JP2008102496A - Toner, and developer, toner-containing container, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner which satisfies both of low-temperature fixability and heat resistance, excels in offset resistance, can control toner structure and has good charging property and cleanerless aptitude without contaminating a development device, etc., and a developer using the toner, a toner-containing container, a process cartridge, an image forming apparatus and an image forming method. <P>SOLUTION: The toner contains at least a binder resin, a colorant, a release agent and a zeolite, is manufactured by an O/W type wet granulation system and has an average circularity of ≥0.970. There are also provided the developer using the toner, the toner-containing container, the process cartridge, the image forming apparatus, and the image forming method. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, a developer using the toner, a container containing the toner, a process cartridge, an image forming apparatus, and an image forming method. About.

  Conventionally, a contact heating fixing method such as a heat roll fixing method has been widely adopted as a toner fixing method. The fixing device used in the heat roll fixing method includes a heating roll and a pressure roll, and a recording medium (recording sheet) carrying a visible image (toner image) is placed between the heating roll and the pressure roll. By passing through the pressure contact portion (nip portion), the toner image is melted and fixed on the recording sheet.

  In the contact heating fixing method represented by the heat roll fixing method, fixing is performed by bringing the surface of a heating member (for example, a heating roll) of a fixing unit (contact heating fixing device) into contact with a toner image on a recording sheet. It is necessary to prevent an offset phenomenon in which a part of the toner image adheres to the member and is transferred to the next recording sheet and becomes dirty.

  For this reason, a technique for applying or impregnating fixing oil such as silicone oil to the heating roll or pressure roll of the fixing device is known, but the fixing oil application mechanism is omitted from the viewpoint of downsizing and cost reduction of the fixing device. An oilless fixing device and a fixing device of a type in which the amount of fixing oil applied is reduced are employed. When such a fixing device is employed, a release agent is added to the toner as an anti-offset agent.

  In the case of the heat fixing method, the heating temperature is preferably as low as possible for energy saving. However, if the thermal properties of the binder resin constituting the toner are designed too low in order to achieve this, Deteriorates and problems such as blocking occur. In order to achieve both the low-temperature fixability and the heat resistance, it is advantageous to use a polyester resin as the binder resin. Since the polyester resin has a low viscosity and high elasticity as compared with the vinyl copolymer resin, it has excellent low-temperature fixability and good heat resistance.

However, when a toner to which a sufficient amount of a release agent is added to prevent offset is produced by a conventional pulverization method, a large amount of the release agent is exposed on the surface of the toner, causing problems such as filming and blocking. .
On the other hand, so-called polymerization methods are known, such as a suspension polymerization method in which a polymerization reactive monomer is polymerized in an aqueous medium, and an emulsion aggregation method in which fine particles are prepared and aggregated in advance by emulsion polymerization. These polymerization methods can contain a larger amount of release agent as compared with the pulverization method. Furthermore, as for the suspension polymerization method, there is a description of a toner whose structure is controlled by adding a polymerizable monomer and polymerizing after completion of normal granulation (see Patent Document 1). In addition, regarding the emulsion aggregation method, there is a description of a toner whose structure is controlled by adding and aggregating emulsion fine particles after completion of granulation by normal aggregation (see Patent Document 2).
However, since these suspension polymerization methods and emulsion aggregation methods perform polymerization in an aqueous medium, vinyl copolymer resins are used, and it is difficult to use a polyester resin that is polymerized at a high temperature of about 200 ° C. .

  As a method for granulating toner using a polyester resin, a so-called dissolution suspension method is known in which a resin polymerized in advance is dissolved in an organic solvent and granulated in an aqueous medium. In this method, the molecular weight of the resin at the time of charging becomes the molecular weight of the toner as it is, and in order to adjust the thermal characteristics of the toner, it is common to use a mixture of a low molecular weight resin and a high molecular weight resin. When the above resin is added, there is a problem that the viscosity of the solution becomes too high and the granulation property is deteriorated, so that many high molecular weight resins cannot be used. Therefore, the molecular weight of the low molecular weight resin must be increased, which is disadvantageous for low temperature fixing.

  In order to solve this, there is a method of adjusting the molecular weight by granulating a modified polyester having a reactive group after the granulation instead of adding a high-molecular-weight resin, followed by elongation or cross-linking reaction. When this method is used, the thermal characteristics of the toner can be adjusted, but the toner structure is not sufficiently controlled, and colorants and release agents tend to be exposed on the surface. However, there was a problem that soiling was caused by continuous use.

  Therefore, it is compatible with low-temperature fixability and heat resistance, has excellent anti-offset properties, can control the toner structure, and has good chargeability and cleanerless suitability without contaminating the developing device and related technology and related technology. Has not been obtained yet, and it is desired to provide it promptly.

Japanese Patent No. 3195362 JP 2002-116574 A

  An object of the present invention is to solve the conventional problems in response to the above-mentioned demands and achieve the following object. That is, the present invention achieves both low-temperature fixability and heat resistance, is excellent in offset resistance, can control the toner structure, and has excellent chargeability and cleanerless suitability without contaminating the developing device. Another object of the present invention is to provide a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method using the toner.

Means for solving the problems are as follows. That is,
<1> A toner comprising at least a binder resin, a colorant, a release agent, and zeolite, and having an average circularity of 0.970 or more produced by an O / W type wet granulation method. .
<2> The toner according to <1>, which has negative chargeability.
<3> The toner according to any one of <1> to <2>, wherein the cation exchange capacity (CEC) of the zeolite is 150 meq / 100 g to 800 meq / 100 g.
<4> The toner according to <3>, wherein the zeolite is a synthetic zeolite having a cation exchange capacity (CEC) of 400 meq / 100 g to 600 meq / 100 g.
<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 oil phase used in the O / W type wet granulation includes an organic solvent.
<7> The toner according to any one of <1> to <6>, which is used for nonmagnetic one-component development.
<8> A method for producing a toner, wherein zeolite is added and the toner is produced by an O / W type wet granulation method.
<9> A developer comprising the toner according to any one of <1> to <7>.
<10> A toner-containing container filled with the toner according to any one of <1> to <7>.
<11> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <7> to be a visible image And a developing means for forming the process cartridge.
<12> The process cartridge according to <11>, further including a recharging unit that recharges residual toner on the surface of the latent electrostatic image bearing member after transfer using a recharging member.
<13> An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of <1> to <7> Development means for forming a visible image by developing using any of the toners, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium The image forming apparatus is characterized by having at least.
<14> Recharging means for recharging residual toner on the surface of the latent electrostatic image bearing member after transfer using a recharging member;
The image forming apparatus according to <13>, which is a cleaner-less system that develops an electrostatic latent image formed on the electrostatic latent image carrier and collects residual toner on the electrostatic latent image carrier. .
<15> The image forming apparatus according to <14>, wherein the recharging member is a conductive sheet disposed so as to be in pressure contact with the surface of the electrostatic latent image carrier.
<16> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <1> to <7> An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.
<17> a recharging step of recharging the residual toner on the surface of the latent electrostatic image bearing member after transfer using a recharging member;
The image forming method according to <16>, wherein the electrostatic latent image formed on the electrostatic latent image carrier is developed and the residual toner on the electrostatic latent image carrier is collected. .
<18> The image forming method according to <17>, wherein the recharging member is a conductive sheet disposed so as to be in pressure contact with the surface of the electrostatic latent image carrier.

The toner of the present invention contains at least a binder resin, a colorant, a release agent, and zeolite, and has an average circularity of 0.970 or more produced by an O / W type wet granulation method.
In this way, it contains zeolite with high cation exchange capacity, and is manufactured by O / W type wet granulation method, so it keeps sufficient chargeability in the development process, and image deterioration such as scumming due to use durability. There are few, and it has both low temperature fixability and heat resistance, and is excellent in offset resistance. Further, since zeolite hardly imparts structural viscosity in oil droplets, it is possible to suppress toner deformation. Therefore, a highly charged spherical toner having an average circularity of 0.970 or more can be obtained.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, a low-temperature fixability and heat resistance are compatible, and an offset-proof and high-quality image can be obtained.

  The toner-containing container of the present invention contains the toner of the present invention in a container. Therefore, when an image is formed by electrophotography using the toner contained in the toner-containing container, both a low-temperature fixability and a heat resistance are compatible, and an excellent anti-offset property and a high-definition image is formed. be able to.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge can be attached to and detached from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that both low temperature fixability and heat resistance are compatible, excellent in offset resistance, and high in resistance. A high-quality image can be obtained.

  The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, it is possible to form a high-quality electrophotographic image having both low-temperature fixability and heat resistance, excellent offset resistance.

  The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step. In the image forming method, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transferring step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, it is possible to form a high-quality electrophotographic image having both low-temperature fixability and heat resistance, excellent offset resistance.

  According to the present invention, conventional problems can be solved, both low-temperature fixability and heat resistance, excellent offset resistance, control of the toner structure, and charging without contaminating the developing device or the like. Toner having good properties and cleanerless suitability, a developer using the toner, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method can be provided.

(toner)
The toner of the present invention includes at least a binder resin, a colorant, a release agent, and zeolite, and further includes a charge control agent, an external additive, a cleaning aid, and other components as necessary. Manufactured by O / W type wet granulation method.

<Average circularity>
The average circularity of the toner is 0.970 or more, preferably 0.975 or more. When the average circularity is less than 0.970, the charge distribution becomes broad and the transferability is inferior.

The average circularity is, for example, an equivalent circle having the same projected area obtained by passing a suspension containing particles through an imaging unit detection zone on a flat plate, optically detecting a particle image with a CCD camera, and analyzing the image. Is obtained by dividing the perimeter of the particle by the perimeter of the actual particle.
More specifically, 0.1 ml to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 ml to 150 ml of water from which impure solids have been removed in advance. About 0.1 g to 0.5 g, and the suspension in which the measurement sample is dispersed is subjected to a dispersion treatment for 1 to 3 minutes with an ultrasonic disperser, and the dispersion concentration is set to 3,000 to 10,000 / μl. It can be obtained by measuring the shape and distribution of toner with a flow type particle image analyzer (FPIA-2000, manufactured by Sysmex Corporation).

<Particle size>
The toner particle diameter is preferably 4 μm to 12 μm, and more preferably 4 μm to 10 μm in terms of volume average particle diameter (Dv). The ratio (Dv / Dp) of the volume average particle diameter (Dv) to the number average particle diameter (Dp) is preferably 1.30 or less, and more preferably 1.20 or less.

  The particle size distribution of the toner can be measured by, for example, a Coulter counter method. Examples of the measuring device using the call counter method include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). A specific measurement method is described below.

First, 0.1 ml to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 ml to 150 ml of an electrolytic aqueous solution. Here, the electrolytic aqueous solution is prepared by preparing a 1% by mass NaCl aqueous solution using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used.
Furthermore, 2 to 20 mg is added to the measurement sample as a solid content. The electrolytic aqueous solution in which the measurement sample is suspended is subjected to a dispersion treatment for 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are measured with the measurement apparatus using a 100 μm aperture. Calculate distribution and number distribution. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dp) of the toner can be obtained.

  The channel is, for example, 2.00 μm or more and less than 2.52 μm; 2.52 μm or more and less than 3.17 μm; 3.17 μm or more and less than 4.00 μm; 4.00 μm or more and less than 5.04 μm; 5.04 μm or more and less than 6.35 μm; 6.35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 13 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm can be targeted.

<Zeolite>
The zeolite is a mineral belonging to the zeolite group. In addition to naturally occurring natural zeolite, synthetic zeolite produced by chemically synthesizing from refined chemicals, coal ash is crystallized as an alkali by treating with alkali. There is an artificial zeolite obtained by As for the artificial zeolite, for example, the zeolite forum website (http://www.zeolite-f.com/info03.html) and the environmental health center website (http: //www.jesc.or. jp / report / sympo05_report / pdf / 209.pdf).
Zeolite is an alkali metal salt or alkaline earth metal salt of aluminosilicate due to its chemical composition, and is a substance having a special crystal structure mainly composed of silicon or alumina and having innumerable small pores and gaps. In the crystal structure, the cation silicon part is electrically neutral, while the aluminum part has a negative charge, which attracts cations such as sodium ions. It is in the state that was. Therefore, when contained in the toner, it is considered that the toner can be highly charged by the negative charge of the aluminum part.

The zeolite is preferably an artificial zeolite or synthetic zeolite having a cation exchange capacity (CEC) of 150 meq / 100 g to 800 meq / 100 g, which is an indicator of negative chargeability, for the purpose of obtaining appropriate charging performance, and the CEC is 400 meq / 100 g. More preferably, the synthetic zeolite is ˜600 meq / 100 g. If the CEC is less than 150 meq / 100 g, sufficient charging performance may not be obtained, and if it is greater than 800 meq / 100 g, synthesis of artificial zeolite and synthetic zeolite becomes difficult.
Here, “CEC” is a capacity that allows a substance of a certain mass to adsorb a cation in a form that can be exchanged with other cations on its surface. It is considered the total amount. Also referred to as base substitution capacity. Generally, it is represented by the number of equivalents of mg per 100 g of substance (meq / 100 g), but may be represented by SI unit (cmol (+) kg ⁻¹ ).
The CEC can be extracted by, for example, the Schollenberger method and measured with a soil / crop body comprehensive analyzer (Fujihira Kogyo Co., Ltd.).

  The amount of the zeolite contained in the toner is preferably 0.1 parts by mass to 5.0 parts by mass, more preferably 0.2 parts by mass to 3.0 parts by mass with respect to 100 parts by mass of the toner base. 0.2 mass part-2.5 mass parts are still more preferable. When the content of the zeolite is less than 0.1 parts by mass, the effect of the present invention may not be exhibited. When the content exceeds 5 parts by mass, the dispersibility of the zeolite in the toner decreases, and the charge distribution is reduced. It becomes broad and leads to dirt and toner spills.

<Binder resin>
The binder resin is not particularly limited, but a polyester resin is preferable from the viewpoint of easily achieving both low-temperature fixability and heat resistance. Moreover, you may use a modified polyester resin together as needed.

-Polyester resin-
There is no restriction | limiting in particular as said polyester resin, According to the objective, it can select suitably, For example, the polycondensate of the following polyols and polycarboxylic acid is mentioned. In addition, the said polyester resin may be used individually by 1 type, and may mix and use 2 or more types of polyester resins.

--Polyol--
Although there is no restriction | limiting in particular as said polyol, For example, alkylene glycol, alkylene ether glycol, alicyclic diol, bisphenol, the alkylene oxide addition product of the said alicyclic diol, the alkylene oxide addition product of the said bisphenol, trivalent Examples thereof include polyhydric aliphatic alcohols, trivalent or higher phenols, and alkylene oxide adducts of the above trivalent or higher polyphenols. These may be used alone or in combination of two or more.

Examples of the alkylene glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like.
Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Examples of the bisphenols include 4,4′-dihydroxybiphenyls, bis (hydroxyphenyl) alkanes, and bis (4-hydroxyphenyl) ethers.
Examples of the 4,4′-dihydroxybiphenyls include bisphenol A, bisphenol F, bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl, and the like.
Examples of the bis (hydroxyphenyl) alkanes include bis (3-fluoro-4-hydroxyphenyl) methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, and 2,2. -Bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), 2,2-bis (3-hydroxy Phenyl) -1,1,1,3,3,3-hexafluoropropane and the like.
Examples of the bis (4-hydroxyphenyl) ethers include bis (3-fluoro-4-hydroxyphenyl) ether.
Examples of the alkylene oxide adduct of the alicyclic diol include an ethylene oxide adduct, a propylene oxide adduct, and a butylene oxide adduct.
Examples of the alkylene oxide adduct of the bisphenol include an ethylene oxide adduct, a propylene oxide adduct, and a butylene oxide adduct.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
Examples of the trivalent or higher phenols include trisphenol PA, phenol novolac, and cresol novolak.

  Of these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, and combined use of alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms is particularly preferable.

--Polycarboxylic acid--
Examples of the polycarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, and aromatic dicarboxylic acid. These may be used alone or in combination of two or more.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. Examples of the alkenylene dicarboxylic acid include maleic acid and fumaric acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetra Fluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5-trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) ) Hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 3,3′-bis (trifluoro) Methyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl)- , 3'-biphenyl dicarboxylic acid, and the like hexafluoroisopropylidene diphthalic anhydride.
Examples of the trivalent or higher polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid. Furthermore, you may make it react with a polyol using the above-mentioned acid anhydride or lower alkyl ester. Examples of the polyol to be reacted at this time include methyl ester, ethyl ester, isopropyl ester and the like.

  Of these, alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.

  The ratio of the polyol and the polycarboxylic acid is usually 2/1 to 1/1 as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH], and 1.5 / 1 to 1/1 is preferable, and 1.3 / 1 to 1.02 / 1 is more preferable.

  The molecular weight of the polyester is a peak molecular weight, preferably 1,000 to 30,000, more preferably 1,500 to 10,000, and still more preferably 2,000 to 8,000. When the peak molecular weight is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.

-Modified polyester resin-
The binder resin used in the present invention may contain a modified modified polyester resin having at least one of urethane and urea groups for adjusting viscoelasticity for the purpose of preventing offset.
The content of the modified polyester resin is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less in the binder resin. When the content exceeds 20% by mass, the low-temperature fixability may be deteriorated.
The modified polyester resin may be directly mixed with the binder resin, but from the viewpoint of manufacturability, the binder resin comprises a relatively low molecular weight prepolymer having an isocyanate group at the terminal and amines that react with the prepolymer. It is preferable that the modified polyester resin is mixed with each other and subjected to chain elongation or crosslinking reaction during or after granulation. Thereby, it becomes easy to contain a relatively high molecular weight modified polyester resin for adjusting the viscoelasticity in the core portion.

--Prepolymer--
Examples of the prepolymer include a polycondensate of the polyol and polycarboxylic acid and a polyester having an active hydrogen group further reacted with polyisocyanate.
Examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

--Polyisocyanate--
Examples of the polyisocyanate include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those obtained by blocking the polyisocyanates with phenol derivatives, oximes, caprolactams, and the like. It is done. These may be used alone or in combination of two or more.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,6-diisocyanatomethyl caproate.
Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.
Examples of the aromatic diisocyanate include tolylene diisocyanate and diphenylmethane diisocyanate.
Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate.

The ratio of the polyisocyanate is preferably 5/1 to 1/1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1.2 / 1 is more preferable, and 2.5 / 1 to 1.5 / 1 is still more preferable. When the [NCO] / [OH] exceeds 5, the low-temperature fixability may be deteriorated. When the [NCO] / [OH] is less than 1, the urea content in the modified polyester resin is lowered, and offset resistance is reduced. Sexuality may worsen.
0.5 mass%-40 mass% are preferable, as for content of the polyisocyanate structural component in the said prepolymer, 1 mass%-30 mass% are more preferable, and 2 mass%-20 mass% are still more preferable. When the content is less than 0.5% by mass, the offset resistance may be deteriorated, and when it exceeds 40% by mass, the low-temperature fixability may be deteriorated.

  The number of isocyanate groups per molecule in the prepolymer is usually 1 or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average. When the number of isocyanate groups is less than 1, the molecular weight of the modified polyester resin after chain extension or crosslinking reaction is lowered, and offset resistance may be deteriorated.

-Chain extension or crosslinking agent-
In the present invention, amines can be used as chain extenders or crosslinking agents. Examples of the amines include diamines, trivalent or higher polyamines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups.

Examples of the diamine include aromatic diamines, alicyclic diamines, and aliphatic diamines.
Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, and tetrafluoro-p-phenylenediamine.
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, hexamethylene diamine, dodecafluorohexylene diamine, and tetracosafluorododecylene diamine.

Examples of the trivalent or higher polyamine include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid include aminopropionic acid and aminocaproic acid.

  Examples of the blocked amino group include ketimine compounds and oxazoline compounds obtained from the amines and ketones. Examples of the ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone.

--Terminator--
In the chain extension or crosslinking reaction, if necessary, the molecular weight of the modified polyester resin after completion of the reaction can be adjusted using a stopper.
Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of the amines is 1/2 to 2/1 as an equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer and amino groups [NHx] in the amines. Preferably, 1.5 / 1 to 1 / 1.5 is more preferable, and 1.2 / 1 to 1 / 1.2 is still more preferable. When the [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the modified polyester resin is lowered, and the hot offset resistance may be deteriorated.

-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, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin 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 green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon. These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics 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, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, 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, 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 An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant 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.

<Release agent>
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

  The content of the release agent is preferably 5% by mass to 15% by mass with respect to all the components of the toner. When the content is less than 5%, the releasing effect is lost, and there is a possibility that the margin for preventing the offset is lost. On the other hand, if the content exceeds 15%, the release agent melts at a low temperature, so that it is easily affected by thermal energy and mechanical energy, and the wax oozes out from the inside of the toner during stirring in the developing unit. It may adhere to the regulating member and the photosensitive member and generate image noise.

  The endothermic peak (melting point) at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the release agent is preferably 65 ° C. to 115 ° C. from the viewpoint of facilitating low-temperature fixing of the toner. If the melting point is less than 65 ° C., the fluidity tends to be poor, and if it is higher than 115 ° C., the fixability tends to be poor.

<Charge control agent>
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, and molybdate chelate pigments. , Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, salicylic acid derivatives And metal salts thereof.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, and bontron S-34 of a metal-containing azo dye. , Oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenol condensate E-89 (above, manufactured by Orient Chemical Industries); quaternary ammonium salt molybdenum complex TP-302 TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.); quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (Above, manufactured by Hoechst); LRA-901, LR-147 which is a boron complex (Japan) Ritto Ltd.); copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, a carboxyl group, and the like and polymeric compounds having a functional group such as a quaternary ammonium salt.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

<External additive>
-Inorganic fine particles-
As the external additive for assisting the fluidity, developability and chargeability of the colored toner particles obtained in the present invention, inorganic fine particles can be preferably used.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, composite oxides such as silicon oxide / magnesium oxide and silicon oxide / aluminum oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride Etc.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Further, BET specific surface area of the inorganic fine ^particles, 20m ² / ^g~500m 2 / g are preferred.
There is no restriction | limiting in particular in content of the said inorganic fine particle, According to the objective, it can select suitably, For example, 0.01 mass%-5 mass% are preferable, 0.01 mass%-2.0 mass% are preferable. More preferred.

-Polymeric fine particles-
As the external additive, in addition to the inorganic fine particles, as polymer fine particles, for example, polystyrene, methacrylic ester or acrylate copolymer, silicone obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, silicone, Examples thereof include polycondensation systems such as benzoguanamine and nylon, and polymer particles made of a thermosetting resin.

-Surface treatment agent-
The external additive can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity.
There is no restriction | limiting in particular as a surface treating agent which can perform such surface treatment, According to the objective, it can select suitably, For example, the silane which has a silane coupling agent, a silylating agent, and a fluorinated alkyl group Preferred examples include coupling agents, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils.

-Cleaning aid-
In the toner of the present invention, a cleaning aid can be used to remove the transferred developer remaining on the photoreceptor or the primary transfer medium. Examples of the cleaning aid include polymer fine particles produced by soap-free emulsion polymerization such as fatty acid metal salts, polymethyl methacrylate fine particles, and polystyrene fine particles. Examples of the fatty acid metal salt include zinc stearate, calcium stearate, stearic acid, and the like.
The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 μm to 1 μm.

(Toner production method)
The toner of the present invention is produced by an O / W type wet granulation method with the addition of zeolite. As the O / W type wet granulation method, specifically, after dissolving or dispersing a toner composition such as a binder resin, a colorant, and a release agent in an organic solvent in an oil phase, It preferably includes at least a granulation step of dispersing and dissolving the dissolved substance or dispersion in an aqueous medium, and optionally including an elongation or crosslinking reaction step, a washing and drying step, an external addition treatment step, and the like.

<Granulation process>
-Organic solvent-
The organic solvent is not particularly limited, and examples thereof include those having a Hansen solubility parameter of 19.5 or less described in “POLYMER HANDBOOK” 4th Edition, WILEY-INTERSCIENCE, Volume 2, Section VII. Among these, those having a boiling point of less than 100 ° C. are preferable from the viewpoint of easy removal of the solvent later.
Examples of such an organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Examples include ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. These may be used individually by 1 type and may be used in combination of 2 or more type.
Among the organic solvents, ester solvents such as methyl acetate and ethyl acetate; aromatic solvents such as toluene and xylene; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable.
The polyester resin, the colorant, and the release agent may be dissolved or dispersed at the same time, but are usually dissolved or dispersed individually. The organic solvents used at that time may be different or the same, but the same is preferable in consideration of the subsequent solvent treatment.

-Dissolution or dispersion of binder resin-
The binder resin is preferably dissolved or dispersed in a resin concentration of 40% by mass to 80% by mass. If the concentration exceeds 80% by mass, it may be difficult to dissolve or disperse and the viscosity will be high and difficult to handle. If the concentration is less than 40% by mass, the amount of toner produced may be reduced.
When the modified polyester resin having an isocyanate group at the terminal is mixed with the binder resin, they may be mixed in the same solution or dispersion, or the solution or dispersion may be prepared separately. Considering solubility and viscosity, it is preferable to prepare separate solutions or dispersions.

-Dissolution or dispersion of colorant-
The colorant may be dissolved or dispersed alone, or may be mixed with the polyester resin dissolved or dispersed liquid. If necessary, a dispersion aid or a polyester resin may be added, or the master batch may be used.

-Dissolution or dispersion of release agent-
When the wax is dissolved or dispersed as the mold release agent, it is used as a dispersion when using an organic solvent in which the wax does not dissolve, but the dispersion is prepared by a general method. That is, an organic solvent and wax may be mixed and dispersed with a disperser such as a bead mill.
Further, after mixing the organic solvent and the wax, it is possible to shorten the dispersion time by once heating to the melting point of the wax, cooling with stirring and then dispersing with a dispersing machine such as a bead mill. The wax may be used as a mixture of a plurality of types, or a dispersion aid or a polyester resin may be added.

-Aqueous medium-
As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Furthermore, an organic solvent having the Hansen solubility parameter of 19.5 or less may be mixed, and an addition amount in the vicinity of the saturation amount with respect to water is preferable from the viewpoint of improving the emulsification or dispersion stability of the oil phase.
Examples of the water-miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like. It is done.
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 composition. When the amount used is less than 50 parts by mass, the toner composition may be poorly dispersed and toner particles having a predetermined particle size may not be obtained. Moreover, when the said usage-amount exceeds 2,000 mass parts, it may not be economical.

-Inorganic dispersant and organic resin fine particles-
When dispersing the dissolved or dispersed toner composition in the aqueous medium, if the inorganic dispersant or the organic resin fine particles are dispersed in the aqueous medium in advance, the particle size distribution becomes sharp and the dispersion is stable. It is preferable in a certain point.
Examples of the inorganic dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
The resin that forms the organic resin fine particles is not particularly limited as long as it is a resin that can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. Resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like. These resins may be used alone or in combination of two or more.
Among these resins, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

  The method for making the resin into an aqueous dispersion of fine organic resin particles is not particularly limited, and examples thereof include the following methods (a) to (g).

(A) In the case of a polyaddition or condensation resin such as a polyester resin, a polyurethane resin, and an epoxy resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant, A method of producing an aqueous dispersion of resin fine particles by heating and then adding a curing agent to cure.

(B) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., after dissolving an appropriate emulsifier in the precursor (monomer, oligomer, etc.) or its solvent solution, water is added. A method of phase inversion emulsification. The solvent solution is preferably a liquid and may be liquefied by heating.

(C) A 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.) A method in which resin fine particles are obtained by pulverization using a fine pulverizer, etc. and then classified, and then dispersed in water in the presence of a suitable dispersant.

(D) A resin solution obtained by dissolving 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.) in a solvent. A method in which fine resin particles are obtained by spraying in the form of a mist and then dispersed in water in the presence of a suitable dispersant.

(E) 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 added to a resin solution dissolved in a solvent. The resin fine particles are precipitated by adding a solvent or cooling a resin solution previously heated and dissolved in the solvent, and then removing the solvent to obtain resin fine particles, which are then added to water in the presence of a suitable dispersant. How to disperse.

(F) A resin solution obtained by dissolving 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.) in a solvent. A method of dispersing in an aqueous medium in the presence of a suitable dispersant and removing the solvent by heating or decompressing.

(G) 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 A suitable emulsifier is dissolved in the mixture, and water is added to perform phase inversion emulsification.

-Surfactant-
In order to emulsify and disperse the oily phase containing the toner composition in an aqueous medium, a surfactant or the like may be used as necessary.
Examples of the surfactant include an anionic surfactant, an amine-type cationic surfactant, a quaternary ammonium salt-type cationic surfactant, and a nonionic surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, and phosphate esters.
Examples of the amine-type cationic surfactants include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and amphoteric surfactant imidazolines.
Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.
Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Among the surfactants, it is preferable to use a surfactant having a fluoroalkyl group because the effect can be obtained in a very small amount.
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 perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6 to C11). Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid Or a metal salt thereof, perfluoroalkylcarboxylic acid (C7 to C13) or a metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid or a metal salt thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) perfluoroo Kutansulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like It is done.
Examples of the cationic surfactant having a fluoroalkyl group include an aliphatic primary, secondary, or tertiary amine acid, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt having a fluoroalkyl group. Aliphatic quaternary ammonium salts such as benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.
In the examples of the surfactant, the numerical value such as C6 represents the number of carbon atoms.

-Protective colloid-
Further, the dispersed droplets may be stabilized by a polymer protective colloid. Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amides Examples thereof include homopolymers or copolymers of compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
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-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing 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.

In order to stabilize the dispersed droplets, a dispersion stabilizer may be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.
When the dispersion stabilizer is used, it can remain on the surface of the toner particles, but it is preferable to remove it by washing from the charged surface of the toner.

  The dispersion method is not particularly limited and, for example, known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be appropriately selected and used. In order to make the diameter 2 μm to 20 μm, a high-speed shearing type is preferable. When the high-speed shearing disperser is used, the rotation speed is not particularly limited, but is preferably 1,000 rpm to 30,000 rpm, more preferably 5,000 rpm to 20,000 rpm. The temperature during dispersion is preferably 0 ° C. to 150 ° C., more preferably 20 ° C. to 80 ° C. under pressure.

  There is no restriction | limiting in particular as a method of removing an organic solvent from the obtained emulsified dispersion, A well-known method can be used. For example, a method of gradually raising the temperature of the entire system under normal pressure or reduced pressure to completely evaporate and remove the organic solvent in the droplets.

<Extension or cross-linking reaction process>
The extension or cross-linking reaction step is a step of introducing a modified polyester resin having at least one of the urethane and urea groups.
In the elongation or crosslinking reaction step, when the modified polyester resin and amines that can react with the modified polyester resin are added, the amines are mixed in the oil phase before dispersing the toner composition in the aqueous medium. Alternatively, amines may be added to the aqueous medium.
The time required for the elongation or crosslinking reaction is appropriately selected depending on the reactivity of the isocyanate group structure of the polyester prepolymer and the added amines, but is usually 1 minute to 40 hours, and 1 hour to 24 hours. preferable. The temperature during the extension or crosslinking reaction is preferably 0 ° C to 150 ° C, more preferably 20 ° C to 98 ° C.
The elongation or cross-linking reaction may be performed before adhesion of the fine particles such as the inorganic fine particles, or may be performed simultaneously during the adhesion of the fine particles. Further, it may be after the fine particle adhesion step is completed. In the elongation or crosslinking reaction, a known catalyst can be used as necessary.

<Washing and drying process>
The washing and drying steps are steps for washing and drying the toner particles dispersed in the aqueous medium.
There is no restriction | limiting in particular as said washing | cleaning and drying process, A well-known method is used. Specifically, for example, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion-exchanged water at room temperature to about 40 ° C., and an acid or alkali is used as necessary. After adjusting the pH, the process of solid-liquid separation again is repeated several times to remove impurities, surfactants, etc., and then drying with an air dryer, circulation dryer, vacuum dryer, vibration fluid dryer, etc. Thus, there is a method for obtaining toner powder. At this time, the fine particle component of the toner may be removed by centrifugal separation or the like, or a desired particle size distribution may be obtained using a known classifier as necessary after drying.

<External treatment process>
In the external addition treatment step, the obtained dried toner powder is mixed with different kinds of particles such as charge control fine particles and fluidizing agent fine particles, or mechanical impact force is applied to the mixed powder on the surface. This is a step of fixing and fusing, and preventing the detachment of foreign particles from the surface of the resulting composite particles.
As specific means in the external addition treatment step, for example, a method of applying an impact force to the mixture with a blade rotating at high speed, a mixture is injected into a high-speed air stream, accelerated, and particles or composite particles are appropriately used. The method of making it collide with a collision board is mentioned.
As an apparatus used for the external addition treatment, 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 lowered, a hybridization system ( Nara Machinery Co., Ltd.), Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), and automatic mortar.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. The developer may be a one-component developer or a two-component developer.
In the case of the one-component developer using the toner according to the present invention, the toner particle diameter hardly fluctuates even if the balance of the toner is performed, and the filming of the toner on the developing roller or the toner is thinned. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time.

  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, It can select suitably from well-known things, For example, a manganese-strontium (Mn-Sr) type material of 50emu / g-90emu / g, manganese-magnesium ( A Mn—Mg) -based material is preferable, and from the viewpoint of securing image density, a highly magnetized material such as iron powder (100 emu / g or more), magnetite (75 emu / g to 120 emu / g) is preferable. In addition, the weakness of the copper-zinc (Cu-Zn) system (30 emu / g to 80 emu / g) is advantageous in that the contact with the photoconductor in which the toner is in a flashing state can be weakened, which is advantageous for improving the image quality. Magnetized materials are preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (mass average particle diameter (D ₅₀ )) of 10 μm to 200 μm, and more preferably 40 μm to 100 μm.
When the average particle size (mass average particle size (D ₅₀ )) is less than 10 μm, in the distribution of carrier particles, the number of fine powder systems increases, and the magnetization per particle may be lowered to cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine And a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

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

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

Since the developer of the present invention contains the toner of the present invention, it is possible to achieve both excellent low-temperature fixability and anti-offset performance and form a good high-definition image.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be used suitably. Further, it can be particularly suitably used for the following toner-containing container, process cartridge, image forming apparatus and image forming method.

(Toner container)
The toner-containing container of the present invention contains the toner or the developer of the present invention in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral unevenness is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container main body is not particularly limited and may be appropriately selected depending on the intended purpose. However, a material having good dimensional accuracy is preferable, for example, a resin is preferable. Among these, for example, polyester Preferred examples include resins, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, polyacryl resins, polycarbonate resins, ABS resins, polyacetal resins, and the like.
The container containing toner is easy to store and transport, has excellent handleability, and can be suitably used for replenishing toner by being detachably attached to a process cartridge, an image forming apparatus, etc. of the present invention described later. .

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using toner to produce a visible image. A developing unit to be formed, and a charging unit, a recharging unit, a transfer unit, a cleaning unit, and other units appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The recharging means is means for recharging the residual toner on the surface of the latent electrostatic image bearing member after transfer using a recharging member. The details of the recharging means will be described later.
The process cartridge can be detachably provided in various image forming apparatuses, and is preferably provided detachably in an image forming apparatus of the present invention described later.

Here, as shown in FIG. 1, the process cartridge includes a photosensitive member 101, and at least one of a charging unit 102, a developing unit 104, a transfer unit 108, a cleaning unit 107, and a charge eliminating unit (not shown). And an apparatus (part) that can be attached to and detached from the image forming apparatus main body.
Here, the image forming process using the process cartridge shown in FIG. 1 will be described. The photosensitive member 101 is exposed to the surface by rotating by the charging unit 102 and exposing 103 by the exposing unit (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the image is formed. The electrostatic latent image is developed with toner by the developing unit 104, and the toner development is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. Other means, for example, a recharging means, a cleaning means, a static elimination means, a recycling means, a control means, etc. are provided.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a recharging step, a cleaning step. Means, static elimination process, recycling process, control process and the like.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, the recharging step can be performed by the recharging unit, and the others. This step can be performed by the other means.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image bearing member (sometimes referred to as “photoconductive insulator”, “electrophotographic photosensitive member”, “photosensitive member”) is particularly about the material, shape, structure, size, etc. There is no limitation, and it can be appropriately selected from known ones, but as its shape, a drum shape is preferably mentioned, and as its material, for example, an inorganic photoreceptor such as amorphous silicon, selenium, polysilane, phthalopolymethine, etc. Organic photoreceptors, and the like. Among these, amorphous silicon or the like is preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method is applied on the support. A photoconductor having a photoconductive layer made of a-Si (hereinafter sometimes referred to as “a-Si-based photoconductor”) can be used by a film forming method such as the above. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

The electrostatic latent image can be formed by, for example, uniformly charging the surface of the electrostatic latent image carrier and then exposing it like an image, and using the electrostatic latent image forming means. Can do.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. 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 the ferrite member, and a magnet roll included therein. . Or when using a brush, for example, as the material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive metal core, Make it a charger by sticking.
The charger is not limited to the contact charger as described above. However, since an image forming apparatus in which ozone generated from the charger is reduced is obtained, a contact charger is used. preferable.

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

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

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

The static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably several Ωcm or more and 10 ³ Ωcm or less. By setting the volume resistance to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means is less likely to remain on the intermediate transfer member. Uneven transfer can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

  The material of the intermediate transfer member is not particularly limited and can be appropriately selected from known materials according to the purpose. For example, (1) a material having a high Young's modulus (tensile elastic modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT (polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend material, carbon black dispersed thermosetting polyimide, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation. (2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery of the belt. Therefore, the line image has a performance capable of preventing the line image from being lost. (3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the belt width is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .

Conventionally, fluorine-based resin, polycarbonate resin, polyimide resin, and the like have been used for the intermediate transfer belt. However, in recent years, an elastic belt using an entire belt layer or a part of the belt as an elastic member has been used. . The transfer of a color image using a resin belt has the following problems.
A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has high hardness and does not deform according to the toner layer, it is easy to compress the toner layer, and the character dropout phenomenon tends to occur.
Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. If the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated.
The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local irregularities, it is possible to obtain a good adhesion without excessively increasing the transfer pressure with respect to the toner layer, and a paper with poor flatness that has no void in characters. In contrast, a transfer image with excellent uniformity can be obtained.

  There is no restriction | limiting in particular as resin of the said elastic belt, According to the objective, it can select suitably, For example, a polycarbonate, a fluororesin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-alpha-methylstyrene, styrene -Butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer (for example, styrene -Methyl methacrylate copolymer, styrene-methacryl Styrene resins such as ethyl copolymers, styrene-phenyl methacrylate copolymers, styrene-α-chloroacrylic acid methyl copolymers, styrene-acrylonitrile-acrylic acid ester copolymers, etc. Containing monopolymer or copolymer), methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (for example, silicone modified acrylic resin, vinyl chloride resin modified acrylic resin, acrylic Urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene 1 or 2 selected from the group consisting of polyvinylidene chloride, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin and polyvinyl butyral resin, polyamide resin, modified polyphenylene oxide resin, etc. More than one type of combination can be used.

  The elastic rubber or elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, butyl rubber, fluorine 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 series Rubber, Ricone rubber, Fluoro rubber, Polysulfide rubber, Polynorbornene rubber, Hydrogenated nitrile rubber, Thermoplastic elastomer (eg polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide) , It can be used polyurea, polyester, one kind or two kinds or more combinations selected from the group consisting of fluorocarbon resin) or the like.

The conductive material for adjusting the resistance value is not particularly limited and can be appropriately selected depending on the purpose. For example, carbon black, graphite, metal powder such as aluminum or nickel, tin oxide, titanium oxide, antimony oxide, oxidation Conductive metal oxides such as indium, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), indium oxide-tin oxide composite oxide (ITO), and the conductive metal oxides are barium sulfate and magnesium silicate. Alternatively, it may be coated with insulating fine particles such as calcium carbonate. Of course, the conductive agent is not limited thereto.
Surface layer materials and surface layers are required to prevent contamination of the photoreceptor with elastic materials, reduce surface friction resistance to the surface of the transfer belt, reduce toner adhesion, and improve cleaning and secondary transfer properties. . For example, materials that use one or a combination of two 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. These powders and particles can be used by dispersing one type, two or more types, or a combination of particles having different particle sizes. 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.
The manufacturing method of the belt is not limited. For example, a centrifugal molding method in which a material is poured into a rotating cylindrical mold to form a belt, a spray coating method in which a liquid paint is sprayed to form a film, a cylindrical mold is used. Examples include, but are not limited to, a dipping method in which the material is dipped in a solution of the material, a casting method in which it is injected into the inner mold and the outer mold, a method in which a compound is wound around a cylindrical mold and vulcanized and polished. In general, a belt is manufactured by combining a plurality of manufacturing methods.

As a method for preventing elongation as an elastic belt, there are a method of forming a rubber layer in a core resin layer with little elongation, a method of putting a material for preventing elongation into a core layer, and the like, but the method is limited to a specific production method is not.
There is no restriction | limiting in particular as a material which comprises the core layer which prevents elongation, According to the objective, it can select suitably, For example, natural fibers, such as cotton and silk; Polyester fiber, nylon fiber, acrylic fiber, Synthetic fibers such as polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers, and phenol fibers; inorganic fibers such as carbon fibers, glass fibers, and boron fibers; iron fibers In addition, a woven fabric or a thread-like material using a metal fiber such as copper fiber is also used.
The yarn may be twisted in any manner, such as one or a plurality of filaments twisted, one-twisted yarn, various twisted yarns, double yarn, or the like. Further, for example, fibers of a material selected from the above material group may be blended. Further, the yarn can be used after an appropriate conductive treatment. On the other hand, as the woven fabric, any woven fabric such as knitted fabric can be used. Interwoven woven fabric can also be used and naturally conductive treatment can be performed.
The production method for providing the core layer is not particularly limited and can be appropriately selected according to the purpose.For example, a method of providing a coating layer on the woven fabric woven in a cylindrical shape on a mold or the like, A method of providing a coating layer on one or both sides of a core layer by immersing a tubular woven fabric in liquid rubber or the like, winding a thread spirally around a mold or the like at an arbitrary pitch, and coating the coating layer thereon The method of providing etc. can be mentioned.
The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. Further, since the amount of expansion / contraction increases, it is not preferable that the image is too thick (about 1 mm or more) due to the expansion / contraction of the image.

The transfer means (the primary transfer means, the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The recharging step is a step of recharging the residual toner on the surface of the latent electrostatic image bearing member after transfer using a recharging member, and can be suitably performed by a recharging unit.
The recharging member is preferably a sheet selected from nylon, PTFE, PVDF, and urethane, and more preferably PTFE or PVDF from the viewpoint of toner chargeability.
The surface resistance of the recharging member is preferably 10 ² to 10 ⁸ Ω / sq, and the volume resistance is preferably 10 ¹ to 10 ⁶ Ω / sq. In addition, examples of the shape of the recharging member include a roller, a brush, a sheet, and the like, and a sheet shape is particularly preferable from the viewpoint of resetting of the adhered toner.
The voltage applied to the recharging member is preferably -1.4 kV to 0 kV from the viewpoint of imparting toner charge.

When the recharging member is a conductive sheet, the thickness is preferably 0.05 mm to 0.5 mm from the viewpoint of the contact pressure with the electrostatic latent image carrier. Moreover, it is preferable that the nip width in contact with the electrostatic latent image carrier is 1 mm to 10 mm from the viewpoint of the contact time when the toner is charged.
About the pure water contact angle of the said conductive sheet, it can measure by the droplet method (based on the instruction manual of the contact angle meter) using the contact angle meter CA-DT * A type made by Kyowa Interface Science Co., Ltd. The pure water contact angle is preferably 108 ° or more.
About the Shore D hardness of the said electrically conductive sheet, the Shore D hardness in 25 degreeC is 50-65 by the method based on ASTMD-2240.

  Here, FIG. 8 is a schematic configuration diagram showing a main part of an image forming apparatus (printer) to which the process cartridge according to the present embodiment can be applied. This printer includes four process cartridges 401Y, 401M, 401C, and 401K for forming toner images of respective colors of yellow, magenta, cyan, and black (hereinafter abbreviated as Y, M, C, and K). . An optical writing unit 450, a registration roller pair 454, a transfer unit 460, and the like are also provided. Subscripts Y, M, C, and K added to the end of each symbol indicate members for yellow, magenta, cyan, and black, respectively.

  An optical writing unit 450 serving as an electrostatic latent image forming unit includes a light source composed of four laser diodes corresponding to each color of Y, M, C, and K, a regular hexahedral polygon mirror, a polygon motor for rotationally driving the mirror, An fθ lens, a lens, a reflection mirror, and the like are included. The laser light L emitted from the laser diode reaches one of four photoconductors described later while being reflected by any one surface of the polygon mirror and deflected as the polygon mirror rotates. The surfaces of the four photosensitive members are optically scanned by the laser beams L emitted from the four laser diodes, respectively.

  The process cartridges 401Y, 401M, 401C, and 401K are drum-shaped photoreceptors 403Y, 403M, 403C, and 403K as electrostatic latent image carriers, and developing devices 440Y, 440M, 440C, and developing units individually corresponding to these. 440K, having a charging device and the like. The photoreceptors 403Y, 403M, 403C, and 403K are driven to rotate in the clockwise direction in the drawing at a predetermined linear velocity by a driving unit (not shown). Then, it is optically scanned in the dark by an optical writing unit 450 that emits a laser beam L that is modulated based on image information sent from a personal computer (not shown) or the like, and static for Y, M, C, and K. Carries an electrostatic latent image.

  FIG. 9 is an enlarged configuration diagram showing the K process cartridge 401K of the four process cartridges 401Y, 401M, 401C, and 401K together with the intermediate transfer belt 461 of the transfer unit (460 in FIG. 8). In the figure, a process cartridge 401K for K has a photosensitive unit 403K, a charging device, a neutralizing lamp (not shown), a developing device 440K as developing means, etc. held in a common unit casing (holding body) as one unit, The printer is detachable from the printer body.

  A photosensitive member 403K for K which is a member to be charged and an electrostatic latent image carrier is a photosensitive layer made of a negatively charged organic photoconductive substance (OPC) on the surface of a conductive substrate made of an aluminum base tube. Is a drum having a diameter of about 24 mm and is driven to rotate in a clockwise direction in FIG. 9 at a predetermined linear velocity by a driving means (not shown). As a result, the surface of the photosensitive member 403K sequentially passes through a primary transfer nip (contact position with the intermediate transfer belt 461), an auxiliary charging nip, a charging nip, an optical writing position, and a development area, which will be described later.

  The developing device 440K for K has a developing roller 442K that exposes a part of the peripheral surface from an opening provided in the casing 441K. The developing roller 442K, which is a developer carrying member, is rotatably supported by bearings (not shown) with shafts protruding from both ends in the longitudinal direction. The casing 441K contains K toner, and is conveyed from the right side to the left side in the drawing by the agitator 443K that is driven to rotate. On the left side of the agitator 443K in the drawing, a toner supply roller 444K that is driven to rotate counterclockwise in the drawing by a driving unit (not shown) is disposed. The roller portion of the toner supply roller 444K is made of an elastic foam such as a sponge and captures the K toner sent from the agitator 443K well. The K toner thus captured is supplied to the developing roller 442K at the contact portion between the toner supply roller 444K and the developing roller 442K. The K toner carried on the surface of the developing roller 442K as the developer carrying member passes through the contact position with the regulating blade 445K as the developing roller 442K rotates in the counterclockwise direction in the drawing. After the layer thickness is regulated or frictional charging is promoted, the layer is transported to the developing area facing the photoreceptor 403K.

  In this developing area, negative K toner is applied from the developing roller 442K side between the developing roller 442K to which a negative developing bias output from a power source (not shown) is applied and the electrostatic latent image on the photoreceptor 403K. A developing potential for electrostatically moving to the latent image side acts. In addition, a non-developing potential that causes the negative K toner to electrostatically move from the background portion side to the developing roller 442K side acts between the developing roller 442K and the uniformly charged portion (background portion) of the photoreceptor 403K. The K toner on the developing roller 442K is separated from the developing roller 442K by the action of the developing potential and is transferred onto the electrostatic latent image on the photoreceptor 403K. By this transfer, the electrostatic latent image on the photoreceptor 403K is developed into a K toner image.

  In this printer, the developing device 440K adopts a one-component developing method using a one-component developer containing K toner as a main component as a developer, but a two-component developer containing K toner and a magnetic carrier. A two-component development method using

  The K toner image developed in the development area is conveyed to the K primary transfer nip where the photoconductor 403K and the intermediate transfer belt 461 come into contact with the rotation of the photoconductor 403K. Intermediate transfer. Residual toner that has not been transferred onto the intermediate transfer belt 461 adheres to the surface of the photoreceptor 403K after passing through the primary transfer nip.

  The charging device includes a charging brush roller 407K that contacts the photoconductor 403K to form a charging nip while being driven to rotate counterclockwise in the drawing, an auxiliary charging member 410K that contacts the photoconductor 403K to form an auxiliary charging nip, and the like. have. In the charging brush roller 407K, a roller portion made of a material that exhibits conductivity and elasticity, such as conductive rubber, is coated on the peripheral surface of a metal rotating shaft member. A charging bias is applied to the rotating shaft member by charging bias supply means including a power source (not shown). By this application, a discharge is generated between the charging brush roller 407K and the photosensitive member 403K, so that the surface of the photosensitive member 403K is uniformly charged to the same polarity as the charging polarity of the toner.

  The auxiliary charging member 410K is obtained by coating the surface of an elastic portion 408K made of an elastic material such as sponge with a conductive sheet (recharging member) 409K made of a conductive material. Then, while being pressed toward the photosensitive member 403K by the elastic portion 408K, the portion of the peripheral surface of the photosensitive member 403K that passes through the primary transfer nip and before entering the charging nip is subjected to its own. The sheet covering surface is in contact. The conductive sheet 409K is supplied with an auxiliary charging bias composed of a DC voltage having the same polarity as the toner charging polarity, or an AC voltage superimposed with the DC voltage, by an auxiliary charging bias supply means including a power source (not shown).

  Among the residual toner adhering to the surface of the photoconductor 403K after passing through the primary transfer nip, in addition to the toner charged to the normal charging polarity, the charging amount is insufficient although it is the normal charging polarity. Low charge amount toner that is charged, and reversely charged toner that is charged to the opposite polarity. Such residual toner enters the auxiliary charging nip as the photoconductor 403K rotates. Then, the reversely charged toner in the residual toner is sufficiently charged to the negative polarity, which is the normal polarity, by discharge between the auxiliary charging member 410K and the photosensitive member 403K or charge injection from the auxiliary charging member 410K. Further, the low charge amount toner in the residual toner is also sufficiently charged to the negative polarity by discharge or charge injection. As a result, the occurrence of scumming caused by transporting the reversely charged toner or the low charge amount toner in the residual toner to the developing region can be suppressed.

  Next, a cleanerless image forming apparatus will be described in detail. There are roughly two types of cleaner-less systems: a scattering passing type, a temporary trapping type, and a combined type. Of these, in the scattering passing type, the residual toner on the electrostatic latent image carrier is scratched by using a scattering member such as a brush that rubs against the electrostatic latent image carrier, so that the residual toner and the electrostatic latent image can be obtained. Decreases adhesion with the carrier. Thereafter, the toner remaining on the electrostatic latent image carrier is applied to the developing member such as the developing roller immediately before or in the developing region where the developing member such as the developing sleeve and the developing roller and the electrostatic latent image carrier are opposed to each other. It is recovered in the developing device by electrostatic transfer. Prior to this collection, the residual toner passes through the optical writing position for writing the latent image. However, if the residual toner amount is relatively small, the latent image writing is not adversely affected. However, if a reversely charged toner charged to a polarity opposite to the normal polarity is contained in the residual toner, it will not be collected on the developing member, which may cause background contamination. In order to suppress the occurrence of scumming due to the reversely charged toner, a toner charging means for charging the residual toner on the electrostatic latent image carrier to a normal polarity is formed by a transfer position (for example, a primary transfer nip) and a scattering member. It is preferable to provide between the scattering position or between the scattering position and the development area.

  Examples of the scattering member include a sheet metal, a fixed brush having a plurality of flocked fibers made of conductive fibers attached to a unit casing, a brush roller in which a plurality of flocked fibers are erected on a metal rotating shaft member, and a conductive member. For example, a roller member (for example, a charging roller) having a roller portion made of a functional sponge or the like can be used. The fixed brush has the advantage of being inexpensive because it can be configured with a relatively small amount of flocked fibers. However, if it is used as a charging member for uniformly charging the electrostatic latent image carrier, sufficient charge uniformity It becomes impossible to get sex. On the other hand, the brush roller is preferable because sufficient charging uniformity can be obtained.

  In the temporary capture type in the cleanerless system, residual toner on the electrostatic latent image carrier is temporarily captured by a capture member such as a rotating brush member that moves endlessly while the surface is in contact with the electrostatic latent image carrier. Then, after the print job is completed or at the timing between papers, the residual toner on the capture member is discharged and transferred again to the electrostatic latent image carrier, and then transferred to the developing member such as the developing roller. And collected in the developing device. In the above-mentioned scattering passing type, there is a possibility that the residual toner such as when a solid image is formed or after the occurrence of a jam is considerably increased, the image may be deteriorated beyond the recovery ability to the developing member. Then, the residual toner captured by the capturing member is gradually collected on the developing member, and the occurrence of such image deterioration can be suppressed.

  In the combined type in the cleaner-less method, the scattered passing type and the temporary capturing type are used in combination. Specifically, a rotating brush member that contacts the electrostatic latent image carrier is used in combination as a scattering member and a capturing member. By applying only a DC voltage to the rotating brush member, etc., the rotating brush member, etc., can function as a scattering member, while the bias is switched from a DC voltage to a superimposed voltage as necessary, so that the rotating brush member can be used as a capturing member. Make it work.

  In the present invention, a scattering transmission type cleanerless system is adopted. Specifically, as shown in FIG. 9, the photosensitive member 403K contacts the front surface of the intermediate transfer belt 461 while rotating at a predetermined linear speed in the clockwise direction in FIG. The next transfer nip is formed. The residual toner on the photoconductor 403K is scratched by the auxiliary charging member 410K (elastic portion 408K, conductive sheet 409K) and the charging brush roller 407K as a scattering member, thereby weakening the adhesion between the residual toner and the photoconductor 403K. . Thereafter, in the developing area, the residual toner on the photoreceptor 403K is electrostatically transferred to the developing roller 442K of the developing device 440K and collected. At this time, if the residual toner contains a large amount of low charge amount toner or reversely charged toner, they are not collected on the developing roller 442K and cause soiling. At this time, if a large amount of the release agent is exposed on the toner surface, adhesion to the charging brush roller 407K (electrostatic latent image carrier charge imparting member) or conductive sheet 409K (recharging member), spent, etc. are induced. Occurrence of fixed matter is likely to occur.

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

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

The recycling step is a step of recycling the electrophotographic toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter also referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and the exposure. An exposure device 30 as a means, a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a final recording medium. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

In the tandem type electrophotographic apparatus in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention, the image on each photoconductor 1 is transferred by the transfer device 2 by the sheet conveying belt 3 as shown in FIG. As shown in FIG. 5, the image on each photoconductor 1 is sequentially transferred to the intermediate transfer body 4 by the primary transfer device 2 as shown in FIG. There is an indirect transfer type in which an image on the transfer body 4 is collectively transferred to a sheet s by a secondary transfer device 5. The transfer device 5 is a transfer conveyance belt, but may be a roller shape.
Comparing the direct transfer type and the indirect transfer type, the former arranges the paper feeding device 6 on the upstream side of the tandem type image forming apparatus T on which the photoconductors 1 are arranged, and the fixing device 7 on the downstream side. There is a drawback in that the size increases in the sheet conveying direction. On the other hand, the latter can set the secondary transfer position relatively freely. The sheet feeding device 6 and the fixing device 7 can be arranged so as to overlap with the tandem image forming apparatus T, and there is an advantage that downsizing is possible.
In the former, in order not to increase the size in the sheet conveyance direction, the fixing device 7 is disposed close to the tandem type image forming apparatus T. For this reason, the fixing device 7 cannot be disposed with a sufficient margin that allows the sheet s to bend, and an impact when the leading edge of the sheet s enters the fixing device 7 (particularly with a thick sheet) or fixing. Due to the speed difference between the sheet conveying speed when passing through the apparatus 7 and the sheet conveying speed by the transfer conveying belt, there is a drawback that the fixing device 7 tends to affect the image formation on the upstream side. On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that allows the sheet s to bend, so that the fixing device 7 hardly affects the image formation.
In view of the above, recently, an indirect transfer type of tandem type electrophotographic apparatus has attracted attention.
In this type of color electrophotographic apparatus, as shown in FIG. 5, residual toner remaining on the photoreceptor 1 after the primary transfer is removed by the photoreceptor cleaning device 8 to clean the surface of the photoreceptor 1. Prepared for re-image formation. Further, residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for the image formation again.

A tandem image forming apparatus 100 shown in FIG. 6 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 6. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer body 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged in parallel and facing each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22.
In the tandem image forming apparatus 100, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

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

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. An exposure device that exposes the photoconductor for each color image corresponding image (L in FIG. 7) and forms an electrostatic latent image corresponding to each color image on the photoconductor; Developing with color toner (black toner, yellow toner, magenta toner and cyan toner) to form a toner image with each color toner, and intermediate transfer of the toner image 50 includes a transfer charger 62 for transferring the toner image on the toner image 50, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 145, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming method and the image forming apparatus of the present invention, both low-temperature fixability and heat resistance are achieved, the offset resistance is excellent, the toner structure can be controlled, and the charging property and cleaner are not contaminated in the developing device. Since the toner of the present invention having a good suitability is used, a high-quality image can be efficiently formed.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.
In the following Examples and Comparative Examples, the measurement of isocyanate group content (NCO%), acid value and hydroxyl value, and glass transition temperature (Tg) was performed as follows. The measurement method of average circularity, toner volume average particle size (Dv), number average particle size (Dp), particle size distribution (Dw / Dn), and cation exchange capacity (CEC) of zeolite has already been described. That's right.

<Measurement of free isocyanate group content (NCO%)>
The free isocyanate group content (NCO%) was measured by a method based on JIS K1603.

<Measurement of acid value and hydroxyl value>
-Method of measuring acid value-
The acid value was measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) was added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Furthermore, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation was performed as follows. Titration was performed in advance with a standardized N / 10 caustic potassium alcohol solution, and the acid value was determined from the consumption amount of the alcohol potassium solution by the following formula.
Acid value = KOH (ml) x N x 56.1 / sample mass (where N is a factor of N / 10 KOH)
-Measurement method of hydroxyl value-
0.5 g of a sample was precisely weighed into a 100 ml volumetric flask, and 5 ml of an acetylating reagent was correctly added thereto. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1 to 2 hours, the flask was taken out of the bath, allowed to cool, then added with water and shaken to decompose acetic anhydride. Then, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more, allowed to cool, and the wall of the flask is thoroughly washed with an organic solvent. This solution was subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the hydroxyl value (according to JIS K0070-1966).

<Measurement of glass transition temperature (Tg)>
The glass transition temperature (Tg) is specifically determined by the following procedure. Shimadzu TA-60WS and DSC-60 were used as measurement devices, and the measurement was performed under the following measurement conditions.
〔Measurement condition〕
・ Sample container: Aluminum sample pan (with lid)
-Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10 mg)
・ Atmosphere: Nitrogen (flow rate 50ml / min)
・ Temperature conditions ・ Starting temperature: 20 ℃
・ Raising rate: 10 ° C / min
・ End temperature: 150 ℃
-Holding time: None-Temperature drop: 10 ° C / min
・ End temperature: 20 ℃
-Holding time: None-Temperature rising rate: 10 ° C / min
・ End temperature: 150 ℃
The measurement results were 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 the peak temperature is determined using the peak analysis function of the analysis software. Ask. 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 glass transition temperature (Tg) of the toner.

(Example 1)
-Synthesis of polyester 1-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 553 parts of bisphenol A ethylene oxide 2-mole adduct, 196 parts of bisphenol A propylene oxide 2-mole adduct, 220 parts of terephthalic acid, 45 parts of adipic acid, And 2 parts of dibutyltin oxide were reacted for 8 hours at 230 ° C. under normal pressure, and after 5 hours under reduced pressure of 10 to 15 mmHg, 46 parts of trimellitic anhydride was added to the reaction vessel at 180 ° C. under normal pressure. And reacted for 2 hours to synthesize [Polyester 1]. [Polyester 1] had a number average molecular weight of 2,200, a weight average molecular weight of 5,600, a glass transition temperature (Tg) of 43 ° C., and an acid value of 13 mgKOH / g.

-Synthesis of prepolymer-
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 trimetic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to synthesize [Intermediate Polyester 1]. The obtained [Intermediate polyester 1] had a number average molecular weight of 2,100, a mass average molecular weight of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 49 mgKOH / g. .
Next, 411 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. [Prepolymer 1] was obtained. [Prepolymer 1] obtained had a free isocyanate mass% of 1.53%.

-Synthesis of master batch-
40 parts of carbon black (manufactured by Cabot, Regal 400R), polyester resin (manufactured by Sanyo Chemical Industries, RS-801, acid value 10 mgKOH / g, mass average molecular weight 20,000, glass transition temperature (Tg) 64 ° C.) 60 Part and 30 parts of water were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., and pulverized to a size of 1 mm in diameter with a pulverizer to obtain [Masterbatch 1].

(Example 1)
-Preparation of pigment / wax dispersion (oil phase)-
In a container equipped with a stirring rod and a thermometer, 378 parts of [Polyester 1], 120 parts of paraffin wax (HNP9), and 1,450 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining for 5 hours, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in the container and mixed for 1 hour to obtain [Raw material solution 1].
Next, 1500 parts of [Raw Material Solution 1] is transferred to a container, and using a beads mill (Ultra Visco Mill, manufactured by IMEX Co., Ltd.), a liquid feeding speed is 1 kg / hour, a disk peripheral speed is 6 m / second, and 0.5 mm zirconia. Filling with 80% by volume of beads, carbon black and wax were dispersed under conditions of 3 passes.
Next, 655 parts of a 65% ethyl acetate solution of [Polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. Ethyl acetate was added and adjusted so that the solid content concentration of [Pigment / Wax Dispersion 1] (130 ° C., 30 minutes) was 50%.

-Preparation of aqueous phase-
953 parts of ion-exchange water, 88 parts of 25% aqueous dispersion of organic resin fine particles for dispersion stabilization (styrene copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate), dodecyl diphenyl ether 90 parts of a 48.5% aqueous solution of sodium disulfonate (manufactured by Sanyo Chemical Industry Co., Ltd., Eleminol MON-7) and 113 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].

-Emulsification process-
[Pigment / Wax Dispersion 1] 967 parts and 1.0% of the synthetic zeolite 1 shown in Table 1 (in terms of toner solid content) were added, 6 parts of isophoronediamine as amines, TK homomixer (special machine) After being mixed for 1 minute at 5,000 rpm with Kabushiki Kaisha), 137 parts of [Prepolymer 1] were added, and after mixing for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) [Aqueous phase 1] 1,200 parts were added and mixed with a TK homomixer for 20 minutes while adjusting at a rotational speed of 8,000 to 13,000 rpm to obtain [Emulsion slurry 1].

-Solvent removal-
[Emulsion slurry 1] was charged into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Dispersion slurry 1].

-Washing and drying-
[Dispersion Slurry 1] 100 parts were filtered under reduced pressure, and then washed and dried as follows.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2) 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at a rotation speed of 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electrical conductivity of the reslurry liquid (filter cake) was 10 μC / cm or less.
(3) 10% hydrochloric acid was added so that the reslurry liquid of (2) had a pH of 4, and the mixture was stirred as it was with a three-one motor for 30 minutes and then filtered.
(4) 100 parts of ion exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered. This operation was repeated so that the electric conductivity of the reslurry liquid (filter cake) was 10 μC / cm or less to obtain [Filter cake 1].

[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with a mesh of 75 μm to obtain [Toner 1]. The obtained [Toner 1] had a volume average particle diameter (Dv) of 6.0 μm, a number average particle diameter (Dp) of 5.3 μm, Dv / Dp of 1.13, and an average circularity of 0.981. It was.
Next, 100 parts of the base toner was mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to prepare [Developer 1].

(Examples 2 to 6)
As shown in Table 1, toners and developers of Examples 2 to 6 were produced in the same manner as in Example 1 except that the type and amount of zeolite were changed.

(Comparative Example 1)
In Example 1, a toner and a developer of Comparative Example 1 were produced in the same manner as in Example 1 except that the synthetic zeolite 1 was not added.

(Comparative Examples 2 to 5)
In Example 1, toners and developers of Comparative Examples 2 to 5 were prepared in the same manner as in Example 1 except that the composite inorganic oxide shown in Table 1 was added instead of the synthetic zeolite 1.

(Comparative Example 6)
A toner and a developer of Comparative Example 6 were obtained in the same manner as in Example 1, except that a toner was prepared by adding 2.0% of synthetic zeolite 1 by the pulverization method described below.

<Preparation of first binder resin>
As a vinyl monomer, 600 g of styrene, 110 g of butyl acrylate and 30 g of acrylic acid, and 30 g of dicumyl peroxide as a polymerization initiator were placed in a dropping funnel. Among polyester monomers, as polyols, 1230 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4 -Hydroxyphenyl) propane 290 g, isododecenyl succinic anhydride 250 g, terephthalic acid 310 g, 1,2,4-benzenetricarboxylic anhydride 180 g, dibutyltin oxide 7 g as an esterification catalyst, paraffin wax (melting point 73.3 ° C.) , 340 g (11.0 parts by mass with respect to 100 parts by mass of charged monomer), 340 g of thermometer, stainless steel stirrer, flow-down type Place in a 5 liter four-necked flask equipped with a condenser and a nitrogen inlet tube. Under a nitrogen atmosphere in a chromatography, with stirring at a temperature of 160 ° C., it was added dropwise a mixed solution of the vinyl monomer resins from the dropping funnel and the polymerization initiator over a period of one hour. Next, after aging the addition polymerization reaction for 2 hours while maintaining the temperature at 160 ° C., the temperature was raised to 230 ° C. to perform the condensation polymerization reaction. The degree of polymerization was tracked by the softening point measured using a constant load extrusion type capillary rheometer, and when the desired softening point was reached, the reaction was terminated to obtain a first binder resin. The softening point of the obtained resin was 130 ° C.

<Preparation of second binder resin>
As a polyol, 2,210 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 850 g of terephthalic acid, and 120 g of 1,2,4-benzenetricarboxylic anhydride were used as an esterification catalyst. 0.5 g of dibutyltin oxide is placed in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen inlet tube, and the temperature is raised to 230 ° C. under a nitrogen atmosphere in a mantle heater to perform condensation polymerization. The reaction was performed. The degree of polymerization was tracked by the softening point measured using a constant load extrusion capillary rheometer, and when the desired softening point was reached, the reaction was terminated to obtain a second binder resin. The softening point of the obtained resin was 115 ° C.

<Preparation of toner particles>
C. for 100 parts by mass (including the mass of the internally added wax) of the binder resin composed of the first binder resin and the second binder resin. I. A master batch equivalent to containing 4 parts by weight of Pigment Red 57-1 was thoroughly mixed with a Henschel mixer, and the two-screw extrusion kneader (PCM-30, manufactured by Ikekai Tekko Co., Ltd.) was used. The resulting kneaded material was rolled to a thickness of 2 mm with a cooling press roller, cooled with a cooling belt, and then roughly pulverized with a feather mill. Thereafter, the mixture is pulverized with a mechanical pulverizer (KTM, manufactured by Kawasaki Heavy Industries, Ltd.) to an average particle size of 10 μm to 12 μm, and further pulverized with a counter jet mill (AFG, manufactured by Hosokawa Micron Co., Ltd.) while pulverizing the fine particles. Classification was carried out using a rotor type classifier (Teplex type classifier type, 100 ATP, manufactured by Hosokawa Micron Corporation) to obtain colored resin particles (toner). The toner of Comparative Example 6 obtained had a volume average particle diameter (Dv) of 6.1 μm and an average circularity of 0.922.

Table 1 summarizes the production methods, compositions, and properties of the toners of Examples 1 to 6 and Comparative Examples 1 to 6.
In Table 1, the formal names of the composite inorganic oxides are as follows.
Synthetic zeolite 1: Zeolum A-3 (manufactured by Tosoh Corporation)
Synthetic zeolite 2: A-type synthetic zeolite (Asahi Glass Co., Ltd.)
・ Artificial zeolite: Zeostar (manufactured by Nippon Chemical Industry Co., Ltd.)
APA: (Clayton, layered inorganic compound)
・ Bentonite: Kunipia F (Kunimine Industry Co., Ltd.)
・ Sepiolite: PANSIL (manufactured by GROPO TOLSA)

  Next, with respect to the obtained toners and developers of Examples 1 to 6 and Comparative Examples 1 to 6, fixing separation property, transfer property, stress resistance, image density, background stain, and cleaner are as follows. The suitability was evaluated. The results are shown in Table 2.

<Fixing separation>
The toner (developer) subjected to the external addition treatment was applied to an image forming apparatus (Ricoh Co., Ltd., ipsio CX2500) using A4 size vertical paper and a solid band image having a width of 36 mm and a width of 36 mm (adhesion amount 9 g / m). ^An unfixed image printed with ² ) was produced. The unfixed image was fixed at a fixing temperature of 10 ° C. in the range of 130 ° C. to 190 ° C., and a separable / non-offset temperature range was obtained. From this temperature range, the following three stages were evaluated. Here, the temperature range is a fixing temperature range in which separation of paper from the heating roller is favorably performed, no offset phenomenon occurs, and image peeling does not easily occur. The paper used and the paper passing direction were 45 g / m ² of Y-long vertical paper that is disadvantageous in separability. The peripheral speed of the fixing device was 120 mm / second.
〔Evaluation criteria〕
A: Separable / non-offset temperature range was 50 ° C. or higher.
(Triangle | delta): The separable / non-offset temperature range was 30 degreeC or more and less than 50 degreeC.
X: The separable / non-offset temperature range was less than 30 ° C.

<Transferability>
Using a toner (developer) subjected to external addition processing, an image forming apparatus (Ricoh Co., Ltd., ipsio CX2500) is used to print a predetermined print pattern with a B / W ratio of 6% in an N / N environment (23 ° C., 45 %) Was continuously printed. After continuous printing of 2,000 sheets in an N / N environment (after durability), the toner on the photoreceptor during solid pattern printing of a certain area was sucked and the mass (A) of the sucked toner was measured. On the other hand, the toner on the paper before fixing was sucked and the mass (B) was measured. Then, the transfer efficiency (%) was obtained by the following formula (A) / (B) × 100. Based on the value of the transfer efficiency, evaluation was performed in the following three stages.
〔Evaluation criteria〕
○: Transfer efficiency 85% or more Δ: Transfer efficiency 75% or more and less than 85% ×: Transfer efficiency less than 75%

<Stress resistance, image density, and background stain>
Using a toner (developer) subjected to external addition processing, an image forming apparatus (Ricoh Co., Ltd., ipsio CX2500) is used to print a predetermined print pattern with a B / W ratio of 6% in an N / N environment (23 ° C., 45 %) Was continuously printed.
(1) Stress resistance After 50 sheets of continuous printing and 2,000 sheets of continuous printing under N / N environment (after endurance), the toner on the developing roller during blank paper pattern printing is sucked and the amount of charge is measured with an electrometer. Measurements were made to determine the difference in charge amount after 50 sheets and after 2,000 sheets, and the evaluation was made in the following three stages.
〔Evaluation criteria〕
○: The absolute value of the charge amount difference is less than 10 μC / g Δ: The absolute value of the charge amount difference is in the range of 10 to 15 μC / g ×: The absolute value of the charge amount difference is more than 15 μC / g (2) Image density and background Dirt Image density was evaluated by visual observation of print samples after continuous printing of 2,000 sheets. As for the background stain on the photoconductor, a colorless transparent tape was applied to the uncleaned portion after development, the background toner on the photoconductor was peeled off, and the density after the blank paper was attached was visually evaluated. All of the evaluation criteria were performed in the following three stages.
〔Evaluation criteria〕
○: Good △: Level of no problem in actual use ×: Unusable

<Evaluation of cleaner-less aptitude>
Using each toner (developer) subjected to external addition processing in the same manner as described above, the charging roller of the image forming apparatus (manufactured by Ricoh Co., Ltd., IPSIO CX3000) is replaced with a brush roller, the photosensitive member cleaning blade is removed, and a conductive sheet is provided there. Was installed so as to be in contact with the surface of the photoconductor, and modified to a cleanerless type image forming apparatus as shown in FIG.
In FIG. 10, 301 represents an electrostatic latent image carrier, 302 represents a transfer belt, 303 represents a conductive sheet, 304 represents an elastic portion, 305 represents a charging brush, 306 represents developing means, and 307 represents a transfer roller.
The conductive sheet 303 was made of PTFE, had a thickness of 0.1 mm, a resistance of 10 ⁵ Ω · cm, a nip width of 5 mm, and a sheet voltage of DC500V.
As the charging brush 305, the material is nylon 6, the thickness is 2d, the resistance is 10 ⁶ Ω · cm, the density is 260,000 pieces / inch ² , the brush outer diameter is 11 mm, the shaft diameter is 5 mm, and the photoreceptor biting amount Was 0.8 mm, the peripheral speed ratio was 2, the AC voltage peak was 1.0 kV, the duty was 45% (PC potential 0 V), and 500 Hz.
Using this cleanerless image forming apparatus, a predetermined print pattern having a B / W ratio of 6% was continuously printed in a monochrome mode in an N / N environment (23 ° C., 45% RH) at 2,000 sheets. At this time, as an evaluation of cleaner-less aptitude, the presence or absence of adhesion to the conductive sheet was evaluated according to the following criteria.
〔Evaluation criteria〕
○: No sticking to the conductive sheet Δ: A little sticking to the conductive sheet (image noise can be confirmed)
×: Severe sticking to the conductive sheet

From the results of Table 2, in Examples 1 to 6 using a toner containing zeolite and manufactured by an O / W type wet granulation method, fixing separation property, transfer property, stress resistance, and cleanerless suitability are good. It was found that the image density and the occurrence of background stains were small. In particular, in Examples 1 to 4 in which 0.2 to 2.5 parts by mass of synthetic zeolite having a CEC of 400 to 600 (meq / 100 g) was added to 100 parts by mass of the toner base, transferability and stress resistance were improved. It turned out to be excellent.

  The toner of the present invention achieves both low-temperature fixability and heat resistance, is excellent in offset resistance, can control the toner structure, has good chargeability without contaminating the developing device, and is cleaner-less suitable. Therefore, it is suitably used for high-quality image formation. The developer, toner-containing container, process cartridge, image forming apparatus, and image forming method of the present invention using the toner of the present invention are suitably used for high-quality electrophotographic image formation.

FIG. 1 is a schematic view showing an example of a process cartridge used in the present invention. FIG. 2 is a schematic explanatory view showing an example of carrying out the image forming method by the image forming apparatus used in the present invention. FIG. 3 is a schematic explanatory view showing another example of carrying out the image forming method by the image forming apparatus used in the present invention. FIG. 4 is a partially enlarged view showing an example of the image forming apparatus used in the present invention. FIG. 5 is a partially enlarged view showing another example of the image forming apparatus used in the present invention. FIG. 6 is a schematic explanatory view showing an example in which the image forming method is carried out by the image forming apparatus (tandem type color image forming apparatus) used in the present invention. FIG. 7 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG. FIG. 8 is a schematic view showing a main part of an image forming apparatus to which the process cartridge of the present invention can be applied. FIG. 9 is an enlarged view of the K process cartridge of FIG. 8 and its surroundings. FIG. 10 is a schematic diagram illustrating an example of a cleaningless type image forming apparatus used in the embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Transfer device 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer device 6 Paper feed device 7 Fixing device 8 Photoconductor cleaning device 9 Intermediate transfer body cleaning device 10 Photoconductor (photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developer 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Development roller Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection Roller 57 Discharge tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 101 Photoconductor 102 Charging means 103 Exposure Exposure by means 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 110 Belt-type image fixing device 120 Tandem type developing device 130 Document table 142 Feed roller 143 Paper bank 1 4 Feeding cassette 145 Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copying device main body 200 Feeding table 210 Image fixing device 220 Heating roller 230 Pressure roller 300 Scanner 303 Conductive sheet 304 Elastic portion 305 Charging brush 400 Document Automatic transfer device (ADF)

Claims (17)

  A toner comprising at least a binder resin, a colorant, a release agent, and zeolite, and having an average circularity of 0.970 or more produced by an O / W type wet granulation method.   The toner according to claim 1, which has negative chargeability.   The toner according to claim 1, wherein the cation exchange capacity (CEC) of the zeolite is 150 meq / 100 g to 800 meq / 100 g.   The toner according to claim 3, wherein the zeolite is a synthetic zeolite having a cation exchange capacity (CEC) of 400 meq / 100 g to 600 meq / 100 g.   The toner according to claim 1, wherein the binder resin includes a polyester resin.   The toner according to claim 1, wherein the oil phase used in the O / W type wet granulation contains an organic solvent.   The toner according to claim 1, which is used in a nonmagnetic one-component development method.   A developer comprising the toner according to claim 1.   A toner-filled container filled with the toner according to claim 1.   An electrostatic latent image carrier and development means for developing a latent image formed on the electrostatic latent image carrier using the toner according to claim 1 to form a visible image. A process cartridge having at least   The process cartridge according to claim 10, further comprising recharging means for recharging residual toner on the surface of the latent electrostatic image bearing member after transfer using a recharging member.   An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of claims 1 to 7 At least developing means for forming a visible image by developing the toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. An image forming apparatus. Recharging means for recharging residual toner on the surface of the latent electrostatic image bearing member after transfer using a recharging member;
13. The image forming apparatus according to claim 12, wherein the image forming apparatus is a cleaner-less system that develops an electrostatic latent image formed on the electrostatic latent image carrier and collects residual toner on the electrostatic latent image carrier.   The image forming apparatus according to claim 13, wherein the recharging member is a conductive sheet disposed so as to be in pressure contact with the surface of the electrostatic latent image carrier.   An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to any one of claims 1 to 7 to form a visible image An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium. A recharging step of recharging the residual toner on the surface of the latent electrostatic image bearing member after transfer using a recharging member;
The image forming method according to claim 15, wherein the image forming method is a cleanerless system that develops an electrostatic latent image formed on the electrostatic latent image carrier and collects residual toner on the electrostatic latent image carrier.   The image forming method according to claim 16, wherein the recharging member is a conductive sheet disposed so as to be in pressure contact with the surface of the electrostatic latent image carrier.