JP4974539B2 - Non-magnetic one-component development system and development device - Google Patents

Description

  The present invention relates to a non-magnetic one-component developing system and a developing device for developing an electrostatic latent image in electrophotography, electrostatic printing, and the like.

As means for developing an electrostatic latent image formed on an electrostatic latent image carrier such as an electrophotographic photosensitive member or an electrostatic recording body, a method using a liquid developer (wet development method), a binder resin, In general, a method in which a toner in which a colorant is dispersed or a one-component or two-component dry developer in which the toner is mixed with a carrier is used (dry development method). Each of these methods has advantages and disadvantages, but at present, the dry development method is widely used. Among these methods, the one-component development method does not require a carrier and does not require a toner concentration controller system, and the apparatus can be downsized and maintained easily because the agitation device in the developing machine may be a simple type. In view of the advantages, various development methods using a one-component developer composed only of toner have been proposed (Patent Documents 1, 2, etc.).
Here, the developing device used in the one-component developing process includes a developing roller that supplies developer to the electrostatic latent image formed on the image carrier, a sponge roller that supplies developer from a bottle containing the developer, and A developer regulating member for regulating the amount of the developer supplied onto the developing roller; As a developer regulating member, a blade type regulating member and a roller type regulating member are known.
FIG. 8 is a schematic view of a process cartridge provided with a developing device using a blade type regulating member. An image carrier and a developing device are provided in the cartridge case. The developing device includes a developing roller, houses a one-component developer in the developer storage unit, and attaches toner as a one-component developer to the developing roller to develop the electrostatic latent image on the image carrier. Then, the toner image formed on the image carrier is transferred by a transfer roller to a transfer material sent out at a timing by a registration roller.

Further, as a developing device using a roller type regulating member, a doctor roller as a roller type regulating member that contacts the developing roller and rotates by a predetermined angle in the opposite direction to the rotation of the developing roller at the end of image formation. There is disclosed a developing device having:
According to this method, since the toner is a non-magnetic one-component system that does not use a magnetic material, there is an advantage that colorization is easy.
However, compared to a two-component developer that can perform sufficient frictional charging between carriers, a one-component developer that does not have a carrier is charged with toner due to frictional charging caused by contact between the toner and the developing roller surface. It is necessary to control the polarity and charge amount. The movement of the toner to the photosensitive member is performed by selecting the image portion and the background portion (non-image portion) of the electrostatic latent image according to the polarity of the toner charge and the developing electric field. When the charge amount of the toner is low and the amount of toner having a reverse polarity is large, the toner adheres to the background, and there is a problem that the output image on the transfer paper appears as a fog on the background. Further, when the charge amount of the toner is low and the start-up is bad, there is a problem that the density stability is deteriorated, for example, a difference in density occurs between the front and rear edges of the paper or a ghost appears. In particular, from the viewpoint of improving the image quality, it is necessary to increase the image density as compared with the prior art.
On the other hand, with the miniaturization of the device, the toner carrier and other members have also been miniaturized, and with the increase in speed, the toner charging time and development time have been shortened, and the toner has been made to have a smaller particle size for higher image quality. The decrease in the charge amount per particle accelerates the occurrence of the above problem.

In order to improve such problems, various proposals have been made. It has become clear that the development ghost can generally be improved by using a means for suppressing toner charge-up. In response to this, for example, by providing the toner carrier with a resin layer made of phenol resin and carbon having conductivity and surface lubricity, the resistance value of the developer carrier (sleeve) is lowered, thereby charging the toner. A technique for reducing the absolute value of the amount and suppressing the development ghost has been proposed (see Patent Document 3).
However, by reducing the toner charge amount, developability from the developer carrying member to the latent image carrying member (photosensitive member) may be lowered, and the image density may be lowered. Particularly in recent years, as the toner has been made smaller in size because of the demand for higher image quality, the amount of charge per toner particle has also decreased, and image density tends to decrease.

In a high-temperature and high-humidity environment, similarly to the ghost and the like, the charge amount of the toner is particularly lowered, the background fog tends to occur, and the density tends to become unstable.
Furthermore, the single-component development system puts a lot of load on the developer and developing roller in order to provide charging capability, so even if this problem does not occur at the beginning, the As the number of sheets increases, toner filming occurs on the surface of the developing roller, the charge amount of the toner decreases, the fog on the background increases, and a sufficient image density cannot be obtained. There are problems such as insufficient durability. Due to such problems, it is important to impart a stable charge amount to the toner even on the environment and long-term use on the surface layer of the developing roller.

One of the important characteristics of toner for solving the above problems is a problem of toner charge control.
Conventionally, for example, Patent Document 4 discloses a method for fixing a charge control agent on the surface of fine particles to the outside of the particles by mechanical energy. A method of fixing resin fine particles and a charge control agent on a surface by mechanical energy is disclosed.
However, in the method in which the charge control agent is fixed to the fine particle surface by mechanical energy, it is difficult to fix the charge control agent uniformly because the particle size distribution of the fine particles is wide, and the heat of the charge control agent and the fine particles is difficult. If the characteristics are different, there is a problem that the fixing characteristics of the fine particles are hindered.
Furthermore, even in the method in which the resin fine particles and the charge control agent are fixed to the surface of the fine particles by mechanical energy, it is difficult to uniformly fix substances having different compositions and properties such as the resin fine particles and the charge control agent, and charge control is difficult. There is a problem that.

In view of this, as a technique for avoiding problems in the method of fixing the charge control agent by the above-described mechanical energy, a method of applying a surface treatment for charging in a liquid has been proposed (see Patent Document 6).
However, in the case of the above method, the surface treatment agent may permeate into the toner component or may not stably exist on the toner surface. The effect of the surface treatment agent thus obtained cannot be sufficiently obtained, and a toner having stable charging characteristics cannot be obtained.
Further, it is difficult to prevent the charge control agent from detaching, and it is easy to cause contamination of the developing sleeve and so-called filming of the photoconductor.

U.S. Pat. No. 3,909,258 U.S. Pat. No. 4,121,931 JP-A-1-276174 Japanese Patent Laid-Open No. 62-209541 JP-A-63-198070 Japanese Patent Laid-Open No. 5-281787

Therefore, the present invention has been made in view of the above-mentioned problems, and the problem is that the rising of the charge is good, the charging property is good, the occurrence of a ghost image can be prevented, the background is less stained, the dot It is an object to provide a non-magnetic one-component developing system and a developing apparatus that are excellent in reproducibility, developability and transferability, and also have good fixability.
Also provided is a non-magnetic one-component developing system and a developing apparatus that can be used sufficiently even in a non-magnetic one-component process that is extremely strong in filming resistance and strong in stress even in a toner containing a release agent. It is.
Furthermore, it is an object of the present invention to provide a high-quality image that is free from abnormal images and excellent in fixability by the non-magnetic one-component developing system and developing device of the present invention.

（式中、Ｘ、Ｙ、Ｒ^１〜Ｒ^４、ｒ及びｓは、それぞれ以下のものを表す。Ｘ：−ＳＯ_２−又は−ＣＯ−、Ｒ^１，Ｒ^２，Ｒ^３，Ｒ^４：水素原子、炭素数１〜１０の低級アルキル基又はアリール基、Ｙ：Ｉ又はＢｒ、ｒ，ｓ：１〜２０の整数。）
ことを特徴とする。
本発明の非磁性一成分現像方法は、さらに、前記表面処理工程における表面処理時間が、０．１〜２４時間であることを特徴とする。
本発明の非磁性一成分現像方法は、さらに、前記トナーのガラス転移点が４５〜６０℃の範囲にあることを特徴とする。
本発明の非磁性一成分現像方法は、さらに、前記表面処理工程が、塩交換による化学結合反応を伴って進行するものであることを特徴とする。
本発明の非磁性一成分現像方法は、さらに、前記含フッ素４級アンモニウム塩化合物の添加量が、０．０３〜５質量部であることを特徴とする。
本発明の非磁性一成分現像方法は、さらに、前記含フッ素４級アンモニウム塩化合物の添加量が、０．０３〜２質量部であることを特徴とする。
本発明の非磁性一成分現像方法は、さらに、前記トナーが、少なくとも、活性水素基を有する化合物と反応可能な部位を有する重合体、ポリエステル、着色剤を有機媒体中にそれぞれ溶解又は分散させたトナー組成物を、樹脂微粒子を含有する水系媒体中で架橋及び／又は伸長反応させて得られることを特徴とする。
本発明の非磁性一成分現像方法は、さらに、前記樹脂微粒子が、酸の官能基を有していることを特徴とする。
本発明の非磁性一成分現像方法は、さらに、前記トナーが、体積平均粒径が３〜８μｍで、体積平均粒径（Ｄｖ）と個数平均粒径（Ｄｎ）との比（Ｄｖ／Ｄｎ）が１．０〜１．４０の範囲にあることを特徴とする。
本発明の非磁性一成分現像方法は、さらに、前記トナーが、平均円形度が０．９３０〜０．９７５であることを特徴とする。
本発明の非磁性一成分現像方法は、さらに、トナー補給を定量的に行う構造を有することを特徴とする。
本発明の非磁性一成分現像方法は、さらに、前記現像ローラのその外周及び規制部材の表面層に、主鎖もしくは側鎖末端にヒドロキシル基を有する樹脂またはプレポリマーとグアナミン、グアナミン誘導体、グアナミン系縮合物のうち１種以上とからなる縮合架橋物を含有する現像ローラを使用することを特徴とする。
また、本発明は、前記非磁性一成分現像方法に使用することを特徴とする現像装置である。 The features of the present invention, which is a means for solving the above problems, are listed below.
The present invention includes a developing roller and a regulating member that uniformly regulates the layer thickness of the developer supplied onto the developing roller, and the image is in contact with or close to an image carrier on which an electrostatic latent image is formed while rotating. In the nonmagnetic one-component development method for visualizing the electrostatic latent image by supplying toner to the surface of the carrier, the toner contains at least a binder resin, a release agent, and a colorant, and has an acid value of 10 the toner composition Monohaha microparticles ～18.8 is dispersed in an aqueous medium by papermaking work, in the aqueous medium in the range of 10 to 30 ° C., treating the mother particle surface by a fluorine-containing quaternary ammonium salt compound obtained through the surface treatment step, and a toner having an external additive on the outermost surface, the surface layer of the prior Symbol developing roller periphery and regulating member, guanamine, guanamine derivatives, among guanamine condensate at least 1 Which is a non-magnetic one-component developing method, wherein when the content.
In the nonmagnetic one-component developing method of the invention, the fluorine-containing quaternary ammonium salt compound is a compound represented by the following formula (1).

(In the formula, X, Y, R ^{1 to} R ⁴ , r and s each represent the following: X: —SO ₂ — or —CO—, R ¹ , R ² , R ³ , R ⁴ : hydrogen Atom, lower alkyl group or aryl group having 1 to 10 carbon atoms, Y: I or Br, r, s: integer of 1-20.)
It shall be the features a.
The nonmagnetic one-component developing method of the present invention is further characterized in that the surface treatment time in the surface treatment step is 0.1 to 24 hours.
The nonmagnetic one-component developing method of the present invention is further characterized in that the toner has a glass transition point in the range of 45 to 60 ° C.
The nonmagnetic one-component developing method of the present invention is further characterized in that the surface treatment step proceeds with a chemical bonding reaction by salt exchange.
The nonmagnetic one-component developing method of the present invention is further characterized in that the addition amount of the fluorine-containing quaternary ammonium salt compound is 0.03 to 5 parts by mass.
The nonmagnetic one-component developing method of the present invention is further characterized in that the addition amount of the fluorine-containing quaternary ammonium salt compound is 0.03 to 2 parts by mass.
In the non-magnetic one-component developing method of the present invention, the toner further dissolves or disperses at least a polymer, a polyester, and a colorant each having a site capable of reacting with a compound having an active hydrogen group in an organic medium. The toner composition is obtained by crosslinking and / or elongation reaction in an aqueous medium containing resin fine particles.
The nonmagnetic one-component developing method of the present invention is further characterized in that the resin fine particles have an acid functional group.
In the nonmagnetic one-component developing method of the invention, the toner further has a volume average particle diameter of 3 to 8 μm, and a ratio (Dv / Dn) of volume average particle diameter (Dv) to number average particle diameter (Dn). Is in the range of 1.0 to 1.40.
The nonmagnetic one-component developing method of the present invention is further characterized in that the toner has an average circularity of 0.930 to 0.975.
The nonmagnetic one-component developing method of the present invention is further characterized by having a structure for quantitatively supplying toner.
The non-magnetic one-component developing method of the present invention further comprises a resin or prepolymer having a hydroxyl group at the main chain or side chain terminal on the outer periphery of the developing roller and the surface layer of the regulating member, and guanamine, a guanamine derivative, a guanamine type characterized by using a free with developing roller fused crosslinked product consisting of one or more of the condensate.
In addition, the present invention is a developing device used for the nonmagnetic one-component developing method.

According to the present invention, the means for solving the problems has good charging characteristics and good charging characteristics, can prevent the generation of ghost images, has little background contamination, dot reproducibility, developability and transferability. In addition, it has become possible to provide a non-magnetic one-component developing system and a developing device that are excellent in fixing performance and excellent in fixability.
Also provided is a non-magnetic one-component developing system and a developing apparatus that can be used sufficiently even in a non-magnetic one-component process that is extremely strong in filming resistance and strong in stress even in a toner containing a release agent. Became possible.
Furthermore, the non-magnetic one-component developing system and developing device of the present invention can provide a high-quality image with no abnormal image and excellent fixability.

The best mode for carrying out the present invention will be described below with reference to the drawings. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

Hereinafter, embodiments of the present invention will be described.
The toner of the present invention comprises at least a binder resin and a colorant. The toner is obtained by dispersing the toner in an aqueous medium and treating the toner surface with a fluorine-containing quaternary ammonium salt compound. The toner has an acid value of 5 to 30, more preferably 10 to 25.
As a result of intensive studies by the present inventors, by performing a surface treatment step on the toner having an acid value of the toner composition within the above range, a toner having stable charging properties and excellent fixing properties can be obtained. I found that I can do it.
Specifically, when the acid value of the toner composition is less than 5, the obtained toner is inferior in chargeability, and generation of scumming is recognized. On the other hand, when the acid value of the toner composition exceeds 30, the chargeability under high humidity is lowered.
In addition, as the fluorine-containing quaternary ammonium salt compound, particularly by using the compound represented by the structural formula (1), it is possible to improve the chargeability and obtain good image quality without impairing the fixability. it can.

（式中、Ｘ、Ｙ、Ｒ ^１ 〜Ｒ ^４ 、ｒ及びｓは、それぞれ以下のものを表す。Ｘ：−ＳＯ_２−又は−ＣＯ−、Ｒ ^１ ，Ｒ ^２ ，Ｒ ^３ ，Ｒ ^４ ：水素原子、炭素数１〜１０の低級アルキル基又はアリール基、Ｙ：Ｉ又はＢｒ、ｒ，ｓ：１〜２０の整数。）

(In the formula , X, Y, R ^{1 to} R ⁴ , r and s each represent the following: X: —SO ₂ — or —CO—, R ¹ , R ² , R ³ , R ⁴ : hydrogen atom, a lower alkyl group or an aryl group having 1 to 10 carbon atoms, Y: I or Br, r, s: number integer of 1 to 20).

  Specifically, for example, it corresponds to the compounds represented by the structural formulas 1) to 54).

  Generally, a toner has an acidic group in its constituent material. Examples of the acidic group include carboxylic acid, and this acidic group undergoes an exchange reaction shown in the following (a) with the fluorine-containing quaternary ammonium salt compound represented by the structural formula (1). It is thought that.

In the toner of the present invention, since the acid value of the toner composition is in the above-mentioned range, the composition has a certain amount of acidic groups, and the fluorine-containing compound represented by the structural formula (1) by the salt exchange reaction. The quaternary ammonium salt compound is adsorbed on the toner particle surface.
That is, since the fluorine-containing quaternary ammonium salt compound is stably present on the surface of the toner particles, the effect of controlling the chargeability by this fluorine-containing quaternary ammonium salt compound can be obtained with certainty.
The toner of the present invention may be produced by either a pulverization method or a polymerization method.
As one aspect of the toner of the present invention, a dispersant such as resin fine particles was appropriately added to an aqueous medium used for polymerizing a toner composition dissolved or dispersed in an organic solvent at the time of preparation . Things are included. This is added in order to improve the dispersibility in the aqueous medium, but after the toner particles are formed, the resin fine particles are mainly present on the surface of the toner particles. Since this toner is produced by using the resin fine particles having an acidic group, the acidic group is also involved in the reaction formula, and the fluorine-containing quaternary ammonium salt compound represented by the structural formula (1) is obtained. This contributes to stable existence on the surface of the toner particles.
Another embodiment of the toner of the present invention includes a kneading and pulverizing toner. In this toner, for example, by using a polyester resin having a carboxylic acid group as an acidic group in the binder resin, the structural formula (1) Is adsorbed on the surface of the toner particles.
As an example of the pulverization method, first, in addition to a binder resin and a colorant, if necessary, a charge control agent, a release agent, other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer, and then a batch type. These components are thoroughly kneaded using a thermal kneader such as a 2-roll, Banbury mixer, continuous twin-screw extruder, continuous single-screw kneader, etc., and cut after rolling and cooling. The toner kneaded product after cutting is crushed, coarsely pulverized using a hammer mill, etc., and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and a classifier or Coanda effect using a swirling airflow Is classified to a predetermined particle size by a classifier using Thereafter, inorganic fine particles are externally added by a mixer and mixed to obtain a toner.

(Temperature regulation)
In addition, the above-described surface treatment agent having the opposite polarity is partially penetrated into the toner if the temperature when acting on the toner particle surface is high. If the amount of penetration increases, the surface abundance that can contribute to charging is reduced, so that the effect of stabilizing the chargeability of the toner cannot be sufficiently obtained.
In the present invention, when the temperature of the aqueous medium in the surface treatment step is set to a temperature range of 10 to 30 ° C., the surface treatment agent is prevented from penetrating into the toner particles.
As a result, the surface treatment agent can be surely present on the surface of the toner particles, so that the influence of the charging property exerted on the toner by the surfactant added at the time of particle formation can be prevented, and the toner having a stable charging property. Can be obtained.
If surface treatment is performed at a temperature lower than 10 ° C., the adsorption itself is difficult to occur, so that the amount of the surface treatment agent necessary for controlling the chargeability cannot be adsorbed.

Generally, the glass transition point of the binder resin of the toner is usually 35 to 70 ° C. If the temperature (Trt) of the aqueous medium used in the surface treatment process is higher than this, the specific volume of the toner particles changes suddenly, The surface treatment agent present in the water is likely to penetrate into the toner particles.
For this reason, by setting the relationship between the temperature (Tg) of the glass transition point of the toner and the temperature (Trt) of the aqueous medium at the time of the surface treatment so that Tg> Trt, Can be suppressed.
This confirms the validity of the temperature range of the aqueous medium in the surface treatment process defined in the present invention.
The toner used in the present invention preferably has a glass transition point in the range of 40 to 60 ° C.

(Amount of surface treatment agent)
In order to solve the problem of a decrease in the amount of the surface treatment agent due to the penetration of the surface treatment agent, means for increasing the amount of the surface treatment agent to be added is also possible. However, in this case, the exudation of the wax added to the toner as a release agent is inhibited, and the effect is reduced. That is, the fixability may be deteriorated due to an adverse effect on the hot offset property.
The toner of the present invention is effective for this problem because the above-described method can efficiently obtain the effect without increasing the amount of the surface treatment agent added.
In addition, as a result of intensive studies by the present inventors, the amount of the surface treatment agent added is preferably 0.03 to 5 parts by mass, and more preferably 0.03 to 2 parts by mass. The reaction time is preferably 0.1 to 24 hours.
The toner of the present invention can exhibit stable charging properties and excellent fixing characteristics by adding the surface treatment agent in the above-described processing temperature, processing time, and addition amount.

In a conventional toner obtained by treating the surface with a charge treating agent, the charge treating agent is easily detached, and the developing sleeve and the photosensitive member are easily contaminated.
However, in the toner of the present invention, the surface treatment is performed on the toner composition having an acid value in the above range, so that the surface treatment agent is adsorbed on the surface by the salt exchange reaction represented by the formula (a). Desorption by the agent alone is suppressed. Thereby, the occurrence of filming is suppressed and the durability of the image forming apparatus main body can be improved.
Furthermore, the influence of the surfactant used when forming the base particles on the chargeability can be more reliably suppressed, and a toner having good chargeability can be provided.

  The image forming toner of the present invention is preferably a toner having a small particle size and a nearly spherical shape so as to output a high-quality and high-definition image. As a method for producing such a toner, there are a suspension polymerization method, an emulsion polymerization method, a polymer suspension method and the like in which an oil phase is emulsified, suspended or aggregated in an aqueous medium to form toner base particles. Hereinafter, these toner production methods and materials, additives and the like used in the production methods will be described.

(Suspension polymerization method)
A colorant, a release agent and the like are dispersed in an oil-soluble polymerization initiator and a polymerizable monomer, and then emulsified and dispersed by an emulsification method described later in an aqueous medium containing a surfactant and other solid dispersants. Thereafter, after the polymerization reaction to form particles, a wet treatment for attaching the inorganic fine particles A to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.
Polymerizable monomers such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, acrylamide, methacrylamide, diacetone Functional groups can be introduced on the surface of toner particles by using a part of acrylate or methacrylate such as acrylamide or these methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate and other amino groups. .
Further, by selecting a dispersant having an acid group or a basic group as a dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

(Emulsion polymerization aggregation method)
A water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by an ordinary emulsion polymerization technique. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, a wet treatment of inorganic fine particles A described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer that can be used in the suspension polymerization method.

(Polymer suspension method)
The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.
In the oil phase of the toner composition, a colorant such as resin, prepolymer and pigment, a release agent, a charge control agent and the like are dissolved or dispersed in a volatile solvent.
An oil phase composed of a toner composition is dispersed in an aqueous medium in the presence of a surfactant, a solid dispersant and the like, and a prepolymer is reacted to form particles. Thereafter, a wet treatment of inorganic fine particles A described later may be performed.
In order to introduce a functional group into the toner particles, a copolymer with a monomer having a functional group used in the suspension polymerization method, or a functional group of an acid group as an acid monomer in the case of a polyester resin is used. It can be obtained by using one having three or more or esterifying the terminal hydroxyl group of the obtained polyester resin with a compound having a plurality of acid groups. Further, as a dispersion stabilizer in an aqueous medium, which will be described later, an acid group-containing surfactant, polar polymer, organic or inorganic resin fine particles can be used, and an acid group can be introduced by remaining on the toner particle surface. Examples of the acid group include a carboxyl group, a sulfone group, a sulfonic acid group, and a phosphoric acid group.

  In any of these toner production methods, the toner particles can be subjected to a surface treatment. This step is preferably performed after the toner particles are formed and the used surfactant and the like are removed by washing. Excess surfactant present in water is removed by solid-liquid separation operations such as filtration and centrifugation, and the resulting slurry is redispersed in an aqueous medium. Here, a surface treatment agent aqueous solution having a polarity opposite to that of the previously used surfactant is gradually added with stirring. The reverse polarity surface treatment agent is preferably used in an amount of 0.03 to 2 parts by mass relative to the solid content of the toner particles. Moreover, it is preferable to perform the time of this surface treatment process in the range of 0.1 to 24 hours.

  In the toner of the present invention, more preferably, at least a polymer having a site capable of reacting with a compound having an active hydrogen group, a polyester, a colorant, and a release agent are dissolved or dispersed in an organic solvent. It is a toner obtained by subjecting a toner material liquid to a crosslinking and / or elongation reaction in an aqueous medium. Hereinafter, the constituent material and the manufacturing method of the toner will be described.

(Modified polyester)
The toner according to the present invention contains modified polyester (I) as a binder resin. The modified polyester (I) refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin by a covalent bond, an ionic bond, or the like. Specifically, the polyester terminal is modified by introducing a functional group such as a carboxylic acid group or an isocyanate group that reacts with a hydroxyl group into the polyester terminal and further reacting with an active hydrogen-containing compound.
Examples of the modified polyester (I) include urea-modified polyester obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and amines (B). As the polyester prepolymer (A) having an isocyanate group, a polyester having a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and having an active hydrogen group is further added to a polyvalent isocyanate compound (PIC). And those reacted with. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

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

  Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred. Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.). The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) ); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; phenol derivatives, oximes, polyisocyanates; Those blocked with Caprolactam, etc .; and combinations of two or more of these.
The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.
The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40% by mass , preferably 1 to 30% by mass , more preferably 2 to 20% by mass. %. If it is less than 0.5% by mass , the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by mass , the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.

Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acid (B5), and amino acid block of B1 to B5 (B6).
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.
The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The modified polyester (I) used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (I) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10000. When the molecular weight is less than 1000, the elongation reaction hardly occurs, the elasticity of the toner is small, and as a result, the resistance to hot offset deteriorates. On the other hand, when it exceeds 10,000, the problem in production becomes high in the deterioration of fixability, particle formation and pulverization. The number average molecular weight of the modified polyester (I) is not particularly limited when the unmodified polyester (II) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. In the case of (I) alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.
In the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B) to obtain the modified polyester (I), a reaction terminator is used as necessary to adjust the molecular weight of the resulting urea-modified polyester. be able to. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

(Unmodified polyester)
In the present invention, not only the modified polyester (I) is used alone, but also the unmodified polyester (II) can be contained as a binder resin component together with the (I). By using (II) in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved, which is preferable to single use. Examples of (II) include polycondensates of polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) similar to the polyester component of (I), and preferred ones are also the same as (I). . Further, (II) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that (I) and (II) are at least partially compatible in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (I) and (II) preferably have similar compositions. When (II) is contained, the weight ratio of (I) to (II) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. When the weight ratio of (I) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The peak molecular weight of (II) is 1000-10000 normally, Preferably it is 2000-8000, More preferably, it is 2000-5000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (II) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (II) is preferably from 1 to 5, more preferably from 2 to 4. Since a high acid value wax is used as the wax, the low acid value binder leads to electrification and high volume resistance, so that it is easy to match the toner used for the two-component developer.

  The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C, preferably 55 to 65 ° C. If the temperature is lower than 35 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat storage stability even when the glass transition point is low, as compared with known polyester-based toners. Show.

(Coloring agent)
As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow 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, bengara, red lead, lead vermilion, cadmium red, cadmium mercurial red, antimon vermilion, permanent red 4R, para red, phise red, parachlor ortho Nitroani Nreddo, Li Saul Fast Scarlet G, Brilliant Fast Scarlet, Brilliant mosquitoes over Mi emissions BS, permanent red (F2R, F4R, FRL, FRLL , F4RH), fast scarlet VD, bell cans Fast Rubin B, brilliant scarlet G, Lithol Rubine GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toulouse Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polya 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, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyani Green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass with respect to the toner.
The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, 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, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.
The amount of the charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Preferably, the range of 0.2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is lowered, and the image density is lowered. Invite.

(Release agent)
As a release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface. The effect on high temperature offset is exhibited without applying a release agent such as oil. Examples of such a wax component include the following. Waxes and waxes include plant waxes such as carnauba wax, cotton wax, and wood roller wax, animal waxes such as mitorollanoline, mineral waxes such as ozokerite and ceresin, and paraffin, microcrystalline, and petrolatum. And petroleum wax. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .
The charge control agent and the release agent can be melt-kneaded together with the master batch and the binder resin, and of course, they may be added when dissolved and dispersed in the organic solvent.

(External additive)
As the external additive, inorganic fine particles such as a metal oxide, a metal carbide, a metal nitride, and a metal carbonate can be used. Specifically, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide Cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like.
Furthermore, organic fine particles can be used as the external additive. Specifically, the high-molecular particles, for example, soap-free emulsion polymerization or suspension polymerization, dispersion polystyrene obtained by polymerization of methacrylic acid ester or acrylic acid ester copolymer, silicone, benzoguanamine, polycondensation system such as nylon, heat Polymer particles made of a curable resin may be used.
Further, the external additive used in the toner of the present invention can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents that may contain alkyl groups, fluorinated alkyl groups, titanate coupling agents, coupling agents such as aluminum coupling agents, silicone oils, higher fatty acids, fluorine compounds and the like are preferable surface treatment agents. Can be mentioned.
In particular, a silane coupling agent, which is an example of a coupling agent, is used for improving the degree of hydrophobicity and fluidity. Specifically, as the silane coupling agent, chlorosilane, alkoxysilane, silazane, special silylating agent and the like can be used, and alkoxysilane is more preferable. Examples of the alkoxysilane include vinyltrimethoxysilane, propyltrimethoxysilane, I-butyltrimethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, and n-dodecyltrimethoxy. A silane etc. can be mentioned.
As the silicone oil, polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane or the like can be used, and fluorine-containing siloxane or the like may be used.
The fluorine compound is preferably an organosilicon compound having a fluorine atom, such as 3,3,4,4,5,5,6,6,6-nonafluorohexyltrichlorosilane, 3,3,3-trifluoropropyl. Trimethoxysilane, methyl-3,3,3-trifluoropropyldichlorosilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,4,4,5,5,6,6,6- Nonafluorohexylmethyldichlorosilane and the like can be mentioned.
Further, examples of higher fatty acids include stearic acid, oleic acid, palmitic acid, and linoleic acid, and metal salts of these higher fatty acids may be used. Specific examples include zinc stearate, aluminum stearate, copper stearate, magnesium stearate, calcium stearate, zinc oleate, manganese oleate, zinc palmitate, zinc linoleate, and calcium linoleate.

In the toner of the present invention, the external additive is dry mixing in which inorganic / organic fine particles such as hydrophobic silica fine powder are externally added in a mixer together with a mixed medium such as glass beads. For mixing external additives, a general mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. The external additive is appropriately added at the beginning or in the middle. Examples of the mixer include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, and a Henschel mixer.
Further, wet mixing is used in which the toner is externally added in an aqueous and / or alcohol solvent. In this wet mixing, an external additive is added to the toner dispersed in an aqueous solvent and adhered to the toner surface. Further, when this external additive has been subjected to a hydrophobic treatment, it may be dispersed after a small amount of alcohol or the like is used in combination to lower the interfacial tension to facilitate wetting. Thereafter, the solvent can be removed by heating and fixed to prevent desorption. As a result, the external additive can be uniformly dispersed on the toner surface. Further, when the toner and the external additive are dispersed in the aqueous solvent, the external additive can be uniformly dispersed on the toner surface by adding the surfactant. Further, it is preferable to use an external additive or a surfactant having a polarity opposite to that of the toner.

Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.
(Toner production method)
1) A toner material solution is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent.
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 mass parts normally with respect to 100 mass parts of polyester prepolymers, Preferably it is 0-100 mass parts, More preferably, it is 25-70 mass parts.

2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by mass of the toner material liquid is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass. If the amount is less than 50 parts by mass, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by mass, it is not economical.

Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like. Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount.

As the resin fine particles, any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin. Examples thereof include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin, two or more of the above resins may be used in combination.
Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained. For example, vinyl resins are polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid-acrylic acid esters. Examples thereof include resins such as a polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer. The average particle size of the resin fine particles is 5 to 200 nm, preferably 20 to 300 nm. In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.
As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl Nitrogen compounds such as pyrrolidone, vinylimidazole, ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene Polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, poly Polyoxyethylenes such as oxyethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

3) At the same time as the preparation of the emulsion, the amines (B) are added to cause a reaction with the polyester prepolymer (A) having an isocyanate group.
This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

5) The obtained base particles are redispersed in an aqueous medium in the range of 10 to 30 ° C. There, the charge control agent is gradually added with stirring, and then the surface treatment agent having the opposite polarity to the surfactant used previously is gradually added. The reaction time is preferably 0.1 to 24 hours.
As the reverse polarity surfactant added here, a compound having the structure shown below is particularly preferable.

6) Toner is obtained by externally adding inorganic fine particles such as silica fine particles and titanium oxide fine particles to the toner base particles obtained above.
The external addition of the inorganic fine particles is performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the true spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.

Furthermore, the toner of the present invention has a volume average particle size in the range of 3.0 to 8.0 μm. By using this toner, the toner can be developed densely with respect to the latent image, and a high-quality image can be obtained. If the volume average particle size is less than 3.0 μm, an appropriate image density cannot be obtained unless a large amount of toner is developed, and thus the burden on the development process increases, making it practically difficult to use in an image forming apparatus. . On the other hand, if the volume average particle diameter exceeds 8.0 μm, the reproducibility of fine lines is lowered, so that a high-quality image cannot be obtained. In particular, in a full-color image, the graininess becomes remarkable, the color halftone part becomes rough visually, and it is difficult to obtain a high-quality color image.
In the toner of the present invention, the degree of dispersion, which is the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn), is in the range of 1.00 to 1.40. By reducing the degree of dispersion and narrowing the particle size distribution, the toner charge amount distribution becomes uniform, a high-quality image with little background fogging can be obtained, and during electrostatic transfer from a photoreceptor. The transfer rate can be increased by allowing the toner on the photoreceptor to receive a uniform electric field.
In these measurements, examples of the measuring device for the particle size distribution of toner particles by the Coulter counter method include Coulter counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, a surfactant (preferably alkylbenzene phon salt) is added 0.1~5mL as a dispersant in an aqueous electrolyte solution 100-150 mL. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

Further, the toner of the present invention has an average circularity of 0.94 or more. Average circularity SR = (peripheral length of circle having the same area as the projected particle area / perimeter length of projected particle image) × 100%. The closer the toner is to a true sphere, the closer to 100%. Toner having a high degree of circularity is easily affected by the developing electric field, and is developed faithfully along the electric field of the electrostatic latent image. When reproducing minute latent image dots, fine line reproducibility is enhanced by dense and uniform development. In addition, toner with a high degree of circularity has a smooth surface and appropriate fluidity, so it is easily affected by the electric field, and is easily transferred faithfully along the electric field, resulting in a high transfer rate and a high-quality image. Can be obtained. However, if the average circularity of the toner is less than 0.94, faithful development and transfer with a high transfer rate cannot be performed. Therefore, the average circularity is preferably 0.94 or more.
This degree of circularity is thermally or mechanically spheroidized with toner produced by dry grinding. Thermally, for example, the spheronization treatment can be performed by spraying toner base particles together with a hot air stream on an atomizer or the like. In addition, a spheroidizing treatment can be performed by mechanically charging the mixture into a mixer such as a ball mill together with a mixed medium such as glass having a low specific gravity and stirring. However, in the thermal spheronization process, toner base particles that are aggregated and have a large particle size or fine particles are generated in the mechanical spheronization process, and thus a second classification step is required. In addition, in a toner manufactured in an aqueous solvent, the shape can be controlled by applying strong stirring in the process of removing the solvent.
The circularity was measured by the following method.

A measurement method using a flow particle image analyzer (Flow Particle Image Analyzer) will be described below.
The measurement of toner, toner particles and external additives using a flow particle image analyzer can be performed using, for example, a flow particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics Co., Ltd.
The measurement is performed by removing fine dust through a filter, and as a result, in 10 mL of water having 10 to 3 particles in a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) in 10 ⁻³ cm ³ water. Add a few drops of nonionic surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.), add 5 mg of the sample to be measured, and use ultrasonic wave disperser STM UH-50 at 20 kHz, 50 W / 10 cm ³ . for 1 minute dispersion treatment, further, the sample dispersion liquid of the total particle concentration of sample was dispersed for 5 minutes from 4000 to 8000 pieces / 10 ^-3 cm ³ (as the target particles measuring circle equivalent diameter range) The particle size distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured.
The sample dispersion liquid is passed through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, the strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter.
In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06-400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

The toner of the present invention has a substantially spherical appearance, and the ratio of the major axis to the minor axis (r2 / r1) is in the range of 0.5 to 1.0, and the ratio between the thickness and the minor axis. (R3 / r2) is in the range of 0.7 to 1.0, and the relationship of major axis r1 ≧ minor axis r2 ≧ thickness r3 is satisfied. The toner has a substantially spherical shape and can be represented by the following shape rule. FIG. 1 is a diagram schematically showing the shape of a toner according to the present invention. In FIG. 1, when a substantially spherical toner is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), the toner of the present invention has a major axis and a minor axis. Ratio (r2 / r1) (see (b)) is 0.5 to 1.0, and ratio of thickness to minor axis (r3 / r2) (see (c)) is 0.7 to 1.0. It is preferable to be in the range. If the ratio of the major axis to the minor axis (r2 / r1) is less than 0.5, the separation from the true spherical shape results in poor fine line reproducibility and transfer rate, and high-quality image quality cannot be obtained. On the other hand, if the ratio of thickness to minor axis (r3 / r2) is less than 0.7, the shape is close to a flat shape, and a high transfer rate like a spherical toner cannot be obtained. In particular, when the ratio of the thickness to the minor axis (r3 / r2) is 1.0, the rotating body has a major axis as a rotation axis, and the fluidity of the toner can be improved.
Note that r1, r2, and r3 were measured with a scanning electron microscope (SEM) while changing the angle of field of view and taking pictures.

The image forming apparatus of the present invention will be described.
The image forming apparatus according to the present invention includes at least a charging device that applies charging by applying an alternating electric field in the image forming apparatus that includes a charging device that uniformly charges the surface of the image carrier, and the above-described development. And a developing device using the agent. FIG. 2 is a schematic diagram showing the configuration of the image forming apparatus of the present invention.
Hereinafter, description will be given with reference to the drawings.

(Intermediate transfer member)
An embodiment of an intermediate transfer member of a transfer system in the present invention will be described. Around a photosensitive drum (hereinafter referred to as a photosensitive member) 10 as an image carrier, a charging roller 20 as a charging device, an exposure device 30, a cleaning device 60 having a cleaning blade, a static elimination lamp 70 as a static elimination device, and development An apparatus 40 and an intermediate transfer member 50 as an intermediate transfer member are provided. The intermediate transfer member 50 is suspended by a plurality of suspension rollers 51 and is configured to run endlessly in the direction of the arrow by a driving unit such as a motor (not shown). A part of the suspension roller 51 also serves as a transfer bias roller for supplying a transfer bias to the intermediate transfer member, and a predetermined transfer bias voltage is applied from a power source (not shown). A cleaning device 90 having a cleaning blade for the intermediate transfer member 50 is also provided. Further, a transfer roller 80 is provided as a transfer means for transferring the developed image onto the transfer paper 100 as a final transfer material, facing the intermediate transfer member 50, and the transfer roller 80 is transferred by a power supply device (not shown). Supplied. Around the intermediate transfer member 50, a corona charger 52 as a charge applying unit is provided.

The developing device 40 includes a developing belt 41 as a developer carrier, a black (hereinafter referred to as Bk) developing unit 45K, a yellow (hereinafter referred to as Y) developing unit 45Y, The developing unit 45M is hereinafter referred to as “M” and the cyan (hereinafter referred to as “C”) developing unit 45C. Further, the developing belt 41 is stretched between a plurality of belt rollers, and is configured to run endlessly in a direction of an arrow by a driving unit such as a motor (not shown), and at the contact portion with the photoconductor 10, the photoconductor. Moves at approximately the same speed as 10.
Since the structure of each developing unit is common, the following description will be given only for the Bk developing unit 45K, and the other developing units 45Y, 45M, and 45C will be described in the parts corresponding to those in the Bk developing unit 45K in the drawing. Y, M, and C are appended to the numbers given to those in the unit, and the description is omitted. The developing unit 45K is disposed so as to immerse a developing tank 42K containing a high-viscosity, high-concentration liquid developer containing toner particles and a carrier liquid component, and a lower part in the liquid developer in the developing tank 42K. And a coating roller 44K that thins the developer pumped up from the pumping roller 43K and applies it to the developing belt 41. The application roller 44K has conductivity, and a predetermined bias is applied from a power source (not shown).
In addition to the apparatus configuration shown in FIG. 2, the image forming apparatus according to the present embodiment includes a developing unit for each color arranged around one photoconductor 40 as shown in FIG. 3. It may be a device configuration.

Next, the operation of the image forming apparatus according to the present embodiment will be described. In FIG. 2, the photosensitive member 10 is uniformly charged by the charging roller 20 while being rotated in the direction of the arrow, and then the reflected light from the original is imaged and projected by an optical system (not shown) by the exposure device 30 on the photosensitive member 10. An electrostatic charge image is formed on the surface. The electrostatic charge image is developed by the developing device 40 to form a toner image as a visible image. The developer thin layer on the developing belt 41 is peeled off from the belt 41 in a thin layer state by contact with the photoconductor in the developing region, and moves to a portion where a latent image is formed on the photoconductor 10. The toner image developed by the developing device 40 is transferred to the surface of the intermediate transfer member 50 at the contact portion (primary transfer region) between the photosensitive member 10 and the intermediate transfer member 50 moving at a constant speed (primary transfer). Transcription). When transferring three or four colors to be superimposed, this process is repeated for each color to form a color image on the intermediate transfer member 50.
The corona charger 52 for applying an electric charge to the superimposed toner image on the intermediate transfer member 50 is a contact facing portion between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. And at a position upstream of the contact facing portion between the intermediate transfer member 50 and the transfer paper 100. The corona charger 52 gives the toner image a true charge having the same polarity as the charge polarity of the toner particles forming the toner image, and is sufficient for good transfer to the transfer paper 100. Charge is applied to the toner image. The toner image is charged by the corona charger 52 and then transferred to the transfer paper 100 conveyed in the direction of the arrow from a paper supply unit (not shown) by the transfer bias from the transfer roller 80 (secondary transfer). Transcription). Thereafter, the transfer paper 100 onto which the toner image has been transferred is separated from the photoconductor 10 by a separation device (not shown), and after a fixing process is performed by a fixing device (not shown), the transfer paper 100 is discharged from the device. On the other hand, after the transfer, the untransferred toner is collected and removed by the cleaning device 60, and the residual charge is discharged by the discharging lamp 70 in preparation for the next charging.

As described above, the static friction coefficient of the intermediate transfer member 50 is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member 50 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 hardly remains on the intermediate transfer member. Transfer unevenness 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 all known materials can be used. An example is shown below. (1) A material having a high Young's modulus (tensile modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT ( Polyalkylene terephthalate) blend materials, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend materials, 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- or 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 thereof. 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 width of the belt 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, fluororesin, polycarbonate resin, polyimide resin, and the like have been used for the intermediate transfer belt. However, in recent years, an elastic belt in which the entire belt layer or a part of the belt is used 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 a high hardness and does not deform according to the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely 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. When 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.

Therefore, the elastic belt is used for the following purposes when transferring to the sheet. 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.
The elastic belt resin is polycarbonate, fluororesin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer. Styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene- Octyl acrylate copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (for example, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacrylic acid). Acid phenyl copolymer, etc.), styrene -Styrenic resins (monopolymer or copolymer containing styrene or a styrene-substituted product) such as methyl α-chloroacrylate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, methyl methacrylate resin, methacrylic acid Butyl 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 resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane resin, silica One or a combination of two or more selected from the group consisting of carbon resins, ketone resins, ethylene-ethyl acrylate copolymers, xylene resins and polyvinyl butyral resins, polyamide resins and modified polyphenylene oxide resins can be used. . However, it is a matter of course that the material is not limited to the above materials.

  Elastic rubbers and elastomers include 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 ter Polymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, ricone rubber, fluororubber, polysulfide rubber, polynorbornene rubber, hydrogenated nitrile rubber , Selected from the group consisting of thermoplastic elastomers (for example, polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea, polyester, fluororesin) It is possible to use one kind or two or more kinds of combinations that. However, it is a matter of course that the material is not limited to the above materials.

There are no particular restrictions on the conductive agent for adjusting the resistance value. For example, carbon black, graphite, metal powder such as aluminum and nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite Conductive metal oxides such as oxides (ATO) and indium oxide-tin oxide composite oxides (ITO), and conductive metal oxides are coated with insulating fine particles such as barium sulfate, magnesium silicate and calcium carbonate But you can. Of course, the conductive agent is not limited thereto.
The surface layer material and the surface layer are required to prevent contamination of the photoconductor by the elastic material, reduce the surface friction resistance to the transfer belt surface, reduce the adhesion of the toner, and improve the cleaning property and the secondary transfer property. . For example, materials that use one or a combination of two or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and improve lubricity, such as fluororesin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide, etc. One kind or two or more kinds of powders and particles or a combination of those having different particle diameters can be dispersed and used. Further, it is also possible to use a material having a reduced surface energy by forming a fluorine-rich layer on the surface by heat treatment, such as a fluorine-based rubber material.

(Charging device)
FIG. 4 is a schematic diagram illustrating a configuration of an image forming apparatus using a contact-type charging device. The photosensitive member 140 serving as a member to be charged and an image carrier is rotationally driven in the direction of the arrow at a predetermined speed (process speed). The charging roller 160, which is a charging member brought into contact with the photosensitive drum, is basically composed of a cored bar and a conductive rubber layer formed concentrically and integrally on the outer periphery of the cored bar. In this case, the charging roller 160 is driven by the rotational drive of the photosensitive member 140, and is pressed against the photosensitive drum by a pressing means (not shown). Rotate. The charging roller 160 is formed to have a diameter of 16 mm by coating a medium resistance rubber layer 522 of about 100,000 Ω · cm on a core metal having a diameter of 9 mm.
The core of the charging roller 160 and a power source (not shown) are electrically connected, and a predetermined bias is applied to the charging roller by the power source. As a result, the peripheral surface of the photoreceptor 140 is uniformly charged to a predetermined polarity and potential.

Of course, the charging device used in the present invention is not limited to the contact-type charging device as described above, but may be non-contacting. It is preferable to use an apparatus.
Further, in the image forming apparatus of the present invention, an alternating electric field is applied to the charging device. In a DC (direct current) electric field, a large number of O ₃ ⁻ and NO ₃ ⁻ are formed in order to charge the photosensitive member to a negative polarity. The ozone and nitrogen oxides adhere to the photoreceptor and deteriorate the surface of the photoreceptor. In particular, the surface of the photoconductor is hardened and wear increases, and the coefficient of friction decreases, so that external additives are likely to adhere and filming often occurs. For this reason, by applying an alternating electric field on which AC (alternating current) is superimposed, generation of ozone and the like can be suppressed and the photosensitive member can be charged uniformly. In particular, by using alternating electric fields, deterioration of the photoreceptor due to ozone can be suppressed due to the generation of H ₃ O ⁺ having a reverse polarity.

  The shape of the charging member used in the present invention 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 image forming 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 it, and a magnet roll included therein. In addition, when using a fur brush, for example, as a 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 core metal. By charging or pasting, it becomes a charging device.

(Tandem type color image forming device)
FIG. 5 is a schematic diagram showing the configuration of the tandem color image forming apparatus of the present invention.
As shown in FIG. 5, the tandem type image forming apparatus includes a direct transfer system that sequentially transfers an image on each photoconductor 1 to a sheet s conveyed by a sheet conveying belt 3 by a transfer device 2. As shown in FIG. 6, the images on the respective photoconductors 1 are once sequentially transferred to the intermediate transfer member 4 by the primary transfer device 2, and then the images on the intermediate transfer member 4 are transferred to the sheet s by the secondary transfer device 5. There are indirect transfer systems that perform batch transfer. The transfer device 5 is a transfer conveyance belt, but there is also a roller-shaped method.
Comparing the direct transfer type and the indirect transfer type, the former arranges the sheet feeding device 6 on the upstream side of the tandem 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 conveying 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. There is a drawback that the fixing device 7 tends to affect image formation on the upstream side due to the difference in speed between the sheet conveyance speed when passing through the apparatus 7 and the sheet conveyance speed by the transfer conveyance belt. On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that the sheet s can be bent, so that the fixing device 7 hardly affects the image formation.
Due to the above, recently, an indirect transfer type among tandem type image forming apparatuses has attracted attention. FIG. 6 is a schematic diagram showing the configuration of an image forming apparatus having an intermediate transfer member, which is a tandem color image forming apparatus of the present invention.
In this type of color image forming apparatus, as shown in FIG. 6, the transfer residual toner remaining on the photoconductor 1 after the primary transfer is removed by the photoconductor cleaning device 8 to clean the surface of the photoconductor 1. In preparation for another image formation. Further, the transfer 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 image formation again.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 7 shows an embodiment of the present invention and is a schematic diagram showing the configuration of a tandem indirect transfer type image forming apparatus. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which it is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) further mounted thereon. The copying machine main body 100 is provided with an endless belt-shaped intermediate transfer member 10 at the center.
Then, as shown in FIG. 7, in the illustrated example, it is wound around three support rollers 14, 15, and 16 so as to be able to rotate and convey clockwise in the figure.
In this illustrated example, an intermediate transfer body cleaning device 17 for removing residual toner remaining on the intermediate transfer body 10 after image transfer is provided on the left of the second support roller 15 among the three.
Among the three images, four images of yellow, cyan, magenta, and black are arranged on the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15 along the conveyance direction. The tandem image forming apparatus 20 is configured by arranging the forming units 18 side by side.
An exposure device 21 is further provided on the tandem image forming apparatus 20 as shown in FIG. On the other hand, a secondary transfer device 22 is provided on the side opposite to the tandem image forming apparatus 20 with the intermediate transfer body 10 interposed therebetween. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via the intermediate transfer body 10. The image on the intermediate transfer body 10 is transferred to a sheet.

A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt.
The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveying function together.
In the illustrated example, under such a secondary transfer device 22 and a fixing device 25, a sheet reversing device 28 for reversing the sheet so as to record images on both sides of the sheet in parallel with the tandem image forming device 20 described above. Is provided.

Now, when making a copy using this color image forming apparatus, the document is set on the document table 30 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34 and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.
When a start switch (not shown) is pressed, one of the support rollers 14, 15 and 16 is rotationally driven by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer body 10 is rotated and conveyed. To do. At the same time, the individual image forming means 18 rotates the photoconductors 40 to form black, yellow, magenta, and cyan single color images on the photoconductors 40, respectively. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10.
On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, so Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.

Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer member 10, the sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.
The sheet after the image transfer is conveyed by the secondary transfer device 22 and sent to the fixing device 25, and heat and pressure are applied to the fixing device 25 to fix the transferred image. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.

On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for another image formation.
Here, the resist roller 49 is generally often used is grounded, Ru possible der applying a bias for removing paper dust of the sheet.
In the tandem image forming device 20 above mentioned, each image forming unit 18, more specifically, for example, as shown in FIG. 8, around a drum-shaped photoreceptor 40, the charging device 60, developing device 61,1 transfer A device 62, a photoconductor cleaning device 63, a charge removal device 64, and the like are provided. Has been the sign will be described 65 on the developing sleeve developer according to FIG. 8, the agitating paddle 68, 69 partition plate, 71 is a toner density sensor, 72 a developing sleeve, 73 a doctor, 75 is a cleaning blade, 76 Is a cleaning brush, 77 is a cleaning roller, 78 is a cleaning blade, 79 is a toner discharge auger, and 80 is a driving device.

(Process cartridge)
FIG. 8 is a schematic view showing a configuration of a tandem indirect transfer type image forming apparatus including the process cartridge of the present invention. In FIG. 8, a represents the entire process cartridge, b represents a photosensitive member, c represents a charging unit, d represents a developing unit, and e represents a cleaning unit.
In the present invention, at least the photosensitive member b and the developing unit d are integrally combined as a process cartridge among the above-described components such as the photosensitive member b, the charging device unit c, the developing unit d, and the cleaning unit e. The process cartridge is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

(Development roller)
The construction of the developing roller according to the present invention will be described for the developing roller.
As for the developing roller, there are those having an elastic layer made of rubber or elastomer around the core shaft (11) made of metal and those made of metal, but a metal roller is preferable from the viewpoint of durability. Furthermore, it is composed of a surface layer (13) coated around it. Such a developing roller can be satisfactorily used in, for example, the developing device of the above example or another type of developing device.
As the elastic layer, for example, a known rubber such as ethylene propylene rubber, butadiene rubber, nitrile rubber, styrene rubber, isoprene rubber, silicone rubber, epicrawler hydrin rubber, urethane rubber or foam can be used.
As for the surface layer, the surface layer is formed around these elastic layers by, for example, coating various known coatings such as a dip method, spray coating, roll coating, or a molded product formed into a tube shape. The surface layer of the developing roller in the present invention is a developing roller characterized by containing at least one of guanamine, a guanamine derivative, and a guanamine-based condensate.

In the above general formulas (2) and (3), X ¹ is a hydrogen atom H, an alkyl group such as a methyl group or an aliphatic or aromatic hydrocarbon residue such as a phenyl residue, and X ² , X ³ , X ⁴ and X ⁵ may be the same or different and each represents a hydrogen atom H or a lower alkanol residue such as a methylol group or a butyrol group, or an alkoxyalkyl residue such as a methoxymethyl group or a butoxymethyl group. is there. Moreover, in General formula (3), n shows an integer.
Here, guanamine is a compound in which X ¹ and X ^{2 to} X ⁵ are both hydrogen atoms in the general formula (2). The guanamine-based condensate includes a condensate represented by the above general formula (3), and includes a condensate obtained by condensation of guanamine or a derivative thereof by dehydration and dealcoholization reaction, and a so-called guanamine resin. This guanamine resin includes, for example, acetoguanamine resin, benzoguanamine resin, and the like, and is a general term for resins obtained by reaction of guanamine or its derivatives (guanamines) with formaldehyde and the like. Commercially available materials for resin or paint can be used.
By incorporating these in the surface layer of the developing roller, it is possible to give the toner, which is the object of the above-described invention, an excellent amount of charge that is stable over a long period of time and to prevent generation of ghosts during development. I found it. Furthermore, by causing a crosslinking reaction product of a resin or prepolymer containing a hydroxyl group_hydroxyl group_ at the terminal of the main chain or side chain and at least one of guanamine, a guanamine derivative or a guanamine-based condensate, photoconductor contamination. This is effective in preventing toner tacking.

(Example)
EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, “part” means part by mass, and “%” means mass%.

Hereinafter, a specific method for producing the toner according to the present invention will be described.
<Synthesis of resin fine particle emulsion>
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 80 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate, 12 parts of butyl thioglycolate and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 4 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion was obtained. This is designated as [fine particle dispersion 1]. The volume average particle diameter of the [fine particle dispersion 1] measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corporation) was 100 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The resin content had a Tg of 52 ° C. and a weight average molecular weight of 28,000.

<Preparation of aqueous phase>
990 parts of water, 65 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (ELEMINOL MON-7 manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This is designated [Aqueous Phase 1].

<Synthesis of non-reactive resin>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 6 hours under reduced pressure of 10-15 mmHg, then put 44 parts of trimellitic anhydride into the reaction vessel, and at 180 ° C. under normal pressure. It reacted for 2 hours and obtained polyester of non-reactive resin [A]. The nonreactive resin [A] had a number average molecular weight of 2500, a weight average molecular weight of 7100, a Tg of 46 ° C., and an acid value of 24.

In the method for producing the non-reactive resin [A], the amount of trimellitic anhydride added is changed, and the acid value is adjusted to the following value to adjust the non-reactive resins [B] to [D]. Got.
Here, for the measurement of the acid value, the specified method described in JISK0070 was used. However, if the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used as the solvent. As for the molecular weight measurement (main binder resin) by GPC, the molecular weight of the chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.

Resin adjusted to 0.05-0.6 mass% as sample concentration by stabilizing the column in a heat chamber at 40 ° C., and flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 mL / min. A THF sample solution of 50 to 200 μL is injected and measured.

<Synthesis of intermediate polyester>
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, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.

<Synthesis of Modified Polyester Resin (hereinafter referred to as “Prepolymer 1”) Reactive with a Compound Having at least an Active Hydrogen Group>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 410 parts of the above [intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours. ] Was obtained. [Prepolymer 1] had a free isocyanate mass% of 1.53%.

<Synthesis of ketimine>
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

<Synthesis of master batch>
1200 parts of water, 40 parts of carbon black (manufactured by Cabot, Regal 400R), 60 parts of the non-reactive resin [A], and further 30 parts of water are added and mixed with a Henschel mixer (manufactured by Mitsui Mining). Was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

< Production of oil phase>
In a container equipped with a stir bar and a thermometer, 400 parts of the non-reactive resin [A], 110 parts of carnauba wax, and 947 parts of ethyl acetate are charged, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. After that, it was cooled to 30 ° C. at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Liquid material 1] is transferred to 1324 parts of the reaction container and dispersed using a bead mill (Ultra Visco Mill, manufactured by Imex Co.), liquid feed rate 1 k g / hr, disc circumferential velocity of 6 m / sec, a 0.5mm zirconia beads 80 The wax was dispersed under the conditions of volume% filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of the non-reactive resin [A] and 34 parts of the [inorganic fine particles 1] are added, and one pass is performed with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. It was. The solid content concentration of [Pigment / Wax Dispersion 1] (130 ° C., 30 minutes) was 50%.

<Emulsification>
[Pigment / Wax Dispersion 1] 648 parts, [Prepolymer 1] 154 parts, [Ketimine Compound 1] 8.5 parts in a container, TK homomixer (manufactured by Tokushu Kika) 1 After mixing for 1 minute, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at a rotation speed of 10,000 rpm for 20 minutes to obtain [Emulsion Slurry 1].
That is, it is dispersed in an aqueous medium containing resin fine particles and an elongation reaction is performed.

<Desolvent>
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

<Washing and drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered twice to obtain a cake. . This is referred to as [mother fine particles A]. The acid value of [base fine particle A] was 18.8.

<Surface treatment>
(1): Add 100 parts of ion-exchanged water to the filter cake of [mother fine particles A], and mix with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes).
(2): N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide (product name Aftergent 310 (manufactured by Neos)) is used as 1% aqueous methanol solution. .
(3): The slurry of (1) is adjusted to 2 ° C. by adjusting the temperature, and while maintaining the temperature, a predetermined amount of (2) is added with stirring, and stirring is performed for 60 minutes.
(4): The product was separated by filtration, and the resulting cake was dried under reduced pressure at 40 ° C. for 24 hours to obtain toner base particles.

<External additive treatment>
A mixture of hydrophobic silica RX-200 (manufactured by Nippon Aerosil Co., Ltd.) 1.5 parts to 100 parts of the toner base particles obtained as described above in a Henschel mixer to obtain a toner 1].

(Example 2)
[Toner 2] was obtained in the same manner as [Toner 1] except that in [Surface Treatment], the slurry temperature of [Base Particle A] was changed to 15 ° C.

(Example 3)
In [Surface Treatment], [Toner 3] was obtained in the same manner as [Toner 1] except that the slurry temperature of [Base Particle A] was changed to 25 ° C.

Example 4
In [Surface Treatment], [Toner 4] was obtained in the same manner as [Toner 1] except that the slurry temperature of [Base Particle A] was changed to 40 ° C.

(Example 5)
In <Surface Treatment>, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide (product name: Footgent 310 (manufactured by Neos)) 1% aqueous methanol solution [Toner 5] was obtained in the same manner as [Toner 2] except that the content was changed to 5%.

(Example 6)
In <Surface Treatment>, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide (product name: Footgent 310 (manufactured by Neos)) 1% aqueous methanol solution “Toner 6” was obtained in the same manner as “Toner 4” except that the content was changed to 5%.

(Example 7)
In <Surface Treatment>, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide (product name: Footgent 310 (manufactured by Neos)) 1% aqueous methanol solution [Toner 7] was obtained in the same manner as [Toner 2] except that the content was changed to 0.3%.

(Example 8)
In <Surface Treatment>, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide (product name: Footgent 310 (manufactured by Neos)) was added to 1% aqueous methanol solution. [Toner 8] was obtained in the same manner as [Toner 1] except that the slurry stirring time of [Mother fine particles A] after addition was 6 minutes.

Example 9
In <Surface Treatment>, N, N, N-trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide (product name: Footgent 310 (manufactured by Neos)) was added to 1% aqueous methanol solution. [Toner 9] was obtained in the same manner as [Toner 1] except that the slurry stirring time of [Mother fine particles A] after addition was 30 (0.5) hours.

(Toner 10)
<Kneading and grinding method>
<Synthesis of linear polyester resin>
As a polycondensation catalyst, 320 parts of bisphenol A / EO2 molar adduct, 480 parts of bisphenol A / EO2 molar adduct, 200 parts of terephthalic acid, 65 parts of phthalic acid and a polycondensation catalyst. 2 parts of potassium titanyl oxalate was added and reacted at 225 ° C. for 10 hours while distilling off the water generated under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and after cooling to room temperature, it grind | pulverized and the linear polyester resin M-1 was obtained. Resin M-1 did not contain THF-insoluble matter, and had an acid value of 14, a hydroxyl value of 40, a Tg of 59 ° C., a number average molecular weight of 5100, a weight average molecular weight of 22000, and a peak top molecular weight of 4400. It was.

< Preparation of master batch>
Using the linear polyester resin M-1, a pigment, a polyester resin, and pure water were mixed at a ratio of 1: 1: 0.5 and kneaded by two rolls. Kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water and prepare a master batch in advance.
Vine Da resins M-1: 100 parts of black pigment (carbon black) 100 parts Pure water: 50 parts

<Synthesis of non-linear polyester resin>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introducing tank, 400 parts of bisphenol A · EO 2 mol adduct, 269 parts of bisphenol A · P03 mol adduct, 50 parts trimellitic acid, 278 parts terephthalic acid, 40 phthalic anhydride parts and input is the 2 parts of potassium titanyl oxalate as a polycondensation catalyst, water was distilled off to produce a stream of nitrogen while the reaction 10 hours at 2 30 ° C.. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg. When the acid value becomes 10 or less, the mixture is cooled to 180 ° C., 6 parts of trimellitic anhydride is added, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. To obtain a non-linear polyester resin H-1.
Resin H-1 contains 5% of THF-insoluble matter, its acid value is 13, hydroxyl value is 67, Tg is 70 ° C., number average molecular weight is 9600, weight average molecular weight is 45000, peak top molecular weight is 11000. there were.
Polyester resin M-1: 10 parts Polyester resin H-1: 90 parts Masterbatch: 20 parts Ester wax: 3 parts (acid value: 5 mg KOH / g, Mw: 1600, particle size: 120 μm)
As the same as the formulation described above were preliminarily mixed using Hensherumiki Sir Mitsui Miike Machinery Co., Ltd. FM10B] to the material, the kneaded product in a twin-screw kneader [Corporation Ikegai Ltd. PCM-30] The kneading was performed at a temperature of 120 ° C. After that it was finely pulverized using a supersonic jet pulverizer lab jet [Nippon Pneumatic Mfg. Co., Ltd.] in the next doctor, classified to the volume average particle size in the air classifier [Nippon Pneumatic Mfg. Co., Ltd., MDS-I] Toner base particles F of 6.8 μm were obtained.
Next Ide, after the toner mother particles F dispersed in an aqueous medium with ion exchange water, wetted sufficiently toner mother particles F stirred for 1 hour. Thereafter, filtration was performed to obtain a filter cake of toner base particles. After that, do the processing of <Surface Treatment> later the same way of the toner 2, to obtain [toner 10].

(Toner 11)
< Production of oil phase>, <Emulsification>, <Desolvation>, <Washing / drying in the same manner as in Example 1 except that [Nonreactive resin A] was changed to [Nonreactive resin C]. Was performed to obtain [Mother fine particles C]. The acid value of [base fine particle C] was 5.2.
Further, the <surface treatment> of [base fine particles C] was performed under the same conditions as in the toner 2, and the subsequent external additive treatment was performed in the same manner as in Example 1 to obtain the toner 11.

(Toner 12)
< Production of oil phase>, <Emulsification>, <Desolvation>, <Washing / drying in the same manner as in Example 1 except that [Nonreactive resin A] was changed to [Nonreactive resin B]. Was performed to obtain [Mother fine particles B]. The acid value of [base fine particle B] was 10.5.
Further, the <surface treatment> of [base fine particles B] was performed under the same conditions as in Example 2, and the subsequent external additive treatment was performed in the same manner as in toner 1 to obtain toner 12.

(Toner 13)
< Production of oil phase>, <Emulsification>, <Desolvation>, <Washing / drying in the same manner as in Example 1 except that [Nonreactive resin A] was changed to [Nonreactive resin D]. > To obtain [Mother fine particles D]. The acid value of [base fine particle D] was 1.5.
Further, the <surface treatment> of [base fine particles D] was performed under the same conditions as in Example 2, and the subsequent external additive treatment was performed in the same manner as in Example 1 to obtain Toner 13.

(Toner 14)
A toner 14 was obtained in the same manner as the toner 2 except that the following points were changed.
<Surface treatment>
(1): Add 100 parts of ion-exchanged water to the filter cake of [mother fine particles A], and mix with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes).
(2): Bontron E-84 (manufactured by Clariant) is used as a 1% aqueous methanol solution.
(3): The slurry of (1) is adjusted to 2 ° C. by adjusting the temperature, and while maintaining the temperature, a predetermined amount of (2) is added with stirring, and stirring is performed for 60 minutes.
(4): The product was separated by filtration, and the resulting cake was dried under reduced pressure at 40 ° C. for 24 hours to obtain toner base particles.

(Toner 15)
A toner 15 was obtained in the same manner as the toner 2 except that the following points were changed.
<Surface treatment>
(1): Add 100 parts of ion-exchanged water to the filter cake of [mother fine particles A], and mix with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes).
(2): Bontron E-84 (manufactured by Clariant) is used as a 1% aqueous methanol solution.
(3): The slurry of (1) is adjusted to 2 ° C. by adjusting the temperature, and while maintaining the temperature, a predetermined amount of (2) is added with stirring, and stirring is performed for 60 minutes.
(4): The product was separated by filtration, and the resulting cake was dried under reduced pressure at 40 ° C. for 24 hours to obtain toner base particles.

(Toner 16)
A toner 16 was obtained in the same manner as the toner 1 except that the following points were changed.
<Surface treatment>
[Base particles A] 100 parts and 3 parts of a fluorine-containing quaternary ammonium salt compound represented by the structural formula (1) were surface-implanted with a hybridizer to obtain toner base particles.

Table 11 shows the volume average particle diameter (Dv) of toners 1 to 16 and [mother fine particles A] to [mother fine particles F], and the ratio of this to the number average particle diameter (Dn).

[Example of developing roller]
[Developing roller A]
The outer diameter of the φ20 mm SUS core shaft was ground, and then a surface layer having the following composition was formed by spray coating, followed by baking at 150 ° C. for 1 hour.
70 parts by mass of acrylic resin 30 parts by mass of benzoguanamine

[Developing roller B]
The outer diameter of the φ20 mm SUS core shaft was ground, a surface layer having the following composition was formed by spray coating, and firing was performed at 150 ° C. for 1 hour.
Cross-linked acrylic polyol 70 parts by weight Polyisocyanate 30 parts by weight

(Evaluation methods)
An IPSIO COLOR6000 modified machine was made and implemented.
(Ground cover)
After 30,000 sheets carried by evaluator causes locked stop during replacement following blank developing sheet passing of the cartridge, the self dirt content on the photoreceptor is transferred to a tape, 0.03 or more was measured ID is shaped dirt dangerous If the area is 0.05 or more, it becomes a level of background contamination.
(Development ghost)
After performing 30,000 sheets with an evaluator, the image is output after the cartridge is replaced, and the density difference between the ghost occurrence part and the non-occurrence part is less than 0.1, and the density difference is 0.1 to 0.15 Those having a density difference of 0.2 or more were marked with ×.
(Fixability)
The fixing roller surface temperature was changed from 120 to 220 ° C. to output a solid image, the toner on the image was transferred to a tape, and the degree of contamination of the tape was evaluated in four stages. The temperature at which the smudge of the tape was below the standard was defined as the minimum fixing temperature, the temperature at which image gloss began to decrease due to hot offset was defined as the maximum fixing temperature, and the difference was defined as the fixing property.
If the temperature range was 50 ° C. or higher, “◯” was set, and “35” to 35-50 were set as “Δ”, and 30 ° or lower were set as “X”.
(Filming)
Judgment was made based on the degree of soiling between the developing sleeve and the photoreceptor after passing 30,000 sheets. “◯” indicates no stain, “Δ” indicates that there is a stain but does not affect the image or chargeability, and “X” indicates that the image is affected.

  In addition, generation | occurrence | production of background dirt and filming was recognized when things other than the surface treating agent shown by Structural formula (1) were used. Further, when the surface treatment agent was not treated in an aqueous medium but by driving, filming was observed and the fixability was poor.

FIG. 3 is a diagram schematically illustrating the shape of a toner according to the present invention. 1 is a schematic diagram illustrating a configuration of an image forming apparatus of the present invention. 1 is a schematic diagram illustrating a configuration of an image forming apparatus of the present invention. 1 is a schematic diagram illustrating a configuration of an image forming apparatus using a contact-type charging device. 1 is a schematic diagram showing a configuration of a tandem color image forming apparatus of the present invention. 1 is a schematic diagram illustrating a configuration of an image forming apparatus having an intermediate transfer member, which is a tandem color image forming apparatus of the present invention. 1 is a schematic diagram illustrating a configuration of an image forming apparatus of a tandem type indirect transfer system according to the present invention. 1 is a schematic diagram illustrating a configuration of a tandem indirect transfer type image forming apparatus including a process cartridge of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Intermediate transfer body 14, 15, 16 Support roller 17 Intermediate transfer body cleaning apparatus 18 Image forming means 20 Tandem image forming part 21 Exposure apparatus 22 Secondary transfer apparatus (transfer roller)
23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt (fixing film)
27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Photoconductor 41 Developing belt 42 Paper feed roller 43 Paper bank 44 Paper feed cassette 45 Separating roller 46, 48 Feeding path 47 Conveying roller 49 Registration roller 50 Feeding roller 51 Manual feed tray 52 Separating roller 53 Manual feed path 55 Switching claw 56 Ejecting roller 57 Ejecting tray 60 Charging device 60a Charging roller 60b Brush roller 60c Core metal 60d Conductive rubber Layer 60e Brush portion 60f Power supply 61 Developing device 62 Primary transfer device 63 Cleaning device 64 Static elimination device (static elimination lamp)
DESCRIPTION OF SYMBOLS 100 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder

Claims (14)

A developing roller and a regulating member that uniformly regulates the layer thickness of the developer supplied onto the developing roller are provided, and the surface of the image carrier is brought into contact with or close to the image carrier on which the electrostatic latent image is formed while rotating. In a non-magnetic one-component development method for visualizing the electrostatic latent image by supplying toner,
The toner is
At least a binder resin, a releasing agent, a colorant, a toner composition Monohaha microparticles acid value from 10 to 18.8 is dispersed in an aqueous medium papermaking work, in the aqueous medium, 10 to 30 ° C. In the range of, obtained through a surface treatment step of treating the surface of the mother fine particles with a fluorine-containing quaternary ammonium salt compound,
And a toner having an external additive on the outermost surface ,
The surface layer before Symbol developing roller periphery and regulating member, guanamine, guanamine derivatives, non-magnetic one-component developing method which is characterized by containing at least one of guanamine condensate. The nonmagnetic one-component developing method according to claim 1,
The fluorine-containing quaternary ammonium salt compound is a compound represented by the following formula (1)

(In the formula, X, Y, R ^{1 to} R ⁴ , r and s each represent the following: X: —SO ₂ — or —CO—, R ¹ , R ² , R ³ , R ⁴ : hydrogen Atom, lower alkyl group or aryl group having 1 to 10 carbon atoms, Y: I or Br, r, s: integer of 1-20.)
And a non-magnetic one-component developing method. The non-magnetic one-component developing method according to claim 1 or 2,
The nonmagnetic one-component developing method, wherein the surface treatment time in the surface treatment step is 0.1 to 24 hours . In the nonmagnetic one-component developing method according to any one of claims 1 to 3,
A nonmagnetic one-component developing method, wherein the toner has a glass transition point in the range of 45 to 60 ° C. In the nonmagnetic one-component developing method according to any one of claims 1 to 4,
The non-magnetic one-component developing method , wherein the surface treatment step proceeds with a chemical bonding reaction by salt exchange . In the nonmagnetic one-component developing method according to any one of claims 1 to 5,
The nonmagnetic one-component developing method , wherein the addition amount of the fluorine-containing quaternary ammonium salt compound is 0.03 to 5 parts by mass with respect to 100 parts by mass of the toner composition . The non-magnetic one-component developing method according to claim 6 ,
The non-magnetic one-component developing method, wherein the addition amount of the fluorine-containing quaternary ammonium salt compound is 0.03 to 2 parts by mass with respect to 100 parts by mass of the toner composition. In the nonmagnetic one-component developing method according to any one of claims 1 to 7 ,
In an aqueous medium containing resin fine particles, a toner composition in which the toner has at least a polymer, polyester, and colorant each having a site capable of reacting with a compound having an active hydrogen group dissolved or dispersed in an organic medium. A non-magnetic one-component developing method, which is obtained by crosslinking and / or elongation reaction . The non-magnetic one-component developing method according to claim 8 ,
The non-magnetic one-component developing method , wherein the resin fine particles have an acid functional group . The nonmagnetic one-component developing method according to any one of claims 1 to 9 ,
The toner has a volume average particle diameter of 3 to 8 μm,
A nonmagnetic one-component developing method, wherein the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.0 to 1.40 . In the nonmagnetic one-component developing method according to any one of claims 1 to 10,
The non-magnetic one-component developing method, wherein the toner has an average circularity of 0.930 to 0.975 . The nonmagnetic one-component developing method according to any one of claims 1 to 11,
A non-magnetic one-component development method characterized by having a structure for quantitatively supplying toner . The nonmagnetic one-component developing method according to any one of claims 1 to 12,
Condensation cross-linked product comprising at least one of a resin or prepolymer having a hydroxyl group at the main chain or side chain terminal and guanamine, a guanamine derivative, or a guanamine-based condensate on the outer periphery of the developing roller and the surface layer of the regulating member A non-magnetic one-component developing method characterized by using a developing roller containing It uses for the nonmagnetic one-component developing method as described in any one of Claims 1 thru | or 13.
A developing device.

Images