JP7587741B2 - Toner, toner storage unit, image forming method and image forming apparatus - Google Patents

Description

The present invention relates to a toner, a toner storage unit, an image forming method, and an image forming device.

In electrophotographic image formation, the toner used in ultra-high-speed printing systems is exposed to harsh operating conditions, such as fluctuations in temperature and humidity in the environment in which the image forming device is used, and the continuous output of a large number of images. In order to continue to output images of consistent quality even under such conditions, it is important that the toner has stable charging properties to prevent toner scattering. In addition, in image forming devices using a heat fixing method, a lot of electricity is required in the process of thermally melting the toner and fixing it on a recording medium such as paper, so from the perspective of energy conservation, it is also important for the toner to have low-temperature fixing properties.

In order to solve the charging characteristics, many inventions have been proposed regarding the type of external additive, various physical properties, and the number of formulations. For example, a toner has been proposed in which the atomic concentration % (at %) of the element Al in X-ray photoelectron spectroscopy (XPS) of the toner is set to 0.50 at % or more, thereby improving the charging stability (see, for example, Patent Document 1). In addition, a toner has been proposed in which the atomic concentration % of a specific metal element, for example Al, when measured by XPS of the toner is A, and the atomic concentration % of the specific metal element when the toner is melt-kneaded and then measured by XPS is B [at %], such that A>B (see, for example, Patent Document 2).

The present invention aims to provide a toner that exhibits low-temperature fixability while suppressing toner scattering.

In order to solve the above problems, the toner of the present invention has the following configuration.
A toner having at least a binder resin, a colorant, and a release agent, the toner having an atomic concentration % of Al when measured by XPS of 0.50 at % or more and 2.50 at % or less, and the ratio of Al when measured by XRF to Al when measured by ICP (XRF [mass %]/ICP [mass %]) is 1.20 or more.
However, the abbreviations XPS, XRF, and ICP in the present invention refer to the following analytical methods.
XPS: X-ray photoelectron spectroscopy XRF: X-ray fluorescence elemental analysis ICP: Inductively coupled plasma optical emission spectroscopy

The present invention provides a toner that exhibits low-temperature fixability while suppressing toner scattering.

FIG. 1 is a schematic diagram showing an example of an image forming apparatus according to the present invention. FIG. 2 is a schematic diagram showing another example of the image forming apparatus of the present invention. FIG. 3 is a schematic diagram showing another example of the image forming apparatus of the present invention. FIG. 4 is a schematic diagram showing another example of the image forming apparatus of the present invention. FIG. 5 is a schematic diagram showing an example of a process cartridge.

<Toner>
The toner of the present invention contains at least a binder resin and a colorant.
The toner of the present invention contains Al, and the atomic concentration (at %) of Al measured by X-ray photoelectron spectroscopy (XPS) is 0.50 at % or more and 2.50 at % or less, and the ratio of the mass concentration of Al measured by X-ray fluorescence elemental analysis (XRF) to the mass concentration of Al measured by inductively coupled plasma atomic emission spectroscopy (ICP) (XRF [mass %]/ICP [mass %]) is 1.20 or more.

As specified in the present invention, by specifying the dispersibility of the specific metal element in addition to specifying the surface concentration of the specific metal element, it is possible to prepare a toner that is advantageous in terms of toner scattering.
There are many prior art techniques for regulating the amount of specific metal elements near the toner surface, but none of them regulate dispersibility and are insufficient for improving toner scattering.
The toner of the present invention having the above-mentioned configuration can exhibit low-temperature fixability while suppressing toner scattering by improving the dispersibility of the specific metal element.

The inventors have discovered that the cause of toner scattering is that when the toner and carrier are mixed in the stage prior to transfer, the toner scattering occurs because the newly replenished toner causes uneven charging. They have confirmed that an effective way to prevent this is to uniformly disperse specific metal elements present near the toner surface, increase the toner's hardness, and improve its stress resistance.

To improve the charging characteristics, it is important to improve the dispersion of specific metal elements such as Al, Fe, Si, and Mg within the toner. It is preferable to use layered inorganic minerals (particularly organically modified layered inorganic minerals), and one possible method is to blend one or more types of bentonite. Another method to improve the dispersion within the toner is to use a master batch in which the organically modified layered inorganic minerals are dispersed in the resin beforehand.

The toner of the present invention is characterized in that the atomic concentration (at%) of Al measured by X-ray photoelectron spectroscopy (XPS) is 0.50 at% or more and 2.50 at% or less, and more preferably 1.00 at% or more and 2.00 at% or less.

If the atomic concentration of Al is less than 0.50 at%, sufficient charging characteristics cannot be obtained, and toner scattering deteriorates. If the atomic concentration of Al is more than 2.50 at%, Al inhibits fixing, and low-temperature fixing properties deteriorate. When the atomic concentration of Al is in the range of 1.00 at% to 2.00 at% inclusive, both toner scattering and low-temperature fixing properties are fully satisfactory.

The toner of the present invention is characterized in that the ratio of the mass % of Al measured by X-ray fluorescence elemental analysis (XRF) to the mass % of Al measured by inductively coupled plasma optical emission spectrometry (ICP) (XRF [mass %]/ICP [mass %]) is 1.20 or more, and more preferably 1.25 or more.

If the ratio of Al mass% (XRF [mass%]/ICP [mass%]) is less than 1.20, the dispersibility of Al will be poor, good charging characteristics will not be obtained, and toner scattering will be at an unsatisfactory level. If the ratio of Al mass% (XRF [mass%]/ICP [mass%]) is 1.20 or more, good charging characteristics will be obtained and toner scattering will be reduced.

<X-ray photoelectron spectroscopy (XPS)>
X-ray photoelectron spectroscopy (XPS) measures the kinetic energy distribution of photoelectrons emitted by X-ray irradiation, and determines the type, abundance, and chemical bond state of elements present on the sample surface (at a depth of about a few nm). It is a method of obtaining information about.
The amount of Al (aluminum) present near the toner surface can be measured by X-ray photoelectron spectroscopy (XPS) without any particular limitation, and can be measured, for example, as follows. XPS is used to measure the amount of Al present near the toner surface. This is photoelectron X-ray that makes it possible to detect the atomic concentration percentage at a depth of about 10 nm from the surface.
Equipment used: PHI 1600S model X-ray photoelectron spectrometer Conditions used: X-ray source MgKα (100 W)
Analysis area 0.8 x 2.0mm
For the sample, the toner is placed on a carbon sheet on a sample holder and then measured.

<X-ray fluorescence elemental analysis (XRF)>
X-ray fluorescence elemental analysis (XRF) is a technique for performing elemental analysis and composition analysis by detecting fluorescent X-rays generated by irradiating X-rays and dispersing the X-rays using energy or a dispersing crystal.
The measurement by X-ray fluorescence elemental analysis (XRF) in the present invention is not particularly limited, but can be carried out, for example, as follows.
The amount of metal elements (Al, Fe, etc.) in the toner is quantified by X-ray fluorescence analysis (ZSX100e: an automatic X-ray fluorescence analyzer manufactured by Rigaku Corporation) to calculate the amount of metal elements (Al) present in the entire toner. Note that for the measurement, a 3.0±0.1 g sample of the toner is pressurized at 6 (MPa/ ^cm2 ) for 60 seconds to prepare a circular pellet of 40 mmΦ.

X-ray fluorescence elemental analysis (XRF) is generally used to quantify elements, but it is known that even when the absolute amount of an element is the same, if the dispersion is high, the reflection intensity increases and the detection value by XRF becomes high, and in this invention it is used as an index of dispersion and absolute amount.

<High frequency inductively coupled plasma emission spectrometry (ICP)>
Inductively Coupled Plasma Optical Emission Spectroscopy (ICP) is a method for qualitative and quantitative analysis in which a solution sample, a gaseous sample, or a sample present in the form of fine particles in a gas is introduced into an Ar inductively Coupled Plasma formed in a doughnut shape, and the light emitted by the sample is used to introduce the sample into the plasma.
ICP is an analytical method that makes it possible to detect elemental concentrations in a sample.
The measurement of the absolute amount of Al (aluminum) present in the toner by ICP is not particularly limited, but can be carried out, for example, as follows.
Equipment used: ICP optical emission spectrometer Hitachi High-Tech Science PS3520VDDII
Sample treatment: The toner was decomposed by heating with nitric acid and sulfuric acid, dissolved by heating with dilute nitric acid, and the insoluble matter was filtered off. The insoluble matter was heated and incinerated, then melted with sodium carbonate, dissolved with dilute nitric acid, and mixed with the filtrate to make a constant volume.

As mentioned above, XRF is a numerical value that combines dispersibility and absolute amount, but by converting it to a mass % ratio with ICP (XRF [mass %] / ICP [mass %]), the influence of absolute amount can be eliminated and it can be used as an index of pure dispersibility.

<Thermomechanical analysis (TMA)>
Thermomechanical analysis is a method of measuring the deformation of a material as a function of temperature or time by applying a non-oscillating load such as compression, tension or bending while changing the temperature of the sample according to a certain program.
The TMA measurement in the present invention is not particularly limited, but can be performed, for example, as follows: 0.2 g of toner is weighed out, pressurized at 6.0 kg/ ^cm2 for 1 minute, and molded to obtain a diameter of 1.0 mm. A 10 mm pellet is prepared. The displacement is calculated at 50° C., 54%, and 1400 mN/60 min using a TMA/SS7100 (manufactured by SII Nano Technology Inc.).

The toner of the present invention preferably has a displacement of 10 μm or less as measured by thermomechanical analysis (TMA).
When the displacement measured by thermomechanical analysis (TMA) is 10 μm or less, it is thought, although not certain, that the hardness of the toner surface increases and the embedding of external additives is suppressed, thereby reducing the change in charging characteristics over time, suppressing the occurrence of uneven charging with replenished toner, and improving toner scattering.

４，０００≦重量平均分子量（Ｍｗ）≦２５，０００・・・式（２）
０．５ｍｏｌ％ ≦ ３価以上の脂肪族アルコール量 ≦ ６．５ｍｏｌ％・・・式（３）
（ただし、前記式（１）及び式（３）中の前記３価以上の脂肪族アルコール量（以下、「分岐成分量」ということがある。）とは、前記アルコール成分に対する前記３価以上の脂肪族アルコールのモル％である。） The toner of the present invention preferably contains a polyester resin and a tetrahydrofuran (THF) insoluble matter as a binder resin. The polyester resin has a skeleton derived from an alcohol component and a skeleton derived from a carboxylic acid component. The alcohol component preferably contains a trivalent or higher aliphatic alcohol, and preferably satisfies the following formulas (1), (2), and (3).

4,000≦weight average molecular weight (Mw)≦25,000...Formula (2)
0.5 mol%≦amount of trihydric or higher aliphatic alcohol≦6.5 mol%...Equation (3)
(Note that the amount of the trivalent or higher aliphatic alcohol in the formulas (1) and (3) (hereinafter sometimes referred to as the "amount of branched components") is the mole percentage of the trivalent or higher aliphatic alcohol relative to the alcohol component.)

Here, when the alcohol component contains two or more types of the trihydric or higher aliphatic alcohol, the "valence of the trihydric or higher aliphatic alcohol" is the average valence calculated from the molar fraction of the trihydric or higher aliphatic alcohol. For example, when the trihydric or higher aliphatic alcohol contains 50 mol% each of a trihydric aliphatic alcohol and a tetrahydric aliphatic alcohol, the "valence of the trihydric or higher aliphatic alcohol" is 3 x 0.5 + 4 x 0.5 = 3.5. Also, when the trihydric or higher aliphatic alcohol contains 60 mol% of a trihydric aliphatic alcohol and 40 mol% of a hexahydric alcohol, the "valence of the trihydric or higher aliphatic alcohol" is 3 x 0.6 + 6 x 0.4 = 4.2.

When the polyester resin for toner satisfies the above formulas (1) to (3), the toner can improve low-temperature fixability, stress resistance, and blocking resistance of the toner image.

The following portion of the formula (1) represents the average distance between branches of the polyester resin (hereinafter, sometimes referred to as the "branch distance").

It is preferable that the polyester resin for toner satisfies the formula (1). When the branch distance is 4,000 or less, the melt viscosity does not become too high, which is advantageous for low-temperature fixability. When the branch distance is 500 or more, the distance between the branches does not become short, the molecular size does not become small, and the stress resistance of the toner does not decrease. In addition, when cooled from a high-temperature state, there is no delay in the start of molecular entanglement, and the blocking resistance of the output toner image does not decrease.

The weight average molecular weight of the polyester resin for a toner preferably satisfies the above formula (2).
When the weight average molecular weight of the polyester resin for a toner is 4,000 or more, the high temperature and high humidity resistant storage stability and stress resistance of the toner are good, and when the weight average molecular weight is 25,000 or less, the melt viscosity does not become too high, so that the low temperature fixability of the toner can be expressed.

It is preferable that the polyester resin for toner satisfies the formula (3). When the "amount of trihydric or higher aliphatic alcohol" (amount of branched components) is 0.5 mol% or more, the toner has good high-temperature and high-humidity storage resistance and filming resistance, and when it is 6.5 mol% or less, the image gloss and low-temperature fixability are good.

Polyester resins with a branched structure can reduce the melt viscosity at high temperatures while maintaining the glass transition temperature, which makes it possible to improve low-temperature fixability. On the other hand, by increasing the amount of branched components inside, it has a dense three-dimensional structure, which suppresses deformation even when a large amount of stress is applied, hardens the toner particles, improves the stress resistance of the toner, and suppresses toner scattering.

A preferred method for producing the polyester resin for toner is to react an alcohol component containing a trivalent or higher aliphatic alcohol with a carboxylic acid component. This makes it possible to form a polyester resin with a branched structure.

<Alcohol content>
Examples of the alcohol component include dihydric alcohols and trihydric or higher alcohols.
The alcohol component contains a trihydric or higher aliphatic alcohol.

Examples of the dihydric alcohol include aliphatic diols, diols having an oxyalkylene group, alicyclic diols, alicyclic diols to which alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) have been added, bisphenols, and alkylene oxide adducts of bisphenols.

Examples of the aliphatic diols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol. Examples of the diols having an oxyalkylene group include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the alicyclic diols include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adducts of the bisphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to bisphenols.

Examples of the trihydric or higher alcohol include the trihydric or higher aliphatic alcohols, etc. Examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane , trimethylolpropane, pentaerythritol, sorbitol, and dipentaerythritol.

As the trihydric or higher aliphatic alcohol, trihydric to tetrahydric aliphatic alcohols are preferred.

<Carboxylic Acid Component>
Examples of the carboxylic acid component include divalent carboxylic acids, trivalent or higher carboxylic acids, etc. Furthermore, anhydrides, lower (1 to 3 carbon atoms) alkyl esters, or halides of these may be used.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.

The aliphatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid. The aromatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.

Examples of the trivalent or higher carboxylic acid include trimellitic acid and pyromellitic acid.

These carboxylic acid components may be used alone or in combination of two or more.

The toner contains a binder resin and a colorant, as well as a predetermined amount of Al. For example, when an organically modified layered inorganic mineral is blended as a toner component, this Al is derived from the organically modified layered inorganic mineral. Other toner components can be appropriately selected depending on the purpose, but the binder resin usually contains either a monomer, a polymer, a compound having an active hydrogen group, or a polymer having reactivity with an active hydrogen group, and may further contain a release agent and other components as necessary.

The organically modified layered inorganic mineral will now be described.
Layered inorganic minerals are inorganic minerals that are made up of layers of several nm thick stacked together, and modification refers to the introduction of organic ions into the ions present between the layers. Specifically, this is described in JP-A-2003-515795, JP-A-2006-500605, and JP-A-2006-503313. This is broadly called intercalation. Known layered inorganic minerals include smectites (montmorillonite, saponite, etc.), kaolinites (kaolinite, etc.), magadiite, and kanemite. Organically modified layered inorganic minerals have low hydrophilicity due to their modified layered structure. Therefore, if layered inorganic minerals are used in a toner that is dispersed in an aqueous medium and granulated without being modified, the layered inorganic minerals will migrate into the aqueous medium and the toner will not be deformed, but by modification, the hydrophilicity is increased, and the toner can be easily deformed during granulation, dispersed, and finely granulated, thereby fully demonstrating the charge adjustment function. Such an organically modified layered inorganic mineral is present in a particularly large amount on the surface portion of the toner particles, and serves to adjust the charge and also contributes to low-temperature fixing. In this case, the content of the organically modified layered inorganic mineral in the toner material is preferably 0.05 to 2% by weight.

The organically modified layered inorganic mineral used in the present invention is preferably one having a basic smectite crystal structure modified with an organic cation. In addition, when the layered inorganic mineral is a hydrotalcite, the ion balance is such that an anion can be introduced by replacing a part of the divalent metal with a trivalent metal. By introducing an organic anion into the layered inorganic mineral in this state, a layered inorganic mineral modified with an organic anion can be used. Examples of organic ion modifiers for the layered inorganic mineral in which at least a part of the ions of the layered inorganic mineral are modified with an organic ion include quaternary alkyl ammonium salts, phosphonium salts, and imidazolium salts, and quaternary alkyl ammonium salts are preferred. Examples of the quaternary alkyl ammonium include trimethylstearyl ammonium, dimethylstearylbenzyl ammonium, dimethyloctadecyl ammonium, and oleyl bis(2-hydroxyethyl)methyl ammonium.

The organic ion modifier may be a sulfate, sulfonate, carboxylate, or phosphate having branched, unbranched, or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, or propylene oxide. Carboxylic acid having an ethylene oxide skeleton is preferred. By modifying at least a portion of the layered inorganic mineral with an organic ion, the toner has a suitable hydrophobicity, the oil phase containing the toner composition and/or the toner composition precursor has a non-Newtonian viscosity, and the toner can be deformed. In this case, the content of the layered inorganic mineral partially modified with an organic ion in the toner material is preferably 0.05 to 2% by weight. The layered inorganic mineral partially modified with an organic ion may be selected as appropriate, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, modified montmorillonite or bentonite is preferred because it does not affect the toner properties, the viscosity can be easily adjusted, and the amount added can be small.

Commercially available products of layered inorganic minerals partially modified with organic cations include quaternium-18 bentonites such as Bentone 3, Bentone 38, Bentone 38V (manufactured by Rheox), Thixogel VP (manufactured by Unitedcat Alyst), Clayton 34, Clayton 40, Clayton XL (manufactured by Southern Clay), etc.; stearalkonium bentonites such as Bentone 27 (manufactured by Rheox), Thixogel LG (manufactured by Unitedcat Alyst), Clayton AF, Clayton APA (manufactured by Southern Clay), etc.; and quaternium-18/benzalkonium bentonites such as Clayton HT, Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. As the layered inorganic mineral partially modified with an organic anion, DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) modified with an organic anion represented by the following general formula (3) is particularly preferred. An example of the material represented by the following general formula (3) is Hitenol 330T (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
General formula (3): R ¹ (OR ² )nOSO ₃ M
[In the formula, ^R1 represents an alkyl group having 13 carbon atoms, ^R2 represents an alkylene group having 2 to 6 carbon atoms, n represents an integer of 2 to 10, and M represents a monovalent metal element]
Since the organically modified layered inorganic mineral has a suitable degree of hydrophobicity, it is likely to be present at the droplet interface, and is unevenly distributed on the surface, thereby making it possible to suppress the occurrence of the above-mentioned filming.

The organically modified layered inorganic mineral may be used as a master batch in which it is composited with a resin. There are no particular limitations on the resin, but it is preferable to use a binder resin or a resin having a structure similar to that of the binder resin in terms of compatibility with the binder resin.
When preparing the master batch, it is possible to control the dispersibility of the organically modified layered inorganic mineral in the toner by adjusting the temperature, humidity and dispersion conditions.

<Toner Manufacturing Method>
The toner manufacturing method and materials of the present invention are not particularly limited and any known method and materials can be used as long as they satisfy the conditions. For example, even in toners produced by a so-called pulverization method, the amount of exposed release agent can be controlled by dry-coating resin particles on the toner surface.
On the other hand, toner produced in an aqueous system, so-called chemical process, is preferable because it is relatively easy to control the position of the release agent within the toner particles when granulating the toner in an aqueous system using an oil phase.
The method for producing the toner will be described in detail below.

<Toner raw materials>
The toner of the present invention may contain other components as required in the toner matrix containing at least a binder resin and a release agent, and may also contain external additives as required.

(Binder resin)
The binder resin is not particularly limited and can be appropriately selected according to the purpose. For example, polyester resin, silicone resin, styrene-acrylic resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol resin, terpene resin, coumarin resin, amide-imide resin, butyral resin, urethane resin, ethylene vinyl acetate resin, etc. can be mentioned. These may be used alone or in combination of two or more. Among these, polyester resin and resins combining polyester resin with other binder resins are preferred in terms of excellent low-temperature fixing property and sufficient flexibility even when the molecular weight is reduced.

(Polyester resin)
The polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but unmodified polyester resins and modified polyester resins are preferred. These may be used alone or in combination of two or more.

(Unmodified polyester resin)
The unmodified polyester resin is not particularly limited and can be appropriately selected depending on the purpose. For example, a polyester resin obtained by polyesterifying a polyol represented by the following general formula (1) and a polycarboxylic acid represented by the following general formula (2) can be given.

In the above general formula (1), A represents an alkyl group, an alkylene group, an aromatic group or a heterocyclic aromatic group having 1 to 20 carbon atoms, which may have a substituent, and m represents an integer from 2 to 4. In addition, in the above general formula (2), B represents an alkyl group, an alkylene group, an aromatic group or a heterocyclic aromatic group having 1 to 20 carbon atoms, which may have a substituent, and n represents an integer from 2 to 4.

The polyol represented by the general formula (1) is not particularly limited and can be appropriately selected according to the purpose. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tetramethylphenyl glycol ... Examples of such compounds include taerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, and hydrogenated bisphenol A propylene oxide adduct. These compounds may be used alone or in combination of two or more.

The polycarboxylic acid represented by the general formula (2) is not particularly limited and can be appropriately selected according to the purpose. For example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isooctylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctylsuccinic acid, isooctylsuccinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarb Examples of such compounds include carboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimer acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and ethylene glycol bis(trimellitic acid). These may be used alone or in combination of two or more.

<Modified polyester resin>
The modified polyester resin is not particularly limited and can be appropriately selected according to the purpose. For example, it can be a resin obtained by elongation reaction and/or crosslinking reaction of an active hydrogen group-containing compound and a polyester (hereinafter, sometimes referred to as "polyester prepolymer") that can react with the active hydrogen group-containing compound. The elongation reaction and/or crosslinking reaction can be terminated by a reaction terminator (diethylamine, dibutylamine, butylamine, laurylamine, monoamine such as ketimine compound, etc.) as necessary.

<Active hydrogen group-containing compound>
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, etc. when the polyester prepolymer undergoes an elongation reaction, a crosslinking reaction, etc. in the aqueous phase.

The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. Among them, when the polyester prepolymer is an isocyanate group-containing polyester prepolymer described later, amines are preferred because they enable high molecular weight.

The active hydrogen group is not particularly limited and can be appropriately selected depending on the purpose. Examples include hydroxyl groups (alcoholic hydroxyl groups or phenolic hydroxyl groups), amino groups, carboxyl groups, and mercapto groups. These may be contained alone or in combination of two or more types.

The amines, which are the active hydrogen group-containing compounds, are not particularly limited and can be appropriately selected depending on the purpose. Examples include diamines, trivalent or higher polyamines, amino alcohols, amino mercaptans, amino acids, and amines in which the amino groups of these amines have been blocked.

Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4'diaminodiphenylmethane, etc.); alicyclic diamines (4,4'-diamino-3,3'dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.).
Examples of the trivalent or higher polyamines include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan include aminoethyl mercaptan, aminopropyl mercaptan, etc. Examples of the amino acid include aminopropionic acid, aminocaproic acid, etc.
Examples of compounds in which the amino group of these amines is blocked include ketimine compounds and oxazoline compounds obtained from any of these amines (diamines, trivalent or higher polyamines, amino alcohols, amino mercaptans, amino acids, etc.) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

These may be used alone or in combination of two or more. Among these, the amines are particularly preferably diamines or mixtures of diamines with small amounts of trivalent or higher polyamines.

(Polymer capable of reacting with active hydrogen group-containing compound)
The polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited as long as it is a polymer having at least a group capable of reacting with the active hydrogen group-containing compound, and can be appropriately selected according to the purpose. Among them, urea bond-forming group-containing polyester resin (RMPE) is preferred, and isocyanate group-containing polyester prepolymer is more preferred, in terms of high fluidity and transparency when melted, ease of adjusting the molecular weight of the polymer component, and excellent oil-less low-temperature fixing property and release property in dry toner.

The isocyanate group-containing polyester prepolymer is not particularly limited and can be appropriately selected depending on the purpose. For example, it may be a polycondensate of a polyol and a polycarboxylic acid, or a product obtained by reacting an active hydrogen group-containing polyester resin with a polyisocyanate.

The polyol is not particularly limited and can be appropriately selected according to the purpose. For example, alkylene glycols (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.), alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), alkylenes of the alicyclic diols, diols such as bisphenols with alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) and the bisphenols with alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.); polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.), trihydric or higher phenols (phenol novolac, cresol novolac, etc.), and trihydric or higher polyols with alkylene oxides; mixtures of diols and trihydric or higher polyols; etc.

These may be used alone or in combination of two or more. Among these, the polyol is preferably the diol alone or a mixture of the diol with a small amount of the trihydric or higher polyol.

As the diol, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols (bisphenol A ethylene oxide 2-mol adduct, bisphenol A propylene oxide 2-mol adduct, bisphenol A propylene oxide 3-mol adduct, etc.) are preferred.

The content of the polyol in the isocyanate group-containing polyester prepolymer is not particularly limited and can be appropriately selected depending on the purpose. For example, 0.5% by mass to 40% by mass is preferable, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable. If the content is less than 0.5% by mass, the hot offset resistance may deteriorate, making it difficult to achieve both the storage stability and low-temperature fixability of the toner, and if it exceeds 40% by mass, the low-temperature fixability may deteriorate.

The polycarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, etc.); and trivalent or higher polycarboxylic acids (aromatic polycarboxylic acids having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid). These may be used alone or in combination of two or more.

Among these, the polycarboxylic acid is preferably an alkenylene dicarboxylic acid having 4 to 20 carbon atoms, or an aromatic dicarboxylic acid having 8 to 20 carbon atoms. In place of the polycarboxylic acid, an anhydride of a polycarboxylic acid, a lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.), or the like may be used.

The mixing ratio of the polyol and the polycarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. The equivalent ratio [OH]/[COOH] of the hydroxyl group [OH] of the polyol to the carboxyl group [COOH] of the polycarboxylic acid is preferably 2/1 to 1/1, more preferably 1.5/1 to 1/1, and particularly preferably 1.3/1 to 1.02/1.

The polyisocyanate is not particularly limited and can be appropriately selected depending on the purpose. For example, aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, 1,5- naphthylene diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, etc.); aromatic aliphatic diisocyanates (α,α,α',α'-tetramethylxylylene diisocyanate, etc.); isocyanurates (tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, etc.); phenol derivatives of these; blocked with oxime, caprolactam, etc. These may be used alone or in combination of two or more.

The mixing ratio of the polyisocyanate and the active hydrogen group-containing polyester resin (hydroxyl group-containing polyester resin) is not particularly limited and can be appropriately selected depending on the purpose. The equivalent ratio [NCO]/[OH] of the isocyanate group [NCO] of the polyisocyanate to the hydroxyl group [OH] of the hydroxyl group-containing polyester resin is preferably 5/1 to 1/1, more preferably 4/1 to 1.2/1, and particularly preferably 3/1 to 1.5/1. If the equivalent ratio [NCO]/[OH] is less than 1/1, the offset resistance may deteriorate, and if it exceeds 5/1, the low-temperature fixability may deteriorate.

The content of the polyisocyanate in the isocyanate group-containing polyester prepolymer is not particularly limited and can be appropriately selected depending on the purpose. 0.5% by mass to 40% by mass is preferable, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable. If the content is less than 0.5% by mass, hot offset resistance may deteriorate, making it difficult to achieve both storage stability and low-temperature fixability, and if the content exceeds 40% by mass, low-temperature fixability may deteriorate.

The average number of isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer is preferably 1 or more, more preferably 1.2 to 5, and even more preferably 1.5 to 4. If the average number is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group will be low, and hot offset resistance may deteriorate.

The mixing ratio of the isocyanate group-containing polyester prepolymer and the amines is not particularly limited and can be appropriately selected depending on the purpose. The mixing equivalent ratio [NCO]/[NHx] of the isocyanate group [NCO] in the isocyanate group-containing polyester prepolymer and the amino group [NHx] in the amines is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, and particularly preferably 1/1.5 to 1.5/1. If the mixing equivalent ratio ([NCO]/[NHx]) is less than 1/3, low-temperature fixability may decrease, and if it exceeds 3/1, the molecular weight of the urea-modified polyester resin may decrease, resulting in poor hot offset resistance.

The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose. The molecular weight distribution of the tetrahydrofuran (t) soluble matter by GPC (gel permeation chromatography) is preferably 3,000 to 40,000, and more preferably 4,000 to 30,000. If the weight average molecular weight (Mw) is less than 3,000, the storage stability may deteriorate, and if it exceeds 40,000, the low-temperature fixability may deteriorate.

The weight average molecular weight (Mw) can be measured, for example, as follows. First, a column is stabilized in a heat chamber at 40° C., tetrahydrofuran (THF) is passed as a column solvent at this temperature at a flow rate of 1 mL per minute, and 50 μL to 200 μL of a tetrahydrofuran sample solution of the resin, the sample concentration of which is adjusted to 0.05 to 0.6 mass %, is injected and measured. When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithm of a calibration curve prepared using several types of monodisperse polystyrene standard samples and the count number. As the standard polystyrene sample for preparing the calibration curve, the polystyrene standard sample manufactured by PressureChemical Al Co., Ltd. Alternatively, it is preferable to use at least about 10 standard polystyrene samples manufactured by Toyo Soda Kogyo Co., Ltd., each having a molecular weight of 6× ¹⁰ , 2.1× ¹⁰ , 4×10, 1.75× ¹⁰ , 1.1× ¹⁰ , 3.9× ¹⁰ , 8.6×10 ^, 2×10 ^, and 4.48× ¹⁰ . As a detector, an RI (refractive index) detector can be used.

<Crystalline polyester>
In addition, crystalline polyester may be used to improve the low-temperature fixing property of the colored resin particles. Crystalline polyester has a thermal melting property that shows a sudden drop in viscosity near the fixing start temperature due to its crystallinity. In other words, the heat-resistant storage stability is good due to the crystallinity until just before the melting start temperature, and a sudden drop in viscosity (sharp melt property) occurs at the melting start temperature and the toner is fixed, so that a toner having both good heat-resistant storage stability and low-temperature fixing property can be designed.
Also, good results are shown with respect to the release width (the difference between the minimum fixing temperature and the hot offset occurrence temperature). The crystalline polyester is preferably a crystalline polyester having a structure represented by the following general formula (4), which is synthesized using an alcohol component containing 80 mol % or more, preferably 85 to 100 mol %, of a diol compound having 2 to 6 carbon atoms, particularly 1,4-butanediol, 1,6-hexanediol, or a derivative thereof, and at least fumaric acid or a carboxylic acid having a double bond (C=C bond), or a derivative thereof, as an acidic component.
General formula (4) [-O-CO-(CR ¹ =CR ² ) _l -CO-O-(CH ₂ ) _n -] _m
(wherein n and m are the numbers of repeating units; l is an integer of 1 to 3; R ¹ and R ² are hydrogen atoms or hydrocarbon groups, and may be the same or different.)

Methods for controlling the crystallinity and softening point of crystalline polyesters include designing and using nonlinear polyesters that are produced by adding a trivalent or higher polyhydric alcohol such as glycerin to the alcohol component during polyester synthesis, or a trivalent or higher polycarboxylic acid such as trimellitic anhydride to the acid component, and then carrying out condensation polymerization.

The molecular structure of the crystalline polyester of the present invention can be confirmed by NMR measurement of a solution or solid, as well as X-ray diffraction, GC/MS, LC/MS, IR measurement, etc., but a simple example can be one having an absorption due to olefin δCH (out-of-plane bending vibration) at 965±10 cm ^-1 or 990±10 cm ^-1 in an infrared absorption spectrum.

With regard to the molecular weight, from the viewpoint that a molecular weight distribution that is sharp and low molecular weight provides excellent low-temperature fixability, it is preferable that the molecular weight distribution of the o-dichlorobenzene soluble portion by GPC has a peak position in the range of 3.5 to 4.0 in a molecular weight distribution diagram with the horizontal axis being log (M) and the vertical axis being weight %, the half-width of the peak is 1.5 or less, the weight average molecular weight (Mw) is 1,000 to 30,000, the number average molecular weight (Mn) is 500 to 6,000, and the Mw/Mn is 2 to 8.

It is preferable that the melting temperature and 1/2 outflow temperature (F1/2 temperature) are low as long as the heat resistance storage stability is not deteriorated, and the DSC endothermic peak temperature is preferably 50 to 150°C. When the melting temperature and F1/2 temperature are 50°C or higher, the heat resistance storage stability is good and blocking is unlikely to occur at the temperature inside the developing device, and when the temperature is 150°C or lower, the minimum fixing temperature is not high and low-temperature fixing stability is obtained.

From the viewpoint of affinity between paper and resin, the acid value of the crystalline polyester is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, in order to achieve the desired low-temperature fixability, while it is preferably 45 mgKOH/g or less in order to improve hot offset properties. Furthermore, the hydroxyl value of the crystalline polymer is preferably 0 to 50 mgKOH/g, more preferably 5 to 50 mgKOH/g, in order to achieve the desired low-temperature fixability and good charging properties.

<Organic Solvent>
The organic solvent is preferably volatile and has a boiling point of less than 100° C., from the viewpoint of facilitating subsequent solvent removal. As such an organic solvent, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. can be used alone or in combination of two or more. When the resin to be dissolved or dispersed in the organic solvent is a resin having a polyester skeleton, it is preferable to use an ester-based solvent such as methyl acetate, ethyl acetate, or butyl acetate, or a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone, in order to obtain a high solubility, and among these, methyl acetate, ethyl acetate, and methyl ethyl ketone, which have a high solvent removal rate, are particularly preferable.

(Aqueous medium)
The aqueous medium may be water alone, or may be used in combination with a solvent miscible with water, such as alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), and lower ketones (acetone, methyl ethyl ketone, etc.).

(Surfactant)
A surfactant is used to disperse an oil phase in an aqueous medium to produce droplets. Examples of the surfactant include anionic surfactants such as alkylbenzenesulfonates, α-olefinsulfonates, and phosphates, cationic surfactants of amine salt type such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, cationic surfactants of quaternary ammonium salt type such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride, nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives, and amphoteric surfactants such as alanine, dodecyldi(aminoethyl)glycine, di(octylaminoethyl)glycine, and N-alkyl-N,N-dimethylammonium betaine.
Furthermore, by using a surfactant having a fluoroalkyl group, the effect can be achieved with a very small amount.

Examples of anionic surfactants having a fluoroalkyl group that are preferably used include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, sodium 3-[ω-fluoroalkyl(C6 to C11)oxy]-1-alkyl(C3 to C4)sulfonate, sodium 3-[ω-fluoroalkanoyl(C6 to C8)-N-ethylamino]-1-propanesulfonate, fluoroalkyl(C11 to C20)carboxylic acids and metal salts, perfluoroalkyl perfluoroalkyl (C7 to C13) carboxylic acids and their metal salts, perfluoroalkyl (C4 to C12) sulfonic acids and their metal salts, perfluorooctanesulfonic acid diethanolamide, N-propyl-N-(2-hydroxyethyl)perfluorooctanesulfonamide, perfluoroalkyl (C6 to C10) sulfonamidopropyl trimethylammonium salts, perfluoroalkyl (C6 to C10)-N-ethylsulfonylglycine salts, and monoperfluoroalkyl (C6 to C16) ethyl phosphate esters.
Examples of the cationic surfactant include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6 to C10)sulfonamidopropyltrimethylammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts.

(Resin particles contained in aqueous medium)
The resin fine particles used as an emulsifier in the present invention will be described. By adding the resin fine particles as an emulsifier to the aqueous medium before the formation of toner particles, it is possible to suppress the coalescence of oil droplets and improve the granulation property. The resin fine particles contained in the aqueous medium can be any resin that can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin, for example, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, a polyamide resin, a polyimide resin, a silicon resin, a phenol resin, a melamine resin, a urea resin, an aniline resin, an ionomer resin, a polycarbonate resin, etc. can be mentioned. As the resin fine particles, two or more of the above resins may be used in combination. Among them, vinyl resin, polyurethane resin, epoxy resin, polyester resin, or a combination of these resins is preferable because it is easy to obtain an aqueous dispersion of fine spherical resin particles. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer, and examples thereof include a styrene-(meth)acrylic acid ester copolymer, a styrene-butadiene copolymer, a (meth)acrylic acid-acrylic acid ester polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, a styrene-(meth)acrylic acid copolymer, etc. The average particle size of the resin fine particles is 35 to 55 nm.

(Protective colloid)
The dispersed droplets may be stabilized by a polymer protective colloid. For example, the polymer protective colloid may be selected from the group consisting of acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and maleic anhydride, (meth)acrylic monomers containing a hydroxyl group, such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin monomethacrylate, N-methylol acrylamide, and N-methylol methacrylamide, vinyl alcohol, or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, and vinyl propyl ether, or vinyl alcohol and carboxylates. Examples of suitable copolymers include esters of compounds containing a carboxyl group, such as vinyl acetate, vinyl propionate, and vinyl butyrate; acrylamide, methacrylamide, diacetone acrylamide, and methylol compounds thereof; acid chlorides such as acrylic acid chloride and methacrylic acid chloride; homopolymers or copolymers having a nitrogen atom or a heterocyclic ring thereof, such as vinylpyridine, vinylpyrrolidone, vinylimidazole, and ethyleneimine; polyoxyethylene-based copolymers such as polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamines, polyoxypropylene alkylamines, polyoxyethylene alkylamides, polyoxypropylene alkylamides, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester; and celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

(Coloring Agent)
As the colorant of the present invention, known dyes and pigments can be used, for example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, yellow ochre, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Balkan fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthrazan yellow BGL, isoindolinone yellow, red iron oxide, red lead, lead Vermilion, Cadmium Red, Cadmium Mercury Red, Antimony Vermilion, Permanent Red 4R, Para Red, Phaysee Red, Parachlor Orthonitroaniline Red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Lithol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidinema Rune, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue Examples of the pigments that can be used include blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine blue, Prussian blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc oxide, lithopone, and mixtures thereof.

(Master batch of colorants)
The colorant used in the present invention can also be used as a masterbatch composited with a resin. Examples of binder resins to be used in the preparation of a masterbatch or to be kneaded together with the masterbatch include, in addition to the above-mentioned binding resins and modified resins, polymers of styrene and its substitutes such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene ... Examples of suitable copolymers include styrene-based copolymers such as styrene-acrylonitrile copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resins, epoxy polyol resins, polyurethanes, polyamides, polyvinyl butyral, polyacrylic acid resins, rosin, modified rosin, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffin, and paraffin wax, which may be used alone or in combination.

(Masterbatch manufacturing method)
The master batch can be obtained by mixing and kneading the resin and colorant for the master batch under high shear force. In this case, an organic solvent can be used to enhance the interaction between the colorant and the resin.
In addition, the so-called flushing method, in which an aqueous paste containing a colorant in water is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and the water and organic solvent components are removed, is also preferably used because it does not require drying since the wet cake of the colorant can be used as is. A high shear dispersion device such as a three-roll mill is preferably used for mixing and kneading.

(Release Agent)
In addition, when the colored resin particles are used as a toner for developing an electrostatic latent image, a release agent may be dispersed in an organic solvent in order to enhance the fixing and releasing properties. As the release agent, a substance such as wax or silicone oil that has a sufficiently low viscosity when heated in the fixing process and is not easily dissolved or swollen with other substances of the colored resin particles on the surface of the fixing member is used, and considering the storage stability of the colored resin particles themselves, it is preferable to use wax that exists as a solid in the colored resin particles during normal storage.

Examples of waxes include long-chain hydrocarbons and carbonyl group-containing waxes. Examples of long-chain hydrocarbons include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); petroleum waxes (paraffin wax, sazol wax, microcrystalline wax, etc.); and Fischer-Tropsch waxes.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitate, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenylamide, etc.); polyalkylamides (tristearyl trimellitate amide, etc.); and dialkyl ketones (distearyl ketone, etc.). Among these, long-chain hydrocarbons, which have particularly good releasability, are preferred. Furthermore, when long-chain hydrocarbons are used as a release agent, carbonyl group-containing waxes may be used in combination.

(Charge control agent)
Furthermore, if necessary, a charge control agent may be contained. Any known charge control agent can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substance or compounds, tungsten simple substance or compounds, fluorine-based activators, salicylic acid metal salts, and salicylic acid derivative metal salts.
Specifically, the nigrosine dye Bontron 03, the quaternary ammonium salt Bontron P-51, the metal-containing azo dye Bontron S-34, the oxynaphthoic acid metal complex E-82, the salicylic acid metal complex E-84, the phenol condensate E-89 (all manufactured by Orient Chemical Industry Co., Ltd.), the quaternary ammonium salt molybdenum complexes TP-302 and TP-415 (all manufactured by Hodogaya Chemical Co., Ltd.), and the quaternary ammonium salt Copy Charge PSY Examples of the pigments include polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts, such as Copy Charge NEGVP2036 and Copy Charge NXVP434 (all manufactured by Hoechst), LRA-901, boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

In addition, the present invention can be applied to toners produced by the so-called pulverization method, but is preferably used as toners produced in an aqueous system. In so-called pulverized toners that undergo a kneading and pulverization process, additives are dispersed uniformly to a certain extent in the kneading process and are present in the toner. For this reason, although the material that becomes the pulverization interface may come to the surface, it is difficult to control the surface uneven distribution. For this reason, in order to obtain a specific metal element on the surface of the above toners that require surface uneven distribution, it is necessary to increase the amount of additive, but as a side effect, problems arise in terms of fixation and spent properties, and sufficient quality cannot be obtained. Surface uneven distribution can be verified using XPS.

In the case of an aqueous system, when the toner is granulated in the aqueous system as an oil phase, the organic ions between the layers are modified to a level suitable for uneven distribution near the surface inside the toner particles, making uneven distribution near the surface of the toner possible. In other words, the organically modified layered inorganic mineral has the property that it moves toward the surface side in the oil droplets and tends to be unevenly distributed on the toner surface. When the amount of modification with the organic ions between the layers is small, the hydrophobicity of the layered inorganic mineral is insufficient, and peeling between the layers of the layered inorganic mineral becomes difficult, making it difficult to disperse in the toner, and the atomic concentration % on the surface is not observed sufficiently. When the amount of modification with the organic ions of the layered inorganic mineral is increased, the ion species is changed, or a surface treatment is performed to increase the hydrophobicity, the layered inorganic mineral tends to be uniformly dispersed in the toner or unevenly distributed in the center of the toner. The present invention makes it possible to achieve the uneven distribution state by appropriately selecting the aqueous phase, oil phase, and layered inorganic mineral so that the uneven distribution state is specified.

<Production Method>
Next, a method for producing the toner will be described. The method is not particularly limited to the following.
In the case of the emulsion aggregation method, when an aluminum-based inorganic metal salt or a divalent or higher metal complex is used as the flocculant, this can be achieved by appropriately adjusting the pH, reaction temperature, formulation amount, etc., and in the case of the pulverization method, this can be achieved by shelling by melting a master batch of an aluminum-containing charge control agent after dry mixing, or by externally adding an aluminum-containing charge control agent after the dry mixing. The preferred method is the ester elongation polymerization method (tentative). The manufacturing method using the ester elongation polymerization method is shown below.

(Oil phase preparation process)
The method for preparing the oil phase in which the resin, colorant, etc. are dissolved or dispersed in the organic solvent may be to gradually add the resin, colorant, etc. to the organic solvent while stirring to dissolve or disperse them. However, when a pigment is used as the colorant or when a substance that is difficult to dissolve in the organic solvent, such as a mold release agent, is added, it is preferable to reduce the particles size before adding them to the organic solvent.
In particular, in the case of a release agent, by miniaturizing the particle size, the release agent is easily encapsulated inside the toner and the amount of exposure to the toner surface is reduced, so it is preferable to miniaturize the particles in advance. For example, a method may be performed in which a dispersion aid is added in an organic solvent, and the release agent is heated while being stirred and dissolved, and then crystallized by cooling while being stirred or sheared to generate microcrystals of the dispersoid. After dispersion, additional dispersion may be performed by another method. For dispersion, a known dispersing machine such as a bead mill or a disk mill can be used. When performing additional dispersion, the dispersion efficiency of the release agent particles can be improved and the miniaturization can be further promoted by adding the dispersion aid.

(Emulsification process)
The method for dispersing the oil phase obtained in the above-mentioned step in an aqueous medium containing at least a surfactant to prepare a dispersion in which toner particles made of the oil phase are dispersed is not particularly limited, but known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic type can be applied. A high-speed shear type is preferred in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shear type dispersing machine is used, the rotation speed is not particularly limited, but is usually 1000 to 30,000 rpm, and preferably 5,000 to 15,000 rpm.

(Desolvation process)
In order to remove the organic solvent from the obtained colored resin dispersion, a method can be adopted in which the temperature is gradually increased while stirring the entire system, and the organic solvent in the droplets is completely evaporated and removed. Alternatively, the obtained colored resin dispersion can be sprayed into a dry atmosphere while stirring, and the organic solvent in the droplets can be completely removed. Alternatively, the colored resin dispersion can be depressurized while stirring, and the organic solvent can be evaporated and removed.
The latter two means can be used in combination with the first means. As the drying atmosphere into which the emulsified dispersion is sprayed, air, nitrogen, carbon dioxide, heated combustion gas, etc., and in particular various air flows heated to a temperature equal to or higher than the boiling point of the highest boiling point solvent used, are generally used. The desired quality can be obtained sufficiently by short-term treatment with a spray dryer, belt dryer, rotary kiln, etc.

(Aging process)
When a modified resin having an isocyanate group at the end is added, an aging step may be carried out to promote the elongation and crosslinking reaction of the isocyanate. The aging time is usually 10 minutes to 30 hours, preferably 2 to 15 hours. The reaction temperature is usually 20 to 65°C, preferably 35 to 50°C.

(Washing and drying process)
The toner particles dispersed in the aqueous medium are washed and dried using known techniques. That is, after solid-liquid separation using a centrifuge, filter press, or the like, the resulting toner cake is redispersed in ion-exchanged water at room temperature to about 40°C. The solid-liquid separation process is repeated several times to remove impurities and surfactants, and then the pH is adjusted with an acid. After these treatments, the toner is dried using an airflow dryer, a circulation dryer, a reduced pressure dryer, a vibration flow dryer, or the like to obtain a toner powder. At this time, fine particle components of the toner may be removed by centrifugation, or after drying, a known classifier may be used to obtain a desired particle size distribution.

(External Addition Treatment)
The resulting dried toner powder can be mixed with different particles such as the charge control microparticles and fluidizing agent microparticles, or the mixed powder can be subjected to a mechanical impact force to fix and fuse the different particles on the surface, thereby preventing the different particles from being detached from the surface of the resulting composite particles.
Specific means include a method of applying an impact force to the mixture with a blade rotating at high speed, a method of throwing the mixture into a high-speed air current, accelerating it, and causing the particles to collide with each other or the composite particles to collide with an appropriate collision plate, etc. Examples of equipment include Nobilta (manufactured by Hosokawa Micron Corporation), Meteor Rainbow (manufactured by Nippon Pneumatic Co., Ltd.), and Hybridization System (manufactured by Nara Machinery Co., Ltd.).

(Developer)
The developer of the present invention contains at least the toner and appropriately selected other components such as a carrier, etc. The developer may be a one-component developer or a two-component developer.

<Career>
The carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably one having core particles and a resin layer (coating layer) that coats the core particles.

<<Core particles>>
The core particles are not particularly limited as long as they are magnetic core particles and can be appropriately selected depending on the purpose, and examples thereof include ferromagnetic metals such as iron and cobalt, iron oxides such as magnetite, hematite and ferrite, resin particles in which magnetic materials such as various alloys and compounds are dispersed in a resin, etc. Among these, Mn-based ferrite, Mn-Mg-based ferrite, Mn-Mg-Sr-based ferrite, etc. are preferred from the viewpoint of environmental consideration.

<<Coating Layer>>
The coating layer contains at least a resin, and may contain other components such as a filler, if necessary.
-resin-
The resin for forming the carrier coating layer is not particularly limited and can be appropriately selected according to the purpose. For example, polyolefin (e.g., polyethylene, polypropylene, etc.) or its modified product, crosslinkable copolymer containing polystyrene, acrylic resin, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl chloride, vinylcarbazole, vinyl ether, etc.; silicone resin consisting of organosiloxane bond or its modified product (e.g., modified product by alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.); polyamide; polyester; polyurethane; polycarbonate; urea resin; melamine resin; benzoguanamine resin; epoxy resin; ionomer resin; polyimide resin, and derivatives thereof. These may be used alone or in combination of two or more. Among these, silicone resin is preferred.

(Toner storage unit)
The toner storage unit in the present invention refers to a unit having a function of storing toner and storing the toner. Here, examples of the toner storage unit include a toner storage container, a developing device, and a process cartridge. The toner storage container refers to a container that stores toner. The developing device refers to a device that stores toner and has a means for developing the toner. The process cartridge refers to a device that integrates at least an electrostatic latent image carrier (also called an image carrier) and a developing device, stores toner, and is detachable from an image forming device. The process cartridge may further include at least one selected from a charging device, an exposure device, and a cleaning device.

By mounting the toner storage unit of the present invention on an image forming device and forming an image, the toner of the present invention is used to form an image, making it possible to achieve low-temperature fixing while suppressing toner scattering.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further includes other means as necessary. The image forming method of the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary. The image forming method can be suitably performed by the image forming apparatus, the electrostatic latent image forming step can be suitably performed by the electrostatic latent image forming means, the developing step can be suitably performed by the developing means, and the other steps can be suitably performed by the other means. The image forming apparatus of the present invention more preferably includes an electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, a developing means provided with a toner for developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a toner image, a transfer means for transferring the toner image formed on the electrostatic latent image carrier to the surface of a recording medium, and a fixing means for fixing the toner image transferred to the surface of the recording medium. More preferably, the image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a toner image, a transferring step of transferring the toner image formed on the electrostatic latent image carrier to the surface of a recording medium, and a fixing step of fixing the toner image transferred to the surface of the recording medium. The toner is used in the developing means and the developing step. Preferably, the toner image is formed by using a developer containing the toner and, if necessary, other components such as a carrier.

<Electrostatic Latent Image Bearing Member>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known materials. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine.

<Electrostatic Latent Image Forming Means>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and may be appropriately selected depending on the purpose. For example, there may be mentioned a means having at least a charging member that charges the surface of the electrostatic latent image carrier, and an exposure member that exposes the surface of the electrostatic latent image carrier to light in an imagewise manner.

<Developing Means>
The developing unit is not particularly limited as long as it is a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image and has a toner, and can be appropriately selected depending on the purpose.

<Other measures>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a discharging means, a recycling means, and a control means.

Next, one embodiment of a method for forming an image using the image forming apparatus of the present invention will be described with reference to the drawings. FIG. 1 shows an example of an image forming apparatus of the present invention. The image forming apparatus 100A has a photoconductor drum (electrostatic latent image carrier) 10 as an electrostatic latent image carrier, a charging roller 20 as a charging means, an exposure device (not shown) as an exposure means, a developing device 40 as a developing means, an intermediate transfer body 50, a cleaning device 60 having a cleaning blade as a cleaning means, and a discharging lamp 70 as a discharging means.

The intermediate transfer body 50 is an endless belt, stretched by three rollers 51 arranged inside it, and can move in the direction of the arrow. Some of the three rollers 51 also function as transfer bias rollers capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer body 50. A cleaning device 90 having a cleaning blade is arranged near the intermediate transfer body 50. Furthermore, a transfer roller 80 as a transfer means capable of applying a transfer bias for transferring (secondary transfer) a toner image to a recording paper 95 is arranged facing the intermediate transfer body 50. A corona charger 52 for applying a charge to the toner image on the intermediate transfer body 50 is arranged around the intermediate transfer body 50 between the contact portion between the photosensitive drum 10 and the intermediate transfer body 50 and the contact portion between the intermediate transfer body 50 and the recording paper 95. The developing devices 40 for each color of black (K), yellow (Y), magenta (M), and cyan (C) include a developing belt 41, a developer container 42, a developer supply roller 43, and a developing roller 44.
In the image forming apparatus 100A, the photoconductor drum 10 is uniformly charged by the charging roller 20, and then the exposure device (not shown) exposes the photoconductor drum 10 to the exposure light L in an imagewise manner to form an electrostatic latent image. Next, the electrostatic latent image formed on the photoconductor drum 10 is developed by supplying a developer from the developing device 40 to form a toner image, and then the toner image is transferred (primary transfer) onto the intermediate transfer body 50 by the transfer bias applied from the roller 51. Furthermore, the toner image on the intermediate transfer body 50 is charged by the corona charger 58, and then transferred (secondary transfer) onto the recording paper 95. The recording paper 95 to which the toner image has been transferred is heated and pressed by the heating roller and pressure roller of the fixing device, whereby the recording paper 95 is heated and melted, and fixed onto the recording paper 95. Meanwhile, the toner remaining on the photoconductor drum 10 is removed by the cleaning device 60, and the photoconductor drum 10 is once discharged by the discharge lamp 70.

2 shows another example of the image forming apparatus of the present invention. The image forming apparatus 100B is a tandem type color image forming apparatus, and includes a copying machine main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400. An endless belt-like intermediate transfer body 50 is provided in the center of the copying machine main body 150. The intermediate transfer body 50 is stretched around support rollers 14, 15, and 16, and can rotate in the direction of the arrow. A cleaning device 17 is disposed near the support roller 15 to remove toner remaining on the intermediate transfer body 50. In addition, a tandem type developing device 120 is disposed on the intermediate transfer body 50 stretched around the support rollers 14 and 15 along the transport direction, in which four image forming means 18 for yellow, cyan, magenta, and black are arranged in a row facing each other.
As shown in Fig. 3, each image forming unit 18 for each color includes a photoconductor drum 10, a charging roller 20 for uniformly charging the photoconductor drum 10, a developing device 40 for developing the electrostatic latent image formed on the photoconductor drum 10 with a developer of each color of black (K), yellow (Y), magenta (M) and cyan (C) to form a toner image, a transfer roller 80 for transferring the toner image of each color onto an intermediate transfer body 50, a cleaning device 60, and a discharging lamp 70. An exposure device 30 is disposed near the tandem type developing device 120. The exposure device 30 exposes the photoconductor drum 10 to exposure light L to form an electrostatic latent image.
Furthermore, a secondary transfer device 22 is disposed on the opposite side of the intermediate transfer body 50 from the side where the tandem type developing device 120 is disposed. The secondary transfer device 22 is composed of a secondary transfer belt 24, which is an endless belt stretched over a pair of rollers 23, and the recording paper transported on the secondary transfer belt 24 and the intermediate transfer body 50 can come into contact with each other. A fixing device 25 is disposed near the secondary transfer device 22. The fixing device 25 has a fixing belt 26, which is an endless belt, and a pressure roller 27, which is disposed while being pressed against the fixing belt 26. One of the rollers stretched over the fixing belt 26 is a heating roller. In addition, a reversing device 28, which reverses the recording paper to form an image on both sides of the recording paper, is disposed near the secondary transfer device 22 and the fixing device 25.

The formation of a full-color image (color copy) in the image forming apparatus 100B having such a configuration will be described. First, an original is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and an original is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed. Next, when a start switch (not shown) is pressed, when an original is set on the automatic document feeder 400, the original is transported and moved onto the contact glass 32, and when an original is set on the contact glass 32, the scanner 300 is immediately driven and the first traveling body 33 and the second traveling body 34 travel. At this time, light from a light source is irradiated by the first traveling body 33, and the reflected light from the original surface is reflected by a mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35. As a result, a color original (color image) is read, and image information of each color of black, yellow, magenta, and cyan is obtained. Furthermore, after the exposure device 30 forms an electrostatic latent image of each color on the photosensitive drum 10 based on the image information of each color obtained, the electrostatic latent image of each color is developed with a developer supplied from the developer 40 of each color to form a toner image of each color. The formed toner images of each color are transferred (primary transfer) in a superimposed manner onto the intermediate transfer body 50 which is rotated by the support rollers 14, 15, and 16, and a composite toner image is formed on the intermediate transfer body 50. In the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed a recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and the recording paper is separated one by one by the separation roller 145 and sent to the paper feed path 146, and is transported by the transport roller 147 to be guided to the paper feed path 148 in the copying machine main body 150, where it is stopped by hitting the registration roller 49. Alternatively, recording paper is fed from a manual feed tray 54, separated one by one by a separation roller 52, and fed into a manual feed path 53, where it is stopped by abutting against a registration roller 49. Although the registration roller 49 is generally grounded, it may be used with a bias applied to it in order to remove paper dust from the recording paper.
Then, the registration roller 49 is rotated in time with the composite toner image formed on the intermediate transfer body 50, and the recording paper is sent between the intermediate transfer body 50 and the secondary transfer device 22, and the composite toner image is transferred (secondary transfer) onto the recording paper. The recording paper to which the composite toner image has been transferred is transported by the secondary transfer device 22 and sent to the fixing device 25. Then, in the fixing device 25, the recording paper is heated and pressed by the fixing belt 26 and the pressure roller 27, and the composite toner image is fixed onto the recording paper. Thereafter, the recording paper is switched by the switching claw 55, discharged by the discharge roller 56, and stacked on the paper discharge tray 57. Alternatively, the recording paper is switched by the switching claw 55, reversed by the reversing device 28, and guided to the transfer position again, an image is formed on the back side as well, and then discharged by the discharge roller 56 and stacked on the paper discharge tray 57. Note that the toner remaining on the intermediate transfer body 50 after the composite toner image has been transferred is removed by the cleaning device 17.

The process cartridge of the present invention is molded so as to be detachably mountable to various image forming apparatuses, and has at least an electrostatic latent image carrier for carrying an electrostatic latent image, and a developing means for developing the electrostatic latent image carried on the electrostatic latent image carrier with the developer of the present invention to form a toner image. The process cartridge of the present invention may further have other means as necessary.
The developing means includes at least a developer container that contains the developer of the present invention, and a developer carrier that carries and transports the developer contained in the developer container. The developing means may further include a regulating member or the like for regulating the thickness of the developer carried.
An example of the process cartridge of the present invention is shown in Fig. 4. The process cartridge has a photosensitive drum 10, a corona charger 52, a developing device 40, a transfer roller 80 and a cleaning device 90.

The present invention will be described in more detail below with reference to examples and comparative examples. Note that the present invention is not limited to the examples and comparative examples exemplified here, and parts in the examples represent parts by weight unless otherwise specified.

(Production of resin fine particle dispersion)
In a reaction vessel equipped with a stirring rod and a thermometer, 683 parts of water, 11 parts of sodium salt of methacrylic acid ethylene oxide adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 5 parts of sodium salt of dodecanol ethylene oxide adduct sulfate (Calipon EN-200, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, 110 parts of butyl acrylate, and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, resulting in a white emulsion. The system was heated to a temperature of 75°C and reacted for 2 hours. Furthermore, 30 parts of a 1% aqueous ammonium persulfate solution was added dropwise, and the mixture was aged at 75°C for 8 hours to obtain a resin fine particle A dispersion of vinyl resin (styrene-methacrylic acid-butyl acrylate-sodium salt of methacrylic acid ethylene oxide adduct sulfate copolymer) with a solid content of 20%. The volume average particle size was 38 nm.

(Synthesis of low molecular weight polyester A)
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 220 parts of an ethylene oxide 2-mol adduct of bisphenol A, 561 parts of a propylene oxide 3-mol adduct of bisphenol A, 218 parts of terephthalic acid, 48 parts of adipic acid, and 2 parts of dibutyltin oxide were placed and reacted at 230° C. under normal pressure for 8 hours.
Next, after reacting for 5 hours under reduced pressure of 10 to 15 mmHg, 45 parts of trimellitic anhydride was placed in the reaction vessel and reacted for 2 hours at normal pressure at 180° C. to synthesize low molecular weight polyester A. The obtained low molecular weight polyester A had a weight average molecular weight of 6,700 and a glass transition temperature (Tg) of 43° C.

(Synthesis of low molecular weight polyester B)
In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide 2 mole adduct (BisA-EO), bisphenol A propylene oxide 3 mole adduct (BisA-PO), trimethylolpropane (TMP), terephthalic acid, and adipic acid were added to the flask in a molar ratio of bisphenol A ethylene oxide 2 mole adduct, bisphenol A propylene oxide 3 mole adduct, and trimethylolpropane (bisphenol A ethylene oxide 2 mole adduct/bisphenol A propylene oxide 3 mole adduct/trimethylolpropane). The mixture was charged with terephthalic acid and adipic acid in a molar ratio (terephthalic acid/adipic acid) of 38.6/57.9/3.5, terephthalic acid and adipic acid in a molar ratio (terephthalic acid/adipic acid) of 85/15, and the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, was 1.12, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at normal pressure and 230°C for 8 hours, and then reacted for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. Then, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and reacted at 180°C and normal pressure for 3 hours to obtain low molecular weight polyester B. The obtained low molecular weight polyester B had a weight average molecular weight of 13,000 and a glass transition temperature (Tg) of 61°C.

(Synthesis of low molecular weight polyester C)
In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide 2 mole adduct (BisA-EO), bisphenol A propylene oxide 3 mole adduct (BisA-PO), trimethylolpropane (TMP), terephthalic acid, and adipic acid were added to the flask in a molar ratio of bisphenol A ethylene oxide 2 mole adduct, bisphenol A propylene oxide 3 mole adduct, and trimethylolpropane (bisphenol A ethylene oxide 2 mole adduct/bisphenol A propylene oxide 3 mole adduct/trimethylolpropane). The mixture was charged with terephthalic acid and adipic acid in a molar ratio (terephthalic acid/adipic acid) of 38.6/57.9/3.5, terephthalic acid and adipic acid in a molar ratio (terephthalic acid/adipic acid) of 85/15, and the molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, was 1.06, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at normal pressure and 230°C for 8 hours, and then reacted for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. Then, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and reacted at 180°C and normal pressure for 3 hours to obtain low molecular weight polyester C. The obtained low molecular weight polyester C had a weight average molecular weight of 18,000 and a glass transition temperature (Tg) of 65°C.

(Synthesis of low molecular weight polyester D)
In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide 2 mole adduct (BisA-EO), bisphenol A propylene oxide 3 mole adduct (BisA-PO), trimethylolpropane (TMP), terephthalic acid, and adipic acid were added to the flask in a molar ratio of bisphenol A ethylene oxide 2 mole adduct, bisphenol A propylene oxide 3 mole adduct, and trimethylolpropane (bisphenol A ethylene oxide 2 mole adduct/bisphenol A propylene oxide 3 mole adduct/trimethylolpropane). The mixture was charged with terephthalic acid and adipic acid in a molar ratio (terephthalic acid/adipic acid) of 95/5 and a molar ratio of hydroxyl groups to carboxyl groups, OH/COOH, of 1.20, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at normal pressure and 230°C for 8 hours, and then reacted for 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. Then, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and reacted at 180°C and normal pressure for 3 hours to obtain low molecular weight polyester D. The obtained low molecular weight polyester D had a weight average molecular weight of 7,500 and a glass transition temperature (Tg) of 61°C.

(Synthesis of crystalline polyester)
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 2070 parts of 1,4-butanediol, 2535 parts of fumaric acid, 291 parts of trimellitic anhydride, and 4.9 parts of hydroquinone were placed and reacted at 160°C for 5 hours, then the temperature was raised to 200°C and the reaction was continued for 1 hour, and further reacted at 8.3 kPa for 1 hour to obtain a crystalline polyester.

(Preparation of Crystalline Polyester Dispersion)
Crystalline polyester was mixed in ethyl acetate at 36% by weight, dissolved at 55°C for 1 hour, and then cooled to 20°C or less using an external heat exchanger with cooling water to precipitate the crystalline polyester and obtain a crystallized liquid. The crystalline polyester crystallized liquid was circulated and pulverized using a bead mill (LMZ25, manufactured by Ashizawa Finetech) to obtain a crystalline polyester dispersion. Zirconia beads with a bead diameter of 0.5 mm were used as the media.

(Preparation of release agent crystallization solution)
12.2 parts of ester wax (LW-13; manufactured by Sanyo Chemical Industries, Ltd.), 7.3 parts of a dispersant (styrene acrylic; manufactured by Sanyo Chemical Industries, Ltd.), and 36.6 parts of the low molecular weight polyester were added to 81.0 parts of ethyl acetate, and the mixture was heated and melted at 60° C. for 3 hours and then cooled to 30° C. or lower using an external heat exchanger to prepare crystallized liquid 2.

(Preparation of release agent dispersion)
The crystallized solution 2 was circulated and dispersed using a bead mill (LMZ60, manufactured by Ashizawa Finetech) to obtain a release agent dispersion 1. Zirconia beads having a bead diameter of 0.5 mm were used as the media.

(Preparation of low molecular weight polyester solution)
The low molecular weight polyesters A, B and C were dissolved in ethyl acetate at 70% by weight, and the dissolution temperature was controlled at 40° C. to obtain low molecular weight polyester solutions A, B and C.

(Preparation of Masterbatch A)
55 parts of organically modified layered inorganic mineral (Clayton APA (manufactured by BYK Japan)), 45 parts of polyester resin A, and 15 parts of ion-exchanged water were mixed and kneaded at 90°C using a two-roll mill to obtain an organically modified layered inorganic mineral master batch A. The organically modified layered inorganic mineral contains Al, Fe, Si, and Mg, which was confirmed by measurement using X-ray fluorescence elemental analysis (XRF).

(Preparation of Masterbatch B)
55 parts of organically modified layered inorganic mineral (Clayton APA (manufactured by BYK Japan)), 45 parts of polyester resin A, and 15 parts of ion-exchanged water were mixed and kneaded at 85° C. using a two-roll mill to obtain an organically modified layered inorganic mineral master batch B. The organically modified layered inorganic mineral contains Al, Fe, Si, and Mg, which was confirmed by measurement using X-ray fluorescence elemental analysis (XRF).

(Preparation of Masterbatch C)
55 parts of organically modified layered inorganic mineral (Clayton APA (manufactured by BYK Japan)), 45 parts of polyester resin A, and 15 parts of ion-exchanged water were mixed and kneaded at 80°C using a two-roll mill to obtain an organically modified layered inorganic mineral master batch C. The organically modified layered inorganic mineral contains Al, Fe, Si, and Mg, which was confirmed by measurement using X-ray fluorescence elemental analysis (XRF).

(Preparation of Masterbatch D)
55 parts of organically modified layered inorganic mineral (Clayton APA (manufactured by BYK Japan)), 45 parts of polyester resin A, and 15 parts of ion-exchanged water were mixed and kneaded at 100°C using a two-roll mill to obtain an organically modified layered inorganic mineral master batch D. The organically modified layered inorganic mineral contains Al, Fe, Si, and Mg, which was confirmed by measurement using X-ray fluorescence elemental analysis (XRF).

[Example 1]
(Preparation of oil phase)
307 parts of the release agent dispersion 1, 212 parts of the solution of the low molecular weight polyester A, 26 parts of black pigment C-60, 78 parts of the crystalline polyester dispersion, 6.8 parts of master batch A, and 22 parts of ethyl acetate were charged into a tank, and dissolved and dispersed for 3 hours to obtain an oil phase 1.

(Synthesis of Prepolymer)
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 795 parts of bisphenol A ethylene oxide 2 mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were respectively charged, and a condensation reaction was carried out at 210°C for 8 hours under normal pressure nitrogen gas flow. Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, and then cooled to 80°C and reacted with 170 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain prepolymer 1. The weight average molecular weight of the obtained prepolymer was 5,000.

(Preparation of aqueous phase)
1,180 parts of water, 51 parts of resin fine particle dispersion, 262 parts of a 50 wt % aqueous solution of sodium dodecyldiphenyletherdisulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 138 parts of ethyl acetate were added and mixed with stirring to obtain an aqueous phase 1.

(Emulsification)
383 parts of oil phase 1, 64 parts of prepolymer 1, and 3.5 parts of a 50% by mass solution of isophorone diamine in ethyl acetate were mixed and stirred with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation speed of 5,000 rpm to uniformly dissolve and disperse the mixture, obtaining an oil phase 2. Next, 550 parts of water phase 1 was placed in another container equipped with a stirrer and a thermometer, and oil phase 2 was added while stirring with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 11,000 rpm, and emulsified for 1 minute to obtain an emulsified slurry 1.

(Removal of solvent and aging)
The obtained emulsified slurry was stored in a SUS tank equipped with a hot water jacket and a vacuum line, and while stirring at a peripheral speed of the stirring blade at the outer periphery end of 10.5 m/sec, the pressure was gradually reduced while avoiding bumping, and the solvent was finally removed under reduced pressure conditions of -95 kPa. During this process, the reduced pressure conditions were adjusted so that the organic solvent concentration in the slurry would change over time as follows. The concentration of the remaining organic solvent in the emulsified slurry was determined by measurement using gas chromatography (GC-2010, manufactured by Shimadzu Corporation).
STEP 1: The solvent was removed for 40 minutes at a slurry temperature of 30° C., and the organic solvent concentration became 15% by mass.
STEP 2: The solvent was removed for 80 minutes at a slurry temperature of 30° C., and the organic solvent concentration became 5% by mass.
STEP 3: The solvent was removed for 180 minutes while increasing the slurry temperature to 36° C., and the organic solvent concentration became 0.1% by mass.
Thereafter, aging was carried out at 50° C. for 4 hours to obtain a dispersion slurry 1.

(Washing and drying process)
The filter cake 1 obtained by pressure filtration of the dispersion slurry was subjected to the following treatment. (1) 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) (at a rotation speed of 6,000 rpm for 5 minutes), and then filtered. (2) 100 parts of ion-exchanged water was added to the filter cake of (1) above, and the mixture was mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) (at a rotation speed of 6,000 rpm for 5 minutes), and then 1% by mass of hydrochloric acid was added under stirring until the pH reached about 5.0, and the mixture was stirred for 1 hour and then filtered. (3) 300 parts of ion-exchanged water was added to the filter cake of (2) above, and the mixture was mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) (at a rotation speed of 6,000 rpm for 5 minutes), and then filtered. This operation was repeated twice to obtain filter cake 1. The obtained filter cake 1 was dried in a circulating air dryer at 40° C. for 48 hours. Thereafter, the mixture was sieved through a mesh with an opening of 75 μm to prepare toner base particles 1.

(mixture)
Hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) was added to the above toner base particles 1 in an amount of 1.5 parts per 100 parts of base particles, and mixed for 5 minutes at a peripheral speed of 33 m/s in a 20 L Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The above was air-sieved through a 500 mesh sieve to obtain toner 1.

[Example 2]
Toner 2 was obtained in the same manner and procedure as in Example 1, except that in the preparation of the oil phase, the amount of the master batch A was changed to 7.2 parts.

[Example 3]
Toner 3 was obtained in the same manner and procedure as in Example 1, except that in the preparation of the oil phase, the amount of the master batch A was changed to 7.3 parts.

[Example 4]
Toner 4 was obtained in the same manner and procedure as in Example 1, except that in the preparation of the oil phase, the amount of the master batch A was changed to 7.8 parts.

[Example 5]
Toner 5 was obtained in the same manner and procedure as in Example 1, except that in the preparation of the oil phase, the amount of Masterbatch A was 8.3 parts.

[Example 6]
Toner 6 was obtained in the same manner and procedure as in Example 1, except that in the preparation of the oil phase, the amount of the master batch A was 8.4 parts.

[Example 7]
Toner 7 was obtained in the same manner and procedure as in Example 1, except that in the preparation of the oil phase, the amount of Masterbatch A was 8.9 parts.

[Example 8]
Toner 8 was obtained in the same manner and procedure as in Example 1, except that the solution of low molecular weight polyester B was used in the preparation of the oil phase.

[Example 9]
Toner 9 was obtained in the same manner and procedure as in Example 1, except that a solution of low molecular weight polyester C was used in the preparation of the oil phase.

[Example 10]
Toner 10 was obtained in the same manner and procedure as in Example 1, except that a solution of low molecular weight polyester D was used in the low oil phase preparation step.

[Example 11]
Toner 11 was obtained in the same manner and procedure as in Example 1, except that Masterbatch B was used in the preparation of the oil phase.

[Example 12]
Toner 12 was obtained in the same manner and procedure as in Example 1, except that Masterbatch C was used in the preparation of the oil phase.

[Comparative Example 1]
Toner 13 was obtained in the same manner and procedure as in Example 1, except that in the preparation of the oil phase, the amount of the master batch A was 6.7 parts.

[Comparative Example 2]
Toner 14 was obtained in the same manner and procedure as in Example 1, except that in the preparation of the oil phase, the amount of the master batch A was changed to 9.0 parts.

[Comparative Example 3]
Toner 15 was obtained in the same manner and procedure as in Example 1, except that Masterbatch D was used in the preparation of the oil phase.

Toners 1 to 15 differ in the type of master batch, the amount added, and the type of low molecular weight polyester used in making the oil phase, and these differences are shown in Table 1 below.

<Evaluation method>
<Low temperature fixability evaluation>
A copy test was conducted by using a modified copy machine MF2200 fixing section manufactured by Ricoh Co., Ltd., which uses a Teflon (registered trademark) roller as the fixing roller, and setting Ricoh Co., Ltd. type 6200 paper in the fixing section. The fixing temperature was changed to obtain the cold offset temperature (lowest fixing temperature). The lowest fixing temperature of conventional low-temperature fixing toner is about 140°C to 150°C. The evaluation conditions for low-temperature fixing were set as a paper feed linear speed of 120 mm/sec to 150 mm/sec, a surface pressure of 1.2 kgf/cm2, and a nip width of 3 mm, and the evaluation conditions for high-temperature offset were set as a paper feed linear speed of 50 mm/sec, a surface pressure of 2.0 kgf/ ^cm2 , and a nip width of 4.5 mm. The criteria for each characteristic evaluation are as follows. The lower the fixing temperature, the better the result is judged to be.
Low-temperature fixability (minimum fixation temperature) (four-level evaluation)
◎: 129°C or less ○: 130-134°C
△: 135-139℃
×: 140°C or higher

<Toner Scattering Evaluation>
A chart with an image area ratio of 20% was continuously printed on 80,000 sheets using a commercially available digital full-color printer (imagio MPC6000, A4 horizontal color 50 sheets/min, manufactured by Ricoh Co., Ltd.), and the degree of toner contamination inside the printer was visually evaluated on a four-point scale according to the following criteria: "△" or better is usable.
[Evaluation Criteria]
⊚: no toner staining is observed; ◯: slight toner staining is observed; Δ: some toner staining is observed; ×: toner staining is observed

<Overall Judgment>
Based on the results of the low-temperature fixing property evaluation and the toner scattering property evaluation, an overall judgment was made according to the following evaluation criteria: "◎", "◯", and "△" were considered to be acceptable, and "×" was considered to be unacceptable.
(Alternative plan)
◎: There is one or more ◎ and no △ or ×.
◯: No ◎, and no △ or ×.
△: △ is present, but × does not exist.
×: One or more ×'s are present.

As is clear from the evaluation results in Table 2, the toners of Examples 1 to 12 show sufficiently excellent results in terms of low-temperature fixability and toner scattering. In particular, the toners of Examples 8 to 10 and 12 show particularly excellent results. In contrast, the toners of Comparative Examples 1 to 3 show inferior results compared to the Examples in terms of at least either low-temperature fixability or toner scattering.

４，０００≦重量平均分子量（Ｍｗ）≦２５，０００・・・式（２）
０．５ｍｏｌ％ ≦ ３価以上の脂肪族アルコール量 ≦ ６．５ｍｏｌ％・・・式（３）
（ただし、前記式（１）及び式（３）中の前記３価以上の脂肪族アルコール量とは、前記アルコール成分に対する前記３価以上の脂肪族アルコールのモル％である。）
（８）上記（１）乃至（７）のいずれか１項に記載のトナーを収容したトナー収容ユニット。
（９）静電潜像担持体上に静電潜像を形成する静電潜像形成工程と、
トナーを用いて、前記静電潜像を現像して可視像を形成する現像工程と、
前記可視像を記録媒体上に転写する転写工程と、
前記記録媒体上に転写された転写像を定着させる定着工程と、を有し、
前記トナーとして上記（１）乃至（７）のいずれか１項に記載のトナーを用いることを特徴とする画像形成方法。
（１０）静電潜像担持体と、該静電潜像担持体表面を帯電させる帯電手段と、帯電された前記静電潜像担持体表面を露光して静電潜像を形成する露光手段と、前記静電潜像をトナーを用いて現像して可視像を形成する現像手段と、前記可視像を記録媒体に転写する転写手段と、前記記録媒体に転写された転写像を定着させる定着手段とを少なくとも有する画像形成装置であって、前記トナーが、上記（１）乃至（７）のいずれかに記載のトナーであることを特徴とする画像形成装置。 The present invention relates to the toner of (1) below, but also includes the following (2) to (10) as embodiments.
(1) A toner having at least a binder resin and a colorant, the toner having an atomic concentration of Al when measured by XPS of 0.50 at % or more and 2.50 at % or less, and a ratio of Al when measured by XRF to Al when measured by ICP (XRF [mass %]/ICP [mass %]) of 1.20 or more.
(2) The toner according to the above (1), wherein the atomic concentration of Al measured by the XPS is 1.00 at % or more and 2.00 at % or less.
(3) The toner according to (1) or (2) above, wherein the ratio (XRF [mass %]/ICP [mass %]) is 1.25 or more.
(4) The toner according to any one of (1) to (3) above, which contains a layered inorganic mineral in which at least a part of the ions between layers is modified with an organic ion. (5) The toner according to any one of (1) to (4) above, which has a TMA displacement of 10 μm or less. (6) The toner according to any one of (1) to (5) above, which contains a release agent.
(7) The toner according to any one of (1) to (6), wherein the binder resin contains a polyester resin and a tetrahydrofuran (THF) insoluble matter, the polyester resin has a skeleton derived from an alcohol component and a skeleton derived from a carboxylic acid component, the alcohol component contains a trivalent or higher aliphatic alcohol, and satisfies the following formulas (1) to (3):

4,000≦weight average molecular weight (Mw)≦25,000...Formula (2)
0.5 mol%≦amount of trihydric or higher aliphatic alcohol≦6.5 mol%...Equation (3)
(Note that the amount of the tri- or higher hydric aliphatic alcohol in the formulas (1) and (3) is the mole percentage of the tri- or higher hydric aliphatic alcohol relative to the alcohol component.)
(8) A toner storage unit that stores the toner according to any one of (1) to (7) above.
(9) a step of forming an electrostatic latent image on an electrostatic latent image carrier;
a developing step of developing the electrostatic latent image with a toner to form a visible image;
a transfer step of transferring the visible image onto a recording medium;
A fixing step of fixing the transferred image on the recording medium,
8. An image forming method, comprising using the toner according to any one of (1) to (7) above as the toner.
(10) An image forming apparatus comprising at least an electrostatic latent image carrier, a charging means for charging the surface of the electrostatic latent image carrier, an exposure means for exposing the charged surface of the electrostatic latent image carrier to form an electrostatic latent image, a developing means for developing the electrostatic latent image with toner to form a visible image, a transfer means for transferring the visible image to a recording medium, and a fixing means for fixing the transferred image transferred to the recording medium, wherein the toner is a toner described in any one of (1) to (7) above.

10, 10K, 10Y, 10M, 10C Photoconductor drum, electrostatic latent image carrier 14, 15, 16 Support roller 17 Cleaning device 18 Image forming means 20 Charging roller 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Reversing device 30 Exposure device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42, 42K, 42Y, 42M, 42C Developer container 43, 43K, 43Y, 43M, 43C Developer supply roller 44, 44K, 44Y, 44M, 44C Developing roller 45, 45K, 45Y, 45M, 45C Developing unit 49 Registration roller 50 Intermediate transfer body 51 Roller 52 Separation roller 53, manual paper feed path 54, manual paper feed tray 55, switching claw 56, discharge roller 57, discharge tray 58, corona charger 60, cleaning device 70, charge removal lamp 80, transfer roller 90, cleaning device 95, recording paper 100A, image forming apparatus 100B, image forming apparatus 120, tandem developing unit 130, document table 142, paper feed roller 143, paper bank 144, paper feed cassette 145, separation roller 146, paper feed path 147, transport roller 148, paper feed path 150, copying apparatus main body 200, paper feed table 300, scanner 400, automatic document feeder (ADF)
L Exposure light

JP 2008-233163 A JP 2007-279707 A

Claims (8)

The toner includes at least a binder resin and a colorant.
the toner contains a layered inorganic mineral in which at least a part of ions between layers is modified with an organic ion,
The binder resin contains a polyester resin,
the polyester resin has a skeleton derived from an alcohol component and a skeleton derived from a carboxylic acid component,
The alcohol component contains a trihydric or higher aliphatic alcohol,
the polyester resin contains a crystalline polyester, and the crystalline polyester is synthesized using a carboxylic acid having a double bond (C=C bond);
The toner has an atomic concentration of Al when measured by XPS of 0.50 at% or more and 2.00 at% or less, and the ratio of Al when measured by XRF to Al when measured by ICP (XRF [mass %]/ICP [mass %]) is 1.20 or more. The toner according to claim 1, wherein the atomic concentration of Al measured by XPS is 1.00 at% or more. The toner according to claim 1 or 2, wherein the ratio (XRF [mass %]/ICP [mass %]) is 1.25 or more. 4. The toner according to claim 1, wherein the TMA displacement of the toner is 10 μm or less. 5. The toner according to claim 1 , wherein the binder resin contains a tetrahydrofuran (THF) insoluble matter and satisfies the following formulae (1) to (3):

4,000≦weight average molecular weight (Mw)≦25,000...Formula (2)
0.5 mol%≦amount of trihydric or higher aliphatic alcohol≦6.5 mol%...Equation (3)
(Note that the amount of the tri- or higher hydric aliphatic alcohol in the formulas (1) and (3) is the mole percentage of the tri- or higher hydric aliphatic alcohol relative to the alcohol component.) A toner storage unit containing the toner according to any one of claims 1 to 5 . an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;
a developing step of developing the electrostatic latent image with a toner to form a visible image;
a transfer step of transferring the visible image onto a recording medium;
A fixing step of fixing the transferred image on the recording medium,
An image forming method, comprising the step of: using the toner according to claim 1 as the toner . 6. An image forming apparatus comprising at least an electrostatic latent image carrier, a charging means for charging a surface of the electrostatic latent image carrier, an exposure means for exposing the charged surface of the electrostatic latent image carrier to light to form an electrostatic latent image, a developing means for developing the electrostatic latent image with a toner to form a visible image, a transfer means for transferring the visible image to a recording medium, and a fixing means for fixing the transferred image transferred to the recording medium, wherein the toner is the toner according to any one of claims 1 to 5 .

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