JP2008233326A - Toner for electrostatic charge image development, method for manufacturing the same and image forming method using the toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oilless dry toner having excellent charging property with a less amount of a charge control agent, having high transfer property/charging property stability without filming, and to provide a toner and an image forming apparatus for obtaining a high quality image with excellent fine dot reproducibility. <P>SOLUTION: The toner is obtained by: dissolving or dispersing at least a binder resin and/or binder resin precursor, a colorant, a release agent and a layered inorganic mineral in which interlayer ions of the layered inorganic mineral are at least partially modified with organic ions, in an organic solvent; dispersing an oil phase comprising the above solution or dispersion liquid in an aqueous medium to obtain an emulsion dispersion liquid; and granulating toner particles from the emulsion dispersion liquid. The aqueous medium phase contains an active hydrogen-containing compound except water, which extends or crosslinks with the binder resin precursor. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  In recent years, the strong demand for higher image quality from the market has spurred the development of an electrophotographic apparatus suitable for it and a toner developer used therefor. As a toner corresponding to high image quality, it is essential that the toner has a uniform particle size. When the toner particle size is uniform and the particle size distribution becomes sharp, the behavior of individual toner particles during development is aligned, and the reproducibility of minute dots is remarkably improved.

  However, a toner having a smaller particle size and a uniform particle size is more difficult to clean than before. Particularly with blade cleaning, it is difficult to stably clean toner having a uniform and small particle diameter. Under such circumstances, various methods for improving the cleaning property by devising the toner have been proposed. One of them is a method for changing the toner particles from a spherical shape to an irregular shape. By changing the shape of the toner particles, the powder fluidity of the toner is reduced, and it is easy to stop by blade cleaning. However, if the degree of toner particle irregularity is too large, the behavior of the toner becomes unstable during development and the like, and the fine dot reproducibility deteriorates.

As described above, by changing the shape of the toner particles, the reliability of the toner with respect to the cleaning is certainly improved, but on the other hand, a defect is caused in terms of fixing. In other words, if the shape of the toner particles is irregular, the toner filling density in the toner layer on the transfer material before fixing becomes small, the thermal conductivity in the toner layer becomes slow during fixing, and the low-temperature fixability deteriorates. Resulting in. In particular, when the pressure at the time of fixing is smaller than the conventional pressure, the thermal conductivity is further deteriorated and the low-temperature fixing is hindered.
Patent Document 1 proposes a toner made of polyester having a Wadell practical sphericity of 0.90 to 1.00. However, since the toner is substantially spherical, the above-described problem of toner cleaning properties is solved. Not.

  In addition to suspension polymerization, there are emulsion polymerization methods and dissolution suspension methods that are relatively easy to modify, but also in the emulsion polymerization method, complete removal of styrene monomers and removal of emulsifiers and dispersants are possible. It is difficult, and the problem with toners is becoming increasingly greater as environmental problems have become particularly close. In addition, the toner particle shape is also made uneven so that silica adhering as a fluidizing agent is weakly attached to the concave portion of the toner particle and the silica is moved to the concave portion of the toner particle during use. Therefore, the problem of contamination of the photoconductor by toner and the problem of toner adhesion to the fixing roller are likely to occur. In addition, the dissolution suspension method has the advantage that a polyester resin that can be fixed at low temperature can be used, but in order to achieve oil-less fixing, the polymer and color are controlled during production and control of the polymer to widen the mold release width. Since the high molecular weight component is added in the step of dissolving or dispersing the agent in the solvent, the viscosity of the liquid rises and productivity problems are likely to occur. And those problems are not solved yet. In particular, in the solution suspension method, in Patent Document 2, the toner particle surface shape is made spherical and uneven to improve cleaning, but since it is an irregularly shaped toner with no regularity, charging stability In addition, a high-quality toner for ensuring basic durability and releasability has not been achieved, and satisfactory toner quality has not been obtained.

In order to control the charging of the toner, a large amount of charge adjusting agent is added. After melt-kneading a thermoplastic resin as a binder resin with a colorant and additives used as required. In the method of producing toner by pulverization and classification, so-called pulverization method, (1) There is a limit to reducing the toner particle diameter and the image quality becomes severe, and (2) each particle for kneading ⇒ pulverization Although it is possible to uniformly disperse the toner, it is impossible to control the arrangement of the materials in the toner particles. (3) When the amount of the charge control agent is increased in order to impart chargeability, a side effect on filming / fixing property occurs. A malfunction occurred.
In recent years, as shown in Cited Documents 3 to 6, modified layered inorganic minerals obtained by modifying some of the ions present between layers in layered inorganic minerals with organic ions have been proposed as charge control agents. This also has the above problems.

Japanese Patent Laid-Open No. 11-133665 JP 9-15903 A JP-T-2003-515795 Special table 2006-500605 gazette JP-T-2006-503313 Special table 2003-202708 gazette

The subject of this invention is as follows.
(1): An oilless dry toner having excellent chargeability with a small amount of charge adjusting agent is provided.
(2): An oilless dry toner having no filming and good transferability and chargeability stability is provided.
(3) To provide a toner and an image forming apparatus capable of obtaining a high-quality image with excellent fine dot reproducibility.
(4): Toner and image forming apparatus capable of achieving the same problems (1) to (3) are provided.

The present inventors have completed the present invention to solve the above-described problems. The present invention is as follows.
(1) “At least a binder resin and / or a binder resin precursor, a colorant, a release agent, and a layered inorganic mineral obtained by modifying at least part of ions between layers of a layered inorganic mineral with an organic ion in an organic solvent. A toner obtained by dissolving or dispersing in an aqueous solution and dispersing an oil phase composed of the solution or dispersion in an aqueous medium to obtain an emulsified dispersion, and granulating toner particles from the emulsified dispersion. A toner containing an active hydrogen-containing compound other than water that extends or crosslinks with the binder resin precursor in the aqueous medium phase ",
(2) "The toner according to item (1), wherein the active hydrogen-containing compound is an amine (excluding tertiary amine)",
(3) “The modified layered inorganic mineral is a layered inorganic mineral in which at least a part of cations between layers of the layered inorganic mineral is modified with an organic cation” (1) or ( Toner described in 2) ”,
(4) “The layered inorganic mineral obtained by modifying at least part of the ions between the layers with organic ions is contained in an amount of 0.1 to 5% in the solid content in the solution or dispersion. The toner according to any one of Items (1) to (3),
(5) "The toner according to any one of (1) to (4) above, wherein the binder resin is a polyester resin",
(6) "The toner according to any one of (1) to (5) above, wherein the binder resin precursor is a modified polyester resin";
(7) “The toner according to any one of (1) to (6) above, wherein the average circularity of the toner is 0.96 to 0.99”;
(8) “The toner according to any one of (1) to (7) above, wherein the toner has a volume average particle diameter of 3 to 7 μm”,
(9) "The toner according to any one of (1) to (8) above, wherein the volume particle diameter Dv / number average particle diameter Dn of the toner is 1.30 or less",
(10) “The toner according to any one of (1) to (9) above, wherein 1 to 20% by number of particles of 2 μm or less of the toner”
(11) Any one of (1) to (10) above, wherein the content of the polyester resin component contained in the binder resin in the binder resin is 50 to 100% by weight. Toner described in ","
(12) The toner according to any one of (1) to (11), wherein the polyester resin has a THF-soluble component having a weight average molecular weight of 1,000 to 30,000. "
(13) The toner according to any one of (1) to (12), wherein the acid value of the binder resin is 1.0 to 50.0 (KOHmg / g). "
(14) “The toner according to any one of (1) to (13) above, wherein the binder resin has a glass transition point of 35 to 65 ° C.”,
(15) “The binder resin precursor has a site capable of reacting with the active hydrogen group-containing compound, and the polymer of the binder resin precursor has a weight average molecular weight of 3,000 to 20,000. The toner according to any one of (1) to (14),
(16) The electrostatic image according to any one of (1) to (15), wherein the acid value of the toner is 0.5 to 40.0 (KOHmg / g). Toner for development ",
(17) “The toner for developing an electrostatic charge image according to any one of (1) to (16) above, wherein the toner has a glass transition point of 40 to 70 ° C.”,
(18) “Toner according to any one of (1) to (17) above, which is a toner used for a two-component developer”,
(19) "Developer comprising the toner according to any one of (1) to (18)",
(20) "Image forming apparatus characterized in that an image is formed using the developer according to item (19)",
(21) "An image forming method characterized by forming an image using the developer according to item (19)",
(22) “At least a binder resin and / or a binder resin precursor, a colorant, a release agent, and a layered inorganic mineral obtained by modifying at least part of ions between layers of a layered inorganic mineral with an organic ion in an organic solvent. The toner obtained by dissolving or dispersing in the solution, dispersing the oil phase comprising the solution or dispersion in an aqueous medium to obtain an emulsion dispersion, and granulating toner particles from the emulsion dispersion. And a method for producing a toner, wherein the aqueous medium phase contains an active hydrogen-containing compound other than water that extends or crosslinks with the binder resin precursor.

  According to the present invention, it is possible to provide an oilless dry toner having no filming and good transferability and chargeability stability.

The present invention has the following features.
Although the layered inorganic mineral is hydrophobic during granulation, depending on the type of interlayer ions, the amount of exchange of interlayer ions, etc., the water phase and the oil phase (the oil phase also varies depending on the polarity of the oil phase itself) The affinity is thought to change.
In the present invention, when particles for toner are granulated from a droplet-like oil phase in an aqueous dispersion, the layer is modified by organic ions between layers to a level suitable for being unevenly distributed near the surface inside the toner particles. In this way, uneven distribution near the surface of the toner is made possible. That is, the modified layered inorganic mineral has a characteristic that the movement from the aqueous phase to the surface side in the oil droplet occurs, and it tends to be unevenly distributed on the toner surface. When the amount of modification with organic ions between layers is small, the hydrophobicity of the layered inorganic mineral is insufficient, and it becomes difficult to separate the layered inorganic mineral from one layer to another, making it difficult to disperse in the toner particles. Not fully observed as a quantity.
When the amount of modification of the layered inorganic mineral with organic ions is increased, the ionic species are changed, or the surface treatment is performed to increase the hydrophobicity, the layered inorganic mineral is uniformly dispersed in the toner particles, There is a tendency to be unevenly distributed.
Generally, it is considered that the chargeability is greatly affected by the charge control agent on the surface of the toner particles. In fact, sufficient chargeability can be obtained by allowing a large amount of the modified layered inorganic mineral to be present on the surface.

From another viewpoint, in a so-called pulverized toner that undergoes a kneading step and a pulverizing step, the additive is uniformly dispersed in the toner particles in the kneading step. For this reason, surface uneven distribution hardly occurs. For this reason, it is disadvantageous in chargeability than the above-mentioned toner capable of uneven surface distribution.
In order to solve this problem, if the amount added is increased and the effect is obtained in the same manner, the fixing property / spent property occurs as a side effect, and sufficient quality cannot be obtained.

  In addition, since the modified layered inorganic mineral can be surface-oriented in an aqueous medium, the modified layered inorganic mineral can sufficiently function with a small amount, which can minimize the effect on fixing properties, and can be produced in an aqueous system. Since it can be granulated, the particle size can be reduced. Since the toner is granulated by being dispersed / or emulsified with an oil / water phase, the modified layered inorganic mineral can be sufficiently dispersed because it can be dispersed in a liquid.

  In the present invention, in a liquid (emulsified dispersion) containing a toner material, the toner material is preferably dissolved or dispersed in a solvent. The solvent preferably contains an organic solvent. The organic solvent is preferably removed when forming the toner base particles or after forming the toner base particles.

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, besides toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples include hydrophilic 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 non-water miscible organic solvents may be used alone or in combination of two or more.
The amount of the organic solvent used can be appropriately selected according to the purpose, but is preferably 40 to 300 parts by weight, more preferably 60 to 140 parts by weight, and more preferably 80 to 140 parts by weight with respect to 100 parts by weight of the toner material. More preferably, 120 parts by weight.

  Toner materials other than the layered inorganic mineral obtained by modifying at least part of the metal cations of the binder resin, colorant, and modified layered inorganic mineral with an organic cation can be appropriately selected according to the purpose. In addition to the active hydrogen group-containing compound and the polymer having reactivity to the active hydrogen group, the binder resin may contain any of a monomer and a polymer. These components may be further contained.

The modified layered inorganic mineral used as a charge control agent will be described.
A layered inorganic mineral refers to an inorganic mineral formed by superposing layers having a thickness of several nanometers, and modifying means introducing an organic ion into ions existing between the layers. Specifically, it is described in the cited documents 4, 5, and 6. This is 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 layered structure. Therefore, when used in toners that are dispersed in an aqueous medium and granulated without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed, but may be modified. Therefore, the hydrophilicity becomes high, and it is easily deformed at the time of granulation, dispersed and refined, and the charge adjusting function is sufficiently exhibited. Such modified inorganic minerals are particularly abundant in the surface portion of the toner particles, and perform a charge control function and contribute to low-temperature fixing. However, the transferability deteriorates due to surface irregularities caused by the irregular shape of the toner.

  In order to solve this problem, in the present invention, at least a binder resin and / or a binder resin precursor, a colorant, a release agent, and a layered layer in which at least part of ions between layers of a layered inorganic mineral are modified with organic ions. Toner obtained by dissolving or dispersing an inorganic mineral in an organic solvent, dispersing an oil phase composed of the solution or dispersion in an aqueous medium to obtain an emulsified dispersion, and granulating toner particles. In the above, the aqueous medium phase contains an active hydrogen-containing compound other than water that extends or crosslinks with the binder resin precursor. When emulsifying and dispersing, it is important to contain an active hydrogen-containing compound in the aqueous medium phase. As a result, toner deformation can be suppressed, toner surface irregularities can be reduced, and a toner having good transferability and chargeability can be obtained. The active hydrogen-containing compound is important to be contained in the aqueous medium phase, but may be contained in the oil phase as long as this is satisfied. The content of the modified layered inorganic mineral in the toner material is preferably 0.1 to 5% by weight based on the total solid content.

The modified layered inorganic mineral used in the present invention is preferably one 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. Examples include sulfates, sulfonates, carboxylates, or phosphates. 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 some inorganic ions between layers with organic ions in the solid toner material is preferably 0.1 to 5% by weight. If it is less than 0.1%, the effect on the toner charging performance is reduced, and if it exceeds 5%, the fixing performance is deteriorated.
The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

Commercially available layered inorganic minerals partially modified with organic cations include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Moreover, as a layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable. The following general formula (1) includes, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
R ₁ (OR ₂ ) _n OSO ₃ M... General formula (1)
[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 the modified layered inorganic mineral, since it has an appropriate hydrophobicity, it becomes easy to move from the aqueous medium to the surface of the oil droplets, so that the surface is unevenly distributed and the charging property can be exhibited.

  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.

  In addition, these phenomena are greatly related to the content of fine powder. In particular, when the particle size of 2 μm or less exceeds 20%, it becomes an obstacle to the adhesion to the carrier and the high level of charging stability. 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.

In the toner of the present invention, the average circularity of the toner is preferably 0.96 to 0.99. When the average circularity is less than 0.96, transferability is deteriorated. This phenomenon is because the toner shape is excessively deformed (toner surface unevenness is large), and toner movement during transfer (photosensitive member surface to transfer paper, photosensitive member surface to intermediate transfer belt, first intermediate transfer belt) To the second intermediate transfer belt, etc.) are not smooth, and the toner particles vary in their 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 fine phenomenon in the developer, which causes a decrease in the durability of the developer.
The toner of the present invention preferably contains 1 to 20% by number of particles of 2 μm or less.

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

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

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

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

The molecular weight according to the present invention is measured by GPC (gel permeation chromatography) as follows. Stabilize the column in a heat chamber at 40 ° C., flow THF at a flow rate of 1 ml / min through the column at this temperature, and prepare a THF sample solution of resin prepared at a sample concentration of 0.05 to 0.6% by weight. Is measured by injecting 50 to 200 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the count using several types of monodisperse polystyrene standard samples. Examples of standard polystyrene samples for preparing a calibration curve include molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , manufactured by Pressure Chemical Co. or Toyo Soda Industry Co., Ltd. Standards of at least about 10 points using 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ Suitably a polystyrene sample is used. An RI (refractive index) detector is used as the detector.

  In addition, by adjusting the acid value of the acidic group-containing polyester resin to 1.0 to 50.0 (KOHmg / g), particle size control by adding a base compound, low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, It is possible to improve toner characteristics such as charging stability. That is, when the acid value exceeds 50.0 (KOHmg / g), the extension or crosslinking reaction of the modified polyester becomes insufficient, and the high-temperature offset resistance is affected, and when it is less than 1.0 (KOHmg / g) This is because a dispersion stabilizing effect due to the base compound during production cannot be obtained, and the elongation or cross-linking reaction of the modified polyester tends to proceed, resulting in a problem in production stability.

(Measurement method of acid value)
The method for measuring the acid value of the polyester resin of the present invention is based on a method based on JIS K0070-1996. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.
The acid value is specifically determined by the following procedure.
Measuring device: potentiometric automatic titrator DL-53 Titrator (manufactured by METTLER TOLEDO)
Electrode used: DG113-SC (Metler Toledo)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C

The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

(Method of measuring acid value)
Moreover, you may convert into a measurement result by the method based on the said JISK0070-1996 the measurement result by the measuring method of JISK0070-1992. For the conversion, the measurement results of both methods obtained from a plurality of samples in advance are used. The measurement based on the measurement method described in JIS K0070-1992 is performed under the following conditions. Sample preparation: 0.5 g of polyester (0.3 g for ethyl acetate-soluble component) is added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, and specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

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

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

  According to a further study of the present invention, the prepolymer for modifying the polyester resin is an important binder resin component for realizing low-temperature fixability and high-temperature offset resistance, and its weight average molecular weight is 3,000 to 20, 000 is preferred. That is, when the weight average molecular weight is less than 3,000, it becomes difficult to control the reaction rate, and problems in production stability begin to occur. On the other hand, when the weight average molecular weight exceeds 20,000, sufficient modified polyester cannot be obtained and the offset resistance starts to be affected.

  Further examination of the present invention revealed that the toner acid value is a more important index than the binder resin acid value for low-temperature fixability and high-temperature offset resistance. The toner acid value of the present invention is derived from the terminal carboxyl group of the unmodified polyester. The unmodified polyester preferably has an acid value of 0.5 to 40.0 (KOHmg / g) in order to control low-temperature fixability (fixing lower limit temperature, hot offset occurrence temperature, etc.) as a toner. In other words, when the toner acid value exceeds 40.0 (KOHmg / g), the modified polyester is insufficiently stretched or cross-linked, affecting high-temperature offset resistance, and less than 0.5 (KOHmg / g). In this case, the dispersion stabilizing effect due to the base compound at the time of production cannot be obtained, and the extension or crosslinking reaction of the modified polyester tends to proceed, resulting in a problem in production stability. The toner acid value is measured by a method based on JIS K0070.

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

  The toner of the present invention is obtained by dissolving or dispersing a toner composition composed of a binder component composed of a modified polyester resin capable of reacting with active hydrogen and a colorant in an organic solvent, and an active hydrogen compound. It is obtained by crosslinking and / or stretching in an aqueous medium containing, and removing the solvent from the resulting dispersion.

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

  An amine is used as a crosslinking agent for the reactive modified polyester resin, and a diisocyanate compound (diphenylmethane diisocyanate or the like) is used as an extender. The amines described in detail later act as a crosslinking agent and an extender for the modified polyester capable of reacting with active hydrogen.

  Modified polyester such as urea-modified polyester obtained by reacting the polyester prepolymer (A) having an isocyanate group with an amine (B) can easily adjust the molecular weight of the polymer component, and is a dry toner, particularly oilless low-temperature fixing. It is convenient to ensure the characteristics (wide releasability and fixability without a release oil application mechanism to the fixing heating medium). Particularly, a polyester prepolymer whose end is modified with urea can suppress adhesion to a heating medium for fixing while maintaining high fluidity and transparency in the fixing temperature range of the unmodified polyester resin itself.

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

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

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

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

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

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

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

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

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

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

  Modified polyester such as urea-modified polyester (UMPE) is produced by a one-shot method or the like. The weight average molecular weight of the modified polyester such as urea-modified polyester (UMPE) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of a modified polyester such as a urea-modified polyester is not particularly limited when a non-modified polyester (PE) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. In the case of a modified polyester such as UMPE alone, the number average molecular weight is usually 2000-15000, preferably 2000-10000, and more preferably 2000-8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

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

  The hydroxyl value (mgKOH / g) of PE is preferably 5 or more, and the acid value (mgKOH / g) of PE is usually 1 to 30, preferably 5 to 20. By giving an acid value, it tends to be negatively charged, and further, the affinity between the paper and the toner is good when fixing to paper, and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly the environmental fluctuation. In the polymerization reaction, if the acid value is touched, it will cause blurring in the granulation process, making it difficult to control the emulsification.

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

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

(Release agent)
In the present invention, the release agent is preferably contained in the toner in an amount of 1 to 10%. If it is less than 1%, the required releasability cannot be obtained, and the fixing property is deteriorated. If it exceeds 10%, there is a problem such as filming. As the wax used in the toner of the present invention, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface, This shows an effect against high temperature offset resistance without applying a release agent such as oil to the fixing roller.
The melting point of the wax in the present invention was the maximum endothermic peak measured by a differential scanning calorimeter (DSC).

  The following materials can be used as the wax component that functions as a release agent that can be used in the present invention. That is, as specific examples, waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, And petroleum waxes such as paraffin, microcrystalline, and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, and chlorinated hydrocarbon, and poly n-stearyl methacrylate and poly n-lauryl methacrylate which are low molecular weight crystalline polymer resins A crystalline polymer having a long alkyl group in the side chain, such as a polyacrylate homopolymer or copolymer (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used.

(Coloring agent)
As the colorant used in the present invention, known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow oxidation Iron, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faisa Red, Parachlor Rutonitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazo Red, polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bituminous Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green , Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin.
As the binder resin to be kneaded together with the production of the master batch or the master batch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

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

An external additive is used to assist the fluidity, developability, and chargeability of the colored particles obtained in the present invention. As this external additive, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, as the fluidity imparting agent, it is preferable to use hydrophobic silica fine particles and hydrophobic titanium oxide fine particles in combination. In particular, when stirring and mixing is performed using an average particle size of both fine particles of 50 mμ or less, the electrostatic force and van der Waals force with the toner are remarkably improved, so that a desired charge level is obtained. It is clear that even with stirring and mixing inside the developing machine, a fluidity-imparting agent is not detached from the toner, a good image quality that does not generate fireflies and the like can be obtained, and the residual toner can be further reduced. became.

  Titanium oxide fine particles are excellent in environmental stability and image density stability, but have a tendency to deteriorate the charge rise characteristics. Therefore, if the amount of titanium oxide fine particles added is larger than the amount of silica fine particles added, the effect of side effects is large. It is possible to become. However, when the addition amount of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is in the range of 0.3 to 1.5 wt%, the charge rising characteristics are not greatly impaired, and the desired charge rising characteristics can be obtained, that is, repeated copying. It has been found that stable image quality can be obtained and toner blowing can be suppressed even if the process is performed.

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

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

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

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

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

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

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

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

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

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

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

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

  In the present invention, it is preferable to remove the solvent at 10 to 50 ° C. prior to the solvent removal from the dispersion (reaction liquid) after the elongation and / or crosslinking reaction. The toner is deformed by liquid agitation before the removal of the solvent. On the other hand, the ratio Dv / Dn of the volume average particle diameter Dv and the number average diameter (Dn) of the toner is mainly determined by adjusting, for example, the water phase viscosity, the oil phase viscosity, the characteristics of the resin fine particles, and the addition amount. Can be controlled. Dv and Dn can be controlled, for example, by adjusting the characteristics, addition amount, etc. of the resin fine particles.

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

  An embodiment for carrying out the image forming method of the present invention will be described with reference to FIG. FIG. 1 is a diagram showing an example of a tandem color image forming apparatus of the present invention. 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-like intermediate transfer member (50) at the center. The intermediate transfer member (50) is stretched around the support rollers (14), (15) and (16) so as to be able to move clockwise in the drawing. An intermediate transfer body cleaning device (17) for removing toner remaining on the intermediate transfer body (50) is disposed in the vicinity of the support roller (15). The intermediate transfer member (50) stretched by the support rollers (14) and (15) is opposed to image forming means (18) of four colors of yellow, cyan, magenta, and black along the conveyance direction. A tandem developing device (120) juxtaposed in parallel is arranged. An exposure device (21) is disposed in the vicinity of the tandem developing device (120). A secondary transfer device (22) is arranged on the opposite side of the intermediate transfer member (50) from the side where the tandem developing device (120) is arranged. In the secondary transfer device (22), a secondary transfer belt (24), which is an endless belt, is stretched between a pair of rollers (23), and the recording paper conveyed on the secondary transfer belt (24) is intermediate to the recording paper. The transfer bodies (50) can contact each other. A fixing device (25) is disposed in the vicinity of the secondary transfer device (22). The fixing device (25) includes a fixing belt (26) that is an endless belt, and a pressure roller (27) that is arranged to be pressed against the fixing belt (26).

  In the image forming apparatus, a sheet reversing device (28) for reversing the transfer paper is disposed in the vicinity of the secondary transfer device (22) and the fixing device (25). Thereby, images can be formed on both sides of the recording paper.

  Next, full color image formation (color copying) using the tandem developing device (120) will be described. First, the document is set on the document table (130) of the automatic document feeder (400), or the automatic document feeder (400) is opened and the document is set on the contact glass (32) of the scanner (300). The automatic document feeder (400) is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder (400), the document is conveyed on the contact glass (32) and then on the contact glass (32). When is set, the scanner (300) is immediately driven, and the first traveling body (33) and the second traveling body (34) travel. At this time, the reflected light from the original surface of the light irradiated by the first traveling body (33) is reflected by the mirror of the second traveling body (34) and passes through the imaging lens (35) to the reading sensor (36). Received light. As a result, a color original (color image) is read and used as image information for each color of black, yellow, magenta, and cyan. Then, the toner images of the respective colors are superimposed on the intermediate transfer member (50) to form a composite color image (color transfer image).

  As shown in FIG. 2, each color image forming means (18) in the tandem developing device (120) includes a photoreceptor (10) and a charger (59) for uniformly charging the photoreceptor (10). And an exposure device (21) that forms an electrostatic latent image on the photoconductor (10) by exposing the photoconductor (10) based on image information of each color (L in the figure), and toner of each color Is used to develop the electrostatic latent image to form a toner image of each color on the photoreceptor (10), and a transfer for transferring the toner image of each color onto the intermediate transfer member (50). A charger (62), a photoreceptor cleaning device (63), and a static eliminator (64) are provided.

On the other hand, in the paper feed table (200), one of the paper feed rollers (142) is selectively rotated to feed recording paper from one of the paper feed cassettes (144) provided in multiple stages in the paper bank (143). The paper is separated one by one by the separation roller (58), sent to the paper feed path (146), transported by the transport roller (147) and guided to the paper feed path (148) in the copying machine main body (150), and the registration roller Stop at (49). Alternatively, the recording roller (142) is rotated to feed out the recording paper on the manual feed tray (54), separated one by one by the separation roller (145) and put into the manual feed path (53). 49) and stop. The registration roller (49) 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 (49) is rotated in time with the color transfer image formed on the intermediate transfer member (50), and the recording paper is interposed between the intermediate transfer member (50) and the secondary transfer device (22). , A color transfer image is formed on the recording paper. The toner remaining on the intermediate transfer body (50) after the transfer is cleaned by the intermediate transfer body cleaning device (17).

  The recording paper on which the color transfer image is formed is conveyed to the fixing device (25) by the secondary transfer device (22), and the color transfer image is fixed on the recording paper by heat and pressure. Thereafter, the recording paper is switched by the switching claw (55), discharged by the discharge roller (56), and stacked on the discharge tray (57). Alternatively, the sheet is switched by the switching claw (55), reversed by the sheet reversing device (28) and led to the transfer position again, and after the image is formed on the back surface, the sheet is discharged by the discharge roller (56) and discharged by the discharge tray (57). ) Is stacked on top.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Hereinafter, a part shows a weight part.
(Example 1)
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propion oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and dibutyltin oxide 2 parts were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure, (unmodified polyester resin 1) Was synthesized.

The obtained (unmodified polyester resin 1) had a number average molecular weight of 2500, a weight average molecular weight of 6700, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.
1200 parts of water, 540 parts of carbon black Printex 35 (manufactured by Dexa; DBP oil absorption = 42 ml / 100 mg, pH = 9.5) and 1200 parts of unmodified polyester resin were mixed using a Henschel mixer (manufactured by Mitsui Mining). . The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare (Masterbatch 1).

In a reaction vessel equipped with a stirring bar and a thermometer, 378 parts of an unmodified polyester resin, 110 parts of carnauba wax, and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and held at 80 ° C. for 5 hours. Then, it cooled to 30 degreeC 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.). The wax dispersion 1 was obtained by performing 3 passes under the condition of a speed of 6 m / sec.

(Adjustment of toner material dispersion 1)
Next, 1324 parts of a 65 wt% ethyl acetate solution of unmodified polyester resin was added to the wax dispersion 1. As a charge control agent, 3 to 0 parts of Kraton APA (manufactured by Southern Clay Products) were added to 200 parts of a dispersion obtained by one pass using Ultraviscomil under the same conditions as described above. K. Using a homodisper (manufactured by Koki Kogyo Co., Ltd.), the mixture was stirred at 7000 rpm for 60 minutes to obtain a dispersion (1) of toner material.

(Adjustment of toner material dispersion 2)
Next, 1324 parts of a 65 wt% ethyl acetate solution of unmodified polyester resin was added to the wax dispersion 1. 4.5 parts of Kraton APA (manufactured by Southern Clay Products) as a charge control agent is added to 200 parts of a dispersion obtained by one pass using Ultraviscomil under the same conditions as described above. K. Using a homodisper (manufactured by Koki Kogyo Co., Ltd.), the mixture was stirred at 7000 rpm for 60 minutes to obtain a dispersion (2) of toner material.

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.

(Adjustment of oil phase mixture 1)
Into a reaction vessel, 749 parts of a dispersion of toner material (1) and 115 parts of a prepolymer were charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika) to obtain an oil phase mixture 1 It was.

  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 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Chemical Industries), 1% by weight aqueous solution of sodium carboxymethylcellulose polymer dispersant 135 parts of BS-H-3 (Daiichi Kogyo Seiyaku Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred to obtain an aqueous medium (1).

(Preparation of emulsified slurry 1)
To 1200 parts of the aqueous medium (1), add 3.0 parts of ketimine compound, mix for 5 minutes at 5000 rpm using a TK homomixer, and further add 864 parts of the oil phase mixture (1) to the mixture. Using a TK homomixer, mixing was carried out at 13000 rpm for 20 minutes to prepare a dispersion (emulsion slurry 1).

Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, 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 obtained dispersion slurry was measured using Multisizer III (manufactured by Beckman Coulter, Inc.). The volume average particle size was 5.1 μm and the number average particle size was 4.5 μm.
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 drier, and sieved with a mesh having an opening of 75 μm to obtain (toner mother particles 1).
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 produced.

(Adjustment of oil phase mixture 2)
In a reaction container, 749 parts of a dispersion (1) of toner material, 115 parts of a prepolymer and 1.0 part of a ketimine compound are charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika). An oil phase mixture 2 was obtained.

(Adjustment of oil phase mixture 3)
In a reaction vessel, 749 parts of the toner material dispersion (1), 115 parts of the prepolymer and 2.5 parts of the ketimine compound are charged, and mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika). The oil phase mixture 3 was obtained.

(Adjustment of oil phase mixture 4)
In a reaction container, 749 parts of a dispersion (2) of toner material and 115 parts of a prepolymer were charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika) to obtain an oil phase mixture 4 It was.

(Adjustment of oil phase mixture 5)
In a reaction container, 749 parts of a dispersion (2) of toner material, 115 parts of a prepolymer and 2.5 parts of a ketimine compound are charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (made by Tokushu Kika). The oil phase mixture 5 was obtained.

(Adjustment of oil phase mixture 6)
In a reaction container, 749 parts of a dispersion (1) of toner material, 115 parts of a prepolymer and 3.0 parts of a ketimine compound are charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika). The oil phase mixture 6 was obtained.

(Adjustment of oil phase mixture 7)
In a reaction container, 749 parts of a dispersion (2) of toner material, 115 parts of a prepolymer and 3.0 parts of a ketimine compound are charged, and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika). An oil phase mixture 7 was obtained.

(Preparation of emulsified slurry 2)
To 1200 parts of aqueous medium (1), add 2.0 parts of ketimine compound, mix for 5 minutes at 5000 rpm using a TK homomixer, and then add 865 parts of oil phase mixture (2) to the mixture. Using a TK homomixer, mixing was performed at 13000 rpm for 20 minutes to prepare a dispersion (emulsion slurry 2).

(Preparation of emulsified slurry 3)
To 1200 parts of the aqueous medium (1), 0.5 parts of a ketimine compound is added and mixed for 5 minutes at 5000 rpm using a TK homomixer. Further, 866.5 parts of an oil phase mixture (3) is added to the mixture. Was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsified slurry 3).

(Preparation of emulsified slurry 4)
To 1200 parts of the aqueous medium (1), add 3.0 parts of ketimine compound, mix for 5 minutes at 5000 rpm using a TK homomixer, and further add 864 parts of the oil phase mixture (4) to the mixture. Using a TK homomixer, mixing was carried out at 13000 rpm for 20 minutes to prepare a dispersion (emulsified slurry 4).

(Preparation of emulsified slurry 5)
Add 0.5 parts of ketimine compound to 1200 parts of aqueous medium (1), mix for 5 minutes at 5000 rpm using a TK homomixer, and further add 866.5 parts of oil phase mixture (5) to the mixture. Was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsified slurry 5).

(Adjustment of the emulsified slurry 6)
To 1200 parts of the aqueous medium (1), 867 parts of the oil phase mixture (6) was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsion slurry 6).

(Preparation of emulsified slurry 7)
To 1200 parts of the aqueous medium (1), 867 parts of the oil phase mixed liquid (7) was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsified slurry 7).

(Example 2)
(Toner base particles 2) (Toner 2) were produced in the same manner as in Example 1 except that (Emulsion slurry 1) was changed to (Emulsion slurry 2).

(Example 3)
(Toner base particles 3) (Toner 3) were produced in the same manner as in Example 1 except that (Emulsion slurry 1) was changed to (Emulsion slurry 3).

Example 4
(Toner base particles 4) (Toner 4) were produced in the same manner as in Example 1 except that (Emulsion slurry 1) was changed to (Emulsion slurry 4).

(Example 5)
A toner was produced in the same manner as in Example 1 except that (Emulsion slurry 1) was changed to (Emulsion slurry 5), and toner base particles 5 (toner 5) were produced.

(Comparative Example 1)
(Toner base particles 6) and (toner 6) were produced in the same manner as in Example 1 except that (Emulsion slurry 1) was changed to (Emulsion slurry 6).

(Comparative Example 2)
A toner was produced in the same manner as in Example 1 except that (Emulsion slurry 1) was changed to (Emulsion slurry 7), and toner base particles 7 (toner 7) were produced.

The toners used in each example and comparative example are shown in Tables 1 and 2.
(Image density)
Using a digital full-color copier (imageColor 2800, manufactured by Ricoh Co., Ltd.), after running 150,000 image charts with a 50% image area in single color mode, a solid image was output to 6000 paper manufactured by Ricoh Co., and the image density was set to XRite. Measurement was carried out by (manufactured by X-Rite).
This was performed for four colors alone, and the average was obtained. When this value is less than 1.2, “x”, when it is 1.2 or more and less than 1.4, “△”, when it is 1.4 or more and less than 1.8, “◯”, 1.8 or more If less than 2, “◎” was assigned.

(Image graininess, sharpness)
Using a digital full-color copying machine (imageColor 2800, manufactured by Ricoh), a photographic image was output in a single color, and the degree of graininess and sharpness was visually evaluated. In order from the best, “◎” is equivalent to offset printing, “○” is slightly worse than offset printing, “△” is much worse than offset printing, “×” is about the same as conventional electrophotographic images (very much Bad).

(Chargeability)
9 g of carrier and 1 g of toner base particles were placed in a stainless steel cylindrical pot having a diameter of 30 mm and a width of 30 mm, and stirred at 600 rpm.
Stirring time was 60 sec, 10 min, 24 hours, and charging property at 3 points was confirmed. After stirring, 1 g of the stirred developer was measured using a blow-off device manufactured by Toshiba Chemical Corporation. Further, after measuring the charge amount, the blown carriers were collected again, new toner base particles were added, and the charge amount was confirmed again after stirring for 10 minutes.
Here, stirring for 60 seconds is used as an index for determining the rising property of the charging property, and it is preferable that the stirring amount is approximately equal to the charging amount after 10 minutes.
In addition, the chargeability needs to be flat when stirring for 10 minutes and stirring for one day. If the charge amount after one day is lowered, the influence of spent or the like, the influence of leakage of chargeability, etc. can be considered.

(Skin cover)
After running 10,000 sheets on the Ricoh ipsio Color 8100, the paper was stopped when the white paper was developed, and the soiled portion on the photoreceptor was transferred, and its id was measured. If it is 0.03 or more, it becomes a background contamination danger area, and if it is 0.05 or more, it becomes background contamination, which is a level that appears in the image.

(Fixability)
The fixing machine is remodeled with Ricoh ipio color 8100, and hot water is adjusted so that 1.0 ± 0.1 mg / cm2 of toner is developed with solid images. The temperature at which no offset occurs on Ricoh type 6200 paper is the upper limit of fixing temperature. The minimum fixing temperature was measured with TYPE 6000/90 W paper manufactured by Ricoh. The minimum fixing temperature was determined as the minimum fixing temperature, which was the roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.
When the fixing lower limit temperature is 150 ° C. or more, it is determined that the margin is insufficient and the fixing cannot be used (×). If it was 140 degrees or less, it was judged that there was a margin (◯).
Further, with respect to the fixing width, those having 50 degrees or more were judged as ◯, 40 to 50 degrees as Δ, and 40 degrees or less as x.

1 is a schematic diagram illustrating an example of a tandem color image forming apparatus of the present invention. FIG. 2 is a schematic diagram illustrating a part of the image forming apparatus illustrated in FIG. 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photoconductor 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta photoconductor 10C Cyan photoconductor 14, 15, 16 Support roller 17 Intermediate transfer body cleaning device 18 Image forming means 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 49 Registration roller 50 Intermediate transfer body 54 Manual feed tray 53 Manual feed path 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Separation roller 59 Charger 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 120 Tandem developer 130 Document table 142 Feed roller 143 Paper Link 144 sheet cassette 145 separating roller 146 feed path 147 transport rollers 148 feed path 150 copier main body 200 feeder table 300 Scanner 400 automatic document feeder

Claims (22)

At least a binder resin and / or a binder resin precursor, a colorant, a release agent, and a layered inorganic mineral obtained by modifying at least part of ions between layers of the layered inorganic mineral with organic ions are dissolved or dispersed in an organic solvent. An oil phase comprising the solution or dispersion is dispersed in an aqueous medium to obtain an emulsified dispersion, and toner is obtained by granulating toner particles from the emulsified dispersion. A toner comprising an active hydrogen-containing compound other than water that extends or crosslinks with the binder resin precursor in a medium phase. The toner according to claim 1, wherein the active hydrogen-containing compound is an amine (excluding a tertiary amine). The toner according to claim 1 or 2, wherein the modified layered inorganic mineral is a layered inorganic mineral in which at least a part of cations between layers of the layered inorganic mineral is modified with an organic cation. The layered inorganic mineral obtained by modifying at least part of the ions between the layers with organic ions is contained in a solid content of the solution or dispersion in an amount of 0.1 to 5%. The toner according to any one of the above. The toner according to claim 1, wherein the binder resin is a polyester resin. The toner according to claim 1, wherein the binder resin precursor is a modified polyester resin. The toner according to claim 1, wherein an average circularity of the toner is 0.96 to 0.99. The toner according to claim 1, wherein the toner has a volume average particle diameter of 3 to 7 μm. The toner according to claim 1, wherein the toner has a volume particle size Dv / number average particle size Dn of 1.30 or less. The toner according to claim 1, wherein 1 to 20% by number of particles of 2 μm or less of the toner is included. The toner according to claim 1, wherein a content of the polyester resin component contained in the binder resin in the binder resin is 50 to 100% by weight. The toner according to claim 1, wherein the polyester resin has a THF-soluble component having a weight average molecular weight of 1,000 to 30,000. The toner according to claim 1, wherein an acid value of the binder resin is 1.0 to 50.0 (KOH mg / g). The toner according to claim 1, wherein the binder resin has a glass transition point of 35 to 65 ° C. The binder resin precursor has a site capable of reacting with the active hydrogen group-containing compound, and the weight average molecular weight of the polymer of the binder resin precursor is 3,000 to 20,000. The toner according to any one of 14. 16. The electrostatic image developing toner according to claim 1, wherein the toner has an acid value of 0.5 to 40.0 (KOH mg / g). The toner for developing an electrostatic charge image according to claim 1, wherein the toner has a glass transition point of 40 to 70 ° C. The toner according to claim 1, wherein the toner is used for a two-component developer. A developer containing the toner according to claim 1. An image forming apparatus, wherein an image is formed using the developer according to claim 19. 20. An image forming method comprising forming an image using the developer according to claim 19. At least a binder resin and / or a binder resin precursor, a colorant, a release agent, and a layered inorganic mineral obtained by modifying at least part of ions between layers of the layered inorganic mineral with organic ions are dissolved or dispersed in an organic solvent. An oil phase comprising the solution or dispersion is dispersed in an aqueous medium to obtain an emulsified dispersion, and toner is obtained by granulating toner particles from the emulsified dispersion. An active hydrogen-containing compound other than water that extends or cross-links with the binder resin precursor in a medium phase.

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