JP2008203785A - Electrostatic charge developing toner and method for manufacturing the same, electrostatic charge developing developer and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge developing toner and a method for manufacturing the electrostatic charge developing toner excellent in blade cleaning property in an electrophotographic process by controlling the structure of a crystalline substance on the toner surface and controlling the frictional coefficient of the toner surface, and to provide an electrostatic charge developing developer and an image forming apparatus. <P>SOLUTION: The electrostatic charge developing toner contains a crystalline polyester resin 12 and a release agent 10, and characterized in that: the surface frictional coefficient μ of the toner ranges from 0.21 to 0.45; a toner cross section dyed with ruthenium shows the presence of a structure 100 where the crystalline polyester resin 12 is in contact with the release agent 10; the cross-sectional area (A) of the structure 100 and the cross-sectional area (B) of the release agent 10 in a single state satisfy 60≤100×A/(A+B)≤100; and the toner surface has a hydrophobicized metal oxide. <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 using an electrophotographic process such as a copying machine, a printer, and a facsimile, a method for producing the toner for developing an electrostatic charge, and image formation Relates to the device.

  In order to reduce the amount of energy used in copying machines and printers, a technique for fixing toner with lower energy is desired, and there is a strong demand for toner for electrophotography that can be fixed at a lower temperature.

  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. However, if the glass transition temperature is too low, powder aggregation (blocking) is likely to occur, and the storability of the toner on the fixed image is lowered, so practically 50 ° C. is the lower limit, preferably 60 ° C is required.

  This glass transition temperature is a design point of many resin for toner that is currently on the market, and it has been difficult to obtain a toner that can be fixed at a lower temperature than before by the method of lowering the glass transition temperature. For example, the use of a plasticizer can lower the fixing temperature, but there is a problem because the toner adheres to the photosensitive member when the toner is stored or the cleaner is fixed to the cleaning blade.

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

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

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

  On the other hand, in order to realize low-temperature fixability, it has been proposed to use a crystalline polyester resin alone for hot roll fixing as much as possible. However, when an amorphous resin is mixed with a crystalline resin, the melting point of the toner is lowered, toner blocking occurs, and image storage stability is deteriorated. 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 singly as a resin for toner, or if a non-crystalline resin is mixed, it is difficult to put it to 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.

  Techniques using crystalline polyester resins include those described in Patent Documents 5, 6, 7 and the like. In these techniques, the crystalline polyester resin has a carbon number of carboxylic acid components of terephthalic acid. It is a resin using a small amount of alkylene glycol or alicyclic alcohol. 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, Patent Document 8 discloses that a toner containing a crystalline polyester resin having a crosslinked structure as a main component is excellent in anti-blocking property and image storability and can realize low-temperature fixing. However, there is a problem that the peeling stability in oilless fixing may be unstable. Further, when the crystalline resin is used alone, the low-temperature fixing, the heat storage property of the toner and the document storage property are improved, but the strength of the fixed image is low, and an easy image defect occurs due to scratching or the like. There was a problem that there was a possibility. Although these toners certainly improve the low-temperature fixability and toner storage stability to some extent, the fixability changes greatly depending on the copying and printer process speeds, and even if they can be put into practical use, they may not be versatile. was there.

  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, the process can be simplified, and polymer particles having a uniform particle diameter can be obtained by a relatively simple operation, so that 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. However, the polymer particles obtained by this phase inversion emulsification method have a spherical shape, a particle size as small as nanometer order, and a smooth surface. If the solvent removal level is not sufficient, the solvent remains relatively large, which may be disadvantageous in terms of odor and total VOC. It is difficult to use such polymer particles as they are as electrophotographic toner. .

  As a means for solving the above-mentioned matters, as in Patent Document 10, a technique has been proposed in which a specific inorganic salt is added to an aqueous medium to obtain shape controllability.

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

  However, with the method described in Patent Document 10, shape controllability is surely 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, the stress generated in the toner is generated between the materials in a compatible state, and particles weaker to the shearing force may be generated.

  The present invention provides the structure of the crystalline substance inside and on the surface of the toner by providing the slurry cooling step in the slurry discharging step in the toner manufacturing process and cooling the slurry at a constant speed by contacting with the specific low-temperature fluid. Toner for controlling electrostatic charge, controlling the surface friction coefficient of the toner, and having excellent blade cleaning in the electrophotographic process, method for producing toner for developing electrostatic charge, and electrostatic charge developing Developer and image forming apparatus are obtained.

  The present invention has the following features.

  (1) A toner containing a crystalline polyester resin and a release agent, wherein the toner has a surface friction coefficient μ of 0.21 to 0.45, and the crystalline resin polyester resin is present on the ruthenium-dyed toner cross section. There is a structure in contact with the release agent, where A is the cross-sectional area of the structure, and B is the cross-sectional area of the release agent alone, 60 ≦ 100 × A / (A + B) ≦ 100, An electrostatic charge developing toner having a metal oxide hydrophobized on the surface of the toner.

  (2) The electrostatic charge developing toner according to the above (1), wherein a covering area ratio of the release agent by the crystalline resin in a transmission electron microscope is 40% to 70%.

  (3) At least non-crystalline polyester resin particles, crystalline polyester resin particles, release agent-dispersed particles, and colorant-dispersed particles are mixed and heteroaggregated using an aggregating agent, and the pH in the aggregating system is set to 6 to After the adjustment to 8.5, coalescence and fusion are performed at a temperature equal to or higher than the glass transition temperature of the amorphous resin, and then the slurry containing the coalesced toner particles is cooled in a discharging step to obtain an electrostatic charge developing toner. This is a method for producing an electrostatic charge developing toner to be produced.

  (4) An electrostatic charge developing developer comprising a carrier obtained by coating the surface of a core particle with a chemical nitrogen-containing resin and the toner described in (1) or (2) above.

  (5) a latent image forming means for forming a latent image on the latent image carrier, a developing means for developing the latent image using an electrostatic charge developing toner, and the developed toner image via an intermediate transfer member or A transfer unit that transfers the toner image on the transfer member without fixing, a fixing unit that fixes and fixes the toner image on the transfer member, and a cleaning unit that removes the toner remaining on the surface of the latent image carrier The electrostatic charge developing toner is the electrostatic charge developing toner according to (1) or (2), and has a hardness at a surface temperature of the cleaning blade in the cleaning unit. Is an image forming apparatus having an angle of 45 ° to 65 ° in accordance with the JIS K6253 hardness test.

  Of the constituent materials of the toner, the softest is usually a release agent, and the hardest is an external additive typified by a metal oxide. The toner is easily subjected to stress deformation by the blade during cleaning, so that the internal release agent tends to come out of the toner, while the external additive is easily embedded in the toner due to the stress. By embedding the external additive, the exposure of the release agent is accelerated, and as a result, the release agent adheres to the photoconductor and the cleaning property is deteriorated.

  According to the invention which concerns on Claim 1, the stress deformation | transformation with respect to a braid | blade is suppressed and the seepage of a mold release agent can be suppressed. Therefore, the cleaning property can be maintained.

  According to the second aspect of the present invention, since the bleeding of the release agent can be suppressed as compared with the conventional case, the cleaning property can be maintained.

  According to the third aspect of the present invention, the surface friction coefficient of the toner is controlled to some extent by cooling in the manufacturing process, and the release agent is coated with the crystalline polyester to suppress the deformation against the stress of the toner. The cleaning is maintained by suppressing the exudation to the stress of the agent to some extent.

  According to the invention of claim 4, it is possible to provide a carrier having high positive chargeability, and even with a toner having a small surface friction coefficient μ, it is difficult to cause a charge fluctuation due to the spent toner, and provides a stable image. can do.

  According to the invention of claim 5, since the cleaning property of the toner is high, the hardness of the cleaning grade can be lowered as compared with the conventional one. As a result, the friction with the latent image carrier such as the photosensitive member is also suppressed, and the blade As a result, the life of the camera can be extended and a stable image can be provided for a long time.

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

[Toner for electrostatic charge development]
The electrostatic charge developing toner (hereinafter also referred to as “toner”) of the present embodiment is a toner containing a crystalline polyester resin and a release agent, and the toner has a surface friction coefficient μ of 0.21 to 0.45. A structure in which the crystalline resin polyester resin is in contact with the release agent is present on the cross section of the toner dyed with ruthenium, and the cross sectional area of the structure is A, and the cross sectional area of the release agent alone is B. In this case, 60 ≦ 100 × A / (A + B) ≦ 100, and the surface of the toner has a hydrophobized metal oxide. This suppresses embedding of the external additive in the toner surface due to uneven composition of the toner surface, while controlling the amount of the release agent present alone in the toner and does not generate stress inside the toner. Thus, it is possible to obtain a toner having an effect on deformation that easily occurs.

  More specifically, the amount of the crystalline polyester resin and the release agent in the toner, phase-inversion emulsification from a solution in which the amorphous polyester resin and the crystalline polyester are simultaneously dissolved, and the resin mixed at the molecular level By aggregating the release agent particles, a similar crystalline polyester resin as a hydrophobic material and the release agent are more agglomerated as a structure inside the agglomerated particles, and after the coalescence, the crystalline polyester and the release agent are cooled. It is presumed that the growth can suppress the generation of stress inside the particle and the surface friction coefficient.

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

  As the crystalline polyester resin, specifically, an aliphatic crystalline polyester resin having an appropriate melting point and an alkyl group having 6 or more carbon atoms 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 such as p-oxybenzoic acid and p- (hydroxyethoxy) benzoic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane Aliphatic dicarboxylic acids such as dicarboxylic acids, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, trimer acid, hydrogenated dimer acid, cyclohexane dicarboxylic acid, cyclohexene dicarboxylic acid Unsaturated aliphatics such as acids Alicyclic dicarboxylic acids, etc., and can be used other trimellitic acid as a polycarboxylic acid, trimesic acid, and the like trivalent or higher polyvalent carboxylic acids such as pyromellitic acid.

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

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

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

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

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

  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. For the sample, an aluminum pan is used, an empty pan is set as a control, and 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 to 25, as measured by molecular weight measurement by gel permeation chromatography (GPC) method of tetrahydrofuran (THF) soluble content. 000, preferably 20,000 to 25,000. If the weight average molecular weight is less than 10,000, the compatibility with the amorphous resin or the release agent proceeds, and plasticity may be generated, and the cleaning property may be lowered. On the other hand, if it 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, the crystalline polyester resin preferably has a melting point (mp) measured according to ASTM D3418-8 of 50 to 120 ° C., more preferably 60 to 100 °. If the melting point is less than 50 ° C, the toner storage stability and the flaw-image storage stability after fixing may become a problem. On the other hand, if it exceeds 120 ° C, sufficient low-temperature fixing cannot be obtained compared to conventional toners. There is.

  The acid value of the crystalline polyester resin (mg number of KOH required to neutralize 1 g of resin) is controlled to 5 to 10 mg KOH / 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), Heat at 150 to 250 ° C. to continuously remove by-product low-molecular compounds out of the reaction system, stop the reaction when a predetermined acid value is reached, cool, and obtain the desired reactant Can be manufactured.

  The glass transition temperature of the amorphous polyester resin used in the 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 amorphous polyester resin used in the toner of the present invention has a weight average molecular weight (Mw) of 20,000 to 50,000 as measured by molecular weight measurement by gel permeation chromatography (GPC) method in which tetrahydrofuran (THF) is soluble. And preferably 25,000 to 50,000. If the weight average molecular weight is less than 25,000, the toner may be easily deformed by contact with the cleaning blade. In addition to exceeding 50,000, the fixability may be deteriorated because the release agent is less likely to appear on the image surface during fixing.

  The acid value of the amorphous polyester resin is controlled to 10 to 15 mgKOH / g. If the acid value is less than 10 mgKOH / g, it is difficult to control the amount of the surface release agent at the time of toner preparation. If the acid value exceeds 15 mgKOH / g, the composition between toner particles at the time of toner preparation. There is a problem that the difference becomes large. 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.

  The binder resin in the toner of the present embodiment is preferably used by simultaneously mixing a crystalline polyester resin and an amorphous polyester resin. Here, the crystalline polyester resin is used in the range of 5 to 50% of the components constituting the binder resin. When the ratio of the crystalline polyester resin exceeds 50%, 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, is reduced and scratched. It may present problems such as becoming easier. On the other hand, if the proportion of the crystalline polyester resin is less than 5%, the sharp melt property derived from the crystalline polyester resin cannot be obtained, and plasticity may simply occur, while ensuring good low-temperature fixability, The toner blocking resistance and image storage stability cannot be maintained.

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

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

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

-Release agent-
Specific examples of the release agent as the release agent used in the present embodiment include low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones that exhibit a softening point by heating; oleic acid amide, erucic acid amide, Fatty acid amides such as ricinoleic acid amide and stearic acid amide; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin Minerals and petroleum waxes such as wax, microcrystalline wax and Fischer-Tropsch wax, ester waxes of higher fatty acids and higher alcohols such as stearyl stearate and behenyl behenate; butyl stearate, propyl oleate, monos Ester waxes of higher fatty acids such as glyceryl acrylate, glyceryl distearate, pentaerythritol tetrabehenate and unit or polyhydric lower alcohols; diethylene glycol monostearate, dipropylene glycol distearate, distearic diglyceride, tetrastearic acid Examples include ester waxes composed of higher fatty acids such as triglycerides 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 30% by weight, more preferably in the range of 1 to 20% by weight, and still more preferably in the range of 5 to 15% by weight with respect to the total amount of the 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 30% by weight, the ratio of the structure to the crystalline resin does not fall within the scope of the present application. This is not preferable because the toner is likely to be destroyed, the release agent is spent on the carrier, and the charge tends to decrease.

  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 flowability of the toner is likely to be deteriorated. In addition, the said volume average particle diameter can be measured using the laser diffraction type particle size distribution measuring instrument etc. which were mentioned above, for example. If the volume average particle size is 0.1 μm or less, the above 100 × A / (A + B) may not be within the scope of the present application, which is not preferable.

  The dispersion medium in the release agent dispersion is preferably an aqueous medium, and water, pure water, or ion exchange water is used. A surfactant is used as the dispersant. Preparation of the wax dispersion used in the toner of the present 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 for dispersing the colorant 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. The range of is preferable.

  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 of the present embodiment includes at least an amorphous polyester resin, a crystalline polyester resin, a release agent, and a colorant, and a cross section of the ruthenium-dyed toner is observed with a transmission electron microscope, and an image obtained is obtained. To analyze.

  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. The toner was 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 transmission (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 particles may be included in one section.

  As a result, the structure 100 in which the crystalline resin polyester resin is in contact with the release agent, the release agent 10 alone, and the crystalline polyester resin 12 alone on the cross section of the toner via the amorphous polyester resin 14. The existence of is confirmed. The toner of the present embodiment has a cross-sectional structure of 60 ≦ 100 × A / (A + B) ≦ 100 when the cross-sectional area of the structure is A and the cross-sectional area of the release agent alone is B. If it is less than 60%, it means that there are many release agents alone, and there is a problem that the stress in the toner is large and therefore weak against deformation in the cleaning part or the like.

  Further, in the scanning microscope observation of the ruthenium staining, the perimeter length of the release agent in a total of 100 toner cross sections is obtained as D, and the length C of the release agent portion in contact with the crystalline resin at the structure forming portion is obtained. From these lengths, the coverage was calculated according to the following equation.

Formula (1): Coverage α = C / D (%)

<Toner characteristics>
The friction coefficient of the toner in this embodiment is measured by using a fully automatic friction wear analyzer manufactured by Kyowa Interface Science Co., Ltd., which is obtained by applying a load of 6 t / cm ² to a toner having a weight of 3 g to form a disk-shaped pellet having a diameter of 40 mm. To do. At this time, a point contact of a 3 mm stainless sphere is used as the contact.

  The dynamic friction coefficient of the toner in the present embodiment is 0.21 to 0.45, and preferably 0.21 to 0.40. This is considered to show the characteristics in a state where the external additive is substantially embedded on the toner surface. When the dynamic friction coefficient is less than 0.21, the frictional property of the toner is lowered, and the blurring occurs when an image is formed. Such defects occur. On the other hand, if the dynamic friction coefficient exceeds 0.48, the fluidity is lowered and the fine reproducibility of the image is lowered, which is not preferable.

  The toner of the present embodiment has a volume average particle diameter of preferably 3 to 12 μm, more preferably 3 to 9 μm, and more preferably 3 to 8 μm. Further, the number average particle diameter of the toner of the present exemplary embodiment is preferably 1 to 10 μm, and more preferably 2 to 8 μm. If the particle size is too small, not only the production becomes unstable, but the inclusion structure control is difficult, the chargeability becomes insufficient, the developability may be lowered, and if it is too large, the resolution of the image is lowered. To do.

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

  In the present exemplary embodiment, the toner particle size, the above-described volume average particle size distribution index GSDv, and number average particle size distribution index GSDp are measured and calculated as follows. First, with respect to the divided particle size range (channel), the toner particle size distribution measured using a Coulter Multisizer II (manufactured by Beckman-Coulter) is accumulated from the smaller diameter side with respect to the divided particle size range (channel). Draw a distribution and define the particle size to be 16% cumulative as the volume average particle size D16v and the number average particle size D16p. The particle size to be 50% cumulative is the volume average particle size D50v and the number average particle The diameter is defined as D50p. Similarly, particle diameters that are 84% cumulative are defined as volume average particle diameter D84v and number average particle diameter D84p. At this time, the volume average particle size distribution index (GSDv) is defined as D84v / D16v, and the number average particle size index (GSDp) is defined as D84p / D16p. (GSDv) and number average particle size index (GSDp) can be calculated.

  The shape factor SF1 of the toner of the present embodiment is preferably 110 ≦ SF1 ≦ 140 from the viewpoint of image formability. For the shape factor SF1, the average value of the shape factor (the square of the maximum length / projection area) is calculated by the following method, for example. That is, the optical microscope image of the toner spread on the slide glass is taken into a Luzex image analyzer through a video camera, and (maximum squared) × π × 100 / (projected area × 4) is calculated from 100 toners. The average value is obtained.

  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 gloss, more preferably 70 to 90 ° C., and even more preferably. Is 90-85 ° C.

  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 melting point is the maximum peak temperature.

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

  As a method for producing a small-diameter toner capable of controlling the shape having a uniform particle diameter, a technique for obtaining shape controllability by adding a specific inorganic salt to an aqueous medium has been proposed as disclosed in JP-A-2001-255698. However, it is difficult to obtain the toner melt fluidity for obtaining the fixability in the 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, particularly the bending resistance of the fixed image may be deteriorated. Therefore, in the present embodiment, the following emulsification process is performed in order to improve the compatibility between the crystalline polyester resin and the amorphous polyester resin.

-Emulsification process-
In the emulsification step of the present invention, at least one kind of crystalline resin or at least one kind of non-crystalline polyester resin is brought to a temperature equal to or higher than the melting point of the resin, the glass transition temperature, and the boiling point of the organic solvent used. After heating and dissolving to obtain a uniform solution, a basic aqueous solution is added thereto as a neutralizing agent, followed by phase inversion by applying stirring shear while maintaining pure pH 7-9 while adding pure water. A mold emulsion (emulsion) is obtained. Next, the obtained emulsion is distilled under reduced pressure to remove the solvent and obtain a resin particle emulsion.

  After neutralization, the pH is 7 to 9, preferably pH 8. As the basic aqueous solution, for example, an aqueous ammonium solution, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be used. When the pH is less than 7, the stability deteriorates depending on the temperature of the emulsified particles, and thus there is a problem that the temperature control tends to be difficult. When the pH exceeds 9, the particle size distribution of the aggregated particles in the subsequent aggregation process There is a problem that sometimes tends to be large.

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

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

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

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

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

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

  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 amorphous 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. As the neutralizing agent, for example, sodium hydroxide, potassium hydroxide, water Examples thereof include inorganic bases such as lithium oxide, 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.

  That is, in the toner manufacturing method of the present embodiment, at least amorphous polyester resin particles, crystalline polyester resin particles, release agent-dispersed particles, and colorant-dispersed particles are mixed and heteroaggregated using an aggregating agent. And adjusting the pH in the agglomeration system to 6 to 8.5, and after fusing at a temperature equal to or higher than the glass transition temperature of the amorphous resin, discharging the slurry containing the fused and fusing toner particles To produce a toner for developing electrostatic charge.

Furthermore, in the toner manufacturing method of the present embodiment, in the step of discharging the toner slurry, a specific heat of 2.8 to 4.2 KJ is applied to the low-temperature fluid used in the spiral heat exchange group using a spiral heat exchanger. / Kg · K and a fluid having a specific gravity of 1.00 to 1.12 g / cm ³ , the slurry is cooled at 10 to 30 ° C./min, and the slurry temperature is made equal to or lower than the glass transition temperature (Tg) of the toner particles. To discharge. Thus, the generation of stress generated in the toner can be suppressed, and the structure of the crystalline polyester and the release agent can be appropriately controlled.

When the specific heat of the low-temperature fluid is less than 2.8 KJ / Kg · K and the specific gravity is less than 10 g / cm ³ , the heat exchange rate is increased, but the exchange efficiency is lowered and the flow rate is increased, which is not preferable in production. On the other hand, if the specific heat exceeds 4.2 KJ / Kg · K and the specific gravity exceeds 1.2 g / cm ³ , the heat exchange rate decreases, and it is necessary to increase the heat transfer area, which is not economically preferable.

  Specifically, a resin particle dispersion containing an ionic surfactant is generally prepared by an emulsion polymerization method or the like, and the colorant particle dispersion and the release agent particle dispersion are mixed, and the ionic surfactant and Forms agglomerated particles of toner diameter by causing heteroaggregation with an aggregating agent having the opposite polarity, then heated to a temperature above the glass transition point of the resin particles to fuse and coalesce the agglomerated particles, Wash and dry to obtain toner.

  In the above release agent dispersion, the release agent is dispersed in the toner for electrostatic charge development as, for example, particles having a volume average particle size in the range of 150 to 1500 nm 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 becomes slow, the heating time becomes long, and the aggregates increase, which is not preferable.

  In the colorant dispersion, the colorant is dispersed in the 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 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.

  In addition, the desired toner can be obtained through any washing process, solid-liquid separation process, and drying process after the completion of the fusion / union, but the washing process is sufficiently ionized to develop and maintain charging properties. It is preferable to perform replacement washing with exchange water. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, centrifugal filtration, decanter and the like are preferably used from the viewpoint of productivity. Further, the drying process is not particularly limited, but from the viewpoint of productivity, aeration drying apparatus, spray drying apparatus, rotary drying apparatus, air flow drying apparatus, fluidized bed drying apparatus, heat transfer heating type drying apparatus, freeze drying apparatus, etc. are preferably used. It is done.

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

  These inorganic particles are preferably surface-treated with a coupling material or the like in order to control conductivity, chargeability, and the like. Specific examples of the coupling material 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 -glycidoxypropyl trimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, titanium coupling agents, etc. Can give.

  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 developer of the present invention is not particularly limited except that it contains the toner of the present invention, and an appropriate component composition can be taken according to the purpose. The developer of the present invention becomes a one-component developer when the toner is used alone, and becomes a two-component developer when the toner and carrier are used in combination.

  The carrier is not particularly limited, and examples thereof include known carriers. For example, known carriers such as resin-coated carriers described in JP-A-62-39879, JP-A-56-11461, etc. Is mentioned.

  Specific examples of the carrier include the following resin-coated carriers. Examples of the core particle of the carrier include normal iron powder, ferrite, magnetite molding, and the like, and the volume average particle size is in the range of about 30 to 200 μm.

  The carrier of the present embodiment is formed by coating the surface of the core particle with a nitrogen-containing resin. More specifically, a nitrogen-containing coupling agent layer is formed on the core particles, and a coating resin layer containing at least an aliphatic hydrocarbon resin is further formed thereon.

As the nitrogen-containing coupling agent used in the present embodiment, a silane coupling agent is suitable. Specifically, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) ) Γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxy Silane etc. can be mentioned, You may mix these 2 or more types. The blending amount of the nitrogen-containing coupling agent is 0.01 to 10 parts by weight in total with respect to 100 parts by weight of the core particles, preferably 0. A range of 05 to 5 parts by weight is suitable. Moreover, 0.01-5.0 g / m < ² > with respect to a core material, Preferably the range of 0.05-1.0 g / m < ² > is suitable.

  Examples of the aliphatic hydrocarbon resin used in the present embodiment include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / butene-1, ethylene / cis-butene-2, polybutene, polyisobutylene, polybutadiene, and polyisoprene. , Isoprene / isobutylene copolymer and the like, and polyethylene, polypropylene, and polyisobutylene are preferable. Moreover, these can also be used in mixture of 2 or more types. Furthermore, as the resin for coating, these aliphatic hydrocarbon resins can be used by mixing two or more other resins, but the content of the aliphatic hydrocarbon resin in the resin for coating is A range of 10 to 100 wt%, preferably 40 to 100 wt% is suitable.

  As the resin mixed with the aliphatic hydrocarbon resin, known synthetic resins and natural resins can be used. For example, one or more vinyl monomers or copolymers. Typical vinyl polymers include styrene, p-chlorostyrene, vinyl naphthalene such as vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate vinyl propionate, vinyl benzoate, vinyl formate, vinyl stearate, capron. Vinyl esters such as vinyl acrylate, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl-α-chloroacrylate, methyl methacrylate, ethyl methacrylate, methacryl Ethylenic monocarboxylic acids such as butyl acid and esters thereof, for example, ethylenic monocarboxylic acid substitution products such as acrylonitrile, methacrylonitrile, acrylamide, etc., for example, dimethyl maleate, diethyl maleate, dibutyl maleate, etc. Carboxylic acids and esters thereof, for example, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, for example, vinyl ethers such as vinyl methyl ether, vinyl isobutyl ether, vinyl ethyl ether, for example, vinylidene chloride And vinylidene halides such as vinylidene fluoride, and N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone.

The amount of the coating resin used is 0.01 to 10 parts by weight, preferably 0.05, based on 100 parts by weight of the core particles in consideration of achieving both image quality, secondary obstruction and chargeability. A range of ˜5 parts by weight is suitable. Moreover, 0.01-100 g / m < ² > with respect to a core material, Preferably the range of 0.05-70 g / m < ² > is suitable. In the present invention, in particular, the rising of charging can be accelerated by combining a nitrogen-containing coupling agent layer and an aliphatic hydrocarbon resin coating layer.

  As the core particles used in the carrier of the present invention, particles having a substantially spherical shape such as ferrite particles and granulated magnetite and having controllable surface properties can be used, and the average particle size is usually about 20 to 120 μm. Is used. Examples of the core material of the charging member of the present invention include a metal sleeve such as stainless steel and aluminum, or an elastic charging blade such as silicone, urethane, and EPDM (ethylene / propylene / diene / methylene rubber). Can do.

  In the production of the carrier of the present invention, a nitrogen-containing coupling agent and core particles are dispersed and mixed in an alcohol such as methanol and ethanol, heat-treated, and sieved to obtain treated core particles. Next, the treated core particles and the coating resin are dispersed and mixed in a solvent such as toluene and heated to coat. Also, after mixing the treated core particles and the coating resin at normal temperature, heat the resin to a temperature higher than the melting start point of the resin, or add and coat only the processed core particles heated to the melting start point or higher. Is also possible.

  In addition, a heating type kneader, a heating type Henschel mixer, a UM mixer, a planetary mixer, etc. can be used for said manufacturing apparatus. The particles coated by the above method can be used as a carrier as it is, but further, can be coated with another resin or coated with another resin dissolved in a solvent by a solution coating method to form a multilayer carrier. It can also be used. The charge-imparting member of the present invention is produced by coating the nitrogen-containing coupling agent and the resin with a dipping method, a spray method, or the like.

  In the developer of the present invention, the mixing ratio of the toner and the carrier is not particularly limited and can be appropriately selected according to the purpose.

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

  FIG. 1 is a schematic diagram illustrating a configuration example of an image forming apparatus for forming an image by the image forming method 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 machine, a release agent is usually supplied to a fixing member in the fixing machine in order to prevent an offset or 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.

  The cleaning blade 416 used as the cleaning unit of the image forming apparatus in the present embodiment has a hardness of 45 ° to 65 ° at the surface temperature of the cleaning blade in accordance with the JIS K6253 hardness test. It is preferable that the rebound resilience is 20% or less.

  If the hardness is less than 45 °, it is soft and easily worn. Therefore, as will be apparent from examples shown later, even if other conditions are within the scope of the present invention, toner slip easily occurs and the hardness exceeds 65 °. Therefore, abrasion is promoted on the photosensitive member side, fogging is likely to occur, and chipping is likely to occur on the blade side, and the cleaning property of the small particle size toner cannot be secured.

  The above-mentioned impact resilience and JIS hardness are in accordance with JIS K6301, and each value is a measured value at 25 ° C. By setting the rebound resilience to 20% or less, it is possible to suppress the occurrence of vibration caused by the catching of the blade tip, so-called stick and slip, and the retention of the resin particles in the nip region is improved. The effect of removing discharge products by the particles is more exhibited. Further, by increasing the hardness of the tip portion, the amount of distortion of the blade tip toward the downstream side in the image carrier rotation direction can be suppressed, and the resin particles are dammed to the blade tip. The dammed resin particles are subjected to a push-back force toward the upstream side of the image carrier rotating direction by the blade tip, improving the retention of the resin particles in the nip region, and generating discharge by the resin particles. The effect of removing objects is more exhibited.

  As a material for the cleaning blade 416, a known rubber material can be used in more detail. For example, urethane rubber, silicon rubber, fluorine rubber, chloroprene rubber, butadiene rubber, or the like can be used. Among them, it is preferable to use a polyurethane elastic body because of its excellent wear resistance. As the polyurethane elastic body, generally used is a polyurethane synthesized through an addition reaction of an isocyanate with a polyol and various hydrogen-containing compounds. Polyol-based polyols such as polypropylene glycol and polytetramethylene glycol as polyol components, and polyester-based polyols such as adipate-based polyols, polycaprolactam-based polyols and polycarbonate-based polyols, and polyisocyanate components include tolylene diisocyanate, 4, Urethane prepolymers using aliphatic polyisocyanates such as aromatic polyisocyanates such as 4 'diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluidine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate To prepare. Subsequently, a curing agent is added to the urethane prepolymer, poured into a predetermined mold, crosslinked and cured, and then aged at room temperature. As the curing agent, a dihydric alcohol such as 1,4-butanediol and a trihydric or higher polyhydric alcohol such as trimethylolpropane or pentaerythritol are usually used in combination.

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

[Preferred embodiment]
In the toner manufacturing method of the present embodiment, in the step of discharging the toner slurry, a specific heat of 2.8 to 4.2 KJ / Kg is applied to the low-temperature fluid used for the spiral heat exchange group using a spiral heat exchanger. The slurry is cooled at 10 to 30 ° C./m using a fluid having a K and a specific gravity of 1.00 to 1.12 g / cm ³ , and the slurry temperature is discharged below the glass transition temperature (Tg) of the toner particles. To do.

  The slurry cooling step is provided in the slurry discharging step in the toner production process, the slurry is cooled at a constant rate by contacting with a specific low-temperature fluid, and the toner slurry outlet temperature is set to the glass transition temperature (Tg) of the toner particles. By making the following, the structure of the crystalline substance on the toner surface can be controlled, the toner surface friction coefficient is controlled, and the blade cleaning property in the electrophotographic process is improved.

  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 electrolytic 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 number particle size to be 16% cumulative as D16p, and the cumulative volume to be 50% cumulative. The particle size is defined as D50v. Furthermore, the cumulative number particle size that is 84% cumulative is defined as D84p.

The volume average particle diameter in the present invention is D50v, and the GSDp under the small diameter side number average particle size index was calculated by the following formula.
Formula: Lower GSDp = {(D84p) / (D16p)} ^0.5

  Moreover, when the particle diameter to measure was less than 2 micrometers, it measured using the laser diffraction type particle size distribution measuring apparatus (LA-700: made by Horiba, Ltd.). As a measurement method, a sample in a dispersion is adjusted 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 toner dispersed on a slide glass was taken into an image analysis device through a video camera, and SF was calculated for 50 or more 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 peak and endothermic amount derived from the crystalline resin and the release agent in the toner were measured using a thermal analyzer of a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-60A) (hereinafter abbreviated as “DSC”). . In the first temperature raising step, the temperature is raised from room temperature to 150 ° C. at a rate of 10 ° C./minute, held at 150 ° C. for 5 minutes, and then cooled to 0 ° C. at a rate of 10 ° C./minute using liquefied nitrogen. After holding at 0 ° C. for 5 minutes, the temperature was raised again from 0 ° C. to 150 ° C. at a rate of 10 ° C. per minute as a second temperature raising step, and measurement was performed.

  Next, the present invention will be described in detail with reference to the following 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 particles, amorphous resin particles, 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 diameter to obtain the toner particle diameter. Next, after adjusting the pH of the system from a weakly acidic to alkaline range with an inorganic hydroxide, it is heated above the main maximum endothermic peak temperature obtained from the differential thermal analysis of the resin particles, and united and fused. A suspension is obtained. 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.

   Examples of how to prepare each material and how to create aggregated particles will be described below.

[Synthesis of resin materials]
-Synthesis of crystalline polyester resin 1-
To a heat-dried three-necked flask, 120 parts by weight of 1,10-decanediol, 90 parts by weight of sebacic acid, 2 parts by weight of sodium dimethyl 5-sulfoisophthalate, 4 parts by weight of dimethyl sulfoxide, and dibutyltin oxide 0 as a catalyst. Then, the air in the container was placed in an inert atmosphere with nitrogen gas by a depressurization operation, and the mixture was stirred 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 to stop the reaction, and a crystalline polyester resin was synthesized.

  The weight average molecular weight (Mw) of the obtained crystalline polyester resin (4) was 21,000 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, 90 parts by weight of sebacic acid, 3 parts by weight of sodium dimethyl 5-sulfoisophthalate, 4 parts by weight of dimethyl sulfoxide, and 2 parts by weight of dibutyltin oxide were placed. Thereafter, the air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and the mixture was stirred 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 it became viscous, it was air-cooled to stop the reaction, and a crystalline polyester resin was synthesized. The weight average molecular weight (Mw) of the obtained crystalline polyester resin was 12,000 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Further, the melting point (Tm) of the crystalline polyester resin was a differential of 64 ° C. by the above-described measuring method.

-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 it became viscous, it was air-cooled to stop the reaction, and a crystalline polyester resin was synthesized. The weight average molecular weight (Mw) of the obtained crystalline polyester resin (4) was 9,800 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Moreover, when the melting point (Tm) of the crystalline polyester resin (4) 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 62 ° C. Met.

-Synthesis of crystalline polyester resin 4-
In a heat-dried three-necked flask, 90 parts by weight of 1,10-decanediol, 110 parts by weight of sebacic acid, 5 parts by weight of sodium dimethyl 5-sulfoisophthalate, 4 parts by weight of dimethyl sulfoxide, and dibutyltin oxide 0 as a catalyst. Then, the air in the container was placed in an inert atmosphere with nitrogen gas by a depressurization operation, and the mixture was stirred 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 to stop the reaction, and a crystalline polyester resin was synthesized.

  The weight average molecular weight (Mw) of the obtained crystalline polyester resin (4) was 30,800 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Further, when the melting point (Tm) of this crystalline polyester 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 79 ° C. It was.

-Synthesis of non-crystalline 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 100 minutes at 220 degreeC and the system pressure of 1-10 mmHg, amorphous polyester resin (1) was obtained. The Mw of the polyester resin was 35000.

-Synthesis of non-crystalline 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 210 degreeC and the system pressure of 1-10 mmHg, amorphous polyester resin (2) was obtained. The Mw of the polyester resin was 23000.

-Synthesis of non-crystalline polyester resin 3-
In a heat-dried three-necked flask,
Dimethyl terephthalate 58 parts by weight Dimethyl isophthalate 78 parts by weight Succinic anhydride 30 parts by weight Bisphenol A-ethylene oxide 2 mol 158 parts by weight Ethylene glycol 100 parts by weight Tetrabutoxy titanate 0.07 parts by weight The transesterification was carried out by heating for a minute. Subsequently, as a result of continuing reaction for 120 minutes at 230 degreeC and the system pressure of 1-10 mmHg, amorphous polyester resin (3) was obtained. The polyester resin had an Mw of 48,000.

-Synthesis of non-crystalline polyester resin 4-
In a heat-dried three-necked flask,
Dimethyl naphthalenedicarboxylate 146 parts by weight Dimethyl terephthalate 78 parts by weight Bisphenol A-ethylene oxide 2 mol adduct 221 parts by weight Ethylene glycol 70 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 200 degreeC and the system pressure of 1-10 mmHg, amorphous polyester resin (4) was obtained. The Mw of the polyester resin was 18000.

-Synthesis of non-crystalline polyester resin 5-
In a heat-dried three-necked flask,
Dimethyl naphthalenedicarboxylate 146 parts by weight Dimethyl terephthalate 78 parts by weight Bisphenol A-ethylene oxide 2 mol adduct 221 parts by weight Ethylene glycol 70 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. Next, the reaction was continued at 240 ° C. under a system pressure of 1 to 10 mmHg for 150 minutes. As a result, an amorphous polyester resin (5) was obtained. The Mw of the polyester resin was 54000.

-Preparation of resin particle dispersion 1-
Resin particle dispersions were prepared using coarsely pulverized resins obtained by synthesizing a crystalline polyester resin and an amorphous polyester resin with a hammer mill.

50 parts by weight of ethyl acetate and 110 parts by weight of IPA were added to a ₂ L separable flask equipped with an anchor blade for supplying stirring power, a reflux device, and a vacuum pump decompression device, and N ₂ was fed at a rate of 0.2 L / m. to replace the air in the system with N _2. Next, 40 parts by weight of the crystalline polyester resin (1) and 160 parts by weight of the amorphous polyester resin (1) were slowly added while being heated to 60 ° C. by an in-system oil bath apparatus, and dissolved while stirring. Next, 20 parts by weight of 10% ammonia water was added thereto, and then 460 parts by weight of ion-exchanged water was added thereto at a rate of 9.6 g / m with stirring using a metering pump. Emulsification was completed when the emulsification system was milky white and the stirring viscosity was reduced.

  Next, the pressure was reduced to -700 Torr, and the mixture was stirred for 40 minutes while stirring. Further, 50 parts by weight of pure water at 60 ° C. was added thereto, and stirring was continued for 20 minutes under reduced pressure. When the reflux amount reached 210 parts by weight, this was taken as the end point, and overheating was stopped and the mixture was cooled to room temperature while stirring.

-Preparation of resin particle dispersion 2-
Resin particle dispersion 2 was prepared in the same manner as in the preparation of resin particle dispersion 1, except that amorphous polyester resin (2) was used.

-Preparation of resin particle dispersion 3-
Resin particle dispersion 3 was prepared in the same manner as in the preparation of resin particle dispersion 1, except that amorphous polyester resin (3) was used.

-Preparation of resin particle dispersion 4-
A resin particle dispersion 4 was prepared in the same manner as in the preparation of the resin particle dispersion 1, except that the amorphous polyester resin (4) was used.

-Preparation of resin particle dispersion 5-
A resin particle dispersion 5 was prepared in the same manner as in the preparation of the resin particle dispersion 1, except that the amorphous polyester resin (5) was used.

-Preparation of resin particle dispersion 6-
A resin particle dispersion 6 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.

-Preparation of resin particle dispersion 7-
A resin particle dispersion 7 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.

-Preparation of resin particle dispersion 8-
A resin particle dispersion 8 was prepared in the same manner as the resin particle dispersion 1 except that the crystalline polyester resin (4) was used.

-Preparation of resin particle dispersion 9-
Resin particle dispersion 9 was prepared in the same manner as in the preparation of resin particle dispersion 1, except that 6 parts by weight of crystalline polyester resin (1) and 194 parts by weight of amorphous polyester resin (1) were used.

-Preparation of resin particle dispersion 10-
Resin particle dispersion 10 was prepared in the same manner as in the preparation of resin particle dispersion 1, except that 12 parts by weight of crystalline polyester resin (1) and 188 parts by weight of amorphous polyester resin (1) were used.

-Preparation of resin particle dispersion 11-
Resin particle dispersion 11 was prepared in the same manner as in the preparation of resin particle dispersion 1, except that 90 parts by weight of crystalline polyester resin (1) and 110 parts by weight of amorphous polyester resin (1) were used.

-Preparation of resin particle dispersion 12-
Resin particle dispersion 12 was prepared in the same manner as in the preparation of resin particle dispersion 1, except that 110 parts by weight of crystalline polyester resin (1) and 90 parts by weight of amorphous polyester resin (1) were used.

-Preparation of resin particle dispersion 13-
A resin particle dispersion 13 was prepared in the same manner as in the preparation of the resin particle dispersion 1, except that 200 parts by weight of only the amorphous polyester resin (1) was used.

-Preparation of resin particle dispersion 14-
Resin particle dispersion 14 was prepared in the same manner as in the preparation of resin particle dispersion 1, except that 140 parts by weight of crystalline polyester resin (1) and 60 parts by weight of amorphous polyester resin (1) were used.

-Preparation of cyan colorant dispersion-
Cyan pigment (CI Pigment Blue 15: 3, manufactured by Dainichi Seika) 200 parts by weight ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 4 parts by weight ion-exchanged water 796 parts by weight The above components are mixed and dissolved, and homogenizer (IKA Ultra Tarrax) was used for 10 minutes to obtain a cyan colorant dispersion.

-Preparation of yellow colorant dispersion-
Yellow pigment (CI Pigment Yellow 74: manufactured by Dainichi Seika) 200 parts by weight ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 4 parts by weight ion-exchanged water 796 parts by weight The above mixture was dissolved and homogenizer (IKA) For 10 minutes to obtain a yellow colorant dispersion.

-Preparation of magenta colorant dispersion-
C. I. PigmentRed 122: (manufactured by Clariant) 200 parts by weight ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 4 parts by weight ion-exchanged water 796 parts by weight The above components are mixed and dissolved, and dispersed for 10 minutes with a homogenizer (Ultra Turrax by IKA) To obtain a magenta colorant dispersion.

-Preparation of black colorant dispersion-
Carbon Black Regal 330: (Cabot Corporation) 200 parts by weight Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 4 parts by weight ion-exchanged water 796 parts by weight The above components are mixed and dissolved, and then homogenizer (Ultra Turrax by IKA) is used. Dispersion for 10 minutes gave a black colorant dispersion.

-Preparation of release agent dispersion-
Paraffin wax FNP92 (melting point 91 ° C., manufactured by Nippon Seiwa Co., Ltd.) 250 parts by weight Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 3 parts by weight Ion-exchanged water 747 parts by weight or more heated to 60 ° C., made by IKA After sufficiently dispersing with an ultra turrax T50, it was dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion.

A toner was produced by the aggregation coalescence method using the material prepared above.

-Toner production example 1
Resin Particle Dispersion 1 80 parts by weight Cyan Colorant Dispersion 60 parts by weight Release Agent Dispersion 60 parts by weight Polyaluminum Chloride 0.4 parts by weight The above was sufficiently mixed and dispersed with a Cavitron in a 60 L kettle. Next, 0.35 parts by weight of polyaluminum chloride was added thereto, and then the dispersion operation was continued for 10 minutes. Thereafter, the mixture was transferred to a flask with a heating oil bath and heated to 45 ° C. with stirring. Hold at 45 ° C. for 30 minutes.

  Thereafter, the pH of the system was adjusted to 8.0 with a 0.5 mol% aqueous sodium hydroxide solution, heated to 85 ° C., and maintained for 2.5 hours.

After completion of the reaction, the slurry was cooled at 25 ° C./min using a fluid having a specific heat of 4.22 KJ / Kg · K and a specific gravity of 1.12 g / cm ³ as the low-temperature fluid. Next, after filtering with a filter press and thoroughly washing with ion exchange water, solid-liquid separation was performed with a filter press. This was further mixed with 40 ° C. ion exchange water, stirred and washed at 4000 rpm for 90 minutes with Tarax, then reslurry washed for 20 minutes, further solid-liquid separated with a filter press, and then mixed with 40 ° C. ion exchange water. The mixture was re-stirred and washed at 4000 rpm for 50 minutes with Turrax. Its conductivity was 0.008 ms / cm. Next, the water content of the toner obtained by drying with an airflow dryer was 0.27%.

  When the volume average particle diameter of the toner at this time was measured, the volume average diameter D50 was 6.3 μm, and the particle size distribution coefficient GSDv was 1.22. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required by the shape observation by Luzex was 124.

-Creation of external toner-
0.5 parts by weight of hydrophobic silica (TS720: manufactured by Cabot) was added to 50 parts by weight of the prepared toner, and mixed at 3000 rpm for 5 minutes with a Henschel mixer. The toner had a surface friction coefficient μ of 0.31.

-Production of carrier-
95 parts by weight of 50 μm ferrite core and 5 parts by weight of 35 μm ferrite core manufactured by Powdertech Co., Ltd. were prepared. 7 parts of γ-aminotriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE903) is dispersed in 500 parts of methanol and mixed in a 5 L small kneader equipped with a heater for 5 minutes at room temperature. And then heated under reduced pressure for 40 minutes, and then the heater was turned off and cooled with stirring for 50 minutes. Thereafter, the treated core particles were obtained by sieving with a 105 μm sieve. This was covered with 1% resin of a styrene-methyl acrylate copolymer (manufactured by Soken Chemical Co., Ltd., weight average molecular weight 81000, copolymerization ratio 40:60), and sieved with a 105 μm sieve to obtain a carrier.

-Development of developer-
The toner was weighed so that the toner concentration was 5% with respect to 100 parts of the carrier, and the developer was prepared by stirring and mixing for 5 minutes with a ball mill.

-Toner production example 2-
Toner Production Example 2 was prepared in the same manner as Toner Production Example 1 except that a magenta colorant dispersion was used instead of the cyan colorant dispersion.

  The toner had a volume average diameter D50 of 6.3 μm and a particle size distribution coefficient GSDv of 1.23. It was also observed that the toner particle shape factor SF1 was 123. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.32.

-Toner Production Example 3-
Toner Production Example 3 was prepared in the same manner as Toner Production Example 1 except that the yellow colorant dispersion was used instead of the cyan colorant dispersion.

The toner had a volume average diameter D50 of 6.3 μm and a particle size distribution coefficient GSDv of 1.23. It was also observed that the toner particle shape factor SF1 was 123. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.30.

-Example of toner production 4-
Toner Production Example 4 was prepared in the same manner as Toner Production Example 1 except that the black colorant dispersion was used instead of the cyan colorant dispersion.

  The volume average particle diameter D50 of the toner is 6.2 μm, and the particle size distribution coefficient GSDv is 1.22. Further, it was observed that the shape factor SF1 of the toner particles was 125. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.31.

-Toner production example 5-
Toner Production Example 5 was prepared in the same manner as Toner Production Example 1 except that Resin Particle Dispersion 2 was used instead of Resin Particle Dispersion 1.

  The toner had a volume average diameter D50 of 6.1 μm and a particle size distribution coefficient GSDv of 1.23. In addition, the shape factor SF1 of the toner particles was observed to be 120. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.35.

-Toner Production Example 6
Toner Production Example 6 was prepared in the same manner as in Toner Production Example 1 except that the resin particle dispersion 3 was used instead of the resin particle dispersion 1.

  The toner had a volume average diameter D50 of 6.0 μm and a particle size distribution coefficient GSDv of 1.23. In addition, it was observed that the shape factor SF1 of the toner particles is 127. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The surface friction coefficient μ of the external additive toner was 0.28.

-Toner Production Example 7-
Toner Production Example 6 was prepared in the same manner as Toner Production Example 1 except that resin particle dispersion 4 was used instead of resin particle dispersion 1.

  The volume average particle diameter D50 of the toner is 6.1 μm, and the particle size distribution coefficient GSDv is 1.22. In addition, it was observed that the shape factor SF1 of the toner particles was 117. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The surface friction coefficient μ of the external additive toner was 0.41.

-Toner production example 8-
Toner Production Example 8 was prepared in the same manner as in Toner Production Example 1 except that the resin particle dispersion 5 was used instead of the resin particle dispersion 1.

  The toner had a volume average diameter D50 of 6.1 μm and a particle size distribution coefficient GSDv of 1.23. In addition, the shape factor SF1 of the toner particles was observed to be 131. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The surface friction coefficient μ of the external additive toner was 0.26.

-Toner production example 9-
Toner Production Example 8 was prepared in the same manner as Toner Production Example 1 except that resin particle dispersion 6 was used instead of resin particle dispersion 1.

  The volume average diameter D50 of the toner is 6.5 μm, and the particle size distribution coefficient GSDv is 1.24. In addition, the shape factor SF1 of the toner particles was observed to be 120. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.39.

-Toner Production Example 10-
A toner production example 10 was produced in the same manner as in the toner production example 1 except that the resin particle dispersion 7 was used instead of the resin particle dispersion 1.

  The volume average diameter D50 of the toner is 6.5 μm, and the particle size distribution coefficient GSDv is 1.24. In addition, it was observed that the shape factor SF1 of the toner particles was 118. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.43.

-Toner Production Example 11-
Toner Production Example 11 was produced in the same manner as Toner Production Example 1 except that Resin Particle Dispersion 1 was used instead of Resin Particle Dispersion 1.

  The volume average diameter D50 of the toner is 6.6 μm, and the particle size distribution coefficient GSDv is 1.25. In addition, the shape factor SF1 of the toner particles was observed to be 126. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.27.

-Toner Production Example 12-
Toner Production Example 12 was prepared in the same manner as in Toner Production Example 1 except that resin particle dispersion 9 was used instead of resin particle dispersion 1.

  The toner had a volume average diameter D50 of 5.8 μm and a particle size distribution coefficient GSDv of 1.22. Further, it was observed that the shape factor SF1 of the toner particles is 130. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The surface friction coefficient μ of the external additive toner was 0.22.

-Toner Production Example 13-
Toner Production Example 13 was prepared in the same manner as in Toner Production Example 1 except that the resin particle dispersion 10 was used instead of the resin particle dispersion 1.

  The toner had a volume average diameter D50 of 6.0 μm and a particle size distribution coefficient GSDv of 1.23. In addition, it was observed that the shape factor SF1 of the toner particles is 127. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The surface friction coefficient μ of the external additive toner was 0.25.

-Toner Production Example 14-
Toner Production Example 14 was prepared in the same manner as Toner Production Example 1 except that Resin Particle Dispersion 11 was used instead of Resin Particle Dispersion 1.

  The volume average diameter D50 of the toner is 6.6 μm, and the particle size distribution coefficient GSDv is 1.27. In addition, the shape factor SF1 of the toner particles was observed to be 120. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The surface friction coefficient μ of the external additive toner was 0.40.

-Toner Production Example 15-
Toner Production Example 15 was prepared in the same manner as Toner Production Example 1 except that the resin particle dispersion 12 was used instead of the resin particle dispersion 1.

  The volume average diameter D50 of the toner is 6.9 μm, and the particle size distribution coefficient GSDv is 1.28. In addition, it was observed that the shape factor SF1 of the toner particles was 118. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.43.

-Toner Production Example 16-
Toner Production Example 16 was produced in the same manner as in Toner Production Example 1 except that the cooling rate was changed to 5 ° C./min instead of 25 ° C./min.

  The toner had a volume average diameter D50 of 6.0 μm and a particle size distribution coefficient GSDv of 1.23. It was also observed that the toner particle shape factor SF1 was 123. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.35.

-Toner Production Example 17-
Toner Production Example 17 was produced in the same manner as in Toner Production Example 1 except that the cooling rate was changed to 15 ° C./min instead of 25 ° C./min.

  The volume average particle diameter D50 of the toner is 6.1 μm, and the particle size distribution coefficient GSDv is 1.22. It was also observed that the toner particle shape factor SF1 was 123. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.33.

-Toner Production Example 18-
Toner Production Example 18 was produced in the same manner as in Toner Production Example 1 except that the cooling rate was changed to 35 ° C./min instead of 25 ° C./min.

  The toner had a volume average diameter D50 of 6.2 μm and a particle size distribution coefficient GSDv of 1.23. It was also observed that the toner particle shape factor SF1 was 123. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The surface friction coefficient μ of the external additive toner was 0.28.

-Toner Production Example 19-
Toner Production Example 19 was prepared in the same manner as Toner Production Example 1 except that the resin particle dispersion 13 was used instead of the resin particle dispersion 1.

  The volume average particle diameter D50 of the toner is 5.9 μm, and the particle size distribution coefficient GSDv is 1.22. In addition, the shape factor SF1 of the toner particles was observed to be 136. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.19.

-Toner Production Example 20-
Toner Production Example 20 was produced in the same manner as in Toner Production Example 1 except that resin particle dispersion 14 was used instead of resin particle dispersion 1, and the cooling rate was 5 ° C./min.

  The toner had a volume average diameter D50 of 6.8 μm and a particle size distribution coefficient GSDv of 1.27. In addition, the shape factor SF1 of the toner particles was observed to be 116. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The surface friction coefficient μ of the external additive toner was 0.48.

-Toner Production Example 21-
Toner Production Example 21 was prepared in the same manner as in Toner Production Example 1 except that the cooling rate was changed from 25 ° C./min to 0.5 ° C./min to 65 ° C. and then 1 ° C./min.

  The toner had a volume average diameter D50 of 6.2 μm and a particle size distribution coefficient GSDv of 1.23. It was also observed that the toner particle shape factor SF1 was 123. In the same manner as in Toner Production Example 1, external additive toner and developer were prepared. The external additive toner had a surface friction coefficient μ of 0.35.

Examples 1-18, Comparative Examples 1-3
The structure and characteristics of the toners produced in Toner Production Examples 1 to 21 were evaluated. Observation of the cross section of the toner by TEM shows that the crystalline resin polyester resin contains at least a non-crystalline polyester resin, a crystalline polyester resin, a release agent, and a colorant, and in the transmission electron microscope image of the ruthenium-dyed toner cross section. There is a structure in contact with the release agent, which is determined from the cross-sectional area A of the structure and the cross-sectional area B of the release agent alone. 100 × A / (A + B) is, for example, 81 in the toner production example 1, and the perimeter of the release agent in a total of 100 toner cross sections in the transmission electron microscope is D, and the crystallinity in the portion where the structure is formed The length C of the part of the release agent in contact with the resin was determined, and the coverage α = C / D (%) calculated from these lengths was 55% in the toner production example 1, for example. Table 1 shows the results of 100 × A / (A + B) and coverage α for other toners.

(Low-temperature fixability evaluation)
The developer using the prepared toner production examples 1 to 21 was changed from 100 ° C. to 150 ° C. using a DocuCentreColor 400CP remodeling machine (adjusted so that the temperature of the fixing device can be changed) shown in FIG. Fixation evaluation was performed in steps of ℃. More specifically, an image of 5 cm × 5 cm was fixed on J paper manufactured by Fuji Xerox Co., Ltd. so that the applied amount of toner was 10 g / m ² and left in a room at a temperature of 22 ° C. and a humidity of 50% for 1 hour. This was folded so that the image was on the inside, pressure was applied at 40 g / cm ² for 1 minute, and then returned to the original, and the maximum width of the underlying paper portion due to destruction of the image portion was evaluated. The lowest temperature at which the width was 0.5 mm or less was defined as the low temperature fixing temperature, and 140 ° C. or less was regarded as no problem. However, it goes without saying that the lower the temperature, the better.

(Image strength evaluation)
Using the image at a fixing temperature of 150 ° C. performed in the low-temperature fixing evaluation, the change in the fixing image when the image surface was rubbed 10 times with an eraser (Taguchi Rubber Industries, Ltd., ST for precision drawing) was evaluated according to the following criteria. did.
G1: The rubbing trace cannot be confirmed by visual glossiness.
G2: The rubbing trace can be confirmed by visual glossiness, but cannot be confirmed by the density difference from the paper base.
G3: The exposure amount of the paper base can be confirmed with a magnifying glass 25 times that of the portion where the rubbing trace is not rubbed, but it cannot be visually confirmed.
G4: The image density difference between the rubbing trace and the non-rubbed portion can be visually confirmed.
The destruction of the fixed image first appears in the glossiness of the image due to the destruction of the surface, and the one with weak fixability extends to the destruction of the bonded portion between the paper and the image, and was evaluated as described above. In addition, if it is G1-G3, there is no problem practically.

(Cleaning blade resistance evaluation)
The prepared developer is a Fuji Xerox DocuCentreColor 400CP remodeling machine (fixed at 160 ° C.) and a cleaning blade with a hardness of 50 °, and a color paper (manufactured by Fuji Xerox Co., Ltd.). J paper) was image-formed with a print test chart having an image density of 1%. In the image formation, as shown in FIG. 3, the image is divided into right and left parts in the transfer direction, one solid image 20 is printed only on one side and no image 22 is printed on the other side, and then 9 blank sheets are output. 10 sheets were set as one set and repeated 10 times. Further, this series of operations of printing one halftone image 24 with a toner applied amount of 0.1 g / cm ² was repeated continuously. Then, the appearance of white streaks in the halftone image 24 was confirmed, and the resistance of the cleaning blade was evaluated based on the total number when the streak image was visually confirmed. The test was performed up to 5000 sheets, and those that did not occur at 5000 sheets were set to> 5000 sheets, and no further tests were performed. In addition, 3000 sheets or more were considered as no problem. It goes without saying that this evaluation is a test in which defective cleaning tends to occur as compared with a cleaning blade used normally.

In addition, toner production example 1 was used, and cleaning blades with different hardnesses (40 °, 60 °, 70 °) were prepared and added as Examples 19 to 21 for evaluation.
Table 2 shows a series of evaluation results.

  The results of Examples and Comparative Examples are summarized in Tables 1 and 2. It has been found that by using the toners of Examples 1 to 18, a toner and an image forming apparatus which are excellent in fixability and image strength and preferable for a cleaning blade can be obtained.

  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. It is a figure explaining the tolerance evaluation test of a cleaning blade.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 Mold release agent, 12 Crystalline polyester resin, 14 Amorphous polyester resin, 20 Solid image, 22 No image, 24 Halftone image, 100 Structure, 200 Image forming apparatus, 401a-401d Electrophotographic photoreceptor, 400 Housing , 401a to 401d Electrophotographic photosensitive member, 402a to 402d charging roll, 403 exposure device, 404a to 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 medium to be transferred.

Claims (5)

A toner comprising a crystalline polyester resin and a release agent,
The surface friction coefficient μ of the toner is 0.21 to 0.45,
When there is a structure in which the crystalline resin 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, and the cross sectional area of the release agent alone is B. 60 ≦ 100 × A / (A + B) ≦ 100,
An electrostatic charge developing toner comprising a metal oxide hydrophobized on the surface of the toner.   2. The electrostatic charge developing toner according to claim 1, wherein a coating area ratio of the release agent by the crystalline resin in a transmission electron microscope is 40% to 70%.   At least non-crystalline polyester resin particles, crystalline polyester resin particles, release agent-dispersed particles, and colorant-dispersed particles are mixed and heteroaggregated using an aggregating agent, and the pH in the aggregation system is 6 to 8.5. And then fusing and fusing at a temperature equal to or higher than the glass transition temperature of the amorphous resin, and then cooling the slurry containing the fusing and fusing toner particles in the discharging step to produce an electrostatic charge developing toner. A method for producing a toner for developing electrostatic charge, characterized by comprising:   A developer for electrostatic charge development, comprising: a carrier obtained by coating a surface of a core particle with a nitrogen-containing resin; and the toner according to claim 1. A latent image forming means for forming a latent image on the latent image carrier, a developing means for developing the latent image using an electrostatic charge developing toner, and the developed toner image with or without an intermediate transfer member. A transfer means for transferring onto the transfer body, a fixing means for adding and fixing the toner image on the transfer body, and a cleaning means having a cleaning blade for removing the toner remaining on the surface of the latent image carrier. An image forming apparatus comprising:
The electrostatic charge developing toner is the electrostatic charge developing toner according to claim 1 or 2,
An image forming apparatus, wherein the cleaning means has a hardness at a surface temperature of the cleaning blade of 45 ° to 65 ° in accordance with a JIS K6253 hardness test.