JP2008112074A - Toner for electrostatic charge image development and method for manufacturing the same, developer for electrostatic charge image development and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development so superior in fixing performance as to make a fixed image surface free of uneven gloss, even when a resin-coated recording medium is used. <P>SOLUTION: The toner for electrostatic charge image development includes a crystalline polyester resin 12 and a release agent 10, wherein a structure 100 in which the crystalline polyester resin 12 comes into contact with the release agent 10 is present in a ruthenium-dyed cross section of the toner, and the relation 50≤(A/B)×100<100 is satisfied, where A is a total cross-sectional area of the release agent 10 in the structure 100; and B is a total cross-sectional area of the release agent 10 in a total cross-sectional area of the toner; and area ratio of internal voids 16 in the toner to a cross section of the toner is 2-10%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  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. Further, for example, the use of a plasticizer can lower the fixing temperature, but there is a problem because blocking occurs during storage of the toner or in the developing machine.

  On the other hand, as a means for achieving both blocking prevention, image storage stability 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). etc).

  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.

  However, the above disclosed technology, for example, the disclosed technology of Patent Document 1 applies a polymer having an alkyl group side chain having 14 or more carbon atoms to the toner, and has a melting point of 62 to 66 ° C. and a low temperature. Due to its strong nature, there was a problem in the reliability of powder and images. Further, the crystalline resins described in Patent Documents 2 and 3 have a problem that the fixing performance to paper is not sufficient. A polyester resin is an example of a crystalline resin that is expected to improve the fixability to paper. A technique using a crystalline polyester resin in a toner is described in Patent Document 2. This is a technique in which an amorphous polyester resin having a glass transition temperature of 40 ° C. or higher and a crystalline polyester resin having a melting point of 130 to 200 ° C. are mixed and used. However, this technique has excellent pulverization properties and blocking resistance, but has a problem in that the low-temperature fixability cannot be achieved since the crystalline polyester resin has a high melting point.

  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. However, when an amorphous resin is mixed with a crystalline resin, the melting point of the toner is lowered to cause toner blocking, and there are practical problems such as deterioration of image storage stability. In addition, when the amount of the amorphous resin component is large, the characteristics of the amorphous resin component are largely reflected, so that it is difficult to lower the fixing temperature than the conventional one. For this reason, if a crystalline resin is used 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. In addition, these toners certainly improve the low-temperature fixability and toner storage stability to some extent, but the fixability changes greatly depending on the process speed of copying and printers, and even if they can be put to 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, when the crystalline material that has partially soaked into the recording medium is crystallized by cooling, the adhesion to the recording medium is lowered, and among the fixing characteristics, particularly the folding resistance of the fixed image may be deteriorated. .

  The present invention provides an electrostatic charge developing toner having excellent fixing performance with no gloss unevenness on a fixed image surface even when a resin-coated recording medium is used.

  The present invention has the following features.

  (1) A toner including a crystalline polyester resin and a release agent, wherein a structure in which the crystalline resin polyester resin is in contact with the release agent is present on the cross section of the ruthenium-dyed toner. When the total cross-sectional area of the release agent is A and the total cross-sectional area of the release agent in the total cross-sectional area of the toner is B, 50 ≦ (A / B) × 100 <100, and the inside of the toner with respect to the cross-sectional area of the toner The toner for electrostatic charge development has a void area ratio of 2 to 10%.

  (2) The crystalline polyester resin particle dispersion, the amorphous polyester resin particle dispersion, the release agent dispersion, and the colorant dispersion are mixed and aggregated using a flocculant, and the crystalline polyester resin This is a method for producing a toner for electrostatic charge development, in which the toner is granulated by coalescence coalescence at a temperature not lower than the glass transition temperature (Tg) and not higher than the melting point of the release agent.

  (3) A developer for electrostatic charge development comprising a carrier having a core particle surface coated with a resin and the toner described in (1) above.

  (4) 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 An image forming apparatus comprising: a transfer unit that transfers the toner image on the transfer medium without any intervention; and a fixing unit that adds and fixes the toner image on the transfer object. And a peripheral speed of the developer conveying means for conveying the developer provided in the developing means is 1200 mm / sec or more and 2000 mm / sec or less.

  In general, in order to ensure high gloss of a fixed image, there is a method of reducing the original unevenness of the paper by coating the resin with the resin and increasing the gloss by suppressing the unevenness of the fixed image, but the resin-coated paper However, since the weight per unit area of the paper tends to increase, the fixing temperature tends to increase. Therefore, it is necessary to increase the heating temperature during fixing. Compared with the temperature rise due to the heating of the paper, the heating of the toner becomes larger, and a small amount of volatile components such as water existing in the voids inside the toner rapidly increase the volume. Unevenness is generated. In the paper covered with resin, this tendency is more remarkable because the volatile matter in the toner cannot move to the paper side.

  According to the first aspect of the present invention, the release of the release agent can be suppressed, and if the internal void ratio is set, the heating of the toner is greater than the temperature rise due to the heating of the paper. Even in this case, a small amount of volatile components such as water existing in the voids inside the toner does not rapidly increase the volume, and it is difficult for minute irregularities to be generated on the fixed image. In particular, in the paper covered with resin, even if the volatile component in the toner cannot move to the paper side, the movement of the volatile component can be reduced, so there is no possibility of generating minute irregularities in the fixed image.

  According to the second aspect of the present invention, the seepage of the release agent can be suppressed as compared with the conventional one, and the movement of the volatile component in the toner at the time of fixing is small. Hard to do.

  According to the third aspect of the present invention, the generation of fine powder when the carrier and the toner are stirred and mixed can be suppressed.

  According to the fourth aspect of the present invention, toner fine powder is not generated even when the peripheral speed of the developer transporting means for transporting the developer is increased, and the predetermined charge amount of the toner is reduced in a shorter time than conventional. Can be obtained.

  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 of the present embodiment (hereinafter also referred to as “toner”) is a toner containing a crystalline polyester resin and a release agent, and the crystalline resin polyester resin is present on the cross section of the ruthenium-dyed toner. When there is a structure in contact with the release agent, where A is the total cross-sectional area of the release agent in the structure, and B is the total cross-sectional area of the release agent in the total cross-sectional area of the toner, 50 ≦ (A / B ) × 100 <100, and the toner internal void area ratio with respect to the cross-sectional area of the toner is 2 to 10%.

-Crystalline polyester resin-
Here, the “crystalline polyester resin” refers to a resin having a clear endothermic peak rather than a stepwise endothermic amount change in differential scanning weight measurement (DSC). A clear endothermic peak is a peak in which the DSC curve returns from the previous baseline and then returns to the baseline as described in JIS K 7121-1987 “Method for measuring plastic transition temperature”. Here, “crystallinity” used in the electrostatic charge developing toner means that it has a clear endothermic peak in differential scanning calorimetry (DSC). Specifically, the temperature rising rate is 10 ° C. / It means that the half-value width of the endothermic peak when measured in min is within 6 ° C.

  As the crystalline polyester resin, specifically, an aliphatic crystalline polyester resin having an appropriate melting point and an alkyl group having 6 or more carbon atoms in the side chain is more preferable. A polyester having an alkyl group having 6 or more carbon atoms can be obtained by using a monomer having an alkyl group having 6 or more carbon atoms in the polyvalent carboxylic acid or polyhydric alcohol, for example, using dodecenyl succinic acid or the like. However, it is not limited to this.

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

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

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

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

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

  In the present embodiment, polyvalent carboxylic acids containing 5 mol% or more of cyclohexanedicarboxylic acid may be used. Furthermore, the amount of cyclohexanedicarboxylic acid used is preferably 10 to 40 mol% in the polyvalent carboxylic acid. 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, fixing characteristics may not be exhibited.

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

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

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

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

  As melting | fusing point of crystalline resin, Preferably it is 50-120 degreeC, More preferably, it is 60-110 degreeC. If the melting point is lower than 50 ° C., the storage stability of the toner and the storage stability of the toner image after fixing may become a problem. On the other hand, if the melting point is higher than 120 ° C., sufficient low-temperature fixing cannot be obtained as compared with the conventional toner. There is a case.

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

  The crystalline resin may show a plurality of melting peaks. In the present invention, the melting point is the maximum peak.

  Furthermore, for example, DSC-7 manufactured by Perkin Elmer can be used for measurement of the melting point of the resin of the present invention. The temperature correction of the detection part of this apparatus uses the melting point of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. 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. When the weight average molecular weight is less than 10,000, the compatibility with the amorphous resin and the release agent proceeds and plasticity is generated. 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 ° C. If the melting point is less 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 exceeds 120 ° C., sufficient low-temperature fixing may not be obtained compared to conventional toners. is there.

  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 may be difficult to encapsulate the toner, and a stable structure may not 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 fixing property is lowered but also the output speed dependency of the apparatus 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. When the weight average molecular weight is less than 25,000, not only the heat storage property of the toner is lowered, but also the strength of the fixed image is lowered. On the other hand, if it exceeds 50,000, it is not only difficult to control the internal structure of the toner, but also the fixing property is deteriorated and the image gloss is lowered.

  It is preferable to control the acid value of the amorphous polyester resin to, for example, 10 to 15 mgKOH / g. When the acid value is less than 10 mg KOH / g and the acid value exceeds 15 mg KOH / g, there is a problem that it may be difficult to obtain a structure in which the crystalline polyester resin is in contact with the release agent. 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 can be obtained by using trimellitic anhydride as a polyvalent carboxylic acid component.

  The binder resin in the toner of the present embodiment is a so-called phase inversion in which a crystalline polyester resin and an amorphous polyester resin are simultaneously dissolved in a solvent, and then a poor solvent in which these resins are difficult to dissolve is added and mixed. It is preferred to use an emulsification method. Here, the crystalline polyester resin is used in the range of 5 to 40% of the components constituting the binder resin. If the proportion of the amorphous polyester resin is less than 5%, sharp melt properties derived from the crystalline polyester resin cannot be obtained, and plasticity may simply occur. On the other hand, the proportion of the amorphous polyester resin may be 40%. On the other hand, although good fixing characteristics can be obtained, the phase separation structure in the fixed image becomes non-uniform, and the strength of the fixed image, particularly the scratch strength, is lowered, which may cause problems such as being easily scratched. Therefore, toner blocking resistance and image storability may not be maintained while ensuring good low-temperature fixability.

  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. In the present embodiment, the melting point is preferably 40 ° C. to 120 ° C. Among these, in order to meet the recent demand for low temperature fixability as a measure for energy saving, it is particularly 50 ° C. to 100 ° C. Is more preferable, and it is 50-80 degreeC more preferably.

  The addition amount of these release agents is preferably in the range of 0.5 to 50% by weight, more preferably in the range of 1 to 30% by weight, and still more preferably in the range of 5 to 15% by weight with respect to the total amount of toner. % Range. When the addition amount is less than 0.5% by weight, there is no effect of adding a release agent. When the addition amount exceeds 50% by weight, the chargeability is likely to be affected, or the toner is easily destroyed inside the developing device, and the release agent is released. In addition to the effect that the mold agent is spent on the carrier and the charge is likely to decrease, for example, when color toner is used, the oozing on the image surface during fixing tends to be insufficient, Since the release agent tends to stay in the image, transparency is deteriorated, which is not preferable.

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

  The dispersion medium in the release agent dispersion is preferably an aqueous medium, and water, pure water, or ion exchange water is used. A surfactant is used as the dispersant. Preparation of the wax dispersion used in the toner of the present invention is, for example, a known dispersion such as a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high pressure type dispersing machine such as a nanomizer, a microfluidizer, an optimizer, or a gorin. Any method and conditions may be used as long as the method can satisfy the particle size and content as described.

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

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

  The dispersion medium 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 in the present embodiment is carried out by a usual method. Specifically, the measurement was carried out 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 scanning electron microscope (SEM), 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 rod-like and lump-like ones are the release agent 10, the protrusions are the periphery of the release agent, and the linear crystals scattered in the toner non-crystalline polyester resin 14 are the 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 presence of the structure 100 in which the crystalline resin polyester resin is in contact with the release agent and the release agent 10 alone is confirmed on the cross section of the toner via the amorphous polyester resin 14. The toner of the present embodiment has a cross-sectional structure of 50 ≦ (A / B) where A is the total cross-sectional area of the release agent in the structure and B is the total cross-sectional area of the release agent in the total cross-sectional area of the toner. ) × 100 <100. Note that the “structure” refers to a structure 100 having a structure in which the crystalline polyester resin 12 is in contact with or recessed into the release agent 10 even at one point, as shown in FIG.

  When the total area of the release agent in the structure is less than 50% with respect to the total release agent cross-sectional area, the release agent oozes out and the heat storage property is impaired.

<Toner characteristics>
The toner internal void area ratio with respect to the cross-sectional area of the toner in the present embodiment is 2 to 10%. The toner internal void area ratio is obtained by using the Luzex image analysis of the image of the toner cross section of the transmission electron microscope (TEM) described above.

  Also, if the toner internal void area ratio with respect to the cross-sectional area of the toner is less than 2%, phase dissolution and mixing with the release agent occur, and the release agent viscosity increases. make worse. If it exceeds 10%, the toner heating becomes larger than the temperature rise due to the heating of the paper at the time of fixing, so that a small amount of volatile components such as water existing in the voids inside the toner rapidly Increases, and minute irregularities are generated in the fixed image. That is, there may be a case where a moving part of the volatile component during fixing cannot be secured.

  The volume average particle diameter of the toner in the exemplary embodiment is preferably 1 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). The distribution is drawn, the particle size that is cumulative 16% is the volume average particle size D16v, the particle size that is cumulative 50%, the volume average particle size D50v, and the particle size that is cumulative 84% is the volume average particle size D84v. It is defined as At this time, the volume average particle size distribution index (GSDv) is defined as (D84v / D16v) ^0.5 , and the volume average particle size distribution index (GSDv) can be calculated.

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

  The shape factor SF1 of the toner 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 that may show a plurality of melting peaks as a main component or may contain a release agent. In the invention, the maximum peak is taken as the melting point.

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

  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 dispersion of the finished resin particle dispersion may be unstable. When the pH exceeds 9, the particle size of the aggregated particles in the subsequent aggregation process is difficult to control. There is a bug.

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

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

  Examples of the aqueous medium include water such as distilled water and 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.

  Further, in the toner manufacturing method of the present embodiment, the internal structure of the particles is controlled in the pre-aggregate formation, aggregate formation, and coalescence of the toner particles in order to control the internal structure of the toner. Therefore, the discharge flow rate (Nqd) and the volume ratio (Nqd / V) of the reaction solution are set to 0.20 to 0.65. If the volume ratio is less than 0.20, stirring and mixing in the reaction tank becomes difficult, and heat to the reaction solution is not uniformly transmitted, and fine powder and coarse powder are generated. On the other hand, when the ratio exceeds 0.65, stirring and mixing can be performed sufficiently, but a stable toner structure may not be constructed due to insufficient shearing force.

  In the toner manufacturing method of the present invention, in order to control the internal structure of the toner, in the formation of a preliminary aggregate of toner particles, the formation of aggregates, and coalescence, the reaction vessel (D) and the stirring blade diameter (d ) Using a stirring blade having a dimensional ratio (d / D) of 0.4 to 0.6. If the dimensional ratio is less than 0.4, stirring and mixing in the reaction tank becomes difficult, heat is not uniformly transmitted to the reaction solution, and fine powder and coarse powder are generated, and a stable toner structure cannot be constructed. On the other hand, when the ratio exceeds 0.6, sufficient stirring and mixing in the reaction vessel can be secured, but a stable toner structure cannot be constructed due to insufficient shearing force.

  Further, in the toner manufacturing method, the inclination angle of the paddle blade having two or more stages of stirring blades for performing pre-aggregation formation of toner particles, formation of aggregates, and stirring and mixing in the system in coalescence is 40 to 60 degrees. Degrees, preferably 45 degrees. Furthermore, although the number of stages of the paddle blades can be determined as appropriate, it is possible to arrange the paddle blades of a predetermined number of stages up to half the height from the bottom surface of the stirring and mixing vessel to the liquid level. preferable.

  Furthermore, specifically, a resin particle dispersion containing an ionic surfactant is generally prepared by an emulsion polymerization method, etc., and the colorant particle dispersion and the release agent particle dispersion are mixed to obtain an ionic surfactant. By forming heteroaggregation with an aggregating agent having a polarity opposite to that of the agent, aggregated particles having a toner diameter are formed, and then heated to a temperature equal to or higher than the glass transition point of the resin particles to fuse and coalesce the aggregated particles. Then, it is washed and dried to obtain a toner.

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

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

  The concentration of the surfactant used in the release agent dispersion is preferably 4% by weight or less with respect to the release agent. When the content is 4% by weight or more, the aggregation rate of particle formation 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.

  Examples of the coating resin for the resin-coated carrier include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, 2-acrylic acid 2- Α-methylene fatty acid monocarboxylic acids such as ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; nitrogen-containing acrylics such as dimethylaminoethyl methacrylate; vinyl such as acrylonitrile and methacrylonitrile Nitriles; Vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl keto Homopolymers such as vinyl ketones such as ethylene; olefins such as ethylene and propylene; vinyl-based fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene and hexafluoroethylene; and copolymers comprising two or more types of monomers Furthermore, silicone resins containing methyl silicone, methyl phenyl silicone, etc., polyesters containing bisphenol, glycol, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like can be mentioned. These resins may be used alone or in combination of two or more. The coating amount of the coating resin is preferably in the range of about 0.1 to 10 parts by weight and more preferably in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the core particles.

  For the production of the carrier, a heating kneader, a heating Henschel mixer, a UM mixer, or the like can be used. Depending on the amount of the coating resin, a heating fluidized rolling bed, a heating kiln, or the like can be used. .

  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.

  In the present embodiment, the peripheral speed of the developer holding body that holds the developer provided in the developing devices 404a to 404d is 1200 mm / sec or more and 2000 mm / sec or less. There is no problem even if the peripheral speed of the developer holding member is less than 1200 mm / sec, but depending on the type of carrier, a sufficient amount of toner charge cannot be obtained, and so-called fogging occurs where toner adheres in addition to the latent image. On the other hand, if it exceeds 2000 mm / sec, fine powder derived from the destruction of the toner is generated. As a result, the fine powder adheres to the carrier, the development amount decreases, and the development density may decrease. is there.

[Preferred embodiment]
(I) A mixed particle dispersion of a crystalline polyester resin and an amorphous polyester resin, a release agent dispersion, and a colorant dispersion are mixed and aggregated using a flocculant, and the glass of the crystalline polyester resin is mixed. In a method for producing a toner for electrostatic charge development in which toner is granulated by coalescence and fusion at a temperature not lower than the transition temperature (Tg) and not higher than the melting point of the release agent, by stirring and mixing using the paddle blade in the aggregation step This is a method for producing a toner for developing electrostatic charge having a motive power (P) and a reaction liquid charge volume ratio (P / V) of 250 × 10 ^{3 to} 500 × 10 ³ .

  (Ii) In the method for producing a toner for electrostatic charge development according to the present embodiment, there are two or more stirrer blades that perform preliminary agglomeration of toner particles, formation of agglomerates, and agitation and mixing in the system for coalescence The inclination angle of the paddle blade is 45 degrees, the discharge flow rate (Nqd) and the reaction liquid volume ratio (Nqd / V) are 0.20 to 0.65, and the reaction vessel diameter (D ) And the stirring blade diameter (d) dimensional ratio is d / D 0.4 to 0.6.

  According to the production method described above, the fine resin particles produced by the phase inversion emulsification method are identified by using an agglomeration coalescence method such as that disclosed in JP-A-2001-255703, and the stirring blade dimensions are specified. By controlling the agitation power (P / V) and pre-aggregate formation, aggregate particle formation, and coalescence, the uneven distribution of the toner composition can be mitigated, thereby enabling precise control of the toner structure. This makes it possible to reduce the voids inside the toner and to form a structure in the toner in which the crystalline polyester is in contact with or coated with the release agent. As a result, the obtained toner is fixed at a lower temperature and secures a path for the release agent to bleed out, and has excellent fixing performance (surface roughness when using resin-coated paper). A manufacturing method can be provided.

  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 volume particle size to be 16% cumulative as D16v, and the cumulative volume to be 50% cumulative The particle size is defined as D50v. Further, the cumulative volume particle size that is 84% cumulative is defined as D84v.

The volume average particle size in the present invention is D50v, and the volume average particle size index GSDv is calculated by the following equation.
Formula: GSDv = {(D84v) / (D16v)} ^0.5

  Moreover, when the particle diameter to measure was less than 2 micrometers, it measured using the laser diffraction type particle size distribution measuring apparatus (LA-700: made by Horiba, Ltd.). As a 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 peaks and endothermic amounts derived from the crystalline resin and the release agent in the toner were measured using a thermal analyzer of a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-60A) (hereinafter abbreviated as “DSC”). . In the first temperature raising step, the temperature is raised from room temperature to 150 ° C. at a rate of 10 ° C./minute, held at 150 ° C. for 5 minutes, and then cooled to 0 ° C. at a rate of 10 ° C./minute using liquefied nitrogen. After holding at 0 ° C. for 5 minutes, the temperature was raised again from 0 ° C. to 150 ° C. at a rate of 10 ° C. 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.

  The preparation examples of each material preparation method and agglomerated particle preparation method are described below.

[Synthesis of resin materials]
-Synthesis of crystalline polyester resin 1-
In a heat-dried three-necked flask, 120.0 parts by weight of 1,10-decanediol, 75.0 parts by weight of dimethyl sebacate, 7.0 parts by weight of sodium dimethyl 5-sulfoisophthalate, 4 parts by weight of dimethyl sulfoxide, Then, 0.03 part by weight of dibutyltin oxide was added as a catalyst, and then the air in the container was brought into an inert atmosphere with nitrogen gas by a depressurization operation, followed by stirring at 180 ° C. for 3 hours by mechanical stirring. Dimethyl sulfoxide was distilled off under reduced pressure, 23.0 parts by weight of dimethyl dodecanedioic acid was added under a nitrogen stream, and the mixture was stirred at 180 ° C. for 1 hour.

  Thereafter, the temperature was gradually raised to 220 ° C. under a reduced pressure of 10 Pa, and the mixture was stirred for 30 minutes. When it became a viscous state, it was air-cooled, the reaction was stopped, and a crystalline polyester resin 1 was synthesized.

  The weight average molecular weight (Mw) of the obtained crystalline polyester resin (1) was 18,000 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 non-crystalline polyester resin 1-
In a heat-dried three-necked flask,
Dimethyl terephthalate 87 parts by weight Dimethyl isophthalate 97 parts by weight Bisphenol A-ethylene oxide 2-mole adduct 158 parts by weight Propylene glycol 85 parts by weight Tetrabutoxy titanate 0.07 parts by weight were charged and heated at 170-220 ° C. for 180 minutes for ester. An exchange reaction was performed. Subsequently, as a result of continuing reaction for 60 minutes at 220 degreeC and the system pressure of 1-10 mmHg, the amorphous polyester resin 1 was obtained. The glass transition point was 65 ° C. and the weight average molecular weight was 27000.

-Synthesis of non-crystalline polyester resin 2-
Amorphous polyester resin 2 was synthesized under the same conditions as the synthesis of amorphous polyester resin 1 except that 0.05 part by weight of tetrabutoxy titanate was used and the reaction condition was changed to 230 ° C. for 100 minutes. The glass transition point was 66 ° C. and the weight average molecular weight was 46000.

-Synthesis of non-crystalline polyester resin 3-
Amorphous polyester resin 3 was synthesized under the same conditions as the synthesis of amorphous polyester resin 1 except that 0.05 part by weight of tetrabutoxy titanate was used and the reaction conditions were changed to 230 ° C. for 120 minutes. The glass transition point was 66 ° C. and the weight average molecular weight was 53,000.

-Synthesis of non-crystalline polyester resin 4-
Amorphous polyester resin 4 was synthesized under the same conditions as those for the synthesis of amorphous polyester resin 1 except that 0.1 part by weight of tetrabutoxy titanate was used and the reaction conditions were changed to 220 ° C. for 40 minutes. The glass transition point was 63 ° C. and the weight average molecular weight was 18,000.

-Synthesis of non-crystalline polyester resin 5-
Amorphous polyester resin 5 was synthesized under the same conditions as those for the synthesis of amorphous polyester resin 1 except that 0.1 parts by weight of tetrabutoxy titanate was used and the reaction conditions were changed to 220 ° C. for 70 minutes. The glass transition point was 63 ° C. and the weight average molecular weight was 22,000.

-Preparation of resin fine particle dispersion 1-
Using a resin obtained by synthesizing the crystalline polyester resin 1 and a resin obtained by synthesizing the amorphous polyester resin 1 by coarse pulverization with a hammer mill, resin fine particle dispersions were respectively prepared.

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 decompression device using a vacuum pump, and N ₂ was rapidly introduced at a rate of 0.2 L / m. and to replace the air in the system with N _2. Next, 21 parts by weight of crystalline polyester resin 1 and 279 parts by weight of 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 while 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. The acid value of this resin by KOH titration was 10 mmKOH / g.

-Preparation of resin fine particle dispersion 2-
It was produced in the same manner as the resin particle dispersion 1 except that the amorphous polyester resin 2 was used instead of the amorphous polyester resin 1. The acid value of this resin by KOH titration was 5 mmKOH / g.

-Preparation of resin fine particle dispersion 3-
It was produced in the same manner as the resin particle dispersion 1 except that the amorphous polyester resin 3 was used in place of the amorphous polyester resin 1. The acid value of this resin by KOH titration was 4 mmKOH / g.

-Preparation of resin fine particle dispersion 4-
It was produced in the same manner as in the preparation of the resin particle dispersion 1 except that the amorphous polyester resin 4 was used instead of the amorphous polyester resin 1. The acid value of this resin by KOH titration was 15 mmKOH / g.

-Preparation of resin fine particle dispersion 5-
It was produced in the same manner as the resin particle dispersion 1 except that the amorphous polyester resin 5 was used in place of the amorphous polyester resin 1. The acid value of this resin by KOH titration was 17 mmKOH / g.

-Preparation of cyan colorant dispersion-
50 parts by weight of cyan pigment (copper phthalocyanine CI Pigment Blue 15: 3, manufactured by Dainichi Seika)
Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight Ion exchange water 195 parts by weight The above components were mixed and dissolved, and dispersed for 10 minutes with a homogenizer (IKA Ultra Tarrax) to obtain a cyan colorant dispersion.

-Preparation of yellow colorant dispersion-
50 parts by weight of yellow pigment (CI Pigment Yellow 74: manufactured by Dainichi Seika)
Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight Ion-exchanged water 195 parts by weight The above was mixed and dissolved and dispersed with a homogenizer (IKA Ultra Tarrax) for 10 minutes to obtain a yellow colorant dispersion.

-Preparation of magenta colorant dispersion-
C. I. Pigment Red 122: (manufactured by Clariant) 50 parts by weight ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by weight ion-exchanged water 195 parts by weight The above components are mixed and dissolved, and then homogenizer (Ultra Turrax by IKA) is used for 10 minutes. Dispersion gave a magenta colorant dispersion.

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

-Preparation of release agent dispersion-
Paraffin wax FNP92 (melting point 91 ° C., manufactured by Nippon Seiwa Co., Ltd.) 50 parts by weight Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight Ion-exchanged water 195 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 wax dispersion.

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

-Production of Toner 1-
Resin fine particle dispersion 1 80 parts by weight Cyan colorant dispersion 60 parts by weight Release agent dispersion 60 parts by weight Polyaluminum chloride (manufactured by Asada Chemical Co., Ltd.) 0.41 parts by weight

  The above was thoroughly mixed and dispersed with an Ultra Turrax T50 in a round stainless steel flask. Subsequently, the dispersion operation was further continued with an ultra turrax. The inclination angle of the paddle blade, which is a stirring blade, is set to 45 degrees, and the inside of the flask is heated to 45 ° C. while stirring and mixing at 240 rpm using a stirring blade having a d / D of 0.5 in a heating oil bath. Held for a minute. At this time, the discharge flow rate and the volume ratio (Nqd / V) were 0.62.

  Next, 31 parts by weight of the resin fine particle 1 dispersion was gradually added.

  Then, after changing the stirring and mixing conditions to 150 rpm, the pH in the system was adjusted to 8.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then heated to 90 ° C. while stirring in the stainless steel flask was continued. And held for 3 hours.

  After completion of the reaction, the reaction mixture was cooled and subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times. When the pH of the filtrate was 7.01, the electric conductivity was 9.8 μS / cm, and the surface tension was 71.1 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Vacuum drying was then continued for 12 hours.

  When the particle diameter was measured, the volume average diameter D50 was 6.5 μm, and the particle size distribution coefficient GSD was 1.22.

-Production of Toner 2-
Toner 2 was produced under the same conditions as for toner 1 except that resin fine particle dispersion 2 was used instead of resin fine particle dispersion 1. The volume average diameter D50 was 6.5 μm, and the particle size distribution coefficient GSD was 1.24.

-Manufacture of toner 3-
The toner 3 was produced under the same conditions as in the production of the toner 1 except that the resin fine particle dispersion 3 was used instead of the resin fine particle dispersion 1. The volume average diameter D50 was 6.6 μm, and the particle size distribution coefficient GSD was 1.26.

-Manufacture of toner 4-
Toner 4 was produced under the same conditions as for toner 1 except that resin fine particle dispersion 4 was used instead of resin fine particle dispersion 1. The volume average diameter D50 was 6.2 μm, and the particle size distribution coefficient GSD was 1.22.

-Production of Toner 5-
The toner 5 was produced under the same conditions as in the production of the toner 1 except that the resin fine particle dispersion 5 was used instead of the resin fine particle dispersion 1. The volume average diameter D50 was 6.3 μm, and the particle size distribution coefficient GSD was 1.22.

-Manufacture of toner 6-
Toner 6 was produced under the same conditions as for toner 1 except that the stirring condition at 240 rpm was changed to 260 rpm. At this time, the discharge flow rate and the volume ratio (Nqd / V) were 0.67. The volume average diameter D50 was 6.3 μm, and the particle size distribution coefficient GSD was 1.22.

-Manufacture of toner 7-
Toner 7 was produced under the same conditions as for toner 1 except that the stirring condition at 240 rpm was changed to 160 rpm. At this time, the discharge flow rate and the volume ratio (Nqd / V) were 0.41. The volume average diameter D50 was 6.1 μm, and the particle size distribution coefficient GSD was 1.23.

-Production of Toner 8-
Toner 8 was produced under the same conditions as for toner 1 except that the stirring condition at 240 rpm was changed to 70 rpm. At this time, the discharge flow rate and the volume ratio (Nqd / V) were 0.23. The volume average diameter D50 was 6.0 μm, and the particle size distribution coefficient GSD was 1.25.

-Manufacture of toner 9-
Toner 9 was produced under the same conditions as for toner 1 except that the stirring condition at 240 rpm was changed to 46 rpm. At this time, the discharge flow rate and the volume ratio (Nqd / V) were 0.12. The volume average diameter D50 was 5.8 μm, and the particle size distribution coefficient GSD was 1.27.

-Production of Toner 10-
Toner 10 was produced under the same conditions as for toner 1 except that a magenta colorant dispersion was used instead of the cyan colorant dispersion. The volume average diameter D50 was 6.5 μm, and the particle size distribution coefficient GSD was 1.21.

-Manufacture of toner 11-
Toner 11 was produced under the same conditions as for toner 1 except that a yellow colorant dispersion was used instead of the cyan colorant dispersion. The volume average diameter D50 was 6.5 μm, and the particle size distribution coefficient GSD was 1.22.

-Manufacture of toner 12-
The toner 12 was produced under the same conditions as in the production of the toner 1 except that the black colorant dispersion was used instead of the cyan colorant dispersion. The volume average diameter D50 was 6.5 μm, and the particle size distribution coefficient GSD was 1.23.

-Creation of external toner-
To 100 parts by weight of the prepared toner, 1.5 parts by weight of hydrophobic silica (TS720: manufactured by Cabot) was added and blended with a Henschel mixer at 3000 rpm for 2 minutes.

<Manufacture of carriers>
1,000 parts of Mn—Mg ferrite (average particle size 35 μm: manufactured by Powder Tech Co., Ltd.) were put into a kneader, and a styrene-methyl methacrylate copolymer (polymerization ratio 40:60, Tg 100 ° C., weight average molecular weight 72,000: Soken) A solution obtained by dissolving 150 parts of Chemical Co., Ltd. in 700 parts of toluene was added, mixed at room temperature for 20 minutes, heated to 70 ° C. and dried under reduced pressure, and then taken out to obtain a coated carrier. Furthermore, the obtained coated carrier was sieved with a mesh having an opening of 75 μm, and coarse powder was removed to obtain a carrier.

<Manufacture of developer>
The carrier and the toner were respectively placed in a V blender at a weight ratio of 95: 5 and stirred for 20 minutes to obtain an electrophotographic developer.

-Evaluation-
The structure and characteristics of the toners produced in the production examples of the toners 1 to 12 were evaluated.
The SEM observation of the toner cross section includes at least an amorphous polyester resin, a crystalline polyester resin, a release agent, and a colorant. The total cross sectional area of the release agent in the structure is A, and the total cross sectional area of the toner is A. Assuming that the total cross-sectional area of the release agent is B, (A / B) × 100 was calculated. Also, the area ratio of the toner internal voids was calculated. The results are shown in Table 1.

Examples 1 to 10, Comparative Examples 1 and 2:
In order to evaluate the toner, the above-described electrophotographic developer was put into a DocuCentreColor400CP remodeling machine (manufactured by Fuji Xerox Co., Ltd.), and a 10 cm × 10 cm image was output at a toner loading of 3 g / m ^2. The condition of the central portion of the image was visually observed, and the surface gloss of the image was evaluated. The results are shown in Table 1. As the fixing paper, resin display paper (manufactured by Oji Paper Co., Ltd .: mirror coated platinum paper, 157.0 g / m ² ) was used. Evaluation was performed based on the following indicators.
A: There is no image defect.
○: There is slight unevenness in the center of the image.
(Triangle | delta): It is a tolerance | permissible_range although there exists an unevenness | corrugation in the image center part.
×: The image has a clear unevenness at the center, and the gloss is lowered.

(Toner structure)
The ruthenium-stained toner cross-section is observed with a transmission electron microscope, and image analysis is performed by the method described above. The total cross-sectional area of the toner in the structure is A, and the total cross-sectional area of the release agent in the total cross-sectional area of the toner is B. 100 × (A / B) was calculated.

(Evaluation of blocking)
The prepared developer has a peripheral speed of 1000 mm / sec, 1300 mm / sec, 1600 mm / sec of the developer holder that holds the developer provided in the developing devices 404a to 404d in an environment of 28 ° C./85% RH. sec, 1900 mm / sec, and 2200 mm / sec. The DocuCentreColor 400CP remodeling machine manufactured by Fuji Xerox shown in FIG. An image was output using 5-1. The developer used for this evaluation is a developer using toners 10, 11, and 12 other than cyan toner. The appearance of white streaks in the solid part of the image after printing 3000 sheets was confirmed. The toner in the developing unit was taken out and the state of the blocked toner was visually confirmed. Judgment criteria are as follows. The results are shown in Tables 1 and 2.
A: White streak is not generated and toner blocked in the developing device is hardly seen.
○: No white streak is generated, but a slight amount of blocked toner is observed in the developing device.
Δ: Little white streak is generated, and some blocked toner is observed in the developing device.
X: Generation of white streaks is clearly seen, and toner blocked in the developing device is seen.

(Toner internal void ratio)
The cross section of the toner was observed with a transmission electron microscope, and Luzex image analysis was performed by the method described above to determine the void ratio.

  The results of Examples and Comparative Examples are summarized in Tables 1 and 2. According to the toners used in Examples and Comparative Examples, blocking was suppressed and the surface gloss of the fixed image was good. Furthermore, even when the peripheral speed of the mag roll in the developing device was increased as compared with the prior art, a high quality image was 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.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 Mold release agent, 12 Crystalline polyester resin, 14 Amorphous polyester resin, 16 Space | gap, 100 structure, 200 Image forming apparatus, 401a-401d Electrophotographic photoreceptor, 400 Housing, 402a-402d Charge roll, 403 Exposure apparatus , 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 (4)

A toner comprising a crystalline polyester resin and a release agent,
There is a structure in which the crystalline polyester resin is in contact with the release agent on the cross section of the toner dyed with ruthenium, and the total cross sectional area of the release agent in the structure is A, and the total release agent in the total cross sectional area of the toner is A. Toner for electrostatic charge development wherein 50 ≦ (A / B) × 100 <100 where the cross-sectional area is B and the toner internal void area ratio to the cross-sectional area of the toner is 2 to 10% .   A crystalline polyester resin particle dispersion, an amorphous polyester resin particle dispersion, a release agent dispersion, and a colorant dispersion are mixed and aggregated using a flocculant, and the glass transition temperature of the crystalline polyester resin. A method for producing a toner for developing an electrostatic charge, wherein the toner is granulated by coalescence coalescence at a temperature equal to or higher than (Tg) and equal to or lower than a melting point of the release agent.   A developer for electrostatic charge development, comprising: a carrier obtained by coating a core particle surface with a 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. An image forming apparatus comprising: a transfer unit that transfers onto a transfer target; and a fixing unit that adds and fixes a toner image on the transfer target;
The electrostatic charge developing toner is the electrostatic charge developing toner according to claim 1,
2. An image forming apparatus according to claim 1, wherein a peripheral speed of the developer conveying means for conveying the developer provided in the developing means is 1200 mm / sec or more and 2000 mm / sec or less.