JP2008096993A - Toner, toner-containing container, developer, image forming apparatus, process cartridge and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner and a developer excellent in cleaning property and low-temperature fixability and capable of forming a high-quality image. <P>SOLUTION: The toner includes at least a modified layered inorganic material in which at least part of interlayer ions is replaced with an organic ion as a toner composition, wherein the toner is surface-coated with a fatty acid metal compound. The toner is prepared by coating a surface of toner base particles with a fatty acid metal compound and depositing an external additive different from the fatty acid metal compound on the surface. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like, and an electrophotographic developing apparatus using the toner. More specifically, electrophotographic toners, toner-containing containers, developers, image forming apparatuses, process cartridges, and image forming methods used in copiers, laser printers, plain paper fax machines, and the like using direct or indirect electrophotographic development systems. About.

In an example of electrophotography, an electrostatic latent image is formed on an image carrier by charging and exposure, and then developed with a developer containing toner to form a toner image. Further, the toner image is transferred to the recording material and then fixed. On the other hand, toner remaining on the image carrier without being transferred to the recording material is cleaned by a cleaning member such as a blade disposed in pressure contact with the surface of the image carrier.
A pulverization method is known as a toner production method. The pulverization method is a method for producing a toner by melt-kneading a thermoplastic resin as a binder resin to which a colorant and additives used as necessary are added, followed by pulverization and classification. However, the toner obtained in this way has a large particle size and it is difficult to form a high-quality image.

Therefore, a method for producing a toner using a polymerization method or an emulsion dispersion method is known. As a polymerization method, a suspension polymerization method is known in which a monomer, a polymerization initiator, a colorant, a charge control agent, and the like are added to an aqueous medium containing a dispersant while stirring to form oil droplets and then polymerized. It has been. Also known is an association method in which particles obtained by emulsion polymerization or suspension polymerization are aggregated and fused.
However, in such a method, although the particle diameter of the toner can be reduced, it is limited to the polymer obtained by radical polymerization of the main component of the binder resin. A toner having an epoxy resin as a main component of a binder resin cannot be produced.

Therefore, a method for producing a toner is known by using an emulsification dispersion method in which a mixture of a binder resin, a colorant, and the like is mixed with an aqueous medium and emulsified (see Patent Documents 1 and 2). Thereby, in addition to being able to cope with the reduction in the particle size of the toner, the selection range of the binder resin is widened. However, when such a method is used, fine particles are generated and emulsification loss occurs.
Therefore, a method for producing a toner by emulsifying and dispersing a polyester resin and then aggregating and fusing the obtained particles is known (see Patent Documents 3 and 4). Thereby, since generation | occurrence | production of microparticles | fine-particles can be suppressed, an emulsification loss can be reduced.

However, the toner obtained by using the polymerization method or the emulsification dispersion method tends to be spherical due to the interfacial tension of the droplets generated in the dispersion step. For this reason, when the blade cleaning method is used, there is a problem that the spherical toner rotates between the cleaning blade and the photosensitive member and enters the gap and is not easily cleaned.
Therefore, a method is known in which high-speed stirring is performed before the polymerization is completed, and mechanical force is applied to the particles to make the particles amorphous (see Patent Document 5). However, when such a method is used, there is a problem that the dispersion state becomes unstable and the particles tend to coalesce.
In addition, a method is known in which aggregated particles having a particle size of 5 to 25 μm are obtained by aggregating particles using polyvinyl alcohol having a specific degree of saponification as a dispersant (see Patent Document 6). However, the aggregate particles obtained in this way have a problem that the particle diameter tends to be large.

  Further, a method is known in which a filler is added to an organic solvent together with a toner composition to make particles indefinite (see Patent Document 7). However, when a filler is added to the toner, the viscoelasticity of the toner increases, and the lower limit of fixing is observed. In addition, when the filler is present on the toner surface, there is almost no increase in the viscoelasticity of the toner. However, if a substance such as a filler is present on the toner surface layer, it inhibits the exudation of wax or the binder resin dissolves. Inhibition of constant temperature fixing property and hot offset property is also observed.

Furthermore, a charge control agent in which ions such as metal cations existing between layers of a layered inorganic mineral are modified with ions such as organic cations has been developed, and it has been proposed to use this for an electrophotographic toner. (See Patent Documents 8, 9, 10, and 11)
However, in general, when a modified layered inorganic mineral is used, the charging stability is inferior, and the fluctuation in the environment is particularly large. Therefore, there is a problem that the image density fluctuation easily occurs due to the environmental fluctuation. On the other hand, the technique described in Patent Document 12 is intended for a toner having good cleaning properties and ensuring basic durability and releasability while using organically modified clay.
JP-A-5-66600 JP-A-8-21655 JP-A-10-020552 JP 11-007156 A Japanese Patent Laid-Open No. 62-266550 JP-A-2-511164 JP 2005-49858 A JP-T-2003-515795 Special table 2006-500605 gazette JP-T-2006-503313 JP 2003-202708 A Japanese Patent Application No. 2005-379321

The subject of this invention is as follows.
(1) Toner and image forming apparatus capable of obtaining a high-quality image with excellent fine dot reproducibility are provided.
(2) To provide a toner and an image forming apparatus that can obtain high reliability especially in cleaning.
(3) To provide a toner and an image forming apparatus excellent in low-temperature fixability.
(4) A toner and an image forming apparatus capable of achieving the same problems (1) to (3) are provided.
(5) To provide a dry toner and an image forming apparatus which are excellent in transfer efficiency and which can obtain a high quality image with little transfer residual toner.
(6) To provide an oilless dry toner having both electric stability and low-temperature fixability.
(7) To provide a novel toner that consumes less power and has both high transferability and OHP transparency required for color images at a high level.
(8) To provide a dry toner and an image forming apparatus that have stable developability and transferability even under harsh environments, and have little fluctuation in image density.

As a result of intensive studies on the above problems, the present invention has the following configuration.
(1) A toner having a layered inorganic mineral in which at least part of ions between layers of the layered inorganic mineral as a toner composition is modified with an organic ion, the toner having a fatty acid metal compound coated on the surface, A toner comprising a base particle surface coated with a fatty acid metal compound and an external additive other than the fatty acid metal compound attached thereto.
(2) The liberation rate of the fatty acid metal compound represented by the ratio of the number of detected metal atoms in the total number of detected metal atoms in the fatty acid metal compound measured by a particle analyzer is 1.0%. The emission voltage due to the carbon derived from the binder resin of the toner particles is X, and the emission voltage due to the element derived from the fatty acid metal compound is Y, and X and Y are approximated by a square curve. The toner for developing an electrostatic charge image according to (1), wherein an absolute deviation is 0.1 or less.

(3) The toner according to (1) or (2), wherein the fatty acid metal compound has a volume average particle size of 0.1 μm to 3.0 μm.
(4) The toner according to any one of (1) to (3), wherein the volume average particle diameter of the external additive other than the fatty acid metal compound is 0.005 μm to 1.000 μm.
(5) The toner according to any one of (1) to (4), wherein the toner has an average circularity of 0.925 to 0.970.

(6) Any of the above (1) to (5), wherein the modified layered inorganic mineral is a layered inorganic mineral obtained by modifying at least a part of cations between layers of the layered inorganic mineral with an organic cation. Toner according to.
(7) The toner (1) to (6), wherein the toner is obtained by dispersing and / or emulsifying a toner composition containing at least the modified modified layered inorganic mineral in an aqueous medium. The toner according to any one of the above.

(8) The toner includes at least a first binder resin, a binder resin precursor, a compound that extends or crosslinks with the binder resin precursor, a colorant, a release agent, and the modified layered inorganic in at least an organic solvent. It is obtained by dissolving or dispersing a toner composition containing minerals, subjecting the solution or dispersion to a crosslinking reaction and / or extension reaction in an aqueous medium, and removing the solvent from the obtained dispersion. The toner according to any one of (1) to (7) above.
(9) The toner according to (8), wherein the first binder resin is a resin having a polyester skeleton.
(10) The toner according to (8) or (9), wherein the first binder resin is a polyester resin.
(11) The toner according to (10), wherein the polyester resin is an unmodified polyester resin.
(12) The toner according to any one of (8) to (11), wherein the acid value of the first binder resin is 1.0 to 50.0 (KOH mg / g).
(13) The toner according to any one of (8) to (12), wherein the glass transition point of the first binder resin is 35 to 65 ° C.

(14) The toner according to any one of (8) to (13), wherein the binder resin precursor is a modified polyester resin.
(15) The binder resin precursor has a site capable of reacting with a compound having an active hydrogen group, and the polymer of the binder resin precursor has a mass average molecular weight of 3,000 to 30,000. The toner according to any one of (8) to (14), wherein:
(16) In the solution or dispersion, the modified layered inorganic mineral is contained in an amount of 0.05 to 10% by mass in the solid content of the solution or dispersion. The toner according to any one of (15).

(17) A ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner is 1.00 to 1.30, and particles having a circularity of 0.950 or less are all toners. The toner according to any one of (1) to (16), wherein 20 to 80% by number of particles are contained.
(18) A ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner is 1.00 to 1.20, (1) to (17) The toner according to any one of the above.
(19) The toner according to any one of (1) to (18), wherein the number of particles having a particle diameter of 2 μm or less is 20% by number or less.

(20) The toner according to any one of (1) to (19), wherein the toner has an acid value of 0.5 to 40.0 (KOH mg / g).
(21) The toner according to any one of (1) to (20) above, wherein the toner has a glass transition point of 40 to 70 ° C.
(22) The toner according to any one of (1) to (21) above, which is a toner used for a two-component developer.

(23) A toner-containing container comprising the toner according to any one of (1) to (22).
(24) A developer containing the toner according to any one of (1) to (22).
(25) An image forming apparatus, wherein an image is formed using the developer according to (24).
(26) A process cartridge comprising a developing unit having the developer according to (24) and an image carrier.

(27) Fatty acid to toner base particles obtained by dispersing and / or emulsifying a toner composition having a modified layered inorganic mineral in which at least part of interlayer ions in the layered inorganic mineral is modified with organic ions in an aqueous medium. Fatty acid metal compound addition step of adding a metal compound and mixing to coat the fatty acid metal compound on the toner surface, and adding the external additive other than the fatty acid metal compound, mixing and coating the toner surface with the fatty acid metal compound The method for producing a toner according to any one of (1) to (22), further comprising an external additive adding step of attaching an external additive to the toner.
(28) A binder resin, a precursor of the binder resin, a compound that extends or crosslinks with the binder resin precursor, a colorant, a release agent, and a modified layered inorganic mineral are dissolved or dispersed in an organic solvent, A fatty acid metal compound is added to and mixed with the toner base particles obtained by cross-linking and / or elongation reaction of the solution or dispersion in an aqueous medium and removing the solvent from the obtained dispersion. Fatty acid metal compound addition step for coating the toner surface with the fatty acid metal compound, and external additives other than the fatty acid metal compound are added and mixed to adhere the external additive to the toner surface coated with the fatty acid metal compound. The method for producing a toner according to any one of (1) to (22), further comprising an agent addition step.

  The dry toner of the present invention has excellent low-temperature fixability, appropriately adjusts the charge, and has little transfer residual toner in an apparatus using blade cleaning, giving a high-quality and high-resolution image.

The modified layered inorganic mineral obtained by modifying at least part of interlayer ions in the layered inorganic mineral used in the present invention with organic ions will be described.
A layered inorganic mineral refers to an inorganic mineral formed by overlapping layers having a thickness of several nanometers, and modifying with organic ions means introducing organic ions into ions existing between the layers. Specifically, it is described in Patent Documents 8, 9, and 10. This is called intercalation in a broad sense. As the layered inorganic mineral, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, and kanemite are known. The layered inorganic mineral is highly hydrophilic due to its layered structure. Therefore, when used in toners that are dispersed in an aqueous medium and granulated without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. As a result, the hydrophobicity becomes moderately high, and the modified inorganic mineral is refined and used in the production of the toner, and the toner is deformed so that it is particularly present on the surface portion of the toner particles and fulfills the charge control function. At the same time, it contributes to low-temperature fixing. At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.05 to 10% by mass, and more preferably 0.05 to 5% by mass.

The layered inorganic mineral modified in the present invention is preferably a layered inorganic mineral having a smectite basic crystal structure modified with an organic cation. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.
Examples of the organic cation modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like. A quaternary alkyl ammonium salt is desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.
As the organic anion modifier, branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, etc. Sulfates, sulfonates, carboxylates, or phosphates having A carboxylic acid having an ethylene oxide skeleton is desirable.

By modifying at least part of the layered inorganic mineral with organic ions, it has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has non-Nutnian viscosity, and the toner is deformed Can be At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05 to 10% by mass, and more preferably 0.05 to 5% by mass.
The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

Commercially available layered inorganic minerals partially modified with organic cations include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Moreover, as a layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable. The following general formula (1) is, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
General formula (1)
R ₁ (OR ₂ ) _n OSO ₃ M
[Wherein, R ₁ represents an alkyl group having 13 carbon atoms, and R ₂ 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]

By using a modified layered inorganic mineral, the toner phase and / or the oil phase containing the toner composition precursor has a non-Newtonian viscosity in the production process of the toner having moderate hydrophobicity, and the toner is deformed. Can be
However, in general, when a modified layered inorganic mineral is used, the variation in charging under the environment becomes large, and thus there is a problem that image density variation due to environmental variation is likely to occur. In order to solve this problem, the fatty acid metal compound is coated on the surface, and the surface of the toner base particle is coated with the fatty acid metal compound, and then an external additive other than the fatty acid metal compound is attached to improve the stability of charging in the environment. Therefore, it is possible to suppress image density fluctuation due to environmental fluctuation.

  The method for producing a toner of the present invention comprises a step of adding a fatty acid metal compound to the toner base particles, mixing and coating the fatty acid metal compound on the toner surface, and an external additive other than the fatty acid metal compound. And an external additive adding step of adding and mixing the external additive to the toner surface coated with the fatty acid metal compound. In the fatty acid metal compound addition process, the base particles and the fatty acid metal compound with a particle size of 0.1 to 3.0 μm are first mixed using a dry mixing device such as a Henschel mixer, and given a certain share, they are present as fine particles. The fatty acid metal compound that has been formed is spread on the surface of the toner base particles and adheres to the toner base particles in a film form. When such a state is achieved, the liberated amount of the fatty acid metal compound is reduced, and the adhesion variation of the fatty acid metal compound on the individual particles of the toner is reduced. According to the toner production method of the present invention, the fatty acid metal compound adheres to the surface of the toner base particles in the form of a film to form a coating film of the fatty acid metal compound, and an external additive other than the fatty acid metal compound adheres to the coating film. The produced toner can be manufactured efficiently.

The volume average particle size of the fatty acid metal compound alone before coating is preferably 0.1 to 3.0 μm, and more preferably 1.0 μm or less. When the volume average particle diameter exceeds 3.0 μm, it is impossible to sufficiently attach the fatty acid metal compound to the toner base particles. Here, the volume average particle diameter of the fatty acid metal compound alone can be measured, for example, by Nikkiso's particle size distribution measuring apparatus Microtrac UPA.
The addition amount of the fatty acid metal compound is preferably 0.1 to 5.0 parts by mass, more preferably 0.3 to 3.0 parts by mass with respect to 100 parts by mass of the toner base particles. If the addition amount is less than 0.1 parts by mass, satisfactory environmental stability, transferability and cleaning properties may not be obtained. If the addition amount exceeds 5.0 parts by mass, sufficient chargeability is obtained. It may not be possible.

  The fatty acid metal compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc oleate, zinc palmitate, palmitic acid Examples thereof include magnesium, zinc myristate, zinc laurate, and zinc behenate. Among these, zinc stearate is particularly preferable because sufficient environmental stability and chargeability can be obtained.

  The external additive other than the fatty acid metal compound is not particularly limited and may be appropriately selected from known ones according to the purpose. Examples thereof include inorganic fine particles and organic fine particles. Is particularly preferred. It is preferable to add at least one external additive other than the fatty acid metal compound, and it is more preferable to add 1 to 3 types.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, Wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and those hydrophobized. Can be mentioned. Of these, silica, titanium oxide, and hydrophobized titanium oxide are particularly preferable.

Examples of the silica fine particles include HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, and HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Nippon Aerosil Co., Ltd.) Company-made).
Examples of the titanium oxide fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.). MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like.
Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF- 1500T (all manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (all manufactured by Teika Co., Ltd.); IT-S (manufactured by Ishihara Sangyo Co., Ltd.).

The hydrophobic treated inorganic fine particles include, for example, silica fine particles, titania fine particles, and alumina fine particles, and hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. It can be obtained by processing. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicon oil with heat if necessary to treat it with inorganic fine particles are also suitable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino acid. Modified silicone oil, epoxy modified silicone oil, epoxy / polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, acrylic, methacryl modified silicone oil, α-methylstyrene modified silicone oil, etc. can be used. .

The volume average particle diameter of the inorganic fine particles is preferably 0.005 to 1.000 μm, and more preferably 0.01 to 0.5 μm. When the volume average particle size is less than 0.005 μm, the inorganic fine particles are easily embedded in the toner base, and thus sufficient fluidity and chargeability may not be obtained. If it exceeds, sufficient fluidity may not be obtained.
The organic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, polystyrene, methacrylic acid ester or acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization. And polycondensation systems such as silicone, benzoguanamine, and nylon, and polymer particles made of thermosetting resin.

  The toner of the present invention has a liberation rate of the fatty acid metal compound, which is measured by a particle analyzer and is represented by the ratio of the number of detected metal atoms in the free fatty acid metal compound in the total number of detected metal atoms in the fatty acid metal compound. The emission voltage due to carbon derived from the binder resin of the toner particles is X, X is the emission voltage due to the element derived from the fatty acid metal compound, and Y is the square curve for X and Y. The absolute deviation when approximated by is preferably 0.1 or less.

  The adhesion rate and the release rate of the externally added particles with respect to the toner base particles are specified by a particle analyzer method. The particle analyzer method is a method for analyzing the adhesion state of external particles to toner base particles {Electrophotographic Society Annual Conference (95 times in total), "Japan Hardcopy '97" Proceedings, "New External Evaluation Method-Particles Toner Analysis by Analyzer ”, Toshiyuki Suzuki, Toshio Takahara, sponsored by the Electrophotographic Society, July 9th to 11th, 1997}, and“ PT1000 ”manufactured by YOKOGAWA Corporation is used as the particle analyzer. be able to.

  The particle analyzer method will be described with reference to a window displayed by “PT1000” manufactured by YOKOGAWA. As an example, toner particles obtained by adding a fatty acid metal compound and silica fine particles as other external additives to toner base particles containing carbon atoms as main elements will be described. When such toner particles are introduced into plasma and excited / emitted, an emission spectrum (frequency) peculiar to each element and emission intensity corresponding to the amount of element can be obtained. Therefore, by measuring the frequency and intensity of light emission, the amount of carbon atoms in the toner base particles, the amount of metal atoms in the fatty acid metal compound, and the amount of silicon atoms in the silica fine particles are measured. At this time, when the toner base particles and the fatty acid metal compound are attached and integrated, the light emission is detected at the same timing, so it is said that they are synchronized (that is, synchronous toner). When is released, light emission is detected at different timings, so it is said to be asynchronous (that is, asynchronous toner base particles, asynchronous fatty acid metal compound).

  The amount of toner base particles in the synchronous toner is indicated by a particle diameter obtained by converting the amount of carbon atoms as a main element into true spherical particles, and is expressed as an “equivalent particle diameter” of the toner base particles. Further, the amount of the fatty acid metal compound in the synchronous toner is represented by a particle diameter obtained by converting the amount of metal atoms attached to the toner base particles into true spherical particles, and is represented as “equivalent particle diameter” of the fatty acid metal compound. The equivalent particle diameter of each carbon atom and metal atom is obtained as the third root voltage of the signal intensity (proportional to mass) of the emission spectrum to be measured (see Japanese Patent Application Laid-Open No. 12-474425).

  FIG. 1 shows a third root voltage (equivalent particle diameter, horizontal axis) due to carbon atoms obtained for each toner particle (base material) and a third root voltage (equivalent particle diameter; It is a figure for demonstrating the synchronous distribution shown by the relationship with a vertical axis | shaft. In the synchronous distribution diagram, the horizontal axis (x axis) and the vertical axis (y axis) are displayed in the range of 0 to 10 (V) as the cube root voltage, and are displayed on the horizontal axis (x axis). This distribution displays the data of the free toner base particle group, and displays the data of the free external additive particle group on the vertical axis (y-axis). The display of each data having both the horizontal axis (x-axis) component and the vertical axis (y-axis) component is data of the toner particle group in which the toner base particles and the external additive particles are synchronized. In addition, the background is measured, the selection line is set in order to eliminate the influence of the noise cut level, and the slope of the synchronized toner particle group in the selected data is calculated by the least square method, as shown in FIG. A two-third approximate curve is displayed as a curve in the synchronous distribution diagram. If each plot is on this curve, the silica is evenly distributed among the particles according to the particle size of the toner particles. Conversely, if there is variation on this curve, it will not be evenly distributed. This deviation (dispersed state) is expressed quantitatively as an absolute deviation. This absolute deviation can be obtained from analysis software, and an example is shown in FIG. When calculating the absolute deviation, it is assumed that the particles with Y = 0 (particles with no silica attached) and the data with X = 0 are free silica, and these data also calculate the standard error. I excluded it. In the above description, the silica fine particles have been noted. However, in the present invention, the Y axis is a metal atom derived from a fatty acid metal compound.

この絶対偏差はパーティクルアナライザ（ＰＴ１０００）に付属の解析ソフトウェアにて求めることができる。 Specifically, assuming that the emission voltage due to carbon derived from the binder resin of the toner particles is X and the emission voltage due to the element derived from the fatty acid metal compound is Y, approximate X and Y with a square curve. The absolute deviation can be obtained as follows.
There is a set of points of the light emission voltage plot (X, Y) of the carbon element indicated by X and the element derived from the fatty acid metal compound indicated by Y, and the error value x of each data is obtained as follows.
x = d / H
d: Length of perpendicular from the data point to the approximate curve H: Length of perpendicular from the intersection to the X axis from the approximate curve and the data point The absolute deviation is obtained from the error value by the following equation.

This absolute deviation can be obtained by analysis software attached to the particle analyzer (PT1000).

The liberation rate of the external additive particles in the toner particles is expressed by the formula (number of detected free additives) / (total number of detected additives) x 100 (%)
However, in “PT1000” manufactured by YOKOGAWA Co., Ltd., it is displayed as a release rate table window, and the formula (additive material asynchronous count) / (additive material asynchronous count + synchronous count) × 100 (%)
The liberation rate of the external additive particles composed of the composite oxide particles in the dry toner is calculated as a relative value and displayed.

  An example of the release rate table window shown in Table 1 for toner particles in which zinc base stearate as a fatty acid metal compound is coated on toner base particles containing carbon atoms as main elements and silica fine particles and titanium oxide fine particles are added as external additives. The analysis results will be described. The release rate table window displays the synchronous count of each atom synchronized with the toner base particle, the asynchronous count of the additive material, and the asynchronous count of the toner base particle, with the carbon atom in the toner base particle as a reference element (◯ in the table). In addition, the number release rate (%) is displayed for each element.

表中のＺｎはトナー表面に存在するステアリン酸亜鉛に起因、Ｔｉは酸化チタンに起因する。

In the table, Zn is attributed to zinc stearate present on the toner surface, and Ti is attributed to titanium oxide.

  In the present invention, the liberation rate of the fatty acid metal compound, which is measured by a particle analyzer and is represented by the ratio of the number of detected metal atoms in the total number of detected metal atoms in the fatty acid metal compound, is 1.0%. Below, more preferably 0.5% or less, X is the emission voltage due to the carbon derived from the binder resin of the toner particles, and Y is the emission voltage due to the element derived from the fatty acid metal compound. The absolute deviation when approximated by a two-third curve is 0.1 or less, more preferably 0.08 or less.

In the present invention, the liberation rate of the fatty acid metal compound represented by the ratio of the number of detected metal atoms in the total number of detected metal atoms in the fatty acid metal compound is 1.0% or less, and is derived from the binder resin of the toner particles. Assuming that the emission voltage due to carbon of X is X and the emission voltage due to an element derived from a fatty acid metal compound is Y, the absolute deviation when X and Y are approximated by a two-third curve is defined as 0.1 or less. The reason is that the fatty acid metal compound cannot be detected by the particle analyzer (it is cut as noise) or free when the fatty acid metal compound is present in a free state because the metal contained in the fatty acid metal compound is very small. It will be detected as a fatty acid metal compound. However, when the fatty acid metal compound is fixed on the surface of the toner base particles or in a coated state, the toner base particles and the fatty acid metal compound are counted synchronously in the particle analyzer. Furthermore, when the fatty acid metal compound is uniformly dispersed and adhered on the toner base particles, there is no variation in charge amount or variation in adhesion caused by the difference in composition on the toner, so that the expected function can be achieved. It is demonstrated to the fullest. In such a state, that is, measured with a particle analyzer, the liberation rate of the fatty acid metal compound represented by the ratio of the number of detected metal atoms in the total number of detected metal atoms in the fatty acid metal compound is 1.0% or less. Yes, when the emission voltage due to carbon derived from the binder resin of the toner particles is X and the emission voltage due to the element derived from the fatty acid metal compound is Y, the absolute value when X and Y are approximated by a two-third curve When a state in which the deviation is 0.1 or less is achieved, the toner base particles and the fatty acid metal compound behave in the apparatus at the same time, and the fatty acid metal compound is evenly adhered between the toner particles. The function of stabilizing the environment by the fatty acid metal compound works effectively.
Here, when the liberation rate of the fatty acid metal compound exceeds 1.0% or the absolute deviation of the matrix exceeds 0.1, many fatty acid metal compounds are present in a liberated state, and the fatty acid metal compound is incorporated into the toner base particles. Since the adhesion amount varies, satisfactory cleaning properties, environmental stability, transfer properties, and charging properties cannot be obtained.

-Fatty acid metal compound addition process-
The fatty acid metal compound addition step is a step of adding a fatty acid metal compound to the toner base particles, mixing them, and attaching the fatty acid metal compound to the toner surface.
The mixing of the fatty acid metal compound is not particularly limited, and a general powder mixer is used. However, it is preferable that the internal temperature can be adjusted by providing a jacket or the like. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Also, a strong load may be given first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer.
The mixing speed in the fatty acid metal compound addition step is preferably 10 m / s or more, and more preferably 10 to 150 m / s. When the mixing speed is less than 10 m / s, the rubbing between the toners is weak, and the fatty acid metal compound may not be able to sufficiently adhere the toner base particles.

-External additive addition process-
The external additive adding step is a step of adding an external additive other than the fatty acid metal compound and mixing to adhere the external additive to the toner surface.
The mixing of the external additive can be performed in the same manner as the fatty acid compound.
Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

The average circularity of the toner of the present invention is preferably from 0.925 to 0.970, more preferably from 0.945 to 0.965. The circularity is a value obtained by dividing the circumference of a circle having an area equal to the projected area of the sample by the circumference of the sample. The content of particles having a circularity of less than 0.925 in the toner is preferably 15% or less. If the average circularity is less than 0.925, satisfactory transferability and a high-quality image free from dust may not be obtained. If it exceeds 0.970, an image forming apparatus employing blade cleaning or the like may not be used. In addition, poor cleaning of the photosensitive member and the transfer belt may occur, and stains on the image may occur. For example, when forming an image with a high image area ratio, such as a photographic image, toner that has formed an untransferred image due to poor paper feed or the like accumulates on the photoconductor, causing image smudges or touching the photoconductor The charging roller or the like to be charged may be contaminated and the original charging ability may not be exhibited.
The average circularity can be measured by an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, a particle image is optically detected by a CCD camera, and analyzed. It can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

  In the toner of the present invention, the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is preferably 1.00 to 1.30, which is high resolution and high image quality. It is possible to obtain the toner. Furthermore, in the case of a two-component developer, even if a long-term balance of the toner is performed, fluctuations in the particle size of the toner in the developer are reduced, and good and stable developability even with long-term stirring in the developing device. Is possible. If Dv / Dn exceeds 1.30, the variation in particle size of individual toner particles is large, and the behavior of the toner varies during development and the like, and the reproducibility of minute dots is impaired. Therefore, a high-quality image cannot be obtained. More preferably, Dv / Dn is in the range of 1.00 to 1.20, and a better image can be obtained.

In the toner of the present invention, the volume average particle diameter Dv is preferably 3.0 to 7.0 μm. In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. When the volume average particle diameter is smaller than the above range, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced. When it is used, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. These phenomena are greatly related to the content of fine powders. In particular, when the number of particles having a particle size of 2 μm or less exceeds 20% by number, it becomes a hindrance in the case where adhesion to a carrier or charging stability at a high level is achieved. Conversely, when the toner particle size is larger than the above range, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particle size when the balance of the toner in the developer is performed. In many cases, fluctuations of It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.30.
As described above, a toner having a small particle size and a uniform particle size has difficulty in cleaning performance. Therefore, it is preferable that the number of particles having a circularity of 0.950 or less is 20 to 80% by number of all toner particles.

  First, the relationship between toner shape and transferability will be described. When using a full-color copier that transfers images with multi-color development, the amount of toner on the photoconductor increases compared to the case of one-color black toner used in black-and-white copiers. It is difficult to improve transfer efficiency. In addition, when ordinary irregular toner is used, a shearing force or friction between the photosensitive member and the cleaning member, between the intermediate transfer member and the cleaning member, and / or between the photosensitive member and the intermediate transfer member. Due to the force, toner fusing or filming occurs on the surface of the photoreceptor or the intermediate transfer member, and transfer efficiency tends to deteriorate. When generating a full-color image, it is difficult to transfer the four-color toner images uniformly. Furthermore, when an intermediate transfer member is used, problems are likely to occur in terms of color unevenness and color balance, and high-quality full-color images are stabilized. Output is not easy.

  From the viewpoint of the balance between blade cleaning and transfer efficiency, the toner having a circularity of 0.950 or less is 20 to 80% by number of the total toner particles, thereby achieving both cleaning and transferability. Cleaning and transferability are greatly related to the material of the blade and how to apply the blade, and transfer also varies depending on the process conditions, so that the design according to the process can be performed within the above range. However, if particles with a toner circularity of 0.950 or less fall below 20% by number of all toner particles, cleaning with a blade becomes difficult. On the other hand, when the number of particles having a circularity of 0.950 or less exceeds 80% by number of all toner particles, the above-described transferability is deteriorated. This phenomenon is caused by excessively deformed toner shape, so that toner movement during transfer (photosensitive member surface to transfer paper, photosensitive member surface to intermediate transfer belt, first intermediate transfer belt to second intermediate transfer belt) , Etc.) are not smooth, and the toner particles vary in behavior, so that uniform and high transfer efficiency cannot be obtained. In addition, unstable charging and brittleness of particles begin to appear. Furthermore, it becomes a pulverization phenomenon in the developer, which causes a decrease in the durability of the developer.

Hereafter, the measuring method regarding the property of the toner of this invention is shown.
(Particle ratio of particle size of 2 μm or less, circularity)
The particle ratio of 2 μm or less, the circularity, and the average circularity of the toner of the present invention can be measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

(Toner particle size)
The average particle size and the particle size distribution of the toner are determined by the car Coulter counter method. Examples of the measuring device for the particle size distribution of toner particles include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, measurement was performed using a Coulter Counter TA-II type connected to an interface (Nichiken Giken) that outputs number distribution and volume distribution and a PC9801 personal computer (manufactured by NEC).

The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture Volume distribution and number distribution are calculated.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm. The volume-based volume average particle diameter (Dv) obtained from the volume distribution according to the present invention and the number average particle diameter (Dn) obtained from the number distribution and the ratio Dv / Dn were obtained.

  The toner of the present invention is preferably obtained by dispersing and / or emulsifying a toner composition containing at least the modified modified layered inorganic mineral in an aqueous medium, and at least a first binder in an organic solvent. A toner composition containing a binder resin, a binder resin precursor, a compound that extends or crosslinks with the binder resin precursor, a colorant, a release agent, and the modified layered inorganic mineral is dissolved or dispersed, and the solution or It is preferable that the dispersion is obtained by causing a crosslinking reaction and / or elongation reaction in an aqueous medium and removing the solvent from the obtained dispersion.

  The binder resin precursor used in the present invention is preferably a reactive modified polyester resin (RMPE) capable of reacting with active hydrogen, and examples thereof include a polyester prepolymer (A) having an isocyanate group. Examples of the prepolymer (A) include a polycondensate of a polyol (PO) and a polycarboxylic acid (PC) and a polyester having active hydrogen further reacted with a polyisocyanate (PIC). Examples of the group containing active hydrogen in the polyester include a hydroxyl group (alcoholic hydrogen group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

  According to a further study of the present invention, the acidic group-containing polyester resin is used to effectively exhibit low-temperature fixability while maintaining heat-resistant storage stability and to impart offset resistance after modification with a prepolymer. It is preferable that the mass average molecular weight of the THF-soluble component is 1,000 to 30,000. This is because when the amount is less than 1,000, the oligomer component increases, the heat-resistant storage stability is deteriorated, and when it exceeds 30,000, the modification with the prepolymer is insufficient due to steric hindrance and the offset resistance is deteriorated.

The molecular weight according to the present invention is measured by GPC (gel permeation chromatography) as follows. The column was stabilized in a heat chamber at 40 ° C., and THF was added to the column at this temperature as a solvent at a flow rate of 1 ml / min. Is measured by injecting 50 to 200 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the count using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Alternatively, the molecular weights of Toyo Soda Kogyo Co., Ltd. are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. It is appropriate to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

An amine is used as a crosslinking agent for the reactive modified polyester resin, and a diisocyanate compound (diphenylmethane diisocyanate or the like) is used as an extender. The amines described in detail later act as a crosslinking agent and an extender for the modified polyester capable of reacting with active hydrogen.
Modified polyester such as urea-modified polyester obtained by reacting the polyester prepolymer (A) having an isocyanate group with an amine (B) can easily adjust the molecular weight of the polymer component, and is a dry toner, particularly oilless low-temperature fixing. It is convenient to ensure the characteristics (wide releasability and fixability without a release oil application mechanism to the fixing heating medium). Particularly, a polyester prepolymer whose end is modified with urea can suppress adhesion to a heating medium for fixing while maintaining high fluidity and transparency in the fixing temperature range of the unmodified polyester resin itself.

  A preferred polyester prepolymer used in the present invention is a polyester having an active hydrogen group such as an acid group or a hydroxyl group at the terminal, and a functional group such as an isocyanate group that reacts with the active hydrogen. A modified polyester (MPE) such as urea-modified polyester can be derived from this prepolymer, but in the case of the present invention, a preferred modified polyester used as a toner binder is a polyester prepolymer (A) having an isocyanate group. It is a urea-modified polyester obtained by reacting amines (B) as a crosslinking agent and / or an extender. The polyester prepolymer (A) having an isocyanate group is obtained by further reacting a polyester having an active hydrogen group, which is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), with a polyisocyanate (PIC). Can do. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (PO) include a diol (DIO) and a trivalent or higher polyol (TO), and (DIO) alone or a mixture of (DIO) and a small amount of (TO) is preferable. Diol (DIO) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene 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.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. Examples of the trivalent or higher polyol (TO) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (Tris) Phenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or more polyphenols.

  Examples of the polycarboxylic acid (PC) include dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), and DIC alone or a mixture of DIC and a small amount of (TC) is preferable. Dicarboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalene) Dicarboxylic acid and the like). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (PC), you may make it react with a polyol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.). The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  As polyisocyanate (PIC), aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

  The ratio of the polyisocyanate (PIC) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a modified polyester is used, the urea content in the ester becomes low and the hot offset resistance deteriorates. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, more preferably 2 to 20% by mass. It is. If it is less than 0.5% by mass, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by mass, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the compound (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the polyester is lowered and the hot offset resistance is deteriorated.

  In the present invention, the polyester resin (polyester) that is preferably used as a toner binder is urea-modified polyester (UMPE), but this polyester may contain a urethane bond as well as a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  Modified polyester such as urea-modified polyester (UMPE) is produced by a one-shot method or the like. The mass average molecular weight of the modified polyester such as urea-modified polyester (UMPE) is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the modified polyester such as urea-modified polyester is not particularly limited when the unmodified polyester (PE) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the mass average molecular weight. In the case of a modified polyester such as UMPE alone, the number average molecular weight is usually 2000-15000, preferably 2000-10000, and more preferably 2000-8000. If it exceeds 15000, the low-temperature fixability and the gloss when used in a full-color device are deteriorated.

  In the present invention, the above modified polyester such as polyester modified with urea bond (UMPE) is not only used alone, but can also contain unmodified polyester (PE) as a binder resin component. . The combined use of PE improves low-temperature fixability and gloss when used in a full-color device, and is preferable to single use. Examples of PE include polycondensates of polyol PO and polycarboxylic acid PC similar to the polyester component of UMPE, and preferred ones are also the same as in UMPE. The mass average molecular weight (Mw) of PE is 10,000 to 300,000, preferably 14,000 to 200,000. Its Mn (number average molecular weight) is 1000 to 10000, preferably 1500 to 6000. For UMPE, not only unmodified polyesters but also those modified with chemical bonds other than urea bonds, such as those modified with urethane bonds, can be used in combination. UMPE and PE are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component of UMPE and PE preferably have similar compositions. The mass ratio of UMPE to PE when PE is contained is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, and particularly preferably 7/93. ~ 20/80. If the mass ratio of UMPE is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The hydroxyl value (mgKOH / g) of PE is preferably 5 or more, and the acid value (mgKOH / g) of PE is usually 1 to 50, preferably 5 to 20. By giving an acid value, it tends to be negatively charged, and further, the affinity between the paper and the toner is good when fixing to paper, and the low-temperature fixability is improved. However, when the acid value exceeds 50, there is a tendency to deteriorate with respect to the stability of charging, particularly the environmental fluctuation. In the polymerization reaction, if the acid value is touched, it will cause blurring in the granulation process, making it difficult to control the emulsification.

  Accordingly, a polyester resin is preferable as the first binder resin, and the basic compound is added by setting the acid value of the polyester resin as the first binder resin to 1.0 to 50.0 (KOHmg / g). The toner characteristics such as grain size control, low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and charging stability can be improved. That is, when the acid value exceeds 50.0 (KOHmg / g), the elongation or cross-linking reaction of the binder resin precursor becomes insufficient, affecting the high-temperature offset resistance, and 1.0 (KOHmg / g). If it is less than), the dispersion stabilizing effect due to the base compound during production cannot be obtained, and the extension or crosslinking reaction of the modified polyester tends to proceed, resulting in problems in production stability.

(Method for measuring acid value of resin)
Measurement is performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of polyester is added to 120 ml of THF and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described below. Specifically, it is calculated as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample mass (where N is a factor of N / 10 KOH)

The detail of the measuring method of the acid value of the polyester resin of this invention is based on the following method based on JISK0070. THF is used as the solvent.
The acid value is specifically determined by the following procedure.
Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C

The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
TitrantCH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump onlyNo
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

(Measurement method of hydroxyl value)
The conditions of the measuring apparatus are the same as those in the above acid value measurement.
Weigh accurately 0.5 g of sample into a 100 ml volumetric flask and add 5 ml of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Furthermore, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to obtain the OH number (according to JISK0070-1966).

  In the present invention, the heat-resistant storage performance of the main component of the polyester resin after modification, that is, the binder resin depends on the glass transition point of the polyester resin before modification, so the first polyester resin (prepolymer (isocyanate-modified polyester)) It is preferable to design the glass transition point of the polyester before modification of 35 to 65 ° C. That is, if it is less than 35 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 65 ° C., it adversely affects low-temperature fixing.

The glass transition point of the present invention is measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature increase rate of 10 ° C./min. A method for measuring Tg will be outlined. As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, the sample was cooled to room temperature and left for 10 min, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the tangent of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

  According to a further study of the present invention, the prepolymer for modifying the polyester resin is an important binder resin component for realizing low-temperature fixability and high-temperature offset resistance, and its mass average molecular weight is 3,000 to 30, 000 is preferred. That is, if the mass average molecular weight is less than 3,000, it becomes difficult to control the reaction rate, and problems in production stability begin to occur. On the other hand, when the mass average molecular weight exceeds 30,000, sufficient modified polyester cannot be obtained, and the offset resistance starts to be affected.

  Further examination of the present invention revealed that the toner acid value is a more important index than the binder resin acid value for low-temperature fixability and high-temperature offset resistance. The toner acid value of the present invention is derived from the terminal carboxyl group of the unmodified polyester. In order to control low temperature fixability (fixing lower limit temperature, hot offset occurrence temperature, etc.) as a toner, it is preferable that the acid value of the toner is 0.5 to 40.0 (KOHmg / g). In other words, when the toner acid value exceeds 40.0 (KOHmg / g), the modified polyester is insufficiently stretched or cross-linked, affecting high-temperature offset resistance, and less than 0.5 (KOHmg / g). In this case, the dispersion stabilizing effect due to the base compound at the time of production cannot be obtained, and the extension or crosslinking reaction of the modified polyester tends to proceed, resulting in a problem in production stability.

Specifically, the acid value of the toner is determined in accordance with the method for measuring the acid value of the polyester resin. When there is THF-insoluble matter, the acid value of the toner refers to the acid value when the acid value is measured using THF as a solvent.
(Method for measuring acid value of toner)
Measurement is performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate-soluble component) was used in place of the polyester.

  The glass transition point of the toner of the present invention is preferably 40 to 70 ° C. in order to obtain low temperature fixability, heat resistant storage stability and high durability. That is, when the glass transition point is less than 40 ° C., blocking in the developing machine and filming to the photoreceptor are liable to occur, and when it exceeds 70 ° C., the low-temperature fixability tends to deteriorate.

  In the present invention, the glass transition point (Tg) of the toner is usually 40 to 70 ° C., preferably 40 to 60 ° C. If it is less than 40 ° C., the heat resistance of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of a modified polyester such as a urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with a known polyester-based toner.

(Release agent)
As the release agent (wax) used for the toner of the present invention, a low melting point wax having a melting point of 50 to 120 ° C. is more effectively used as a release agent in the dispersion with the binder resin. Thus, it exhibits an effect on high temperature offset resistance without applying a release agent such as oil to the fixing roller.
The melting point of the wax in the present invention was the maximum endothermic peak measured by a differential scanning calorimeter (DSC).
The following materials can be used as the wax component that functions as a release agent that can be used in the present invention. That is, as specific examples, waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, And petroleum waxes such as paraffin, microcrystalline, and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and poly n-stearyl methacrylate, poly n-lauryl methacrylate, which are low molecular weight crystalline polymer resins A crystalline polymer having a long alkyl group in the side chain, such as a polyacrylate homopolymer or copolymer (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used.

(Coloring agent)
As the colorant used in the present invention, all 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, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R , Para red, phissa red, parac Luort Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, 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, Pi Zoron 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, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Gree Lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass with respect to the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin.
As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substitution products thereof. Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α -Methyl chloromethacrylate copolymer, styrene -Acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrenic copolymers such as ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacryl Acid resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be used, and these can be used alone or in combination.

  The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

  The toner of the present invention may contain a charge control agent as necessary. Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined uniquely by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. Although it is not a thing, Preferably it is used in 0.1-10 mass parts with respect to 100 mass parts of binder resin. Preferably, the range of 0.2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents and mold release agents can be melt-kneaded together with the masterbatch and resin, and of course, they may be added when dissolved and dispersed in an organic solvent.

  The binder resin can be produced by the following method. Polyol (PO) and polycarboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (PIC) at 40 to 140 ° C. to obtain a polyester prepolymer (A) having an isocyanate group. Further, this A is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester (UMPE) modified with a urea bond. The number average molecular weight of this modified polyester is 1000 to 10000, preferably 1500 to 6000. When reacting PIC and when reacting A and B, a solvent can be used if necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to isocyanates (PIC), such as tetrahydrofuran (such as tetrahydrofuran). When polyester (PE) that is not modified with a urea bond is used in combination, PE is produced in the same manner as the polyester having a hydroxyl group, and this is dissolved in the solution after completion of the UMPE reaction and mixed.

The dry toner of the present invention can be produced by the following method, but is not limited thereto.
(Toner production method in aqueous medium)
As the aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
In the present invention, a urea-modified polyester (UMPE) or the like can be obtained by reacting a reactive modified polyester such as a polyester prepolymer (A) having an isocyanate group with an amine (B) in an aqueous medium. As a method for stably forming a dispersion comprising a modified polyester such as urea-modified polyester or a reactive modified polyester such as prepolymer (A) in an aqueous medium, a modified polyester such as urea-modified polyester or a pre-polymer can be used in an aqueous medium. Examples thereof include a method in which a composition of a toner raw material made of reactive modified polyester such as polymer (A) is added and dispersed by shearing force. Reactive modified polyester such as prepolymer (A) and other toner composition (hereinafter referred to as toner raw material) colorant, colorant masterbatch, release agent, charge control agent, unmodified polyester resin, etc. are water-based Mixing may be performed when the dispersion is formed in the medium, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the urea-modified polyester or prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous medium used is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass with respect to 100 parts of the toner composition containing polyester such as urea-modified polyester and prepolymer (A). If the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle size cannot be obtained. If it exceeds 20000 parts by mass, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

Various dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed are used in the liquid containing water. Such a dispersant includes a surfactant, an inorganic fine particle dispersant, a polymer fine particle dispersant and the like.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

Examples of cationic surfactants include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzaza. Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) Megafac F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).
In addition, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant that is hardly soluble in water.

  Further, the same effect as that of the inorganic dispersant was confirmed for the fine particle polymer. For example, MMA polymer fine particles 1 μm and 3 μm, styrene fine particles 0.5 μm and 2 μm, styrene-acrylonitrile fine particle polymer 1 μm, (PB-200H (Kao) SGP (Soken), Technopolymer SB (Sekisui Plastics), SGP-3G (Soken) Micropearl (Sekisui Fine Chemical)).

  In addition, as a dispersant that can be used in combination with the above inorganic dispersant and fine particle polymer, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Pinyl acetate, pinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having nitrogen atoms or heterocyclic rings thereof, polyoxyethylene, polyoxypropylene, polymers Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

The resulting emulsified dispersion (reactant) is stirred and converged in a certain temperature range lower than the resin glass transition temperature and in an organic solvent concentration range (region where the organic solvent remains before or during solvent removal). Thus, in order to produce coalesced particles and remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and the shaped toner particles can be produced by removing the solvent. In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant can remain on the toner particle surface.

Furthermore, in order to reduce the viscosity of the dispersion medium containing the toner composition, a solvent in which a polyester such as urea-modified polyester or prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp.
The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include 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 and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of the solvent with respect to 100 parts of prepolymers (A) is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, the solvent (solvent) is removed from the obtained reaction product under normal pressure or reduced pressure after the extension and / or crosslinking reaction of the modified polyester (prepolymer) with an amine.

  The elongation and / or crosslinking reaction time is selected, for example, depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. It's time. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate. In addition, as an extender and / or a crosslinking agent, the above-described amines (B) are used.

In the present invention, prior to desolvation from the dispersion (reaction liquid) after the elongation and / or cross-linking reaction, the dispersion is stirred and converged in a certain temperature range lower than the resin glass transition temperature and in the organic solvent concentration range. It is preferable to remove the solvent at 10 to 50 ° C. after preparing the coalesced particles and confirming the shape. The toner is deformed by liquid agitation before the removal of the solvent. Since this condition is not an absolute condition, it is necessary to appropriately select the condition. When the concentration of the organic solvent contained in the granulation is high, the viscosity of the emulsion is lowered, and when the droplets are united, the particle shape tends to be spherical. Further, when the concentration of the organic solvent contained in the granulation is low, when the droplets coalesce, the viscosity of the droplets is high and the particles do not become complete particles but come off. For this reason, it is necessary to set an optimum condition, and the toner shape can be appropriately adjusted by selecting a condition. Further, the shape can be adjusted by the content of the organically modified inorganic mineral. The organically modified inorganic mineral is preferably contained in an amount of 0.05 to 10% by mass in the solid content in the solution or dispersion. If it is less than 0.05% by mass, the target oil phase viscosity cannot be obtained, and the target shape cannot be obtained. Since the droplet viscosity is low, even if the droplets coalesce during the stirring and converging, the target coalesced particles cannot be obtained, resulting in a spherical shape. If it exceeds 10% by mass, the manufacturability deteriorates, the droplet viscosity becomes too high, the particles do not become coalesced particles, and the fixing performance further deteriorates.
On the other hand, the ratio Dv / Dn of the volume average particle diameter Dv and the number average diameter (Dn) of the toner is controlled mainly by adjusting, for example, the water layer viscosity, the oil layer viscosity, the characteristics of the resin fine particles, the addition amount, and the like. can do. Further, Dv and Dn can be controlled by adjusting, for example, characteristics of resin fine particles, addition amount, and the like.

The toner of the present invention can be used as a two-component developer. In this case, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is preferably 1 to 10 parts by mass of the toner with respect to 100 parts by mass of the carrier. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Hereinafter, a part shows a mass part.
Example 1
Example of Resin Production 8400 g of propylene oxide adduct of bisphenol A (2.2 mol), 24700 g of ethylene oxide adduct of bisphenol A (2.2 mol) and 14276 g of terephthalic acid were stirred at 230 ° C. in a nitrogen atmosphere, and ASTM D36 The reaction was continued until the softening point measured by the method according to -86 reached 101 ° C. The obtained resin is referred to as Resin A.

Production Example of Charge Control Agent A solution in which 150 g of a layered inorganic mineral montmorillonite (manufactured by Kraton APA Southern Clay Products) at least partially modified with a quaternary ammonium salt having a benzyl group was dissolved in 5000 g of water, and distearyldimethylammonium A solution prepared by dissolving 80 g of chloride in 5000 g of water was mixed, and the precipitate was taken out by filtration. The precipitate was washed and dried to obtain a charge control agent A.

Resin A: 100 parts by mass, charge control agent A: 0.4 parts by mass, polypropylene wax: 3 parts by mass, pigment (cyan, CIPB 15: 3): 4 parts by mass after mixing in advance using a Henschel mixer, biaxial ext The mixture was melt-kneaded with a lider and pulverized and classified using a collision plate pulverizer and a dispersion separator to obtain an untreated toner having a volume average particle diameter of 6.8 μm.
To 100 parts of the toner base particles thus prepared, 1.0 part of zinc myristate having a volume average particle size of 0.3 μm is added as a fatty acid metal compound, and mixed for 5 minutes using a Henschel mixer at a peripheral speed of 15 m / s. The mixture was further mixed for 10 minutes under the condition of a peripheral speed of 33 m / s. To this, 1.5 parts of external additive (A) (HDK2000H (manufactured by Clariant, silica)) and 0.5 part of external additive (C) (SMT-150AI (manufactured by Taika, titanium oxide)) are added. The Henschel mixer was mixed for 5 minutes under the condition of a peripheral speed of 33 m / s. The mixed powder was passed through a mesh having an opening of 100 μm to remove coarse powder, and a toner to which a fatty acid metal compound and inorganic fine particles were externally added was prepared.
This toner had a liberation rate of fatty acid metal compound of 0.89% by the Particle Analyzer method, and the absolute deviation was 0.0625.

Example 2
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propion oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and dibutyltin oxide 2 parts were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize an unmodified polyester resin. .
The obtained unmodified polyester resin had a number average molecular weight of 2500, a mass average molecular weight of 6700, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.
1200 parts of water, 540 parts of carbon black Printex 35 (manufactured by Dexa; DBP oil absorption = 42 ml / 100 mg, pH = 9.5) and 1200 parts of unmodified polyester resin were mixed using a Henschel mixer (manufactured by Mitsui Mining). . The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

In a reaction vessel equipped with a stirrer and a thermometer, 378 parts of unmodified polyester resin, 110 parts of carnauba wax, 22 parts of salicylic acid metal complex E-84 (manufactured by Orient Chemical Co., Ltd.) and 947 parts of ethyl acetate were charged and stirred. The temperature was raised to 80 ° C., held at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of a master batch and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution.
1324 parts of the obtained raw material solution was transferred to a reaction vessel, and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill Ultra Visco Mill (manufactured by Imex Co., Ltd.). Carnauba wax was dispersed by three passes under the condition of a speed of 6 m / sec to obtain a wax dispersion.

  Next, 1324 parts of a 65 mass% ethyl acetate solution of an unmodified polyester resin was added to the wax dispersion. A layered inorganic mineral montmorillonite (Clayton APA Southern Clay modified at least partly with a quaternary ammonium salt having a benzyl group) was added to 200 parts of a dispersion obtained by one pass using Ultraviscomyl under the same conditions as above. 3 parts) (manufactured by Products) are added. K. The mixture was stirred for 30 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a toner material dispersion.

In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester resin was synthesize | combined.
The obtained intermediate polyester resin had a number average molecular weight of 2100, a mass average molecular weight of 9,500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.
Next, 410 parts of the intermediate polyester resin, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Was synthesized. The free isocyanate content of the obtained prepolymer was 1.53% by mass.

In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound. The amine value of the obtained ketimine compound was 418 mgKOH / g.
In a reaction vessel, 749 parts of a dispersion of toner material, 115 parts of a prepolymer and 2.9 parts of a ketimine compound are charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika). A mixture was obtained.

  In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of reactive emulsifier (sodium salt of sulfuric acid ester of methacrylic acid ethylene oxide adduct), Eleminol RS-30 (manufactured by Sanyo Chemical Industries), styrene 83 Parts, 83 parts of methacrylic acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain an emulsion. The emulsion was heated, heated to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% by mass ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to prepare a resin particle dispersion.

990 parts of water, 83 parts of resin particle dispersion, 37 parts of 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Chemical Industries), 1% by weight aqueous solution of sodium carboxymethylcellulose polymer dispersant 135 parts of BS-H-3 (Daiichi Kogyo Seiyaku Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred to obtain an aqueous medium.
To 1200 parts of the aqueous medium, 867 parts of the oil phase mixed liquid was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsified slurry).
Next, the emulsified slurry was charged into a reaction vessel in which a stirrer and a thermometer were set, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 4 hours to obtain a dispersed slurry.

After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered.
To the obtained filter cake, 10% by mass hydrochloric acid was added to adjust the pH to 2.8, and the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer, followed by filtration.
Furthermore, 300 parts of ion-exchanged water was added to the obtained filter cake, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and sieved with a mesh having a mesh size of 75 μm to obtain toner mother particles.
To 100 parts of the toner base particles thus prepared, 1.0 part of zinc myristate having a volume average particle size of 0.3 μm is added as a fatty acid metal compound, and mixed for 5 minutes using a Henschel mixer at a peripheral speed of 15 m / s. The mixture was further mixed for 10 minutes under the condition of a peripheral speed of 33 m / s. To this, 1.5 parts of the external additive (A) and 0.5 part of the external additive (C) were added and mixed for 5 minutes in a Henschel mixer under the condition of a peripheral speed of 33 m / s. . The mixed powder was passed through a mesh having an opening of 100 μm to remove coarse powder, and a toner to which a fatty acid metal compound and inorganic fine particles were externally added was prepared.
The toner had a fatty acid metal compound liberation rate of 0.79% according to the Particle Analyzer method, and the absolute deviation was 0.0785.

Example 3
A toner was produced in the same manner as in Example 1 except that the fatty acid metal compound was zinc stearate having a volume average particle size of 0.3 μm.
This toner had a fatty acid metal compound liberation rate of 0.72% by particle analyzer method and an absolute deviation of 0.0695.
Example 4
A toner was produced in the same manner as in Example 1 except that the fatty acid metal compound was zinc stearate having a volume average particle diameter of 0.1 μm.
This toner had a fatty acid metal compound liberation rate of 0.58% according to the Particle Analyzer method, and the absolute deviation was 0.0625.
Example 5
A toner was produced in the same manner as in Example 1 except that the fatty acid metal compound was changed to 2.0 parts of zinc stearate having a volume average particle diameter of 0.1 μm.
This toner had a fatty acid metal compound liberation rate of 0.88% according to the Particle Analyzer method, and the absolute deviation was 0.0599.

Example 6
A toner was produced in the same manner as in Example 2 except that the amount of the modified layered inorganic mineral (trade name Kraton APA) was changed from 3 parts to 0.1 part.
The release rate of the fatty acid metal compound by the particle analyzer method of this toner was 0.73%, and the absolute deviation was 0.0688.
Example 7
A toner was produced in the same manner as in Example 2 except that Clayton APA was changed to a layered inorganic mineral montmorillonite (manufactured by Kraton HY Southern Clay Products) at least partially modified with an ammonium salt having a polyoxyethylene group.
The toner had a fatty acid metal compound liberation rate of 0.68% by particle analyzer method, and the absolute deviation was 0.0552.
Example 8
A toner was produced in the same manner as in Example 2 except that the addition amount of Clayton APA was changed from 3 parts to 1.4 parts.
This toner had a fatty acid metal compound liberation rate of 0.82% according to the Particle Analyzer method, and the absolute deviation was 0.0698.
Example 9
A toner was produced in the same manner as in Example 2 except that the addition amount of Clayton APA was changed from 3 parts to 4 parts.
The release rate of the fatty acid metal compound by the particle analyzer method of this toner was 0.67%, and the absolute deviation was 0.0532.
Example 10
A toner was produced in the same manner as in Example 2 except that the addition amount of Clayton APA was changed from 3 parts to 6 parts.
This toner had a fatty acid metal compound liberation rate of 0.52% according to the Particle Analyzer method, and the absolute deviation was 0.0685.

Example 11
-Preparation of colorant dispersion (1)-
・ Carbon black (Degussa: Printex 35) 125 parts ・ Azisper PB821 (Azinomoto Finetech) 18.8 parts ・ Ethyl acetate (Wako Pure Chemical Industries, Ltd .: Special grade) 356.2 parts Ultraviscomyl ( A colorant dispersion liquid (1) was prepared by dissolving / dispersing using an Imex Corporation and dispersing a colorant (black pigment).
(Preparation of release agent dispersion)
-Preparation of release agent dispersion (1) (wax component A)-
・ Carnauba wax (melting point: 83 ° C., acid value 8 mgKOH / g, saponification value 80 mgKOH / g) 30 parts ・ ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd .: special grade) 270 parts or more Ultraviscomil (made by Imex) Was used for wet pulverization to prepare a release agent dispersion (1).

-Preparation of a layered compound modified with an organic cation (a deforming agent dispersion A)-
・ Clayton APA (manufactured by Southern Clay Products) 30 parts ・ Ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd .: special grade) 270 parts or more Wet-ground with Ultraviscomyl (manufactured by Imex) and disperse the deforming agent Liquid A was prepared.

・ Polyester (1)
Polyester resin composed of bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, terephthalic acid derivative (Mw 50,000, Mn 3,000, acid value 15 mgKOH / g, hydroxyl value 27 mg
17. KOH / g, Tg 55 ° C., softening point 112 ° C.) 350 parts / colorant dispersion (1) 237 parts / release agent dispersion (1) 376 parts / hydrophobic silicon oxide fine particles (Aerosil R972) 8 parts or more were mixed and stirred well until uniform (this liquid was designated as A liquid).

  On the other hand, 100 parts of calcium carbonate dispersion in which 40 parts of calcium carbonate fine particles were dispersed in 60 parts of water, 200 parts of 1% aqueous solution of Serogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.), and 157 parts of water were added. K. The mixture was stirred for 3 minutes using a homodisper fmodel (manufactured by Primix) (this solution was designated as solution B). In addition, T.W. K. Using a homomixer mark2 fmodel (manufactured by Primix), 345 parts of the solution B and 250 parts of the solution A were stirred at 10,000 rpm for 2 minutes to suspend the mixed solution, and then propeller type at room temperature and normal pressure for 48 hours. The solvent was removed by stirring with a stirrer. Next, hydrochloric acid was added to remove calcium carbonate, followed by washing with water, drying and classification to obtain toner base particles. The average particle size of the toner base particles was 6.2 μm.

To 100 parts of the toner base particles thus prepared, 1.0 part of zinc myristate having a volume average particle size of 0.3 μm is added as a fatty acid metal compound, and mixed for 5 minutes using a Henschel mixer at a peripheral speed of 15 m / s. The mixture was further mixed for 10 minutes under the condition of a peripheral speed of 33 m / s. To this, 1.5 parts of the external additive (A) and 0.5 part of the external additive (C) were added and mixed for 5 minutes in a Henschel mixer under the condition of a peripheral speed of 33 m / s. . The mixed powder was passed through a mesh having an opening of 100 μm to remove coarse powder, and a toner to which a fatty acid metal compound and inorganic fine particles were externally added was prepared.
The toner had a fatty acid metal compound liberation rate of 0.85% according to the Particle Analyzer method, and the absolute deviation was 0.0865.

Example 12
(Adjustment of solvent-free resin)
Monomer mixed solution in which 100 parts by mass of styrene and 0.7 parts by mass of di-tertiary butyl peroxide are uniformly mixed in an autoclave equipped with a stirrer, a heating device and a cooling device controlled at 215 ° C. Was continuously added in 30 minutes, and further maintained at 215 ° C. for 30 minutes to obtain a solventless resin. The obtained solvent-free resin had a molecular weight peak Mp of 4,150 and a mass average molecular weight Mw of 4,800.

(Adjustment of resin emulsion dispersion)
In a container equipped with a stirrer and a dropping pump, 27 parts by mass of deionized water and 1 part by mass of an anionic emulsifier (Daiichi Kogyo Seiyaku Co., Ltd .: trade name Neogen SC-A) were charged, stirred and dissolved, and then styrene 75 A monomer mixture composed of parts by mass, 25 parts by mass of butyl acrylate, and 0.05 parts by mass of divinylbenzene was added dropwise with stirring to obtain a monomer emulsified dispersion.
Next, in a pressure-resistant reaction vessel equipped with a stirrer, a pressure gauge, a thermometer, and a dropping pump, 120 parts by mass of deionized water was charged and purged with nitrogen, and then the temperature was raised to 80 ° C. 5% by mass was added to a pressure resistant reactor, and 1 part by mass of a 2% by mass aqueous potassium persulfate solution was further added, and initial polymerization was performed at 80 ° C. After completion of the initial polymerization, the temperature was raised to 85 ° C. and the remaining monomer emulsified dispersion and 4 parts by mass of 2% by weight potassium persulfate were added over 3 hours, and then maintained at the same temperature for 2 hours. A styrene-based resin emulsion dispersion having a solid content concentration of 0.15 μm was obtained. The obtained resin emulsion dispersion had a high polymerization conversion rate and could be polymerized stably. As a result of analyzing the molecular weight of the resin emulsified dispersion after separating the resin with an ultracentrifuge, the mass average molecular weight Mw was 950,000 and the molecular weight peak Mp was 700,000.
100 parts by mass of the above solvent-free resin, 135 parts by mass of the above resin emulsified dispersion continuously mixed and heated at a jacket temperature of 215 ° C. with a continuous kneader (trade name: KRC Kneader, manufactured by Kurimoto Steel Works). Then, a water removal treatment was performed to obtain an evaporative dehydration kneaded product having a water content of 0.1% or less. The residual monomer content in the obtained evaporative dehydration kneaded product was 80 ppm. The evaporative dehydrated kneaded product was cooled and then roughly crushed with a hammer mill and then finely pulverized with a jet mill to obtain a styrene acrylic resin (1).
The same operation as in Example 11 was performed except that the polyester (1) in Example 11 was changed to the styrene acrylic resin (1). This toner had a fatty acid metal compound liberation rate of 0.65% according to the Particle Analyzer method, and the absolute deviation was 0.0856.

Example 13
After introducing 5 parts by mass of Na ₃ PO ₄ into 500 parts by mass of ion-exchanged water and heating to 60 ° C., a Claremix high-speed stirrer (manufactured by M Technique, peripheral speed 22 m / s) is installed and stirred. did. To this, an aqueous solution in which ₂ parts by mass of CaCl ₂ was dissolved in 15 parts by mass of ion exchange water was quickly added to obtain an aqueous dispersion medium containing Ca ₃ (PO ₄ ) ₂ .
Polymerizable monomer styrene 85 parts by mass n-butyl acrylate 20 parts by mass Colorant (CI Pigment Blue 15: 3) 7.5 parts by mass Charge control agent (E-88, Orient Chemical Industries, Ltd.) 1 part by mass / Plastic resin (saturated polyester) 5 parts by mass (acid value 10 mgKOH / g, peak molecular weight: 7,500)
・ Release agent (ester wax)
(Maximum endothermic peak temperature in DSC: 72 ° C.) 15 parts by mass / Clayton APA (manufactured by Southern Clay Products) 15 parts by mass On the other hand, the above materials are heated to 60 ° C. and stirred to make each material a polymerizable monomer. Was uniformly dissolved or dispersed. To this was added 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator to prepare a polymerizable monomer composition.

The polymerizable monomer composition is introduced into the aqueous dispersion medium, and then at a temperature of 60 ° C. and N ₂ atmosphere for 15 minutes with a CLEARMIX high-speed stirrer (manufactured by M Technique, peripheral speed 22 m / s). Stirring to produce particles of the polymerizable monomer composition in the aqueous dispersion medium. After the dispersion, the stirring apparatus was stopped and introduced into a polymerization apparatus equipped with a full zone stirring blade (manufactured by Shinko Pantech Co., Ltd.). In the polymerization apparatus, the polymerizable monomer was reacted for 5 hours while stirring the stirring blade at the maximum peripheral speed of stirring: 3 m / s in a N ₂ atmosphere at a temperature of 60 ° C. Thereafter, the temperature was raised to 80 ° C. and the polymerizable monomer was further reacted for 5 hours. After completion of the polymerization reaction, the toner was obtained by washing with water, drying and classification. The average particle size of the toner was 5.8 μm.

To 100 parts of the toner base particles thus prepared, 1.0 part of zinc myristate having a volume average particle size of 0.3 μm is added as a fatty acid metal compound, and mixed for 5 minutes using a Henschel mixer at a peripheral speed of 15 m / s. The mixture was further mixed for 10 minutes under the condition of a peripheral speed of 33 m / s. To this, 1.5 parts of the external additive (A) and 0.5 part of the external additive (C) were added and mixed for 5 minutes in a Henschel mixer under the condition of a peripheral speed of 33 m / s. . The mixed powder was passed through a mesh having an opening of 100 μm to remove coarse powder, and a toner to which a fatty acid metal compound and inorganic fine particles were externally added was prepared.
The release rate of the fatty acid metal compound by the Particle Analyzer method of this toner was 0.50%, and the absolute deviation was 0.0655.

Comparative Example 1
A toner was prepared in the same manner as in Example 2 except that the fatty acid metal compound was not added in Example 2.

Comparative Example 2
A toner was produced in the same manner as in Example 2 except that the fatty acid metal compound and Kraton APA were not added.
Comparative Example 3
The toner was manufactured in the same manner as in Example 2 except that the amount of Clayton APA added was changed from 3 parts to 10 parts. However, the viscosity of the dispersion liquid of the toner material was very high and emulsification or dispersion was performed. The toner could not be obtained.

Comparative Example 4
Clayton APA (manufactured by Southern Clay Products) was changed to 45 parts of organosilica sol (dispersion of silica in an organic medium) (MEK-ST-UP (Nissan Chemical Industries)), and the procedure was carried out except that no fatty acid metal compound was added. Toner was produced in the same manner as in Example 2.
Comparative Example 5
Clayton APA (manufactured by Southern Clay Products) was changed to unmodified layered inorganic mineral montmorillonite (trade name: manufactured by Kunipia Kunimine Kogyo Co., Ltd.), and toner was produced in the same manner as in Example 2.
This toner had a fatty acid metal compound liberation rate of 0.85% by particle analyzer method and an absolute deviation of 0.0935.

The obtained toner was evaluated as follows.
In the present invention, a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation) is used to measure the circularity of the toner, and analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10) is used. The analysis was performed using. Specifically, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and each toner 0.1 to 0 is added. 0.5 g was added and stirred with a microspatel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the density of the dispersion was 5000 to 15000 / μl. In this measurement method, it is important that the concentration of the dispersion liquid is 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated. If the amount is too small, the toner cannot be sufficiently wetted. It becomes insufficient. Further, the toner addition amount differs from the particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0. By adding 0.5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.

  SF1 was measured as follows. After vapor deposition on the toner, 100 or more toners were observed using an ultrahigh resolution FE-SEM S-5200 (manufactured by Hitachi, Ltd.) under the condition of an acceleration voltage of 2.5 keV. Next, SF1 was calculated using the image processing apparatus and image processing software of the image analysis apparatus Luzex AP (manufactured by Nireco).

Using the obtained toner, a developer having a toner concentration of 7% by mass was prepared, and 10K continuous output was performed at an image density of 5%, and evaluation was performed as follows.
For cleaning performance, the toner remaining on the photoconductor after passing through the cleaning process at the initial stage and after printing 1000 sheets and 10,000 sheets is transferred to white paper using Scotch tape (manufactured by Sumitomo 3M), and the Macbeth reflection densitometer RD514. Measurement was performed using a mold, and a difference from the blank of 0.01 or less was determined as good (◯), and a difference exceeding 0.01 was determined as defective (x).

(Fixability evaluation)
Using a device obtained by remodeling the fixing unit MF2200 manufactured by Ricoh Co., Ltd., which uses a Teflon (registered trademark) roller as a fixing roller, type 6200 paper manufactured by Ricoh was set in this, and a copying test was performed. The cold offset temperature (fixing lower limit temperature) and the hot offset temperature (hot offset resistant temperature) were determined by changing the fixing temperature. The minimum fixing temperature of the conventional low-temperature fixing toner is about 140 to 150 ° C. The evaluation conditions for low-temperature fixing are as follows: the paper feed linear speed is 120 to 150 mm / sec, the surface pressure is 1.2 kgf / cm ² , the nip width is 3 mm, and the high temperature offset is the paper feed linear speed of 50 mm / sec. The contact pressure was set to 2.0 kgf / cm ² and the nip width was 4.5 mm. The criteria for each characteristic evaluation are as follows.

(1) Low temperature fixability (five-level evaluation)
◎; Less than 120 ° C ○; 120-130 ° C
□; 130-140 ° C
Δ: 140-150 ° C.
×: 150 ° C. or higher (2) Hot offset property (five-level evaluation)
◎; 201 ° C or higher ○; 200-191 ° C
□: 190-181 ° C
Δ: 180-171 ° C.
×: 170 ° C. or less

(Image density)
Using a digital full-color copier (imageColor 2800, manufactured by Ricoh Co., Ltd.), after running 150,000 image charts with a 50% image area in single color mode, a solid image was output to 6000 paper manufactured by Ricoh Co., and the image density was set to XRite. Measurement was carried out by (manufactured by X-Rite) and the average was determined. When this value is less than 1.2, “x”, when it is 1.2 or more and less than 1.4, “△”, when it is 1.4 or more and less than 1.8, “◯”, 1.8 or more If less than 2, “◎” was assigned. These were carried out in HH environment (30 ° C. 80%) and LL environment (10 ° C. 15%), respectively.
The evaluation results of the above toner are shown in Table 2.

  From this, it can be seen that the toners of the examples are excellent in cleaning properties from the initial stage to the long term. Further, the toners of Comparative Examples 2, 4, and 5 had poor cleaning from the beginning, and could not be evaluated over a long period of time.

Depending on the relationship between the cube root voltage (equivalent particle diameter, horizontal axis) of carbon atoms obtained for each toner particle (base material) and the cube root voltage (equivalent particle diameter, vertical axis) of externally added particles (additive material) It is a graph for demonstrating the synchronous distribution shown. It is the graph analyzed in order to obtain | require the absolute deviation of the graph shown in FIG.

Claims (28)

  A toner having a layered inorganic mineral in which at least part of ions between layers of the layered inorganic mineral as a toner composition is modified with an organic ion, the toner having a fatty acid metal compound coated on the surface thereof, and a toner base particle surface After the toner is coated with a fatty acid metal compound, an external additive other than the fatty acid metal compound is attached.   The liberation rate of the fatty acid metal compound represented by the ratio of the number of detected metal atoms in the total number of detected metal atoms in the fatty acid metal compound, measured with a particle analyzer, of the toner is 1.0% or less. , Where X is the emission voltage due to carbon derived from the binder resin of the toner particles, and Y is the emission voltage attributable to the element derived from the fatty acid metal compound. The electrostatic image developing toner according to claim 1, wherein the deviation is 0.1 or less.   The toner according to claim 1, wherein the fatty acid metal compound has a volume average particle size of 0.1 μm to 3.0 μm.   The toner according to claim 1, wherein a volume average particle diameter of the external additive other than the fatty acid metal compound is 0.005 μm to 1.000 μm.   The toner according to claim 1, wherein an average circularity of the toner is 0.925 to 0.970.   The toner according to any one of claims 1 to 5, wherein the modified layered inorganic mineral is a layered inorganic mineral in which at least a part of cations between layers of the layered inorganic mineral is modified with an organic cation.   7. The toner according to claim 1, wherein the toner is obtained by dispersing and / or emulsifying a toner composition containing at least the modified modified layered inorganic mineral in an aqueous medium. Toner.   The toner includes at least a first binder resin, a binder resin precursor, a compound that extends or crosslinks with the binder resin precursor, a colorant, a release agent, and the modified layered inorganic mineral in an organic solvent. It is obtained by dissolving or dispersing a toner composition, subjecting the solution or dispersion to a crosslinking reaction and / or elongation reaction in an aqueous medium, and removing the solvent from the obtained dispersion. The toner according to claim 1.   The toner according to claim 8, wherein the first binder resin is a resin having a polyester skeleton.   The toner according to claim 8, wherein the first binder resin is a polyester resin.   The toner according to claim 10, wherein the polyester resin is an unmodified polyester resin.   The toner according to claim 8, wherein the acid value of the first binder resin is 1.0 to 50.0 (KOH mg / g).   The toner according to claim 8, wherein the glass transition point of the first binder resin is 35 to 65 ° C.   The toner according to claim 8, wherein the binder resin precursor is a modified polyester resin.   The binder resin precursor has a site capable of reacting with a compound having an active hydrogen group, and the mass average molecular weight of the polymer of the binder resin precursor is 3,000 to 30,000, The toner according to claim 8.   In the said solution or dispersion, 0.05-10 mass% of modified | denatured layered inorganic minerals are contained in the solid content in this solution or dispersion, The any one of Claims 8-15 characterized by the above-mentioned. The toner described in 1.   A ratio Dv / Dn of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner is 1.00 to 1.30, and particles having a circularity of 0.950 or less are 20% of all toner particles. The toner according to claim 1, wherein the toner is contained in an amount of ˜80% by number.   18. The ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner is 1.00-1.20. toner.   The toner according to claim 1, wherein the number of particles having a particle diameter of 2 μm or less is 20% by number or less.   The toner according to claim 1, wherein the toner has an acid value of 0.5 to 40.0 (KOH mg / g).   The toner according to claim 1, wherein the toner has a glass transition point of 40 to 70 ° C.   The toner according to claim 1, wherein the toner is used for a two-component developer.   A toner-containing container comprising the toner according to claim 1.   A developer comprising the toner according to claim 1.   An image forming apparatus, wherein an image is formed using the developer according to claim 24.   25. A process cartridge comprising developing means having the developer according to claim 24 and an image carrier.   A fatty acid metal compound is added to a toner base particle obtained by dispersing and / or emulsifying a toner composition having a modified layered inorganic mineral obtained by modifying at least a part of interlayer ions in a layered inorganic mineral with an organic ion in an aqueous medium. Adding and mixing the fatty acid metal compound to coat the surface of the toner with the fatty acid metal compound, and adding an external additive other than the fatty acid metal compound, mixing and externally adding to the toner surface coated with the fatty acid metal compound The method for producing a toner according to any one of claims 1 to 22, further comprising an external additive adding step for adhering an agent.   In an organic solvent, a binder resin, a precursor of the binder resin, a compound that extends or crosslinks with the binder resin precursor, a colorant, a release agent, and a modified layered inorganic mineral are dissolved or dispersed, and the solution or A fatty acid metal compound is added to and mixed with a toner base particle obtained by subjecting the dispersion to a crosslinking reaction and / or elongation reaction in an aqueous medium and removing the solvent from the resulting dispersion. Fatty acid metal compound addition step for coating the fatty acid metal compound, and external additive addition step for adding an external additive other than the fatty acid metal compound, and mixing and adhering the external additive to the toner surface coated with the fatty acid metal compound The method for producing a toner according to claim 1, comprising:

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