JP2011197264A - Toner, and image forming method and process cartridge using the toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner superior in charging characteristics, durability, charge environmental stability, and suitability for granulation; to provide an image forming method and to provide a process cartridge.SOLUTION: A method of manufacturing the toner includes: a dissolution/dispersion liquid-preparing step of dissolving and dispersing a toner substance into an organic solvent, wherein the toner substance includes a charge control agent and at least one of a binder resin and a binder resin precursor; an emulsification/dispersion liquid-preparing step of emulsifying and dispersing the resultant dissolved and dispersed liquid by adding it to an aqueous medium; and an organic solvent-removing step of removing an organic solvent from the resultant emulsified and dispersed liquid, wherein the charge control agent contains a pyrone compound expressed by a general formula (I). In the general formula (I), Rto Reach are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a phenyl group, or a fluoroalkyl group. Adjacent pairs among the Rto Rmay be bonded to each other to form a ring.

Description

  The present invention relates to a toner used for developing an electrostatic latent image, an image forming method using the toner, and a process cartridge.

In recent years, in the field of electrophotographic image forming technology, higher color full-color image formation has been demanded, and developers have been designed to improve image quality. In order to meet the demand for higher image quality, particularly full-color image quality, toners are increasingly becoming smaller in particle size and are being studied to faithfully reproduce latent images. In order to reduce the particle size, a toner production method using a polymerization method has been proposed as a means for controlling the toner to a desired toner shape and surface structure (for example, Patent Document 1 and Patent Document 1). 2).
In the polymerization toner, in addition to controlling the particle size of the toner particles, shape control is possible. By reducing the particle size in conjunction with shape control, the reproducibility of dots and fine lines is improved, the pile height (image layer thickness) can be reduced, and higher image quality can be expected. The toner is usually composed of a binder resin, a colorant, a charge control agent, and other external additives.

So far, toners with various charge control agents added have been proposed for the purpose of imparting good charging characteristics, stability over time, and environmental stability. In this case, since a colored material cannot be used as a charge control agent for a full color toner, a colorless, white, or light-color charge control agent that does not affect the hue must be used.
Examples of such charge control agents include metal complex compounds of salicylic acid derivatives (see Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6), aromatic dicarboxylic acid metal salt compounds (see Patent Document 7). In addition, metal complex salt compounds of anthranilic acid derivatives (see Patent Document 8), organoboron compounds (see Patent Document 9 and Patent Document 10), and the like have been proposed.
However, these charge control agents are chromium-containing compounds that are concerned about environmental stability, and have drawbacks such as insufficient durability, insufficient charging effect, and insufficient environmental stability. The charge control agent did not have satisfactory performance.

  In addition, in the case of the polymerization toner, the charge control agent derived from the toner constituent material is decomposed or it is difficult to disperse in the toner. Therefore, in many cases, the function as the charge control agent can be sufficiently exerted. There is no problem. Therefore, by using and controlling the charge control agent applicable to the polymerized toner, it is expected that the toner has excellent chargeability, durability, and environmental stability, and is compatible with high image quality by reducing the particle size. The toner that can be used and the related technology have not been provided yet, and it is desired to provide the toner promptly.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a toner excellent in charging characteristics, durability, charging environment stability, and granulation property, an image forming method using the toner, and a process cartridge.

Means for solving the problems are as follows. That is,
<1> a dissolving or dispersing liquid preparing step in which a toner material containing at least one of a binder resin and a binder resin precursor and a charge control agent is dissolved or dispersed in an organic solvent to prepare a dissolved or dispersed liquid of the toner material; An emulsification or dispersion preparation step in which the dissolution or dispersion is added to an aqueous medium and emulsified or dispersed to prepare an emulsification or dispersion; and an organic solvent removal step in which the organic solvent is removed from the emulsification or dispersion. And the charge control agent contains a pyrone compound represented by the following general formula (I).
However, in said general formula (I), R < ¹ > -R < ⁵ > represents either hydrogen, a halogen, a hydroxyl group, an alkyl group, a phenyl group, and a fluoroalkyl group, respectively, Of said R < ¹ > -R < ⁵ > Adjacent ones may be combined to form a ring.
<2> The toner according to <1>, wherein the pyrone compound is contained in the toner.
<3> The toner according to any one of <1> to <2>, wherein the volume average particle diameter is 1 μm to 6 μm.
<4> The toner according to any one of <1> to <3>, wherein the aqueous medium in the emulsification or dispersion preparation step includes anionic resin fine particles having an average particle diameter of 5 nm to 50 nm and an anionic surfactant. is there.
<5> The toner according to any one of <1> to <4>, wherein the binder resin includes a polyester resin.
<6> The toner according to any one of <1> to <5>, wherein the pyrone compound is contained in an amount of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the toner.
<7> The toner according to any one of <1> to <6>, wherein an average dispersion diameter of the pyrone compound is 10 nm to 500 nm.
<8> The toner according to any one of <1> to <7>, wherein the charge amount is from −80 μC / g to −10 μC / g.
<9> The log ρ which is a common logarithm of the volume specific resistance ρ (Ω · cm) of the toner is 10.9 Ω · cm to 11.4 Ω · cm, according to any one of <1> to <8>. Toner.
<10> The ratio between the volume average particle diameter (Dv) and the number average particle diameter (Dn), Dv / Dn is 1.05 to 1.25, or any one of <1> to <9> Toner.
<11> The toner according to any one of <1> to <10>, wherein the average circularity is 0.950 to 0.990.
<12> BET specific surface area ^is a toner according the a 0.5m ² /g~4.0m 2 / g to any one of <1> to <11>.
<13> The toner according to any one of <1> to <12>, wherein the toner material includes an active hydrogen group-containing compound and a modified polyester resin capable of reacting with the active hydrogen group-containing compound.
<14> A charging step for charging the electrophotographic photosensitive member, an exposure step for forming an electrostatic latent image on the charged electrophotographic photosensitive member, and an electrophotographic photosensitive member on which the electrostatic latent image is formed. A developing step for forming a toner image using the toner according to any one of <1> to <13>, and primary transfer for primary transfer of the toner image formed on the electrophotographic photosensitive member onto an intermediate transfer member A secondary transfer step of secondarily transferring a toner image primarily transferred onto the intermediate transfer member onto a recording material, and applying heat and pressure to the toner image secondarily transferred onto the recording material. A fixing process for fixing the recording material on the recording material, and a cleaning process for cleaning the transfer residual toner adhering to the surface of the electrophotographic photosensitive member after either the primary transfer or the secondary transfer. An image forming method characterized by The
<15> The image according to <14>, wherein in the secondary transfer step, the linear velocity at which the toner image is transferred to the recording material is 300 mm / sec to 1,000 mm / sec, and the transfer time is 0.5 msec to 20 msec. It is a forming method.
<16> A plurality of image forming steps including a charging step, an exposure step, a developing step, a primary transfer step, a secondary transfer step, a fixing step, and a cleaning step are simultaneously performed in a tandem manner for one image formation. <14 > To <15>.
<17> An electrophotographic photosensitive member, a charging unit for charging the electrophotographic photosensitive member, an exposure unit for forming an electrostatic latent image on the charged electrophotographic photosensitive member, and formed on the electrophotographic photosensitive member. Developing means for converting the electrostatic latent image formed into a toner image using the toner according to any one of <1> to <13>, and a toner image formed on the electrophotographic photosensitive member on an intermediate transfer member Primary transfer means for primary transfer, secondary transfer means for secondary transfer of the toner image primarily transferred onto the intermediate transfer member onto the recording material, and toner image secondary transferred onto the recording material. A fixing means for fixing the recording material by applying heat and pressure, and a cleaning for cleaning residual toner adhering to the surface of the electrophotographic photosensitive member after either the primary transfer or the secondary transfer. And an image forming apparatus comprising: In the process cartridge, at least the electrophotographic photosensitive member and the developing unit are integrally supported so as to be detachable from the main body of the image forming apparatus.
<18> The process cartridge according to <17>, further including at least one unit selected from a charging unit, a transfer unit, and a cleaning unit.

  According to the present invention, the conventional problems can be solved, the object can be achieved, and the toner having excellent charging characteristics, durability, charging environment stability, and granulation property, and an image using the toner A forming method as well as a process cartridge can be provided.

FIG. 1 is a diagram showing a schematic structure of the toner of the present invention. FIG. 2 is a schematic configuration diagram of an example of a contact-type roller charging device. FIG. 3 is a schematic configuration diagram of an example of a contact-type brush charging device. FIG. 4 is a schematic configuration diagram of an example of a magnetic brush charging device. FIG. 5 is a schematic configuration diagram of an example of a developing device. FIG. 6 is a schematic configuration diagram of an example of the fixing device. FIG. 7 is a diagram illustrating a layer configuration of the fixing belt. FIG. 8 is a schematic configuration diagram of an example of the process cartridge of the present invention. FIG. 9 is a schematic configuration diagram of an example of an image forming apparatus. FIG. 10 is a schematic configuration diagram of another example of the image forming apparatus. FIG. 11 is a diagram showing image data obtained by electron micrograph of the toner of the present invention and data obtained by mapping N part of the image data.

(toner)
The toner of the present invention is manufactured by the dissolution or dispersion preparation step A, the emulsification or dispersion preparation step B, and the organic solvent removal step C.

<Dissolution or dispersion preparation step A>
In the dissolution or dispersion preparation step A, a toner material containing at least one of a binder resin and a binder resin precursor and a charge control agent is dissolved or dispersed in an organic solvent to prepare a solution or dispersion of the toner material. As a process to do.
Examples of the binder resin precursor include a polymer (prepolymer) capable of reacting with an active hydrogen group-containing compound. When the binder resin precursor is used instead of the binder resin, the emulsion or dispersion is used. In the preparation step B, the binder resin derived from the binder resin precursor is obtained by reacting with the active hydrogen group-containing compound.
The toner material is not particularly limited as long as it includes either a binder resin or a binder resin precursor and the charge control agent, and can be appropriately selected according to the purpose. For example, a colorant, and further necessary Depending on the above, examples of other components include a release agent.
The organic solvent is removed in the organic solvent removal step C during or after granulation of the toner in the emulsification or dispersion preparation step B.

-Organic solvent-
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. However, the toner can be easily removed during granulation or after granulation. In view of the properties, those having a boiling point of less than 150 ° C. are preferred, such as toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, Dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used. Further, ester solvents are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as a compounding quantity of the said organic solvent, Although it can select suitably according to the objective, 40 mass parts-300 mass parts are preferable with respect to 100 mass parts of said toner materials, 60 mass parts-140 mass parts. Mass parts are more preferable, and 80 to 120 parts by mass are particularly preferable.
The toner material is dissolved or dispersed in the organic solvent by using the binder resin, the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, or the release agent. It can be carried out by dissolving or dispersing toner materials such as the colorant and the charge control agent.
Further, in the toner material, the component used in the dissolution or dispersion process may include at least one of the binder resin and the binder resin precursor. In the preparation of the aqueous medium in the emulsification or dispersion preparation step, the aqueous medium may be added and mixed, or when the dissolution or dispersion of the toner material is added to the aqueous medium, the dissolution or dispersion In addition, it may be added to the aqueous medium.

-Charge control agent-
The charge control agent contains a pyrone compound represented by the following general formula (I).
However, in said general formula (I), R < ¹ > -R < ⁵ > represents either hydrogen, a halogen, a hydroxyl group, an alkyl group, a phenyl group, and a fluoroalkyl group, respectively, Of said R < ¹ > -R < ⁵ > Adjacent ones may be combined to form a ring.

Examples of the alkyl group include linear or branched alkyl groups having 1 to 12 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, and tert-butyl. Groups and the like.
As said fluoroalkyl group, the C1-C12 linear or branched fluoroalkyl group can be mentioned, A trifluoromethyl group etc. are mentioned.
Among the R ^{1 to} R ⁵ , those adjacent to form a ring form a naphthyl group and an anthryl group sharing one side with the phenyl group substituted with the R ^{1 to} R ^5. And the like.
Below, the specific example of the said pyrone compound is shown.

The pyrone compound is preferably contained inside the toner.
That is, the pyrone compound can be internally added by utilizing the difference in affinity for the resin in the toner particle body.
When the pyrone compound is internally added, toner filming on the photoreceptor can be prevented and low-temperature fixability can be improved as compared with the case where the pyrone compound is externally added.
Heretofore, various charge control agents such as salicylic acid derivative metal complex compounds have been proposed as charge control agents for the purpose of improving the chargeability of the toner, and these charge control agents are incorporated in the toner. In such a case, there is a problem that the toner material reacts and decomposes.
The pyrone compound does not have such a problem even if it is internally added to the toner, and can impart excellent charging characteristics, durability, charging environment stability, and granulation properties to the toner. It is possible to provide a toner that is different from the conventional toner.
In this specification, the term “contained in the toner” means that the pyrone compound is contained in the vicinity of the toner surface so that a part of the pyrone compound is exposed to the outside, in addition to the case where the pyrone compound is contained in the toner without being exposed to the outside. Including cases where

The average dispersion diameter of the pyrone compound in the dissolution or dispersion prepared in the dissolution or dispersion preparation step A is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm to 500 nm. 10 nm to 300 nm is more preferable, and 50 nm to 300 nm is particularly preferable.
When the average dispersion diameter is less than 10 nm, the pyrone compound aggregates inside the toner particle main body and sufficient charging characteristics may not be obtained. When the average dispersion diameter exceeds 500 nm, the surface properties of the toner deteriorate, and the carrier And the sufficient charging characteristics cannot be maintained over a long period of time, and the environmental stability of the charging characteristics may be hindered.

There is no restriction | limiting in particular as addition amount of the said pyrone compound, Although it can select suitably according to the objective, 5-25 mass parts is with respect to 100 mass parts of organic-solvent dispersion liquid which disperse | distributes the said pyrone compound. preferable.
If the amount added is less than 5 parts by mass, improvement in chargeability may not be expected. If the amount added exceeds 25 parts by mass, fixing characteristics may deteriorate and carrier contamination may occur.

Further, the content of the pyrone compound with respect to 100 parts by mass of the toner is preferably 0.01 parts by mass to 5.0 parts by mass, and more preferably 0.1 parts by mass to 3.0 parts by mass.
When the content is less than 0.01 parts by mass, improvement in chargeability may not be expected. When the content exceeds 5.0 parts by mass, fixing characteristics may be deteriorated and carrier contamination may occur.

There is no restriction | limiting in particular as a manufacturing method of the said pyrone compound, According to the objective, it can select suitably, For example, it can manufacture with reference to international publication 2006/101144 pamphlet (especially Example 2). it can.
The compound of Example 2 can also be produced as follows using thionyl chloride.
To 3.0 L of toluene, 150.0 g (0.751 mol) of 4-oxo-4H-pyran-2,6-dicarboxylic acid monohydrate was added, and 308.6 g (2.59 mol) of thionyl chloride and 2 mL of DMF were added thereto. Add to reflux for 6 hours. After standing to cool, the solvent is distilled off under reduced pressure, and 3.0 L of THF is added to the residue and dissolved. To this, 262.4 g (2.59 mol) of triethylamine is added, and 243.6 g (1.63 mol) of 4-t-butylaniline is added dropwise while cooling with ice water. After stirring overnight at room temperature, the crystals are filtered off with suction and washed with 2 L of THF. The crystals are added to 8 L of water and stirred for 8 hours at room temperature, after which the crystals are filtered off with suction and washed with 3 L of water. After drying at 80 ° C., recrystallization from ethyl acetate can yield 231.3 g (69.0%) of 2,6-di (4-tert-butylphenylaminocarbonyl) -γ-pyrone.
Moreover, it can also manufacture by referring to the method of Unexamined-Japanese-Patent No. 2009-42750 and Unexamined-Japanese-Patent No. 2009-86655, and changing suitably.

  The charge control agent is not particularly limited as long as the pyrone compound is used. Examples of the charge control agent externally added to the toner include a nigrosine dye, a triphenylmethane dye, a chromium-containing metal complex dye, and molybdic acid. Chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine activators, salicylic acid Examples thereof include metal salts and metal salts of salicylic acid derivatives. These may be used individually by 1 type and may use 2 or more types together.

  As the charge control agent other than the pyrone compound, commercially available products may be used. Examples of the commercially available products include resins or compounds having an electron-donating functional group, azo dyes, and metal complexes of organic acids. Etc. can be used. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84 (above, manufactured by Orient Chemical Co., Ltd.), TN-105 of salicylic acid metal complex, TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary Copy charge PSY VP2038 of ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR- which is a boron complex 147 (manufactured by Nippon Carlit), copper phthalocyanine, perylene, ki Examples include nacridon, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

-Binder resin and binder resin precursor-
The binder resin is not particularly limited and can be appropriately selected according to the purpose. For example, polyester resin, silicone resin, styrene / acryl resin, styrene resin, acrylic resin, epoxy resin, diene resin, Known binder resins such as phenol resin, terpene resin, coumarin resin, amideimide resin, butyral resin, urethane resin, ethylene / vinyl acetate resin can be used.
Among these, a polyester-based resin having sufficient flexibility even when the molecular weight is lowered is preferable in that it can be sharply melted at the time of fixing and the image surface can be smoothed. When the polyester resin is used, another resin may be used in combination.

The polyester-based resin is one or more polyols represented by the following general formula (1):
A- (OH) m (1)
However, in said general formula (1), A represents either a C1-C20 alkyl group, an alkylene group, the aromatic group which may have a substituent, and a heterocyclic aromatic group. m represents an integer of 2 to 4.
What polyesterified the 1 type (s) or 2 or more types of polycarboxylic acid represented by following General formula (2) is preferable.
B- (COOH) n (2)
However, in said general formula (2), B represents either a C1-C20 alkyl group, an alkylene group, the aromatic group which may have a substituent, and a heterocyclic aromatic group. n represents an integer of 2 to 4.

  Specific polyols represented by the general formula (1) include 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- Tylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide Examples include adducts, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, and the like.

  Specific polycarboxylic acids represented by the general formula (2) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebatin. 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-methylenecarboxyl Bread, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid , Butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, ethylene glycol bis (trimellitic acid), and the like.

There is no restriction | limiting in particular as addition amount of the said binder resin, Although it can select suitably according to the objective, 5 mass parts-25 mass parts are preferable with respect to 100 mass parts of said organic solvent dispersion liquids.
If the amount of the binder resin is less than 5 parts by mass, the dispersion diameter of the calixarene derivative may not be reduced. If the amount of the binder resin is more than 25 parts by mass, the toner material may be added to the solution or dispersion. Aggregation occurs, and there is a possibility that the deforming and charge imparting effects cannot be sufficiently obtained.
The organic solvent dispersion preferably contains 5 parts by mass of the calixarene derivative and 5 parts by mass of the binder resin with respect to 100 parts by mass of the organic solvent dispersion.

-Active hydrogen group-containing compound-
By including an active hydrogen group-containing compound and a modified polyester resin capable of reacting with the compound in the toner material, the mechanical strength of the resulting toner is increased, and the burying of the external additive can be suppressed. Further, the fluidity of the toner during heat fixing can be adjusted, and the fixing temperature range can be widened.
In the present specification, the active hydrogen group-containing compound and the modified polyester resin capable of reacting with the active hydrogen group-containing compound correspond to a binder resin precursor.

The active hydrogen group-containing compound is used as an extender, a crosslinking agent, etc. when the polymer capable of reacting with the active hydrogen group-containing compound undergoes an extension reaction, a crosslinking reaction, etc. in the aqueous medium in the emulsification or dispersion preparation step. Works.
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. For example, a polymer capable of reacting with the active hydrogen group-containing compound is an isocyanate group. In the case of the containing polyester prepolymer (A), the amines (B) are preferable because they can have a high molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A).

  The active hydrogen group is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. Examples thereof include a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), amino group, carboxyl group, mercapto group. Groups, etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said amine (B), According to the objective, it can select suitably, For example, diamine (B1), trivalent or more polyamine (B2), amino alcohol (B3), amino mercaptan ( B4), amino acids (B5), amino acids blocked in (B1) to (B5) (B6), and the like can be used. These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) is preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines.
Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, and the like.
Examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine.
Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.

Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.

  Examples of (B6) in which the amino group in (B1) to (B5) is blocked include (B1) to (B5) amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Examples thereof include ketimine compounds and oxazolyzone compounds obtained.

In order to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound, it is preferable to use a reaction terminator.
When the reaction terminator is used, the molecular weight and the like of the adhesive substrate can be controlled within a desired range.
There is no restriction | limiting in particular as said reaction terminator, Monoamine (diethylamine, dibutylamine, butylamine, laurylamine etc.) or what blocked these (ketimine compound) etc. can be used.

The mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A) is not particularly limited, but the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A), The mixing equivalent ratio ([NCO] / [NHx]) of amino groups [NHx] in the amines (B) is preferably 1/3 to 3/1, and preferably 1/2 to 2/1. Is more preferable, and it is particularly preferable that the ratio is 1 / 1.5 to 1.5 / 1.
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.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. For example, a polyol resin, a polyacrylic resin, a polyester resin, an epoxy resin, a derivative resin thereof, or the like can be used. Among these, a polyester resin is preferable in terms of high fluidity and transparency during melting. In addition, these may be used individually by 1 type and may use 2 or more types together.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, an acid A chloride group, and the like. These may be contained singly or in combination of two or more. Among these, an isocyanate group is preferable.
Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixing even in the absence of a release oil coating mechanism for a heating medium for fixing. From the viewpoint of ensuring the properties, a urea bond-forming group-containing polyester resin (RMPE) containing a urea bond-forming group is preferable.

As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example.
When the urea bond generating group in the urea bond generating group-containing polyester resin (RMPE) is the isocyanate group, the polyester resin (RMPE) is preferably an isocyanate group-containing polyester prepolymer (A) or the like.
The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), In addition, there may be mentioned those obtained by reacting an active hydrogen group-containing polyester resin with polyisocyanate (PIC).
There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol And a mixture with (TO). These may be used individually by 1 type and may use 2 or more types together. Among these, diol (DIO) alone or a mixture of diol (DIO) and a small amount of trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned.
Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol.
Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S.
Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
Examples of the trihydric or higher polyphenols include trisphenol bodies (such as Trisphenol PA manufactured by Honshu Chemical Industry Co., Ltd.), phenol novolacs, cresol novolacs, and the like.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to trihydric or higher polyphenols.

  The mixing mass ratio (DIO: TO) of the diol (DIO) and the trihydric or higher polyol (TO) in the mixture of the diol (DIO) and the trihydric or higher polyol (TO) is 100: 0.01. To 10 is preferable, and 100: 0.01 to 1 is more preferable.

  There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tri- or higher valent polycarboxylic acid. These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of dicarboxylic acid (DIC) and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.

Examples of the dicarboxylic acid (DIC) include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid.
As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned.
As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TC) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

The polycarboxylic acid (PC) is selected from dicarboxylic acid (DIC), trivalent or higher polycarboxylic acid (TC), and a mixture of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid. Any acid anhydride or lower alkyl ester may be used.
Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  As a mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC), There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] and the carboxyl group [COOH] in the polycarboxylic acid (PC) is preferably 2/1 to 1/1, and 1.5 / The ratio is more preferably 1-1 / 1, and particularly preferably 1.3 / 1-1.02 / 1.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5 mass%-40 mass% are Preferably, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable. When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

There is no restriction | limiting in particular as said polyisocyanate (PIC), According to the objective, it can select suitably, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurates And those blocked with these phenol derivatives, oxime, caprolactam and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate.
Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.
Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like.
Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate.
Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate.
These may be used alone or in combination of two or more.

  The mixing ratio for reacting the polyisocyanate (PIC) with the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) is the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing polyester. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the resin is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1. Particularly preferred is 3/1 to 1.5 / 1. When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5 mass%-40 mass% Is preferable, 1 mass%-30 mass% is more preferable, and 2 mass%-20 mass% is still 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 heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

  The average number of isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A) is not particularly limited, but is preferably 1 or more, more preferably 1.2 to 5, and more preferably 1.5 to 4 Is more preferable. When the average number of the isocyanate groups 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.

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

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows.
That is, first, the column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a column solvent was allowed to flow at a flow rate of 1 mL per minute at this temperature to prepare a sample concentration of 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μL of a tetrahydrofuran sample solution of the resin. 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. Alternatively, Toyo Soda Kogyo's molecular weight is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6. It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector can be used as the detector.

The binder resin is an adhesive that shows adhesion to a recording material such as paper, and is obtained by reacting the active hydrogen group-containing compound with a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium. It preferably contains an adhesive polymer.
There is no restriction | limiting in particular as a weight average molecular weight of the said binder resin, Although it can select suitably according to the objective, 3,000 or more are preferable, 5,000-1,000,000 are more preferable, 7, 000 to 500,000 is particularly preferred. This is because, when the weight average molecular weight is less than 3,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said binder resin, Although it can select suitably according to the objective, For example, 30 to 70 degreeC is preferable and 40 to 65 degreeC is more preferable. When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.
In the toner, since a polyester resin subjected to a crosslinking reaction and an elongation reaction coexists, the toner exhibits good storage stability even when the glass transition temperature is low as compared with a conventional polyester-based toner.

The glass transition point (Tg) is specifically determined by the following procedure. Measurement is performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.
Measurement conditions 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 Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

  The measurement result is analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method specifies a range of ± 5 ° C around the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature rise, and uses the peak analysis function of the analysis software to specify the peak temperature Ask for. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the Tg of the toner.

Hereinafter, more specific production examples of the binder resin and the binder resin precursor will be described.
There is no restriction | limiting in particular as said binder resin, Although it can select suitably according to the objective, A polyester-type resin is especially suitable.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester resin and an unmodified polyester resin are mentioned as a particularly suitable thing.
The urea-modified polyester resin comprises an amine (B) as an active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound in an aqueous medium. It is obtained by reacting with
The urea-modified polyester resin may include a urethane bond in addition to the urea bond. In this case, the content molar ratio of the urea bond and the urethane bond (urea bond / urethane bond) is not particularly limited and may be appropriately selected depending on the intended purpose, but is 100/0 to 10/90. Preferably, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable. This is because when the urea bond is less than 10, the hot offset resistance may be deteriorated.

Preferable specific examples of the urea-modified polyester resin and the unmodified polyester resin include the following. That is,
(1) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid It is a mixture with a polycondensate.
(2) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and isophthalic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2-mole adduct and terephthalic acid It is a mixture with a polycondensate.
(3) A bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and a polyester prepolymer obtained by reacting a polycondensate of terephthalic acid with isophorone diisocyanate and urethanized with isophorone diamine, and bisphenol A ethylene It is a mixture of an oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and a polycondensate of terephthalic acid.
(4) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate, and bisphenol A propylene It is a mixture of an oxide 2 mol adduct and a polycondensate of terephthalic acid.
(5) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, bisphenol A ethylene oxide 2-mole adduct, and terephthalate It is a mixture with an acid polycondensate.
(6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A Mixture of propylene oxide 2 mol adduct and polycondensate of terephthalic acid (7) Polyester prepolymer obtained by reacting bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate with isophorone diisocyanate was ureaated with ethylenediamine And a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid.
(8) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with diphenylmethane diisocyanate, and urethanized with hexamethylenediamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid It is a mixture with the polycondensate.
(9) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate was uread with hexamethylenediamine. And a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid.
(10) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with toluene diisocyanate and uread with hexamethylenediamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid It is a mixture with the polycondensate.

  Examples of the method for producing the urea-modified polyester resin include (1) a solution or dispersion of the toner material containing a polymer (for example, an isocyanate group-containing polyester prepolymer (A)) that can react with an active hydrogen group-containing compound. Is emulsified or dispersed in the aqueous medium together with the active hydrogen group-containing compound (for example, amines (B)), oil droplets are formed, and both are subjected to an extension reaction or a crosslinking reaction in the aqueous medium. (2) The solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form oil droplets, and both are subjected to extension reaction or crosslinking in the aqueous medium. (3) The toner material dissolved or dispersed in the aqueous medium is added and mixed in the aqueous medium, and then the active hydrogen group-containing compound is added to form oil droplets. How to elongation reaction or crosslinking reaction from particle interfaces in the system media, and the like. In the case of (3), the modified polyester resin is preferentially produced on the surface of the toner to be produced, and it becomes possible to provide a concentration gradient on the toner particles.

  The reaction conditions for producing the binder resin by emulsification or dispersion are not particularly limited, and are appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. can do. In addition, as reaction time, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.

  In the aqueous medium, as a method for stably forming a dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, an isocyanate group-containing polyester prepolymer (A)), for example, in the aqueous medium In addition, a toner such as a polymer that can react with the active hydrogen group-containing compound (for example, an isocyanate group-containing polyester prepolymer (A)), the colorant, the mold release agent, the charge control agent, and the unmodified polyester resin. Examples thereof include a method in which a solution or dispersion of a toner material prepared by dissolving or dispersing the material in an organic solvent is added and dispersed by shearing force.

  In the emulsification or dispersion, the amount of the aqueous medium used is preferably 50 parts by mass to 2,000 parts by mass, and more preferably 100 parts by mass to 1,000 parts by mass with respect to 100 parts by mass of the toner material. When the amount used is less than 50 parts by mass, the toner material is poorly dispersed, and toner particles having a predetermined particle diameter may not be obtained. When the amount exceeds 2,000 parts by mass, the production cost increases.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a coloring agent, a mold release agent, an inorganic fine particle, a fluid improvement agent, a cleaning property improvement agent, a magnetic material, metal soap , Etc.

--Colorant--
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include degreen lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and litbon. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content in the toner of the said coloring agent, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable, and 3 mass%-10 mass% are more preferable. When the content of the colorant is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor dispersion of the pigment in the toner occurs, and the coloring power decreases. In some cases, the electrical characteristics of the toner may be degraded.

The colorant may be used as a master batch combined with a resin.
The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, polyester, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate, poly Butyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene N-acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymers and the like.

The masterbatch can be produced by mixing or kneading the resin for the masterbatch and the colorant with a high shear force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin.
The so-called flushing method is also suitable in that the wet cake of the colorant can be used as it is, and it does not need to be dried.
This 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 moisture and organic solvent components.
For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.
The colorant can be optionally contained in both the first resin phase and the second resin phase by utilizing the difference in affinity for the two resins.
It is well known that the colorant deteriorates the charging performance of the toner when it is present on the toner surface. Therefore, the charging performance (environmental stability, charge retention ability, charge amount, etc.) of the toner can be improved by selectively incorporating a colorant into the first resin phase present in the inner layer.

--- Mold release agent--
There is no restriction | limiting in particular as said mold release agent, Although it can select suitably according to the objective, Melting | fusing point has a low melting point mold release agent of 50 to 120 degreeC.
The low melting point release agent, when dispersed with the resin, effectively works between the fixing roller and the toner interface as the release agent, thereby oilless (the release roller such as oil is used in the fixing roller). Even if no agent is applied), the hot offset property is good.

Suitable examples of the mold release agent include waxes and waxes.
Examples of the waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin, And natural waxes such as petroleum waxes such as microcrystalline and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of a polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used. These may be used alone or in combination of two or more.

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, 50 to 120 degreeC is preferable and 60 to 90 degreeC is more preferable. If the melting point is less than 50 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 120 ° C., a cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as measured at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.
There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0 mass%-40 mass% are preferable, and 3 mass%-30 mass% are more preferable. . When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

The release agent can be arbitrarily contained in both the first resin phase and the second resin phase by utilizing the difference in affinity between the two resins. When it is selectively contained in the second resin phase present in the toner outer layer, the release agent oozes out sufficiently even in a short heating time at the time of fixing, so that sufficient releasability can be obtained.
Further, by selectively containing the release agent in the first resin phase present in the inner layer, it is possible to suppress the spent of the release agent to other members such as a photoreceptor and a carrier.

--Inorganic fine particles--
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability and the like to the toner particles.
The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Silicon, silicon nitride, or the like can be used. These may be used individually by 1 type and may use 2 or more types together.

As the inorganic fine particles for assisting the fluidity, developability and chargeability of the toner, in addition to the large inorganic particles having a primary average particle size of 80 nm to 500 nm, small inorganic particles are preferable. Can be used.
The inorganic fine particles having a small particle diameter are preferably hydrophobic silica and / or hydrophobic titanium oxide.
The primary average particle diameter of the small inorganic particles is preferably 5 nm to 50 nm, more preferably 10 nm to 30 nm.
As the specific surface area by BET method of the inorganic fine particles is not particularly ^limited, it is preferably 20m ² / g~500m 2 / g.
The blending amount of the inorganic fine particles is preferably 0.01% by mass to 5% by mass of the toner, and more preferably 0.01% by mass to 2.0% by mass.

--- Fluidity improver ---
The fluidity improver is an agent having a function of surface treatment to increase hydrophobicity and to prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, silylated Agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like.
Silica and titanium oxide in the inorganic fine particles are preferably subjected to surface treatment with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

--- Cleanability improver--
The cleaning property improving agent is added to the toner in order to remove the developer after transfer remaining on the photoreceptor and the primary transfer medium.
Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles.
The polymer fine particles preferably have a relatively narrow particle size distribution, and the volume average particle size of the polymer fine particles is preferably 0.01 μm to 1 μm.

--- Magnetic material ---
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. can be used. Among these, white is preferable in terms of color tone.

<Emulsification or dispersion preparation step B>
The emulsification or dispersion preparation step B is a step of preparing an emulsification or dispersion by adding the dissolution or dispersion into an aqueous medium and emulsifying or dispersing.

A method for emulsifying or dispersing the solution or dispersion of the toner material in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable to disperse with stirring.
There is no restriction | limiting in particular as said dispersion | distribution method, According to the objective, it can select suitably, For example, it can carry out using a well-known disperser etc.
The disperser is not particularly limited, and examples thereof include a low speed shear disperser and a high speed shear disperser.
In the emulsification or dispersion, when the active hydrogen group-containing compound and a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a cross-linking reaction, an adhesive substrate (binder resin) Produces.

-Aqueous medium-
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with water, these mixtures etc. can be used, Among these, water Is preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water. For example, alcohol, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones, and the like can be used.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like.
Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as an aqueous medium in the said emulsification thru | or dispersion liquid preparation process B, Although it can select suitably according to the objective, It is preferable that anionic resin microparticles | fine-particles and an anionic surfactant are included.

In this case, the aqueous medium is preferably prepared by, for example, dispersing the anionic resin fine particles in an aqueous medium in the presence of the anionic surfactant.
There is no restriction | limiting in particular as addition amount with respect to the aqueous medium of the said anionic surfactant and the said anionic resin fine particle, According to the objective, it can select suitably, For example, 0.5 mass%-10 mass%, respectively. preferable.

--Anionic resin fine particles--
The anionic resin fine particles adhere to the toner surface, and are fused and fused to form a relatively hard surface. Further, since the anionic resin fine particles have an anionic property, they have an effect of adsorbing to the droplets containing the toner material and suppressing coalescence of the droplets, and are important for controlling the particle size distribution of the toner. Furthermore, the negative chargeability of the toner can be given. In order to exert these effects, the average particle diameter of the anionic resin fine particles is preferably 5 nm to 50 nm, and more preferably 10 nm to 25 nm.
The average particle size corresponds to the average particle size of primary particles of anionic resin fine particles, and the average particle size of the primary particles can be measured by SEM, TEM, light scattering method, etc., for example, Horiba by laser scattering measurement method What is necessary is just to measure by diluting to an appropriate density | concentration so that it may enter into a measurement range with LA-920 made from a manufacturing company.
The average particle diameter of the primary particles is obtained as a volume average diameter.

The resin for the anionic resin fine particles is not particularly limited as long as it can form an aqueous dispersion in the aqueous medium, and can be appropriately selected from known resins according to the purpose.
The resin is not particularly limited and may be a thermoplastic resin or a thermosetting resin. For example, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, a polyamide resin, a polyimide resin, a silicon resin, a phenol resin, Melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like can be used. These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins is preferable because an aqueous dispersion of fine spherical resin fine particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

The anionic resin fine particles are required to be anionic. This is because they are not aggregated when used together with the anionic surfactant shown above.
The anionic resin fine particles can be prepared by using an anionic activator by a production method described later or by introducing an anionic group such as a carboxylic acid group or a sulfonic acid group into the resin.

There is no restriction | limiting in particular as a preparation method of the said anionic resin fine particle, According to the objective, it can select suitably, The method of making it superpose | polymerize by a well-known polymerization method, The method of obtaining as an aqueous dispersion of a resin fine particle is mentioned. Among these, a method of obtaining an aqueous dispersion of resin fine particles is preferable.
As a method for preparing the aqueous dispersion of resin fine particles, for example, the following method is preferable. That is,
(1) In the case of vinyl resin, aqueous dispersion of resin fine particles A directly by a polymerization reaction selected from a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method using a vinyl monomer as a starting material This is a method for producing a liquid.
(2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof was dispersed in an aqueous medium in the presence of an appropriate dispersant. Then, it is a method for producing an aqueous dispersion of resin fine particles A by heating or adding a curing agent to cure.
(3) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., precursor (monomer, oligomer, etc.) or solvent solution thereof (preferably liquid. It may be liquefied by heating) In this method, a suitable emulsifier is dissolved therein, and then water is added to perform phase inversion emulsification.
(4) Resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) After the resin fine particles are obtained by pulverizing using, and then classified, they are dispersed in water in the presence of an appropriate dispersant.
(5) A spray of a resin solution prepared by previously dissolving a resin prepared in a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. In this method, after the resin fine particles are obtained, the resin fine particles are dispersed in water in the presence of an appropriate dispersant.
(6) A poor solvent is added to a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Or by precipitating resin fine particles by cooling a resin solution previously dissolved in a solvent by heating, and then removing the solvent to obtain resin fine particles. Then, the resin fine particles are dispersed in water in the presence of an appropriate dispersant. It is a method to make it.
(7) A resin solution prepared by previously dissolving a resin prepared by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent is appropriately dispersed. In this method, the solvent is removed by heating or decompression after being dispersed in an aqueous medium in the presence of an agent.
(8) A suitable emulsifier in a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Is dissolved, and then water is added to perform phase inversion emulsification.

-Anionic surfactant-
The anionic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like, and fluoroalkyl groups Preferable examples include anionic surfactants having Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (having 6 to 6 carbon atoms). 11) Sodium oxy] -1-alkyl (C3-4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl ( Carbon number 11-20) carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (carbon number 7-13) or metal salt thereof, perfluoroalkyl (carbon number 4-12) sulfonic acid or metal salt thereof, perfluorooctane Sulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) par -Fluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number 6-6) 16) Ethyl phosphate, sodium dodecyl diphenyl ether disulfonate, and the like.

  As a commercial item of the anionic surfactant which has the said fluoroalkyl group, for example, Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC-129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (Manufactured by Dainippon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Neos), etc.

In a toner obtained using an aqueous medium containing the anionic resin fine particles having an average particle diameter of 5 nm to 50 nm and the anionic surfactant, a toner material mainly composed of the colorant and the binder resin is used. The anionic resin fine particles adhere to the surface of the toner particle body as a nucleus.
The average particle diameter of the toner is adjusted by emulsification or dispersion conditions such as stirring of the aqueous medium in the emulsification or dispersion preparation step B.

  In addition to the anionic surfactant and the resin fine particles, the following inorganic compound dispersant and polymer protective colloid can be used in combination in the aqueous medium. Examples of the dispersant for the hardly water-soluble inorganic compound include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

  The polymer protective colloid is not particularly limited, and examples thereof include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or vinyl alcohol ether compounds, compounds containing vinyl alcohol and carboxyl groups. Esters, amide compounds or their methylol compounds, chlorides, homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, celluloses, and the like. Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-hydroxy acrylate. Propyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol mono Examples include methacrylic acid esters, N-methylol acrylamide, N-methylol methacrylamide and the like.

Examples of the vinyl alcohol or the vinyl alcohol ether compound include vinyl methyl ether, vinyl ethyl ether, and vinyl propyl ether.
Examples of the esters of the compound containing vinyl alcohol and a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate.
Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds.
Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride.
Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine.
Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester.
Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

  When using a dispersion stabilizer that is soluble in acids and alkalis such as calcium phosphate, remove the calcium phosphate from the fine particles by dissolving the calcium phosphate with an acid such as hydrochloric acid and then washing with water or decomposing with an enzyme. It becomes possible to do.

<Organic solvent removal step C>
The organic solvent removing step C is a step of removing the organic solvent from the emulsified or dispersed liquid (emulsified slurry).
The method for removing the organic solvent is not particularly limited and may be appropriately selected according to the purpose. (1) The temperature of the entire reaction system is gradually raised to completely evaporate the organic solvent in the oil droplets. (2) A method in which the emulsified dispersion is sprayed in a dry atmosphere to completely remove the water-insoluble organic solvent in the oil droplets to form toner fine particles, and the aqueous dispersant is removed by evaporation. Etc.
When the organic solvent is removed, toner particles are formed. The formed toner particles are washed, dried, etc., and then classified as desired. The classification is performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like. The classification operation may be performed after obtaining the powder after drying.

The toner particles thus obtained are mixed with particles such as a colorant, a release agent, and a charge control agent, and further, a mechanical impact force is applied to the particles such as a release agent from the surface of the toner particles. Can be prevented from desorbing.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board is mentioned.
As an apparatus used in this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.), and a pulverization air pressure are lowered, a hybridization system (Nara Machinery Co., Ltd.) Mfg. Co., Ltd.), Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

<Toner characteristics>
The toner produced by the above steps has the following toner characteristics.

  The average particle diameter measured as the volume average particle diameter (Dv) of the toner is not particularly limited, but is preferably 1 μm to 6 μm, and more preferably 2 μm to 5 μm. If the volume average particle size is less than 1 μm, toner dust is likely to occur in primary transfer and secondary transfer. If the volume average particle size exceeds 6 μm, dot reproducibility becomes insufficient, and the graininess of the halftone part deteriorates and increases. Fine images may not be obtained.

The charge amount of the toner is preferably −10 μC / g to −80 μC / g when the toner concentration is 7% by mass with stirring with carrier particles for 15 seconds and 600 seconds.
When the charge amount is less than −10 μC / g, the adsorptive power with the magnetic carrier is low, and the amount of toner to be developed increases even with a low development electric field, so that a high-quality image with gradation cannot be obtained. Sometimes. In addition, the amount of reversely charged toner increases, and the amount of toner developed on a white background portion is large, so that the image quality may deteriorate due to ground fogging. When the charge amount exceeds -80 μC / g, the attractive force with the magnetic carrier increases, and the amount of toner to be developed is small, and the image density may be lowered.

The common logarithm Log ρ of the volume specific resistance ρ (Ω · cm) of the toner is preferably 10.9 Ω · cm to 11.4 Ω · cm. In this case, the dispersion state of the colorant and the like in the toner is good, excellent charge stability of the toner is obtained, and toner scattering and fogging are improved.
If the Log ρ is less than 10.9 Ω · cm, the conductivity becomes high, which results in poor charging and tends to increase background contamination and toner scattering. In addition, an abnormal image is generated due to an electrostatic offset or the like, and a high-quality image cannot be stably obtained. On the other hand, if Log ρ exceeds 11.4 Ω · cm, the resistance increases and the charge amount increases, and the image density may decrease.

The average circularity of the toner is not particularly limited, but is preferably 0.950 to 0.990.
If the average circularity is less than 0.950, the image uniformity during development deteriorates, the toner transfer efficiency from the electrophotographic photosensitive member to the intermediate transfer member or from the intermediate transfer member to the recording material decreases, and uniform transfer is achieved. It may not be obtained. If the average circularity exceeds 0.990, the toner may rub through the cleaning blade and cause a cleaning failure.
Further, the toner is produced by emulsification in an aqueous medium, and such a production method is particularly suitable for reducing the particle size of color toner and obtaining the shape having the average circularity. It is effective.

The average circularity of the toner is defined by an average circularity X = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image) × 100%. The average circularity can be measured by the following method.
That is, it can be measured using a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation) and measured using analysis software (FPIA-2100 Data Processing Program For FPIA Version 00-10).

The ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. Is preferable, and 1.05-1.25 is more preferable.
When the (Dv / Dn) is less than 1.05, in the two-component developer, the toner is fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier is lowered or the cleaning property is deteriorated. It is easy to connect to. In the case of a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When (Dv / Dn) exceeds 1.25, 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 change in the particle size of the toner May increase. In addition, since the toner charge amount distribution is wide, it is difficult to obtain a high-quality image.
On the other hand, by setting the (Dv / Dn) to 1.25 or less, the charge amount distribution becomes uniform, and the background fog can be reduced.
Further, when the ratio is (Dv / Dn) 1.05 to 1.25, the toner is easily excellent in all of storage stability, low-temperature fixability, and hot offset resistance. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. Even if the toner balance for a long time is performed in the two-component developer, the fluctuation of the toner particle diameter in the developer is small, and good and stable developability can be obtained even in the long-term stirring in the developing device. With toner balance, the fluctuation of the toner particle size is reduced, and there is no toner filming on the developing roller and no toner fusion to the member to the blade for thinning the toner. Good and stable developability can be obtained even during long-term use (stirring) of the apparatus, and high-quality images can be obtained.

The BET specific surface area of the toner is not particularly ^limited, preferably ^{0.5m 2 /g~4.0m 2 / g, 0.5m} 2 /g~2.0m 2 / g is more preferable.
When the BET specific surface area is less than 0.5 m ² / g, the entire toner surface is covered tightly, and the anionic resin fine particles A inhibit the adhesiveness between the binder resin component inside the toner and the fixing paper. An increase in the minimum fixing temperature is observed. Further, the anionic resin fine particles A inhibit the exudation of the wax, the wax releasing effect cannot be obtained, and the occurrence of offset is observed. On the other hand, when the BET specific surface area exceeds 4.0 m ² / g, the organic fine particles remaining on the toner surface largely protrude as convex portions, or the resin fine particles A remain as a coarse multi-layer. The resin fine particles A inhibit the adhesiveness between the binder resin component inside the toner and the fixing paper, and an increase in the minimum fixing temperature is observed. Further, the anionic resin fine particles A inhibit the exudation of the wax, the wax releasing effect cannot be obtained, and the occurrence of offset is observed. Further, the additive is raised, and the image quality is likely to be affected by the unevenness of the surface.

FIG. 1 shows an outline of the toner structure of the present invention. As shown in FIG. 1, as shown in FIG. 1, the toner 1 is composed of base particles 2 made of a toner material and external additives that assist the flowability, developability, and chargeability of the colored toner particles. The external additive 3 is formed on the outermost surface of the base particle 2. The toner structure is not limited to the structure shown in FIG. 1. For example, the toner structure may be deformed using a deforming agent.
FIG. 11 shows how the pyrone compound is internally added to the toner. FIG. 11 is a diagram showing image data obtained by electron micrograph of the toner of the present invention and data obtained by mapping N part of the image data. In FIG. 11, N element mapping is performed by paying attention to the concavo-convex portion contained in the toner. As a result, the pyrone compound containing nitrogen atoms is identified, and the pyrone compound can be internally added to the toner. I was able to confirm.

<Developer>
The toner can be used as a two-component developer together with a carrier.
Although there is no restriction | limiting in particular as a weight average particle diameter of the said carrier, It is preferable that it is 15 micrometers-40 micrometers.

  When the weight average particle diameter is less than 15 μm, carrier adhesion is likely to occur in which the carrier is transferred together in the transfer process. When the weight average particle diameter exceeds 40 μm, carrier adhesion is unlikely to occur, but high image quality. If the toner concentration is increased in order to obtain the concentration, scumming may be likely to occur. In addition, when the dot diameter of the latent image is small, the variation in dot reproducibility increases, and the graininess of the highlight portion may be deteriorated.

The number average particle diameter Dp in the carrier and the core particles of the carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 μm to 150 μm, more preferably 20 μm to 80 μm.
When the number average particle diameter Dp is less than 10 μm, fine particles increase in the particle size distribution of the carrier, so that the magnetization per particle may decrease and carrier scattering may occur. In some cases, if the thickness exceeds 150 μm, the specific surface area of the carrier decreases, and toner scattering may occur. As a result, the reproducibility of the solid portion may be deteriorated particularly in a full color with many solid portions.

The developer is not particularly limited as long as it has the toner, and can be appropriately selected according to the purpose, and may further have a carrier component, for example, a one-component developer composed of the toner, the toner And a two-component developer composed of a carrier.
It is preferable to use a two-component developer in a high-speed printer or the like corresponding to the recent improvement in information processing speed from the viewpoint of improving the service life. Such a developer can be used in various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. When the developer is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the particle size of the toner, such as a filming of the toner on the developing roller and a blade for thinning the toner. The toner can be prevented from being fused to the member, and good and stable developability can be obtained even in the long-term use (stirring) of the developing device. In addition, when the developer is used as a two-component developer, even if the toner balance is maintained over a long period of time, there is little fluctuation in the particle size of the toner, and good and stable developability even with long-term stirring in the developing device. Is obtained.

  There is no restriction | limiting in particular as content of the carrier in the said two-component developer, Although it can select suitably according to the objective, It is preferable that it is 90 mass%-98 mass%, and 93 mass%-97 mass%. % Is more preferable. When the content of the carrier is in the more preferable range, it is advantageous in terms of development stability.

There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, According to the objective, it can select suitably, For example, a manganese-strontium (Mn-Sr) type material of 50 emu / g-90 emu / g, manganese-magnesium (Mn -Mg) type material etc. are mentioned, 1 type may be used individually and 2 or more types may be used together. The core material is preferably a highly magnetized material such as iron powder (100 emu / g or more), magnetite (75 to 120 emu / g) in terms of ensuring image density. Further, as a core material, a copper-zinc (Cu-Zn) system (30 emu / g to 80 emu) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state, and is advantageous in improving the image quality. / G) and the like are preferred.

There is no restriction | limiting in particular as a volume average particle diameter (D50) of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 20 micrometers-80 micrometers are more preferable.
If D50 is less than 10 μm, fine particles increase in the particle size distribution of the carrier, so that the magnetization per particle may decrease and carrier scattering may occur. If it exceeds 150 μm, the specific surface area of the carrier may be reduced, and toner scattering may occur. As a result, the reproducibility of the solid portion may be deteriorated particularly in a full color with many solid portions.
When the content of the carrier is in the more preferable range, it is advantageous in terms of development stability.

  The material for the resin layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyester resins, and polycarbonate resins. , Polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride , Fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, and the like. These may be used alone or in combination of two or more. You may use together.

  There is no restriction | limiting in particular as said amino-type resin, According to the objective, it can select suitably, For example, urea-formaldehyde resin, a melamine resin, a benzoguanamine resin, a urea resin, a polyamide resin, an epoxy resin etc. are mentioned.

  There is no restriction | limiting in particular as said polyvinyl-type resin, According to the objective, it can select suitably, For example, an acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, etc. are mentioned. .

  There is no restriction | limiting in particular as said polystyrene resin, According to the objective, it can select suitably, For example, a polystyrene, a styrene-acryl copolymer, etc. are mentioned.

  There is no restriction | limiting in particular as said halogenated olefin resin, According to the objective, it can select suitably, For example, a polyvinyl chloride etc. are mentioned.

  The polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyethylene terephthalate and polybutylene terephthalate.

The resin layer may contain conductive powder or the like as necessary.
There is no restriction | limiting in particular as a material of the said electrically-conductive powder, According to the objective, it can select suitably, For example, a metal, carbon black, a titanium oxide, a tin oxide, a zinc oxide etc. are mentioned.
There is no restriction | limiting in particular as an average particle diameter of the said electrically-conductive powder, Although it can select suitably according to the objective, 1 micrometer or less is preferable. If the average particle size exceeds 1 μm, it may be difficult to control the electrical resistance.

The resin layer is formed, for example, by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then applying the coating solution to the surface of the core material by a known coating method, followed by drying and baking. be able to.
There is no restriction | limiting in particular as said application | coating method, According to the objective, it can select suitably, For example, the immersion method, the spray method, the brush coating method etc. are mentioned.
Moreover, there is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
Furthermore, the baking method is not particularly limited and may be appropriately selected depending on the purpose. Either an external heating method or an internal heating method may be used. Examples include a method using a furnace, a rotary electric furnace, a burner furnace, and the like, a method using a microwave, and the like.

  There is no restriction | limiting in particular as content of the resin layer in the said carrier, Although it can select suitably according to the objective, 0.01 mass%-5.0 mass% are preferable. When the content is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. When the content exceeds 5.0% by mass, the resin layer becomes too thick and the carriers are combined. Granulation may occur and a uniform carrier may not be obtained.

The characteristics of the carrier can be measured by the following method.
<Weight average particle size>
The weight average particle diameter Dw of the carrier is calculated based on the particle diameter distribution (relationship between the number frequency and the particle diameter) of the particles measured on the basis of the number. The weight average particle diameter Dw in this case is represented by the formula (1).
Dw = {1 / Σ (nD ³ )} × {Σ (nD ⁴ )} (1)
In the formula (1), D represents a representative particle size (μm) of particles present in each channel, and n represents the total number of particles present in each channel. The channel indicates a length for equally dividing the particle size range in the particle size distribution diagram, and 2 μm is adopted in the present invention. In addition, as the representative particle size of the particles present in each channel, the lower limit value of the particle size of the particles stored in each channel was adopted.

The number average particle diameter Dp of the carrier and the core particles of the carrier is calculated based on the particle diameter distribution of the particles measured on the basis of the number. The number average particle diameter Dp in this case is represented by the formula (2).
Dp = (1 / ΣN) × (ΣnD) (2)
In formula (2), N represents the total number of particles measured, n represents the total number of particles present in each channel, and D represents the lower limit of the particle size of the particles stored in each channel (2 μm). Show.

As a particle size analyzer for measuring the particle size distribution, a microtrack particle size analyzer model HRA9320-X100 (manufactured by Honeywell) can be used. The measurement conditions are as follows.
[1] Particle size range: 8 to 100 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

(Image forming method)
The image forming method of the present invention includes a charging step for charging an electrophotographic photosensitive member, an exposure step for forming an electrostatic latent image on the charged electrophotographic photosensitive member, and an electron on which the electrostatic latent image is formed. A development step for developing a toner image by using the toner of the present invention on a photographic photoreceptor, and a primary transfer step for primary transfer of the toner image formed on the electrophotographic photoreceptor onto an intermediate transfer member; A secondary transfer step of secondarily transferring the toner image transferred onto the intermediate transfer member onto the recording material, and the toner image transferred onto the recording material onto the recording material by fixing means including a heat and pressure fixing member. A fixing step of fixing the toner image on the surface of the electrophotographic photosensitive member having the toner image transferred onto the intermediate transfer member by the primary transfer unit, and a cleaning step of cleaning the transfer residual toner adhering to the surface of the electrophotographic photosensitive member.
The image forming method is not particularly limited and may be appropriately selected depending on the intended purpose, but is suitable as a full color image forming method.
The linear speed of transfer of the toner image onto the recording material in the secondary transfer process, so-called printing speed, is not particularly limited and can be appropriately selected according to the purpose, but is 300 mm / sec to 1,000 mm / sec. The transfer time in the secondary transfer step is preferably 0.5 msec to 20 msec. The transfer time indicates a transfer time at a nip portion of a transfer roller used for secondary transfer.

The image forming method is not particularly limited and may be appropriately selected according to the purpose. However, the charging process, the exposure process, the developing process, the primary transfer process, and the secondary transfer process are performed for one image formation. It is preferable that a plurality of image forming processes including a fixing process and a cleaning process are simultaneously performed by a tandem method.
In the tandem method, a plurality of the electrophotographic photosensitive members are provided, and one color is developed at each rotation.
According to the tandem image forming process, the charging process, the exposing process, the developing process, and the transferring process are performed for each color to form a toner image of each color. The difference from the full-color image forming speed is small, and there is an advantage that it can cope with high-speed printing.

In general, in a tandem image forming method, a toner image of each color is formed on a separate electrophotographic photosensitive member, and a full color image is formed by stacking (color superposition) of each color toner layer. If there are variations in characteristics, such as different chargeability, the difference in the development toner amount due to the toner particles of each color will occur, the change in the hue of the secondary color due to color superposition will increase, and the color reproducibility will deteriorate. is there. Stabilize the amount of developing toner to control the balance of each color (no variation among toner particles of each color), and uniform adhesion to the electrophotographic photosensitive member and recording material among toner particles of each color is required.
In this regard, according to the image forming method using the toner of the present invention in the developing step, the charging characteristics are uniform, there is no variation among the toner particles of each color, and the electrophotographic photosensitive member and the recording material between the toner particles of each color. Therefore, the advantages of the tandem image forming method can be fully exhibited.

In the charging step, although there is no particular limitation, it is preferable to apply a DC voltage on which at least an alternating voltage is superimposed. By applying a DC voltage on which the alternating voltage is superimposed, the surface voltage of the electrophotographic photosensitive member can be stabilized to a desired value as compared with the case where only the DC voltage is applied, so that the charging is performed more uniformly. Is possible.
The charging step is not particularly limited, but it is preferable to perform charging by bringing a charging member into contact with the electrophotographic photosensitive member and applying a voltage to the charging member. A charging member is brought into contact with the electrophotographic photosensitive member, and charging is performed by applying a voltage to the charging member, thereby particularly improving the uniform charging effect obtained by applying a DC voltage superimposed with the alternating voltage. It becomes possible to make it.

  The fixing step is not particularly limited, and includes a heating roller made of magnetic metal and heated by electromagnetic induction, a fixing roller arranged in parallel with the heating roller, the heating roller and the fixing roller. A heating belt as an endless belt-like toner heating medium that is stretched and heated by the heating roller and rotated by the heating roller and the fixing roller, and is pressed against the fixing roller via the heating belt It is preferable that the fixing unit includes a pressure roller that rotates in the forward direction with respect to the heating belt to form a fixing nip portion. According to the fixing step, the temperature of the fixing belt rises in a short time, and stable temperature control is possible. Even when a recording material having a rough surface is used, the fixing belt acts in a state corresponding to the surface of the transfer paper to some extent at the time of fixing, so that sufficient fixing property can be obtained.

The fixing unit is not particularly limited, but is preferably an oilless type or a type of fixing unit that applies a small amount of oil. In order to achieve this, it is preferable to fix a toner containing a release agent (WAX) in which the release agent is finely dispersed in the toner particles. The toner in which a small amount of the release agent is dispersed in the toner particles makes it easy for the release agent to ooze out during fixing, and the oil application effect is reduced when an oil-less fixing device is used or when the oil-less fixing device is used. Even in this case, the transfer of the toner to the belt side can be suppressed.
In order for the release agent to exist in a dispersed state in the toner particles, it is preferable that the release agent and the binder resin are not compatible. Further, in order to finely disperse the release agent in the toner particles, for example, there is a method using a shearing force of kneading at the time of toner production. The dispersion state of the release agent can be determined by observing a thin film slice of toner particles with a TEM. There is no restriction | limiting in particular as the dispersion diameter of the said mold release agent, The smaller one is preferable, However, When too small, the ooze-out at the time of fixing may be inadequate. Therefore, if the release agent can be confirmed at a magnification of 10,000, it is determined that the release agent exists in a dispersed state. If the size is 10,000 times and the release agent cannot be confirmed, even if finely dispersed, there is a case where the bleeding at the time of fixing is insufficient.

  Each step in the image forming method will be described in more detail with reference to the drawings together with means for performing each step.

  As the charging device used in the charging step, for example, a contact charging device such as a roller charging device shown in FIG. 2 and a fur brush charging device shown in FIG. 3 can be used.

  FIG. 2 shows a schematic configuration of an example of a roller charging device (500) which is a kind of contact charging device. A photosensitive member (505) as an image bearing member, which is a member to be charged, is driven to rotate at a predetermined speed (process speed) in the direction of the arrow. The charging roller (501), which is a charging member brought into contact with the photosensitive member (505), has a core metal (502) and a conductive rubber layer (503) formed on the roller concentrically and integrally on the outer periphery of the core metal (502). The basic structure is such that both ends of the core metal are held freely rotating by a bearing member (not shown), and are pressed against the photosensitive drum with a predetermined pressure by a pressing means (not shown). The roller (501) rotates following the rotational drive of the photoreceptor (505). The charging roller (501) is formed to a diameter of 16 mm by coating a medium resistance conductive rubber layer (503) of about 100,000 Ω · cm on a core metal having a diameter of 9 mm. The cored bar (502) of the charging roller (501) and the illustrated power source (504) are electrically connected, and a predetermined bias is applied to the charging roller (501) by the power source (504). As a result, the peripheral surface of the photoconductor (505) is uniformly charged to a predetermined polarity and potential.

  The charging device may take any form such as a magnetic brush type charging device or a fur brush type charging device in addition to the roller type charging device, and can be selected according to the specifications and form of the electrophotographic apparatus. . When a magnetic brush charging device is used, the magnetic brush is composed of various ferrite particles such as Zn-Cu ferrite as a charging member, a non-magnetic conductive sleeve for supporting the charging member, and a magnet roll included therein. The Further, when using a fur brush type charging device, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal, and metal oxide is used, and this is treated with a metal or other conductive treated core. A charging device is formed by winding or sticking on gold.

  FIG. 3 shows a schematic configuration of an example of a contact-type brush charging device (510). A photoconductor (515) as an image carrier as a member to be charged is driven to rotate at a predetermined speed (process speed) in the direction of the arrow. A fur brush roller (511) constituted by a fur brush is brought into contact with the photoconductor (515) with a predetermined nip width with a predetermined pressing force against the elasticity of the brush portion (513).

  A fur brush roller (511) as a contact-type charging device has a metal cored bar (512) having a diameter of 6 mm that also serves as an electrode, and conductive rayon fibers REC-B manufactured by Unitika Ltd. as a brush part (513). A pile brush is wound in a spiral shape to form a roll brush having an outer diameter of 14 mm and a longitudinal length of 250 mm. The brush of the brush portion (513) has a density of 300 denier / 50 filaments and 155 brushes per square millimeter. This roll brush is inserted into a pipe having an inner diameter of 12 mm while being rotated in one direction, set so that the brush and the pipe are concentric, and left in a high-temperature and high-humidity atmosphere to bend and bevel.

The resistance value of the fur brush roller (511) is 1 × 10 ⁵ Ω at an applied voltage of 100V. This resistance value is converted from a current that flows when a fur brush roller is brought into contact with a metal drum having a diameter of 30 mm with a nip width of 3 mm and a voltage of 100 V is applied. The resistance value of the brush-type charging device (510) is such that even when a low-voltage defective portion such as a pinhole is generated on the photosensitive member (515) to be charged, an excessive leak current flows into this portion. In order to prevent an image defect in which the nip portion is poorly charged, it is necessary to be 10 ⁴ Ω or more, and in order to sufficiently inject charges onto the surface of the photoreceptor (515), it is necessary to be 10 ⁷ Ω or less.

  As a material for the brush, in addition to REC-B manufactured by Unitika Ltd., REC-C, REC-M1, REC-M10, SA-7 manufactured by Toray Industries, Inc., manufactured by Nippon Kashiwa Co., Ltd. Possible examples include Sanderlon, Kanebo Beltron, Kuraray Co., Ltd., Krabobo, carbon dispersion in rayon, Mitsubishi Rayon Co., Ltd. global. One brush is 3 to 10 denier, and preferably has a density of 10 to 100 filaments / bundle and 80 to 600 brushes / mm. The hair foot is preferably 1 to 10 mm.

The fur brush roller (511) is rotationally driven at a predetermined peripheral speed (surface speed) in a direction (counter) opposite to the rotation direction of the photoconductor (515), and contacts the photoconductor surface with a speed difference. A predetermined charging voltage is applied to the brush roller (511) from the power source (514), so that the surface of the rotating photosensitive member is uniformly contact-charged to a predetermined polarity and potential.
Contact charging of the photoreceptor (515) by the fur brush roller (511) is performed by direct injection charging, and the surface of the rotating photoreceptor is charged to a potential substantially equal to the applied charging voltage to the fur brush roller (511). The
As the shape of the charging member, in addition to the fur brush roller (511), any form such as a charging roller or a fur brush may be used, and can be selected according to the specifications and form of the electrophotographic apparatus. When using a charging roller, it is common to coat a medium resistance rubber layer of about 100,000 Ω · cm on a cored bar. In the case of using a magnetic brush, the magnetic brush is composed of various ferrite particles such as Zn—Cu ferrite as a charging member, a non-magnetic conductive sleeve for supporting it, and a magnet roll included therein.

  FIG. 4 shows a schematic configuration of an example of a magnetic brush charging device. A photoreceptor (515) as a charged body and an image carrier is driven to rotate at a predetermined speed (process speed) in the direction of the arrow. A brush roller (511) constituted by a magnetic brush is brought into contact with the photoreceptor (515) with a predetermined nip width with a predetermined pressing force against the elasticity of the brush portion (513).

As a magnetic brush as a contact charging member, for example, Zn—Cu ferrite particles having an average particle diameter of 25 μm and Zn—Cu ferrite particles having an average particle diameter of 10 μm are mixed at a mass ratio of 1: 0.05, respectively. Magnetic particles having a peak at the position of the average particle diameter and having ferrite particles with an average particle diameter of 25 μm coated with a medium resistance resin layer are used.
The contact charging member is constituted by, for example, the coated magnetic particles, a nonmagnetic conductive sleeve for supporting the coated magnetic particles, and a magnet roll included therein, and the coated magnetic particles are formed on the sleeve with a thickness of 1 mm. To form a charging nip having a width of about 5 mm between the photosensitive member and the photosensitive member. The gap between the magnetic particle holding sleeve and the photosensitive member is, for example, about 500 μm. Further, the magnet roll is rotated so that, for example, the sleeve surface slides in the opposite direction at a speed twice that of the circumferential speed of the surface of the photoconductor, so that the photoconductor and the magnetic brush are made uniform. Make contact.

  In the development step, it is preferable to apply an alternating electric field. FIG. 5 shows an example of a developing device that applies an alternating electric field. In the developing device (600) shown in FIG. 5, during development, a vibration bias voltage obtained by superimposing an AC voltage on a DC voltage is applied to the developing sleeve (601) as a developing bias by a power source (602). The background portion potential and the image portion potential are located between the maximum value and the minimum value of the vibration bias potential. As a result, an alternating electric field whose direction changes alternately is formed in the developing portion (603). In this alternating electric field, the developer toner and the carrier vibrate vigorously, and the toner (605) flies to the photosensitive member (604) by shaking off the electrostatic binding force to the developing sleeve (601) and the carrier. It adheres corresponding to the latent image. The toner (605) is the toner of the present invention.

  The difference (maximum peak voltage) between the maximum value and the minimum value of the vibration bias voltage is preferably 0.5 to 5 kV, and the frequency is preferably 1 to 10 kHz. As the waveform of the vibration bias voltage, a rectangular wave, a sine wave, a triangular wave, or the like can be used. As described above, the DC voltage component of the vibration bias is a value between the background part potential and the image part potential, but the value closer to the background part potential than the image part potential is more likely to cover the background part potential region. This is preferable for preventing toner adhesion.

  When the vibration bias voltage waveform is a rectangular wave, the duty ratio is preferably 50% or less. Here, the duty ratio is a ratio of time during which the toner is directed to the photosensitive member during one period of the vibration bias. By doing so, the difference between the peak value at which the toner is directed to the photoreceptor and the time average value of the bias can be increased, so that the movement of the toner is further activated and the potential of the latent image surface is increased. It can adhere to the distribution and improve the roughness and resolution. In addition, since the difference between the peak value of the carrier having a charge opposite to that of the toner and the time average value of the bias toward the photosensitive member can be reduced, the movement of the carrier is reduced, and the background portion of the latent image is reduced. The probability of carriers adhering to the substrate can be greatly reduced.

  As the fixing device used in the fixing step, for example, the fixing device shown in FIG. 6 can be used. The fixing device shown in FIG. 6 includes a heating roller (710) heated by electromagnetic induction of the induction heating means (760), a fixing roller (720) (opposite rotating body) arranged in parallel with the heating roller (710). And an endless belt-like fixing belt that is stretched between a heating roller (710) and a fixing roller (720), heated by the heating roller (710), and rotated in the direction of arrow A by at least rotation of any of these rollers. A heat-resistant belt (toner heating medium) (730) and a pressure roller (740) that is pressed against the fixing roller (720) via the fixing belt (730) and rotates in the forward direction with respect to the fixing belt (730). (Pressure rotator).

The heating roller (710) is made of, for example, a hollow cylindrical magnetic metal member such as iron, cobalt, nickel, or an alloy of these metals, and has an outer diameter of, for example, 20 to 40 mm and a wall thickness of, for example, 0.3 to 1.0 mm. It has a low heat capacity and quick temperature rise.
The fixing roller (720) (opposite rotating body) is made of, for example, a metal core (721) made of stainless steel or the like and a heat-resistant silicone rubber that is solid or foamed and covered with the core (721). It consists of a member (722). In order to form a contact portion having a predetermined width between the pressure roller (740) and the fixing roller (720) by the pressing force from the pressure roller (740), the outer shape is set to about 20 to 40 mm. 710). The elastic member (722) has a thickness of about 4 to 6 mm. With this configuration, since the heat capacity of the heating roller (710) is smaller than the heat capacity of the fixing roller (720), the heating roller (710) is rapidly heated and the warm-up time is shortened.

  The fixing belt (730) stretched between the heating roller (710) and the fixing roller (720) is heated at the contact portion (W1) with the heating roller (710) heated by the induction heating means (760). . Then, the inner surface of the fixing belt (730) is continuously heated by the rotation of the heating roller (710) and the fixing roller (720). As a result, the entire belt is heated.

FIG. 7 shows a layer structure of the fixing belt (730). The belt (730) has the following four layers from the inner layer to the surface layer, and can be configured as follows.
-Substrate (731): Resin layer such as polyimide (PI) resin-Heat generation layer (732): Conductive material layer such as Ni, Ag, SUS-Intermediate layer (733): Elastic layer for uniform fixing-Release layer (734): Resin layer such as fluorine resin material for releasing effect and oil-less

  As thickness of a mold release layer (734), 10 micrometers-300 micrometers are preferable, and about 200 micrometers is especially preferable. In this manner, in the fixing device (700) as shown in FIG. 6, the toner image (T) formed on the recording material (770) is sufficiently wrapped by the surface layer portion of the fixing belt (730). The image (T) can be heated and melted uniformly. The thickness of the release layer (734), that is, the surface release layer, needs to be at least 10 μm in order to ensure wear resistance over time. Further, when the thickness of the release layer (734) is larger than 300 μm, the heat capacity of the fixing belt (730) is increased and the time required for warm-up is increased. Further, the surface temperature of the fixing belt (730) is hardly lowered in the toner image fixing step, and the effect of aggregation of the melted toner at the fixing portion outlet cannot be obtained, and the releasability of the fixing belt (730) is lowered. The toner of the toner image (T) adheres to the fixing belt (730), and so-called hot offset occurs. The heat generating layer (732) made of the metal may be used as the base of the fixing belt (730), but the heat resistance of fluorine resin, polyimide resin, polyamide resin, polyamideimide resin, PEEK resin, PES resin, PPS resin, etc. A resin layer having properties may be used.

  The pressure roller (740) includes, for example, a metal core (741) made of a metal cylindrical member having high thermal conductivity such as copper or aluminum, and heat resistance and toner separation provided on the surface of the metal core (741). It is comprised from the elastic member (742) with high moldability. In addition to the metal, SUS may be used for the core metal (741). The pressure roller (740) presses the fixing roller (720) via the fixing belt (730) to form a fixing nip (N). In this embodiment, the pressure roller (740) By making the hardness harder than that of the fixing roller (720), the pressure roller (740) bites into the fixing roller (720) (and the fixing belt (730)), and by this biting, the recording material (770) becomes. The recording material (770) is easily separated from the surface of the fixing belt (730) because it follows the circumferential shape of the surface of the pressure roller (740). The outer diameter of the pressure roller (740) is about 20 mm to 40 mm, which is the same as that of the fixing roller (720), but the wall pressure is about 0.5 mm to 2.0 mm, which is thinner than the fixing roller (720).

  As shown in FIG. 6, the induction heating means (760) for heating the heating roller (710) by electromagnetic induction includes an excitation coil (761) as a magnetic field generation means and a coil around which the excitation coil (761) is wound. And a guide plate (762). The coil guide plate (762) has a semi-cylindrical shape disposed close to the outer peripheral surface of the heating roller (710), and the excitation coil (761) has a single long excitation coil wire as the coil guide plate (762). Along the axial direction of the heating roller (710). The excitation coil (761) has an oscillation circuit connected to a drive power supply (not shown) whose frequency is variable. On the outside of the exciting coil (761), a semi-cylindrical exciting coil core (763) made of a ferromagnetic material such as ferrite is fixed to the exciting coil core support member (764) and is disposed close to the exciting coil (761). Yes.

(Process cartridge)
The process cartridge of the present invention includes an electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, an exposure unit that forms an electrostatic latent image on the charged electrophotographic photosensitive member, and the electrophotographic photosensitive member. A developing means for converting the electrostatic latent image formed on the body into a toner image using the toner according to any one of claims 1 to 7, and the toner image formed on the electrophotographic photosensitive member as an intermediate transfer body. A primary transfer means for primary transfer; a secondary transfer means for secondary transfer of the toner image primarily transferred onto the intermediate transfer member onto the recording material; and a toner image secondary transferred onto the recording material. On the other hand, fixing means for fixing on the recording material by applying heat and pressure, and cleaning residual toner adhering to the surface of the electrophotographic photoreceptor either after the primary transfer or after the secondary transfer. With cleaning means Among the means, at least the electrophotographic photoconductor, and the developing unit, is obtained by detachable to the image forming apparatus main body integrally supported.
As the developing means and the charging means, the developing device and the charging device can be preferably used.

  An example of the process cartridge is shown in FIG. The process cartridge (800) shown in FIG. 8 includes a photoreceptor (801), a charging unit (802), a developing unit (803), and a cleaning unit (806). The operation of the process cartridge (800) will be described. The photosensitive member (801) is rotationally driven at a predetermined peripheral speed. In the rotating process, the photosensitive member (801) is uniformly charged at a predetermined positive or negative potential on its peripheral surface by the charging means (802), and then from an image exposure means (not shown) such as slit exposure or laser beam scanning exposure. In this way, an electrostatic latent image is sequentially formed on the peripheral surface of the photoreceptor (801), and the formed electrostatic latent image is then developed with the developing means (805) and the toner of the present invention. The toner image formed by the agent (804) and developed is fed from the paper feeding unit between the photosensitive member (801) and a transfer unit (not shown) in synchronization with the rotation of the photosensitive member (801). The recording material is sequentially transferred by the transfer means. The recording material that has undergone image transfer is separated from the photoreceptor surface, introduced into an image fixing means (not shown), image-fixed, and printed out as a copy (copy). The surface of the photoconductor (801) after the image transfer is cleaned by removing the transfer residual toner by the cleaning means (806), and after being further discharged, it is repeatedly used for image formation.

(Image forming device)
As a full-color image forming apparatus used in the image forming method, for example, the tandem image forming apparatus (100) shown in FIGS. 9 and 10 can be used. In FIG. 9, an image forming apparatus (100) includes an image writing unit (120Bk, 120C, 120M, 120Y), an image forming unit (130Bk, 130C, 130M, 130Y), a supply for performing color image formation by electrophotography. It is mainly composed of a paper portion (140). Based on the image signal, an image processing unit (not shown) performs image processing, and converts it into black (Bk), cyan (C), magenta (M), and yellow (Y) color signals for image formation, It transmits to an image writing part (120Bk, 120C, 120M, 120Y). The image writing unit (120Bk, 120C, 120M, 120Y) is, for example, a laser scanning optical system including a laser light source, a deflector such as a rotary polygon mirror, a scanning imaging optical system, and a mirror group (none of which are shown). There are four writing optical paths corresponding to the respective color signals, and image writing corresponding to the respective color signals is performed in the image forming units (130Bk, 130C, 130M, 130Y).

  The image forming unit (130Bk, 130C, 130M, 130Y) includes photoconductors (210Bk, 210C, 210M, 210Y) for black, cyan, magenta, and yellow, and photoconductors (210Bk, 210C, 210M and 210Y) are usually OPC photoreceptors. Around each photoconductor (210Bk, 210C, 210M, 210Y), there are a charging device (215Bk, 215C, 215M, 215Y), and an exposure unit for laser light from the image writing unit (120Bk, 120C, 120M, 120Y). , Developing devices for respective colors (200Bk, 200C, 200M, 200Y), primary transfer devices (230Bk, 230C, 230M, 230Y), cleaning devices (300Bk, 300C, 300M, 300Y), static eliminators (not shown), etc. Is arranged. The developing device (200Bk, 200C, 200M, 200Y) uses a two-component magnetic brush developing system. An intermediate transfer belt (220) is interposed between each photoconductor (210Bk, 210C, 210M, 210Y) and the primary transfer device (230Bk, 230C, 230M, 230Y), and the intermediate transfer belt (220). The toner images of the respective colors are sequentially transferred from the respective photoconductors so as to carry the toner images on the respective photoconductors.

  In some cases, a pre-transfer charger (262) as a pre-transfer charging unit is disposed outside the intermediate transfer belt (220) at a position after passing the primary transfer position of the final color and before passing the secondary transfer position. It is preferable. The pre-transfer charger (262) transfers the toner image before transferring the toner image on the intermediate transfer belt (220) transferred to the photosensitive member (210) to the transfer paper as a recording material. The toner image is uniformly charged to the same polarity as the toner image.

  The toner image on the intermediate transfer belt (220) transferred from each photoconductor (210Bk, 210C, 210M, 210Y) includes a halftone portion and a solid portion, or includes a portion where the amount of toner overlap is different. Therefore, the charge amount may vary. Further, when the discharge amount generated in the gap adjacent to the downstream side of the primary transfer portion in the movement direction of the intermediate transfer belt causes variation in charge amount in the toner image on the intermediate transfer belt (220) after the primary transfer. There is also. Such variation in the charge amount in the same toner image lowers the transfer margin in the secondary transfer portion that transfers the toner image on the intermediate transfer belt (220) onto the transfer paper. Therefore, the toner image before being transferred to the transfer paper by the pre-transfer charger is uniformly charged to the same polarity as the toner image, thereby eliminating the variation in the charge amount in the same toner image and the transfer margin in the secondary transfer portion. Has improved.

  As described above, according to this image forming method, the toner image on the intermediate transfer belt (220) transferred from each photoconductor (210Bk, 210C, 210M, 210Y) is uniformly charged by the pre-transfer charger (502). Even if there is a variation in the charge amount in the toner image on the intermediate transfer belt (220), the transfer characteristics in the secondary transfer portion are made almost constant across the portions of the toner image on the intermediate transfer belt (220). Can do. Therefore, it is possible to suppress a decrease in transfer margin when transferring to transfer paper and to stably transfer a toner image.

  In this image forming method, the amount of charge charged by the pre-transfer charger varies depending on the moving speed of the intermediate transfer belt (220) that is the object to be charged. For example, if the moving speed of the intermediate transfer belt (220) is slow, the time for the same portion of the toner image on the intermediate transfer belt (220) to pass through the charging area by the pre-transfer charger becomes long, and the charge amount increases. Conversely, when the moving speed of the intermediate transfer belt (220) is fast, the charge amount of the toner image on the intermediate transfer belt (220) becomes small. Therefore, when the moving speed of the intermediate transfer belt (220) changes while the toner image on the intermediate transfer belt (220) passes through the charging position by the pre-transfer charger, the intermediate transfer belt (220 It is desirable to control the pre-transfer charger so that the charge amount with respect to the toner image does not change in the middle according to the movement speed of ().

  Conductive rollers (241), (242), and (243) are provided between the primary transfer devices (230Bk, 230C, 230M, and 230Y). The transfer paper is fed from the paper feed unit (140) and then carried on the secondary transfer belt (180) via the registration roller pair (160), and the intermediate transfer belt (220) and the secondary transfer belt (180). ), The toner image on the intermediate transfer belt (220) is transferred onto the transfer paper by the secondary transfer roller, and a color image is formed.

  The transfer paper after image formation is conveyed to the fixing device (150) by the secondary transfer belt (180), and the image is fixed to obtain a color image. The toner on the intermediate transfer belt (220) remaining without being transferred is removed from the belt by the intermediate transfer belt cleaning device (260).

  Since the toner polarity on the intermediate transfer belt (220) before transfer onto the transfer paper is the same negative polarity as that during development, a positive transfer bias voltage is applied to the secondary transfer roller (170), and the toner is transferred. It is transferred onto paper. The nip pressure at this portion affects the transfer property and greatly affects the fixability. Further, the toner on the intermediate transfer belt (220) remaining without being transferred is discharged and charged to the positive polarity side and charged from 0 to the positive side at the moment when the transfer paper and the intermediate transfer belt (220) are separated. Note that the toner image formed when the transfer paper is jammed or in the non-image area is not affected by the secondary transfer, and therefore remains negative.

  The thickness of the photosensitive layer is 30 μm, the beam spot diameter of the optical system is 50 × 60 μm, and the light quantity is 0.47 mW. The developing process is carried out with the charging (exposure side) potential V0 of the photoconductor (black) (210Bk) set to -700V, the post-exposure potential VL set to -120V, and the developing bias voltage set to -470V, that is, the developing potential 350V. The visible image of the toner (black) formed on the photoconductor (black) (210Bk) is then transferred (intermediate transfer belt and transfer paper) and completed as an image through a fixing process. First, all colors are transferred from the primary transfer device (230Bk, 230C, 230M, 230Y) to the intermediate transfer belt (220), and then applied to a transfer sheet by applying a bias to another secondary transfer roller (170). Transcribed.

  Next, the photoconductor cleaning device will be described in detail. In FIG. 9, each developing device (200Bk, 200C, 200M, 200Y) and each cleaning device (300Bk, 300C, 300M, 300Y) are connected to each other by a toner transfer pipe (250Bk, 250C, 250M, 250Y). (Dotted line in FIG. 9). Each toner transfer pipe (250Bk, 250C, 250M, 250Y) contains a screw (not shown), and the toner collected by each cleaning device (300Bk, 300C, 300M, 300Y) Each developing device (200Bk, 200C, 200M, 200Y) is transferred.

  In the direct transfer method using a combination of the four photosensitive drums and the belt conveyance, paper dust adheres when the photoconductor and the transfer paper come into contact with each other, and the paper dust is contained when the toner is collected. Sometimes image deterioration such as toner loss occurs and cannot be used. In addition, in a system that combines a single photosensitive drum and intermediate transfer, the use of an intermediate transfer member eliminates paper dust from adhering to the photosensitive member during transfer paper transfer. When it is done, it is practically impossible to separate the mixed color toner. In addition, there is an image forming method using mixed color toner as black toner, but even if all colors are mixed, it does not become black, and the color changes depending on the print mode. Therefore, it is impossible to recycle the toner with one photoconductor configuration. .

  On the other hand, in this full-color image forming apparatus, since the intermediate transfer belt (220) is used, paper dust is hardly mixed, and adhesion of paper dust to the intermediate transfer belt (220) during paper transfer is prevented. The Since each photoconductor (210Bk, 210C, 210M, 210Y) uses independent color toner, it is not necessary to contact or separate each photoconductor cleaning device (300Bk, 300C, 300M, 300Y), and only the toner is reliably collected. can do.

  The positively charged toner remaining on the intermediate transfer belt (220) is cleaned by a conductive fur brush (262) to which a negative voltage is applied. The method of applying a voltage to the conductive fur brush (262) is exactly the same as that of the conductive fur brush (261) except for the polarity. The toner remaining without being transferred is also almost cleaned by the two conductive fur brushes (261) and (262). Here, toner, paper powder, talc, and the like remaining without being cleaned by the conductive fur brush (262) are negatively charged by the negative voltage of the conductive fur brush (262). The next black primary transfer is a transfer using a positive voltage, and negatively charged toner or the like is attracted to the intermediate transfer belt (220) side, so that the transfer to the photoconductor (black) (210Bk) side can be prevented.

  Next, the intermediate transfer belt (220) used in this image forming apparatus will be described. As described above, the intermediate transfer belt is preferably a single resin layer, but may have an elastic layer or a surface layer as necessary.

  The resin material constituting the resin layer is not particularly limited, and polycarbonate, fluororesin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride. Copolymer, Styrene-vinyl acetate copolymer, Styrene-maleic acid copolymer, Styrene-acrylic acid ester copolymer (Styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, Styrene-acrylic Acid butyl copolymer, styrene-octyl acrylate copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer) Polymer, styrene-phenyl methacrylate copolymer Styrene-α-chloromethyl acrylate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, and other styrene resins (monopolymer or copolymer containing styrene or styrene-substituted product), methacrylic acid Methyl resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (silicone modified acrylic resin, vinyl chloride resin modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate Polymer, vinyl chloride-vinyl acetate copolymer, rosin modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane resin , Silicone resins, ketone resins, ethylene - can be used ethyl acrylate copolymer, xylene resin and polyvinyl butyral resin, polyamide resin, one kind or two kinds or more selected from the group consisting of modified polyphenylene oxide resin.

  The elastic material (elastic material rubber, elastomer) constituting the elastic layer is not particularly limited, and is butyl rubber, fluorine-based rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene rubber natural rubber, isoprene rubber, Styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, Ricone rubber, fluororubber, polysulfide rubber, polynorbornene rubber, hydrogenated nitrile rubber, thermoplastic elastomer (eg polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea) It is possible to use one kind or two kinds or more selected from the group consisting of polyester, fluorocarbon resin) or the like.

  Further, the material for the surface layer is not particularly limited, but a material for reducing the adhesive force of the toner to the surface of the intermediate transfer belt and improving the secondary transfer property is required. For example, materials that use one or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and increase lubricity, such as fluorine resin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide, etc. One kind or two or more kinds of powders and particles or particles having different particle diameters can be dispersed and used. Further, it is also possible to use a material having a surface energy reduced by forming a fluorine-rich layer on the surface by heat treatment, such as a fluorine-based rubber material.

As the resin layer and the elastic layer, a resistance value adjusting conductive agent is preferably added.
The resistance value adjusting conductive agent is not particularly limited, and examples thereof include carbon black, graphite, metal powders such as aluminum and nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, and antimony oxide-oxidation. Examples thereof include conductive metal oxides such as tin composite oxide (ATO) and indium oxide-tin oxide composite oxide (ITO).
The conductive metal oxide may be coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate.

  FIG. 10 shows another example of an image forming apparatus used in the full-color image forming method of the present invention, which is a copying apparatus (100) provided with an electrophotographic image forming apparatus of a tandem indirect transfer system. . In FIG. 10, (110) is a copying apparatus main body, (200) is a paper feed table on which it is placed, (300) is a scanner mounted on the copying apparatus main body (110), and (400) is an automatic document feeder mounted thereon. Device (ADF). The copying apparatus main body (110) is provided with an endless belt-shaped intermediate transfer member (50) in the center.

  Then, as shown in FIG. 10, in this example, it is wound around three support rollers (14), (15), (16) so that it can be rotated and conveyed clockwise in the figure. In this illustrated example, an intermediate transfer member cleaning device (17) for removing residual toner remaining on the intermediate transfer member (50) after image transfer is provided on the left of the second support roller (15) among the three. Further, among the three, the intermediate transfer member (50) stretched between the first support roller (14) and the second support roller (15) has yellow, cyan and magenta along the transport direction. The black image forming means (18) are arranged side by side to constitute a tandem image forming apparatus (120).

  An exposure device (21) is further provided on the tandem image forming device (120) as shown in FIG. On the other hand, a secondary transfer device (22) is provided on the opposite side of the intermediate transfer member (50) from the tandem image forming device (120). In the illustrated example, the secondary transfer device (22) includes a secondary transfer belt (24), which is an endless belt, spanned between two rollers (23), and the second transfer device (22) passes through an intermediate transfer member (50). 3 is pressed against the support roller (16) to transfer the image on the intermediate transfer member (50) onto the sheet. Next to the secondary transfer device (22), a fixing device (25) for fixing the transferred image on the sheet is provided. The fixing device (25) is configured by pressing a pressure roller (27) against a fixing belt (26) which is an endless belt. The secondary transfer device (22) described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device (25). Of course, as the secondary transfer device (22), a transfer roller or a non-contact charger may be arranged. In such a case, it is difficult to provide this sheet conveying function together. In the illustrated example, a sheet is placed under such a secondary transfer device (22) and a fixing device (25) to record an image on both sides of the sheet in parallel with the tandem image forming device (120). A sheet inverting device (28) for inverting is provided.

  Now, when making a copy using this color electrophotographic apparatus, the document is set on the document table (130) of the automatic document feeder (400). Alternatively, the automatic document feeder (400) is opened, a document is set on the contact glass (32) of the scanner (300), and the automatic document feeder (400) is closed and pressed by it.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder (400), the document is transported and moved onto the contact glass (32), and then the other contact glass (32). When a document is set on the scanner, the scanner (300) is immediately driven to travel on the first traveling body (33) and the second traveling body (34). Then, the first traveling body (33) emits light from the light source, and the reflected light from the document surface is further reflected toward the second traveling body (34) and reflected by the mirror of the second traveling body (34). Then, the image is placed in the reading sensor (36) through the imaging lens (35) and the content of the original is read.

  When a start switch (not shown) is pressed, one of the support rollers (14), (15), and (16) is driven to rotate by the drive motor (not shown), and the other two support rollers are driven to rotate. The transfer body (50) is rotated and conveyed. At the same time, the individual image forming means (18) rotates the photoconductor (10) to form black, yellow, magenta, and cyan single-color images on the photoconductors (10Y, 10C, 10M, and 10K), respectively. . Then, along with the conveyance of the intermediate transfer member (50), these single color images are sequentially transferred to form a composite color image on the intermediate transfer member (50).

  On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers (142) of the paper feed table (200) is selectively rotated, and one of paper feed cassettes (144) provided in multiple stages in the paper bank (143). The sheet is fed out from the sheet, separated one by one by a separation roller (145), put into a sheet feeding path (146), and conveyed by a conveying roller (147) to a sheet feeding path (148) in the copying machine main body (100). Guide and stop against the registration roller (49).

  Alternatively, the sheet feeding roller (67) is rotated to feed out the sheets on the manual feed tray (51), separated one by one by the separation roller (58), and put into the manual sheet feeding path (53). ) And stop.

  Then, the registration roller (49) is rotated in time with the composite color image on the intermediate transfer member (50), and the sheet is fed between the intermediate transfer member (50) and the secondary transfer device (22). The image is transferred by the next transfer device (22) and a color image is recorded on the sheet.

  The sheet after the image transfer is conveyed by the secondary transfer device (22) and sent to the fixing device (25). The fixing device (25) applies heat and pressure to fix the transferred image, and then the switching claw. It is switched at (55), discharged by the discharge roller (56), and stacked on the discharge tray (57). Alternatively, it is switched by the switching claw (55) and put into the sheet reversing device (28), where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then the paper discharge tray (56) is discharged by the discharge roller (56). 57) Drain up.

  On the other hand, the intermediate transfer member (50) after image transfer is removed by an intermediate transfer member cleaning device (17) to remove residual toner remaining on the intermediate transfer member (50) after image transfer, and the tandem image forming device (120). To prepare for image formation again. Here, the registration roller (49) is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited to the Example and comparative example which are illustrated here. In the examples, “part” and “%” represent “part by mass” and “% by mass” unless otherwise specified.

Example 1
<Preparation of solution or dispersion of toner material>

-Preparation of dispersion of pyrone compound-
As a pyrone compound, a pyrone compound A represented by the following structural formula (A) was produced with reference to WO 2006/101144 pamphlet (particularly, Example 2).

  5 parts by mass of the pyrone compound A, 15 parts by mass of the following unmodified polyester, and 30 parts by mass of ethyl acetate were charged in a beaker, and a feed rate of 1 kg / hr was used using a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation). Then, a dispersion liquid of Compound A was prepared by performing 3 passes under the condition that the disk peripheral speed was 6 m / s, and 80% by volume of 0.5 mm zirconia beads were filled. The average particle diameter (average dispersion diameter) of Compound A in the dispersion was 100 nm.

-Synthesis of unmodified polyester (low molecular weight polyester)-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin oxide 2 parts by mass were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 55 ° C.

-Preparation of masterbatch (MB)-
1,000 parts by weight of water, 540 parts by weight of carbon black (“Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5), and 1,200 parts by weight of the unmodified polyester were added to Henschel. Mixing was performed using a 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 (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

-Synthesis of prepolymer-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined. The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized. The free isocyanate content of the obtained prepolymer was 1.60% by mass, and the solid content concentration of the prepolymer (after standing at 150 ° C. for 45 minutes) was 50% by mass.

<Preparation of anionic resin fine particles>
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 16 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [resin fine particle dispersion A] was obtained. The volume average particle diameter of the dispersed particles of [resin fine particle dispersion A] (measured with LA-920 manufactured by Horiba, Ltd.) was 42 nm.

<Dissolution or dispersion preparation step A>
-Preparation of toner material phase-
100 parts by mass of the unmodified polyester and 130 parts by mass of ethyl acetate were added to a beaker and dissolved by stirring. Then, 10 parts by mass of carnauba wax (molecular weight = 1,800, acid value = 2.5, penetration = 1.5 mm (40 ° C.)), 10 parts by mass of the master batch, and dispersion 1 of pyrone compound A 3 parts were charged under the condition that a mass part was charged and a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / s, and 80% by volume of 0.5 mm zirconia beads were filled using a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation). After passing, a raw material solution was prepared, and 40 parts by mass of the prepolymer was added and stirred, and then a toner material solution or dispersion was prepared.

<Emulsification or dispersion preparation step B>
-Preparation of aqueous medium phase-
660 parts by mass of water, 1.25 parts by mass of resin fine particle dispersion A, 25 parts by mass of an aqueous solution of 48.5% by mass of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and ethyl acetate 60 Mass parts were mixed and stirred to obtain a milky white liquid (aqueous medium phase).

-Preparation of emulsification or dispersion A-
150 parts by mass of the aqueous medium phase is placed in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and 100 parts by mass of the solution or dispersion of the toner material is added thereto. The mixture was added and mixed for 10 minutes to prepare an emulsified dispersion (emulsified slurry).

<Organic solvent removal step C>
-Removal of organic solvent-
100 parts by mass of the emulsified slurry was charged into a flask equipped with a degassing pipe, a stirrer, and a thermometer, and the solvent was removed under reduced pressure at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min. It was.

-Cleaning and drying-
After filtering the whole amount of the solvent-removed slurry under reduced pressure, 300 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer, redispersed (at 12,000 rpm for 10 minutes) and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added and mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered three times. The obtained filter cake was dried at 45 ° C. for 48 hours in a forward air dryer, and sieved with a mesh having an opening of 75 μm to obtain toner base particles A.

-External treatment-
To 100 parts by mass of toner base particles A, 0.6 parts by mass of hydrophobic silica having an average particle size of 100 nm, 1.0 part by mass of titanium oxide having an average particle size of 20 nm, and hydrophobic silica fine powder having an average particle size of 15 nm 0.8 part was mixed with a Henschel mixer to produce toner a in Example 1. The common logarithm Log ρ of the volume specific resistance ρ of the toner a was 11.3 (Ω · cm).

(Example 2)
Toner b in Example 2 was produced in the same manner as in Example 1, except that the average dispersion diameter in the dispersion of pyrone compound A in Example 1 was changed from 100 nm to 30 nm.
The common logarithm of the volume specific resistance of the toner b was 11.3 (Ω · cm).

(Example 3)
Toner c in Example 3 was produced in the same manner as in Example 1, except that the average dispersion diameter in the dispersion of pyrone compound A in Example 1 was changed from 100 nm to 200 nm.
The common logarithm value Log ρ of the volume specific resistance ρ of the toner c was 11.4 (Ωcm).

Example 4
In Example 1, the toner d in Example 4 was used in the same manner as in Example 1 except that instead of the pyrone compound A, a pyrone compound B represented by the following structural formula (B) was used as the pyrone compound. Manufactured. The common logarithm Log ρ of the volume specific resistance ρ of the toner d was 11.1 (Ω · cm). The average dispersion diameter in the dispersion of pyrone compound B was 55 nm.
The pyrone compound B was produced with reference to WO 2006/101144 pamphlet (particularly, Example 2).

(Example 5)
In Example 1, the toner e in Example 5 was used in the same manner as in Example 1 except that instead of the pyrone compound A, a pyrone compound C represented by the following structural formula (C) was used as the pyrone compound. Manufactured. The common logarithm Log ρ of the volume specific resistance ρ of the toner e was 11.2 (Ω · cm). The average dispersion diameter in the dispersion of pyrone compound C was 72 nm.

(Example 6)
In Example 1, the toner f in Example 6 was used in the same manner as in Example 1 except that instead of the pyrone compound A, a pyrone compound D represented by the following structural formula (D) was used as the pyrone compound. Manufactured. The common logarithm value Log ρ of the volume specific resistance ρ of the toner f was 11.0 (Ω · cm). Moreover, the average dispersion diameter in the dispersion liquid of the pyrone compound D was 300 nm.

(Example 7)
In Example 1, the toner g in Example 7 was used in the same manner as in Example 1 except that instead of the pyrone compound A, the pyrone compound E represented by the following structural formula (E) was used as the pyrone compound. Manufactured. The common logarithm value Log ρ of the volume specific resistance ρ of the toner g was 11.1 (Ω · cm). Moreover, the average dispersion diameter in the dispersion liquid of the pyrone compound E was 270 nm.

(Comparative Example 1)
In Example 1, in place of the pyrone compound A, a charge control agent (TN-105, salicylic acid derivative zirconia complex) manufactured by Hodogaya Chemical Co., Ltd. was used. Toner h was produced. The common logarithm Log ρ of the volume specific resistance ρ of the toner h was 10.8 (Ω · cm). The average dispersion diameter in the dispersion of the charge control agent (TN-105) was 140 nm.

(Comparative Example 2)
In Example 1, instead of the pyrone compound A, a charge control agent (E-84, salicylic acid derivative zinc complex) manufactured by Orient Chemical Industry Co., Ltd. was used. Toner i was produced.

  The physical properties of the toners a to i in Examples 1 to 7 and Comparative Examples 1 and 2 are shown in Tables 1 and 2 below. The measuring method of physical properties is as follows.

<Charging characteristics and durability (Q / M)>
Fuji and Xerox DocuColor 8000 Digital Press linear velocity by modifying and transfer time adjustably tuned evaluation machine, using a toner a to i, A4 size, the toner adhesion amount 0.6 mg / cm ² As a solid pattern printed, 100,000 running tests were performed.
Here, as an index of durability, a part of the toner before and after the running test was sampled and the charge amount was measured by the blow-off method.

<Charging environment stability>
A part of each toner was sampled and the charge amount was measured by the blow-off method.
Here, the measurement was performed under each environment of normal temperature and normal humidity (temperature 25 ° C., humidity 50%), low temperature and low humidity (temperature 10 ° C., humidity 15%), and high temperature and high humidity (temperature 40 ° C., humidity 90%). The test was performed on the toner stored for a week.

<Volume average particle diameter and volume average particle diameter / number average particle diameter>
The volume average particle diameter (Dv) and the volume average particle diameter / number average particle diameter (Dv / Dn) were measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.).

<Circularity>
The circularity of the toners a to i was measured as follows.
That is, 0.1% to 0.5 mL of 10% by weight surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass 100 mL beaker, and each toner 0.1 g to 0.5 g. The mixture was added and stirred with a microspatel, and then 80 ml of ion exchange water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation) until the concentration became 5,000 to 15,000 / μL.

<BET specific surface area>
According to the BET method, nitrogen gas was adsorbed on the surface of each toner using a specific surface area measuring device (“Tristar 3000”; manufactured by Shimadzu Corporation), and measurement was performed by the BET multipoint method.

<Average dispersion diameter>
1 g of each toner is immersed in 100 g of chloroform for 10 hours, and the dispersion of the pyrone compound is centrifuged at 5,500 rpm (9,545 G) in a centrifuge (H-9R, LN angle rotor manufactured by Kokusan Co., Ltd.). separated. The pyrone compound particles were present in the centrifuged supernatant, and the particle size of the particles was measured using “LA-920” (manufactured by Horiba, Ltd.). When measuring LA-920, analysis was performed using an application dedicated to LA-920 (Ver 3.32, manufactured by Horiba, Ltd.).

<Volume resistivity ρ>
A commercially available dielectric loss measuring machine (TR-10C type: manufactured by Ando Electric Co., Ltd.) was formed by pressing 3.0 g of toner about 500 kgf / aJ and molding it into a tablet having an area of 12.5 cd and a thickness of about 3 mm to 4 mm. The measurement was performed with 1 frequency applied at 1 kHz, and the volume resistivity and dielectric constant were calculated from the measurement.

In Tables 1 and 2, the notation “-” indicates that measurement could not be performed because toner could not be formed.

The toners a to e in Examples 1 to 5 are excellent in charging characteristics, durability, charging environment stability, and granulation properties (Dv, Dv / Dn, circularity, BET specific surface area), and can sufficiently solve the problems. Met.
In the toners f and g in Examples 6 and 7, the same results as the toners a to e in Examples 1 to 5 were obtained with respect to the granulation property, but the charge amount was low with respect to the charging characteristics. Regarding environmental stability, the fluctuations in each environment of low temperature and low humidity and high temperature and high humidity were relatively large, but there was no problem in practical use.
The charge control agent (TN-105) used in the production of the toner h in Comparative Example 1 has a zirconium salicylate complex structure and exhibits a high charge imparting effect in the pulverized toner, but the granulating property is extremely poor. The surface properties of the toner were also extremely bad. Regarding durability, the spent to the carrier was remarkable after 100,000 sheets were run, and the fluctuation of Q / M was large. Regarding the environmental stability, in each case of storage in a low-temperature and low-humidity environment and a high-temperature and high-humidity environment, variation in Q / M was large, and improvement could not be expected.
The charge control agent (E-84) used in the production of the toner i in Comparative Example 2 has a zinc salicylate complex structure and exhibits a high charge imparting effect in the pulverized toner, but the granulation property is remarkably poor. The toner could not be formed.

<Manufacture of carriers>
Next, a specific example of manufacturing the carrier used for the actual toner evaluation will be described.
Acrylic resin solution (solid content 50% by mass) 21.0 parts Guanamin solution (solid content 70% by mass) 6.4 parts Alumina particles [0.3 μm, specific resistance 10 ¹⁴ (Ω · cm)] 7.6 parts Silicone resin Solution 65.0 parts [Solid content 23% by mass (SR2410: manufactured by Toray Dow Corning Silicone)]
Aminosilane 1.0 part [Solid content 100% by mass (SH6020: manufactured by Toray Dow Corning Silicone)]
Toluene 60 parts Butyl cellosolve 60 parts

The carrier raw material was dispersed with a homomixer for 10 minutes to obtain a coating film forming solution of acrylic resin and silicone resin containing alumina particles.
Firing ferrite powder [(MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 : average particle size; 25 μm] as the core material so that the coating film forming solution has a film thickness of 0.15 μm on the surface of the core material The coated ferrite powder was obtained by applying and drying with a Spira coater (Okada Seiko Co., Ltd.).
The obtained coated ferrite powder was fired in an electric furnace at 150 ° C. for 1 hour. After cooling, the ferrite powder bulk was pulverized using a sieve having an aperture of 106 μm to obtain carrier A.
The measurement of the binder resin film thickness was performed by observing the cross section of the carrier with a transmission electron microscope so that the coating film covering the carrier surface could be observed. Thus, carrier A having a weight average particle diameter of 35 μm was obtained.

(Examples 8 to 14 and Comparative Examples 3 and 4)
Using the toners a to i in Examples 1 to 7 and Comparative Examples 1 and 2 and the carrier A, a type of tumbler mixer in which a container rolls and stirs 7 parts by mass of toner with respect to 100 parts by mass of the carrier. The two-component developers a to i in Examples 8 to 14 and Comparative Examples 3 and 4 were produced by uniformly mixing and charging. The subscripts a to i in the two-component developer indicate that the two-component developers a to i were produced corresponding to the toners a to i.

(Evaluation of two-component developer)
<Charging characteristics and durability (Q / M)>
An evaluation machine that is tuned so that the linear speed and transfer time can be adjusted by modifying DocuColor 8000 Digital Press manufactured by Fuji Xerox Co., Ltd., and each of the two-component developers a to i in Examples 8 to 14 and Comparative Examples 3 and 4 A running test of 100,000 sheets was carried out by printing a solid pattern having an A4 size and a toner adhesion amount of 0.6 mg / cm ² .
As a durability index, after a running test with 100,000 sheets passed, a two-component developer is partially sampled, the charge amount is measured by the blow-off method, and the toner is charged after the running test from the initial value before the running test. Durability was evaluated by judging the decrease in the amount based on the following evaluation criteria.
-Evaluation criteria-
◎ ・ ・ ・ Charge reduction is less than 3μc / g ○ ・ ・ ・ Charge reduction is 3μc / g or more and less than 5μc / g Δ ・ ・ ・ Charge reduction is 5μc / g or more and less than 10μc / g × ・ ・・ Reduction of charge amount is 10μc / g or more

<Charging environment stability>
A part of each two-component developer was sampled and the charge amount was measured by a blow-off method to evaluate the charging environment stability of the two-component developers a to i in Examples 8 to 14 and Comparative Examples 3 and 4.
The stability of the charging environment is evaluated in each environment of normal temperature and normal humidity (temperature 25 ° C, humidity 50%), low temperature and low humidity (temperature 10 ° C, humidity 15%), and high temperature and high humidity (temperature 40 ° C, humidity 90%). The evaluation method is based on the following evaluation criteria through the amount of change in the charge amount of the toner after the running test as seen from the initial value before the running test. It was made by judging.
-Evaluation criteria-
◎ ・ ・ ・ Change in charge amount less than 3 μc / g ○ ・ ・ ・ Change in charge amount from 3 μc / g to less than 5 μc / g Δ ・ ・ ・ Change in charge amount from 5 μc / g to less than 10 μc / g・ Charge change is 10μc / g or more

<Granulation>
Evaluation of the granulation property was carried out with respect to each of the two-component developers a to i in Examples 8 to 14 and Comparative Examples 3 and 4, volume average particle diameter (Dv) and volume average particle diameter / number average particle diameter (Dv / Dn). ) Was measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.), and whether or not the target Dv and Dv / Dn were obtained was evaluated as follows.
-Evaluation criteria for Dv-
◎: Target Dv ± 0.1 μm or less ○: Target Dv ± 0.1 μm or more and less than 0.3 μm △: Target Dv ± 0.3 μm or more and less than 0.5 μm ×: Target Dv ± 0.5 μm or more * Target : 5.2 μm
-Evaluation criteria for Dv / Dn-
◎: Less than 1.15 ○: 1.15 or more and less than 1.18 Δ: 1.18 or more and less than 1.25 ×: 1.25 or more * Aim: 1.15 or less

  The toner of the present invention is excellent in toner chargeability, durability, and environmental stability in a full-color image forming method, and can obtain a desired particle size and stably obtain a high-quality image. Therefore, it can be suitably used for electrophotographic toner, developer, full-color image forming method and image forming apparatus, process cartridge, and the like.

(Reference in FIG. 1)
1 Toner 2 Base particle 3 External additive (reference numerals in FIGS. 2 to 4)
500 Roller Charging Device 501 Charging Roller 502 Core Bar 503 Conductive Rubber Layer 504 Power Supply 505 Photoconductor 510 Brush Charging Device 511 Fur Brush Roller 513 Brush Unit 514 Power Supply 515 Photosensitive Member (reference numeral in FIG. 5)
600 Developing Device 601 Developing Sleeve 602 Power Supply 603 Developing Unit 604 Photoconductor 605 Toner (reference numerals in FIGS. 6 and 7)
760 Induction heating means 710 Heating roller 720 Fixing roller 721 Core metal 722 Elastic member 730 Endless belt-like fixing belt 731 Base body 732 Heat generation layer 733 Intermediate layer 734 Release layer 740 Pressure roller 741 Core metal 742 Elastic member 760 Induction heating means 761 Excitation Coil 762 Coil guide plate 763 Excitation coil core 764 Excitation coil core support member 770 Recording material (reference numeral in FIG. 8)
800 Process cartridge 801 Photoconductor 802 Charging means 803 Developing means 804 Developer 805 Developing means 806 Cleaning means (reference numeral in FIG. 9)
120Bk, 120C, 120M, 120Y Image writing unit 130Bk, 130C, 130M, 130Y Image forming unit 140 Paper feeding unit 262 Pre-transfer charger 215Bk, 215C, 215M, 215Y Charging device 200Bk, 200C, 200M, 200Y Developing device 230Bk, 230C , 230M, 230Y Primary transfer device 250Bk, 250C, 250M, 250Y Toner transfer tube 300Bk, 300C, 300M, 300Y Cleaning device 220 Intermediate transfer belt (reference numeral in FIG. 10)
10Y, 10C, 10M, 10K photoconductor 14 first support roller 15 second support roller 16 third support roller 17 intermediate transfer body cleaning device 18 image forming means 21 exposure means 22 secondary transfer means 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 49 Registration roller 50 Intermediate transfer body 51 Manual feed tray 53 Paper feed path 55 switching claw 56 discharge roller 57 discharge tray 58 separation roller 62 primary transfer device 100 image forming apparatus 110 copying apparatus main body 120 tandem image forming apparatus 130 document table 142 paper feed roller 143 paper bank 144 paper feed cassette 145 separation roller 146 feed Paper path 47 conveying rollers 148 feed path 200 feeder table 300 Scanner 400 automatic document feeder

Japanese Patent No. 3640918 Japanese Patent Laid-Open No. 06-250439 Japanese Patent Publication No.55-42752 JP-A 61-69073 JP 61-221756 A Japanese Patent Laid-Open No. 09-124659 JP-A-57-111541 JP 62-94856 A Japanese Patent Publication No. 07-31421 Japanese Patent Publication No. 07-104620

Claims (18)

A dissolution or dispersion preparation step of dissolving or dispersing a toner material containing at least one of a binder resin and a binder resin precursor and a charge control agent in an organic solvent to prepare a solution or dispersion of the toner material; and the dissolution A toner comprising: an emulsification or dispersion preparation step for preparing an emulsification or dispersion by adding a dispersion into an aqueous medium and emulsifying or dispersing; and an organic solvent removal step for removing the organic solvent from the emulsification or dispersion. Manufactured by the manufacturing method of
A toner wherein the charge control agent contains a pyrone compound represented by the following general formula (I).
However, in said general formula (I), R < ¹ > -R < ⁵ > represents either hydrogen, a halogen, a hydroxyl group, an alkyl group, a phenyl group, and a fluoroalkyl group, respectively, Of said R < ¹ > -R < ⁵ > Adjacent ones may be combined to form a ring.   The toner according to claim 1, wherein the pyrone compound is contained in the toner.   The toner according to claim 1, which has a volume average particle diameter of 1 μm to 6 μm.   The toner according to claim 1, wherein the aqueous medium in the emulsification or dispersion preparation step includes anionic resin fine particles having an average particle diameter of 5 nm to 50 nm and an anionic surfactant.   The toner according to claim 1, wherein the binder resin includes a polyester-based resin.   The toner according to claim 1, comprising 0.01 to 5.0 parts by mass of a pyrone compound with respect to 100 parts by mass of the toner.   The toner according to claim 1, wherein an average dispersion diameter of the pyrone compound is 10 nm to 500 nm.   The toner according to claim 1, wherein the charge amount is −80 μC / g to −10 μC / g.   The toner according to claim 1, wherein Logρ, which is a common logarithmic value of the volume specific resistance ρ (Ω · cm) of the toner, is 10.9 Ω · cm to 11.4 Ω · cm.   The toner according to any one of claims 1 to 9, wherein the ratio of the volume average particle diameter (Dv) to the number average particle diameter (Dn), Dv / Dn, is 1.05 to 1.25.   The toner according to claim 1, wherein the average circularity is 0.950 to 0.990. BET specific surface ^area, the toner according to any one of claims 1 to 11 is 0.5m ² /g~4.0m 2 / g.   The toner according to claim 1, wherein the toner material comprises an active hydrogen group-containing compound and a modified polyester resin capable of reacting with the active hydrogen group-containing compound.   2. A charging step for charging the electrophotographic photosensitive member, an exposure step for forming an electrostatic latent image on the charged electrophotographic photosensitive member, and an electrophotographic photosensitive member on which the electrostatic latent image is formed. A developing step for forming a toner image using the toner according to any one of claims 13 to 13, a primary transfer step for primary transfer of a toner image formed on the electrophotographic photosensitive member onto an intermediate transfer member, and the intermediate transfer A secondary transfer step in which the toner image primarily transferred onto the body is secondarily transferred onto the recording material; and heat and pressure are applied to the toner image secondary transferred onto the recording material to An image forming method comprising: a fixing step of fixing; and a cleaning step of cleaning a transfer residual toner adhering to the surface of the electrophotographic photosensitive member after either the primary transfer or the secondary transfer. Method.   The image forming method according to claim 14, wherein in the secondary transfer step, the linear velocity at which the toner image is transferred to the recording material is 300 mm / sec to 1,000 mm / sec, and the transfer time is 0.5 msec to 20 msec.   16. A plurality of image forming processes including a charging process, an exposure process, a developing process, a primary transfer process, a secondary transfer process, a fixing process, and a cleaning process are simultaneously performed in a tandem manner for one image formation. The image forming method according to any one of the above. An electrophotographic photosensitive member; a charging unit that charges the electrophotographic photosensitive member; an exposure unit that forms an electrostatic latent image on the charged electrophotographic photosensitive member; and a static image formed on the electrophotographic photosensitive member. A developing means for converting the electrostatic latent image into a toner image using the toner according to any one of claims 1 to 13, and a primary transfer for primarily transferring the toner image formed on the electrophotographic photosensitive member onto an intermediate transfer member. Means, secondary transfer means for secondary transfer of the toner image primary-transferred on the intermediate transfer member onto the recording material, and application of heat and pressure to the toner image secondary-transferred on the recording material And fixing means for fixing on the recording material, and cleaning means for cleaning the transfer residual toner adhering to the surface of the electrophotographic photosensitive member after either the primary transfer or the secondary transfer. Means in image forming apparatus Among them,
A process cartridge characterized in that at least the electrophotographic photosensitive member and the developing means are integrally supported to be detachable from a main body of the image forming apparatus.   The process cartridge according to claim 17, further comprising at least one means selected from a charging means, a transfer means, and a cleaning means.