JP2008070710A - Method for manufacturing toner and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a toner by which a deformed state of a toner granulated in an aqueous medium is suitable and a sharp particle size distribution is obtained to make a classification step unnecessary. <P>SOLUTION: The method for manufacturing a toner includes at least emulsifying/dispersing an oil phase containing a binder resin and/or a binder resin precursor in an aqueous medium to granulate a toner, wherein the difference ΔDv between a minimum volume average particle diameter Dv1 of the toner during granulation during the emulsifying/dispersing and a volume average particle diameter Dv2 of the granulated toner after the emulsifying/dispersing is 0.5-3.0 μm, and the granulated toner has an average circularity of 0.925-0.970 and a volume average particle diameter (Dv) to number average particle diameter (Dn) ratio, Dv/Dn of 1.00-1.30. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and a toner obtained by the production method. More specifically, a method for producing a toner for electrophotography used in a copying machine, a laser printer, a plain paper fax machine or the like using a direct or indirect electrophotographic developing method, a toner obtained by the production method, a container containing the toner, The present invention relates to a developer using toner, an image forming apparatus, an image forming method, and a process cartridge.

  In an example of electrophotography, an electrostatic latent image is formed on an image carrier (hereinafter also referred to as a photoreceptor) by charging and exposure, and then developed with a developer containing toner to form a toner image. The 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, since the toner obtained in this manner has a wide distribution, classification is essential, productivity is lowered, particle size is increased, 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, such a method is known to be an advantageous production method for achieving a sharp distribution that can reduce the particle size of the toner and does not require classification. Although an improvement in potential with a sharp particle size distribution can be seen with water-based granulated toner, it has not been possible to achieve a sharp distribution at a level that does not require classification.

On the other hand, the water-based granulated toner produces a spherical toner due to the influence of surface tension or the like because the oil phase generally has a Newtonian viscosity. However, since spherical toner causes a cleaning failure at the time of blade cleaning on the photosensitive member, a deformed toner is used in an image forming apparatus that employs blade cleaning.
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 1). However, when such a method is used, the dispersion state becomes unstable and the particles are likely to coalesce, and superfine powder is generated by shearing, which deteriorates the cleaning property and causes filming on the photoreceptor. There is a problem that occurs.

In addition, a method is known in which aggregated particles having a particle diameter 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 2). However, the aggregate particles obtained in this way have a problem that the particle diameter is large and a large amount of coarse powder is generated, which easily causes toner scattering during development, transfer dust, and image omission.
Japanese Patent Laid-Open No. 62-266550 JP 2005-49858 A

  It is an object of the present invention to provide a toner production method in which a deformed state in a toner that is granulated in an aqueous system is suitable, a particle size distribution is sharp, and a classification step is unnecessary.

In the production method of a toner that is granulated in an aqueous system, when the toner is granulated by emulsifying / dispersing an oil phase containing a binder resin and / or a binder resin precursor in an aqueous medium, The difference ΔDv between the volume average particle diameter Dv1 that minimizes the particle size distribution of the toner during dispersion and the volume average particle diameter Dv2 after the stable state of the granulated toner after emulsification / dispersion is obtained. It has been clarified that this has an influence on the deformed state and the particle size distribution, and the present invention has been completed.
ΔDv has a dominant correlation with the degree of circularity, which is a scale indicating the deformed state, and Dv / Dn, a scale indicating the sharpness of the toner particle size distribution, the amount of ultrafine powder, and the amount of coarse powder. By controlling this, the toner's deformed state and sharp particle size distribution are achieved in a high dimension.

That is, the present invention is as follows.
(1) A method for producing a toner comprising granulating a toner by emulsifying / dispersing an oil phase containing at least a binder resin and / or a binder resin precursor in an aqueous medium,
The difference ΔDv between the volume average particle diameter Dv1 that is the minimum of the toner being granulated during emulsification / dispersion and the volume average particle diameter Dv2 of the granulated toner after emulsification / dispersion is 0.5 to 3.0 μm. And the average circularity of the granulated toner is 0.925 to 0.970, and the ratio Dv / Dn of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00 to 1. A method for producing toner, which is 1.30.
(2) In the toner production method, an oil phase which is a solution and / or a dispersion obtained by dissolving and / or dispersing a toner composition containing at least a binder resin and / or a binder resin precursor in an organic solvent. The method for producing a toner according to (1), wherein the toner is used.

(3) The method for producing a toner according to (1) or (2), wherein the oil phase contains inorganic fine particles.
(4) The method for producing a toner according to (3), wherein the inorganic fine particles have a layered inorganic mineral obtained by modifying at least a part of ions between layers of the layered inorganic mineral with an organic ion.
(5) The toner according to (4), wherein the oil phase contains 0.05 to 10 wt% of a layered inorganic mineral modified with organic ions in a solid content in the oil phase. Production method.
(6) The layered inorganic mineral modified with organic ions is a layered inorganic mineral in which at least a part of cations between layers of the layered inorganic mineral is modified with organic cations (4) or (5) The method for producing a toner according to (1).

(7) The method for producing a toner according to any one of (1) to (6), wherein particles having a circularity of 0.950 or less are contained in an amount of 20 to 80% of all toner particles.
(8) The ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner is 1.0 to 1.20. The method for producing a toner according to any one of the above.
(9) The method for producing a toner according to any one of (1) to (8), wherein the toner has a particle size of 2 to 20% by number of particles having a particle size of 2 μm or less.

(10) The method for producing a toner according to any one of (1) to (9), wherein the binder resin contained in the toner contains at least two kinds of binder resins.
(11) The method for producing a toner according to (10), wherein the first binder resin contained in the binder resin is a resin having a polyester skeleton.
(12) The method for producing a toner according to (10) or (11), wherein the first binder resin is a polyester resin.
(13) The method for producing a toner according to (12), wherein the polyester resin is an unmodified polyester resin.
(14) The method for producing a toner according to any one of (1) to (13), wherein the binder resin precursor is a modified polyester resin.

(15) The toner manufacturing method dissolves or disperses a binder resin, a binder resin precursor, a compound that extends or crosslinks with the binder resin precursor, a colorant, and a release agent in at least an organic solvent. Of an oil phase, which is a dissolved or dispersed liquid, is emulsified / dispersed in an aqueous medium to cause a crosslinking reaction and / or elongation reaction, and the solvent is removed from the obtained dispersion liquid to produce a toner. The method for producing a toner according to any one of (1) to (14), wherein the toner is a method.

(16) A toner obtained by the method for producing a toner according to any one of (1) to (15).
(17) The toner according to (16) above, which is a toner used for a two-component developer.
(18) A toner-containing container comprising the toner according to (16) or (17).
(19) A developer containing the toner according to (16) or (17).

(20) An image forming apparatus that forms an image using the developer described in (19).
(21) A process cartridge comprising a developing means having the developer according to (19) and an image carrier.
(22) An image forming method, wherein an image is formed using the developer according to (19).

  According to the present invention, it is possible to obtain a toner having a sharp particle size distribution, which is suitable for a deformed state in a toner that is granulated in an aqueous system. Therefore, it is possible to ensure the cleaning performance while making good use of the water-based granulation, obtain an excellent high image quality without generation of transfer dust and filming, and obtain a toner with high reliability. .

During emulsification / dispersion during granulation, shearing is required when the oil phase changes to oil droplets, and the particle size changes with time due to emulsification / dispersion (FIG. 1). Then, the dispersion force is weakened (= stirring / standing) to obtain a target particle size (Dv2) to be obtained, and then the toner is obtained through steps such as washing and drying. At this time, there may be a particle size smaller than the target particle size Dv2 due to emulsification / dispersion. (The minimum particle size at this time is Dv1)
The present inventors have found a relationship between the shape and the particle size distribution in the minimum volume average particle diameter Dv1 and the volume average particle diameter Dv2 after granulation.

That is, by controlling this ΔDv (= Dv2−Dv1), it is possible to make the particle size distribution a target shape. The larger the ΔDv, the more the shape can be made different, but this is a trade-off with the particle size distribution.
This is because the smallest particles formed during emulsification / dispersion are in an unstable state, and it is considered that shearing / unification is repeated. At this time, if the shear force is strong and sufficient energy is temporarily applied to the oil phase, a state of minimum particle size can be obtained, but the coalescence energy exceeds the shear force and increases the coalescence. It is thought that the particle size is reached.

At the time of coalescence, if the oil droplet is a complete Newtonian liquid, it becomes a spherical toner due to the influence of surface tension. However, in the toner oil phase containing pigments and other components, it does not become a complete Newtonian liquid, and ΔDv By enlarging the value, it is considered that the shape does not return to a sufficient sphere at the same time and becomes atypical.
On the other hand, regarding the particle size distribution, if ΔDv is small, a state in which the oil phase is not sufficiently sheared occurs, and there are many coarse components, and it is considered that the toner has a poor distribution. For this reason, in order to carry out uniform emulsification / dispersion, it is necessary to provide ΔDv with a certain degree of shearing force.
However, if this ΔDv becomes too large, there will be particles that do not coalesce when coalescing / the coalescence is promoted too much, and there will be particles that become coarse, and the distribution will deteriorate.
In the present invention, if ΔDv is less than 0.5 μm, it becomes spherical and the desired circularity cannot be obtained. Also, the toner does not have a sufficient particle size distribution. On the other hand, if ΔDv exceeds 3.0 μm, coalescence is promoted too much and a toner having a target particle size distribution cannot be obtained.

  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 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 properties. Therefore, it is preferable that 20-80% of the toner particles have a circularity of 0.950 or less.
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 a balance between blade cleaning and transfer efficiency, particles having a toner circularity of 0.950 or less are 20 to 80% 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 the toner circularity is 0.950 or less than 20% of all toner particles, cleaning with a blade becomes difficult. On the other hand, when the particles having a circularity of 0.950 or less exceed 80% of the total 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, circularity, and average circularity of the toner of the present invention having a particle diameter of 2 μm or less 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 an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. About 0.1 to 0.5 g. 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 volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner and the particle size distribution (Dv / Dn) calculated from the volume average particle size (Dv / Dn) were measured using a particle size measuring instrument [Multisizer III] (manufactured by Beckman Coulter). Measurement is performed with an aperture diameter of 100 μm, and analysis is performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51).
About the measuring method of Dv1, it carries out as follows.
Specifically, 80 ml of ion exchange water is added to a glass 100 ml beaker. Oil droplets being emulsified / dispersed are poured into the ion-exchanged water immediately after sampling, instantaneous solvent removal is performed, the particle size is confirmed, and the dispersion is measured using the Multisizer III. Measurement was performed using Isoton III (manufactured by Beckman Coulter, Inc.) as the solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important to adjust the concentration to 8 ± 2% from the viewpoint of the reproducibility of the particle size.

For Dv2, the toner in the aqueous system from which the oil droplets have been removed may be measured by the same method as Dv1, or the toner after washing / drying / pulverizing may be measured as follows.
However, since they may be aggregated, the measurement may be carried out after the treatment with an ultrasonic disperser in the same manner as described below by the following method or the measurement method of Dv1.
The measurement method was 0.5 ml of 10 wt% surfactant (alkyl benzene sulfonate neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.5 g of each toner was added, and the mixture was stirred with microspatel, and then 80 ml of ion-exchanged water was added. . The obtained dispersion is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important to adjust the concentration to 8 ± 2% from the viewpoint of the reproducibility of the particle size.

  The ratio Dv / Dn was determined from the volume-based volume average particle diameter (Dv) determined from the volume distribution according to the present invention and the number average particle diameter (Dn) determined from the number distribution.

In the toner production method of the present invention, at least an oil phase containing a binder resin and / or a binder resin precursor is emulsified / dispersed in an aqueous medium to granulate the toner. The oil phase is preferably a solution and / or dispersion in which a toner composition containing at least a binder resin and / or a binder resin precursor is dissolved and / or dispersed in an organic solvent.
The organic solvent can be appropriately selected according to the purpose, but since the removal is easy, the boiling point is preferably less than 150 ° C. Specifically, 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, And methyl isobutyl ketone. Of these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used alone or in combination of two or more.
An appropriate amount of the organic solvent is necessary to aim at ΔDv. If the amount of the organic solvent is too small, the viscosity of the oil phase becomes high, and Dv1 cannot be reduced unless sufficient shearing is applied. Moreover, when there is too much solvent, (DELTA) Dv will become large too much and a particle size distribution will deteriorate. The organic solvent is preferably 40 to 300 parts by weight, more preferably 60 to 140 parts by weight, and still more preferably 80 to 120 parts by weight with respect to 100 parts by weight of the toner composition.

  The toner composition other than the binder resin and / or the binder resin precursor can be appropriately selected according to the purpose, but usually at least as the binder resin and / or the binder resin precursor, Containing any one of a monomer, a polymer, and a polymer having reactivity to active hydrogen groups, and if necessary, a compound having an active hydrogen group, a colorant, inorganic fine particles, a release agent, and other components. You may contain.

Inorganic fine particles may be used as the oil phase viscosity modifier.
There is no restriction | limiting in particular as an inorganic fine particle, According to the objective, it can select from a well-known thing suitably.
Examples thereof include oxides, titanates, sulfates, carbonates, nitrides, and the like. These may be used alone or in combination of two or more. Examples of the oxide include silicon dioxide (silica), titanium dioxide (titania), aluminum oxide (alumina), iron oxide, copper oxide, zinc oxide, tin oxide, antimony trioxide, magnesium oxide, zirconium oxide, chromium oxide, and oxidation. And cerium. Examples of the titanate include barium titanate, magnesium titanate, calcium titanate, and strontium titanate. Examples of the sulfate include barium sulfate. Examples of the carbonate include barium carbonate, calcium carbonate, and silicon carbide. Examples of the nitride include silicon nitride. Other examples include silica sand, clay, mica, wollastonite, and diatomaceous earth.

Among these, a layered inorganic mineral represented by clay and the like is preferable, and a layered inorganic mineral obtained by modifying at least a part of ions between layers of the layered inorganic mineral with organic ions is more preferable. The modified layered inorganic mineral 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. Specific examples are described in JP-A-8-21655, JP-A-10-020552, and JP-A-11-007156. 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 modified layered inorganic mineral is highly hydrophilic due to its modified layered structure. Therefore, it is preferable because it can be easily deformed during granulation, and can be easily deformed without deteriorating the particle size distribution. At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.05 to 2% by weight.

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 ion 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 and imidazolium salts. A quaternary alkyl ammonium salt is desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

  Examples of the organic ion modifier include branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, and the like. Sulfates, sulfonates, carboxylates or phosphates are raised. 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 2% by weight.
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 the layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) using a compound represented by the following general formula (1) is particularly preferable. Examples of the compound represented by the following general formula (1) include Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
General formula (1)
R ₁ (OR ₂ ) nOSO 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, it has an appropriate hydrophobicity, and therefore, it tends to be present at the interface of the droplets, and is likely to be atypified.

  The colorant can be appropriately selected from known dyes and pigments according to the purpose. 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, Iso Indolinone Yellow, Bengala, Pangdan, Pepper Red, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Para Red, Faise Red, p-Chloro-o-nitroaniline red, Resol Fast Scarlet G, Brilli Fast Scarlet, Brilliant Carmine 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, Pogment Scarlet 3B, Bordeaux 5B, Toluidine 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, pyrazolone red, polyazo red, chrome vermilion, benzidine oren , Perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene 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, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Examples thereof include zinc white, litbon, and mixtures thereof. Colorants that can be used particularly preferably include pigment red such as PR122, PR269, PR184, PR57: 1, PR238, PR146, and PR185; pigment yellow such as PY93, PY128, PY155, PY180, and PY74; PB15: 3 Pigment blue, etc. These may be used alone or in combination of two or more.

  The colorant may be used by being dispersed in a solvent together with the binder resin or the like, or may be used as a dispersion of a colorant obtained by dispersing the colorant in the solvent. In addition, when dispersing the colorant, in order to apply an appropriate shearing force, a part of a binder resin or the like may be added to adjust the viscosity.

The dispersed particle diameter of the colorant is preferably 1 μm or less. When a toner produced using a colorant having a dispersed particle diameter exceeding 1 μm is used, the image quality may be easily deteriorated, and in particular, the OHP light transmittance may be easily deteriorated.
The dispersed particle size of the colorant can be measured using a particle size distribution measuring apparatus Microtrac ultrafine particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.) using a laser Doppler method.
The content of the colorant in the toner can be appropriately selected according to the purpose, but is usually 1 to 15% by weight, and preferably 3 to 10% by weight. When the content of the colorant is less than 1% by weight, the coloring power of the toner decreases. When the content of the coloring agent exceeds 15% by weight, poor pigment dispersion occurs in the toner. May be reduced.

  The method for forming the toner base particles can be appropriately selected from known methods. Specifically, a method for forming toner base particles using a suspension polymerization method, an emulsion polymerization aggregation method, a dissolution suspension method, or the like, a method for forming toner base particles while producing an adhesive substrate, etc. Among these, a method of forming toner base particles while producing an adhesive substrate is preferable. Here, the adhesive base material is a base material having adhesiveness to a recording medium such as paper.

A method of forming toner base particles while forming an adhesive substrate includes a toner composition containing a compound having an active hydrogen group and a polymer having a reactivity to the active hydrogen group (binder resin precursor). In this method, toner base particles are formed while an adhesive substrate is formed by reacting a compound having an active hydrogen group with a polymer having reactivity to the active hydrogen group in an aqueous medium. In addition, the adhesive base material may further contain a known binder resin.
The toner thus obtained preferably contains a colorant, and may further contain other components such as a release agent and a charge control agent that are appropriately selected as necessary.

The weight average molecular weight of the adhesive substrate is preferably 3000 or more, more preferably 5000 to 1000000, and particularly preferably 7000 to 500000. When the weight average molecular weight is less than 3000, the hot offset resistance may be lowered.
The glass transition temperature of the adhesive substrate is preferably 30 to 70 ° C, more preferably 40 to 65 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient. Note that a toner containing a polyester resin subjected to a crosslinking reaction or an elongation reaction as an adhesive substrate has good storage stability even when the glass transition temperature is low.
The glass transition temperature can be measured as follows using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, the glass transition temperature can be calculated from the contact point between the tangent line and the base line of the endothermic curve near the glass transition temperature using the analysis system in the TG-DSC system.

The adhesive substrate is appropriately selected according to the purpose, but a polyester resin or the like is preferably used.
The polyester resin is appropriately selected depending on the purpose, but a urea-modified polyester resin or the like is preferably used.
The urea-modified polyester resin is obtained by reacting an amine as a compound having an active hydrogen group and a polyester prepolymer having an isocyanate group as a polymer having reactivity with the active hydrogen group in an aqueous medium. In addition, when synthesizing the urea-modified polyester resin, a urethane bond may be formed by adding an alcohol in addition to the amine. The molar ratio of the urethane bond to the urea bond thus formed (to distinguish it from the urethane bond of the polyester prepolymer having an isocyanate group) is preferably from 0 to 9, and preferably from 1/4 to 4. Is more preferable, and 2/3 to 7/3 is particularly preferable. If this ratio is greater than 9, the hot offset resistance may decrease.

  Specific examples of the adhesive substrate include a polyester prepolymer obtained by reacting a 2-condensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 Mixtures of polyadducts of molar adducts and isophthalic acid; bisphenol A ethylene oxide 2 molar adducts and polycondensates of isophthalic acid reacted with isophorone diisocyanate and uread with isophorone diamine, and bisphenol A mixture of ethylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid A mixture of a polyester prepolymer obtained by reacting a condensate with isophorone diisocyanate and uread with isophorone diamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid; Polyester prepolymer prepared by reacting bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate with isophorone diisocyanate, and oleaminated with isophoronediamine, 2 mol of bisphenol A propylene oxide Mixture of adduct and polycondensate of terephthalic acid; bisphenol A ethylene oxide 2-mole adduct and polycondensate of terephthalic acid with isophorone diisocyanate A mixture of a polyester prepolymer obtained by urea formation with hexamethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid; polycondensation of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid A mixture of a polyester prepolymer obtained by reacting a product with isophorone diisocyanate with urea and hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid; A polyester prepolymer obtained by reacting a bicondensate of bisphenol A ethylene oxide 2 mol and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with ethylenediamine, and bisphenol A polyester prepolymer prepared by reacting bisphenol A ethylene oxide 2-mole adduct and isophthalic acid polycondensate with diphenylmethane diisocyanate in urea with hexamethylenediamine Of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride A polyester prepolymer obtained by reacting a polycondensate with diphenylmethane diisocyanate and uread with hexamethylenediamine, and a bisphenol A ethylene oxide 2-mole adduct / bisphenol A mixture of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate reacted with toluene diisocyanate in urea with hexamethylenediamine And a mixture of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate.

The compound having an active hydrogen group acts as an elongation agent, a crosslinking agent or the like when a polymer having reactivity to the active hydrogen group undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous medium.
Specific examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group and the like. In addition, an active hydrogen group may be individual, and 2 or more types of mixtures may be sufficient as it.
The compound having an active hydrogen group can be appropriately selected according to the purpose. However, when the polymer having reactivity to the active hydrogen group is a polyester prepolymer having an isocyanate group, an elongation reaction with the polyester prepolymer. Amines are preferred because they can have a high molecular weight by a crosslinking reaction or the like.

The amines can be appropriately selected depending on the purpose, and specific examples include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Diamines and mixtures of diamines and small amounts of trivalent or higher amines are preferred. These may be used alone or in combination of two or more.
Examples of diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines. Specific examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, and the like. Specific examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, isophorone diamine and the like. Specific examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, hexamethylene diamine and the like. Specific examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine. Specific examples of amino alcohols include ethanolamine and hydroxyethylaniline. Specific examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan. Specific examples of amino acids include aminopropionic acid and aminocaproic acid. Specific examples of those in which the amino group is blocked include ketimine compounds and oxazolidone compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

  In addition, a reaction terminator can be used in order to stop the elongation reaction, the crosslinking reaction, and the like of the compound having an active hydrogen group and a polymer having reactivity with the active hydrogen group. When a reaction terminator is used, the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Specific examples of the reaction terminator include monoamines such as diethylamine, dibutylamine, butylamine and laurylamine, and ketimine compounds in which these amino groups are blocked.

  The ratio of the equivalent of the isocyanate group of the polyester prepolymer to the equivalent of the amino group of the amine is preferably 1/3 to 3, more preferably 1/2 to 2, and particularly preferably 2/3 to 1.5. . If this ratio is less than 1/3, the low-temperature fixability may be lowered. If it exceeds 3, the molecular weight of the urea-modified polyester resin may be lowered, and the hot offset resistance may be lowered.

  The polymer having reactivity to active hydrogen groups (hereinafter sometimes referred to as “prepolymer”) can be appropriately selected from known resins and the like, and can be selected from polyol resins, polyacrylic resins, polyester resins, and epoxy resins. And derivatives thereof. Among them, it is preferable to use a polyester resin in terms of high fluidity and transparency at the time of melting. These may be used alone or in combination of two or more.

Examples of the functional group capable of reacting with the active hydrogen group of the prepolymer include an isocyanate group, an epoxy group, a carboxyl group, and a functional group represented by the chemical structural formula -COCl. Of these, an isocyanate group is preferable. The prepolymer may have one of such functional groups or two or more kinds.
As a prepolymer, the molecular weight of the polymer component can be easily adjusted, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. Since it can ensure, it is preferable to use the polyester resin which has an isocyanate group etc. which can produce | generate a urea bond.

  The polyester prepolymer containing an isocyanate group can be appropriately selected depending on the purpose. Specific examples include a reaction product of a polyester resin having an active hydrogen group obtained by polycondensation of a polyol and a polycarboxylic acid, and a polyisocyanate.

The polyol can be appropriately selected according to the purpose, and a diol, a trihydric or higher alcohol, a mixture of a diol and a trihydric or higher alcohol, etc. can be used, but the diol or the diol and a small amount of a trihydric or higher alcohol. Is preferred. These may be used alone or in combination of two or more.
Specific examples of the diol include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol; diethylene glycol, triethylene glycol, dipropylene Diols having an oxyalkylene group such as glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols including ethylene oxide and propylene oxide , With addition of alkylene oxide such as butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols with ethyleneoxy , Propylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. In addition, it is preferable that carbon number of alkylene glycol is 2-12. Among these, alkylene glycols having 2 to 12 carbon atoms or alkylene oxide adducts of bisphenols are preferred, alkylene oxide adducts of bisphenols or alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbons. The mixture of is particularly preferred.

Examples of trihydric or higher alcohols include trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols. Specific examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Specific examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak and the like. Specific examples of adducts of trivalent or higher polyphenols with alkylene oxides include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.
When a diol and a trihydric or higher alcohol are mixed and used, the weight ratio of the trihydric or higher alcohol to the diol is preferably 0.01 to 10%, more preferably 0.01 to 1%.

  The polycarboxylic acid can be appropriately selected according to the purpose, and dicarboxylic acid, trivalent or higher carboxylic acid, a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, and the like can be used. And a small amount of a trivalent or higher polycarboxylic acid mixture is preferred. These may be used alone or in combination of two or more.

  Specific examples of the dicarboxylic acid include divalent alkanoic acid, divalent alkenoic acid, and aromatic dicarboxylic acid. Specific examples of the divalent alkanoic acid include succinic acid, adipic acid, sebacic acid and the like. The number of carbon atoms of the divalent alkenoic acid is preferably 4 to 20, and specific examples include maleic acid and fumaric acid. The aromatic dicarboxylic acid preferably has 8 to 20 carbon atoms, and specific examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, a divalent alkenoic acid having 4 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.

As the trivalent or higher carboxylic acid, trivalent or higher aromatic carboxylic acid or the like can be used. The carbon number of the trivalent or higher aromatic carboxylic acid is preferably 9 to 20, and specific examples thereof include trimellitic acid and pyromellitic acid.
As the polycarboxylic acid, an acid anhydride or lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid can be used. Specific examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.
In the case of using a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, the weight ratio of trivalent or higher carboxylic acid to dicarboxylic acid is preferably 0.01 to 10%, more preferably 0.01 to 1%. preferable.

  As for the mixing ratio at the time of polycondensation of the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid is usually preferably 1 to 2, more preferably 1 to 1.5, 1.02-1.3 is particularly preferred.

The content of the structural unit derived from the polyol in the polyester prepolymer having an isocyanate group is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, and particularly preferably 2 to 20% by weight. When this content is less than 0.5% by weight, the hot offset resistance is lowered, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by weight. In this case, the low-temperature fixability may be lowered.
Polyisocyanate can be appropriately selected according to the purpose, but aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurates, and these are blocked with phenol derivatives, oximes, caprolactam, etc. And the like.

  Specific examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate. Specific examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Specific examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl. 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like. Specific examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Specific examples of the isocyanurates include tris (isocyanatoalkyl) isocyanurate, tris (isocyanatocycloalkyl) isocyanurate, and the like. These may be used alone or in combination of two or more.

When the polyisocyanate and the polyester resin having a hydroxyl group are reacted, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is usually preferably 1 to 5, more preferably 1.2 to 4, more preferably 1 .5-3 are particularly preferred. When the equivalent ratio exceeds 5, the low-temperature fixability may decrease, and when it is less than 1, the offset resistance may decrease.
The content of the structural unit derived from polyisocyanate in the polyester prepolymer containing an isocyanate group is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, further 2 to 20% by weight. preferable. When this content is less than 0.5% by weight, the hot offset resistance may be lowered, and when it exceeds 40% by weight, the low-temperature fixability may be lowered.

  The average number of isocyanate groups that the polyester prepolymer has per molecule is preferably 1 or more, more preferably 1.2 to 5, and even more preferably 1.5 to 4. When the average number is less than 1, the molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be lowered.

1000-30000 is preferable and, as for the weight average molecular weight of the polymer which has the reactivity with respect to an active hydrogen group, 1500-15000 are more preferable. When the weight average molecular weight is less than 1000, the heat resistant storage stability may be lowered, and when it exceeds 30000, the low temperature fixability may be lowered. In addition, a weight average molecular weight is obtained by measuring tetrahydrofuran soluble part using a gel permeation chromatography (GPC).
The GPC measurement can be performed as follows, for example. First, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran is used as a column solvent at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran solution adjusted to a sample concentration of 0.05 to 0.6% by weight is injected and measured. In measuring the molecular weight, the molecular weight is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of standard samples and the number of counts. As a standard sample for preparing a calibration curve, the molecular weight is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ and 4.48 × 10 ⁶ monodisperse polystyrene (manufactured by Pressure Chemical or Toyo Soda Industry Co., Ltd.) can be used. At this time, it is preferable to use about 10 kinds of standard samples. A refractive index detector can be used as the detector.

In the present invention, the binder resin can be appropriately selected according to the purpose, and a polyester resin or the like can be used, but an unmodified polyester resin that is not modified is preferable. Thereby, low temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include a polycondensate of a polyol and a polycarboxylic acid. The non-modified polyester resin is preferably partially compatible with the urea-modified polyester resin, that is, has a similar structure compatible with each other in terms of low-temperature fixability and hot offset resistance. .

  The weight average molecular weight of the unmodified polyester resin is preferably 1000 to 30000, and more preferably 1500 to 15000. When the weight average molecular weight is less than 1000, the heat resistant storage stability may be lowered. For this reason, it is preferable that content of the component whose weight average molecular weight is less than 1000 is 8-28 weight%. On the other hand, if the weight average molecular weight exceeds 30000, the low-temperature fixability may be lowered.

The glass transition temperature of the unmodified polyester resin is usually 30 to 70 ° C, more preferably 35 to 60 ° C, and still more preferably 35 to 55 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g or more, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. When the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 50.0 mgKOH / g, and more preferably 1.0 to 30.0 mgKOH / g. Thereby, the toner is easily negatively charged.

  When the toner contains an unmodified polyester resin, the weight ratio of the polyester prepolymer having an isocyanate group to the unmodified polyester resin is preferably 5/95 to 25/75, more preferably 10/90 to 25/75. preferable. When the weight ratio is less than 5/95, the hot offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the glossiness of the image may be lowered.

In the present invention, the toner may further contain a release agent, a charge control agent, resin fine particles, inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, and the like.
The release agent can be appropriately selected from known ones according to the purpose, and waxes having a carbonyl group, polyolefin waxes, long-chain hydrocarbons, and the like can be used. Waxes having a carbonyl group are preferred. These may be used alone or in combination of two or more.

  Specific examples of the wax having a carbonyl group include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18- An ester having a plurality of alkanoic acid residues such as octadecandiol diol stearate; an ester having a plurality of alkanol residues such as tristearyl trimellitic acid and distearyl maleate; a plurality of alkanoic acid residues such as dibehenyl amide Amides; amides having a plurality of monoamine residues such as trimellitic acid tristearyl amide; dialkyl ketones such as distearyl ketone and the like, and esters having a plurality of alkanoic acid residues are particularly preferred. Specific examples of the polyolefin wax include polyethylene wax and polypropylene wax. Specific examples of the long chain hydrocarbon include paraffin wax and sazol wax.

The melting point of the release agent is preferably 40 to 160 ° C, more preferably 50 to 120 ° C, and particularly preferably 60 to 90 ° C. When the melting point is less than 40 ° C., the wax may adversely affect the heat resistant storage stability, and when it exceeds 160 ° C., cold offset may occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps and more preferably 10 to 100 cps at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving the hot offset resistance and the low-temperature fixability may not be obtained.
The content of the release agent in the toner is preferably 0 to 40% by weight, and more preferably 3 to 30% by weight. When the content exceeds 40% by weight, the fluidity of the toner may be lowered.

The resin particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. A thermosetting resin may be used. Specific examples include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like. Among these, one or more resins selected from the group consisting of vinyl resins, polyurethane resins, epoxy resins, and polyester resins are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained. These may be used alone or in combination of two or more.
The vinyl resin is a resin obtained by homopolymerizing or copolymerizing a vinyl monomer. Specifically, a styrene- (meth) acrylic acid ester copolymer, a styrene-butadiene copolymer, (meth) Acrylic acid-acrylic acid ester polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

  Moreover, as the resin particles, a copolymer obtained by polymerizing a monomer having a plurality of unsaturated groups can also be used. The monomer having a plurality of unsaturated groups can be appropriately selected according to the purpose. Specifically, sodium salt eleminol RS-30 of methacrylic acid ethylene oxide adduct sulfate (manufactured by Sanyo Chemical Industries), divinylbenzene 1,6-hexanediol diacrylate and the like.

  The resin particles can be obtained by polymerization using a known method, but are preferably used as an aqueous dispersion of resin particles. As a method for preparing an aqueous dispersion of resin particles, in the case of a vinyl resin, an aqueous dispersion of resin particles is obtained by polymerizing a vinyl monomer using a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method. In the case of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, a precursor such as a monomer or oligomer or a solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant. After that, heating or adding a curing agent to cure, a method for producing an aqueous dispersion of resin particles, a precursor such as a monomer or oligomer, or an appropriate emulsifier is dissolved in the solution, and then water is added. Method of phase inversion emulsification: Resin is pulverized and classified using a mechanical pulverizer or jet pulverizer to obtain resin particles, which are then dispersed in water in the presence of an appropriate dispersant. After obtaining resin particles by spraying a resin solution in the form of a mist, the resin particles are dispersed in water in the presence of an appropriate dispersant, a poor solvent is added to the resin solution, or the solvent is heated. By cooling the dissolved resin solution, the resin particles are precipitated, and after removing the solvent to obtain resin particles, a method of dispersing the resin particles in water in the presence of an appropriate dispersant, a resin solution, Disperse in an aqueous medium in the presence of an appropriate dispersant, then remove the solvent by heating, reduced pressure, etc., dissolve an appropriate emulsifier in the resin solution, and then add water to emulsify the phase. Methods and the like.

Inorganic particles may be used as the fluidity improver. The inorganic particles can be appropriately selected from known ones according to the purpose. Specifically, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, oxidation Zinc, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, nitride Silicon etc. are mentioned. These may be used alone or in combination of two or more.
The primary particle diameter of the inorganic particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method of an inorganic particle is 20-500 m < ² > / g.
The content of inorganic particles in the toner is preferably 0.01 to 5.0% by weight, more preferably 0.01 to 5.0% by weight.

  When surface treatment is performed using a fluidity improver, the hydrophobicity of the toner surface is improved, and deterioration of fluidity and charging characteristics can be suppressed even under high humidity. Specific examples of fluidity improvers include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. Etc.

When the cleaning property improving agent is added to the toner, the transferred developer remaining on the photoreceptor or the primary transfer medium is easily removed. Specific examples of the cleaning improver include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, resin particles obtained using soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles. . The resin particles preferably have a narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 to 1 μm.
The magnetic material can be appropriately selected from known materials according to the purpose, and examples thereof include iron powder, magnetite, and ferrite. Among them, a white magnetic material is preferable in terms of color tone.

As an example of a toner production method, a method for forming toner base particles while producing an adhesive substrate will be described below. In such a method, preparation of an aqueous medium phase, preparation of an oil phase containing a toner composition (hereinafter also referred to as toner material), emulsification or dispersion of the toner material, formation of an adhesive substrate, removal of the solvent, activity Synthesis of a polymer having reactivity with a hydrogen group, synthesis of a compound having an active hydrogen group, and the like are performed.
The aqueous medium can be prepared by dispersing the resin particles in the aqueous medium. The addition amount of the resin particles in the aqueous medium is preferably 0.5 to 10% by weight.

The oil phase containing the toner material is prepared in a solvent by a compound having an active hydrogen group, a polymer having reactivity to the active hydrogen group, a rheology additive, a colorant, a release agent, a charge control agent, an unmodified material. The toner material such as polyester resin can be dissolved or dispersed.
In the toner material, components other than the unmodified polyester resin and / or the polymer having reactivity with active hydrogen groups may be added and mixed in the aqueous medium when the resin particles are dispersed in the aqueous medium. In addition, when the oil phase containing the toner material is added to the aqueous medium, it may be added to the aqueous medium.
The emulsification or dispersion of the toner material can be performed by dispersing an oil phase containing the toner material in an aqueous medium. Then, when the toner material is emulsified or dispersed, an adhesive base is formed by subjecting a compound having an active hydrogen group and a polymer having reactivity to the active hydrogen group to an extension reaction and / or a crosslinking reaction.

  Adhesive substrates such as urea-modified polyester-based resins contain, for example, an oil phase containing a polymer having reactivity with active hydrogen groups such as polyester prepolymers having isocyanate groups, and active hydrogen groups such as amines. The oil phase containing the toner material may have an active hydrogen group in advance. The oil phase may be emulsified or dispersed in an aqueous medium together with the compound to be produced, and then both may be subjected to an extension reaction and / or a crosslinking reaction in the aqueous medium. The oil phase containing the toner material may be emulsified or dispersed in an aqueous medium by emulsifying or dispersing it in an aqueous medium to which a compound is added, and subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium. Then, a compound having an active hydrogen group is added, and an extension reaction and / or a cross-linking reaction are performed in the aqueous medium from the particle interface. It may be. When both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, a urea-modified polyester resin is preferentially formed on the surface of the toner to be produced, and a concentration gradient of the urea-modified polyester resin can be provided in the toner.

  The reaction conditions for producing the adhesive substrate can be appropriately selected according to the combination of the polymer having reactivity with active hydrogen groups and the compound having active hydrogen groups. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours. The reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

  In a water-based medium, a method for stably forming a dispersion containing a polymer capable of reacting with an active hydrogen group such as a polyester prepolymer having an isocyanate group includes a reaction with an active hydrogen group in the aqueous medium phase. Examples thereof include a method of adding an oil phase prepared by dissolving or dispersing a toner material such as a polymer, a colorant, a release agent, a charge control agent, and an unmodified polyester resin in a solvent, and dispersing by shearing force.

The emulsification / dispersion can be performed using a known disperser, etc., and the dispersers include a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, and an ultrasonic disperser. However, since the particle diameter of the dispersion can be controlled to 2 to 20 μm, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, it is necessary to select conditions such as the rotational speed, dispersion time, dispersion temperature, etc. that make ΔDv appropriate. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. The dispersion time may be changed according to the purpose, and is generally preferably about 0.1 to 30 minutes. The dispersion temperature is preferably 0 to 150 ° C, more preferably 20 to 98 ° C under pressure. The dispersion temperature is generally easier to disperse when the temperature is higher.

The amount of the aqueous medium used when emulsifying or dispersing the toner material is preferably 50 to 2000 parts by weight, and more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the toner material. When the amount used is less than 50 parts by weight, the dispersion state of the toner material is deteriorated, and toner base particles having a predetermined particle diameter may not be obtained. When the amount used exceeds 2000 parts by weight, the target ΔDv is It may be difficult to obtain and the production cost may increase.
In the step of emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoints of stabilizing the dispersion such as oil droplets to obtain a desired shape and sharpening the particle size distribution.

  In the present invention, the aqueous medium preferably contains a polymer dispersant. The polymer dispersant is preferably a water-soluble polymer. The water-soluble polymer can be appropriately selected from known ones, and examples thereof include sodium carboxymethyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol. These may be used alone or in combination of two or more.

The dispersant can be appropriately selected according to the purpose, and examples thereof include surfactants, sparingly water-soluble inorganic compound dispersants, and polymeric protective colloids, and surfactants are preferred. These may be used alone or in combination of two or more.
As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used.

  Examples of the anionic surfactant include alkylbenzene sulfonate, α-olefin sulfonate, phosphate ester, and the like, and those having a fluoroalkyl group are preferably used. As an anionic surfactant having a fluoroalkyl group, a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6-C11) oxy ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid or Its metal salt, perfluoroalkylcarboxylic acid (C7 to C13) or its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid or its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2 -Hydroxyethyl) perfluorooctance Examples include sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate. Commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.), Fluorard FC-93, FC-95, FC-98, FC-129. (Above, manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F- 833 (above, manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products), Footage 100, 150 (above, manufactured by Neos).

  As cationic surfactants, amine salt type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts And quaternary ammonium salt type surfactants such as alkylisoquinolinium salts and benzethonium chloride. Among them, aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzalkonium salts, benzethonium chloride, Examples include pyridinium salts and imidazolinium salts. Commercially available cationic surfactants include Surflon S-121 (Asahi Glass Co., Ltd.); Florard FC-135 (Sumitomo 3M Co.); Unidyne DS-202 (Daikin Kogyo Co., Ltd.), MegaFuck F-150, F -824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products);

Examples of nonionic surfactants include fatty acid amide derivatives and polyhydric alcohol derivatives.
Specific examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

Specific examples of the hardly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Polymeric protective colloids include monomers having carboxyl groups, alkyl (meth) acrylates having hydroxyl groups, vinyl ethers, vinyl carboxylates, amide monomers, acid chloride monomers, monomers having nitrogen atoms or heterocyclic rings thereof, and the like. Examples thereof include homopolymers or copolymers obtained by polymerization, polyoxyethylene resins, and celluloses. In addition, the homopolymer or copolymer obtained by polymerizing the above monomers includes those having a structural unit derived from vinyl alcohol.

  Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride and the like. Specific examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Is mentioned. Specific examples of vinyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether and the like. Specific examples of vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate and the like. Specific examples of the amide monomer include acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like. Specific examples of the acid chloride monomer include acrylic acid chloride and methacrylic acid chloride. Specific examples of the monomer having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethyleneimine. Specific examples of the polyoxyethylene-based resin include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, Examples include polyoxyethylene lauryl phenyl ether, polyoxyethylene phenyl stearate, and polyoxyethylene pelargonate phenyl. Specific examples of celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

When calcium phosphate is used as the dispersant, the calcium phosphate salt can be removed by dissolving the calcium salt with hydrochloric acid or the like and washing it with water or decomposing with an enzyme.
A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the adhesive substrate. Specific examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

As a method for removing the organic solvent from the dispersion liquid such as an emulsified slurry, the temperature of the entire reaction system is gradually raised to evaporate the organic solvent in the oil droplets, and the dispersion liquid is sprayed in a dry atmosphere to obtain the oil. Examples include a method of removing the organic solvent in the droplets.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. Classification may be performed by removing fine particle portions by a cyclone, decanter, centrifugation, or the like in the liquid, or classification may be performed after drying.

The obtained toner base particles may be mixed with particles such as a colorant, a release agent, and a charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent particles such as a release agent from detaching from the surface of the toner base particles.
As a method of applying mechanical impact force, a method of applying impact force to a mixture using a blade rotating at a high speed, throwing the mixture into a high-speed air current, and accelerating the particles or particles to an appropriate collision plate The method of making it collide etc. is mentioned. As an apparatus used in this method, an Ong mill (manufactured by Hosokawa Micron Corporation), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure are lowered, a hybridization system (manufactured by Nara Machinery Co., Ltd.) Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

The toner of the present invention is manufactured using the toner manufacturing method of the present invention.
Since the toner of the present invention has a smooth surface, it has excellent properties such as transferability and chargeability, and can form a high-quality image. Further, when the toner of the present invention contains an adhesive substrate obtained by reacting a compound having an active hydrogen group with a polymer having reactivity to the active hydrogen group in an aqueous medium, the transferability and fixability are improved. Further excellent properties such as Therefore, the toner of the present invention can be used in various fields and can be suitably used for image formation by electrophotography.

  The developer of the present invention contains the toner of the present invention, and may further contain other components appropriately selected such as a carrier. For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.

When the developer of the present invention is used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, the blade for thinning the toner, etc. Therefore, good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer of the present invention is used as a two-component developer, there is little fluctuation in the particle diameter of the toner even if the toner balance is maintained over a long period of time, and good and stable developability even with long-term agitation in the developing device. An image is obtained.

The carrier can be appropriately selected according to the purpose, but a carrier having a core material and a resin layer covering the core material is preferable.
The material of the core material can be appropriately selected from known materials, and examples thereof include 50 to 90 emu / g manganese-strontium-based material, manganese-magnesium-based material, and the like. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g. In addition, it is preferable to use a low-magnetization material such as 30-80 emu / g of copper-zinc system because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for high image quality. . These may be used alone or in combination of two or more.

  The volume average particle diameter of the core material is preferably 10 to 150 μm, and more preferably 40 to 100 μm. If the volume average particle size is less than 10 μm, fine particles are increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. If it exceeds 150 μm, the specific surface area is decreased, and In the case of a full color with many solid portions, the reproduction of the solid portions may be deteriorated.

  The material of the resin layer can be appropriately selected from known resins according to the purpose, but amino resin, polyvinyl resin, polystyrene resin, polyhalogenated olefin, polyester resin, polycarbonate resin, polyethylene , Polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Examples include fluoroterpolymers such as copolymers of monomers having no fluoro group, silicone resins, and the like. These may be used alone or in combination of two or more.

  Specific examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Specific examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Specific examples of the polystyrene resin include polystyrene and styrene-acrylic copolymer. Specific examples of the polyhalogenated olefin include polyvinyl chloride. Specific examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.

The resin layer may contain conductive powder or the like as necessary. Specific examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of the conductive powder is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control the electric resistance.
The resin layer can be formed by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then applying and drying the coating solution on the surface of the core using a known coating method, followed by baking. it can. As a coating method, a dip coating method, a spray method, a brush coating method, or the like can be used. The solvent can be appropriately selected depending on the purpose, and examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and butyl cellosolve. The baking may be an external heating method or an internal heating method, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, a method using a microwave, or the like. Is mentioned.

The content of the resin layer in the carrier is preferably 0.01 to 5.0% by weight. When this content is less than 0.01% by weight, a uniform resin layer may not be formed on the surface of the core material. May occur, and the uniformity of the carrier may be reduced.
The content of the carrier in the two-component developer is preferably 90 to 98% by weight, and more preferably 93 to 97% by weight.
The developer of the present invention can be used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

The toner-containing container of the present invention has the toner of the present invention. The toner-containing container of the present invention includes the case of having the developer of the present invention.
The container of the toner container can be appropriately selected from known containers, and those having a container body and a cap are preferably used.
The size, shape, structure, material and the like of the container body can be appropriately selected according to the purpose.
The shape is preferably cylindrical or the like, and preferably has spiral irregularities formed on the inner peripheral surface, and part or all of the spiral portion has a bellows function. By rotating such a container main body, the toner as the contents can be transferred to the discharge port side.
The material of the container body is preferably a material with good dimensional accuracy, and examples thereof include resins such as polyester resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.
The toner-containing container of the present invention can be easily stored and transported, has excellent handleability, and can be removably attached to a process cartridge, an image forming apparatus or the like to supply toner.

The process cartridge of the present invention has a developing means and an image carrier having the developer of the present invention, and may further have other means appropriately selected as necessary. As a result, the electrostatic latent image carried on the image carrier can be developed using the developer to form a visible image.
The developing means preferably includes the toner-containing container of the present invention and a developer carrier for carrying and transporting the developer, and further includes a layer thickness regulating member for regulating the thickness of the toner layer to be carried. May be.
The process cartridge of the present invention can be detachably attached to the image forming apparatus main body.

The image forming method of the present invention forms an image using the developer of the present invention. For this reason, high image quality can be obtained efficiently.
The image forming method of the present invention preferably includes an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step. If necessary, a static elimination step, a cleaning step, a recycling step, a control step, etc. You may have a process further.

An image forming apparatus for forming an image using the developer of the present invention includes an image carrier, an electrostatic latent image forming unit, a developing unit having the developer of the present invention, a transfer unit, and a fixing unit. Preferably, it may further include means such as a static elimination means, a cleaning means, a recycling means, and a control means as necessary.
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the image carrier. The material, shape, structure, size and the like of the image carrier can be appropriately selected from known ones. Examples of the material include inorganic substances such as amorphous silicon and selenium, and organic substances such as polysilane and phthalopolymethine. Amorphous silicon is preferable because of its long life. Further, the shape is preferably a drum shape. The electrostatic latent image can be formed by uniformly charging the surface of the image carrier and then exposing it imagewise, and can be performed by an electrostatic latent image forming unit. The electrostatic latent image forming means preferably has a charger that uniformly charges the surface of the image carrier and an exposure device that exposes the surface of the image carrier.

Charging can be performed by applying a voltage to the surface of the image carrier using a charger. The charger can be appropriately selected according to the purpose, but a known contact charger equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc., or corona discharge such as corotron or scorotron is used. Non-contact chargers and the like.
The exposure can be performed by exposing the surface of the image carrier using an exposure device. The exposure device can be appropriately selected according to the purpose, but various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used. It should be noted that an optical back side system in which exposure is performed from the back side of the image carrier may be adopted.

  The development step is a step of forming a visible image by developing the electrostatic latent image using the developer of the present invention. The visible image can be formed using a developing unit. The developing means can be appropriately selected from known ones, and preferably has a developing device that accommodates the developer of the present invention and can apply the developer to the electrostatic latent image in a contact or non-contact manner. As the developing device, it is preferable to use a developing device provided with the toner container of the present invention. The developing device may be a dry development system or a wet development system. Further, it may be a single color developer or a multicolor developer. Specifically, a stirrer for charging the developer by friction stirring and a developer having a rotatable magnet roller can be used. The developer accommodated in the developing device is the developer of the present invention, but may be a one-component developer or a two-component developer.

  In a developing device having a two-component developer, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a visible image is formed with toner on the surface of the image carrier.

The transfer step is a step of transferring a visible image to a recording medium. The intermediate transfer member is used to primarily transfer the visible image onto the intermediate transfer member, and then the secondary transfer of the visible image onto the recording medium. It is preferable. At this time, the toner used is usually two or more colors, and it is preferable to use a full-color toner. For this reason, it is more preferable to have a primary transfer process in which a visible image is transferred onto an intermediate transfer member to form a composite transfer image, and a secondary transfer process in which the composite transfer image is transferred onto a recording medium.
The transfer can be performed by charging the image carrier using a transfer unit. The transfer means preferably has a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. The intermediate transfer member can be appropriately selected from known transfer members according to the purpose, and a transfer belt or the like can be used.

  The transfer means preferably has a transfer device that peels and charges the visible image formed on the image carrier to the recording medium side. There may be one transfer means or a plurality of transfer means. Specific examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium can be appropriately selected from known recording media, and recording paper or the like can be used.

  The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be fixed each time the toner of each color is transferred to the recording medium, or each color toner is laminated. You may fix at once in the state. The fixing unit can be appropriately selected according to the purpose, but a known heating and pressing unit can be used. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressurizing means is usually preferably 80 ° C to 200 ° C. A known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

The neutralization step is a step of neutralizing by applying a neutralization bias to the image carrier, and can be performed using a neutralization unit. The neutralization means can be appropriately selected from known neutralizers, and a neutralization lamp or the like can be used.
The cleaning step is a step of removing toner remaining on the image carrier, and can be performed using a cleaning unit. The cleaning means can be appropriately selected from known cleaners, and a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner, or the like can be used.

The recycling process is a process in which the toner removed in the cleaning process is recycled by the developing unit, and can be performed using the recycling unit. The recycling means can be appropriately selected according to the purpose, and a known conveying means or the like can be used.
The control means is a process for controlling each process, and can be performed using the control means. The control means can be appropriately selected according to the purpose, and devices such as a sequencer and a computer can be used.

  One mode of carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. An image forming apparatus 800 shown in FIG. 2 includes a photosensitive drum 810 (hereinafter referred to as “photosensitive member 810”) as the electrostatic latent image carrier, a charging roller 820 as the charging unit, and an exposure as the exposure unit. The apparatus 830 includes a developing device 840 as the developing means, an intermediate transfer member 850, a cleaning device 860 as the cleaning means having a cleaning blade, and a static elimination lamp 870 as the static elimination means.

  The intermediate transfer member 850 is an endless belt, and is designed to be movable in the direction of an arrow in the figure by three rollers 851 that are arranged on the inner side and stretch the belt. Part of the three rollers 851 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 850. An intermediate transfer body cleaning blade 890 is disposed in the vicinity of the intermediate transfer body 850, and a transfer bias for transferring (secondary transfer) a visible image (toner image) to the recording medium 895 is applied. Possible transfer rollers 880 as the transfer means are arranged to face each other. Around the intermediate transfer member 850, a corona charger 858 for applying a charge to the visible image on the intermediate transfer member 850 is arranged with the electrostatic latent image carrier 810 in the rotation direction of the intermediate transfer member 850. It is disposed between a contact portion with the intermediate transfer member 850 and a contact portion between the intermediate transfer member 850 and the recording medium 895.

  The developing device 840 includes a developing belt 841 as a developer carrier and a black developing unit 845K, a yellow developing unit 845Y, a magenta developing unit 845M, and a cyan developing unit 845C provided around the developing belt 841. Yes. The black developing unit 845K includes a developer containing portion 842K, a developer supply roller 843K, and a developing roller 844K. The yellow developing unit 845Y includes a developer accommodating portion 842Y, a developer supply roller 843Y, and a developing roller 844Y. The magenta developing unit 845M includes a developer accommodating portion 842M, a developer supply roller 843M, and a developing roller 844M. The cyan developing unit 845C includes a developer accommodating portion 842C, a developer supply roller 843C, and a developing roller 844C. Further, the developing belt 841 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 810.

  In the image forming apparatus 800 illustrated in FIG. 2, for example, the charging roller 820 uniformly charges the photosensitive drum 810. The exposure device 830 performs imagewise exposure on the photosensitive drum 810 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 810 is supplied with toner from the developing device 840 and developed to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer body 850 by the voltage applied from the roller 851, and further transferred onto the transfer paper 895 (secondary transfer). As a result, a transfer image is formed on the transfer paper 895. The residual toner on the photoconductor 810 is removed by the cleaning device 860, and the charge on the photoconductor 810 is temporarily removed by the charge eliminating lamp 870.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The image forming apparatus 900 shown in FIG. 3 does not include the developing belt 841 in the image forming apparatus 800 shown in FIG. 2, and a black developing unit 845K, a yellow developing unit 845Y, a magenta developing unit 845M, and the like around the photoconductor 810. Except for the fact that the cyan developing unit 845C is arranged directly opposite, it has the same configuration as the image forming apparatus 800 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 4 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The copying machine main body 150 is provided with an endless belt-shaped intermediate transfer member 1050 at the center. The intermediate transfer member 1050 is stretched around support rollers 1014, 1015, and 1016 and can rotate clockwise in FIG. 4. An intermediate transfer body cleaning device 1017 for removing residual toner on the intermediate transfer body 1050 is disposed in the vicinity of the support roller 1015. The intermediate transfer member 1050 stretched by the support roller 1014 and the support roller 1015 has a tandem type in which four image forming units 1018 of yellow, cyan, magenta, and black face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 1021 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 1022 is disposed on the side of the intermediate transfer body 1050 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 1022, a secondary transfer belt 1024, which is an endless belt, is stretched around a pair of rollers 1023, and the transfer sheet conveyed on the secondary transfer belt 1024 and the intermediate transfer body 1050 are in contact with each other. Is possible. A fixing device 1025 is disposed in the vicinity of the secondary transfer device 1022. The fixing device 1025 includes a fixing belt 1026 that is an endless belt, and a pressure roller 1027 that is pressed against the fixing belt 1026.

  In the tandem image forming apparatus, a sheet reversing device 1028 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 1022 and the fixing device 1025. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 1032 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when a document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 1032 and then the document is set on the contact glass 1032. Immediately after that, the scanner 300 is driven, and the first traveling body 1033 and the second traveling body 1034 travel. At this time, the light from the light source is emitted from the first traveling body 1033 and the reflected light from the document surface is reflected by the mirror in the second traveling body 1034 and is received by the reading sensor 1036 through the imaging lens 1035 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 1018 (black image forming unit, yellow image forming unit, magenta image forming unit, cyan image) in the tandem developing unit 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 1018 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing means 120 is a static image as shown in FIG. An electrostatic latent image carrier 1110 (an electrostatic latent image carrier for black 1010K, an electrostatic latent image carrier for yellow 1010Y, an electrostatic latent image carrier for magenta 1010M, and an electrostatic latent image carrier for cyan 1010C); The electrostatic latent image carrier 1110 is uniformly charged, and the electrostatic latent image carrier is exposed for each color image corresponding image based on each color image information (L in FIG. 5). An exposure apparatus for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image for each color toner (black toner, yellow toner, magenta toner, and the like). A developing device 61 that develops the toner image using each color toner by developing with a cyan toner, a transfer charger 1062 for transferring the toner image onto the intermediate transfer body 1050, a cleaning device 63, and a static eliminator. 64, each monochrome image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to an electrostatic latent image carrier 1010K for black on an intermediate transfer member 1050 that is rotated by support rollers 1014, 1015, and 1016. The black image formed above, the yellow image formed on the yellow electrostatic latent image carrier 1010Y, the magenta image formed on the magenta electrostatic latent image carrier 1010M, and the electrostatic latent image carrier for cyan The cyan image formed on 1010C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 1050 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one and sent to the sheet feeding path 146, conveyed by the conveying roller 147, guided to the sheet feeding path 148 in the copying machine main body 150, and abutted against the registration roller 1049 to stop. Alternatively, the sheet feeding roller 142 is rotated to feed out the sheets (recording paper) on the manual feed tray 1054, separated one by one by the separation roller 1058, put into the manual feed path 1053, and abutted against the registration roller 1049 and stopped. . The registration roller 1049 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 1049 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 1050, and a sheet (recording paper) is interposed between the intermediate transfer member 1050 and the secondary transfer device 1022. And transferring the composite color image (color transfer image) onto the sheet (recording paper) by the secondary transfer device 1022, thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 1050 after the image transfer is cleaned by the intermediate transfer member cleaning device 1017.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 1022 and sent to the fixing device 1025, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 1055 and discharged by the discharge roller 1056 and stacked on the paper discharge tray 1057 or switched by the switching claw 1055 and reversed by the sheet reversing device 1028 and transferred again. After being guided to the position and recording an image on the back side, it is discharged by the discharge roller 1056 and stacked on the discharge tray 1057.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. In addition, a part means a weight part in an Example.

(Preparation of non-reactive resin)
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. for 7 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 4 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. (Nonreactive Resin 1) Was synthesized.
The obtained (Nonreactive Resin 1) had a weight average molecular weight of 5040, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.

Comparative Example 1 (Production of Toner 1)
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 (non-reactive resin 1) were used with a Henschel mixer (manufactured by Mitsui Mining). And mixed. 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 (Masterbatch 1).

In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of (non-reactive resin 1), 110 parts of carnauba wax, and 947 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining the time, it was 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 wt% ethyl acetate solution of (non-reactive resin 1) was added to the wax dispersion. To 200 parts of the dispersion obtained in one pass using Ultraviscomil under the same conditions as above, 2.0 parts of Kraton APA (manufactured by Southern Clay Products), a modified layered inorganic mineral, is added as a viscosity modifier. T. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred at 7000 rpm for 60 minutes 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 2,100, a weight 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 weight.

  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 toner material dispersion, 40 parts of ethyl acetate, 115 parts of a prepolymer and 2.9 parts of a ketimine compound are charged and mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika). As a result, an oil phase mixture (A) 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 weight aqueous ammonium persulfate solution was added and aged at 75 ° C. for 5 hours to prepare a resin particle dispersion.

  The volume average particle size of the resin particles contained in the obtained resin particle dispersion was measured using a particle size distribution measuring apparatus Microtrac Ultra Fine Particle Size Distribution Meter UPA-EX150 (manufactured by Nikkiso Co., Ltd.) using a laser Doppler method. However, it was 105 nm. Further, a part of the resin particle dispersion was dried to isolate the resin, and the glass transition temperature of the resin was measured. As a result, it was 59 ° C. and the weight average molecular weight was 150,000.

  990 parts of water, 83 parts of resin particle dispersion, 37 parts of a 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Kasei Kogyo Co., Ltd.), 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 (A) was added and mixed for 6 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsion slurry).
As for the particle diameter during emulsification, 80 ml of ion-exchanged water is added to a glass 100 ml beaker as described in the measuring method every minute. Oil droplets being emulsified / dispersed are poured into the ion-exchanged water immediately after sampling, instantaneous solvent removal is performed, the particle size is confirmed, and the dispersion is measured using the Multisizer III. Measurement was performed using Isoton III (manufactured by Beckman Coulter, Inc.) as the solution. The measurement was performed by dropping the toner sample dispersion so that the concentration indicated by the apparatus was 8 ± 2%. Table 1 shows the particle size for each hour when mixed at 13000 rpm for 20 minutes.
When a dispersion is prepared by mixing at 13000 rpm for 6 minutes, the particle size after 6 minutes is minimized from the measurement result of the particle size during the above emulsification, and then the particle size increases by stopping the stirring. . Therefore, Dv1 = 5.2 μm.

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.
The volume average particle size of the toner in the obtained dispersion slurry was measured to obtain Dv2.

After 100 parts by weight 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.
The obtained filter cake was added with 10% by weight phosphoric acid to adjust the pH to 3.7, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered.
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 obtained toner base particles, 1.0 part of hydrophobic silica as an external additive and 0.5 part of hydrophobized titanium oxide are added and mixed using a Henschel mixer (Mitsui Mining Co., Ltd.). Toner 1 was manufactured.

Examples 1 to 3 and Comparative Example 2 (Production of Toners 2 to 5)
Comparison except that the oil phase mixture was added to the aqueous medium at 13000 rpm for 8 minutes (toner 2), 10 minutes (toner 3), 15 minutes (toner 4), and 20 minutes (toner 5). In the same manner as in Example 1, toners 2 to 5 were produced.

Example 4 (Production of Toner 6)
Toner 6 was prepared in the same manner as toners 1 to 5 except for the following.
In a reaction vessel, 749 parts of a dispersion of toner material, 0 parts of ethyl acetate, 115 parts of a prepolymer and 2.9 parts of a ketimine compound are charged, and mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika). As a result, an oil phase mixture (B) was obtained.
Further, 867 parts of the oil phase mixed liquid (B) was added to 1200 parts of the aqueous medium, and mixed at 13000 rpm for 20 minutes using a TK homomixer to prepare a dispersion (emulsion slurry).
Also for this, the particle diameter was confirmed every 1 min, but the particle diameter after mixing for 20 minutes was the smallest and Dv1 = 3.1 μm.

Example 5 and Comparative Example 3 (Production of Toners 7 and 8)
Toners 7 and 8 were produced in the same manner as toners 1 to 5 except for the following.
In a reaction vessel, 749 parts of a dispersion of toner material, 80 parts of ethyl acetate, 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). As a result, an oil phase mixture (C) was obtained.
Further, 867 parts of the oil phase mixed liquid is added to 1200 parts of the aqueous medium, and the dispersion liquid (emulsified slurry) is mixed by using a TK homomixer at 13000 rpm for 6 minutes (toner 7) and 11 minutes (toner 8). Prepared.
The results of confirming the particle size every 1 min are also shown in Table 2.

表２より、粒径が一番小さくなるのは、混合５分後であり、トナー７、８のＤｖ１はどちらも３．９μｍである。

From Table 2, the smallest particle size is after 5 minutes of mixing, and the Dv1 of the toners 7 and 8 are both 3.9 μm.

Example 6 (Preparation of toner 9)
Toner 9 was prepared in the same manner as toners 1 to 5 except for the following.
To the wax dispersion, 1324 parts of a 65 wt% ethyl acetate solution of (non-reactive resin 1) was added. In 200 parts of a dispersion obtained by one pass using Ultraviscomil under the same conditions as those of toners 1 to 5, Kraton APA (manufactured by Southern Clay Products) 5.0 which is a modified layered inorganic mineral as a viscosity modifier. Part, and T. K. The oil phase mixture (D) was prepared in the same manner as in the preparation of the toners 1 to 5 except that the mixture was stirred for 60 minutes at 7000 rpm using a homodisper (manufactured by Koki Kogyo Co., Ltd.) to obtain a dispersion of the toner material. Obtained.
Moreover, 867 parts of oil phase liquid mixture (D) was added to 1200 parts of aqueous media, and it mixed for 10 minutes at 13000 rpm using the TK type homomixer, and prepared the dispersion liquid (emulsion slurry).
Also for this, the particle size was confirmed every 1 min, but the particle size after mixing for 10 minutes was the smallest and Dv1 = 4.4 μm.

Example 7 (Production of Toner 10)
Toner 10 was prepared in the same manner as toners 1 to 5 except for the following.
To the wax dispersion, 1300 parts of a 65 wt% ethyl acetate solution of (non-reactive resin 1) was added. MEK-ST (manufactured by Nissan Chemical Industries, Ltd., solid content 20%) 35.0 as a viscosity modifier was added to 200 parts of a dispersion obtained by one pass using Ultraviscomil under the same conditions as those of toners 1 to 5. Part, and T. K. The oil phase mixture (E) was prepared in the same manner as in the preparation of the toners 1 to 5 except that the mixture was stirred at 7000 rpm for 60 minutes using a homodisper (manufactured by Koki Kogyo Co., Ltd.) to obtain a dispersion of the toner material. Obtained.
Moreover, 867 parts of oil phase liquid mixture (E) was added to 1200 parts of aqueous media, and it mixed for 10 minutes at 13000 rpm using the TK type homomixer, and prepared the dispersion liquid (emulsion slurry).
Also for this, the particle size was confirmed every 1 min, but the particle size after mixing for 10 minutes was the smallest and Dv1 = 4.2 μm.

Comparative Example 4 (Production of Toner 11)
Toner 11 was prepared in the same manner as toners 1 to 5 except for the following.
To the wax dispersion, 1300 parts of a 65 wt% ethyl acetate solution of (non-reactive resin 1) was added. To 200 parts of the dispersion obtained by one pass using Ultraviscomil under the same conditions as in Toners 1 to 5, T.P. K. The oil phase mixture (F) was prepared in the same manner as in the preparation of the toners 1 to 5 except that the mixture was stirred at 7000 rpm for 60 minutes using a homodisper (manufactured by Koki Kogyo Co., Ltd.) to obtain a dispersion of the toner material. Obtained.
Moreover, 867 parts of oil phase liquid mixture (F) was added to 1200 parts of aqueous medium, and it mixed for 10 minutes at 13000 rpm using the TK type | mold homomixer, and prepared the dispersion liquid (emulsion slurry).
Also for this, the particle size was confirmed every 1 min, but the particle size after mixing for 10 minutes was the smallest and Dv1 = 5.3 μm.

The toner was evaluated as follows.
(Cleanability)
The cleaning property was evaluated as follows.
After printing 100,000 sheets using Ricoh's Imagio NEO C600PRO, the remaining toner on the photoconductor after passing through the cleaning process is transferred to white paper using Scotch tape (manufactured by Sumitomo 3M), and the Macbeth reflection densitometer. Measured with the RD514 type, those having a difference from the blank of 0.01 or less were judged as good (◯), and those exceeding 0.01 were judged as bad (x).

(Filming)
After the cleaning property evaluation (after printing 100,000 sheets), all solid images were output, and it was confirmed whether there was any image omission. If filming has occurred on the photoconductor, image omission occurs and becomes a problem.
The case where the image was clearly missing was judged as x, the case where the density unevenness was generated but the image was not greatly affected was judged as Δ, and the case where there was no problem was judged as ○.

(Toner scattering)
After the cleaning / filming evaluation, 100 sheets of blank paper were printed, and images were confirmed / scattered in the machine.
When there is clearly toner due to scattering on 100 blank pages
Even if there is no occurrence in the image, △
The ones with no problems were marked with ○.

The physical properties and evaluation results of each toner are as follows.

6 is a graph showing changes in volume average particle diameter of toner particles during emulsification / dispersion in an aqueous medium. 1 is a schematic view of an example of an image forming apparatus of the present invention. It is the schematic of the other example of the image forming apparatus of this invention. It is the schematic of the other example of the image forming apparatus of this invention. FIG. 5 is a schematic diagram illustrating a part of the image forming apparatus illustrated in FIG. 4.

Explanation of symbols

810 Photoconductor (Photoconductor drum)
1010K electrostatic latent image carrier for black 1010Y electrostatic latent image carrier for yellow 1010M electrostatic latent image carrier for magenta 1010C electrostatic latent image carrier for cyan 1014 support roller 1015 support roller 1016 support roller 1017 intermediate transfer cleaning device 1018 Image forming means 820 Charging roller 1021 Exposure device 1022 Secondary transfer device 1023 Roller 1024 Secondary transfer belt 1025 Fixing device 1026 Fixing belt 1027 Pressure roller 1028 Sheet reversing device 830 Exposure device 1032 Contact glass 1033 First traveling body 1034 Second Traveling body 1035 Imaging lens 1036 Reading sensor 840 Developing device 841 Developing belt 842K Developer container 842Y Developer container 842M Developer container 842C Developer container 8 3K developer supply roller 843Y developer supply roller 843M developer supply roller 843C developer supply roller 844K development roller 844Y development roller 844M development roller 844C development roller 845K black development unit 845Y yellow development unit 845M magenta development unit 845C cyan Development unit 1049 Registration roller 850 Intermediate transfer member 1050 Intermediate transfer member 851 Roller 1052 Separation roller 1053 Manual feed path 1054 Manual feed tray 1055 Switching claw 1056 Discharge roller 1057 Discharge tray 858 Corona charger 1058 Separation roller 860 Cleaning device 61 Development device 1062 Transfer Charger 63 Cleaning device 64 Charger 870 Charger lamp 880 Transfer roller 890 Cleaner Guburedo 895 transfer paper (recording medium)
800 Image forming apparatus 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier main body 160 Charging device 200 Paper feed table 300 Scanner 400 Automatic Document Feeder (ADF)

Claims (22)

A method for producing a toner comprising granulating a toner by emulsifying / dispersing an oil phase containing at least a binder resin and / or a binder resin precursor in an aqueous medium,
The difference ΔDv between the volume average particle diameter Dv1 that is the minimum of the toner being granulated during emulsification / dispersion and the volume average particle diameter Dv2 of the granulated toner after emulsification / dispersion is 0.5 to 3.0 μm. And the average circularity of the granulated toner is 0.925 to 0.970, and the ratio Dv / Dn of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00 to 1. A method for producing toner, which is 1.30.   The toner manufacturing method uses an oil phase which is a solution and / or a dispersion obtained by dissolving and / or dispersing a toner composition containing at least a binder resin and / or a binder resin precursor in an organic solvent. The toner production method according to claim 1, wherein:   The method for producing a toner according to claim 1, wherein inorganic particles are contained in the oil phase.   4. The toner manufacturing method according to claim 3, wherein the inorganic fine particles have a layered inorganic mineral obtained by modifying at least a part of ions between layers of the layered inorganic mineral with an organic ion.   The method for producing a toner according to claim 4, wherein the oil phase contains 0.05 to 10 wt% of a layered inorganic mineral modified with organic ions in a solid content in the oil phase.   6. The toner according to claim 4, wherein the layered inorganic mineral modified with organic ions is a layered inorganic mineral in which at least a part of cations between layers of the layered inorganic mineral is modified with organic cations. Production method.   The method for producing a toner according to claim 1, wherein particles having a circularity of 0.950 or less are contained in an amount of 20 to 80% of all toner particles.   The ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner is 1.0 to 1.20. Toner manufacturing method.   The toner production method according to claim 1, wherein the toner has a particle diameter of 2 μm or less of 1 to 20% by number.   The method for producing a toner according to claim 1, wherein the binder resin contained in the toner contains at least two kinds of binder resins.   The method for producing a toner according to claim 10, wherein the first binder resin contained in the binder resin is a resin having a polyester skeleton.   The method for producing a toner according to claim 10, wherein the first binder resin is a polyester resin.   The method for producing a toner according to claim 12, wherein the polyester resin is an unmodified polyester resin.   The method for producing a toner according to claim 1, wherein the binder resin precursor is a modified polyester resin.   The toner production method is a solution in which a binder resin, a binder resin precursor, a compound that extends or crosslinks with the binder resin precursor, a colorant, and a release agent are dissolved or dispersed in at least an organic solvent. Alternatively, it is a method for producing a toner, in which an oil phase as a dispersion is emulsified / dispersed in an aqueous medium to cause a crosslinking reaction and / or elongation reaction, and the solvent is removed from the obtained dispersion to granulate the toner. The method for producing a toner according to claim 1, wherein:   A toner obtained by the method for producing a toner according to claim 1.   The toner according to claim 16, wherein the toner is used for a two-component developer.   A toner-containing container comprising the toner according to claim 16.   A developer containing the toner according to claim 16 or 17.   An image forming apparatus that forms an image using the developer according to claim 19.   20. A process cartridge comprising a developing unit having the developer according to claim 19 and an image carrier.   An image forming method comprising forming an image using the developer according to claim 19.

Images