JP2008268334A - Toner for electrostatic charge development, developer for electrostatic charge development, cartridge, method for manufacturing toner for electrostatic charge development, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge development, excellent in image storage property while achieving low temperature fixing. <P>SOLUTION: The toner for electrostatic charge development contains an amorphous polyester resin, a crystalline polyester resin and a colorant, and has a metal M (metal M represents group IIa metals in the periodic table (long-form periodic table) of elements) on the toner surface. The abundance XPS(M) [atm%] of the metal M on the toner surface measured by use of X-ray electron spectroscopy (XPS) and an average acid value of the toner surface AV(TN*Ave) [mgKOH/g] satisfy the formula (1):AV(TN*Ave)×5.62×10<SP>-2</SP>≤XPS(M)≤AV(TN*Ave)×1.31×10<SP>-1</SP>. <P>COPYRIGHT: (C)2009,JPO&INPIT

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 developing toner, an image forming apparatus, and an image forming method.

  In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, an electrostatic latent image is developed with a developer containing toner to form a toner image, and the toner image is transferred to a recording medium. Fix and form an image. The developer used here includes a two-component developer comprising a toner and a carrier, and a one-component developer using a magnetic toner or a non-magnetic toner alone. In the production of toner, a so-called 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, cooled, finely pulverized, and further classified. Yes.

  In the toner prepared by the usual kneading and pulverizing method, the shape of the toner particles is indeterminate, and the surface structure of the toner particles slightly changes depending on the pulverization properties of the materials used and the conditions of the pulverization process. It is difficult to intentionally control the shape and surface structure.

  On the other hand, in recent years, a toner manufacturing method using a wet manufacturing method has been proposed as a means capable of intentionally controlling the shape and surface structure of the toner. Examples of the wet production method include a wet spheronization method capable of controlling the shape, a suspension granulation method capable of controlling the surface composition, a suspension polymerization method capable of controlling the internal composition, and an agglomeration and coalescence method.

  On the other hand, as the demand for energy saving increases, in order to save power in the fixing process occupying a certain amount of power in the copying machine and expand the fixing area, the toner fixing temperature is lowered. It is necessary to make it. Lowering the toner fixing temperature not only saves power and expands the fixing area, but also reduces the waiting time until the fixing temperature on the surface of the fixing roll at the time of power input to the copying machine, so-called warm-up time. This makes it possible to shorten the time and extend the life of the fixing roll.

  By the way, lowering the fixing temperature of the toner causes a decrease in the glass transition temperature of the toner at the same time, and there is a problem of deteriorating the storage stability of the toner. It was difficult to plan. In order to achieve both low temperature fixing and toner storage stability, it is necessary to have a so-called sharp melt property in which the toner viscosity rapidly decreases in a high temperature region while maintaining the glass transition temperature of the toner at a higher temperature. Become.

  However, since the resin used for the toner usually has a variation range in the glass transition temperature, the molecular weight, and the like, it is necessary to extremely align the resin composition and the molecular weight in order to obtain sharp melt properties. In order to obtain such a resin, it becomes necessary to adjust the molecular weight of the resin by using a special production method or by treating the resin with a chromatograph or the like, so that the production cost of the resin becomes very high, and In this case, unnecessary resin is by-produced, which is not preferable from the viewpoint of environmental protection.

  As a method for lowering the toner fixing temperature, it has been proposed to use a crystalline resin as a binder resin (see, for example, Patent Document 1 to Patent Document 19).

  Although these methods can lower the fixing temperature, since the change in the resin viscosity with respect to the temperature change is large, a sufficient viscosity cannot be obtained at the time of preparation of the toner, for example, during kneading. As a result, the dispersibility of the toner is not stable, and a toner with uneven coloring and fixing properties is likely to be produced. Further, when the toner is produced using the kneading and pulverizing method, it becomes difficult to pulverize the kneaded product, which causes a problem that it is difficult to obtain a toner having a small particle diameter. In order to solve this problem, for example, there is a method of adding an auxiliary agent such as a thickener and a grinding auxiliary agent. However, these auxiliary agents are dispersed in the resin to break the crystallinity of the binder resin. Therefore, it is not preferable.

  From such a point of view, a toner particle production technique by the above-described wet manufacturing method that does not require excessive temperature and kneading energy has been actively studied.

  However, achieving the melt-melt property by means such as the molecular weight of the binder resin, the molecular weight distribution, the melt viscosity, and the inclusion of the crystalline resin results in a decrease in the resin strength, resulting in a decrease in the toner strength. In some cases, the image strength may be lowered, and it is not easy to achieve a plurality of characteristics.

  In addition, the addition of the crystalline resin may reduce the encapsulation stability such as particle size, particle shape control, etc. It affects other than the quality of toner.

  On the other hand, in recent years, from the viewpoint of waste tonerless, an image forming method using a cleaner-less, toner recycling method has been proposed. In particular, toner used in an image forming method using a toner recycling method has a particle strength, Particle size and shape uniformity are required. However, these characteristics often hinder the attempt to achieve the sharp melt property.

  Further, in recent years, long-life xerography has been desired in consideration of environmental load. In particular, in order to achieve a longer life, a photoreceptor using a material having a high hardness such as a-Si, a photoreceptor having a protective layer having a three-dimensional cross-linked structure on the outermost surface, and the like have been used. It's getting on.

  Since the surface of these photoconductors is generally difficult to clean, when a mechanical cleaning means such as a cleaning blade is used as the cleaning means, it is necessary to apply a large pressure to the contact portion between the cleaning means and the photoconductor. . In this case, since the pressure exerted on the toner particles passing through the contact portion also tends to increase, a toner having a high particle strength is required particularly in the toner recycling system.

  However, when a crystalline resin is used as the binder resin, the toner particles become soft, so that the strength is insufficient for a large pressure, making it difficult to use the toner recycling method or for a long-term use. The external additive is embedded in the toner surface and causes a decrease in toner fluidity.

  In addition, in order to compensate for such a decrease in durability (strength), in a toner using a combination of an amorphous resin and a crystalline resin as a binder resin, a crystalline resin or a release agent is used in the toner particles. Since the dispersibility and compatibility between the amorphous resin and the release agent and the crystalline resin are poor, the crystalline resin and the release agent are exposed on the surface of the toner, resulting in a decrease in storage stability and charging stability. I will.

  Furthermore, for the purpose of achieving both low-temperature fixability and toner durability, as an attempt to control the dispersibility of the release agent and crystalline resin in the toner, it contains a crystalline polyester resin and a release agent. Toners with controlled dispersion structure and surface exposure have been proposed.

  Specifically, the toner is produced by multistage polymerization and contains a release agent in addition to the outermost layer (see, for example, Patent Document 20), and includes a crystalline polyester and an amorphous polyester as a binder resin. A polyester using a block polyester obtained by copolymerization of an amorphous block and a crystalline block constituting an amorphous polyester (see, for example, Patent Document 21), produced using a master batch. Examples thereof include toner (see, for example, Patent Document 22).

  However, these toners are not practical because the production method is limited to a specific production method and is complicated. Furthermore, if the amount of the crystalline resin or the release agent contained in the toner is increased in order to improve the low-temperature fixability or the release property, it becomes difficult to control the dispersibility of the release agent. Coming is a problem.

  In order to solve the above problems, as a toner manufacturing method capable of achieving both low temperature fixability, toner durability, shape controllability, etc., a wet manufacturing method using a crystalline polyester resin and an amorphous polyester resin as a binder resin, The agglomeration and coalescence method is particularly effective.

  In this aggregation / unification method, a resin dispersion is prepared by a method such as emulsion polymerization or dispersion emulsification, and on the other hand, a colorant particle dispersion in which a colorant is dispersed in a solvent is prepared, and these are mixed to produce a toner. In this method, aggregated particles corresponding to the particle diameter are formed and then fused to form toner particles. According to this aggregation / unification method, the toner shape can be arbitrarily controlled from an indeterminate shape to a spherical shape by selecting a heating temperature condition.

  However, the polyester resin is difficult to disperse in an aqueous medium, and it is difficult to produce the fine emulsified particles required by the aggregation / unification method. Therefore, there is a method of improving the affinity for water by copolymerizing a sulfonic acid component to the resin and facilitating emulsification, but increasing the amount of copolymerization causes a significant decrease in resin resistance, which is a problem. Therefore, in order to emulsify the polyester resin without copolymerizing a large amount of the sulfonic acid component, it is necessary to control the amount of carboxylic acid component (acid value) at the terminal of the resin, and the polyester resin has a sufficient acid value. Then, the fine particle aggregation control (toner structure control) in the aggregation / unification method becomes easier.

  As described above, in order to achieve both low-temperature fixability, toner durability, shape controllability, and the like, a toner based on an aggregation / unification method using crystalline polyester and amorphous polyester as a binder resin is effective. However, the polyester used as the binder resin needs to have a sufficient acid value.

  However, when the polyester has a sufficient acid value, the hygroscopicity of the toner particles becomes high, and when the toner that has absorbed a large amount of moisture is subjected to heat fixing, the polyester is hydrolyzed. The problem that image storability deteriorates occurs.

  For example, when a styrene-butyl acrylate-acrylic acid copolymer is used as the binder resin in order to improve charging stability against environmental changes, the carboxyl group of the binder resin present on the toner surface is divalent or higher. An electrostatic charge developing toner formed by forming a salt with a metal has been proposed (for example, see Patent Document 23).

JP 62-129867 A JP-A-62-170971 JP 62-170972 A JP 62-205365 A JP-A-62-276565 JP-A-62-276666 JP-A-63-038949 Japanese Unexamined Patent Publication No. 63-038950 Japanese Patent Laid-Open No. 63-038951 JP-A-63-038952 JP-A-63-038953 JP-A-63-038954 Japanese Unexamined Patent Publication No. 63-038955 JP 63-038956 A JP 05-001217 A Japanese Patent Laid-Open No. 06-148936 Japanese Patent Laid-Open No. 06-194874 JP 05-005056 A Japanese Patent Laid-Open No. 05-112715 JP 2002-49180 A JP 2005-62510 A JP 2004-264331 A JP 2001-305789 A

The present invention mainly has an object of an electrostatic charge developing toner excellent in image storability, an electrostatic charge developing developer, a cartridge, and a method for producing an electrostatic charge developing toner, while realizing low-temperature fixing. An object is to provide an image forming apparatus.

  The present invention is as follows.

(1) It contains an amorphous polyester resin, a crystalline polyester resin, and a colorant, and has a metal M (metal M is a group IIa metal in the periodic table of elements (long-period type)) on the toner surface. In addition, the metal M abundance ratio XPS (M) [atm%] on the toner surface measured using X-ray electron spectroscopy (XPS), and the toner surface average acid value AV (TN · Ave) [mg KOH / g] Satisfies the following formula (1): AV (TN · Ave) × 5.62 × 10 ⁻² ≦ XPS (M) ≦ AV (TN · Ave) × 1.31 × 10 ⁻¹ This is an electrostatic charge developing toner.

  (2) The electrostatic charge developing toner according to (1), wherein the metal M is beryllium, magnesium, or calcium.

  (3) The electrostatic charge developing toner according to (1), wherein the metal M is calcium.

  (4) An electrostatic charge image developing developer comprising the electrostatic charge developing toner according to any one of (1) to (3) above and a carrier.

  (5) A latent image forming unit that forms a latent image on the latent image holding member, a developing unit that develops the latent image using a developer for developing an electrostatic charge, 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 comprises the electrostatic charge developing toner according to any one of (1) to (3).

  (6) A resin fine particle dispersion in which amorphous polyester resin fine particles and crystalline polyester resin fine particles are dispersed and mixed with a colorant fine particle dispersion in which colorant fine particles are dispersed, and the resin fine particles and colorant fine particles are mixed. Agglomeration step of forming the aggregated particles, a step of adjusting the pH in the aggregated system to stop the aggregation growth, and heating the aggregated particles to a temperature higher than the glass transition temperature of the resin fine particles while fusing and coalescing, Addition of a predetermined amount of metal M chloride aqueous solution (metal M is a group IIa metal of the periodic table of elements (long-period type)) and add the metal M to the toner surface. And a process for producing an electrostatic charge developing toner having a step.

  (7) In the method for producing an electrostatic charge developing toner according to the above (6), the metal M chloride aqueous solution is a beryllium chloride aqueous solution, a magnesium chloride aqueous solution, or a calcium chloride aqueous solution. is there.

  (8) 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. Alternatively, the image forming apparatus includes: a transfer unit that transfers the toner image on the transfer body without being interposed; and a fixing unit that adds and fixes the toner image on the transfer body. An image forming apparatus, which is the developer for electrostatic charge development according to 4).

  According to the present invention, it is possible to provide an electrostatic charge developing toner excellent in image storability while realizing low-temperature fixing as compared with a conventional electrostatic charge developing toner.

<Toner for electrostatic charge development>
The electrostatic charge developing toner of the present embodiment (hereinafter sometimes abbreviated as “toner”) contains an amorphous polyester resin, a crystalline polyester resin, and a colorant, and has a specific metal M (metal) on the toner particle surface. M is a group IIa metal of the periodic table of elements (long period type)), and the metal M abundance ratio XPS (M) [of the toner surface measured using X-ray electron spectroscopy (XPS) [ [atm%] and the toner surface average acid value AV (TN · Ave) [mg KOH / g] satisfy the following formula.

AV (TN · Ave) × 5.62 × 10 ⁻² ≦ XPS (M) ≦ AV (TN · Ave) × 1.31 × 10 ⁻¹ ... Equation (1)

  In general, the agglomeration and coalescence method is effective as a means for intentionally controlling the shape of a “toner containing a polyester resin as a binder resin” that can lower the fixing temperature. In order to produce fine polyester resin emulsified particles necessary by one method, the polyester resin needs to have a sufficient acid value.

  However, a toner prepared by agglomeration and coalescence using a polyester having an acid value sufficient for emulsification has many carboxyl groups on the surface, and the carboxyl groups adsorb water by hydrogen bonding, The toner produced by the aggregation / unification method has a high hygroscopicity.

  When a toner containing water due to its high hygroscopicity is used for heat fixing, the polyester resin as a binder resin is hydrolyzed, resulting in a problem that the image storage stability of the fixed image obtained by heat fixing is lowered. End up.

  In the toner of the present embodiment, a carboxyl group on the toner surface and a specific metal M (the metal M is a group IIa metal of the periodic table of elements (long period type)), preferably beryllium, magnesium or calcium. By forming a stable and divalent salt, water adsorption due to hydrogen bonding of the carboxyl group that causes moisture absorption of the toner is inhibited, and polyester hydrolysis during thermal fixing is suppressed, resulting in excellent image storage stability. Can be realized.

  In the toner of the present embodiment, a specific metal M on the toner surface measured using X-ray electron spectroscopy (XPS) (metal M is a group IIa metal in the periodic table of elements (long period type), The abundance ratio XPS (M) [atm%] of beryllium, magnesium or calcium is preferably in the range of the following formula when the toner surface acid value is AV (TN · Ave) [mg KOH / g]. It is essential.

AV (TN · Ave) × 5.62 × 10 ⁻² ≦ XPS (M) ≦ AV (TN · Ave) × 1.31 × 10 ⁻¹ ... Equation (1)

  The range of the above formula (1) is the range in which the specific metal M is present in the range of 0.3 molar equivalent to 0.7 molar equivalent relative to the carboxyl group present on the toner surface, that is, the carboxyl group present on the toner surface. The range in which the specific metal M in an amount capable of forming a divalent salt with 60% to 14% is present.

XPS (M) <AV (TN · Ave) × 5.62 × 10 ⁻² (that is, the proportion of carboxyl groups present on the toner surface that form a divalent salt with a specific metal M is 6) If it is less than 100%, water adsorption due to hydrogen bonding of carboxyl groups, which causes moisture absorption of the toner, cannot be inhibited. As a result, polyester hydrolysis during thermal fixing cannot be suppressed, and the fixed image is stored. Problems arise.

XPS (M)> AV (TN · Ave) × 1.31 × 10 ⁻¹ (that is, a specific metal M is present in an amount such that more than 14% of the carboxyl groups present on the toner surface can form a divalent salt, In an excessive state), less than 60% of the carboxyl groups present on the toner surface form a stable divalent salt, and the remaining 40% or more is an unstable salt of -COO ^- M2 ^+. Therefore, the salt cannot be continuously formed during storage of the toner or during heat fixing. As a result, less than 60% of the carboxyl groups form a salt, so that the effect of the present embodiment described above cannot be obtained, resulting in a problem in the image storage stability of the fixed image.

XPS (M) is
AV (TN · Ave) × 6.55 × 10 ⁻² ≦ XPS (M) ≦ AV (TN · Ave) × 1.22 × 10 ⁻¹ ... Expression (2)
(Ie, an amount capable of forming a divalent salt with 70% to 13% of the carboxyl groups present on the toner surface).

  In the toner of the present embodiment, beryllium, magnesium, or calcium is preferable as the specific metal that forms a salt with a carboxyl group present on the toner surface. For example, in the case of strontium, barium, and the like, it may be difficult to sufficiently obtain the effect of the present embodiment described above. Among beryllium, magnesium, and calcium, calcium is particularly preferable, and better results can be obtained.

  In the present embodiment, when beryllium, magnesium, and calcium are used, the above-described effects in the present embodiment are sufficiently exhibited, and the reason why calcium is particularly preferable is not clear, but it is probably the electronegativity of these metals. Is suitable for forming a divalent salt in which the ion radius of the divalent ion of the metal and the distance between carboxyl groups present on the toner surface are stable. It is inferred that the balance between the electronegativity and the ionic radius is suitable.

  The XPS measurement can be performed using a device such as “JPS9000MX” manufactured by JEOL Ltd. Here, XPS measurement is obtained near the surface (about 0.01 to 0.5 μm), but in the present embodiment, it can be obtained by measurement near the surface of the toner. 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 element content by XPS measurement contained in the toner in the present embodiment was calculated by performing surface composition analysis by ESCA (X-ray photoelectron spectroscopy). An ESCA apparatus and measurement conditions in this embodiment will be described later.

  In the present embodiment, the atomic concentration (atm%) was calculated from the measured peak intensity of each element using the 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 having a depth of about 0.01 to 0.5 μm from the surface of the toner can be obtained. In addition, 0.02 atm% or more and 0.2 atm% in the metal element unit indicates the ratio of the metal element of the metal M described above in atm% out of all atoms that can be measured by the X-ray photoelectron spectrometer. is there.

  The method for measuring the toner surface acid value AV (TN · Ave) will be described later.

  In the toner of the present embodiment, the volume average particle diameter D50v of the toner particles is preferably 3 to 8 μm, and more preferably 4 to 7 μm. When the volume average particle diameter D50v of the toner particles is less than 3 μm, the chargeability becomes insufficient and the developability may be deteriorated, and when it exceeds 8 μm, the resolution of the image may be deteriorated.

  Here, in the present embodiment, the volume average particle diameter D50v is measured using, for example, Multisizer II (manufactured by Beckman-Coulter) and the electrolyte using ISOTON-II (manufactured by Beckman-Coulter). Can do. In the measurement, 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 is added to 100-150 ml of electrolyte.

  The electrolytic solution in which the sample is suspended is dispersed for about 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle diameter in the range of 2 to 50 μm is obtained using the Multisizer II type with an aperture diameter of 100 μm. taking measurement. The number of particles to be sampled is 50,000.

  For the particle size range (channel) divided on the basis of the particle size distribution measured in this way, the cumulative distribution is drawn from the smaller diameter side for each volume and number, and the particle size that becomes 50% cumulative is the cumulative volume average particle size. It is defined as a diameter D50v.

  Further, the average circularity of the toner particles in the toner of the present embodiment is preferably in the range of 0.940 to 0.980, and more preferably in the range of 0.950 to 0.970. When the average circularity is less than 0.940, the shape becomes more irregular and the transferability, durability, fluidity, and the like may decrease. On the other hand, when the average circularity exceeds 0.980, the ratio of spherical particles increases and the cleaning property may deteriorate.

  The average circularity of the toner can be measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measurement method, a surfactant, preferably an alkylbenzene sulfonate, is added in an amount of 0.1 to 0.5 ml as a dispersant in 100 to 150 ml of water from which impure solids have been removed in advance. Add about 1-0.5g. The suspension in which the measurement sample is dispersed is subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic wave disperser, and the average circularity of the toner is measured by the above apparatus with the dispersion concentration being 3000 to 10000 / μl.

  Hereinafter, components constituting the toner of the exemplary embodiment will be described in detail.

  As described above, the components constituting the toner of the present embodiment include amorphous polyesters, crystalline polyesters, and colorants, but include other components such as a release agent as necessary. May be.

<Binder resin>
In the electrostatic charge developing toner of the present embodiment, a crystalline polyester and an amorphous polyester are used in combination as a binder resin from the viewpoint of low-temperature fixability and toner strength. In the present invention, “crystalline polyester” refers to those having a clear endothermic peak, not a stepwise endothermic change in differential scanning calorimetry (DSC), but at least a weight average molecular weight (Mw). It means a crystalline polyester exceeding 5000, and usually means a crystalline polyester having a weight average molecular weight (Mw) of 10,000 or more.

[Crystalline polyester]
As the crystalline polyester used in the binder resin of the present embodiment, a known crystalline polyester can be used.

  Since the crystalline polyester has a melting point, the viscosity is greatly reduced at a specific temperature, and when the toner is heated at the time of fixing, the temperature difference between the crystalline polyester molecule starting the thermal activity and the fixable region is increased. Since it can be made small, further excellent low-temperature fixability can be imparted. The preferred content of the crystalline polyester in the toner particles is in the range of 1 to 10% by mass, more preferably in the range of 2 to 8% by mass.

  Further, the number average molecular weight (Mn) of the crystalline polyester is preferably 2000 or more, and more preferably 4000 or more. If the number average molecular weight (Mn) is less than 2000, the toner may permeate into the surface of a recording medium such as paper at the time of fixing to cause uneven fixing, or the bending strength of the fixed image may be reduced.

  The crystalline polyester is synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component. Hereinafter, the acid (dicarboxylic acid) component and the alcohol (diol) component will be described in more detail. In the present invention, a copolymer obtained by copolymerizing other components at a ratio of 50% by mass or less with respect to the main chain of the crystalline polyester is also referred to as a crystalline polyester.

  The acid (dicarboxylic acid) component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear dicarboxylic acid. For example, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,10-undecanedicarboxylic acid Acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof An acid anhydride is mentioned, However, It is not limited to these.

  The acid (dicarboxylic acid) component may include components such as a dicarboxylic acid component having a double bond and a dicarboxylic acid component having a sulfonic acid group in addition to the aliphatic dicarboxylic acid component described above. The dicarboxylic acid component having a double bond includes a component derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond, in addition to a component derived from a dicarboxylic acid having a double bond. Is also included. The dicarboxylic acid component having a sulfonic acid group includes a component derived from a dicarboxylic acid having a sulfonic acid group, a lower alkyl ester of a dicarboxylic acid having a sulfonic acid group, or an acid anhydride. Is also included.

  The dicarboxylic acid having a double bond can be suitably used to prevent hot offset at the time of fixing because the entire resin can be crosslinked using the double bond. Examples of such dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, fumaric acid, maleic acid and the like are preferable in terms of cost.

  The dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. Further, if a sulfonic acid group is present when the entire resin is emulsified or suspended in water to produce fine particles, it can be emulsified or suspended without using a surfactant, as will be described later. Examples of the dicarboxylic acid having a sulfonic acid group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, 5-sulfoisophthalic acid sodium salt and the like are preferable in terms of cost.

  As the content of the acid (carboxylic acid component) of the acid (dicarboxylic acid) component other than these aliphatic dicarboxylic acid components (dicarboxylic acid component having a double bond and / or dicarboxylic acid component having a sulfonic acid group), 1 component mol% or more and 20 component mol% or less are preferable, and 2 component mol% or more and 10 component mol% or less are more preferable.

  When the content is less than 1 component mol%, the dispersibility of the pigment in the toner may not be good. Further, when a toner is produced using an aggregation / unification method, the emulsion particle size in the dispersion becomes large, and it may be difficult to adjust the toner diameter by aggregation.

  On the other hand, when it exceeds 20 component mol%, the crystallinity of the crystalline polyester resin is lowered, the melting point is lowered, and the storage stability of the toner may be deteriorated. In addition, when a toner is produced using an agglomeration method, the emulsion particle size in the dispersion may be too small to dissolve in water, and latex may not occur. In the present invention, “constituent mol%” refers to a percentage when each constituent component [acid (carboxylic acid) component, alcohol (diol) component] in the polyester resin is 1 unit (mol).

  On the other hand, the alcohol (diol) component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, , 14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like, but are not limited thereto.

  The alcohol (diol) component preferably has an aliphatic diol component content of 80 constituent mol% or more, and includes other components as necessary. As the alcohol (diol) component, the content of the aliphatic diol component is more preferably 90 constituent mol% or more.

  When the content is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, toner storage stability and low-temperature fixability may be deteriorated.

  On the other hand, examples of other components included as necessary include diol components having a double bond and diol components having a sulfonic acid group.

  Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol and the like. On the other hand, as the diol having a sulfonic acid group, 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, 2-sulfo-1,4-butane Examples include diol sodium salt.

  When adding an alcohol (diol) component other than these linear aliphatic diol components, the content of (diol component having a double bond and / or diol component having a sulfonic acid group) in the alcohol (diol) component The amount is preferably from 1 to 20 mol%, more preferably from 2 to 10 mol%. When the content is less than 1 constituent mol%, pigment dispersion may be poor, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, when it exceeds 20 mol%, the crystallinity of the polyester resin is lowered, the melting point is lowered, the storage stability of the toner is deteriorated, or the emulsion particle size is too small to be dissolved in water, and no latex is produced. There is a case.

  The method for producing the crystalline polyester resin is not particularly limited and can be produced by a general polyester polymerization method in which a carboxylic acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Produced separately depending on the type of monomer. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The crystalline polyester can be produced at a polymerization temperature of 180 to 230 ° C., and the reaction system is reduced in pressure as necessary, and the reaction is carried out while removing 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. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the carboxylic acid component or alcohol component to be polycondensed are condensed in advance and then polycondensed together with the main component. Good.

  Catalysts usable in the production of the crystalline polyester 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 Compound: Phosphorous acid compound, phosphoric acid compound, amine compound and the like are mentioned, and specifically, the following compounds are mentioned.

  For example, sodium acetate, sodium carbonate, lithium acetate, calcium acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetra Butoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate , Zirconyl octylate, germanium oxide, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite Ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  In addition to the above polymerizable monomers, compounds having shorter chain alkyl groups, alkenyl groups, aromatic rings and the like can also be used for the purpose of adjusting the melting point, molecular weight and the like of the crystalline polyester.

  Specific examples include dicarboxylic acids, alkyl dicarboxylic acids such as succinic acid, malonic acid, and oxalic acid, and phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, 4,4′-dibenzoic acid, 2,6- Examples include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid, and nitrogen-containing aromatic dicarboxylic acids such as dipicolinic acid, dinicotinic acid, quinolinic acid, and 2,3-pyrazinedicarboxylic acid. Short chain alkyl diols such as succinic acid, malonic acid, acetone dicarboxylic acid and diglycolic acid. These polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

  In addition, a monofunctional monomer may be introduced into the crystalline polyester for the purpose of blocking the polar group at the terminal of the crystalline polyester and improving the environmental stability of the toner charging characteristics.

  Monofunctional monomers include benzoic acid, chlorobenzoic acid, bromobenzoic acid, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, n-dodecylaminocarbonylbenzoic acid, tertiary butyl. Benzoic acid, naphthoic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenylacetic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, octanecarboxylic acid, lauric acid, stearyl acid, and lower Monocarboxylic acids such as alkyl esters; or monoalcohols such as aliphatic alcohols, aromatic alcohols, and alicyclic alcohols can be used.

[Amorphous polyester]
As the amorphous polyester used in the toner of the present embodiment, a known amorphous polyester can be used.

  The range of the glass transition temperature (Tg) of the amorphous polyester is preferably 50 ° C. or higher and 80 ° C. or lower, more preferably 55 ° C. or higher and 65 ° C. or lower. If the glass transition temperature (Tg) is lower than 50 ° C., it may be difficult to store the toner. If the glass transition temperature (Tg) is higher than 80 ° C., the effect of low-temperature fixability may not be obtained.

  The weight average molecular weight (Mw) of the amorphous polyester is preferably in the range of 8000 to 30000, but the weight average molecular weight (Mw) is in the range of 8000 to 16000 from the viewpoint of low temperature fixability and mechanical strength. It is more preferable that The third component may be copolymerized from the viewpoints of low-temperature fixability and mixing properties.

  The method for producing the amorphous polyester is not particularly limited, as with the method for producing the crystalline polyester described above, and can be produced by a general polyester polymerization method.

  As the acid (dicarboxylic acid) component used for the synthesis of the amorphous polyester, various dicarboxylic acids mentioned for the crystalline polyester can be used similarly. As the alcohol (diol) component, various diols used for the synthesis of the amorphous polyester resin can be used. In addition to the aliphatic diols mentioned for the crystalline polyester, bisphenol A and bisphenol A ethylene oxide adducts are used. Bisphenol A propylene oxide adduct, hydrogenated bisphenol A, bisphenol S, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct, etc. can be used, but from the viewpoint of toner productivity, heat resistance and transparency, It is particularly preferable to use bisphenol S derivatives such as bisphenol S, bisphenol S ethylene oxide adduct, and bisphenol S propylene oxide adduct. Moreover, both an acid (dicarboxylic acid) component and an alcohol component may contain a plurality of components. In particular, bisphenol S has an effect of improving heat resistance.

  Similarly to the crystalline polyester described above, a compound having a shorter chain alkyl group, alkenyl group, aromatic ring, etc. can be used for the purpose of adjusting the melting point and molecular weight of the amorphous polyester. The various dicarboxylic acids and diols mentioned in the above can be used.

  Similarly to the above-mentioned crystalline polyester, when a monofunctional monomer is introduced into the amorphous polyester for the purpose of blocking the polar group at the end of the amorphous polyester and improving the environmental stability of the toner charging characteristics. There is. As the monofunctional monomer, various compounds mentioned for the crystalline polyester can be used.

<Release agent>
The toner of this embodiment may contain a release agent. The release agent used is not particularly limited as long as it is a known release agent. For example, natural waxes such as carnauba wax, rice wax, and candelilla wax, low molecular weight polypropylene, low molecular weight polyethylene, sasol wax, Examples include, but are not limited to, synthesis of microcrystalline wax, Fischer-Tropsch wax, paraffin wax, montan wax and the like, and ester-based waxes such as mineral / petroleum wax, fatty acid ester, and montanic acid ester. Moreover, these mold release agents may be used individually by 1 type, and may be used together 2 or more types.

  The melting point of the release agent is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of storage stability. Moreover, it is preferable that it is 110 degrees C or less from a viewpoint of offset resistance, and it is more preferable that it is 100 degrees C or less.

  The content of the release agent is preferably in the range of 3 to 20 parts by mass, more preferably in the range of 5 to 18 parts by mass with respect to 100 parts by mass of the binder resin. If the content of the release agent is less than 3 parts by mass, there is no effect of addition of the release agent, and hot offset at a high temperature may be caused. On the other hand, when the amount exceeds 20 parts by mass, the charging property is adversely affected, and the mechanical strength of the toner is lowered. Therefore, the toner is easily destroyed by stress in the developing machine, and may cause carrier contamination.

<Colorant>
Known colorants can be used as the colorant used in the toner of the exemplary embodiment. For example, examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.

  Examples of yellow pigments include yellow lead, 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. Can be given.

  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, Eoxin 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. For example, a rater.
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. Furthermore, these can be used alone or in combination and further in a solid solution state.

  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, these colorants are dispersed in an aqueous system by the homogenizer using a polar surfactant.

  The colorant of the present embodiment is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the resin.

  When a magnetic material is used for the black colorant, 30 to 100 parts by weight is added unlike other colorants.

  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, in this embodiment, in order to obtain toner in the aqueous layer, it is necessary to pay attention to the water layer's ability to migrate, dissolve, and oxidize, and surface modification, such as hydrophobization treatment, is preferably performed. It is preferable to keep it.

<Other ingredients-various additives>
The other components used in the toner in the exemplary embodiment are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include various known additives such as inorganic fine particles and a charge control agent.

  As the inorganic fine particles, known inorganic fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, or those obtained by hydrophobizing the surface thereof can be used alone or in combination of two or more kinds. From the viewpoint of not impairing the color developability, silica fine particles having a refractive index smaller than that of the binder resin are preferably used. Further, the silica fine particles may be subjected to various surface treatments, and for example, those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, silicone oil or the like are preferably used.

  The addition amount of these inorganic fine particles is preferably in the range of 0.5% by weight to 20% by weight and more preferably in the range of 1% by weight to 15% by weight of the total toner mass.

  Known external additives such as inorganic fine particles and organic fine particles can be added to the toner in the present exemplary embodiment as necessary.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, Examples include Bengala, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, and silicon nitride. Among them, silica fine particles and titanium oxide fine particles are preferable, and hydrophobized fine particles are particularly preferable.

  Inorganic fine particles are generally used for the purpose of improving fluidity. The primary particle diameter of the inorganic fine particles is preferably in the range of 1 nm to 200 nm, and the addition amount is in the range of 0.01 parts by weight to 20 parts by weight with respect to 100 parts by weight of the toner. It is preferable.

  Organic fine particles are generally used for the purpose of improving cleaning properties and transfer properties, and specific examples include polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and the like.

<Toner production method>
The toner of the present embodiment can be produced by an aggregation / unification method.

  The aggregation / unification method of the present embodiment includes, for example, a resin fine particle dispersion in which amorphous polyester resin fine particles and crystalline polyester resin fine particles are dispersed and mixed, a colorant fine particle dispersion in which colorant fine particles are dispersed, Mixing with the release agent fine particle dispersion in which the release agent fine particles are dispersed to form an aggregated particle of resin fine particles, colorant fine particles and release agent fine particles, and further adjusting the pH in the aggregation system A specific amount of a specific metal M chloride aqueous solution (the metal M chloride aqueous solution is an elemental element) while aggregating particles are heated to a temperature equal to or higher than the glass transition temperature of the resin fine particles and fused and united. In the periodic table (long-period type) of Group IIa metal chloride aqueous solution, preferably beryllium chloride aqueous solution, magnesium chloride aqueous solution or calcium chloride aqueous solution) It is a manufacturing method and a specific step coalescence-metal addition to allowed to adding the metal M of the toner surface. In addition, the aggregation / unification method may include a shell forming step of adding other resin fine particles to adhere to the surface of the aggregated particles after the aggregation step, if necessary.

  Hereinafter, each process in an example of the aggregation / unification method mentioned above is demonstrated in detail. The toner manufacturing method in the present embodiment is not limited to this.

[Aggregation process]
In the aggregation step, first, a resin fine particle dispersion, a colorant fine particle dispersion, and a release agent fine particle dispersion are prepared.

  For the resin fine particle dispersion, a known phase inversion emulsification method is used, or a method in which the resin fine particle dispersion is heated to a temperature higher than the glass transition temperature of the resin and emulsified by a mechanical shearing force is used. At this time, an ionic surfactant may be added.

  The colorant fine particle dispersion is prepared by dispersing colorant fine particles of a desired color such as blue, red, and yellow in a solvent using an ionic surfactant.

  In addition, the release agent fine particle dispersion is obtained by dispersing the release agent together with a polymer electrolyte (for example, an ionic surfactant, a polymer acid, or a polymer base) in water and heating it above the melting point of the release agent. At the same time, the fine particles are adjusted by a homogenizer or a pressure discharge type disperser that can be subjected to strong shearing.

  Next, the resin fine particle dispersion, the colorant fine particle dispersion, and the release agent fine particle dispersion are mixed, and the resin fine particles, the color fine agent particles, and the release agent fine particles are hetero-agglomerated to obtain a diameter that is approximately close to the desired toner diameter. Aggregated particles having a core (core aggregated particles) are formed.

[Shell formation process]
In the shell forming step, the surface of the core aggregated particles is formed by attaching resin fine particles to the surface of the core aggregated particles using a resin fine particle dispersion containing resin fine particles to form a coating layer (shell layer) having a desired thickness. Aggregated particles having a core / shell structure in which a shell layer is formed (core / shell aggregated particles) are obtained.

  In addition, the aggregation process and the shell formation process may be repeatedly performed in a plurality of stages.

  Here, the volume average particle size of the resin fine particles, colorant fine particles, and release agent fine particles used in the aggregation step and the shell formation step is to facilitate adjustment of the toner diameter and the particle size distribution to desired values. It is preferable that it is 1 micrometer or less, and it is more preferable that it exists in the range of 100-300 nm.

  The volume average particle size is measured using a laser diffraction type laser diffraction type particle size distribution measuring device (LA-700: manufactured by Horiba, Ltd.). As a measurement method, a sample in a dispersion is adjusted to have a solid content of about 2 g, and ion exchange water is added thereto to make about 40 ml. This is put into the cell until an appropriate concentration is reached, waits for about 2 minutes, and is measured when the concentration in the cell becomes almost stable. The obtained volume average particle diameter for each channel is accumulated from the smaller volume average particle diameter, and the place where the accumulation reaches 50% is defined as the volume average particle diameter.

[Stop process]
In the stopping step, the aggregation growth of particles is stopped by adjusting the pH in the aggregation system. Specifically, the growth of particles is stopped by adjusting the pH in the aggregation system to 6-9.

[Fusion, unity, metal addition process]
In the fusion / unification / metal addition step, first, in a solution containing the aggregated particles obtained through the aggregation step and the shell formation step performed as necessary, the resin fine particles contained in the aggregated particles The toner is obtained by heating to a temperature not lower than the glass transition temperature, and fusing and coalescing, and in a state heated to a temperature not lower than the glass transition temperature of the resin fine particles, a predetermined amount of the solution is contained in the solution containing aggregated particles. Specific metal M chloride aqueous solution (metal M chloride aqueous solution is a chloride aqueous solution of group IIa metal of the periodic table of elements (long period type), preferably beryllium chloride aqueous solution, magnesium chloride aqueous solution or calcium chloride aqueous solution) To add a specific metal M to the toner surface.

  Here, the temperature equal to or higher than the glass transition temperature of the resin fine particles refers to a temperature equal to or higher than the glass transition temperature of the resin fine particles having the highest glass transition temperature. Further, the “predetermined amount” of the specific metal M chloride aqueous solution (the metal M chloride aqueous solution is a group IIa metal chloride aqueous solution of the periodic table of elements (long period type), preferably a beryllium chloride aqueous solution or Magnesium chloride aqueous solution or calcium chloride aqueous solution) is added so as to be 0.3 molar equivalent or more and 0.7 molar equivalent with respect to the carboxyl group on the surface of the aggregated particles, and the kind of binder resin used for the aggregated particles Accordingly, the addition amount of the metal M chloride aqueous solution is appropriately adjusted.

[Other processes]
After completion of aggregation, fusion, coalescence, and metal addition, a desired toner is obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. 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. Furthermore, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used.

[Other processes]
The agglomeration and coalescence method can also be performed by mixing and aggregating together. Specifically, for example, the balance of the ionic dispersant amount of each polarity is shifted in advance at the initial stage of the aggregation step. More specifically, for example, a polymer of at least one metal salt is ionically neutralized to form a first-stage matrix aggregation at a temperature lower than the glass transition temperature, and After stabilization, as a second step, a second stage addition resin particle dispersion treated with a dispersing agent having a polarity and an amount so as to compensate for the imbalance is added. Slightly heated at a temperature lower than the glass transition temperature of the resin contained in the resin particles for the two-stage addition, and after stabilizing the temperature, the second-stage addition is performed by heating to a temperature higher than the glass transition temperature. This is a method in which the resin particles are united while being adhered to the surface of the base aggregated particles. Furthermore, the stepwise operation of aggregation may be repeated several times.

  By adding a predetermined amount of the above-mentioned specific metal M chloride aqueous solution at the stage of heating and uniting to a temperature equal to or higher than the glass transition temperature of the resin, the specific metal M can be added to the toner surface.

  The metal salt polymer is preferably a tetravalent aluminum salt polymer, or a mixture of a tetravalent aluminum salt polymer and a trivalent aluminum salt polymer, specifically, calcium nitrate. And a polymer of an inorganic metal salt such as polyaluminum chloride. The metal salt polymer is preferably added so that its concentration is 0.11 to 0.25% by weight based on the entire particle dispersion.

<Developer for electrostatic charge development>
The developer for developing an electrostatic charge of the present embodiment is not particularly limited except that it contains the toner for developing an electrostatic latent image of the present embodiment described above, and can have an appropriate component composition depending on the purpose. . The electrostatic charge image developer of the present invention becomes a one-component electrostatic charge image developer when the electrostatic charge developing toner is used alone, and a two-component electrostatic charge image developer when used in combination with a carrier. Become.
Hereinafter, the developer for electrostatic charge development according to the present embodiment (hereinafter may be abbreviated as “developer”) will be described.

  There is no restriction | limiting in particular as a carrier, A well-known carrier can be used. Examples of the carrier include a resin-coated carrier having a resin coating layer in which a core resin surface is coated with a coating resin. The carrier may be a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin.

  Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic. Examples thereof include, but are not limited to, acid copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, epoxy resins and the like.

  Examples of the conductive material include metals (for example, gold, silver, copper, etc.), carbon black, titanium oxide, zinc oxide, barium sulfide, aluminum borate, potassium titanate, tin oxide, carbon black, and the like. However, it is not limited to these.

  In addition, examples of the carrier core material include magnetic metals (for example, iron, nickel, cobalt, etc.), magnetic oxides (for example, ferrite, magnetite, etc.), glass beads, etc., because the carrier is used for the magnetic brush method. In this case, the core material of the carrier is preferably a magnetic material. The volume average particle size of the core material of the carrier is preferably in the range of 10 μm to 500 μm, and more preferably in the range of 30 μm to 100 μm.

  In order to coat the surface of the carrier core material with a resin, a method of coating with a coating layer forming solution in which a coating resin and, if necessary, various additives are dissolved in an appropriate solvent can be mentioned. The solvent is not particularly limited, and may be appropriately selected in consideration of the coating resin to be used, application suitability, and the like.

  Specific resin coating methods include (1) a dipping method in which the carrier core material is immersed in a coating layer forming solution, (2) a spray method in which the coating layer forming solution is sprayed on the surface of the carrier core material, 3) Fluidized bed method in which the coating layer forming solution is sprayed in a state where the carrier core material is floated by flowing air. (4) The carrier core material and the coating layer forming solution are mixed in a kneader coater, and the solvent is added. The kneader coater method to remove is mentioned.

  The mixing ratio (weight ratio) of the toner and the carrier in the developer containing the carrier is preferably in the range of toner: carrier = 1: 100 to 30: 100, and more preferably in the range of 3: 100 to 20: 100. preferable.

<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 charge 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, a release agent is usually supplied to a fixing member in the fixing device in order to prevent offset and the like. 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.

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

<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.

(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 melting point of the crystalline polyester resin and the glass transition temperature (Tg) of the amorphous polyester resin were measured using a differential scanning calorimeter (manufactured by Perkin Elmer: DSC-7) according to ASTM D3418-8. It calculated | required from the maximum peak. The temperature correction of the detection part of this apparatus (DSC-7) uses the melting point of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan was used, an empty pan was set as a control, and the measurement was performed at a heating rate of 10 ° C./min.

(Metal element content of metal M on toner surface)
The element content 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.

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

[Toner surface acid value AV (TN · Ave)]
As a dispersant, 10 g of a measurement sample (toner) is added to 100 ml of a 2% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, and a toner dispersion is prepared by performing a dispersion treatment with an ultrasonic disperser for about 3 minutes. Next, neutralization titration of the above-mentioned toner dispersion was performed using 0.3N aqueous sodium hydroxide solution, and 0. required for neutralization titration of 100 ml of an aqueous dispersant solution (2% sodium alkylbenzene sulfonate) without addition of toner. The amount of sodium hydroxide required to neutralize the acidic groups on the toner surface is calculated from the difference from the amount of 3N sodium hydroxide aqueous solution. AV (TN · Ave) [mg KOH / g] can be obtained by replacing the amount of sodium hydroxide required for neutralizing 1 g of toner with the amount of equimolar potassium hydroxide.

<Preparation of each dispersion>
[Preparation of Crystalline Polyester Resin Fine Particle Dispersion 1]
Into a heat-dried three-necked flask, 269 parts of 1,12-dodecanedicarboxylic acid and 167 parts of 1,10-decanediol and 0.035 part of tetrabutoxytitanate as a catalyst were placed, and the inside of the container was then reduced by pressure reduction. The air was decompressed, and the atmosphere was made inert with nitrogen gas, and the mixture was refluxed at 180 ° C. for 6 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 220 ° C. by vacuum distillation and stirred for 2.5 hours. When the solution became viscous, the resin acid value was measured, and the resin acid value became 13.9 mgKOH / g. By the way, vacuum distillation was stopped and air-cooled to obtain a crystalline polyester resin 1.

  It was 12000 when the weight average molecular weight (Mw) of the obtained crystalline polyester resin 1 was measured by the above-mentioned method. Moreover, it was 72 degreeC when melting | fusing point of the obtained crystalline polyester resin 1 was measured using the differential scanning calorimeter (DSC) by the above-mentioned measuring method.

  Next, 180 parts of this crystalline polyester resin 1 and 585 parts of deionized water were placed in a stainless beaker, placed in a warm bath, and heated to 95 ° C. When the crystalline polyester resin 1 was melted, the mixture was stirred at 8000 rpm using a homogenizer (manufactured by IKA: Ultra Turrax T50), and at the same time, diluted ammonia water was added to adjust the pH to 7.0. Next, while 20 parts of an aqueous solution obtained by diluting 0.8 part of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) is added dropwise, the emulsion is dispersed and a crystalline polyester having a volume average particle size of 0.24 μm. Resin fine particle dispersion 1 [resin fine particle concentration: 12.4%] was prepared.

[Preparation of Crystalline Polyester Resin Fine Particle Dispersion 2]
Into a heat-dried three-necked flask, 264 parts of 1,12-dodecanedicarboxylic acid, 171 parts of 1,10-decanediol, and 0.034 part of tetrabutoxy titanate as a catalyst were placed, and the inside of the container was then reduced by a vacuum operation. The air was decompressed, and the atmosphere was made inert with nitrogen gas, and the mixture was refluxed at 180 ° C. for 6 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 220 ° C. by vacuum distillation and stirred for 2.5 hours. When the solution became viscous, the resin acid value was measured, and the resin acid value was 8.1 mgKOH / g. By the way, vacuum distillation was stopped and air-cooled to obtain a crystalline polyester resin 2.

  It was 16000 when the weight average molecular weight (Mw) of the obtained crystalline polyester resin 2 was measured by the above-mentioned method. Moreover, it was 75 degreeC when melting | fusing point of the obtained crystalline polyester resin 2 was measured using the differential scanning calorimeter (DSC) by the above-mentioned measuring method.

  Next, 180 parts of this crystalline polyester resin 2 and 585 parts of deionized water were placed in a stainless beaker, placed in a warm bath, and heated to 95 ° C. When the crystalline polyester resin 2 was melted, the mixture was stirred at 8000 rpm using a homogenizer (manufactured by IKA: Ultra Tarrax T50), and at the same time, diluted ammonia water was added to adjust the pH to 7.0. Next, while 20 parts of an aqueous solution obtained by diluting 0.8 part of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) is added dropwise, the emulsion is dispersed and a crystalline polyester having a volume average particle size of 0.22 μm. Resin fine particle dispersion 2 [resin fine particle concentration: 12.3%] was prepared.

[Preparation of Amorphous Polyester Resin Fine Particle Dispersion 1]
In a heat-dried two-necked flask, 74 parts of dimethyl adipate, 192 parts of dimethyl terephthalate, 216 parts of bisphenol A-ethylene oxide adduct, 38 parts of ethylene glycol, and 0.037 parts of tetrabutoxy titanate as a catalyst were placed in a container. After introducing nitrogen gas into the reactor and raising the temperature while maintaining an inert atmosphere, the copolycondensation reaction was carried out at 150 to 230 ° C. for about 12 hours, and then the pressure was gradually reduced at 210 to 250 ° C. to produce an amorphous polyester resin 1 Was synthesized.

  It was 62 degreeC when the glass transition temperature of the obtained amorphous polyester 1 was measured using the differential scanning calorific value system (DSC) with the above-mentioned measuring method. Moreover, when the molecular weight of the obtained amorphous polyester 1 was measured using GPC by the above-mentioned measuring method, the weight average molecular weight (Mw) was 10,000 and the number average molecular weight (Mn) was 5500. Moreover, when the acid value of the obtained amorphous polyester 1 was measured, it was 15.1 KOHmg / g.

  Next, 115 parts of this amorphous polyester resin 1, 180 parts of deionized water, and 5 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) were mixed and heated to 120 ° C. Then, after sufficiently dispersing with a homogenizer (manufactured by IKA: Ultra Tarrax T50), the dispersion treatment is carried out for 1 hour with a pressure discharge type gorin homogenizer, whereby amorphous polyester resin fine particle dispersion 1 (resin particle concentration: 40 % By weight) was adjusted.

[Preparation of Amorphous Polyester Resin Fine Particle Dispersion 2]
In a heat-dried two-necked flask, 69 parts of dimethyl adipate, 179 parts of dimethyl terephthalate, 202 parts of bisphenol A-ethylene oxide adduct, 41 parts of biphenol, 26 parts of ethylene glycol, and 0.035 part of tetrabutoxy titanate as a catalyst And nitrogen gas was introduced into the container, and the temperature was maintained in an inert atmosphere, followed by a copolycondensation reaction at 150 to 230 ° C. for about 12 hours. Thereafter, the pressure was gradually reduced at 210 to 250 ° C. -Soluble polyester resin 2 was synthesized.

  It was 65 degreeC when the glass transition temperature of the obtained amorphous polyester 2 was measured using the differential scanning calorific value system (DSC) with the above-mentioned measuring method. Moreover, when the molecular weight of the obtained amorphous polyester 2 was measured by GPC by the above-mentioned measuring method, the weight average molecular weight (Mw) was 15000 and the number average molecular weight (Mn) was 7100. Moreover, it was 9.2 KOHmg / g when the acid value of the obtained amorphous polyester 2 was measured.

  Next, 115 parts of this amorphous polyester resin 2, 180 parts of deionized water, and 5 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) were mixed and heated to 120 ° C. Then, after sufficiently dispersing with a homogenizer (manufactured by IKA: Ultra Tarrax T50), the dispersion treatment is carried out for 1 hour with a pressure discharge type gorin homogenizer, whereby amorphous polyester resin fine particle dispersion 2 (resin particle concentration: 40 % By weight) was adjusted.

[Preparation of colorant dispersion]
-Preparation of cyan colorant dispersion-
99 parts by weight of a cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)), 15 parts by weight of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 ion-exchanged water Cyan colorant by mixing with parts by weight and dispersing for 10 minutes using a homogenizer (manufactured by IKA: Ultra Tarrax T50) and then applying to a circulating ultrasonic disperser (RUS-600TCVP, manufactured by Nippon Seiki Seisakusho). A dispersion was obtained.

  When the volume average particle size of the colorant (cyan pigment) in the obtained cyan colorant dispersion was measured using a laser diffraction particle size measuring instrument according to the measurement method described above, the volume average particle size was 0.18 μm. there were. The solid content ratio of the cyan colorant dispersion was 24% by weight.

-Preparation of yellow colorant dispersion-
99 parts by weight of a yellow pigment (PY74: manufactured by Dainichi Seika), 15 parts by weight of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 parts by weight of ion-exchanged water are mixed together to produce a homogenizer (IKA). (Manufactured by Ultra Turrax T50) for 10 minutes, and then subjected to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) to obtain a yellow colorant dispersion.

  The volume average particle size of the colorant (yellow pigment) in the obtained yellow colorant dispersion was measured using a laser diffraction particle size measuring instrument according to the measurement method described above. The volume average particle size was 0.20 μm. there were. The solid content ratio of the yellow colorant dispersion was 24% by weight.

-Preparation of magenta colorant dispersion-
99 parts by weight of a magenta pigment (CI Pigment Red 122: manufactured by Clariant), 15 parts by weight of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 parts by weight of ion-exchanged water are mixed, and the homogenizer is mixed. After being dispersed for 10 minutes using (IKA Corp .: ULTRA TALLAX T50), a magenta colorant dispersion was obtained by applying to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP).

  The volume average particle diameter of the colorant (magenta pigment) in the obtained magenta colorant dispersion was measured using a laser diffraction particle size measuring instrument according to the measurement method described above. The volume average particle diameter was 0.19 μm. there were. The solid content ratio of the magenta colorant dispersion was 24% by weight.

-Preparation of black colorant dispersion-
Carbon black Legal 330: 99 parts by weight (manufactured by Cabot), 15 parts by weight of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 parts by weight of ion-exchanged water are mixed together, and a homogenizer (IKA Co., Ltd.) is mixed. (Manufactured by Ultra Turrax T50) for 10 minutes, and then applied to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) to obtain a black colorant dispersion.

  When the volume average particle diameter of the colorant (carbon black) in the obtained black colorant dispersion was measured using a laser diffraction particle size measuring instrument according to the measurement method described above, the volume average particle diameter was 0.25 μm. there were. The solid content ratio of the black colorant dispersion was 24% by weight.

[Adjustment of release agent dispersion]
Fischer-Tropsch wax FNP92 (melting point 92 ° C .: manufactured by Nippon Seiki Co., Ltd.), anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) 3.6 parts by weight, and ion-exchanged water 400 parts by weight The mixture was heated to 100 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion.

  When the volume average particle size of the release agent in the obtained release agent dispersion was measured using a laser diffraction particle size measuring instrument by the above-described measurement method, the volume average particle size was 0.23 μm. The solid content ratio of the release agent dispersion was 20% by weight.

<Manufacture of toner>
[Production of Toner 1]
(Manufacture of Toner Surface Average Acid Value AV (TN · Ave) Toner 1)
105 parts of the crystalline polyester resin fine particle dispersion 1, 336 parts of the amorphous polyester resin fine particle dispersion 1, 45 parts of the colorant dispersion, 115 parts of the release agent dispersion, 402 parts of deionized water, Was placed in a round stainless steel flask and thoroughly mixed and dispersed with Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 3 hours, 175 parts of amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 3 hours.

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

  This was repeated five more times. When the pH of the filtrate was 7.00, the electric conductivity was 8.7 μS / cm, and the surface tension was 7.08 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 1 for confirming toner surface average acid value AV (TN · Ave).

  The surface average acid value of the obtained toner surface average acid value AV (TN · Ave) confirmation toner 1 was measured by the above-mentioned method and found to be 12.8 mgKOH / g.

(Manufacture of metal-added toner)
When heated to 90 ° C., except that 15.8 g of a 20% CaCl ₂ aqueous solution was added, the same operation as in the above (Manufacturing of toner surface average acid value AV (TN · Ave) toner 1) was performed. Toner 1 was obtained. The volume average particle size of the obtained toner 1 was measured by the above-described measuring method and found to be 5.8 μm. Further, the average circularity of the toner 1 was measured by the above-described measuring method and found to be 0.960. Further, the surface Ca existing ratio of the toner 1 was measured by using XPS by the above-described measuring method, and found to be 1.2 atm%.

[Production of Toner 2]
(Production of Toner 2 for Confirming Toner Surface Average Acid Value AV (TN · Ave))
35 parts of crystalline polyester resin fine particle dispersion 1, 358 parts of amorphous polyester resin fine particle dispersion 1, 45 parts of colorant dispersion, 115 parts of release agent dispersion, 450 parts of deionized water, Was placed in a round stainless steel flask and thoroughly mixed and dispersed with Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 4 hours, 175 parts of amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 2 hours.

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

  This was further repeated 5 times. When the pH of the filtrate was 7.12, the electric conductivity was 8.8 μS / cm, and the surface tension was 7.1 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 2 for toner surface average acid value AV (TN · Ave) confirmation.

  The surface average acid value of the obtained toner surface average acid value AV (TN · Ave) confirmation toner 2 was measured by the above-mentioned method and found to be 12.8 mgKOH / g.

(Manufacture of metal-added toner)
When heated to 90 ° C., except that 10.3 g of 20% CaCl ₂ aqueous solution was added, the same operation as described above (production of toner 2 for confirming toner surface average acid value AV (TN · Ave)) was performed. Toner 2 was obtained. The volume average particle size of the obtained toner 2 was measured by the above-described measuring method and found to be 7.2 μm. Further, the average circularity of the toner 2 was measured by the above-described measuring method and found to be 0.948. Further, the surface Ca existing ratio of the toner 2 was measured by XPS by the above-described measurement method, and found to be 0.78 atm%.

[Production of Toner 3]
(Manufacture of Toner 3 for Confirming Toner Surface Average Acid Value AV (TN · Ave))
175 parts of crystalline polyester resin fine particle dispersion 1, 314 parts of amorphous polyester resin fine particle dispersion 1, 45 parts of colorant dispersion, 115 parts of release agent dispersion, 354 parts of deionized water, Was placed in a round stainless steel flask and thoroughly mixed and dispersed with Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 2 hours, 175 parts of amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 4 hours.

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

  This was repeated five more times, and when the pH of the filtrate was 6.98, the electric conductivity was 9.1 μS / cm, and the surface tension was 6.99 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain a toner 3 for confirming the toner surface average acid value AV (TN · Ave).

  The surface average acid value of the obtained toner surface average acid value AV (TN · Ave) confirmation toner 3 was measured by the above-mentioned method and found to be 12.7 mgKOH / g.

(Manufacture of metal-added toner)
When heated to 90 ° C., except that 21.3 g of 20% CaCl ₂ aqueous solution was added, the same operation as in the above (Manufacturing of toner surface average acid value AV (TN · Ave) confirmation toner 3) was performed, Toner 3 was obtained. The volume average particle size of the obtained toner 3 was measured by the above-described measuring method and found to be 3.5 μm. In addition, the average circularity of the toner 3 was 0.975 as measured by the measurement method described above. Further, the surface Ca existing ratio of the toner 3 was measured using XPS by the above-described measurement method, and found to be 1.60 atm%.

[Production of Toner 4]
(Manufacture of Toner 4 for Confirming Toner Surface Average Acid Value AV (TN · Ave))
70 parts of crystalline polyester resin fine particle dispersion 2, 347 parts of amorphous polyester resin fine particle dispersion 2, 45 parts of colorant dispersion, 115 parts of release agent dispersion, 426 parts of deionized water, Was placed in a round stainless steel flask and thoroughly mixed and dispersed with Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 3 hours, 175 parts of amorphous polyester resin fine particle dispersion 2 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 2 hours.

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

  This was repeated five more times, and when the pH of the filtrate was 7.01, the electric conductivity was 9.0 μS / cm, and the surface tension was 7.00 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 4 for toner surface average acid value AV (TN · Ave) confirmation.

  The surface average acid value of the obtained toner surface average acid value AV (TN · Ave) confirmation toner 4 was measured by the above-mentioned method, and found to be 7.8 mgKOH / g.

(Manufacture of metal-added toner)
When heated to 90 ° C., except that 9.6 g of 20% CaCl ₂ aqueous solution was added, the same operation as described above (production of toner surface average acid value AV (TN · Ave) confirmation toner 4) was performed, Toner 4 was obtained. The volume average particle diameter of the obtained toner 4 was measured by the above-described measuring method and found to be 5.8 μm. Further, the average circularity of the toner 4 was measured by the above-described measuring method and found to be 0.945. Further, the surface Ca existing ratio of the toner 4 was measured by XPS by the above-described measurement method, and found to be 0.73 atm%.

[Production of Toner 5]
(Production of Toner 5 for Confirming Toner Surface Average Acid Value AV (TN · Ave))
140 parts of crystalline polyester resin fine particle dispersion 1, 325 parts of amorphous polyester resin fine particle dispersion 1, 45 parts of colorant dispersion, 115 parts of release agent dispersion, 378 parts of deionized water, Was placed in a round stainless steel flask and thoroughly mixed and dispersed with Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 4 hours, 175 parts of amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 3 hours.

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

  This was repeated five more times, and when the pH of the filtrate was 6.95, the electric conductivity was 9.0 μS / cm, and the surface tension was 7.01 Nm, No. was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 5 for confirming toner surface average acid value AV (TN · Ave).

  The surface average acid value of the obtained toner surface average acid value AV (TN · Ave) confirmation toner 5 was measured by the above-mentioned method, and found to be 12.8 mgKOH / g.

(Manufacture of metal-added toner)
When heated to 90 ° C., except that 11.4 g of 20% BeCl ₂ aqueous solution was added, the same operation as described above (production of toner 5 for confirming toner surface average acid value AV (TN · Ave)) was performed. Toner 5 was obtained. The volume average particle diameter of the obtained toner 5 was measured by the above-described measuring method and found to be 7.3 μm. In addition, the average circularity of the toner 5 was 0.958 as measured by the measurement method described above. Further, the surface Be existence ratio of the toner 5 was measured using XPS by the above-described measurement method, and found to be 1.22 atm%.

[Production of Toner 6]
105 parts of the crystalline polyester resin fine particle dispersion 1, 336 parts of the amorphous polyester resin fine particle dispersion 1, 45 parts of the colorant dispersion, 115 parts of the release agent dispersion, 402 parts of deionized water, Was placed in a round stainless steel flask and thoroughly mixed and dispersed with Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 3 hours, 175 parts of amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 3 hours.

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

  This was further repeated 5 times. When the pH of the filtrate was 6.98, the electric conductivity was 9.0 μS / cm, and the surface tension was 7.05 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 6.

  The surface average acid value of the obtained toner 6 was measured by the above-described method, and found to be 12.8 mgKOH / g. The volume average particle diameter of the toner 6 was measured by the above-described measurement method and found to be 5.7 μm. Further, the average circularity of the toner 6 was measured by the above-described measuring method and found to be 0.962.

[Production of Toner 7]
(Manufacture of Toner 7 for Confirming Toner Surface Average Acid Value AV (TN · Ave))
141 parts of crystalline polyester resin fine particle dispersion 1, 325 parts of amorphous polyester resin fine particle dispersion 1, 45 parts of colorant dispersion, 115 parts of release agent dispersion, 377 parts of deionized water, Was placed in a round stainless steel flask and thoroughly mixed and dispersed with Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 2 hours, 175 parts of amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 4 hours.

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

  This was repeated five more times, and when the pH of the filtrate was 6.99, the electric conductivity was 9.0 μS / cm, and the surface tension was 6.96 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain a toner 7 for toner surface average acid value AV (TN · Ave) confirmation.

  The surface average acid value of the obtained toner surface average acid value AV (TN · Ave) confirmation toner 7 was measured by the above-mentioned method, and found to be 12.8 mgKOH / g.

(Manufacture of metal-added toner)
When heated to 90 ° C., except that 23.8 g of 20% CaCl ₂ aqueous solution was added, the same operation as described above (production of toner 7 for confirming toner surface average acid value AV (TN · Ave)) was performed. Toner 7 was obtained. The volume average particle diameter of the obtained toner 7 was measured by the above-described measuring method and found to be 3.8 μm. Further, the average circularity of the toner 7 was measured by the above-described measuring method and found to be 0.976. Further, the surface Ca existing ratio of the toner 7 was measured using XPS by the above-described measurement method, and found to be 1.80 atm%.

[Production of Toner 8]
(Production of Toner 8 for Confirming Toner Surface Average Acid Value AV (TN · Ave))
35 parts of the crystalline polyester resin fine particle dispersion 1, 357 parts of the amorphous polyester resin fine particle dispersion 1, 45 parts of the colorant dispersion, 115 parts of the release agent dispersion, 450 parts of deionized water, Was placed in a round stainless steel flask and thoroughly mixed and dispersed with Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 4 hours, 175 parts of amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 2 hours.

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

  This was repeated 5 times. When the pH of the filtrate was 7.02, the electric conductivity was 9.1 μS / cm, and the surface tension was 6.94 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain a toner 8 for confirming the toner surface average acid value AV (TN · Ave).

  The surface average acid value of the obtained toner surface average acid value AV (TN · Ave) confirmation toner 8 was measured by the above-mentioned method and found to be 12.8 mgKOH / g.

(Manufacture of metal-added toner)
When heated to 90 ° C., except that 7.9 g of 20% CaCl ₂ aqueous solution was added, the same operation as described above (production of toner 8 for confirming toner surface average acid value AV (TN · Ave)) was performed. Toner 8 was obtained. The volume average particle diameter of the obtained toner 8 was measured by the above-described measuring method and found to be 7.5 μm. Further, the average circularity of the toner 8 was measured by the above-described measuring method and found to be 0.945. Further, the surface Ca existing ratio of the toner 8 was measured by XPS by the above-described measurement method, and found to be 0.6 atm%.

[Production of Toner 9]
Based on the method for producing toner 2 for confirming toner surface average acid value AV (TN · Ave), the toner 2 for confirming surface average acid value AV (TN · Ave) is produced, and the obtained toner surface average acid value is obtained. The surface average acid value of the toner 2 for AV (TN · Ave) confirmation was measured by the above-mentioned method, and found to be 12.8 KOHmg / g.

(Manufacture of metal-added toner)
When heated to 90 ° C., except that 13.6 g of 20% MgCl ₂ aqueous solution was added, the same operation as described above (production of toner 2 for confirming toner surface average acid value AV (TN · Ave)) was performed, Toner 9 was obtained. The volume average particle diameter of the obtained toner 9 was measured by the above-described measuring method and found to be 7.1 μm. Further, the average circularity of the toner 9 was measured by the above-described measuring method and found to be 0.947. Further, the surface Mg content of the toner 9 was measured using XPS by the above-described measurement method and found to be 1.19 atm%.

[Production of Toner 10]
Based on the method for producing toner 2 for confirming toner surface average acid value AV (TN · Ave), the toner 2 for confirming surface average acid value AV (TN · Ave) is produced, and the obtained toner surface average acid value is obtained. The surface average acid value of the toner 2 for AV (TN · Ave) confirmation was measured by the above-mentioned method, and found to be 12.8 mgKOH / g.

(Manufacture of metal-added toner)
When heated to 90 ° C., except that 22.6 g of a 20% aqueous SrCl ₂ solution was added, the same operation as described above (production of toner 2 for confirming toner surface average acid value AV (TN · Ave)) was performed. Toner 10 was obtained. The volume average particle diameter of the obtained toner 10 was measured by the above-described measuring method and found to be 7.3 μm. In addition, the average circularity of the toner 10 was 0.949 as measured by the measurement method described above. Further, the surface Sr existence ratio of the toner 10 was measured by XPS by the above-described measurement method, and found to be 1.21 atm%.

[Production of Toner 11]
A toner 11 was obtained in the same manner as in the production method of the toner 4 except that the cyan colorant dispersion was changed to a yellow colorant dispersion. The volume average particle size of the obtained toner 11 was measured by the measurement method described above, and was 5.7 μm. Further, the average circularity of the toner 11 was measured by the above-described measuring method and found to be 0.946. Further, the surface Ca existing ratio of the toner 11 was measured using XPS by the above-described measurement method, and found to be 0.73 atm%.

[Production of Toner 12]
A toner 12 was obtained in the same manner as in the toner 4 production method except that the cyan colorant dispersion was changed to a magenta colorant dispersion. The volume average particle diameter of the obtained toner 12 was measured by the above-described measuring method and found to be 5.8 μm. Further, the average circularity of the toner 12 was measured by the above-described measuring method and found to be 0.947. Further, the surface Ca existing ratio of the toner 12 was measured using XPS by the above-described measurement method, and found to be 0.73 atm%.

[Production of Toner 13]
A toner 13 was obtained in the same manner as in the production method of the toner 4 except that the cyan colorant dispersion was changed to a black colorant dispersion. The volume average particle diameter of the obtained toner 13 was measured by the measurement method described above, and was 5.7 μm. Further, the average circularity of the toner 13 was measured by the above-described measuring method and found to be 0.947. Further, the surface Ca existing ratio of the toner 13 was measured using XPS by the above-described measurement method, and found to be 0.73 atm%.

<Manufacture of external toner>
To 50 g of the manufactured toner, 0.21 g of hydrophobic silica (Cabot, TS720) was added and blended in a sample mill to prepare an externally added toner.

<Adjustment of developer>
The externally added toner is weighed so that the toner concentration is 5% with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% methyl methacrylate (manufactured by Soken Chemical Co., Ltd.), and stirred and mixed for 5 minutes with a ball mill. The developer was adjusted.

<Evaluation method>
[Evaluation of low-temperature fixability]
The obtained developer was filled in a developing unit of a DocuCentreColor400CP remodeling machine (manufactured by Fuji Xerox Co., Ltd.) shown in FIG. 1 with the fixing device removed, and an unfixed image was collected. Transferability was evaluated.

The image conditions were a solid image of 40 mm × 50 mm, the toner amount was 4.5 g / m ² , and the recording paper was mirror-coated platinum paper (basis weight: 127 gsm).

  Next, using a DocuCentreColor400CP fixing device modified so that the fixing temperature can be varied, the fixing temperature is raised between 70 ° C. and 200 ° C. at 10 ° C. intervals to form a fixed image, and the low temperature fixing property is evaluated. did. Low temperature fixability is an index of low temperature fixability by bending the fixed image with a constant load weight, grading the degree of image loss at that part, and setting the fixing temperature that exceeds a certain grade as the minimum fixing temperature. It was.

[Evaluation of fixed image storage stability]
For the evaluation of fixed image storage stability, two fixed images fixed at a temperature 20 ° C. higher than the minimum fixing temperature are overlapped so that the image portion and the image portion, and the non-image portion and the image portion overlap each other. Then, a weight was placed on the overlapped portion so as to correspond to 80 g / cm ^2, and left in a constant temperature and humidity chamber having a temperature of 60 ° C. and a humidity of 50% for 7 days.

After the standing, the image defect degree of the two superimposed fixed images was graded in the following five grades “G1” to “G5”. Up to G3 is set as an allowable range, and up to G4 is more preferable.
G1: Since the image portions are adhered to each other, the paper on which the image is fixed is peeled off, image loss is severe, and clear image transfer to the non-image portion is observed.
G2: Since the images are bonded to each other, white spots of image defects are generated in some parts of the image portion.
G3: When separating two superimposed images, image blurring or gloss reduction occurs on the fixing surfaces of each other, but the image has an acceptable level with almost no image loss. Some transition is seen in the non-image area.
G4: When the two overlapped images are separated, a crisp sound is heard, and a slight image shift is observed in the non-image part, but there is no image loss and there is no problem at all. G5: Both the image part and the non-image are completely absent. There is no image loss or image transfer.

<Example 1>
The minimum fixing temperature measured by the above-described method using a developer prepared using toner 1 was 110 ° C. The evaluation result of the fixed image storability in the above method was G5, which was an acceptable range.

<Example 2>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 2 was 115 ° C. The evaluation result of the fixed image storage stability in the above-described method was G4, which was an acceptable range.

<Example 3>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 3 was 105 ° C. The evaluation result of the fixed image storage stability in the above-described method was G4, which was an acceptable range.

<Example 4>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 4 was 115 ° C. The evaluation result of the fixed image storability in the above method was G5, which was an acceptable range.

<Example 5>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 5 was 108 ° C. The evaluation result of the fixed image storage stability in the above-described method was G4, which was an acceptable range.

<Example 6>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 9 was 115 ° C. The evaluation result of the fixed image storage stability in the above-described method was G4, which was an acceptable range.

<Example 7>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 10 was 115 ° C. The evaluation result of the fixed image storage stability in the above-mentioned method was G3, which was an acceptable range.

<Example 8>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 11 was 115 ° C. The evaluation result of the fixed image storability in the above method was G5, which was an acceptable range.

<Example 9>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 12 was 115 ° C. The evaluation result of the fixed image storability in the above method was G5, which was an acceptable range.

<Example 10>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 13 was 115 ° C. The evaluation result of the fixed image storability in the above method was G5, which was an acceptable range.

<Comparative Example 1>
The minimum fixing temperature measured by the above-described method using a developer prepared using toner 6 was 110 ° C. The evaluation result of the fixed image storability in the above-described method was G1, and the storability was poor.

<Comparative example 2>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 7 was 107 ° C. The evaluation result of the fixed image storability in the above method was G2, and the storability was poor.

<Comparative Example 3>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 8 was 115 ° C. The evaluation result of the fixed image storability in the above method was G2, and the storability was poor.

  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 (8)

An amorphous polyester resin, a crystalline polyester resin, and a colorant, and a metal M (metal M is a group IIa metal in the periodic table of elements (long-period type)) on the toner surface; The relationship between the metal M existing ratio XPS (M) [atm%] on the toner surface and the toner surface average acid value AV (TN · Ave) [mg KOH / g] measured using the line electron spectroscopy (XPS) ,
AV (TN · Ave) × 5.62 × 10 ⁻² ≦ XPS (M) ≦ AV (TN · Ave) × 1.31 × 10 ⁻¹ ... Equation (1)
An electrostatic charge developing toner characterized by satisfying: The electrostatic charge developing toner according to claim 1,
The toner for electrostatic charge development, wherein the metal M is beryllium, magnesium, or calcium. The electrostatic charge developing toner according to claim 1,
The electrostatic charge developing toner, wherein the metal M is calcium.   An electrostatic charge developing developer comprising the electrostatic charge developing toner according to any one of claims 1 to 3 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 cartridge having the electrostatic charge developing, wherein the electrostatic charge developing developer includes the electrostatic charge developing toner according to any one of claims 1 to 3. A resin fine particle dispersion in which amorphous polyester resin fine particles and crystalline polyester resin fine particles are dispersed and mixed, and a colorant fine particle dispersion in which colorant fine particles are dispersed are mixed, and the resin fine particles and the colorant fine particles are aggregated. An agglomeration step to form
Adjusting the pH in the flocculation system to stop flocculation growth;
While the agglomerated particles are heated to a temperature equal to or higher than the glass transition temperature of the resin fine particles, and fused and united, a predetermined amount of metal M chloride aqueous solution (metal M is a group IIa of the periodic table of elements (long period type)). A method of producing a toner for developing electrostatic charge, comprising: a fusion, coalescence, and metal addition step of adding a metal M) to the toner surface. The method for producing a toner for electrostatic charge development according to claim 6,
The method for producing a toner for developing electrostatic charge, wherein the metal M chloride aqueous solution is a beryllium chloride aqueous solution, a magnesium chloride aqueous solution, or a calcium chloride aqueous solution. 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 4, wherein the developer for developing an electrostatic charge is the developer for developing an electrostatic charge according to claim 4.

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