JP2019164200A - Toner, developer, toner storage unit, image forming apparatus, and image forming method - Google Patents

Abstract

To provide a toner that can prevent white dots due to separation of an external additive, scattering inside the apparatus when printing a large number of sheets with a low image area, and degradation of an image due to the occurrence of white streaks.SOLUTION: The above-mentioned problem is solved by a toner that is obtained by adding an external additive to a toner base particle containing an organically modified layered inorganic compound containing Al, a binder resin, and a mold release agent, wherein the Al content C1 from the surface of the toner base particle to a depth of 0.2 μm is 0.1 mass%≤C1≤0.3 mass%, and the ratio of C1 to the Al content C2 from the surface of the toner to a depth of 0.4 μm (C1/C2) is 1.0≤(C1/C2)≤1.5.SELECTED DRAWING: Figure 1

Description

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

  In electrophotographic image formation, an electrostatic charge image (latent image) is formed on an electrostatic latent image carrier, charged toner is conveyed by a developer carrier, and the latent image is developed to form a toner image. After the formation, the toner image is transferred onto a recording medium such as paper and fixed by a method such as heating to obtain an output image. Further, a technique is known in which toner remaining on an electrostatic latent image carrier after transfer is collected from the electrostatic latent image carrier by a cleaning member and discharged to a waste toner storage unit.

  In the toner, a charge control agent is generally applied to the surface of the toner base particles for the purpose of improving the charging characteristics of the toner. The charge control agent is used for the purpose of controlling the triboelectric charge amount of the toner and maintaining the triboelectric charge amount. In general, the charge control agent develops charging ability by being unevenly distributed on the surface of toner base particles that are largely involved in charging. A synthetic method such as a chemical toner is effective as one means for more effectively distributing the charge control agent on the surface of the toner base particles. In a toner synthesis method such as a pulverization method, since the charge control agent is uniformly dispersed in the binder resin, it is difficult to selectively disperse it on the surface. On the other hand, in a chemical toner synthesis method such as the dissolution suspension method, a slightly hydrophilic charge control agent tends to be unevenly distributed on the surface of the toner base particles in the granulation process.

  Further, as another means for improving the charging property, it is generally known to add and mix a fine powder having an average particle diameter of 5 to 25 nm as an external additive to the toner base particles. For example, in order to improve the hydrophobicity and charging characteristics of the surface, a technique using an external additive surface-treated with an organic silicon compound such as silane or silicone oil is known. A technique using titanium oxide, tin oxide or the like having low resistance is known. In addition, a technique of externally adding silica, titanium dioxide or the like for improving flow characteristics is also known.

  However, when these charge control agents and external additives are used in combination, the surface of the toner base particles becomes hard because the inorganic charge control agents are unevenly distributed on the surface of the toner base particles, so that the external additives are fixed on the surface of the toner base particles. It becomes difficult to become. As a result, the external additive peeled off from the toner base particles forms an agglomerate, which adheres to the surface of the photosensitive member, and a phenomenon of white spots occurs in which only the attached portion is not printed.

  In addition, a toner using an external additive may be exposed to the outside of the toner base particle surface when used for a long time due to, for example, stress with a carrier of a two-component developer, stress with a toner conveying member or a thinning blade in one-component development. The additive is embedded in the toner, which causes problems such as a decrease in toner fluidity and in-machine scattering due to a change in charging characteristics.

  As means for reducing the embedding of the external additive, there are an improvement means on the resin side such as hardening the toner base particle surface and an improvement means on the external additive side such as using a large particle size external additive in combination. It is valid.

  However, when the surface of the toner base particles is hardened by increasing the molecular weight of the resin, the external additive becomes difficult to be fixed to the toner base particles as described above, and problems such as white spots due to the detached external additive occur. To do. Further, since the resin characteristics change, the low temperature fixing characteristics are also adversely affected.

  On the other hand, the large particle size external additive is difficult to be fixed to the toner base particles, and the large particle size external additive is selectively discharged from the developer to embed the small particle size external additive to reduce the fluidity. However, there is a problem that the image density is reduced, or that the large particle size external additive is accumulated in the developer, the development characteristics are changed, and the background is likely to be stained.

  For this reason, various improvements have been made so far in order to prevent the external additive from being detached from the toner. For example, when the external additive having a large particle size is resin particles, a method of immobilizing by physical force by using a hybridization system and treating at 12000 rpm for 2 minutes has been proposed (for example, see Patent Document 1).

  Further, a large particle size external additive having a primary particle average particle size of 30 to 500 nm and a surface treated with silicone oil, and a silica having a primary particle average particle size of 5 to 20 nm and a surface treated with alkoxysilane or silazane. By preparing a mixed fine powder and using a powder whose particle size distribution has one peak, the small particle size external additive prevents the large particle size external additive from detaching from the toner base particles. A method has been proposed (see, for example, Patent Document 2).

However, the technique disclosed in Patent Document 1 has a problem in that the charging performance of the toner base particles deteriorates due to the fixing process, and is difficult to employ.
Further, the technique disclosed in Patent Document 2 has a problem that the effect of preventing an increase in the desorption rate is insufficient.
SUMMARY OF THE INVENTION An object of the present invention is to provide a toner capable of preventing white spots due to the detachment of external additives, image scattering due to the occurrence of white streaks in the machine during printing of a large number of sheets with a low image area. .

The above problem is solved by the following configuration 1).
1) A toner obtained by adding an external additive to toner base particles containing an organically modified layered inorganic compound containing Al, a binder resin, and a release agent,
The Al content C1 from the toner base particle surface to a depth of 0.2 μm is 0.1 mass% ≦ C1 ≦ 0.3 mass%, and the Al content C2 from the toner surface to 0.4 μm. (C1 / C2) is 1.0 ≦ (C1 / C2) ≦ 1.5.

  According to the present invention, it is possible to provide a toner capable of preventing white spots due to the detachment of the external additive, scattering in the machine at the time of printing a large number of sheets with a low image area, and image deterioration due to white streaks.

It is a figure for demonstrating one Embodiment of a process cartridge. 1 is a diagram for explaining an embodiment of an image forming apparatus of the present invention. It is a figure for demonstrating another embodiment of the image forming apparatus of this invention. It is a figure for demonstrating another embodiment of the image forming apparatus of this invention. It is a figure for demonstrating an image forming unit.

  Hereinafter, embodiments of the toner and developer according to the present invention will be described in detail. However, the present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like by those skilled in the art. It can be changed within the range that can be conceived, and any embodiment is included in the scope of the present invention as long as the effects and effects of the present invention are exhibited.

(toner)
The toner of the present invention is obtained by adding an external additive to toner base particles containing an organically modified layered inorganic compound containing Al, a binder resin, and a release agent, and has a depth of 0. 0 from the surface of the toner base particles. The Al content C1 up to 2 μm is 0.1 mass% ≦ C1 ≦ 0.3 mass%, and the ratio (C1 / C2) to the Al content C2 from the toner surface to 0.4 μm is 1 0.0 ≦ (C1 / C2) ≦ 1.5.

  As a means for suppressing the embedding of the external additive in the toner base particles, there is a means for hardening the surface of the toner base particles. In the present invention, an organically modified layered inorganic compound containing Al is used to harden the toner base particle surface.

  When the layered inorganic compound is contained in the toner, a layered inorganic compound that has been rendered hydrophobic by organic modification is usually used. Since the layered inorganic compound before the organic modification treatment has hydrophilicity, the organic modification layered inorganic compound is not as hydrophobic as the binder resin used for the toner base particles even if the organic modification treatment is performed. This causes the charging ability to be exerted. However, if it is unevenly distributed on the outermost surface of the toner base particles, the inside of the toner in which the organically modified layered inorganic compound does not exist is soft. Streaks and in-flight scattering will occur. As a result of intensive studies on such problems, the present inventors have determined that the Al content C1 from the toner base particle surface to a depth of 0.2 μm is 0.1 mass% ≦ C1 ≦ 0.3 mass%. In addition, it is important that the ratio (C1 / C2) to the Al content C2 from the toner base particle surface to 0.4 μm is 1.0 ≦ (C1 / C2) ≦ 1.5. I found it.

  The reason is that the organic modified layered inorganic compound on the outermost surface of the toner base particles is not made dense but slightly sparse so that the external additive is fixed in the binder resin part and the organic modified layered layer is also slightly inside. By arranging an inorganic compound, it plays the role of a wall and is considered to suppress the burying of external additives due to in-flight stress. As a result, the toner of the present invention can suppress both embedding and detachment of the external additive.

The organically modified layered inorganic compound containing Al used in the present invention can measure the Al content in the depth direction of the toner base particles by SEM-EDS. In order to suppress both burying and desorption of the external additive, the Al content C1 measured by SEM-EDS is 0.1% by mass ≦ C1 ≦ 0.3% by mass, and C1 and The ratio of C2 (C1 / C2) is preferably 1.0 ≦ (C1 / C2) ≦ 1.5, more preferably 1.0 ≦ (C1 / C2) ≦ 1.2. When the ratio (C1 / C2) is greater than 1.5, the ratio of the organically modified layered inorganic compound containing Al inside the toner base particles becomes low, and the external additive is buried due to stress in the machine. On the other hand, when the ratio (C1 / C2) is smaller than 1.0, the ratio of the organically modified layered inorganic compound containing Al on the surface to the toner base particles becomes low, and the effects of the present invention are not achieved and the heat resistance is reduced. Preservability deteriorates.
Further, when the Al content C1 is higher than 0.3% by mass, the ratio of the organically modified layered inorganic compound containing Al on the surface of the toner base particles becomes high, so that the external additive is easily detached. On the other hand, when the Al content C1 is lower than 0.1% by mass, sufficient charging characteristics cannot be obtained, and the amount of toner scattering at the time of printing a large number of sheets with a high image area tends to deteriorate.

  Since the organically modified layered inorganic compound containing Al has moderate hydrophobicity, it is selectively distributed at the droplet interface during granulation and exhibits high charging ability. On the other hand, as one of means for letting the organically modified layered inorganic compound containing Al into a position deeper than the attachment position of the external additive, an organic cation modifying agent in preparing the organically modified layered inorganic compound containing Al It is effective to adjust the type and amount. As the type of the organic cation modifier, it is preferable to use a compound having a higher affinity with the binder resin. Examples of the organic cation modifier include dimethyl stearyl benzyl ammonium (DMSB), dimethyl distearyl ammonium (DMDS), dimethyl oleyl benzyl ammonium (DMOB), dimethyl dioleyl ammonium (DMDO), and the like described below. Dimethyl distearyl ammonium (DMDS), dimethyl oleyl benzyl ammonium (DMOB), and dimethyl dioleyl ammonium (DMDO) having higher affinity with the resin are preferable.

The addition amount of the organic cation modifier is a ratio when the addition amount of the organic cation modifier used at the time of modification is A (mol) and the cation contained in the layered inorganic compound before modification is B (mol) (A / B) is preferably 1.0 ≦ (A / B) ≦ 1.5. When the ratio (A / B) is 1.5 or less, the organically modified layered inorganic compound containing Al is dispersed inside the toner base particles so as to satisfy the Al content C1 and the ratio (C1 / C2). The effect of the present invention is excellent, and the heat resistant storage stability is also good. Further, when the ratio (A / B) is 1.0 or more, the organically modified layered inorganic compound containing Al is not excessively unevenly distributed in the toner base particles, and the external additive is prevented from being detached, and white spots are lost. Can be further suppressed.
A more preferable ratio (A / B) is 1.0 ≦ (A / B) ≦ 1.2.

  In the present invention, in order to satisfy the Al content C1 and the ratio (C1 / C2), for example, the ratio (A / B) is appropriately set as described above; the organically modified layered inorganic compound containing Al It can be achieved by adjusting the amount used; combining these.

  The organically modified layered inorganic compound containing Al is 0.1 to 3.0% by mass, preferably 0.5 to 2.0% by mass, and more preferably 1.0 to 1.5% by mass with respect to the toner. Is preferred.

<Layered inorganic compound>
The organically modified layered inorganic compound containing Al used in the toner of the present invention is obtained by modifying a layered inorganic compound formed by superimposing layers having a thickness of several nm with organic ions. Denaturing refers to introducing organic ions into ions present between the layers. As the layered inorganic compound, a smectite group (montmorillonite, saponite, etc.), a kaolin group (kaolinite, etc.), magadiite, and kanemite are known. The layered inorganic compound 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 compound, the layered inorganic compound migrates into the aqueous medium and cannot be dispersed in the toner, but is modified. As a result, the hydrophobicity becomes high, and it is easily dispersed in the toner during granulation to make it finer, so that the charge adjusting function is sufficiently exhibited.

  As the organically modified layered inorganic compound containing Al, one layered inorganic compound selected from montmorillonite, bentonite, hectorite, attapulgite and sepiolite is organically modified, or two or more types are organically modified. A mixture etc. are mentioned. Among these, montmorillonite or bentonite modified is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be made small.

  As the organically modified layered inorganic compound containing Al used in the present invention, commercially available ones can be used. For example, Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP ( Quartium 18 bentonite such as United Catalyst), Clayton 34, Clayton 40, Clayton XL (above, Southern Clay), etc .; Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA Stearalkonium bentonite such as Clayton HT, Clayton PS (manufactured by Southern Clay), etc., and kuratenium 18 / benzalkonium bentonite AF, Clayton APA is preferable.

-Al content of toner base particles-
Here, the measurement of the Al content in the depth direction of the toner base particles in the present invention can be performed, for example, as follows. In the present invention, the measurement was performed using SEM-EDS (scanning electron microscope / energy dispersive X-ray spectroscopy): Ultra55 (manufactured by Carl Zeiss Microscopy Co., Ltd.). As the measurement sample, 10 toners arbitrarily selected from those prepared by dispersing the prepared toner on an Al-based carbon tape and removing ultrafine powder, coarse particles, etc., are subjected to the following conditions. The Al content in the depth direction of the particles was measured and the average value was used.
As for the detection depth of the electron beam, the acceleration voltage applied by Monte Carlo simulation was calculated.
Acceleration voltage: 2.0-4.0kV
Aspect: 60 μm
High Current: On
Work distance: 10mm
Magnification: 15k

  The shape, size, etc. of the toner of the present invention are not particularly limited and may be appropriately selected depending on the intended purpose. The average circularity, volume average particle size, volume average particle size and number are as follows: It is preferable to have a ratio (volume average particle diameter / number average particle diameter) to the average particle diameter.

The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected shape as the shape of the toner by the circumference of the actual particles. For example, 0.950 to 0.980 is preferable, and 0.960 to 0 is preferable. .975 is more preferred. In addition, it is preferable that the particles having an average circularity of less than 0.95 are 15% or less.
If the average circularity is less than 0.950, a satisfactory transferability and a high-quality image free from dust may not be obtained. If it exceeds 0.980, in an image forming system employing blade cleaning or the like, a cleaning failure occurs on the photosensitive member or the transfer belt, and dirt on the image, for example, a high image area ratio such as a photographic image is high. In the case of image formation, the toner on which an untransferred image has been formed due to poor paper feed or the like may be stained on the photosensitive member as a transfer residual toner, resulting in background smudges. Alternatively, the charging roller that contacts and charges the photosensitive member may be contaminated, and the original charging ability may not be exhibited.

  The average circularity is measured using a flow particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). It was. Specifically, 0.1 to 0.5 ml of 10% by mass surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 ml beaker, and each toner is added in an amount of 0.1%. 1-0.5g was added and it stirred with the microspatel, and 80 mL of ion-exchange water was then added. The obtained dispersion is subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner are measured with the FPIA-2100 until the concentration of the dispersion reaches 5,000 to 15,000 / μL.

  In this measurement method, it is important that the concentration of the dispersion is 5,000 to 15,000 / μL from the viewpoint of measurement reproducibility of average circularity. In order to obtain the concentration of the dispersion, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated, and if it is too small, the toner cannot be sufficiently wetted. It will be enough. The amount of toner added varies depending on the particle size, and is small when the particle size is small, and needs to be increased when the particle size is large. When the toner particle size is 3 μm to 10 μm, the toner amount is 0.1 g to 0.00 g. By adding 5 g, the dispersion concentration can be adjusted to 5,000 / μl to 15,000 / μl.

  The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 3 μm to 10 μm, and more preferably 4 μm to 7 μm. When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. Therefore, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle size may increase.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, and more preferably 1.00 to 1.15.
The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.). The measurement can be performed with an aperture diameter of 100 μm and the analysis can be performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51).

  As a specific example, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and 0.5 g of each toner is added. Stir with a microspatel and then add 80 ml of ion-exchanged water. The obtained dispersion is subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion is measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution.

  In the measurement, the toner sample dispersion is dropped so that the concentration indicated by the apparatus is 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

<Toner component>
The toner of the present invention is prepared by adding an external additive and, if necessary, other components to toner base particles containing an organically modified layered inorganic compound containing Al, a binder resin and a release agent.

<< Binder resin >>
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably. For example, polyester resin, silicone resin, styrene / acrylic resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol resin, terpene resin, coumarin resin, amidoimide resin, butyral resin, urethane resin, ethylene vinyl acetate resin, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, polyester resins and resins obtained by combining polyester resins with the above other binder resins are preferable because they are excellent in low-temperature fixability and have sufficient flexibility even when the molecular weight is reduced. Moreover, it is preferable that the said binder resin is polyester and / or a polyester derivative.

-Polyester resin-
There is no restriction | limiting in particular as said polyester resin, Although it can select suitably according to the objective, An unmodified polyester resin and a modified polyester resin are preferable. These may be used individually by 1 type and may use 2 or more types together.

--Unmodified polyester resin--
There is no restriction | limiting in particular as said unmodified polyester resin, According to the objective, it can select suitably. Examples thereof include resins obtained by polyesterification of a polyol represented by the following general formula (1) and a polycarboxylic acid represented by the following general formula (2), a crystalline polyester resin, and the like.

However, in the said General formula (1), A represents the aromatic group or heterocyclic aromatic group which may have a C1-C20 alkyl group, an alkylene group, and a substituent, m is 2- Represents an integer of 4.
In the general formula (2), B represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, an aromatic group that may have a substituent, or a heterocyclic aromatic group, and n represents 2 to 2 Represents an integer of 4.

  There is no restriction | limiting in particular as a polyol represented by the said General formula (1), According to the objective, it can select suitably. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, Pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2, -Butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A oxidation Examples include ethylene adducts, hydrogenated bisphenol A propylene oxide adducts, and the like. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as polycarboxylic acid represented by the said General formula (2), According to the objective, it can select suitably. For example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid , Isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2, , 5,7-Naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl- 2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, te La (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, etc., cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, And ethylene glycol bis (trimellitic acid). These may be used alone or in combination of two or more.

--Modified polyester resin--
There is no restriction | limiting in particular as said modified polyester resin, According to the objective, it can select suitably. For example, an active hydrogen group-containing compound, a resin obtained by subjecting a polyester capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “polyester prepolymer”) to an extension reaction and / or a crosslinking reaction, etc. Can be mentioned. The extension reaction and / or the cross-linking reaction may be stopped by a reaction terminator (blocked monoamine such as diethylamine, dibutylamine, butylamine, laurylamine, ketimine compound, etc.) as necessary.

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

  The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. However, when the polyester prepolymer is an isocyanate group-containing polyester prepolymer described later. An amine is preferable in that a high molecular weight can be obtained.

  There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be contained singly or in combination of two or more.

  There is no restriction | limiting in particular as said amines which are the said active hydrogen group containing compound, According to the objective, it can select suitably. Examples thereof include diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, and those obtained by blocking the amino group of these amines.

Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine, etc.); aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyamine include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid include aminopropionic acid and aminocaproic acid.
In addition, examples of those in which the amino group of these amines is blocked include, for example, any of these amines (diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, etc.) and ketones (acetone, Methyl ethyl ketone, methyl isobutyl ketone and the like) and ketimine compounds, oxazolyson compounds and the like.

  These may be used individually by 1 type and may use 2 or more types together. Among these, the amines are particularly preferably diamine and a mixture of a diamine and a small amount of a trivalent or higher polyamine.

--- Polymer capable of reacting with active hydrogen group-containing compound ---
The polymer that can react with the active hydrogen group-containing compound is not particularly limited as long as it is a polymer having at least a group that can react with the active hydrogen group-containing compound, and can be appropriately selected according to the purpose. Among them, a urea-bond-forming group-containing polyester resin (RMPE) is excellent in that it has excellent fluidity and transparency when melted, easily adjusts the molecular weight of the polymer component, and is excellent in oilless low-temperature fixability and releasability in dry toners. ) Is preferred, and an isocyanate group-containing polyester prepolymer is more preferred.

  There is no restriction | limiting in particular as said isocyanate group containing polyester prepolymer, According to the objective, it can select suitably. Examples thereof include polycondensates of polyols and polycarboxylic acids, and those obtained by reacting active hydrogen group-containing polyester resins with polyisocyanates.

  There is no restriction | limiting in particular as said polyol, According to the objective, it can select suitably. For example, 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, 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 alicyclic diol, alkylene oxide of the bisphenol Diols such as adducts (ethylene oxide, propylene oxide, butylene oxide, etc.); polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.), trivalent or higher phenols (phenol novolac) , Cresol novolac, etc.) trihydric or higher polyols such as alkylene oxide adducts of trihydric or higher polyphenols; mixtures of diols and trihydric or higher polyols.

These may be used individually by 1 type and may use 2 or more types together.
Among these, the polyol is preferably the diol alone or a mixture of the diol and a small amount of the trivalent or higher polyol.

  Examples of the diol include alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols (bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, etc.) Is preferred.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer of the said polyol, According to the objective, it can select suitably. For example, 0.5 mass%-40 mass% are preferable, 1 mass%-30 mass% are more preferable, and 2 mass%-20 mass% are more preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both the storage stability of the toner and the low-temperature fixability. Fixability may deteriorate.

  There is no restriction | limiting in particular as said polycarboxylic acid, According to the objective, it can select suitably. For example, alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.); Examples thereof include polycarboxylic acids (such as aromatic polycarboxylic acids having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid). These may be used individually by 1 type and may use 2 or more types together.

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

  There is no restriction | limiting in particular as a mixing ratio of the said polyol and the said polycarboxylic acid, According to the objective, it can select suitably. The equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] of the polyol and the carboxyl group [COOH] of the polycarboxylic acid is preferably 2/1 to 1/1, and 1.5 / 1 to 1/1. Is more preferable, and 1.3 / 1 to 1.02 / 1 is more preferable.

  There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably. For example, aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane Diisocyanates, etc.); cycloaliphatic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4 '-Diisocyanato-3,3'-dimethyldiphenyl, 3-methyl Diphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate, etc.); araliphatic diisocyanate (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates (Tris-isocyanate) Natoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, etc.); these phenol derivatives; those blocked with oxime, caprolactam and the like. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as a mixing ratio of the said polyisocyanate and the said active hydrogen group containing polyester resin (hydroxyl group containing polyester resin), According to the objective, it can select suitably. The equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] of the polyisocyanate and the hydroxyl group [OH] of the hydroxyl group-containing polyester resin is preferably 5/1 to 1/1, and 4/1 to 1.2. / 1 is more preferable, and 3/1 to 1.5 / 1 is particularly preferable. When the equivalent ratio [NCO] / [OH] is less than 1/1, the offset resistance may be deteriorated, and when it exceeds 5/1, the low-temperature fixability may be deteriorated.

  There is no restriction | limiting in particular as content of the said polyisocyanate in the said isocyanate group containing polyester prepolymer, According to the objective, it can select suitably. 0.5 mass%-40 mass% are preferable, 1 mass%-30 mass% are more preferable, 2 mass%-20 mass% are especially preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both storage stability and low-temperature fixability. May get worse.

  The average number of isocyanate groups contained in one molecule of the isocyanate group-containing polyester prepolymer is preferably 1 or more, more preferably 1.2 to 5, and more preferably 1.5 to 4. When the average number is less than 1, the molecular weight of the polyester resin (RMPE) modified with a urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  There is no restriction | limiting in particular as a mixing ratio of the said isocyanate group containing polyester prepolymer and the said amines, According to the objective, it can select suitably. The mixing equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the isocyanate group-containing polyester prepolymer and the amino group [NHx] in the amines is preferably 1/3 to 3/1. / 2 to 2/1 is more preferable, and 1 / 1.5 to 1.5 / 1 is particularly preferable. If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be reduced. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin is reduced. Hot offset resistance may deteriorate.

--- Method for synthesizing polymer capable of reacting with active hydrogen group-containing compound ---
There is no restriction | limiting in particular as a synthesis method of the polymer which can react with the said active hydrogen group containing compound, According to the objective, it can select suitably. For example, in the case of the isocyanate group-containing polyester prepolymer, the polyol and the polycarboxylic acid are heated to 150 ° C. to 280 ° C. in the presence of a known esterification catalyst (titanium tetrabutoxide, dibutyltin oxide, etc.). And a method of synthesizing by reacting the polyisocyanate with the hydroxyl group-containing polyester at 40 ° C. to 140 ° C. after the water is distilled off to obtain the hydroxyl group-containing polyester. .

  There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the polymer which can react with the said active hydrogen group containing compound, According to the objective, it can select suitably. The molecular weight distribution by GPC (gel permeation chromatography) of the soluble portion of tetrahydrofuran (THF) is preferably 3,000 to 40,000, more preferably 4,000 to 30,000. When the weight average molecular weight (Mw) is less than 3,000, the storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

  The weight average molecular weight (Mw) can be measured, for example, as follows. First, the column was stabilized in a 40 ° C. heat chamber, and at this temperature, tetrahydrofuran (THF) as a column solvent was flowed at a flow rate of 1 mL / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 μL to 200 μL of a tetrahydrofuran sample solution.

In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared by several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical co. The molecular weights are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 manufactured by Toyo Soda Kogyo Co., Ltd. It is preferable to use 1.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector can be used as the detector.

<< Releasing agent >>
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably. For example, plant wax (carnauba wax, cotton wax, wood wax, rice wax, etc.), animal wax (beeswax, lanolin, etc.), mineral wax (ozokerite, cercin etc.), petroleum wax (paraffin, microcrystalline, petrolatum, etc.) ) Waxes and waxes; synthetic hydrocarbon waxes (Fischer-Tropsch wax, polyethylene wax, etc.), synthetic waxes other than natural waxes (esters, ketones, ethers, etc.); 1,2-hydroxystearic acid amide, Fatty acid amides such as stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; homopolymers or copolymers of polyacrylates such as poly (n-stearyl methacrylate) and poly (n-lauryl methacrylate) which are low molecular weight crystalline polymers ( Acrylic acid n- Crystalline polymer having a stearyl over long chain alkyl group in the side chain of ethyl methacrylate copolymer, etc.) and the like; and the like.

  Among these, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, monoester wax, and rice wax are preferable because less unnecessary volatile organic compounds are generated during fixing.

  A commercial item can be used for the mold release agent. Examples of the microcrystalline wax include “HI-MIC-1045”, “HI-MIC-1070”, “HI-MIC-1080”, “HI-MIC-1090” manufactured by Nippon Seiki Co., Ltd. “Bsquare 180 White”, “Bsquare 195” manufactured by WAX Petrolife, “CAREVALAC WN-1442” manufactured by Cray Valley, and the like.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 60 to 100 degreeC is preferable and 65 to 90 degreeC is more preferable. When the melting point is 60 ° C. or more, even when stored at a high temperature of about 30 to 50 ° C., it is possible to suppress the exudation of the release agent from the toner base material and maintain good heat-resistant storage stability. When the temperature is 100 ° C. or lower, it is preferable because cold offset hardly occurs during fixing at a low temperature.

  The melting point is measured by DSC. For example, it can be measured under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.

[Measurement condition]
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 mL / min)
Temperature conditions 1st. Temperature rise Start temperature: 20 ° C., Temperature rise rate: 10 ° C./min, End temperature: 150 ° C., Holding time: None 1st. Temperature drop Temperature drop: 10 ° C./min, end temperature: 20 ° C., retention time: none 2nd. Temperature rise Temperature rise rate: 10 ° C / min, end temperature: 150 ° C
The measurement results are analyzed using data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation.
The melting point is 2nd. The temperature at the top of the endothermic peak measured at elevated temperature is used.

  The release agent is preferably present in a dispersed state in the toner base particles, and for this purpose, the release agent and the binder resin are preferably incompatible with each other. The method for finely dispersing the release agent in the toner base particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method of dispersing by applying a shearing force of kneading at the time of toner production may be mentioned.

  The dispersion state of the release agent can be confirmed by observing a thin film slice of toner particles with a transmission electron microscope (TEM). The dispersion diameter of the release agent is preferably small, but if it is too small, there are cases where bleeding during fixing is insufficient. Therefore, if the release agent can be confirmed at a magnification of 10,000, the release agent is present in a dispersed state. When the release agent cannot be confirmed at 10,000 times, even when finely dispersed, the dyeing at the time of fixing becomes insufficient.

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, According to the objective, it can select suitably. Especially, 3 mass%-15 mass% are preferable, and 5 mass%-10 mass% are more preferable. When the content is less than 3% by mass, the hot offset resistance may be deteriorated, which is not preferable. When the content exceeds 15% by mass, the exudation amount of the release agent during fixing tends to be excessive. This is not preferable because the heat-resistant storage stability tends to deteriorate.

<< Other ingredients >>
-Colorant-
There is no restriction | limiting in particular as a coloring agent used for the said toner, According to the objective, it can select suitably from a well-known coloring agent.

  The color of the colorant of the toner is not particularly limited and may be appropriately selected depending on the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. The toner of each color can be obtained by appropriately selecting the type of the colorant, but is preferably a color toner.

  Examples of black products include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45 and copper phthalocyanine pigments in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner may occur. The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. Such a resin is not particularly limited, but it is preferable to use a binder resin or a resin having a structure similar to the binder resin from the viewpoint of compatibility with the binder resin.

  The masterbatch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

<< External additive >>
There is no restriction | limiting in particular as said external additive, According to the objective, it can select suitably from well-known things. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (eg, zinc stearate, aluminum stearate, etc.); metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoro Examples thereof include polymers. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the hydrophobized silica fine particles include HDK H2000T, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303VP (all manufactured by Clariant Japan); R972, R974, RX200, RY200, R202, R805, R812, NX90G (all manufactured by Nippon Aerosil Co., Ltd.) and the like.

  Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); MT-150W. , MT-500B, MT-600B, MT-150A (all of which are manufactured by Teica).

  Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T (any Also, manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika); IT-S (produced by Ishihara Sangyo Co., Ltd.).

  There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.3 mass part-3.0 mass parts are preferable with respect to 100 mass parts of toner base particles. 0.5 parts by mass to 2.0 parts by mass is more preferable.

  The total coverage of the external additive with respect to the toner base particles is not particularly limited, but is preferably 50% to 90%, and more preferably 60% to 80%.

<Toner production method>
The toner production method and materials in the present invention can be any known ones as long as they satisfy the conditions, and are not particularly limited. For example, the toner particles may be mixed in a kneading and pulverization method or an aqueous medium. There is a so-called chemical method of granulating.

  Examples of the chemical method include a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, a dispersion polymerization method, etc., in which a monomer is used as a starting material; a resin or a resin precursor is dissolved in an organic solvent and the like in an aqueous medium. Dispersing or emulsifying dissolution suspension method; in the dissolution suspension method, an oil phase composition containing a resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group is contained in resin fine particles. A method of emulsifying or dispersing in an aqueous medium and reacting the active hydrogen group-containing compound and the reactive group-containing prepolymer in the aqueous medium (production method (I)); Phase inversion emulsification method in which water is added to a solution composed of an emulsifier; the resin particles obtained by these methods are aggregated in a state of being dispersed in an aqueous medium and granulated into particles of a desired size by heating and melting. Aggregation And the like.

Among these, the toner obtained by the dissolution suspension method, the production method (I), and the aggregation method is preferable from the viewpoint of granulation properties (particle size distribution control, particle shape control, etc.), and the production method (I). The resulting toner is more preferred.
In the following, detailed description of these production methods will be given.

  The kneading and pulverizing method is, for example, a method of producing the toner base particles by pulverizing and classifying a toner material having at least a colorant, a binder resin, and a release agent melted and kneaded.

  In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay, a PCM type twin screw extruder manufactured by Ikegai Iron Works, and a Kneader manufactured by Buss Co., Ltd. are suitable. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

  In the dissolution suspension method, for example, an oil phase composition in which a toner composition containing at least a binder resin or a resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent is used. This is a method for producing toner base particles by dispersing or emulsifying in a medium.

The organic solvent used for dissolving or dispersing the toner composition is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later.
Examples of the organic solvent include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl. Ether solvents such as ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2 -Alcohol solvents, such as ethyl hexyl alcohol and benzyl alcohol, and these 2 or more types of mixed solvents are mentioned.

In the dissolution suspension method, when the oil phase composition is dispersed or emulsified in an aqueous medium, an emulsifier or a dispersant may be used as necessary.
As the emulsifier or dispersant, known surfactants, water-soluble polymers and the like can be used. The surfactant is not particularly limited, and is an anionic surfactant (alkyl benzene sulfonic acid, phosphate ester, etc.), a cationic surfactant (quaternary ammonium salt type, amine salt type, etc.), an amphoteric surfactant (carbon carboxyl). Acid salt type, sulfate ester type, sulfonate salt type, phosphate ester salt type, etc.), nonionic surfactants (AO addition type, polyhydric alcohol type, etc.) and the like. One surfactant may be used alone, or two or more surfactants may be used in combination.

Examples of the water-soluble polymer include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan. , Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized sodium hydroxide of polyacrylic acid) , Sodium acrylate-acrylic acid ester copolymer), sodium hydroxide of styrene-maleic anhydride copolymer ( Min) neutralized product water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.
Moreover, said organic solvent, a plasticizer, etc. can also be used together as an auxiliary | assistant of emulsification or dispersion | distribution.

  The toner according to the present invention includes at least a binder resin, a binder resin precursor having a functional group capable of reacting with an active hydrogen group (reactive group-containing prepolymer), a colorant, a release agent, in a dissolution suspension method. And the oil phase composition containing the charge control agent is dispersed or emulsified in the aqueous medium containing the resin fine particles, and the reactive hydrogen group-containing compound contained in the oil phase composition and / or the aqueous medium, and the reactivity It is preferable to obtain the toner base particles by a method of reacting with the group-containing prepolymer (Production Method (I)).

The resin fine particles can be formed using a known polymerization method, but is preferably obtained as an aqueous dispersion of resin fine particles. Examples of the method for preparing an aqueous dispersion of resin fine particles include the methods shown in the following (a) to (h).
(A) A method in which an aqueous dispersion of resin fine particles is directly prepared from a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method.
(B) After dispersing a precursor of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin (monomer, oligomer, etc.) or a solvent solution thereof in an aqueous medium in an aqueous medium, A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent to cure.
(C) Polyaddition or condensation resin precursors (monomers, oligomers, etc.) such as polyester resins, polyurethane resins, and epoxy resins, or solvent solutions thereof (preferably liquids, which may be liquefied by heating). A method for preparing an aqueous dispersion of resin fine particles by dissolving a suitable emulsifier in the mixture and then adding water to effect phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. A method of preparing an aqueous dispersion of resin fine particles by obtaining resin fine particles and then dispersing in water in the presence of an appropriate dispersant.
(E) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Then, resin fine particles are dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of resin fine particles.
(F) A poor solvent is added to a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or heated to a solvent in advance. By cooling the dissolved resin solution, the resin fine particles are precipitated, the solvent is removed to form the resin fine particles, and then the resin fine particles are dispersed in water in the presence of an appropriate dispersant to disperse the resin fine particles in water. A method for preparing a liquid.
(G) A resin solution obtained by dissolving a resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing in a solvent and then removing the solvent by heating, decompression or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, and then water To prepare an aqueous dispersion of resin fine particles by phase inversion emulsification.

  The volume average particle diameter of the resin fine particles is preferably 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 120 nm or less. When the volume average particle size of the resin fine particles is less than 10 nm or more than 300 nm, the particle size distribution of the toner may be deteriorated.

  The solid content concentration of the oil phase is preferably about 40 to 80%. If the concentration is too high, dissolution or dispersion becomes difficult, and the viscosity becomes high and difficult to handle. If the concentration is too low, the productivity of the toner decreases.

  The toner composition other than the binder resin such as the colorant, the release agent, and the charge control agent, and the masterbatch thereof are individually dissolved or dispersed in an organic solvent, and then the binder resin solution or dispersion. You may mix with a liquid.

  As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  If the amount of the active hydrogen group-containing compound added is too large, the particle size distribution of the toner may deteriorate, and the variation in surface potential between the toner particles may increase. is there.

  The dispersion or emulsification method in the aqueous medium is not particularly limited, and known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable from the viewpoint of reducing the particle size of the particles. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

  In order to remove the organic solvent from the obtained emulsified dispersion, there is no particular limitation, and a known method can be used. For example, the whole system is gradually raised while stirring the whole system under normal pressure or reduced pressure. A method of warming and completely evaporating and removing the organic solvent in the droplets can be employed.

  As a method of washing and drying the toner base particles dispersed in the aqueous medium, a known technique is used. That is, after solid-liquid separation with a centrifuge, a filter press or the like, the obtained toner cake is redispersed in ion-exchanged water at room temperature to about 40 ° C., and the pH is adjusted with acid or alkali as necessary. After that, the process of solid-liquid separation is repeated several times to remove impurities and surfactants, and further, the toner is dried by an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. Obtain a powder. At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

  In the agglomeration method, for example, a toner base particle is produced by mixing and aggregating a resin fine particle dispersion comprising at least a binder resin, a colorant particle dispersion, and a release agent particle dispersion as necessary. is there. The resin fine particle dispersion is obtained by a known method such as emulsion polymerization, seed polymerization, phase inversion emulsification, and the like. The colorant particle dispersion and the release agent particle dispersion are obtained by a known wet dispersion method. It can be obtained by dispersing a colorant or a release agent in an aqueous medium.

For the control of the aggregation state, methods such as applying heat, adding a metal salt, and adjusting pH are preferably used.
There is no restriction | limiting in particular as said metal salt, The monovalent metal which comprises salts, such as sodium and potassium; The bivalent metal which comprises salts, such as calcium and magnesium; The trivalent metal which comprises salts, such as aluminum, etc. Is mentioned.
Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion, and sulfate ion. Among these, magnesium chloride, aluminum chloride, and complexes and multimers thereof are preferable. .
Also, heating between the agglomeration and after completion of the agglomeration can promote fusion between the resin fine particles, which is preferable from the viewpoint of toner uniformity. Furthermore, the shape of the toner can be controlled by heating. Normally, the toner becomes more spherical when heated further.

  As the method for washing and drying the toner base particles dispersed in the aqueous medium, the above-described method and the like can be used.

Further, in order to improve the fluidity, storage stability, developability, and transferability of the toner, the coalesced particles are added to and mixed with the toner base particles produced as described above. Inorganic fine particles may be added and mixed.
For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

(Developer)
The developer of the present invention contains at least the toner and contains other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

In the case of the one-component developer using the toner, toner agglomeration hardly occurs over time even against stress due to the developing means, and toner filming on the developing roller as the developer carrying member, The toner is not fused to a layer thickness regulating member such as a blade for reducing the thickness of the toner, and a good and stable image quality can be obtained by maintaining good image density stability and transferability.
In addition, in the case of the two-component developer using the toner, toner agglomeration is less likely to occur over time with respect to agitation stress by the developing unit, and the occurrence of abnormal images is suppressed and image density stability is achieved. In addition, by maintaining good transferability, good and stable image quality can be obtained.

<Career>
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core particle and the resin layer (coating layer) which coat | covers this core particle is preferable.

<< Core particle >>
The core particles are not particularly limited as long as they are magnetic core particles, and can be appropriately selected according to the purpose. Examples thereof include ferromagnetic metals such as iron and cobalt; iron oxides such as magnetite, hematite and ferrite; and resin particles in which magnetic materials such as various alloys and compounds are dispersed in the resin. Among these, Mn-based ferrite, Mn-Mg-based ferrite, Mn-Mg-Sr-based ferrite and the like are preferable from the viewpoint of environmental considerations.

-Weight average particle diameter Dw of core particles-
The weight average particle diameter Dw of the core particles refers to the particle diameter at an integrated value of 50% in the particle size distribution of the core particles obtained by a laser diffraction or scattering method. There is no restriction | limiting in particular as the weight average particle diameter Dw of the said core particle, Although it can select suitably according to the objective, 10 micrometers-80 micrometers are preferable, and 20 micrometers-65 micrometers are more preferable.

The weight average particle diameter Dw of the core particles is measured by using a microtrac particle size distribution meter (HRA9320-X100, manufactured by Honeywell) as a particle diameter distribution (relationship between number frequency and particle diameter) of particles measured on a number basis. Measured under the conditions described below using the following formula (I). Each channel represents a length for dividing the particle size range in the particle size distribution chart into measurement width units, and the lower limit value of the particle size stored in each channel is adopted as the representative particle size.
Dw = {1 / Σ (nD ₃ )} × {Σ (nD ₄ )} (I)
However, in said formula (I), D represents the representative particle size (micrometer) of the core particle which exists in each channel, and n represents the total number of the core particle which exists in each channel.

[Measurement condition]
[1] Particle size range: 100 μm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

<< Coating layer >>
The coating layer contains at least a resin, and may contain other components such as a filler as necessary.

-Resin-
There is no restriction | limiting in particular as resin for forming the coating layer of a carrier, According to the objective, it can select suitably. For example, a crosslinkable copolymer containing polyolefin (for example, polyethylene, polypropylene, etc.) or a modified product thereof, polystyrene, acrylic resin, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc .; consisting of an organosiloxane bond Silicone resins or modified products thereof (for example, modified products by alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.); polyamide; polyester; polyurethane; polycarbonate; urea resin; melamine resin; benzoguanamine resin; Examples thereof include polyimide resins and derivatives thereof. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is preferable.

  There is no restriction | limiting in particular as said silicone resin, According to the objective, it can select suitably from the silicone resin generally known. For example, a straight silicone resin composed only of an organosiloxane bond, a silicone resin modified with alkyd, polyester, epoxy, acrylic, urethane, or the like can be used.

  Examples of the straight silicone resin include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2405, SR2406 (manufactured by Toray Dow Corning Silicone).

  Specific examples of the modified silicone resin include epoxy-modified product: ES-1001N, acrylic-modified silicone: KR-5208, polyester-modified product: KR-5203, alkyd-modified product: KR-206, and urethane-modified product: KR-. 305 (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified product: SR2115, alkyd-modified product: SR2110 (manufactured by Toray Dow Corning Silicone), and the like.

The silicone resin can be used alone, but a crosslinking reactive component, a charge amount adjusting component, and the like can be used at the same time.
Examples of the crosslinking reactive component include a silane coupling agent. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, aminosilane coupling agent, and the like.

-Filler-
There is no restriction | limiting in particular as said filler, According to the objective, it can select suitably, For example, a conductive filler, a nonelectroconductive filler, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to contain a conductive filler and a non-conductive filler in the coating layer.

The conductive filler refers to a filler having a powder specific resistance value of 100 Ω · cm or less.
The said nonelectroconductive filler points out the filler whose powder specific resistance value exceeds 100 ohm * cm.
The powder specific resistance value of the filler is measured by a powder resistance measurement system (MCP-PD51, manufactured by Dia Instruments) and a resistivity meter (4-terminal 4-probe system, Loresta GP, manufactured by Mitsubishi Chemical Analytech). Can be measured under the conditions of a sample of 1.0 g, an electrode interval of 3 mm, a sample radius of 10.0 mm, and a load of 20 kN.

--Conductive filler--
There is no restriction | limiting in particular as said electroconductive filler, According to the objective, it can select suitably. For example, a conductive filler formed as a layer of tin dioxide or indium oxide on a substrate such as aluminum oxide, titanium oxide, zinc oxide, barium sulfate, silicon oxide, zirconium oxide, etc .; a conductive filler formed using carbon black, etc. It is done. Among these, a conductive filler containing aluminum oxide, titanium oxide, and barium sulfate is preferable.

--Non-conductive filler--
There is no restriction | limiting in particular as said nonelectroconductive filler, According to the objective, it can select suitably, For example, it forms using aluminum oxide, titanium oxide, barium sulfate, zinc oxide, silicon dioxide, zirconium oxide etc. Non-conductive filler etc. are mentioned. Among these, non-conductive fillers containing aluminum oxide, titanium oxide, and barium sulfate are preferable.

<< Carrier manufacturing method >>
There is no restriction | limiting in particular as a manufacturing method of the said carrier, Although it can select suitably according to the objective, The said resin and the said filler are contained in the surface of the said core particle using a fluid bed type coating apparatus. The method of manufacturing by apply | coating a coating layer forming solution is preferable. In addition, when apply | coating the said coating layer forming solution, you may advance condensation of the resin contained in the said coating layer, and after apply | coating the said coating layer forming solution, condensation of the resin contained in the said coating layer You may proceed. There is no restriction | limiting in particular as the condensation method of the said resin, According to the objective, it can select suitably, For example, the method etc. which give a heat | fever, light, etc. to the said coating layer formation solution, etc. are mentioned. .

-Weight average particle diameter Dw of carrier-
The weight average particle diameter Dw of the carrier refers to the particle diameter at an integrated value of 50% in the particle size distribution of the core particles obtained by a laser diffraction / scattering method. There is no restriction | limiting in particular as the weight average particle diameter Dw of the said carrier, Although it can select suitably according to the objective, 10 micrometers-80 micrometers are preferable, and 20 micrometers-65 micrometers are more preferable.

For the measurement of the weight average particle diameter Dw of the carrier, the particle size distribution (relationship between the number frequency and the particle diameter) of the particles measured on the basis of the number is used using a Microtrac particle size distribution meter (HRA9320-X100, manufactured by Honeywell). Measured under the conditions described below and calculated using the following formula (II). Each channel represents a length for dividing the particle size range in the particle size distribution chart into measurement width units, and the lower limit value of the particle size stored in each channel is adopted as the representative particle size.
Dw = {1 / Σ (nD ₃ )} × {Σ (nD ₄ )} (II)
However, in said formula (II), D represents the representative particle size (micrometer) of the carrier which exists in each channel, and n represents the total number of the carriers which exist in each channel.

[Measurement condition]
[1] Particle size range: 100 μm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

  When the developer is a two-component developer, the mixing ratio of the toner and the carrier in the two-component developer is preferably such that the mass ratio of the toner to the carrier is 2.0 to 12.0% by mass, More preferably, it is 2.5-10.0 mass%.

(Toner storage unit)
The toner storage unit in the present invention refers to a unit in which toner is stored in a unit having a function of storing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, and a process cartridge.
The toner container is a container that contains toner.
The developing device is a unit having a means for containing and developing toner.
The process cartridge is a cartridge in which at least the electrostatic latent image carrier and the developing unit are integrated, accommodates toner, and is detachable from the image forming apparatus. The process cartridge may further include at least one selected from charging means, exposure means, and cleaning means.

Next, an embodiment of the process cartridge is shown in FIG. As shown in FIG. 1, the process cartridge according to this embodiment includes an electrostatic latent image carrier 101, includes a charging device 102, a developing device 104, and a cleaning unit 107, and further includes other means as necessary. . In FIG. 2, reference numeral 103 denotes exposure from the exposure apparatus, and reference numeral 105 denotes recording paper.
As the electrostatic latent image carrier 101, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used for the charging device 102.
An image forming process using the process cartridge shown in FIG. 1 will be described. The electrostatic latent image carrier 101 is rotated clockwise, and an electrostatic latent image corresponding to the exposure image is formed on the surface by charging by the charging device 102 and exposure 103 by an exposure unit (not shown). .
The electrostatic latent image is developed with toner by the developing device 104, and the toner development is transferred to the recording paper 105 by the transfer roller 108 and printed out. Next, the surface of the latent image carrier after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming method and image forming apparatus)
The image forming method used in the present invention preferably includes a step of forming an image by a one-component developing method, and includes an electrostatic latent image forming step (charging step and exposure step), a developing step, a transfer step, and a fixing step. And other processes appropriately selected as necessary, for example, a static elimination process, a cleaning process, a recycling process, a control process, and the like.
The image forming apparatus of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit (charging unit and exposure unit) that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic unit. Developing means for developing a latent image using a developer to form a visible image, transfer means for transferring the visible image onto a recording medium, and fixing for fixing the transferred image transferred onto the recording medium And at least means. Furthermore, other means appropriately selected as necessary, for example, a static elimination means, a cleaning means, a recycling means, a control means and the like are provided.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. It can be selected appropriately. The shape is preferably a drum shape, and examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors (OPC) such as polysilane and phthalopolymethine. Among these, an organic photoreceptor (OPC) is preferable in that a higher definition image can be obtained.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by electrostatic latent image forming means. Can do.
The electrostatic latent image forming unit includes, for example, a charging unit (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure that exposes the surface of the electrostatic latent image carrier imagewise. Means (exposure unit).

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.
The charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying a direct current and an alternating voltage.
Further, the charger is a charging roller disposed in a non-contact proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is carried by applying a direct current and an alternating voltage to the charging roller. Those that charge the body surface are preferred.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the latent electrostatic image bearing member charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image with the toner to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner, and can be performed by the developing unit.
The developing unit preferably includes, for example, at least a developing unit that accommodates the toner and can apply the toner to the electrostatic latent image in a contact or non-contact manner, and includes a toner-containing container. Etc. are more preferable.

The developing device may be a monochromatic developing device or a multi-color developing device, and has, for example, an agitator that frictionally agitates and charges the toner and a rotatable magnet roller. A thing etc. are mentioned suitably.
In the developing unit, for example, the toner is mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means, the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. The number of the transfer means may be one, or two or more.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the developer of each color is transferred to the recording medium, or the developer of each color. On the other hand, it may be carried out at the same time in a state where these are laminated.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt.
The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member It is preferably a unit that heats and fixes a recording medium on which an unfixed image is formed. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

-Other processes and other means-
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning unit is not particularly limited, and may be selected from known cleaners as long as it can remove the toner remaining on the electrostatic latent image carrier. For example, a magnetic brush cleaner Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit. There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.
The control step is a step of controlling each step, and each step can be suitably performed by a control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  FIG. 2 shows a first example of the image forming apparatus of the present invention. The image forming apparatus 100 </ b> A includes a photosensitive drum 10, a charging roller 20, an exposure device, a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a static elimination lamp 70.

  The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged on the inner side, and can move in the direction of the arrow in the figure. A part of the three rollers 51 also functions as a transfer bias roller that can apply a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer belt 50. Further, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring the toner image to the transfer paper 95 is disposed opposite to the intermediate transfer belt 50. Further, around the intermediate transfer belt 50, a corona charging device 58 for applying a charge to the toner image transferred to the intermediate transfer belt 50 is connected to the photosensitive drum 10 with respect to the rotation direction of the intermediate transfer belt 50. It is disposed between the contact portion of the intermediate transfer belt 50 and the contact portion of the intermediate transfer belt 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Each color developing unit 45 includes a developer container 42, a developer supply roller 43, and a developing roller (developer carrier) 44. The developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can move in the direction of the arrow in the figure. Further, a part of the developing belt 41 is in contact with the photosensitive drum 10.

  Next, a method for forming an image using the image forming apparatus 100A will be described. First, the charging roller 20 is used to uniformly charge the surface of the photosensitive drum 10, and then the exposure light L is exposed to the photosensitive drum 10 using an exposure device (not shown) to form an electrostatic latent image. Form. Next, the electrostatic latent image formed on the photosensitive drum 10 is developed with the toner supplied from the developing device 40 to form a toner image. Further, after the toner image formed on the photosensitive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, the transfer bias applied from the transfer roller 80 is used. Then, it is transferred (secondary transfer) onto the transfer paper 95. On the other hand, the photosensitive drum 10 on which the toner image is transferred to the intermediate transfer belt 50 is discharged by the discharging lamp 70 after the toner remaining on the surface is removed by the cleaning device 60.

  FIG. 3 shows a second example of the image forming apparatus used in the present invention. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are arranged directly facing each other around the photosensitive drum 10 without providing the developing belt 41. Other than that, the configuration is the same as that of the image forming apparatus 100A.

  FIG. 4 shows a third example of the image forming apparatus used in the present invention. The image forming apparatus 100 </ b> C is a tandem type color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The intermediate transfer belt 50 provided at the center of the copying apparatus main body 150 is an endless belt stretched around three rollers 14, 15 and 16, and can move in the direction of the arrow in the figure. In the vicinity of the roller 15, a cleaning device 17 having a cleaning blade for removing toner remaining on the intermediate transfer belt 50 on which the toner image has been transferred onto the recording paper is disposed. The image forming units 120Y, 120C, 120M, and 120K for yellow, cyan, magenta, and black are juxtaposed along the conveyance direction while facing the intermediate transfer belt 50 stretched by the rollers 14 and 15.

  An exposure device 21 is disposed in the vicinity of the image forming unit 120. Further, the secondary transfer belt 24 is disposed on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is disposed. The secondary transfer belt 24 is an endless belt stretched around a pair of rollers 23, and the recording paper and the intermediate transfer belt 50 conveyed on the secondary transfer belt 24 are between the rollers 16 and 23. Can touch.

  Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 is provided with a fixing belt 26 that is an endless belt stretched between a pair of rollers, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26. Is arranged. A sheet reversing device 28 for reversing the recording paper when an image is formed on both sides of the recording paper is disposed in the vicinity of the secondary transfer belt 24 and the fixing device 25.

Next, a method for forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a color document is set on the contact glass 32 of the scanner 300 to automatically convey the document. The device 400 is closed.
When the start switch is pressed, when an original is set on the automatic document feeder 400, after the original is conveyed and moved onto the contact glass 32, on the other hand, when the original is set on the contact glass 32, Immediately, the scanner 300 is driven, and the first traveling body 33 including the light source and the second traveling body 34 including the mirror travel. At this time, the reflected light from the original surface of the light irradiated from the first traveling body 33 is reflected by the second traveling body 34 and then received by the reading sensor 36 via the imaging lens 35, whereby the original is received. It is read and image information of black, yellow, magenta and cyan is obtained.

The image information for each color is transmitted to the image forming unit 120 for each color, and a toner image for each color is formed. As shown in FIG. 5, each color image forming unit 120 includes a photosensitive drum 10, a charging roller 160 that uniformly charges the photosensitive drum 10, and the image information of each color, respectively. An exposure device that exposes the exposure light L to form an electrostatic latent image of each color; a developing device 61 that develops the electrostatic latent image with a developer of each color to form a toner image of each color; A transfer roller 62 for transferring onto the transfer belt 50, a cleaning device 63 having a cleaning blade, and a static elimination lamp 64 are provided.
The toner images of the respective colors formed by the image forming units 120 of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is stretched and moved by the rollers 14, 15, and 16, and superimposed to form a composite toner image. It is formed.

  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, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, guided to the manual paper feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied in order to remove paper dust from the recording paper.

  Next, by rotating the registration roller 49 in synchronization with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is sent. The toner image is transferred onto the recording paper (secondary transfer). The toner remaining on the intermediate transfer belt 50 to which the composite toner image has been transferred is removed by the cleaning device 17.

  The recording paper on which the composite toner image has been transferred is conveyed by the secondary transfer belt 24 and then the composite toner image is fixed by the fixing device 25. Next, the conveyance path of the recording paper is switched by the switching claw 55, and the recording paper is discharged onto the paper discharge tray 57 by the discharge roller 56. Alternatively, the recording path of the recording paper is switched by the switching claw 55, reversed by the sheet reversing device 28, an image is similarly formed on the back side, and then discharged onto the discharge tray 57 by the discharge roller 56. .

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to the following example. In the description in the examples, [%] indicates mass%, and unless otherwise specified, when “part” is simply indicated, it indicates “part by mass”.

(Example 1)
-Synthesis of polyester resin A-
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A propylene oxide 2 mol adduct and bisphenol A propylene oxide 3 mol adduct in a molar ratio of 80/20, isophthalic acid and adipine The acid was adjusted to a molar ratio of 70/30, OH / COOH = 1.33, and reacted with 500 ppm of titanium tetraisopropoxide at 230 ° C. for 10 hours at normal pressure. Next, 26 parts of benzoic acid was added to the reaction vessel and reacted at a reduced pressure of 10 mmHg to 15 mmHg for 5 hours. Then, 11 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. and normal pressure for 3 hours. ] Was obtained.

(Preparation of masterbatch (MB) 1)
1,200 parts of water, carbon black (manufactured by Printex 35 Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5] 540 parts and [polyester resin A] 1,200 parts were added, and Henschel mixer (Mitsui Mining Co., Ltd.) The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

(Synthesis of polyester prepolymer 1)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts by mass of terephthalic acid, 22 parts by mass of merit acid and 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Furthermore, [intermediate polyester] was synthesized by reacting under reduced pressure of 10 mmHg to 15 mmHg for 5 hours. Next, 410 parts by mass of the synthesized [intermediate polyester], 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and 100 ° C. Was reacted for 5 hours to synthesize [Polyester Prepolymer 1].

(Preparation of organically modified layered inorganic compound containing Al)
Montmorillonite is used as the layered inorganic compound, dimethylstearylbenzylammonium (DMSB) is used as the organic cation modifier, and dimethylstearylbenzylammonium chloride (A) sufficiently dissolved in water in montmorillonite dispersed in water is used as the cation of montmorillonite. An organically modified layered inorganic compound was prepared by adding, mixing, washing, dehydrating and drying so that the molar ratio (A / B) to (B) was 0.8.

<Preparation of toner>
-Preparation of release agent dispersion-
70 parts by weight of Carnauba wax (WA-05, manufactured by Celerica Noda), 140 parts by weight of [Polyester Resin A], and 290 parts by weight of ethyl acetate are placed in a container equipped with a stirring bar and a thermometer, and the mixture is stirred at 75 ° C. The temperature was raised and held at 75 ° C. for 1.5 hours, then cooled to 30 ° C. in 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), the liquid feeding speed was 5 kg / hr, and the disk peripheral speed was 6 m. / Sec, filled with 80% by volume of 0.5 mm zirconia beads and dispersed under the conditions of 3 passes to obtain a [release agent dispersion].

-Production of oil phase 1-
In a container equipped with a thermometer and a stirrer, 113 parts by weight of [polyester resin A], 88 parts by weight of [release agent dispersion], 42 parts by weight of [masterbatch 1], organically modified layered inorganic compound 2 containing Al 0.0 mass% (converted to polyester resin + mold release agent) and 150 parts by mass of ethyl acetate, pre-dispersed with a stirrer, and then rotated with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) The mixture was stirred at 5,000 rpm and uniformly dissolved and dispersed to obtain [Oil Phase 1].

-Production of aqueous dispersion of resin fine particles-
In a reaction vessel equipped with a stirrer and a thermometer, 600 parts by mass of water, 120 parts by mass of styrene, 100 parts by mass of methacrylic acid, 45 parts by mass of butyl acrylate, sodium salt of alkylallylsulfosuccinate (Eleminol JS-2, Sanyo Chemical Industries) 10 parts by mass) and 1 part by mass of ammonium persulfate were charged and stirred for 20 minutes at 400 rpm, and a white emulsion was obtained. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Further, 30 parts by mass of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 6 hours to obtain [Aqueous dispersion of resin fine particles]. The volume average particle diameter of the particles contained in this [resin fine particle aqueous dispersion] was 60 nm, the weight average molecular weight of the resin component was 140,000, and Tg was 73 ° C.

-Preparation of aqueous phase-
990 parts by mass of water, 83 parts by mass of an aqueous dispersion of resin fine particles, 37 parts by mass of a 48.5% by mass aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries), and 90 parts by mass of ethyl acetate Parts were mixed and stirred to obtain [Aqueous phase].

-Emulsification or dispersion-
To 393 parts by mass of [Oil Phase 1], 58 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 1] and 3.5 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine are added. The product was stirred at a rotational speed of 5,000 rpm and dissolved and dispersed uniformly to obtain [Oil Phase 1 ′]. Next, 550 parts by mass of [Aqueous Phase] is put in another container in which a stirrer and a thermometer are set, and while stirring at 11,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), [Oil Phase] 1 '] was added and emulsified for 1 minute to obtain [Emulsified slurry 1].

-Solvent removal-Washing-Drying-
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Slurry 1]. The obtained [Slurry 1] was kept at 40 ° C. for 4 hours, then filtered under reduced pressure, and the following washing treatment was performed.
(1) 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(2) After adding 100 parts by mass of ion-exchanged water to the filter cake of (1) and mixing with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), 1% by mass hydrochloric acid is about pH 3.3 with stirring. The mixture was added until the mixture was stirred, and stirring was continued for 1 hour in that state, followed by filtration.
(3) N, N, N, -trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium iodide (product name: Footage 310 (manufactured by Neos)) A 1% by weight aqueous solution was gradually added with stirring to 0.1% by weight with respect to the toner. Thereafter, the mixture was stirred at room temperature for 1 hour and then separated by filtration to obtain a filter cake 1.

  The obtained filter cake 1 was dried at 40 ° C. for 48 hours in a circulating dryer. Thereafter, the mixture was sieved with a 75 μm mesh to produce [Toner Base Particles 1].

-Mixed-
Hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) is added to 100 parts of the base particles based on [Toner Base Particle 1], and a 20 L Henschel mixer (Mitsui Mining Co., Ltd.) is used. Mixing was performed at a peripheral speed of 33 m / s for 5 minutes. The above was air sieved with a 500 mesh sieve to obtain [Toner 1].

(Example 2)
[Toner 2] was prepared in the same manner as in Example 1 except that the organically modified layered inorganic compound containing Al was changed to 0.8% by mass in the preparation of the oil phase 1 of Example 1.

(Example 3)
[Toner 3] was produced in the same manner as in Example 1 except that the ratio (A / B) was changed to 1.2 in the synthesis of the organically modified layered inorganic compound containing Al in Example 1.

Example 4
[Toner 4] was produced in the same manner as in Example 1 except that the ratio (A / B) was changed to 1.5 in the synthesis of the organically modified layered inorganic compound containing Al in Example 1.

(Example 5)
[Toner 5] was produced in the same manner as in Example 1 except that the ratio (A / B) was changed to 1.7 in the synthesis of the organically modified layered inorganic compound containing Al in Example 1.

(Example 6)
In the synthesis of the organic modified layered inorganic compound containing Al in Example 1, the ratio (A / B) was changed to 1.5, and dimethyl distearyl ammonium (DMDS) was used as the organic cation modifier. [Toner 6] was prepared in the same manner as in Example 1.

(Example 7)
In the synthesis of the organically modified layered inorganic compound containing Al in Example 1, the ratio (A / B) was changed to 1.5, and dimethyloleylbenzylammonium (DMOB) was used as the organic cation modifier. In the same manner as in Example 1, [Toner 7] was produced.

(Example 8)
In the synthesis of the organically modified layered inorganic compound containing Al in Example 1, the ratio (A / B) was changed to 1.5, and dimethyldioleylammonium (DMDO) was used as the organic cation modifier. In the same manner as in Example 1, [Toner 8] was produced.

(Comparative Example 1)
[Toner 9] was produced in the same manner as in Example 1 except that the organically modified layered inorganic compound containing Al was changed to 2.2% by mass in the production of the oil phase 1 of Example 1.

(Comparative Example 2)
[Toner 10] was produced in the same manner as in Example 1 except that the organically modified layered inorganic compound containing Al was changed to 0.6% by mass in the production of the oil phase 1 of Example 1.

(Comparative Example 3)
In the synthesis of the organically modified layered inorganic compound containing Al in Example 1, the ratio (A / B) was changed to 1.8, and dimethyloleylbenzylammonium (DMOB) was used as the organic cation modifier. [Toner 11] was prepared in the same manner as in Example 1, except that the oil-modified layered inorganic compound containing Al was changed to 0.8% by mass in the preparation of the oil phase 1 of Example 1.

(Evaluation method and evaluation results)
The following evaluation was performed using the obtained toner. The evaluation results are shown in Table 1.

<Outline>
Each toner and image forming apparatus (“RICOH MPC8002”; manufactured by Ricoh Co., Ltd.) are used to output using a character image pattern with an image area ratio of 10%. After continuous output of 100,000 sheets, one halftone image was output, and the number of white spots on the image was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: None ○: 1 to 3 △: 4 to 9 ×: 10 or more
* ◎ ~ △ was passed, × was rejected.

<White stripe>
Each toner and image forming apparatus (“RICOH MPC8002”; manufactured by Ricoh Co., Ltd.) are used to output using a character image pattern with an image area ratio of 0.5%. After continuous output of 100,000 sheets, one solid image was output, and the occurrence of white streaks on the image was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: None ○: One slight streak □: Two light streaks △: Three or more light streaks ×: Clear streaks occurred .

<Charge amount>
7 wt% of toner was weighed on 6 g of a carrier and allowed to stand for 2 hours at a room temperature of 22 ° C. and a humidity of 55%. Then, the developer was charged in a metal cylinder that could be sealed and stirred and mixed at 280 rpm for 60 seconds. As the carrier, a resin-coated ferrite carrier obtained by applying or drying a coating film forming solution of an acrylic resin and a silicone resin containing alumina particles on the surface of a fired ferrite powder (weight average particle diameter: 35 μm) was used. After stirring and mixing, 1 g of the developer was weighed into a 635 mesh cage having an opening of 635, and the charge amount of the toner was measured by a V blow-off device (manufactured by Ricoh Creative Development Co., Ltd.) single mode. Here, the single mode method is the V blow-off device (manufactured by Ricoh Creative Development Co., Ltd.), the single mode was selected according to the device manual, and the measurement conditions were 5 mm height, suction 100, and double blow. Evaluation was performed according to the following criteria.
〔Evaluation criteria〕
The chargeability was determined according to the following criteria.
Charge amount -38 to -42 μC / g ...
Charge amount −34 to −38 μC / g or −42 to −45 μC / g
Charge amount -30 to -34 μC / g or −45 to −50 μC / g
Charge amount -25 to -30 [mu] C / g or -50 to -60 [mu] C / g
Charge amount -1 to -25 [mu] C / g or -60 to -80 [mu] C / g
* ◎ ~ △ was passed, × was rejected.

<Low image area toner scattering property>
Each toner and image forming apparatus (“RICOH MPC8002”; manufactured by Ricoh Co., Ltd.) are used to output using a character image pattern with an image area ratio of 0.5%. The state of toner contamination in the copying machine when 50,000 sheets were continuously output was visually observed and evaluated based on the following criteria.
〔Evaluation criteria〕
A: Toner stains are not observed at all and are in a good state. O: Slightly observed stains are not a problem. Δ: Stain is observed within the allowable range. X: Very dirty outside the allowable range. There was a problem * ◎ ~ △ was passed, × was rejected.

  As is apparent from the evaluation results in Table 1, the toner of each example was sufficiently excellent in white spots, white lines, charge amount, and toner scattering properties as compared with the comparative examples.

10 Electrostatic latent image carrier (photosensitive drum)
10K Black electrostatic latent image carrier 10Y Yellow electrostatic latent image carrier 10M Magenta electrostatic latent image carrier 10C Cyan electrostatic latent image carrier 14 Roller 15 Roller 16 Roller 17 Cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading Sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developing roller 44M Developing roller 44C Developing roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer belt 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charging device 60 Cleaning device 61 Developing device 62 Transfer roller 63 Photoconductor cleaning device 64 Static elimination lamp 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A, 100B, 100C Image forming device 101 Electrostatic latent image carrier 102 Charging device 103 From exposure device Exposure device 104 developing device 105 recording paper 107 cleaning unit 108 transfer roller 120 image forming unit 130 document table 142 paper feed roller 143 paper bank 144 paper feed cassette 45 the separation roller 146 feed path 147 transport rollers 148 feed path 150 copier main body 160 a charging roller 200 feeder table 300 Scanner 400 automatic document feeder (ADF)

Japanese Patent Laid-Open No. 2004-246057 Japanese Patent Laid-Open No. 11-143118

Claims (8)

A toner obtained by adding an external additive to toner base particles containing an organically modified layered inorganic compound containing Al, a binder resin and a release agent,
The Al content C1 from the toner base particle surface to a depth of 0.2 μm is 0.1 mass% ≦ C1 ≦ 0.3 mass%, and the Al content C2 from the toner surface to 0.4 μm. (C1 / C2) is 1.0 ≦ (C1 / C2) ≦ 1.5.   The toner according to claim 1, wherein the ratio (C1 / C2) is 1.0 ≦ (C1 / C2) ≦ 1.2.    The organically modified layered inorganic compound containing Al is obtained by modifying a layered inorganic compound with an organic cation modifier, and the organic cation modifier is dimethyl distearyl ammonium (DMDS), dimethyl oleyl benzyl ammonium (DMOB) and The toner according to claim 1, wherein the toner is at least one selected from dimethyldioleyl ammonium (DMDO).   The ratio (A / B) of the amount A (mol) of the organic cation modifier used during the modification and the amount of cation B (mol) contained in the layered inorganic compound before the modification is 1.0 ≦ (A / The toner according to claim 3, wherein B) ≦ 1.5.   A developer comprising the toner according to claim 1.   A toner storage unit for storing the toner according to claim 1. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means for developing the electrostatic latent image with a developer to form a visible image;
Transfer means for transferring the visible image onto a recording medium;
Fixing means for fixing the transferred image transferred on the recording medium,
An image forming apparatus, wherein the developer is the toner according to claim 1. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
A developing step of developing the electrostatic latent image with a developer to form a visible image;
A transfer step of transferring the visible image onto a recording medium;
A fixing step of fixing the transferred image transferred onto the recording medium,
The image forming method, wherein the developer is the toner according to claim 1.

Images