 “Method for measuring plastic transition temperature”. 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 in the side chain is more preferable. A polyester having an alkyl group having 6 or more carbon atoms can be obtained by using a monomer having an alkyl group having 6 or more carbon atoms in the polyvalent carboxylic acid or polyhydric alcohol, for example, using dodecenyl succinic acid or the like. However, it is not limited to this.

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

  Examples of the polyvalent carboxylic acids used in the production of the polyester resin used in the present embodiment include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and diphenic acid. Aromatic dicarboxylic acids, p-oxybenzoic acids, aromatic oxycarboxylic acids such as p- (hydroxyethoxy) benzoic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid Aliphatic dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, trimer acid, hydrogenated dimer acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, etc. Unsaturated aliphatic and alicyclic The dicarboxylic acids and the like, also 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 weight based on 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 is lower than 50 ° C., the storage stability of the toner and the storage stability of the toner image after fixing may become a problem. On the other hand, if the melting point is higher than 120 ° C., sufficient low-temperature fixing cannot be obtained as compared with the conventional toner. There is a case.

  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.

  The crystalline resin may show a plurality of melting peaks. In 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 of the present invention. 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 point of the non-crystalline polyester resin described later can be similarly measured.

  The crystalline polyester resin used in the toner of the present embodiment has a weight average molecular weight (Mw) of 10,000, for example, by molecular weight measurement by a gel permeation chromatography (GPC) method in which tetrahydrofuran (THF) is soluble. ˜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 and the release agent proceeds, and there is a possibility that plasticity is 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.

  In the toner of the present embodiment, 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 heat storage property of the toner is lowered, and when it exceeds 75 ° C., the image glossiness at the time of toner fixing is lowered.

  The acid value of the crystalline polyester resin (mg number of KOH required to neutralize 1 g of resin) is 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 and it becomes difficult to coat the surface of the release agent, and the crystalline resin particles are present in the toner independently or large. It may grow 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 is difficult to encapsulate the toner in the toner, and a stable structure cannot be constructed.

-Amorphous polyester resin-
The amorphous polyester resin is obtained by polycondensation of the above-described polyvalent carboxylic acids and polyhydric alcohols using the above catalyst.

  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), For example, by heating at 150 to 250 ° C., low-molecular compounds produced as a by-product are continuously removed from the reaction system, and when a predetermined acid value is reached, the reaction is stopped, cooled, and the desired reactant is removed. It can be manufactured by acquiring.

  The glass transition temperature of the amorphous polyester resin used in the present embodiment is required to be 50 ° C. or higher when calculated in accordance with ASTM D3418-8, and more preferably 55 ° C. or higher. 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 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 point 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 point exceeds 90 ° C., the fixing property is hindered. Further, since it is necessary to heat the fixing roll to a high temperature, the material of the fixing roll and the material of the base material to be copied are limited.

  The non-crystalline polyester resin used in the toner of the present embodiment has a molecular weight measurement by a gel permeation chromatography (GPC) method that is soluble in tetrahydrofuran (THF), and has a weight average molecular weight (Mw) of 20, for example. 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 is controlled to, for example, 10 to 15 mgKOH / g. When the acid value is less than 10 mgKOH / g, there is a problem that fogging is likely to occur because a difference in charge amount between toner particles due to stirring tends to occur. In addition, when the acid value exceeds 15 mgKOH / g, there is a problem that fogging after standing may easily occur because the increase in charge amount by stirring after standing is slow. 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 of the present embodiment, the weight ratio of the crystalline polyester resin to the amorphous polyester 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, when the proportion of the non-crystalline polyester resin exceeds 95%, the sharp melt property derived from the crystalline polyester resin cannot be obtained, and plasticity may simply occur, while ensuring good low-temperature fixability. Further, toner blocking resistance and image storage stability cannot be maintained.

  The resin particle dispersion of crystalline polyester resin and non-crystalline polyester resin 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 a resin prepared by other methods, if the resin is soluble in a solvent that is oily and has a relatively low solubility in water, the resin can be dissolved in those solvents and an ionic surfactant or polymer in water. The resin particle dispersion can be prepared by dispersing the particles in water with a disperser such as a homogenizer together with the electrolyte, and then evaporating the solvent by heating or decompressing. 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 diameter 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 present embodiment include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene, silicones which show a softening point by heating; oleic amide, erucic acid amide, ricinoleic acid amide, stearin Fatty acid amides such as acid amides; 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, microcrystalline wax , Ester waxes of higher fatty acids and higher alcohols such as mineral oil such as Fischer-Tropsch wax, petroleum wax, stearyl stearate and behenyl behenate; butyl stearate, propyl oleate, glyceryl monostearate Ester waxes of higher fatty acids such as Lido, distearic glyceride, pentaerythritol tetrabehenate and unit or polyhydric lower alcohols; diethylene glycol monostearate, dipropylene glycol distearate, distearic diglyceride, tetrastearic 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 among them, and 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. When the addition amount is less than 0.5% by weight, there is no effect of adding a release agent. When the addition amount exceeds 50% by weight, the chargeability is likely to be affected, or the toner is easily destroyed inside the developing device, and the release agent is released. In addition to the effect that the mold agent is spent on the carrier and the charge is likely to decrease, for example, when color toner is used, the oozing on the image surface during fixing tends to be insufficient, Since the release agent tends to stay in the image, transparency is deteriorated, which is not preferable.

  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 is a problem that the release agent particles are not included in the coalescing step and are dropped in the coalescing step. In particular, in the case of obtaining a color toner, if the release agent particles are large, the OHP permeability is lowered due to irregular reflection, and the color reproducibility is also 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. When the volume average particle size is less than 0.1 μm, it is not preferable because sufficient releasability cannot be imparted to the toner.

  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 invention is, for example, a known dispersion such as a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high pressure type dispersing machine such as a nanomizer, a microfluidizer, an optimizer, or a gorin. Any method and conditions may be used as long as the method can satisfy the particle size and content as described.

-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. The colorant used in the production method of the present invention is not particularly limited, and a known colorant can be used and can be appropriately selected according to the purpose. 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 in the colorant 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 colorant dispersion used in the toner of the present invention is known in the art, for example, media-type dispersers such as ball mills, sand mills, and attritors, and high-pressure dispersers such as nanomizers, microfluidizers, optimizers, and gorin. Any method and conditions may be used as long as the particle size and content as described can be satisfied using a dispersion method.

<Other ingredients>
Other components that can be used in the electrostatic charge developing toner of the present invention are not particularly limited and may be appropriately selected depending on the purpose. For example, known inorganic particles, organic particles, charge control agents, release agents, and the like are known. Various additives etc. are mentioned.

  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 present embodiment includes a crystalline polyester resin and a release agent, and the 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.

  As a result, the structure 100 in which the crystalline polyester resin 12 is in contact with the release agent 10 via the amorphous polyester resin 14, the release agent 10 alone, and the crystalline polyester resin 12 alone on the toner cross section. Existence is confirmed. The toner according to the present embodiment has a cross-sectional structure of 40 ≦ 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 polyester resin alone is C. 100 × A / (A + B + C) ≦ 70. In addition, as a specific method of setting 100 × A / (A + B + C) to 40 to 70, 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 create 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.

  In the present embodiment, when the structure is less than 40%, the exposure of the crystalline resin or the compatibility with the amorphous resin proceeds, which may induce plasticity, resulting in a decrease in charge during storage of the toner. In particular, fogging after standing under high temperature and high humidity tends to occur. Moreover, when the structure exceeds 70%, plasticity due to compatibility with the amorphous resin can be suppressed, but phase dissolution and mixing with the release agent occur, and the release agent viscosity increases. Deteriorates the peelability during oilless fixing.

<Toner characteristics>
In the toner of the present embodiment, it is preferable that the residual alcohol component is present in an amount of 0.1 ppm to 80 ppm with respect to the total amount of toner. If the residual alcohol component exceeds 80 ppm, it is difficult to control the alcohol component in the structure. Further, when the residual alcohol component is removed to less than 0.1 ppm, there is no problem in charging characteristics, but there may be a problem that the production equipment is enlarged or the processing time is increased.

  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. Image quality is 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 average particle size 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 less than 0.95, toner chargeability may be reduced, toner scattering, fogging, and the like may occur, leading to image defects.

In the present embodiment, the particle size of the toner particles and the value of the volume average particle size distribution index GSDv 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. The cumulative distribution is drawn, the particle size that becomes 16% cumulative is the volume average particle size D16v, the particle size that becomes 50% cumulative, the volume average particle size D50v, and the particle size that becomes 84% cumulative is the volume average particle size. It is defined as D84v. At this time, the volume average particle size distribution index (GSDv) is defined as (D84v / D16v) ^0.5 . The volume average particle size distribution index (GSDv) can be calculated using this relational expression.

  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 the summer (high temperature and high humidity) of the toner of the present invention to the charge amount in the winter (low temperature and low humidity) is preferably 0.5 to 1.5, preferably 0.7 to 1.3. Is more preferable. 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 of the present embodiment, the maximum endothermic value obtained by suggestive thermal analysis is preferably 70 to 120 ° C. from the viewpoint of fixability and image glossiness, more preferably 70 to 90 ° C. Preferably it is 90-85 degreeC.

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

[Toner Production Method]
Next, a method for producing the toner of the present invention will be described.

  The toner particles of the present invention are obtained 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, phase-inverting, and then adding an O / W type resin. It is obtained by forming 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 present invention, one or more kinds of crystalline resins and one or more kinds of non-crystalline polyester resins are heated at a temperature not lower than the melting point of the resin or the glass transition temperature, and not higher than the boiling point of the organic solvent used. After heating and dissolving to make a uniform solution, a basic aqueous solution is added as a neutralizing agent, and then the phase is changed by maintaining stirring at pH 7 to 9 while adding pure water to give a stirring shear, and O / of the resin. A W-type emulsion (emulsion) is obtained. Next, the obtained emulsion is distilled under reduced pressure to remove the solvent and obtain a resin particle emulsion.

  In the operation of removing the organic solvent in preparing the resin particle dispersion in the emulsification step of the present invention, the inner wall temperature of the reaction vessel 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 invention, the internal pressure of the reaction tank is preferably 5 to 50 kPa [abs] under reduced pressure. When the internal pressure of the reaction tank is less than 5 kPa, water evaporation increases and the organic solvent may be lost under the preferential evaporation condition, which is disadvantageous in terms of production such as the amount of waste water and processing time. In addition, 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 becomes difficult to remove the organic solvent.

  In the operation of removing the organic solvent in the emulsification step of the present invention, 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 invention, it is preferable to distill until the remaining amount of the alcohol component in the resin particle dispersion becomes 20 ppm to 900 ppm. When the alcohol component is less than 20 ppm, it becomes difficult to suppress foaming by stirring in a reaction tank for forming a preliminary aggregate during toner production and particle formation of the aggregate. This is because it is impossible to build. On the other hand, if the alcohol component exceeds 900 ppm, the ionized stability of the aqueous dispersion particles tends to be lost in the formation of aggregate particles during the production of the toner, and the particle size distribution may be deteriorated. May occur. By removing the solvent so that the residual amount of the alcohol component in the resin particle dispersion is about 20 ppm to 900 ppm, the residual alcohol component in the obtained toner can be generally controlled to 0.1 ppm to 80 ppm. Become.

  In the emulsification step of the present invention, the pH after neutralization with a basic aqueous solution is 7 to 9, preferably pH 8. Examples of the basic aqueous solution include ammonium aqueous solution, sodium hydroxide, potassium hydroxide and the like. Alkali metal hydroxides may also 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 cause deterioration in 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.

  The dispersion medium in the dispersion is preferably water.

  In the present embodiment, 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.

  When the resin particle is a crystalline polyester or an amorphous polyester resin, it has a self-water dispersibility containing a functional group that can become an anionic type by neutralization, and a part or all of the functional group that can become hydrophilic is a base. A stable aqueous dispersion can be formed under the action of an aqueous medium neutralized with. In the crystalline polyester and the non-crystalline polyester resin, the functional group that can become a hydrophilic group by neutralization is an acidic group such as a carboxyl group or a sulfone group, and examples of the neutralizing agent include sodium hydroxide, potassium hydroxide, Examples thereof include inorganic bases such as lithium hydroxide, calcium hydroxide, sodium carbonate and ammonia, and organic bases such as diethylamine, triethylamine and isopropylamine.

  When a polyester resin that does not disperse in water, that is, does not have self-water dispersibility, is used as a binder resin, the resin solution and / or an aqueous medium mixed with the resin solution as described later will be ionic. Disperse with polymer electrolytes such as surfactants, polymer acids, polymer bases, etc., heat above melting point, and process with a homogenizer or pressure discharge type disperser that can apply a strong shearing force. Of particles. 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 is dispersed, and the resin particles, An aggregating step for forming an aggregated particle dispersion of the colorant particles and the release agent particles, and a fusing and coalescing step for fusing and coalescing by heating to a temperature above the glass transition point of the resin particles. It has a manufacturing method. Here, the resin particle dispersion refers to a mixture of both a crystalline polyester resin particle dispersion and an amorphous polyester resin particle dispersion, and the release agent dispersion refers to a crystalline polyester resin particle dispersion and an amorphous resin. At the same time as the conductive polyester resin particle dispersion, they are mixed in a mixing step, and toner particles are produced through the above-described aggregation step and fusion / unification step.

  Specifically, a resin particle dispersion containing an ionic surfactant is generally prepared by an emulsion polymerization method or the like, and a colorant particle dispersion and a 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. , Washed and dried to obtain toner particles.

  In the above release agent dispersion, the release agent is dispersed, for example, as particles having a volume average particle size in the range of 150 to 1500 nm in the toner for electrostatic charge development and contained in the range of 5 to 25% by weight. Thus, the peelability of the fixed image in the oilless 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 of 1 μm or less can be prepared.

  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 is slow, the heating time is lengthened, and the aggregates increase, which is not preferable.

  In the colorant dispersion, the colorant is dispersed in the electrostatic charge developing toner as particles having a volume average particle diameter in the range of 100 to 330 nm, and is contained in the range of 4 to 15% by weight. In addition to color developability, OHP permeability is 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. A high-pressure opposed collision type disperser or the like is preferably used.

  In the toner production method of the present invention, a surfactant 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 is used. For example, it is possible to use anionic surfactants such as sulfate ester type, sulfonate type, phosphate ester type and soap type, and cationic surfactants such as amine salt type and quaternary ammonium salt type. it can. 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 in suppressing the liberation of the colorant added to the aggregated particles and improving the dependency of the chargeable colorant.

  Further, a desired toner can be obtained through a washing step, a solid-liquid separation step, and a drying step that are optionally performed after the completion of the fusion / unification. In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged 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.

  In addition, for the toner, inorganic particles and resin particles can be used for the purpose of securing the charge amount and fluidity. Specific examples of the inorganic particles include all particles that are usually used as external additives on the toner surface, such as silica, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide. As the resin particles, for example, all particles usually used as an external additive on the surface of the toner, such as vinyl resin, polyester resin, and silicone resin can be used. These inorganic particles and resin particles can also be used as fluidity aids.

  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 propyl methyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, titanium coupling agents, etc. Can be mentioned.

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

[Developer]
Next, the developer of the present invention will be described.

  The toner of the present invention is used in a method called a two-component developer comprising a toner and a carrier, in addition to being used in a method of using a one-component developer having a charge imparting structure in a developing device.

  The carrier in the two-component developer is preferably a carrier coated with a resin using ferrite, iron powder or the like as a core agent. The core material (carrier core material) to be used is not particularly limited, and examples thereof include magnetic metals such as iron, steel, nickel and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. From the viewpoint of using a magnetic carrier, a magnetic carrier is desirable. The average particle diameter of the carrier core material is preferably 3 to 10 times the average particle diameter of the toner.

  Examples of the coating resin include an acrylic resin, a styrene resin, an urea resin, an amino resin containing urethane, melamine, guanamine, aniline, an amide resin, a urethane resin, and a resin having a siloxane structure. Among them, a resin having a polysiloxane bond has high water repellency, and in addition to being hard to lower the charge amount in a high temperature and high humidity environment, it also has strong alcohol resistance, so it suppresses the decrease in charge amount due to leaving the toner of the present application. Can do. Examples of the resin having a polysiloxane bond include polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, or a mixture thereof.

  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. Spraying 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 flowing air, and a kneader for mixing the carrier core material and the coating layer forming solution 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.

  The amount of the resin film formed by the above method is used by coating the carrier core material in an amount of 0.5 to 10% by weight, for example. The mixing ratio (weight ratio) between the toner and the carrier is in the range of toner: carrier = 1: 100 to 30: 100, and more preferably in the range of 3: 100 to 20: 100.

[Image forming apparatus]
Next, the image forming apparatus of the present embodiment will be described.

  The image forming method of the present invention comprises a step of uniformly charging the surface of an electrostatic latent image holding member (photosensitive member) by a charging means, and an optical image corresponding to image information on the surface of the charged electrostatic latent image holding member. Forming an electrostatic latent image on the electrostatic latent image holding member by exposure means for irradiating the electrostatic latent image, and developing the electrostatic latent image on the latent charge image holding member with an electrostatic photographic developer containing toner. Forming a toner image; transferring the toner image; and fixing the toner image. Each process itself is a general process, and is described in, for example, Japanese Patent Laid-Open Nos. 56-40868 and 49-91231. The image forming method of the present invention can be carried out using a known image forming apparatus such as a copying machine or a facsimile machine.

  The charging method is not particularly limited, and any of a known corotron, non-contact charging method using scorotron, or contact charging method may be used, but a contact charging method that generates less ozone is preferable.

  The formation of the electrostatic latent image is a step of forming an electrostatic latent image by exposing the surface to an electrostatic latent image holding member whose surface is uniformly charged by an exposure unit such as a laser optical system or an LED array. The exposure method is not particularly limited.

  In the transfer, the toner image is transferred onto the transfer target. Examples of the transfer target include transfer paper, an intermediate drum used for color image creation, and an intermediate transfer belt.

  In the fixing, a toner image transferred onto a transfer paper or the like is fixed on a fixing base material such as paper by heating from the fixing member, and the fixing base material such as paper is passed between two fixing members. In the meantime, the toner image on the fixing substrate is heated and melted to be fixed. The fixing member is in the form of a roll or a belt, and a heating device is attached to at least one of them. As the fixing member, a roll or a belt is used as it is, or its surface is coated with a resin.

  The fixing roll is made by coating the surface of the roll core material with silicone rubber, viton rubber or the like.

  For the fixing belt, polyamide, polyimide, polyethylene terephthalate, polybutylene terephthalate, or the like is used alone or in admixture of two or more. The roll and belt coating resins include, for example, styrenes such as styrene, parachlorostyrene, and α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, and 2-ethylhexyl acrylate. , Α-methylene fatty acid monocarboxylic acids such as methyl methacrylate, n-propyl methacrylate, lauryl methacrylate and 2-ethylhexyl methacrylate, nitrogen-containing acrylics such as dimethylaminoethyl methacrylate, vinyl nitriles such as acrylonitrile and methacrylonitrile Vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone and other vinyl ethers. Nyl ketones, olefins such as ethylene and propylene, homopolymers such as vinyl-based fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene and hexafluoroethylene, or copolymers composed of two or more monomers, methyl silicone, Examples thereof include silicones such as methylphenyl silicone, polyesters containing bisphenol and glycol, epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like. These resins may be used alone or in combination of two or more. Specific examples include homopolymers of fluorine-containing compounds such as polytetrafluoroethylene, vinylidene fluoride, and ethylene and / or copolymers thereof, homopolymers of unsaturated hydrocarbons such as ethylene and propylene, and / or Alternatively, a copolymer thereof can be used.

  Paper, resin film, or the like is used as the transfer target for fixing the toner. As the fixing paper, a coated paper in which a part or all of the paper surface is coated with a resin can be used. The fixing resin film can also be a resin-coated film whose surface is partially or entirely coated with another type of resin. In addition, it prevents friction between paper and resin film and / or double feeding of the transfer target due to static electricity caused by friction, and the release agent elutes at the interface between the transfer target and the fixed image during fixing. Resin particles and inorganic particles can be added for the purpose of preventing deterioration of the adhesion of the fixed image.

  FIG. 1 is a schematic diagram illustrating a configuration example of an image forming apparatus for forming an image by the image forming method of the present embodiment. 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, and then discharged to the outside of the housing 400.

  The image forming method of the present embodiment 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 is formed on the surface of the latent image holding member. A developing step of developing the electrostatic latent image formed to form a toner image, a transfer step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a transfer to the surface of the transfer target And a fixing step for thermally fixing 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 the shower method, it is necessary to use a separate blade or the like.

  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.

  The toner used in the image forming apparatus according to the present embodiment may be replenished only with toner, and includes a toner storage unit that stores the supplied toner therein, and is attached to or detached from the developing unit of the image forming apparatus or in the vicinity thereof. It may be by exchanging possible cartridges.

  As the cartridge, any known cartridge such as polystyrene, acrylic resin, polystyrene-acrylic copolymer, ABS resin, polycarbonate resin, polypropylene resin, polyethylene resin, polyester resin, acrylonitrile resin, or PET resin may be used. In view of strength, workability, stability, etc., more preferably, polystyrene, acrylic resin, polystyrene-acrylic copolymer, ABS resin, and polycarbonate resin are used. Moreover, you may use structural materials, such as a well-known metal material, paper, and a nonwoven fabric.

  The shape of the cartridge may be any shape such as a cylindrical shape, a column shape, a box shape, a bottle shape, a composite shape of these shapes, and other shapes. The image forming apparatus can be arbitrarily selected from the viewpoints of the internal layout, replacement / mountability, and supply toner replenishment. The arrangement of the cartridges in the image forming apparatus can be arbitrarily selected from the viewpoints of the internal layout of the image forming apparatus, exchangeability / mountability, supplyability of replenishing toner, etc. Due to the high integration of the layout accompanying the downsizing of the image forming apparatus, the cartridge shape is suitable for the cylindrical shape, the columnar shape, or the combined shape of the cylindrical shape and the box shape. However, it is not limited to this.

  In the present embodiment, the cartridge may be a replenishment cartridge containing replenishment toner inside, or a cartridge containing replenishment toner and carrier inside. Further, for example, an exchange unit that further accommodates, for example, a photosensitive drum or a developing sleeve may be used. This replacement unit may include a so-called process cartridge which is preferably used in an image forming apparatus using a one-component developer.

[Preferred embodiment]
In the step of removing the organic solvent, the reaction vessel inner wall temperature is maintained at 45 to 65 ° C., and the reaction vessel internal pressure is distilled under reduced pressure of 5 to 50 kPa [abs], and the residual alcohol component of the resin particle dispersion is removed. This is a method for producing a toner for developing electrostatic charge, which is 20 ppm to 900 ppm.

  By controlling the reaction vessel inner wall temperature and reaction vessel internal pressure to appropriate values, it becomes possible to make the residual alcohol component of the resin particle dispersion liquid have an appropriate value, and to suppress the leakage of the residual alcohol component during toner preparation. Can do. Therefore, stable charging characteristics can be maintained even after being left in a high temperature and high humidity environment.

  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”) 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 solution 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 counter TA-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 volume particle size to be 16% cumulative as D16v, and the cumulative volume to be 50% cumulative The particle size is defined as D50v. Further, the cumulative volume particle size that is 84% cumulative is defined as D84v.

The volume average particle size in the present invention is the D50v, and the GSDv under the volume average particle size index was calculated by the following formula.
Formula: GSDv = {(D84v) / (D16v)} ^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 ion exchange 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 shape factor SF1-
The shape factor SF1 of the toner 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. For the measurement of the shape factor SF1, first, an optical microscope image of the toner spread on the slide glass was taken into an image analysis device through a video camera, and SF was calculated for 50 toners to obtain an average value.

-Method for measuring 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 peaks and endothermic amounts 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, the temperature was raised again from 0 ° C. to 150 ° C. at a rate of 10 ° C./minute as a second temperature raising step, and measurement was performed.

-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) was precisely weighed and extracted by adding 10 mL of carbon disulfide, and 1 μL 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 1.0, 2.0, 4.0, 6.0, 8.0, 10.0, 12.0, 15.0, 20.0 ppm, respectively. The isopropyl alcohol was quantified using the calibration curve data of isopropyl alcohol prepared in advance from the contained sample and prepared.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. The toner of the present invention can be obtained by the following method.

  That is, the following crystalline resin particle dispersion, amorphous 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. Next, 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 a desired toner is 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 (1)-
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.

  Thereafter, the temperature was gradually raised to 220 ° C. under reduced pressure, and the mixture was stirred for 30 minutes. When the mixture became viscous, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (1) was synthesized.

  The weight average molecular weight (Mw) of the obtained crystalline polyester resin (1) was 20,000 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Further, when the melting point (Tm) of this resin was measured by a differential scanning calorimeter (DSC) by the above-described measuring method, it had a clear peak and the peak top temperature was 75 ° C.

-Synthesis of crystalline polyester resin (2)-
In a heat-dried three-necked flask, 124 parts by weight of ethylene glycol was used instead of 120.0 parts by weight of 1,10-decanediol, and sodium dimethyl 5-sulfoisophthalate was changed to 2.0 parts by weight. A crystalline polyester resin (2) was synthesized under the same conditions as the synthesis of the crystalline polyester resin (1) except that the stirring was changed to 3 hours.

  Mw of the obtained crystalline polyester resin (2) was 11,000 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Moreover, when Tm of this crystalline polyester resin was measured by DSC by the above-mentioned measuring method, it had a clear peak and the peak top temperature was 64 ° C.

-Synthesis of crystalline polyester resin (3)-
Into a heat-dried three-necked flask, 144 parts by weight of ethylene glycol, 178 parts by weight of sebacic acid, 2 parts by weight of dimethyl sulfoxide, and 2 parts by weight of dibutyltin oxide as a catalyst were placed, The air was brought into an inert atmosphere with nitrogen gas, and stirring was performed at 120 ° C. for 3 hours by mechanical stirring. 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 200 ° C. for 3 hours.

  Thereafter, the temperature was gradually raised to 220 ° C. under reduced pressure, and the mixture was stirred for 30 minutes. When the mixture became viscous, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (3) was synthesized.

  Mw of the obtained crystalline polyester resin (3) was 9,800 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Moreover, when Tm of crystalline polyester resin (3) was measured by DSC by the above-mentioned measuring method, it had a clear peak and the peak top temperature was 62 degreeC.

-Synthesis of crystalline polyester resin (4)-
In a heat-dried three-necked flask, 90.0 parts by weight of 1,10-decanediol, 100.0 parts by weight of dimethyl sebacate, 15.0 parts by weight of sodium dimethyl 5-sulfoisophthalate, 4 parts by weight of dimethyl sulfoxide, Then, 0.02 part by weight of dibutyltin oxide was added as a catalyst, and then the air in the container was brought into an inert atmosphere with nitrogen gas by a depressurization operation, followed by stirring at 180 ° C. for 3 hours by mechanical stirring. 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.

  Thereafter, the temperature was gradually raised to 220 ° C. under reduced pressure, and the mixture was stirred for 30 minutes. When it became viscous, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (4) was synthesized.

  Mw of the obtained crystalline polyester resin (4) was 30,200 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Moreover, when Tm of this crystalline polyester resin was measured by DSC by the above-mentioned measuring method, it had a clear peak and the peak top temperature was 79 ° C.

-Synthesis of Amorphous Polyester Resin (1)-
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 (1) was obtained. The polyester resin had a glass transition temperature of 65 ° C. and Mw of 21,000.

-Synthesis of amorphous polyester resin (2)-
In a heat-dried three-necked flask,
Dimethyl terephthalate 87 parts by weight Dimethyl isophthalate 97 parts by weight Bisphenol A-ethylene oxide 2 mol adduct 158 parts by weight Ethylene glycol 110 parts by weight Tetrabutoxy titanate 0.07 parts by weight were charged and heated at 170-220 ° C. for 180 minutes for ester. An exchange 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 (2) was obtained. The polyester resin had a glass transition temperature of 55 ° C. and Mw of 22,000.

-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.

105 parts by weight of ethyl acetate and 105 parts by weight of IPA were added to a ₂ L flask equipped with an anchor blade for giving stirring power, N ₂ was supplied, and the air in the system was replaced with N ₂ . Next, 21 parts by weight of the crystalline polyester resin (1) and 279 parts by weight of the amorphous polyester resin (1) were slowly added while being heated to 60 ° C. by an in-system oil bath device, and dissolved while stirring. Next, 16 parts by weight of 10% aqueous ammonia was added thereto, and then 2000 parts by weight of ion-exchanged 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 vacuum pump pressure reducing device. 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 800 parts by weight, this was taken as the end point, and the reaction tank internal pressure 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 282 nm.

-Preparation of resin particle dispersion (2)-
A resin particle dispersion (2) was prepared in the same manner as in the preparation of the resin particle dispersion (1) except that the crystalline polyester resin (2) was used in place of the crystalline polyester resin (1). The average particle size of the resin particles in the obtained resin particle dispersion (2) was 86 nm.

-Preparation of resin particle dispersion (3)-
A resin particle dispersion (3) was prepared in the same manner as in the preparation of the resin particle dispersion (1) except that the crystalline polyester resin (3) was used in place of the crystalline polyester resin (1). The average particle size of the resin particles in the obtained resin particle dispersion (3) was 72 nm.

-Preparation of resin particle dispersion (4)-
A resin particle dispersion (4) was prepared in the same manner as the resin particle dispersion (1) except that the crystalline polyester resin (4) was used in place of the crystalline polyester resin (1). The average particle size of the resin particles in the obtained resin particle dispersion (4) was 365 nm.

-Preparation of resin particle dispersion (5)-
A resin particle dispersion (5) was prepared in the same manner as the resin particle dispersion (1) except that the amorphous polyester resin (2) was used instead of the amorphous polyester resin (1). The average particle size of the emulsified resin particles in the obtained resin particle dispersion (5) was 318 nm.

-Preparation of resin particle dispersion (6)-
Instead of 21 parts by weight of the crystalline polyester resin (1) and 279 parts by weight of the amorphous polyester resin (1), 9 parts by weight of the crystalline polyester resin (1) and 291 parts by weight of the amorphous polyester resin (2) were used. Except for the above, the same operation as in the preparation of the resin particle dispersion (1) was performed to obtain a resin particle dispersion (6) having resin particles with an average particle size of 82 nm.

-Preparation of resin particle dispersion (7)-
Instead of 21 parts by weight of the crystalline polyester resin (1) and 279 parts by weight of the amorphous polyester resin (1), 60 parts by weight of the crystalline polyester resin (1) and 240 parts by weight of the amorphous polyester resin (1) were used. Except for the above, the same operation as in the preparation of the resin particle dispersion (1) was performed to obtain a resin particle dispersion (7) having resin particles with an average particle size of 101 nm.

-Preparation of resin particle dispersion (8)-
Instead of 21 parts by weight of the crystalline polyester resin (1) and 279 parts by weight of the amorphous polyester resin (1), 114 parts by weight of the crystalline polyester resin (1) and 186 parts by weight of the amorphous polyester resin (1) were used. Except for the above, the same operation as in the preparation of the resin particle dispersion (1) was performed to obtain a resin particle emulsion (8) having resin particles with an average particle size of 108 nm.

-Preparation of resin particle dispersion (9)-
Instead of 21 parts by weight of the crystalline polyester resin (1) and 279 parts by weight of the amorphous polyester resin (1), 1320 parts by weight of the crystalline polyester resin (1) and 168 parts by weight of the amorphous polyester resin (1) were used. Except for the above, the same operation as in the preparation of the resin particle dispersion (1) was performed to obtain a resin particle dispersion (9) having resin particles with an average particle size of 96 nm.

-Preparation of resin particle dispersion (10)-
Resin except that the reaction vessel inner wall temperature was 58 ° C. and the reaction vessel internal pressure was 8 kPa [abs], and the reaction vessel inner wall temperature was 60 ° C. and the reaction vessel internal pressure was 55 kPa [abs]. The same operation as in the preparation of the particle dispersion (1) was performed to obtain a resin particle dispersion (10) having resin particles with an average particle size of 96 nm.

-Preparation of resin particle dispersion (11)-
Resin except that the reaction vessel inner wall temperature was 58 ° C. and the reaction vessel internal pressure was 8 kPa [abs], and the reaction vessel inner wall temperature was 58 ° C. and the reaction vessel internal pressure was 4 kPa [abs]. The same operation as the preparation of the particle dispersion (1) was performed to obtain a resin particle dispersion (11) having resin particles with an average particle size of 111 nm.

-Preparation of cyan colorant dispersion-
Cyan pigment (CI Pigment Blue 15: 3: manufactured by Dainichi Seika) 50 parts by weight ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by weight ion-exchanged water 195 parts by weight (IKA Ultra Tarrax) was dispersed for 10 minutes to obtain a cyan colorant dispersion having a center particle size of 168 nm and a solid content of 20% by weight.

-Preparation of yellow colorant dispersion-
Yellow pigment (CI Pigment Yellow 74: manufactured by Dainichi Seika) 50 parts by weight ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight ion-exchanged water 195 parts by weight The above mixture was dissolved and homogenizer (IKA Ultra) (Turrax) for 10 minutes to obtain a yellow colorant dispersion having a center particle size of 168 nm and a solid content of 20% by weight.

-Preparation of magenta colorant dispersion-
C. I. Pigment Red 122: (manufactured by Clariant) 50 parts by weight ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight ion-exchanged water 195 parts by weight The above components are mixed and dissolved, and then homogenizer (Ultra Turrax by IKA) for 10 minutes Dispersion gave a magenta colorant dispersion having a central particle size of 185 nm and a solid content of 20% by weight.

-Preparation of black colorant dispersion-
Carbon Black Legal 330: (Cabot Corporation) 50 parts by weight Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by weight ion-exchanged water 195 parts by weight The above components were mixed and dissolved, and then homogenizer (Ultra Turrax by IKA) was used. Dispersion for 10 minutes gave a black colorant dispersion having a central particle size of 240 nm and a solid content of 20% by weight.

-Preparation of release agent dispersion-
Paraffin wax FNP92 (melting point 91 ° C., manufactured by Nippon Seiwa Co., Ltd.) 50 parts by weight Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by weight Ion-exchanged water 195 parts by weight or more heated to 60 ° C., made by IKA After sufficiently dispersing with Ultra Turrax T50, it was 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 Cyan 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 Ultra Talux. 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, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more 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. 3 was obtained by Nutsche suction filtration. 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 is measured, the volume average diameter D50 is 6.5 μm and the particle size distribution coefficient GSDv is 1.25. 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 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 is measured, the volume average diameter D50 is 6.1 μm and the particle size distribution coefficient GSDv is 1.21. 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 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 is measured, the volume average diameter D50 is 6.1 μm and the particle size distribution coefficient GSDv is 1.21. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 129.3.

-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 5.8 μm, and the particle size distribution coefficient GSDv was 1.24. 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 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 is measured, the volume average diameter D50 is 6.7 μm and the particle size distribution coefficient GSDv is 1.31. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 132.5.

-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 is measured, the volume average diameter D50 is 5.8 μm, and the particle size distribution coefficient GSDv is 1.23. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 130.2.

-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 is measured, the volume average diameter D50 is 6.6 μm, and the particle size distribution coefficient GSDv is 1.25. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 126.1.

-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 6.9 μm and the particle size distribution coefficient GSDv is 1.26. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 122.2.

-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 is measured, the volume average diameter D50 is 7.2 μm and the particle size distribution coefficient GSDv is 1.28. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 120.5.

-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 6.4 μm and the particle size distribution coefficient GSDv is 1.29. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 133.3.

-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 is measured, the volume average diameter D50 is 5.4 μm and the particle size distribution coefficient GSDv is 1.29. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 134.2.

-Toner particle production example 12-
Toner particles 12 were obtained in the same manner as in Toner Particle Production Example 1 except that a magenta colorant dispersion was used instead of the cyan colorant dispersion.

  When the volume average particle diameter of the obtained toner particles 12 was measured, the volume average diameter D50 was 6.5 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 133.0.

-Toner particle production example 13-
Toner particles 13 were obtained in the same manner as in Toner Particle Production Example 1 except that a yellow colorant dispersion was used instead of the cyan colorant dispersion.

  When the volume average particle diameter of the obtained toner particles 13 is measured, the volume average diameter D50 is 6.6 μm and the particle size distribution coefficient GSDv is 1.25. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 135.5.

-Toner particle production example 14-
Toner particles 14 were obtained in the same manner as in Toner Particle Production Example 1 except that a black colorant dispersion was used instead of the cyan colorant dispersion.

  When the volume average particle diameter of the obtained toner particles 14 is measured, the volume average diameter D50 is 6.2 μm and the particle size distribution coefficient GSDv is 1.23. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 130.8.

-Toner particle production example 15-
In the preparation of the resin particle dispersion (1), 300 parts by weight of the crystalline polyester (1) and the non-crystalline polyester (1) are separately emulsified under the same conditions as the resin particle dispersion (1). Toner particles 15 were produced in the same manner as in Toner Particle Production Example 1 except that 70 parts by weight of crystalline polyester (1) and 970 parts by weight of amorphous polyester (1) were used instead of (1).

  When the volume average particle diameter of the obtained toner particles 15 is measured, the volume average diameter D50 is 6.5 μm, and the particle size distribution coefficient GSDv is 1.24. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 132.2.

-Creation of external toner-
To 100 parts of each toner particle, 1.5 parts of an external silica additive (manufactured by Nippon Aerosil Co., Ltd., R972) is added and mixed with a Henschel mixer at 3,000 rpm for 5 minutes. Obtained.

<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 prepared by dissolving parts by weight in 500 parts by weight of toluene was added, mixed at 50 rpm at room temperature, heated to 70 ° C., dried under reduced pressure, further heated to 150 ° C. and allowed to stand for 2 hours to cure. Thus, a resin having a dimethylsiloxane structure was formed. 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.) A solution obtained by dissolving 150 parts by weight 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, taken out, and coated carrier Got. Further, the obtained coated carrier was sieved with a mesh having an opening of 75 μm, and coarse powder was removed to obtain Carrier 2.

Example 1.
The structure of the toner produced in Toner Production Example 1 was evaluated. When the cross section of the toner is observed with a TEM, the crystalline polyester resin contains at least a non-crystalline polyester resin, a crystalline polyester resin, a release agent, and a colorant, and the crystalline polyester resin is in a transmission electron microscopic image of the ruthenium-dyed toner cross section. There is a composite coated with a release material, a part of the composite is exposed, and each domain is further present, and a cross-sectional area A of the structure, a cross-sectional area B of the release agent alone, When the cross-sectional area C of the crystalline polyester resin alone was 100 × A / (A + B + C) = 65.

  The alcohol content in the toner 1 using a gas chromatograph was 3.2 ppm. These results are shown in Tables 1 and 2.

Examples 2 to 14, Comparative Example 1
The structures of the toners produced in Toner Production Examples 2 to 15 and the alcohol content in these toners were evaluated. The results are shown in Tables 1 and 2.

<Manufacture and evaluation of developer>
Each externally added toner and carrier 1 or 2 are respectively 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 subjected to DocuCenter Color 400CP (Fuji Xerox ( The product was put into a developing machine of a modified machine, and a half-tone image was output so that 1,000 sheets and an applied amount of toner were 0.1 g / m ² in an environment of a temperature of 30 ° C. and a humidity of 85%. . After outputting 1,000 sheets, the sheet was allowed to stand for 12 hours under the above-mentioned environmental conditions. Thereafter, a blank paper image was copied, and the number of sheets where the fog of the output image was recovered was evaluated. Note that the criterion is the number of sheets in which the fog has disappeared, and if the number does not occur, the number is one. The allowable range is up to the 10th sheet. The paper used was A4 size of J paper manufactured by Fuji Xerox.

The fixability is such that a 5 cm × 5 cm patch is prepared so that the applied toner amount becomes 10 g / m ² for the developer whose fog has disappeared, and the image is fixed every 5 ° C. from 200 ° C. to 220 ° C. The temperature at which no 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 where 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.

  The results of Examples and Comparative Examples are summarized in Tables 1 and 2. As shown in Tables 1 and 2, by using the toner and developer of the example, the generation of fog and the offset at high temperature were suppressed due to the decrease in the charge amount after storage at high temperature and high humidity.

  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

  DESCRIPTION OF SYMBOLS 10 Mold release agent, 12 Crystalline polyester resin, 14 Amorphous polyester resin, 100 Structure, 200 Image forming apparatus, 400 Housing, 401a-401d Electrophotographic photoreceptor, 402a-402d Charging roll, 403 Exposure apparatus, 404a- 404d developing device, 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 (5)

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 dyed with ruthenium, the cross-sectional area of the structure is A, the cross-sectional area of the release agent alone is B, and the crystalline polyester Toner for electrostatic charge development, wherein 40 ≦ 100 × A / (A + B + C) ≦ 70 and the residual alcohol component in the toner is 0.1 ppm to 80 ppm, where C is the sectional area of the resin alone .   A neutralizing agent and an aqueous medium are added to a resin solution obtained by dissolving an amorphous polyester resin and a crystalline polyester resin in an organic solvent to cause phase inversion, and after adding an alkaline substance, each O / W resin The electrostatic charge developing toner according to claim 1, wherein emulsion particles are formed and the resin particle dispersion obtained by removing the organic solvent from both resin emulsion particle dispersions is aggregated and united. A method for producing a toner for developing electrostatic charge, characterized by comprising: 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 dyed with ruthenium, the cross-sectional area of the structure is A, the cross-sectional area of the release agent alone is B, and the crystalline polyester A toner in which 40 ≦ 100 × A / (A + B + C) ≦ 70 and the residual alcohol component in the toner is 0.1 ppm to 80 ppm, where C is the sectional area of the resin alone,
A carrier containing a resin having a polysiloxane structure;
A developer for electrostatic charge development, comprising: A toner container for storing toner for replenishment;
The cartridge according to claim 1, wherein the replenishing toner is the electrostatic charge developing toner according to claim 1. A latent image forming unit that forms a latent image on the latent image holding member, a developing unit that develops the latent image using toner for developing electrostatic charge, and a transfer unit that transfers the developed toner image onto the transfer target. And a fixing unit that fixes the toner image on the transfer target,
The image forming apparatus according to claim 1, wherein the electrostatic charge developing toner is the electrostatic charge developing toner according to claim 1.