JP4853309B2 - Toner for developing electrostatic charge, developer for developing electrostatic charge, cartridge, method for producing toner for developing electrostatic image, image forming apparatus and image forming method - Google Patents

Description

  The present invention relates to an electrostatic charge developing toner (hereinafter also referred to as electrophotographic toner), an electrostatic charge developing developer, a cartridge, a method for producing an electrostatic charge image developing toner, an image forming apparatus, and an image forming method.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, the electrostatic latent image is developed with a developer containing toner, and visualized through a transfer and fixing process.

  As the developer used here, a two-component developer composed of a toner and a carrier, and a one-component developer using a magnetic toner or a non-magnetic toner alone are known. As a method for producing the toner, a kneading and pulverizing method is generally used in which a thermoplastic resin is melt-kneaded together with a release agent such as a pigment, a charge control agent, and a wax, and after cooling, is finely pulverized and classified. This method can produce a very good toner. However, the toner shape is irregularly shaped, fine powder is easily generated, and the release agent is easily exposed on the surface. There are some problems such as deterioration of image quality, deterioration of image quality, and contamination of other members.

  In recent years, there has been a growing demand for higher image quality, and in particular, in the formation of color images, there has been a significant tendency to reduce the toner diameter in order to achieve high-definition images. In particular, in digital full-color copiers and printers, a color image original is color-separated with B (blue), R (red), and G (green) filters, and then a dot in the range of 20 to 70 μm corresponding to the original original. A latent image consisting of a diameter is developed using Y (yellow), M (magenta), C (cyan), and Bk (black) developers using a subtractive color mixing effect, but compared to conventional black and white machines. In digital full-color copiers, etc., a large amount of developer needs to be transferred, and in order to correspond to the above small dot diameter, in addition to the above small diameter, there is uniform chargeability, durability, toner strength, and sharpness of particle size distribution. Becoming more important.

  On the other hand, as a means for intentionally controlling the toner shape and the toner surface structure, a toner production method using an emulsion polymerization aggregation method has been proposed (see, for example, Patent Documents 1 and 2). These are generally prepared by dispersing resin fine particles by emulsion polymerization or the like, while preparing a colorant dispersion in which a colorant is dispersed in a solvent, and then mixing these to form aggregated particles corresponding to the toner particle size, This is a method for producing toner by fusing and coalescing by heating. When this method is used, not only the toner having a sharp particle size distribution and a small particle diameter can be produced, but also the toner shape can be controlled and the exposure of the release agent to the toner surface can be suppressed.

  In addition, a metal element that can be an ion may be used mainly in the production process by the emulsion polymerization aggregation method. In particular, when a divalent or higher valent ion is used, it is often used because the cohesion is superior to that of a monovalent ion.

  On the other hand, in recent years, it is also assumed that the toner is used in an image environment where the transfer is burdensome, such as an image having a large amount of toner per unit area in a high humidity environment, and the transfer property of black toner has been improved so far. A method has been invented. For example, a method of improving the carbon black dispersion state in the toner by paying attention to the polarity of the dispersing agent (see, for example, Patent Document 3), or by using carbon black surface-treated with a polymer, the carbon black dispersion in the toner Examples thereof include a method for improving the state (for example, see Patent Document 4). In addition, there are reports mainly focusing on coloring by improving the dispersion of carbon black (for example, Patent Documents 5 to 9).

Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 JP-A-10-198070 JP 09-324134 A JP 2006-171501 A JP 2005-345881 A JP 2005-345881 A Japanese Patent Laid-Open No. 2003-207926 JP 2002-82492 A

  However, in the case of a toner containing a metal element capable of taking a valence of 2 or more, the metal element has a high water absorption property, so that the metal element has a strong water absorption, so it hydrates easily and takes an ion form, which further increases the water absorption property. As a result, the water content of the toner increases. For this reason, the electric resistance of the toner is lowered, the toner charge is likely to leak, and the charge amount may not be maintained. In addition, although there is no problem in a normal environment, there is a possibility that transferability may be deteriorated in an image environment in which transfer is burdensome, such as transfer of an image having a large amount of toner per unit area in a high humidity environment. In recent years, in the image quality and diversification of copying machines and printers, the above-mentioned requirements under the environment are important, and countermeasures need to be considered.

  Further, the improvement in transferability in the transfer situation as described above is still insufficient.

  Therefore, the present invention is for electrostatic charge development capable of suppressing deterioration in transferability in an image environment where the transfer is burdensome, such as an image having a large amount of toner per unit area in a high humidity environment. An object of the present invention is to provide a toner, a developer for developing an electrostatic charge, a cartridge, a method for producing a toner for developing an electrostatic image, an image forming apparatus, and an image forming method.

  The present invention is as follows.

(1) An electrostatic charge image developing toner containing a binder resin, a colorant, and a metal element capable of taking a valence of 2 or more, wherein the toner has a valence of 2 or more and is internally added to the electrostatic image development toner . The metal element capable of taking a valence is contained in 0.02 atm% or more and 0.2 atm% or less in a metal element unit measured by X-ray photoelectron spectroscopy, and the binder resin contains a dialcohol component, a dicarboxylic acid component, or the weight average molecular weight obtained by polymerizing a polycarboxylic acid component comprises 45000 or 55000 or less polyester resin, saw including any of the dialcohol component is bisphenol A- propylene oxide adduct or bisphenol A- ethylene oxide adducts, the dicarboxylic acid component is dodecenylsuccinic acid, the polycarboxylic acid component is trimellitic acid or pyromellitic acid polyethylene An ether resin, the coloring agent is a toner for developing electrostatic images comprising carbon black of the following BET specific surface area of ^70m 2 / g by volume primary particle diameter is not more 30nm or 50nm or less.

(2) An electrostatic image developing toner containing a binder resin, a colorant, and a metal element capable of taking a valence of 2 or more, wherein the toner has a valence of 2 or more and is internally added to the electrostatic image development toner . The metal element capable of taking a valence is aluminum, and is contained at 0.02 atm% or more and 0.2 atm% or less in terms of aluminum element measured by X-ray photoelectron spectroscopy of the aluminum. A weight average molecular weight obtained by polymerizing an alcohol component and a dicarboxylic acid component or a polycarboxylic acid component is a polyester resin having a weight average molecular weight of 45,000 or more and 55000 or less, and the dialcohol component is either a bisphenol A-propylene oxide adduct or a bisphenol A-ethylene oxide adduct. or only contains a said dicarboxylic acid component is dodecenylsuccinic acid, the polycarboxylic acid component A polyester resin is trimellitic acid or pyromellitic acid, the colorant, the volume primary particle size is characterized in that it comprises the following carbon black was at 30nm or more 50nm or less BET specific surface area of 70m 2 / ^g This is a toner for developing an electrostatic image.

( 3 ) An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to (1) or ( 2) and a carrier.

( 4 ) A latent image forming unit that forms a latent image on a latent image holding member, a developing unit that develops the latent image using an electrostatic charge developing developer, and a transfer of the developed image onto the transfer target A detachable cartridge having a transfer means for transferring, wherein the electrostatic charge developing developer includes the electrostatic charge developing toner described in (1) or ( 2) .

( 5 ) A method for producing a toner for developing an electrostatic charge image according to (1) or ( 2 ) above, wherein at least one resin particle dispersion and one or more colorant dispersions are mixed. An agglomeration step of forming aggregated particles in the presence of a metal element capable of taking a valence of 2 or more; and a toner by fusing and coalescing the aggregated particles by heating to a temperature above the glass transition point of the resin particles And a fusing step for forming particles.

( 6 ) 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 developer, and the developed toner image via an intermediate transfer member or a transfer unit that transfers onto the transfer member not through, said an image forming apparatus comprising a fixing unit that a toner image pressurizing fixing on the transfer member, wherein the electrostatic latent image developing developer, the ( An image forming apparatus which is the developer for electrostatic charge development described in 3) .

( 7 ) a latent image forming step of forming a latent image on the surface of the electrostatic charge image carrier, a development step of developing the latent image on the surface of the electrostatic charge image carrier with a developer containing toner, and obtaining a toner image; In the image forming method comprising a transfer step of transferring a toner image to the surface of the transfer target and a fixing step of thermally fixing the transferred toner image to the surface of the transfer target, the developer for developing electrostatic charge is the above ( An image forming method, which is the developer for electrostatic charge development according to 3) .

  According to the present invention, it is possible to suppress deterioration in transferability in a stressful transfer environment such as transfer in which the amount of toner per unit area is large in a high humidity environment.

According to the first aspect of the present invention, a metal element that uses a polyester resin having a highly hydrophobic dialcohol component and a highly hydrophobic colorant and can take a valence of 2 or more is contained within the above range. Therefore, while maintaining good cohesiveness at the time of toner production, the water content of the toner is not deteriorated, and as a result, the transferability of the toner in an image environment that imposes a burden on the transfer described above is a valence of 2 or more. This can be improved as compared with a conventional toner using a metal element capable of removing as a flocculant. Also, by making the dicarboxylic acid component or polycarboxylic acid component highly hydrophobic, the water content of the toner is improved compared to conventional toners that use a metal element capable of taking a valence of 2 or more as a flocculant. can do.

According to the invention of claim 2, by containing trivalent aluminum ions within the above range, the water content of the toner can have a valence of 2 or more while maintaining good cohesiveness during toner production. This can be improved as compared with a conventional toner using a metal element as a flocculant. Also, by making the dicarboxylic acid component or polycarboxylic acid component highly hydrophobic, the water content of the toner is improved compared to conventional toners that use a metal element capable of taking a valence of 2 or more as a flocculant. can do.

According to the third aspect of the invention, since the toner having improved water content is used, the transferability of the toner under the image environment that imposes a burden on the transfer described above is a metal element that can take a valence of two or more. This can be improved as compared with conventional toners using a flocculating agent.

According to the invention of claim 4 , since the cartridge uses toner with improved water content, the transferability of the toner in an image environment that imposes a burden on the transfer described above is improved, and even in the stress transfer environment described above. Excellent image quality can be obtained.

According to the fifth aspect of the present invention, the agglomeration is performed in the presence of a metal element capable of taking a valence of 2 or more capable of chelate coordination. Therefore, the content of the metal element in the toner can be reduced.

According to the inventions according to claims 6 and 7 , since the toner having improved water content is used, the transferability of the toner in an image environment that imposes a burden on the transfer described above is improved. Image quality can be obtained.

[Toner for electrostatic image development]
The toner for developing an electrostatic charge image (hereinafter also referred to as “toner”) of the present embodiment is a toner for developing an electrostatic charge image containing a binder resin and a colorant, and is a metal having a valence of 2 or more. The metal element containing an element and having a valence of 2 or more is contained in a metal element unit measured by X-ray photoelectron spectroscopy in an amount of 0.02 atm% to 0.2 atm%, and the binder resin is The weight average molecular weight obtained by polymerizing a dialcohol component and a dicarboxylic acid component or a polycarboxylic acid component is a polyester resin having a weight average molecular weight of 20,000 to 55,000, and the dialcohol component is a bisphenol A-propylene oxide adduct or a bisphenol A-ethylene oxide adduct. The colorant has a volume primary particle diameter of 30 nm to 50 nm and a BE. A toner for developing electrostatic images which is less carbon black specific surface area 70m 2 / ^g.

  In order to improve transfer in a high-humidity environment, it is required to remove excess water from the toner and to reduce the water content of the toner. As a cause of excessive moisture in the toner, ionization due to hydration of metal elements contained in the toner can be mentioned. Ions are generally known to have water content, but in particular, polyvalent metal ions that are divalent and higher than monovalent tend to increase water content. As a factor of containing a metal ion in the toner, there is a case where a compound that can be converted into a metal ion when produced by an emulsion polymerization aggregation method is used as an aggregating agent. Multivalent metal ions are preferably used because of their high cohesive strength.

  In the present embodiment, it is easy to selectively remove moisture from the toner by using, as a toner material, a highly hydrophobic polyester resin as a binder resin and a colorant containing carbon black with high hydrophobicity. Thus, the water content of the toner can be improved in a high humidity environment.

  The polyester resin of the binder resin includes a highly hydrophobic dialcohol component and a highly hydrophobic dicarboxylic acid component. The dialcohol component is a highly hydrophobic bisphenol A-propylene oxide adduct or bisphenol A-ethylene oxide adduct. Examples of the dicarboxylic acid component include highly hydrophobic dodecenyl succinic acid and the polycarboxylic acid component. Trimellitic acid or pyromellitic acid having high hydrophobicity. These polyester resins having high hydrophobicity are used, and the weight average molecular weight (Mw) is 20,000 to 55,000 which is relatively high and higher in hydrophobicity. If the weight average molecular weight of the polyester resin is less than 20000, sufficient hydrophobicity cannot be obtained and the moisture content in the toner cannot be sufficiently eliminated. If the weight average molecular weight of the polyester resin exceeds 55,000, sufficient Although hydrophobicity is obtained, the viscoelasticity of the toner increases, the movement of moisture content is suppressed, and conversely, it becomes difficult to be excluded from the toner. In the bisphenol A-propylene oxide adduct or bisphenol A-ethylene oxide adduct, the number of propylene oxide additions is 1 or more and 4 or less, and the number of ethylene oxide additions is 1 or more and 4 or less.

Carbon black contained in the colorant is highly hydrophobic. That is, the colorant includes carbon black particles having a relatively large volume primary particle diameter of 30 to 50 nm and a BET specific surface area of 70 m ² / g or less. When the volume primary particle size of the carbon black is less than 30 nm, the carbon black particles tend to agglomerate with each other. For this reason, moisture tends to be involved between the agglomerated particles, and a sufficient effect for eliminating moisture content cannot be exhibited. If the volume primary particle diameter of the carbon black exceeds 50 nm, the carbon black particles are too large, so that the toner may not be taken into the toner during production and may be exposed to the toner surface. In addition, when the BET specific surface area of the carbon black exceeds 70 m ² / g, the hydrophobicity is excessively improved, so that it is not possible to exert a sufficient effect for eliminating moisture contained in the carbon black from the beginning.

  In all the color toners other than the yellow toner, the colorant can contain the above-described highly hydrophobic carbon black. If the yellow toner does not contain the highly hydrophobic carbon black, and if the yellow toner is transferred last after the transfer of other color toners, good image quality can be achieved even in image formation under high temperature and high humidity. Is obtained.

  As the metal element capable of taking a valence of 2 or more, for example, a metal element capable of taking a valence of 2 or more, such as aluminum, copper, molybdenum, cobalt, iron, zinc, calcium, is used. The metal element capable of taking a valence is 0.02 atm% or more and 0.2 atm% or less in the metal element unit measured by X-ray photoelectron spectroscopy, and is contained in the toner. In addition, the metal element capable of taking a valence of 2 or more may be added as an aggregating agent, for example, when a toner is produced by an emulsion polymerization aggregation method (also referred to as “emulsion aggregation method”). Needless to say, a metal element that can take a valence of 2 or more is a solute that can be ionized by a solvent such as water and does not represent only a single element, more specifically, a valence of 2 or more. It refers to a compound having a metal element that can take a number.

  In addition, when aluminum that can take a trivalent valence is used as the metal element that can take a valence of 2 or more, the aluminum is an aluminum element unit measured by X-ray photoelectron spectroscopy (XPS) in the toner. By setting it to 0.02 atm% or more and 0.08 atm% or less, the stability of cohesiveness during production and the elimination of metal elements in the toner are improved, and the object of the present invention can be achieved. all right. Further, when a toner is produced by an emulsion polymerization aggregation method, the amount of a metal element capable of taking a valence of 2 or more in the toner is reduced by causing a chelating agent described later to act on the aggregated particles. It has been found that the removal and the manufacturability are most stable.

  In the present embodiment, as described above, the content of the metal element capable of taking a valence of 2 or more as measured by XPS is 0.02 atm% or more in metal element units as measured by X-ray photoelectron spectroscopy. In the case of an aluminum element, the content is preferably 0.02 atm% or more and 0.08 atm% or less. When the content of the metal element and the aluminum element supplying the metal element capable of taking a valence of 2 or more is less than 0.02 atm%, the water content can be improved, but the hot offset property is deteriorated when fixing the toner. There is. On the other hand, if the metal element content that supplies a metal element capable of taking a valence of 2 or more exceeds 0.2 atm%, a problem occurs in water content. In particular, when the aluminum element content exceeds 0.08 atm%, aluminum may have a problem because of its high water content. The aluminum element content is preferably in the range of 0.03 to 0.07 atm%, and more preferably in the range of 0.04 to 0.06 atm%.

  As will be described later, the metal element and aluminum content by XPS measurement is obtained near the surface of the toner (about 0.01 to 0.5 μm). In this embodiment, the vicinity of the toner surface is obtained. It can be obtained by measuring. Under high temperature and high humidity conditions, moisture enters from the outside through the toner surface to the inside. On the other hand, chargeability is caused by friction on the surface of the toner and is considered to leak from the surface. Therefore, if the measurement in the vicinity of the surface is performed, it is considered that the characteristics of the whole toner are shown.

  The contents of elements and aluminum elements by XPS measurement contained in the toner in the present embodiment were calculated by performing surface composition analysis by ESCA (X-ray photoelectron spectroscopy).

The ESCA apparatus and measurement conditions in the present embodiment are as follows.
Apparatus used: 1600S type X-ray photoelectron spectrometer manufactured by PHI (Physical Electronics Industries, Inc.).
Measurement conditions: X-ray source MgKα (400 W).
Spectroscopic region: 800 μm in diameter.

  In the present embodiment, the atomic concentration (atm%) was calculated from the measured peak intensity of each element using a relative sensitivity factor provided by PHI. The above measurement was performed by sputtering the toner surface in the depth direction with an Ar ion beam. After performing the sputtering treatment with the Ar ion beam, it was confirmed using a transmission electron microscope. The depth was in the range of 0.01 to 0.5 μm.

  Under the above conditions, the content of the metal element and aluminum element at a depth of about 0.01 to 0.5 μm from the surface of the toner can be determined. In addition, 0.02 atm% or more and 0.2 atm% in metal element units means the ratio of metal elements that can take a valence of 2 or more in the whole atom that can be measured by the X-ray photoelectron spectrometer. It is shown.

  Furthermore, as described above, the electrostatic image developing toner of the present embodiment includes at least a binder resin (binder resin) and a colorant, and further includes other components such as a release agent as necessary. The toner of the present invention will be described in detail by dividing it into each component.

(Binder resin)
A polyester resin is used as the binder resin in the present embodiment. An amorphous resin is used as the main component, but a crystalline resin may be used in combination. The polyester resin as the binder resin is composed of a highly hydrophobic dialcohol component and a highly hydrophobic dicarboxylic acid component. The dialcohol component is a highly hydrophobic bisphenol A-propylene oxide adduct or bisphenol A-ethylene oxide adduct. Examples of the dicarboxylic acid component include highly hydrophobic dodecynyl succinic acid and the polycarboxylic acid component. Trimellitic acid or pyromellitic acid having high hydrophobicity. These polyester resins having high hydrophobicity are used, and the weight average molecular weight (Mw) is 20,000 or more and 55,000 or less, which is relatively higher and more hydrophobic. In the latter part, the bisphenol A-propylene oxide adduct is abbreviated as “bisphenol A-PO adduct”, and the bisphenol A-ethylene oxide adduct is abbreviated as “bisphenol A-EO adduct”.

  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. In the present embodiment, the “crystallinity” of the crystalline resin refers to a resin having a clear endothermic peak rather than a step-like endothermic change in differential thermal analysis (DSC) described later. Specifically, it means that the half-value width of the endothermic peak when measured at a temperature elevation rate of 10 ° C./min is within 6 ° C. In the case of a polymer obtained by copolymerizing other components with the crystalline main chain, if the other components are 50% by mass or less, this copolymer is also called a crystalline resin. In addition, the amorphous resin in the present invention refers to a resin having only a stepwise endothermic change, not a clear endothermic peak in the DSC. More specifically, the base line of the DSC curve formed by the temperature and the endothermic amount shows an endothermic peak, and what does not fall on the extension line of the base line when the peak returns is called stepwise endothermic change.

  In addition to the polyester resin as the binder resin in the present embodiment, the following resins may be used in some cases.

  Specific examples include homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, acrylic acid Homopolymers or copolymers of esters having vinyl groups such as lauryl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; acrylonitrile, Homopolymers or copolymers of vinyl nitriles such as methacrylonitrile; Homopolymers or copolymers of vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketones Alone Polymer or copolymer, ethylene, propylene, butadiene, homopolymers or copolymers of olefins and isoprene; or mixtures thereof and the like. Further, silicone resins containing methyl silicone, methyl phenyl silicone, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, non-vinyl condensation resins such as polycarbonate resins, or mixtures of these with the vinyl resins Alternatively, a graft polymer obtained by polymerizing a vinyl monomer by coexistence thereof may be used.

  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 described above, after preparing the polyester resin, it can be dispersed together with the dispersion stabilizer under high temperature and high pressure conditions to prepare a resin particle dispersion.

(Coloring agent)
The carbon black contained in the colorant in the present embodiment is selected in view of hue angle, saturation, brightness, weather resistance, and dispersibility in the toner. Although carbon black black pigment is mainly used, each color toner is manufactured using some of the following pigments.

  That is, examples of the yellow pigment include chrome yellow, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa yellow, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow. NCG etc. are mentioned.

  Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK and the like.

  Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, lake red C , Rose bengal, oxin red, alizarin lake and the like.

  Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate and so on.

  Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.

  Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.

  Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine.

  These colorants can be used alone or in combination and further in the form of a solid solution. These colorants are dispersed by a known method, and for example, a rotary shear type homogenizer, a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like is preferably used.

  Further, when these colorants are used in the emulsion aggregation method described later, a polar surfactant is used and dispersed in an aqueous system by the homogenizer.

  In the present invention, the addition amount of the colorant dispersed in the toner is preferably in the range of 4 to 15% by mass with respect to the total mass of the toner.

  Further, when the toner is used as magnetism, magnetic powder may be contained. As such magnetic powder, a substance magnetized in a magnetic field is used, and it is a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite. In particular, when a toner is obtained in an aqueous phase, it is necessary to pay attention to the water layer's ability to migrate, dissolve and oxidize, and it is preferable to carry out surface modification, for example, a hydrophobic treatment. Is preferred.

  When a magnetic material is used as the black colorant, it is added in the range of 30 to 100 parts by mass with respect to the binder resin, unlike other colorants.

  In this Embodiment, a mold release agent can be used as needed.

  Specific examples of releasing agents that can be used include low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones having a softening point; fatty acid amides such as oleic acid amide, erucic acid amide, 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 wax, microcrystalline wax, Fischer-Tropsch wax, etc. Mineral / petroleum waxes; ester waxes of higher alcohols with higher fatty acids such as stearyl stearate and behenyl behenate; butyl stearate, propyl oleate, glyceryl monostearate, diste Ester waxes of higher fatty acids such as glyceryl acrylate, pentaerythritol tetrabehenate and unit price or polyhydric lower alcohols; higher grades such as diethylene glycol monostearate, dipropylene glycol distearate, distearic diglyceride, tetrastearic acid triglyceride Examples include ester waxes composed of fatty acids and polyhydric alcohol multimers; higher sorbitan fatty acid ester waxes such as sorbitan monostearate; higher cholesterol fatty acid ester waxes such as cholesteryl stearate.

  In the present invention, these release agents may be used alone or in combination of two or more.

  As an addition amount of a mold release agent, the range of 5-25 mass parts is preferable with respect to 100 mass parts of binder resin, and it is more preferable that it is the range of 7-20 mass parts.

  In the present embodiment, other components (particles) such as an internal additive, a charge control agent, and inorganic fine particles are added in addition to the binder resin, the colorant, and the release agent depending on the purpose. It is possible.

  Examples of internal additives include metals such as ferrite, magnetite, reduced iron, cobalt, manganese, and nickel, alloys, and magnetic materials such as compounds containing these metals, and inhibit charging properties as toner characteristics. A small amount can be used.

  The charge control agent is not particularly limited, but when a color toner is used, a colorless or light-colored agent can be preferably used. Examples include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments. From the viewpoint of controlling strength and reducing wastewater contamination, a material that is difficult to dissolve in water is preferred.

  In addition, inorganic fine particles can be added in a wet manner to the toner of the present embodiment in order to stabilize the chargeability. As the inorganic fine particles to be added, all of those usually used as external additives on the toner surface such as silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate can be used. It is preferable to use by dispersing with a molecular acid or a polymer base.

  The content of the other components only needs to be a level that does not hinder the purpose of the present embodiment, is generally a very small amount, specifically in the range of 0.01 to 5% by mass, Preferably it is the range of 0.5-2 mass%.

  The toner of the present embodiment preferably has at least one kind of metal oxide particles or organic particles on the surface for the purpose of imparting fluidity and improving cleaning properties.

  Specific examples of the metal oxide particles include silica, titania, zinc oxide, strontium oxide, aluminum oxide, calcium oxide, magnesium oxide, cerium oxide, and composite oxides thereof. Of these, silica and titania are preferably used from the viewpoints of particle size, particle size distribution, and manufacturability. These metal oxide particles are preferably subjected to surface modification such as hydrophobization, and conventionally known methods can be used as means for surface modification. Specific examples include coupling treatments such as silane, titanate, and aluminate.

  Examples of organic particles include resin particles such as vinyl resin, polyester, and silicone. These particles may be used alone or as a mixture of plural kinds. The amount added to these toners is not particularly limited, but is preferably used in the range of 0.1 to 10% by mass. More specifically, it is in the range of about 0.2 to 8% by mass.

  The gold oxide particles and organic particles are preferably added to the toner particle surfaces while being sheared.

  The volume average particle diameter of the toner according to the exemplary embodiment is preferably in the range of 3 to 9 μm, and more preferably in the range of 3 to 8 μm. When the volume average particle diameter of the toner particles exceeds 9 μm, the ratio of coarse particles increases, and the reproducibility and gradation of fine lines and fine dots of the image obtained through the fixing process are lowered. On the other hand, when the volume average particle size of the toner particles is less than 3 μm, the powder fluidity, developability, or transferability of the toner deteriorates, and the cleaning property of the toner remaining on the surface of the image carrier decreases. Various problems occur in other processes due to the deterioration of characteristics.

  Further, as the particle size distribution index of the toner particles used in the present embodiment, the volume average particle size distribution index GSDv is preferably 1.30 or less, and the ratio GSDv / GSDp to the number average particle size distribution index GSDp is 0.00. More preferably, it is 95 or more. When the volume distribution index GSDv exceeds 1.30, the unevenness of the fixed image described above becomes large, and uneven glossiness may easily occur. Further, when the ratio between the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp is less than 0.95, the amount of small particle size toner increases, and the amount of release agent contained per toner is uneven. May occur, and as a result, peeling failure may occur and a desired glossiness may not be obtained.

The volume average particle size and the particle size distribution index were measured and calculated as follows. First, the volume and number of individual toner particles are accumulated from the smaller diameter side with respect to the divided particle size range (channel) measured using Multisizer II (manufactured by Beckman-Coulter) as a measuring instrument. A distribution is drawn, and the particle size of 16% cumulative is defined as volume average particle size D16v and number average particle size D16p, and the particle size of 50% cumulative is defined as volume average particle size D50v (this value is the volume average particle size). And D50p. Similarly, particle diameters that are 84% cumulative are defined as volume average particle diameters D84v and D84p. Using these, the volume average particle size distribution index GSDv is defined as (D84v / D16v) ^1/2 and the number average particle size distribution index GSDp is defined as (D84p / D16p) ^1/2 .

  Furthermore, the toner shape factor SF1 in the present embodiment is preferably in the range of 110 to 145. When the shape factor SF1 is less than 110, the blade cleaning property of the transfer residual toner on the photosensitive member is impaired. When the shape factor SF1 exceeds 145, the fluidity of the toner is lowered, and the transfer property may be adversely affected from the beginning.

Here, the shape factor SF1 is obtained by the following equation (1).
SF1 = (ML ² / A) × (π / 4) × 100 (1)
In the above formula (1), ML represents the maximum length of the toner particles, and A represents the projected area of the toner particles.

  The SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and can be calculated as follows, for example. That is, an optical microscope image of the toner spread on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, the maximum length and the projected area of 50 or more toner particles are obtained, calculated by the above formula (1), and the average Obtained by determining the value.

  As long as the toner particles in the present embodiment are a production method containing a metal element capable of taking a valence of 2 or more in the toner, a kneading and pulverization method, a suspension polymerization method, a dissolution suspension method, and an emulsion aggregation coalescence Any production method such as a method can be used, but it is particularly effective for the emulsion polymerization aggregation coalescence method using a flocculant containing metal ions in the aggregation step as described above. It is also effective for a method of reducing the aluminum content by acting a chelating agent.

<Method for producing toner for developing electrostatic image>
The manufacturing method of the electrostatic charge image developing toner of the present embodiment is not particularly limited. However, as described above, the toner of the present invention limits the water absorption by the metal ions in the toner, so that the metal ions are actively used. It is effective for the method produced by the emulsion polymerization aggregation method used in the above.

  Hereinafter, the production method of the electrostatic image developing toner in the present embodiment will be described in detail by an emulsion polymerization aggregation method.

  The method for producing a toner for developing an electrostatic charge image according to the present embodiment is a metal that can take a valence of 2 or more by mixing at least one resin particle dispersion and one or more colorant dispersions. An aggregating step of forming aggregated particles in the presence of an element; and a fusing step of heating the resin particles to a temperature equal to or higher than the glass transition point of the resin particles to fuse and coalesce the aggregated particles to form toner particles.

  That is, the above production method generally uses a dispersion of an ionic surfactant of resin particles produced by emulsion polymerization or the like, and a colorant dispersion dispersed in an ionic surfactant of opposite polarity is mixed with this, This is a method in which agglomerated particles corresponding to the diameter of the toner are formed by hetero-aggregation and then heated to a temperature higher than the glass transition temperature of the resin so that the agglomerated particles are fused and united, washed and dried to obtain toner. The shape can be appropriately manufactured from an indeterminate shape to a spherical shape. In the toner of the present invention, a release agent fine particle dispersion may be added as appropriate.

  The manufacturing method is a method of mixing raw material dispersions in a lump, and aggregating and fusing them, but shifting the balance of the amount of the polar ionic dispersant in the initial stage of the aggregation process, For example, an inorganic metal salt containing a metal element capable of taking a valence of at least two or more, or a polymer containing at least aluminum is ionically neutralized to form core aggregated particles below the glass transition temperature. After stabilization, if necessary, after further stabilization by slightly heating at a high temperature below the glass transition temperature or melting point of the resin contained in the core aggregated particles or additional particles, the second As a step, a particle dispersion liquid having a polarity and quantity so as to compensate for the above-described balance deviation is added, and if necessary, the glass transition temperature of the resin contained in the core aggregated particles or additional particles After stabilizing by slight heating at high under temperature, fusing and coalescing remain adhered to the surface of the second stage added particles of core aggregated particles is heated above the glass transition temperature.

  In the toner manufacturing method in the present embodiment, it is preferable to add a chelating agent to the aggregated particles at least immediately before the actual fusion start in the fusion step. By adding a chelating agent to the aggregated particles before fusion / unification, the chelating agent coordinates to the metal ions introduced into the aggregated particles for aggregation in the aggregation process, and chelate coordination in the subsequent washing process Metal ions are removed from the toner, and as a result, the content of metal ions in the toner can be reduced.

  In order to reduce the content of the metal element capable of taking a valence of 2 or more in the toner as much as possible, for example, less than 0.02 atm%, for example, when the toner is manufactured, the amount of the aggregating agent is reduced in advance, Although it is conceivable to reduce the charged amount of metal ions, it is difficult to control from the viewpoint of ensuring the stability of particle growth in the aggregation process. On the other hand, even if a chelating agent is allowed to act on the toner particles that have been fused in the fusing process, the chelating agent cannot enter the toner particles, so that the chelate coordination metal ions are not removed from the toner in the subsequent washing process. It is not possible to obtain toner particles having a reduced metal ion content. Therefore, the metal ion content in the toner (including the inside of the toner particles) can be controlled by adding the chelating agent at the latest after the aggregation before the actual fusion start in the fusion step.

  In the following, description will be given in order. When the vinyl monomer is used as a raw material, the resin particle dispersion can be prepared by emulsion polymerization using an ionic surfactant or the like. In the case of other resins, use those that are oily and soluble in solvents with relatively low solubility in water. Dissolve the resin in those solvents and disperse the homogenizer together with the ionic surfactant or polymer electrolyte in water. A resin particle dispersion can be prepared by dispersing particles in water using a machine and then heating or reducing the pressure to evaporate the solvent.

  Examples of the dispersion medium in the resin particle dispersion, the colorant dispersion described later, the release agent dispersion, and other components in the present embodiment include an aqueous medium.

  Examples of the aqueous medium include water such as distilled water and ion exchange water, alcohol, and the like. These may be used individually by 1 type and may use 2 or more types together.

  A surfactant can be used for the purpose of stabilizing the dispersion of each dispersion. Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol type And nonionic surfactants such as alkylphenol ethylene oxide adducts and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable.

  In the toner of the present invention, an anionic surfactant generally has a strong dispersion power and is excellent in dispersion of resin particles and colorants. Therefore, an anionic surfactant is used as a surfactant for dispersing a release agent. It is advantageous to use a surfactant.

  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 be used in combination of 2 or more type.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Sodium alkylnaphthalene sulfonate such as dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate; sulfones such as naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Acid salts; lauryl phosphate, isopropyl phosphate, nonylphenyl ether Phosphoric acid esters such as Sufeto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate; sulfosuccinate salts such as sulfosuccinate lauryl disodium; and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene Trimethylammonium chloride, Quaternary ammonium salts such as quilts trimethyl ammonium chloride; and the like.

  Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Alkyl phenyl ethers such as ethylene nonyl phenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene Alkylamines such as oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate And so on.

  The content of the surfactant in each dispersion may be a level that does not inhibit the present invention, generally a small amount, specifically in the range of about 0.01 to 10% by mass, More preferably, it is the range of 0.05-5 mass%, More preferably, it is the range of about 0.1-2 mass%. When the content is less than 0.01% by mass, each dispersion such as a resin particle dispersion, a colorant dispersion, and a release agent dispersion becomes unstable, so that aggregation occurs, and each particle during aggregation There are problems such as the release of specific particles due to the difference in stability between them, and when the amount exceeds 10% by mass, the particle size distribution of the particles becomes wide, and the control of the particle size becomes difficult. It is not preferable for the reason. In general, a suspension polymerization toner dispersion having a large particle size is stable even if the amount of the surfactant used is small.

  Also, a room temperature solid aqueous polymer or the like can be used. Specifically, cellulose compounds such as carboxymethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, gelatin, starch, gum arabic and the like can be used.

  In addition, the colorant dispersion is prepared by using colorant particles having a desired color such as blue, red, and yellow using an ionic surfactant having a polarity opposite to that of the ionic surfactant used in the preparation of the resin particle dispersion. Prepare by dispersing in solvent. Furthermore, the release agent dispersion liquid is a homogenizer that disperses the release agent in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid, or a polymer base, and heats above the melting point and applies strong shear. Or by making fine particles with a pressure discharge type disperser.

  The resin particle diameter of the resin particle dispersion in the present embodiment is 1 μm or less in volume average particle diameter, and is preferably in the range of 100 to 300 nm. When the volume average particle size exceeds 1 μm, the particle size distribution of the toner particles obtained by agglomeration and fusion is widened, or free particles are generated, leading to a decrease in toner performance and reliability. If it is less than 100 nm, it may take time to coagulate and grow the toner, which may not be industrially suitable. If it exceeds 300 nm, the dispersion of the release agent and the colorant becomes non-uniform and control of the toner surface properties. May be difficult.

  In addition, particle diameters, such as a resin particle dispersion liquid, can be measured with a laser diffraction type particle size distribution measuring apparatus (LA-700 by Horiba, Ltd.), for example.

  In the aggregation step, the resin particle dispersion, the colorant dispersion, and, if necessary, the particles in the release agent dispersion are aggregated to form aggregated particles. The agglomerated particles are formed by heteroaggregation or the like. For the purpose of stabilizing the agglomerated particles and controlling the particle size / particle size distribution, the ionic surfactant having a polarity different from that of the agglomerated particles, or a monovalent or higher monovalent metal salt, A charged compound is added.

  Further, even if the process is performed by mixing and agglomerating all at once, in the agglomeration step, the initial balance of the amount of the ionic dispersant of each polarity is shifted in advance, and the ionic surfactant is Or a salt having a monovalent or higher charge such as a metal salt, which is ionically neutralized to form a first-stage matrix aggregation below the glass transition point, and then stabilized as a second-stage balance. After adding and coating a resin particle dispersion treated with a polar and quantity dispersing agent that compensates for the deviation, further heat below the glass transition point of the resin contained in the matrix or additional particles as necessary. After stabilization at a higher temperature, the particles added in the second stage of agglomeration by heating above the glass transition point are combined in a state of adhering to the surface of the agglomerated particles (attached particles) But it ’s okay. Furthermore, the stepwise operation of aggregation may be repeated several times.

  In the method for producing a toner for developing an electrostatic charge image according to the present embodiment, particles can be prepared by causing aggregation by pH change in the aggregation step. At the same time, a flocculant is added in order to stably and rapidly aggregate the particles, or to obtain agglomerated particles having a narrower particle size distribution.

  The flocculant is not particularly limited, and a metal salt of an inorganic acid is used as the flocculant in consideration of the stability of the flocculent particles, the stability of the flocculant with respect to heat and time, and removal during washing. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate. In the present embodiment, the effects described above are included. From the above viewpoint, an aggregating agent containing a divalent or higher polyvalent metal ion, for example, polyaluminum chloride, aluminum sulfate, potassium alum and the like is used.

  The amount of the flocculant added varies depending on the valence of the charge, but the amount is small, and in the case of trivalent such as aluminum, it is about 0.5% by mass or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

  In the present embodiment, a chelating agent may be further mixed after the temperature increase in the aggregation process. When the chelating agent is mixed at this stage, since the desired aggregated particles are formed, aggregation of the chelating agent is not hindered. Note that the addition of the chelating agent is not necessarily performed at this stage, and may be performed at the latest before the start of actual fusion as described above, and therefore may be added at the start of heating for fusion, that is, The chelating agent may be mixed after the aggregation step and before or during the fusion step.

  The chelating agent in the present embodiment is a general term for a metal ion sequestering effect generally called a chelating agent, and the chelating agent is preferably water-soluble. If it is not water-soluble, it may have poor dispersibility in the liquid and may not be sufficiently coordinated with metal ions in the toner.

  Examples of chelating agents that can be used include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, and diethylenetriamine. Aminopolycarboxylic acids such as pentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraaminehexaacetic acid and the like can be suitably used. Of these, aminopolycarboxylic acids such as EDTA are preferably used because they do not cause deterioration of the electrical characteristics and various characteristics of the toner.

  These chelating agents are desirably used in a state of being dissolved and diluted in water or the like. When using a composite consisting of a resin and a colorant, the resin and the colorant are dissolved and dispersed in a solvent, then dispersed in water together with the appropriate dispersant, and the solvent is removed by heating and decompression. It can be made to act on the aggregated particles by a method of obtaining, a method of imparting to the surface of resin particles produced by emulsion polymerization with a mechanical shear force, or a method of electrically adsorbing and fixing. These methods are effective in, for example, suppressing the liberation of the colorant as additional particles or improving the chargeable colorant dependency.

  As the addition amount of the chelating agent, the addition amount of the chelating agent is preferably in the range of 0.1 to 15 parts by mass, and in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. More preferably. When the addition amount of the chelating agent is less than 0.1 part by mass, the effect of adding the chelating agent is not obtained even if hexavalent aminopolycarboxylic acid is used, and the water content in the toner may not be improved. On the other hand, when the amount exceeds 15 parts by mass, the water content in the toner is improved, but the viscoelasticity of the toner is lowered and the fixability may be adversely affected.

  After the aggregated particles (including adhered particles) are formed and further a chelating agent is added, the aggregated particles are united in a fusion step. In the fusion step, under the same agitation as in the agglomeration step, the pH of the suspension of the agglomerated particles is set in the range of 6.0 to 9.5 to stop the agglomeration, and this agglomeration is performed in the solution. Glass transition temperature of amorphous resin particles (including shell layer-constituting resin) contained in the particles (if there are two or more types of resins, the glass transition temperature of the resin having the highest glass point transition temperature), and crystals When the crystalline resin is contained, the toner particles are obtained by heating to the highest temperature among the melting points of the crystalline resin, and fusing and coalescing.

  After completion of the aggregation and fusion process, a desired toner is obtained through an arbitrary washing process, solid-liquid separation process, and drying process. In the washing process, replacement washing with ion-exchanged water is sufficiently performed from the viewpoint of chargeability. preferable. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Further, although the drying process is not particularly limited, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  The toner for developing an electrostatic charge image in this embodiment is produced by preparing toner particles (mother particles) as described above, adding the inorganic fine particles to the toner particles, and mixing with a Henschel mixer or the like. be able to.

<Electrostatic image developer>
The electrostatic charge image developer of the present embodiment is not particularly limited except that it contains the above-described electrostatic latent image developing toner of the present embodiment, and can have an appropriate component composition depending on the purpose. The electrostatic image developer of the present invention becomes a one-component electrostatic image developer when the toner for developing an electrostatic image is used alone, and a two-component electrostatic image developer when used in combination with a carrier. It becomes.

  For example, when the carrier is used, the carrier is not particularly limited, and examples thereof include known carriers, such as those described in JP-A Nos. 62-39879 and 56-11461. A known carrier such as a resin-coated carrier can be used.

  Specific examples of the carrier include the following resin-coated carriers. Examples of the core particle of the carrier include ordinary iron powder, ferrite, magnetite molding, and the like, and the volume average particle diameter 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, 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; acrylonitrile, methacrylonitrile, etc. Vinyl 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 Homopolymers such as vinyl ketones such as ketones; olefins such as ethylene and propylene; vinyl-based fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene and hexafluoroethylene; and copolymers composed of 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 mass, more preferably in the range of 0.5 to 3.0 parts by mass with respect to 100 parts by mass 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. .

  The mixing ratio of the electrostatic latent image developing toner of the present invention and the carrier in the electrostatic image developer is not particularly limited and may be appropriately selected according to the purpose.

<Image forming apparatus>
Next, an example of the image forming apparatus according to 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.

<Image forming method>
The image forming method of the present embodiment includes a latent image forming step, a developing step, a transfer step, and a fixing step. Each of the above steps is a general step, and is described in, for example, Japanese Patent Laid-Open Nos. 56-40868 and 49-91231 in addition to the above-described image forming apparatus. The image forming method of the present invention can be carried out using an image forming apparatus such as a copier or a facsimile machine known per se.

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

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

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

  The latent image forming step forms a latent image on the surface of the electrostatic image carrier. In the development step, the latent image is developed with a developer layer on the surface of the developer carrying member to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of the present embodiment containing the electrostatic image developing toner of the present embodiment. In the transfer step, the toner image is transferred to the surface of the transfer target. In the fixing step, the toner image transferred onto the surface of the transfer medium is fixed to the recording medium by heating from the fixing member.

  In the case where a secondary transfer process using an intermediate transfer member is included, the transfer member includes an intermediate transfer member. Further, in the case of heat fixing by the fixing device, in order to prevent an offset or the like, a release agent is usually supplied to a fixing member in the fixing device. Examples of the transfer target (recording material) to which the toner image is transferred include plain paper, OHP sheet, and the like used in electrophotographic copying machines and printers.

[Preferred embodiment]
(I) A method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein at least one resin particle dispersion and one or more colorant dispersions. And agglomeration step in which aggregated particles are formed in the presence of a metal element capable of taking a valence of 2 or more, and the aggregated particles are fused and combined by heating to a temperature above the glass transition point of the resin particles. A toner for electrostatic image development, comprising: a fusing step for forming toner particles, wherein a chelating agent is added after the agglomeration step or before the fusing step or before completion of fusing in the fusing step It is a manufacturing method.

  (Ii) In the method for producing a toner for developing an electrostatic charge image according to (i), the chelating agent includes oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), and ethylenediamine. This is a method for producing a toner for developing an electrostatic charge image, which is at least one selected from the group consisting of tetraacetic acid (EDTA), nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, and triethylenetetraaminehexaacetic acid.

  (Iii) In the method for producing a toner for developing an electrostatic charge image of (i) above, the chelating agent is ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraamine 6 A method for producing a toner for developing an electrostatic image, which is an aminopolycarboxylic acid selected from at least one selected from the group consisting of acetic acid.

  Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. In the following description, “part” represents “part by mass” and “%” represents “% by mass” unless otherwise specified.

<Measuring method of various characteristics>
First, methods for measuring physical properties of toners and the like used in Examples and Comparative Examples will be described.

(Toner particle size and particle size distribution measurement method)
In the present invention, the toner particle size and particle size distribution were measured using Multisizer II (Beckman-Coulter) as the measuring device and ISOTON-II (Beckman-Coulter) 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 to 150 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 2 to 60 μm particles is measured using the Multisizer II type with an aperture diameter of 100 μm. Thus, the volume average particle diameter, GSDv, and GSDp were obtained. The number of particles to be measured was 50,000.

(Toner shape factor SF1 measurement method)
The toner shape factor SF1 is obtained by taking an optical microscope image of toner dispersed on a slide glass into a Luzex image analysis apparatus through a video camera and calculating the square of the maximum length of ten toners (ML ² ) and the projected area (A). The shape factor SF1 of each toner obtained by the following formula is calculated, and the average value is obtained.
SF1 = (ML ² / A) × (π / 4) × 100 (where π is the circumference)

(Measurement method of weight average molecular weight and molecular weight distribution of resin)
In the present invention, the molecular weight and molecular weight distribution of the binder resin and the like are those obtained under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)”, and the column uses two “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” 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 ”.

(Volume average particle diameter of resin fine particles, colorant particles, etc.)
Volume average particle diameters of resin fine particles, colorant particles, and the like were measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

(Measurement method of glass transition temperature of resin)
The glass transition point (Tg) of the amorphous resin was measured according to ASTM D3418-8 using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001), and the temperature rising rate from room temperature to 150 ° C. was 10 It was determined by measuring under the conditions of ° C / min. The glass transition point was the temperature at the intersection of the extension line of the base line and the absorption line in the endothermic part (so-called onset temperature).

(Metallic element content that can take a valence of 2 or more)
The content of elements and aluminum elements by XPS measurement was calculated by performing surface composition analysis by ESCA (X-ray photoelectron spectroscopy). The ESCA apparatus and measurement conditions are as follows.
Apparatus used: 1600S type X-ray photoelectron spectrometer manufactured by PHI (Physical Electronics Industries, Inc.).
Measurement conditions: X-ray source MgKα (400 W).
Spectroscopic region: 800 μm in diameter.
The atomic concentration (atm%) was calculated from the measured peak intensity of each element using a relative sensitivity factor provided by PHI. The above measurement was performed by sputtering the toner surface in the depth direction with an Ar ion beam. After performing the sputtering treatment with the Ar ion beam, it was confirmed using a transmission electron microscope. The depth was in the range of 0.01 to 0.5 μm.

<Preparation of each dispersion>
For the toners used in Examples and Comparative Examples, the following resin particle dispersions and colorant dispersions were prepared, mixed at a predetermined ratio and stirred, and at least a valence of 2 or more was taken. A polymer of an inorganic metal salt containing aluminum was added as a supply source of a possible metal element, and ionized neutralized to form aggregated particles. Thereafter, the pH in the system was adjusted from weakly acidic to neutral with a chelating agent and an inorganic hydroxide, and then heated to a temperature higher than the glass transition temperature of the resin fine particles to be fused and united. Then, the desired toner was obtained through sufficient steps of washing, solid-liquid separation, and drying.

-Preparation of resin particle dispersion (1)-
Bisphenol A-propylene oxide adduct (PO 3 mol addition): 814 parts by mass Dodecenyl succinic acid: 1392 parts by mass The above was added to a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column. After charging the monomer and raising the temperature to 190 ° C. over 1 hour and confirming that the inside of the reaction system was uniformly stirred, 1.2 parts by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was raised to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued for an additional 4 hours at 240 ° C. A resin particle dispersion liquid having a weight average molecular weight of 45000 (1 ) Subsequently, this was transferred in a molten state to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37 wt% diluted ammonia water diluted with ion-exchanged water with reagent-exchanged water, and heated at 120 ° C with a heat exchanger at a rate of 0.1 liter per minute. The polyester resin melt was transferred to the Cavitron (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² , and a resin particle dispersion (1) (resin particle concentration: 30% by weight) made of polyester resin having an average particle size of 0.14 μm was obtained. Obtained.

-Preparation of resin particle dispersion (2)-
Bisphenol A-ethylene oxide adduct (EO 2 mol addition): 820 parts by mass
Dodecenyl succinic acid: 1390 parts by mass A resin particle dispersion (2) having a weight average molecular weight of 40,000 is obtained in the same manner as in the preparation of the resin dragon dispersion (1) except that the duration of the dehydration condensation reaction is 3 hours. It was. Next, this was emulsified and dispersed with Cavitron in the same manner as the preparation conditions of the resin particle dispersion (1), and a resin particle dispersion (2) (resin particle concentration: 30% by weight) made of a polyester resin having an average particle size of 0.16 μm was obtained. Obtained.

-Preparation of resin particle dispersion (3)-
Bisphenol A-propylene oxide adduct (PO 3 mol addition): 814 parts by weight trimellitic acid: 1392 parts by weight Resin particles having a weight average molecular weight of 45,000, reacted in the same manner as in the preparation of the resin particle dispersion (1). A dispersion (3) was obtained. Next, this was emulsified and dispersed with Cavitron in the same manner as the preparation conditions of the resin particle dispersion (1), and a resin particle dispersion (3) (resin particle concentration: 30% by weight) made of a polyester resin having an average particle size of 0.16 μm was obtained. Obtained.

-Preparation of resin particle dispersion (4)-
Bisphenol A-propylene oxide adduct (PO 2 mol addition): 800 parts by mass pyromellitic acid: 1400 parts by mass The same procedure as in the preparation of the resin particle dispersion (1) except that the time for the dehydration condensation reaction was 5 hours. To obtain a resin particle dispersion (4) having a weight average molecular weight of 50,000. Next, this was emulsified and dispersed with Cavitron in the same manner as the preparation conditions of the resin particle dispersion (1), and a resin particle dispersion (4) (resin particle concentration: 30% by weight) made of a polyester resin having an average particle size of 0.16 μm was obtained. Obtained.

-Preparation of resin particle dispersion (5)-
Bisphenol A-ethylene oxide adduct (EO 1 mol addition): 820 parts by mass Dodecinyl succinic acid: 1390 parts by mass Except for setting the duration of the dehydration condensation reaction to 2 hours, A resin particle dispersion (5) having a weight average molecular weight of 15000 was obtained. Subsequently, this was emulsified and dispersed with Cavitron in the same manner as the preparation conditions for the resin particle dispersion (1), and a resin particle dispersion (5) (resin particle concentration: 30% by weight) made of a polyester resin having an average particle size of 0.16 μm was obtained. Obtained.

-Resin particle dispersion (6)-
Ethylene glycol: 486 parts by mass Neopentyl glycol: 650 parts by mass Terephthalic acid: 957 parts by mass The reaction was carried out in the same manner as in the preparation of the resin particle dispersion (1). A resin particle dispersion (6) having a weight average molecular weight of 9,200 was obtained. Next, this was emulsified and dispersed with Cavitron in the same manner as the preparation conditions for the resin particle dispersion (1), and a resin particle dispersion (6) (resin particle concentration: 30% by weight) made of a polyester resin having an average particle size of 0.16 μm was obtained. Obtained.

-Preparation of resin particle dispersion (7)-
Bisphenol A-ethylene oxide adduct (EO 1 mol addition): 820 parts by mass
Terephthalic acid: 1390 parts by mass A resin particle dispersion (7) having a weight average molecular weight of 30000 was obtained in the same manner as in the preparation of the resin particle dispersion (1). Next, this was emulsified and dispersed with Cavitron in the same manner as the preparation conditions for the resin particle dispersion (1), and a resin particle dispersion (7) (resin particle concentration: 30% by weight) made of a polyester resin having an average particle size of 0.16 μm was obtained. Obtained.

-Preparation of resin particle dispersion (9)-
Bisphenol A-propylene oxide adduct (PO 3 mol addition): 780 parts by mass pyromellitic acid: 1420 parts by mass Except for setting the time for the dehydration condensation reaction to 5 hours, the same procedure as in the preparation of the resin particle dispersion (1) was performed. To obtain a resin particle dispersion (9) having a weight average molecular weight of 53,000. Next, this was emulsified and dispersed with Cavitron in the same manner as the preparation conditions of the resin particle dispersion (1), and a resin particle dispersion (9) (resin particle concentration: 30% by weight) comprising a polyester resin having an average particle size of 0.16 μm was obtained. Obtained.

-Preparation of resin particle dispersion (10)-
Bisphenol A-propylene oxide adduct (PO 4 mol addition): 800 parts by mass pyromellitic acid: 1400 parts by mass The same procedure as in the preparation of the resin particle dispersion (1) except that the time for the dehydration condensation reaction was changed to 6 hours. To obtain a resin particle dispersion (10) having a weight average molecular weight of 60000. Next, this was emulsified and dispersed with a Cavitron under the same conditions as for the preparation of the resin particle dispersion (1), and a resin particle dispersion (10) (resin particle concentration: 30% by weight) comprising a polyester resin having an average particle size of 0.16 μm was obtained. Obtained.

-Preparation of colorant dispersion (1)-
Carbon black (Mitsubishi Kasei Co., Ltd., # 25; primary particle size 47 nm, BET specific surface area 40 m ² / g): 90 parts by mass anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC): 10 parts by mass ion Exchanged water: 240 parts by weight The above mixture is mixed and dispersed for 15 minutes using a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then applied to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP). A particle dispersion (1) was prepared. The number average particle diameter of the colorant in the colorant dispersion (1) was 145 nm.

-Preparation of colorant dispersion (2)-
Carbon black (Asahi Carbon Co., # 60HMAF; primary particle size 35 nm, BET specific surface area 49 m ² / g): 90 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC): 10 parts by mass Part / ion exchange water: 240 parts by mass The above was mixed to prepare a colorant particle dispersion (2) under the same conditions as in the colorant dispersion (1). The number average particle diameter of the colorant in the colorant dispersion (2) was 150 nm.

-Preparation of colorant dispersion (3)-
Carbon black (manufactured by Cabot, REGAL 330; primary particle diameter 25 nm, BET specific surface area 94 m ² / g): 90 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC): 10 parts by mass Ion-exchanged water: 240 parts by mass The above was mixed to prepare a colorant particle dispersion (3) under the same conditions as the colorant dispersion (1). The number average particle diameter of the colorant in the colorant dispersion (3) was 150 nm.

-Preparation of cyan colorant dispersion-
CI Pigment Blue 15: 3: manufactured by Dainichi Seika Co., Ltd. 50 parts by mass ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by mass ion-exchanged water 195 parts by mass The above components are mixed and dissolved, and a homogenizer (IKA Ultra Tarax) ) For 10 minutes to obtain a colorant dispersion having a central particle size of 168 nm.

-Preparation of yellow colorant dispersion-
CI Pigment Yellow 74: manufactured by Dainichi Seika Co., Ltd. 50 parts by mass ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by mass ion-exchanged water 195 parts by mass The above components are mixed and dissolved, and homogenizer (IKA Ultra Tarax) is used. Dispersion for 10 minutes gave a colorant dispersion with a central particle size of 168 nm.

-Preparation of magenta colorant dispersion-
C. I. PigmentRed 122: (manufactured by Clariant) 50 parts by mass ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 6 parts by mass ion-exchanged water 200 parts by mass The above is mixed and dissolved for 10 minutes using a homogenizer (IKA Ultra Tarax). Thus, a magenta colorant dispersion having a center particle size of 185 nm and a solid content of 23.5 parts by weight was obtained.

<Example 1>
(Manufacture of toner 1)
Ion exchange water: 500 parts by mass Resin particle dispersion (1): 175 parts by mass Colorant dispersion (1): 35 parts by mass flocculant (Asada Chemical Co., Ltd., 1% aqueous solution of polyaluminum chloride): 0.5 mass Part The above components were mixed and mixed and dispersed with a homogenizer (Ultra Turrax T50, manufactured by IKA) in a round stainless steel flask. Next, the agglomeration temperature was heated to 40 ° C. while stirring the flask in a heating oil bath and held for 30 minutes. Then, it heated to 45 degreeC and hold | maintained for 1.5 hours. 25 parts by mass of the resin particle dispersion (1) was further slowly added to the prepared dispersion containing aggregated particles, and the temperature of the heating oil bath was raised and maintained at 46 ° C. for 1 hour.

  Then, 1 mol / L sodium hydroxide aqueous solution was added so that the pH in the system was 7.5, and then the stainless steel flask was sealed and gently heated to 85 ° C. while continuing stirring using a magnetic seal. And then heated to 90 ° C. and held for 5 hours.

  After the completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then dried using a vacuum dryer to prepare toner particles 1. The toner particles 1 have a volume average particle size of 5.9 μm and a volume particle size distribution index GSDv of 1.23. In addition, the particle shape factor SF1 obtained from the shape observation by the Luzex image analyzer was 130. Furthermore, the aluminum content rate calculated | required from the XPS measurement was 0.08 atm%.

(Preparation of developer 1)
To 100 parts by mass of the produced toner particles, 0.70 part of hydrophobic silica (TS720, manufactured by Cabot) was added and blended in a sample mill. A ferrite carrier having a volume average particle diameter of 50 μm coated with 1% of polymethyl methacrylate (manufactured by Soken Chemical Co., Ltd .: Mw = 80000) was weighed so that the toner concentration would be 5%, and stirred and mixed in a ball mill for 5 minutes. Developer 1 was prepared.

<Example 2>
In the production of the toner in Example 1, the toner 2 and the developer 2 were prepared in the same manner except that the resin particle dispersion (2) was used instead of the resin particle dispersion (1), and the same evaluation was performed. . Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 3>
In the production of the toner in Example 1, the resin particle dispersion (3) was used instead of the resin particle dispersion (1), and the colorant dispersion (2) was used instead of the colorant dispersion (1). Similarly, toner 3 and developer (3) were prepared and evaluated in the same manner. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 4>
In the production of the toner in Example 1, the resin particle dispersion (4) was used instead of the resin particle dispersion (1), and the colorant dispersion (2) was used instead of the colorant dispersion (1). Similarly, a toner 4 and a developer 4 were produced and evaluated in the same manner. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 5>
In the production of the toner in Example 1, the resin particle dispersion (4) was used instead of the resin particle dispersion (1), and the temperature of the heating oil bath was raised and held at 46 ° C. for 1 hour. Ethylenediaminetetraacetic acid Na salt (manufactured by Chubu Kirest Co., Ltd., Kirest 40) was added as a chelating agent so as to be 5% of the total liquid. Otherwise, toner 5 and developer 5 were prepared in the same manner as in Example 1, and the same evaluation was performed. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 7>
In the production of the toner in Example 1, the resin particle dispersion (9) is used instead of the resin particle dispersion (1), and a 1 mol / L sodium hydroxide aqueous solution is adjusted so that the pH in the system becomes 7.5. After the addition, Toner 7 and developer were similarly sealed except that the stainless steel flask was sealed, gently heated to 85 ° C. while continuing to stir using a magnetic seal, then heated to 90 ° C. and held for 3 hours. 7 was produced and evaluated in the same manner. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 8>
In the production of the toner in Example 1, the resin particle dispersion (9) is used instead of the resin particle dispersion (1), and a 1 mol / L sodium hydroxide aqueous solution is adjusted so that the pH in the system becomes 7.5. After the addition, Toner 8 and developer were similarly sealed except that the stainless steel flask was sealed, gently heated to 85 ° C. while continuing to stir using a magnetic seal, then heated to 90 ° C. and held for 2 hours. 8 was produced and evaluated in the same manner. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 9>
In the production of the toner in Example 5, the same procedure was performed except that the addition amount of the flocculant (manufactured by Asada Chemical Co., Ltd., 1% aqueous solution of polyaluminum chloride) was changed to 0.15 parts by weight instead of 0.5 parts by weight. Toner 9 and developer 9 were prepared and evaluated in the same manner. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 10>
In the production of the toner in Example 5, the toner 10 and the toner 10 and the flocculant were similarly replaced except that instead of 1% aqueous solution of polyaluminum chloride, 0.45 parts by weight of 1% aqueous solution of iron (III) chloride was replaced. Developer 10 was prepared and evaluated in the same manner. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 11>
In the production of the toner in Example 1, the toner 11 and the developer 11 are the same except that the flocculant is replaced with 0.57 parts by weight of 1% aqueous solution of copper chloride instead of 1% aqueous solution of polyaluminum chloride. The same evaluation was performed. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 12>
In the production of the toner in Example 1, the toner 12 and the developer 12 are the same except that the flocculant is replaced with 0.59 parts by weight of a 1% aqueous solution of cobalt nitrate instead of a 1% aqueous solution of polyaluminum chloride. The same evaluation was performed. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 13>
In the production of the toner in Example 1, instead of 35 parts by weight of the colorant dispersion (1), 1 part by weight of the colorant dispersion (1) and 40 parts by weight of the cyan colorant dispersion were added. In the same manner, the toner 13 and the developer 13 were produced, and the same evaluation was performed. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 14>
In the production of the toner in Example 1, instead of 35 parts by mass of the colorant dispersion (1), 0.5 part by mass of the colorant dispersion (1) and 48 parts by mass of the magenta colorant dispersion were added. Except for the above, toner 14 and developer 14 were produced in the same manner, and the same evaluation was performed. Table 1 summarizes the characteristics and evaluation results of the toner.

<Example 15>
In the production of the toner in Example 1, instead of the colorant dispersion (1): 35 parts by mass, the colorant dispersion (1): 1 part by mass, the cyan colorant dispersion: 25 parts by mass, and the yellow colorant dispersion Liquid: Toner 15 and developer 15 were prepared in the same manner except that 25 parts by mass were added, and the same evaluation was performed. Table 1 summarizes the characteristics and evaluation results of the toner.

<Comparative Example 1>
In the production of the toner in Example 1, the resin particle dispersion (6) was used instead of the resin particle dispersion (1), and the colorant dispersion (3) was used instead of the colorant dispersion (1). In the same manner, the toner 16 and the developer 16 were produced, and the same evaluation was performed. Table 1 summarizes the characteristics and evaluation results of the toner.

<Comparative example 2>
In the production of the toner in Example 1, the toner 17 and the developer 17 were prepared in the same manner except that the resin particle dispersion (5) was used instead of the resin particle dispersion (1), and the same evaluation was performed. It was. Table 1 summarizes the characteristics and evaluation results of the toner.

<Comparative Example 3>
In the production of the toner in Example 1, the toner 18 and the developer 18 were prepared in the same manner except that the colorant dispersion (3) was used instead of the colorant dispersion (1), and the same evaluation was performed. It was. Table 1 summarizes the characteristics and evaluation results of the toner.

<Comparative example 4>
In the production of the toner in Example 1, the toner 19 and the developer 19 were prepared in the same manner except that the resin particle dispersion (7) was used instead of the resin particle dispersion (1), and the same evaluation was performed. It was. Table 1 summarizes the characteristics and evaluation results of the toner.

<Comparative Example 5>
In the production of the toner in Example 1, the toner 20 and the developer 20 were prepared in the same manner except that the resin particle dispersion (10) was used instead of the resin particle dispersion (1), and the same evaluation was performed. It was. Table 1 summarizes the characteristics and evaluation results of the toner.

(Evaluation of toner)
Developer (1) was loaded into a DocuCentreColor400CP remodeling machine (manufactured by Fuji Xerox Co., Ltd.) shown in FIG. 1, and the transferability was evaluated. In this DocuCentreColor400CP remodeling machine, a contact charging system is adopted as the charging system of the photoreceptor. First, each developer having a toner concentration of 5% by mass was accommodated in the developing device of the image forming apparatus and left in a high-temperature and high-humidity environment at a temperature of 30 ° C. and a humidity of 90% RH for 72 hours. Thereafter, development conditions were set so that the toner development amount of each color on the surface of the photoreceptor can be maintained in the range of 4 to 5 g / m ² at the time of evaluation, and A4 size white paper (Fuji Xerox Office Supply, JD Coat 157 Paper, width: 210 mm, length: 297 mm, 157 g / m ² ) and A4 size white paper (manufactured by Fuji Xerox Office Supply, ST paper, width: 210 mm, length: 297 mm, 52.3 g / m ² ) A print test was alternately performed for each sheet.

The transferability was evaluated by the ratio of the recovered toner amount to the used toner weight. Specifically, the toner consumption amount a used in the evaluation is obtained from the change in the weight of the toner cartridge before and after the evaluation, and the transfer residual toner amount b is obtained from the change in the weight of the waste toner collection box before and after the evaluation. Asked.
Transfer efficiency η (%) = {1− (b / a)} × 100
The target transfer efficiency is 90% or more, and evaluation was made according to the following criteria.
η ≧ 90%: ◎
80% ≦ η <90%: ○
70% ≦ η <80%: Δ
η <70%: ×

  As an evaluation, initial transfer efficiency after 50,000 sheets was evaluated. The results are shown in Table 1.

  Developers 1 to 15 obtained in Examples 1 to 15 had good transferability even after the initial copying of 50,000 sheets. On the other hand, the developer 16 obtained in Comparative Example 1 had poor transferability from the beginning, and was the same even after copying 50,000 sheets. Developers 17 to 19 obtained in Comparative Examples 2 to 5 were deteriorated after copying 50,000 sheets, although the initial transferability was not significantly deteriorated.

  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.

Explanation of symbols

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

Claims (7)

An electrostatic charge image developing toner containing a binder resin, a colorant, and a metal element capable of taking a valence of 2 or more ,
The metal element capable of taking a valence of 2 or more internally added to the toner for developing an electrostatic charge image is contained in a metal element unit measured by X-ray photoelectron spectroscopy in a range of 0.02 atm% to 0.2 atm%. ,
The binder resin comprises a polyester resin having a weight average molecular weight of 45000 to 55000 obtained by polymerizing a dialcohol component and a dicarboxylic acid component or a polycarboxylic acid component, and the dialcohol component is a bisphenol A-propylene oxide adduct or bisphenol. A- either only contains ethylene oxide adduct, wherein a dicarboxylic acid component dodecenylsuccinic acid, the polycarboxylic acid component is a polyester resin is trimellitic acid or pyromellitic acid,
The toner for developing an electrostatic charge image, wherein the colorant contains carbon black having a volume primary particle size of 30 nm to 50 nm and a BET specific surface area of 70 m ² / g or less. An electrostatic charge image developing toner containing a binder resin, a colorant, and a metal element capable of taking a valence of 2 or more ,
The metal element capable of taking the valence of 2 or more internally added to the electrostatic image developing toner is aluminum, and 0.02 atm% or more in aluminum element unit measured by X-ray photoelectron spectroscopy of the aluminum Contained at 0.2 atm% or less,
The binder resin comprises a polyester resin having a weight average molecular weight of 45000 to 55000 obtained by polymerizing a dialcohol component and a dicarboxylic acid component or a polycarboxylic acid component, and the dialcohol component is a bisphenol A-propylene oxide adduct or bisphenol. A- either only contains ethylene oxide adduct, wherein a dicarboxylic acid component dodecenylsuccinic acid, the polycarboxylic acid component is a polyester resin is trimellitic acid or pyromellitic acid,
The toner for developing an electrostatic charge image, wherein the colorant contains carbon black having a volume primary particle size of 30 nm to 50 nm and a BET specific surface area of 70 m ² / g or less. An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1 or 2 and a carrier. A latent image forming unit that forms a latent image on a latent image holding member, a developing unit that develops the latent image using a developer for developing an electrostatic charge, and a transfer unit that transfers the developed image onto a transfer target. a removable cartridge having a cartridge in which the electrostatic latent image developing developer, characterized in that it comprises a toner for electrostatic development according to claim 1 or claim 2. A method for producing a toner for developing an electrostatic charge image according to claim 1 or 2 ,
An aggregating step of mixing at least one kind of resin particle dispersion and one or more kinds of colorant dispersions to form aggregated particles in the presence of a metal element capable of taking a valence of 2 or more; and the resin And a fusing step of fusing and coalescing the agglomerated particles to form toner particles by heating to a temperature equal to or higher than the glass transition point of the particles. A latent image forming unit that forms a latent image on the latent image carrier, a developing unit that develops the latent image using a developer for developing an electrostatic charge, and the developed toner image via an intermediate transfer member or not. An image forming apparatus including: a transfer unit that transfers the toner image on the transfer member; and a fixing unit that adds and fixes the toner image on the transfer member.
The image forming apparatus according to claim 3 , wherein the developer for developing an electrostatic charge is the developer for developing an electrostatic charge according to claim 3 . A latent image forming step of forming a latent image on the surface of the electrostatic charge image carrier, a development step of developing the latent image on the surface of the electrostatic charge image carrier with a developer containing toner, and obtaining the toner image; In an image forming method comprising: a transfer step of transferring to the surface of the transfer target; and a fixing step of thermally fixing the transferred toner image to the surface of the transfer target;
The image forming method according to claim 3 , wherein the developer for developing an electrostatic charge is the developer for developing an electrostatic charge according to claim 3 .

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