JP6525674B2 - Image formation method - Google Patents

Description

The present invention relates to a toner used by adhering toner to the latent image formed on an image bearing member copier such as an electrophotographic method or an electrostatic recording method to visualize the image forming apparatus of a printer over such is there.

  Recently, demands for smaller size, lighter weight, high reliability, and the like have been intensified in copiers and printers, and the demand for performance has also become severe.

  For example, electrophotographic technology used for copiers, printers, facsimile receivers, etc. has been increasingly demanded by users with the development of the devices. In recent trends, it has been strongly demanded to provide stable image quality independent of the environment, because printing on a large number of sheets is possible and that the environment used by the expansion of the market has expanded. .

  In order to satisfy the above requirements, toners having high durability and high image quality are required more than ever, and many improvements have been made to solve the above-mentioned problems. For example, an invention is disclosed in which the coefficient of friction of a photoconductor provided with brush cleaning is defined (for example, Patent Document 1). Also, an invention in which the friction coefficient of toner is defined is disclosed (for example, Patent Document 2). Furthermore, the invention which specified the friction coefficient of the toner, the regulation means, and the carrier is disclosed (for example, Patent Document 3).

Certainly, by defining various friction coefficients in this manner, it has become possible to obtain constant high durability and high image quality stability in one process of image formation. However, the situation still Ru have a need to improve the properties is performed a large number printing in a more severe environment.

  In addition, there is a need for a balanced image forming method that is not harmful to one step or the entire step.

JP 2004-233612 A JP 2004-258625 A Unexamined-Japanese-Patent No. 2000-275964

In view of the above circumstances, an object of high-speed, high image quality, to provide an image forming method to satisfy the high durability 及 beauty high environmental stability.

The above object is achieved by the present invention described below.
That is, carrying the toner to the toner carrying member for developing the electrostatic latent image on the image bearing member, and conveyed to an image forming method for regulating the toner by a toner regulating member,
The image forming method
The toner over regulating member, and,
It has a toner regulating process by the toner regulating means for have a tree fat material laminated on the surface of the toner regulating member,
The volume resistivity B of the resin material is 4.9 × 10 ^{6 to} 8.6 × 10 ⁸ Ωcm,
Relationship between the volume resistivity B of the volume resistivity A and RESIN material of the toner, satisfy the ^{5.2 × 10 4 ≦ A / B} ≦ 4.1 × 10 8,
The dynamic friction coefficient μd of the toner carrier is 0.47 to 0.74 ,
Dynamic friction coefficient μb surface of RESIN material is a 0.16 to 0.21,
The difference (μd− μb ) between the dynamic friction coefficient μd and the dynamic friction coefficient μb is 0.28 to 0.55,
The toner comprises toner particles and a hydrophobized external additive,
The addition amount of the hydrophobizing processing external additive is 1.50 to 2.10 parts by mass relative to the toner particles 100 parts by weight,
The average circularity measured by the flow type particle image measuring device of the toner is 0.961 to 0.991 ,
Dynamic friction coefficient μt surface that the toner over to pellets is a 0.09 to 0.18,
The difference between the animal friction coefficient .mu.b and animals friction coefficient μt (μb-μt) is, the present invention is achieved by a 0 to 0.1.

  According to the present invention, it is possible to obtain an image forming method which is excellent in fixing ability in a printer with high speed.

  Furthermore, according to the present invention, it is possible to obtain an image forming method which is excellent in developability in a high-speed printer.

FIG. 2 is a cross-sectional view of a developing device used in the image forming apparatus of the present invention. FIG. 1 is a cross-sectional view of an image forming apparatus of the present invention. It is structure explanatory drawing of the apparatus used for the measurement of this invention. It is structure explanatory drawing of another apparatus used for the measurement of this invention.

The present invention is an image forming method in which a toner is carried on a toner carrier and conveyed in order to develop an electrostatic latent image on an image carrier, and the toner is regulated by a toner regulating member. Then, a toner regulating process by the toner regulating means volume resistivity laminated on the surface of the toner over regulating member had a resin material ^{10 5} ~ 10 10 Ωcm, the volume resistivity value A and the toner of the toner The relationship of the volume resistivity B of the resin material laminated on the regulation means is 10 ⁴ ≦ A / B ≦ 10 ⁹ , and the toner carrier has a dynamic friction coefficient μd of 0.45 to 0.80, and it is on the toner regulation means The coefficient of dynamic friction μb of the resin material surface laminated on the surface is 0.13 to 0.22, and the difference (μd−μb) is 0.25 to 0.60, and the toner contains toner particles and a hydrophobized external additive. The addition amount of the hydrophobized external additive is 1.4 parts by mass or more with respect to 100 parts by mass of the toner particles, and the average circularity measured by the flow type particle image measuring device of the toner is 0.960 to 0. 995, the toner (on the surface of the toner pelletized) The friction coefficient μt is 0.03 to 0.19, and the difference (μb−μt) between the dynamic friction coefficient μb of the resin material surface laminated on the toner regulation means and the toner dynamic friction coefficient μt is 0 to 0.20. It features.

  The present invention is a developing configuration in which the coefficient of friction in the developing step has an appropriate width and the volume resistance value is appropriate. Specifically, it will be described in detail below.

In the present invention, it is first necessary to volume resistivity laminated on the surface of the toner over restricting member has a resin material ^{10 5} ~ 10 10 Ωcm. Furthermore, it is necessary that the relationship between the volume resistivity B of the resin material laminated on a volume resistance value A and the toner regulating means of the toner is ^{10 4 ≦ A / B ≦ 10} 9. Within this range, charges are efficiently injected when applying charges to the blade, which tends to produce an effect, and image defects due to excessive charge accumulation (charge up) on the toner hardly occur.

If the volume resistance value is less than 10 ⁵ Ω cm, charges are efficiently injected when applying charges to the blade and it is easy to exert the effect, and image defects due to excessive charge accumulation (charge up) on toner are unlikely to occur. It is easy to place charge discharge (leakage) from the toner, and the charge amount is reduced, and the phenomenon of fogging on the white background portion tends to occur.

When the volume resistivity value conversely exceeds 10 ¹⁰ [Omega] cm, or difficult out Dzu Raku effect injected charges in case of applying the charge to the blade, image defect tends to occur due to the extra charge accumulation in the toner (charge-up) .

In the present invention, the dynamic friction coefficient μd of the toner carrier is 0.45 to 0.80, and the dynamic friction coefficient μb of the surface of the resin material laminated on the toner regulating means is 0.13 to 0.22, It is necessary that the difference (.mu.d-.mu.b) be 0.25 to 0.60.

The dynamic friction coefficient μd of the toner carrier exceeds 0.80, the dynamic friction coefficient μb of the surface of the resin material laminated on the toner regulating means is less than 0.13, and the difference (μd−μb) exceeds 0.60 When the toner and carrier, the toner and the difference in friction regulating means toner will remain on the toner carrying member too large, it becomes impossible to friction 及 beauty basis weight regulation between the regulating means.

Conversely, if the dynamic friction coefficient μd of the toner carrier is less than 0.45, the dynamic friction coefficient μb of the surface of the resin material laminated on the toner regulation means exceeds 0.22 and the difference (μd−μb) is less than 0.25 If this is the case, the difference in friction between the toner and the carrier and between the toner and the regulating means is too small to place the toner on the toner carrier, making it difficult to charge the regulating means, and as a result it becomes impossible to regulate the basis weight.

In the present invention, the dynamic friction coefficient μt of the toner (on the surface of the toner pelletized) is 0.03 to 0.19, the dynamic friction coefficient μb of the surface of the resin material laminated on the toner regulation means and the dynamic friction coefficient μt of the toner It is necessary that the difference (.mu.b-.mu.t) be between 0 and 0.20.

  In the development process, the stress applied to the toner is not determined solely by the process conditions (regulating means pressure and nip width) of the development process. The toner design, the toner control means design and the toner carrier design, especially the frictional force between the toner and the control means, is considered to be important, and the control of this friction is important.

  When the dynamic friction coefficient μt of the toner (surface on which the toner is pelletized) exceeds 0.19, the friction coefficient of the toner itself is high and the stress to various members is high. In particular, the toner is fixed on the toner regulating means, and the toner is rubbed against the opposite toner carrier, so that streak-like fusion occurs on the carrier and the uniformity of the image tends to be deteriorated. When the coefficient of friction μt is less than 0.03, the stress of the toner is reduced, but the contact area with the high temperature environment is large and the adhesion with the toner and external additive is increased and the image is easily stored. Are concerned. In addition, since the friction between the toner and the toner carrier or the latent image carrier is too low, color misregistration or scattering easily occurs.

When the difference (μb−μt) between the dynamic friction coefficient μb of the surface of the resin material laminated on the toner regulation means and the toner dynamic friction coefficient μt exceeds 0.20, the friction factor of the regulation means is high, and the friction between toner and resin This is the case when the coefficient difference becomes large. Due to the high coefficient of friction of the toner regulation member , the toner on the toner carrier receives stress, and the toner is rubbed against the opposite toner carrier, and streak-like fusion occurs on the toner carrier, resulting in an image. Uniformity tends to deteriorate. Further, since the control force is strong, the toner may not be placed on the carrier after printing a large number of sheets. If the difference (.mu.b-.mu.t) is less than 0, the friction coefficient of the toner is higher than the friction coefficient of the regulating means, and charging of the toner by the regulating means tends to be insufficient, causing a transfer failure or fogging. It is easy to cause bad effects such as images. Further, the toner basis weight may not be sufficiently regulated, and white spots may occur.

The blade member used for the toner regulating blade is made of a film mainly composed of a resin or an elastomer formed on a support member having a contact support surface for supporting a contact surface with the toner carrier. The support member is covered at least from the contact support surface to the tip end surface. By coating is formed by coating over the distal end surface of the contact supporting surface not only the contact supporting surface of the support member, to ensure a constant toner uptake opening between the toner carrying member, the toner carrying member The amount of toner on the top can be made proper and uniform. Furthermore, the film includes an angle (edge) at which the contact support surface and the tip surface intersect, and having no inflection point makes it easy to take in the toner , and a toner film with a uniform film thickness is formed on the toner carrier. It is preferable because it can be formed.

The support member used for the toner control member of the present invention is not particularly limited as long as it has a strength capable of supporting the toner control member. Such a supporting member is fixed to, for example, the opening edge of the developing container, and the toner regulating member places a desired pressing force F on the toner carrier disposed at the opening of the developing container with the tangent to the opening edge as a fulcrum (line). It is preferable to support the toner regulating member so as to hold and contact it. Such a configuration makes it easy to charge the toner uniformly with the toner carrier.

The material of the support member, the metal may be either a resin, specifically, stainless steel, or phosphor bronze, etc. aluminum metal, polyethylene terephthalate, include acrylic, polyethylene, a resin such as polyester Can. The support member preferably has a desired conductivity so as to function as an electrode of the toner regulating member, and in the case of a resin, preferably contains a conductive agent.

  The shape of the supporting member may be any shape as long as the toner regulating member can be brought into contact with the toner carrier with a desired pressure, but it may be flat or curved. Is preferred.

  The toner regulating member is made of a conductive molded body molded of resin or elastomer, and the molded body is attached to one end of the support member and abuts on the toner carrier over the entire length in the longitudinal direction. The material of the molded body is selected from resin or elastomer. When the resin or elastomer is not sufficiently conductive as a blade member, it is preferable to make the resin or elastomer contain a conductive agent.

  As a resin or elastomer used for the said molded-body material, as a thing preferable to use with a electrically conductive agent, the following can be mentioned, for example. Polyester, polyester elastomer, polyethylene terephthalate, polyurethane, silicone rubber, silicone resin, polyamide, polyamide elastomer, melamine resin etc.

  Further, as the resin or elastomer used for the molded body material, for example, polypyrrole, polythiophene, polyaniline and the like can be mentioned as the resin or elastomer having conductivity as a toner regulating member and making the use of the conductive agent unnecessary.

  The above resins or elastomers can be used in combination of two or more, regardless of the conductivity.

  When any of polypyrrole, polythiophene and polyaniline is used as the above resin or elastomer, containing 50 parts by mass or more of the resin or elastomer as a whole imparts good conductivity to the molded body. Can be preferred.

  As the conductive agent to be contained in the above-mentioned resin or elastomer, either an electron conductive system or an ion conductive system can be used. Specifically, carbon black, graphite, metal oxides such as conductive titanium oxide, metal powder and the like can be mentioned as the electron conductive system conductive agent. Examples of ion conductive conductive agents include cationic surfactants such as lauryl trimethyl ammonium chloride, zwitterionic surfactants such as lauryl betaine, quaternary ammonium salts such as tetraethylammonium perchlorate, lithium perchlorate, and imides. Organic acid lithium salts such as sulfonates such as lithium salts, organic boron complex lithium salts and the like can be mentioned. These may be used alone or in combination of two or more.

The amount of the conductive agent used can be adjusted so that the molded body has a volume resistivity of 10 ⁵ Ω or more and 10 ¹⁰ Ω or less, more preferably 10 ⁶ Ω or more and 10 ⁹ Ω or less. If the volume resistance value of the molded body is 10 ¹⁰ Ω or less, it is possible to give an appropriate charge to the toner, and it is possible to reduce the occurrence of image defects such as unevenness and fogging. The amount of the conductive agent used is preferably selected in accordance with the type of resin or elastomer used or the conductive agent.

  Here, the volume resistance value of a molded object can employ | adopt the measured value by the measuring method according to JISK6911.

<Toner 及 beauty external additive volume resistivity measurement method>
The volume resistivity of the toner was measured by the following method.

That is, after tap-filling 0.3 to 1.0 g of a conductive material in a cylinder having a lower electrode of 5 mm in diameter, the upper electrode of 15 mm in diameter was placed and measured under a load of 350 g (3.43 N) It is a thing. At this time, the thickness of the sample was measured, and then the applied voltage was swept at intervals of 0 V to 100 V. The electric field was calculated from the resistance value of the sample to be measured, the sample thickness, and the applied voltage, and the volume resistance value at 1 × 10 ⁴ V / cm was determined. An apparatus used to measure the volume resistance is shown in FIG.

In FIG. 3, 21 indicates a lower electrode, 22 indicates an upper electrode, 24 indicates an ammeter, 25 indicates a constant voltage device, 27 indicates a measurement sample, 28 indicates a guide ring, d indicates measurement The thickness of a sample is shown, and A shows a volume resistance measurement cell. The cell A was filled with a sample, the electrodes 21 and 22 were disposed in contact with the filled sample 27, voltage was applied between the electrodes, and the current flowing at that time was measured by an ammeter 24. As the measurement conditions, an environment of 23 ° C. and 65%, and a sample thickness of 0.5 to 1.0 mm were performed.

<Method of measuring volume resistance of members>
In the present invention, for example, a volume resistivity measurement apparatus - at (fuse over Rettopakka de Co. 4140BpA MATER), can be measured at 23 ° C., 65% of the environment.

  The addition amount of the hydrophobized external additive is preferably 1.4 parts by mass or more with respect to 100 parts by mass of the toner particles. If the amount is less than 1.4 parts by mass, the effects of the present invention may be difficult to obtain.

In the present invention, it is preferable that the above-described effects be enhanced as the average circularity measured by the flow type particle image measuring device for toner is 0.960 to 0.995.

  If it is less than 0.960, the transfer residue of the toner tends to be large, and the filming of the toner to the intermediate transfer member tends to occur, and the charging roller contamination and the fusion in the cleaning portion may occur. If it exceeds 0.995, the degree of circularity is too high, and there is no problem in the endurance test in a normal environment, but the external additive on the toner is deteriorated and the image defect is caused in the durability that exceeds 20,000 sheets in a high temperature environment. It may happen.

<Method of measuring average circularity of toner>
The average circularity of the toner is measured using a flow type particle image measuring apparatus "FPIA-2100" (manufactured by Sysmex Corporation). The details are as follows.

Also not a, is calculated by the following formula circularity.
Circularity = (perimeter of circle with same area as particle projected area) / (peripheral length of particle projected image)

  Here, "particle projected area" is the area of the binarized particle image, and "peripheral length of the particle projected image" is the length of the outline obtained by connecting the edge points of the particle image. . The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (0.3 μm × 0.3 μm pixels).

  The degree of circularity in the present invention is an index showing the degree of asperity of the particles, and it shows 1.00 when the particles are completely spherical, and the degree of circularity becomes a smaller value as the surface shape becomes more complicated.

  Further, an average circularity C, which means an average value of circularity frequency distribution, is calculated from the following equation, assuming that the circularity at the dividing point i of the particle size distribution is ci and the number of measured particles is m.

  The specific measurement method is as follows. First, about 10 ml of ion exchanged water from which impure solids and the like have been removed in advance is placed in a glass container. Among them, “contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning consisting of organic builders as a dispersing agent, Wako Pure Chemical Industries, Ltd. Add about 0.1 ml of a diluted solution of about 3 times by volume diluted with deionized water. Furthermore, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 5 minutes using an ultrasonic dispersion device to obtain a dispersion for measurement. As a means to disperse | distribute, the ultrasonic dispersion machine UM-50 made from SMT Co., Ltd. (a vibrator | oscillator is a titanium alloy tip of 5 (phi)) was used. In addition, in order to suppress the variation in the degree of circularity, the installation environment of the flow type particle image analyzer FPIA-2100 is controlled to 23 ° C ± 0.5 ° C so that the temperature inside the machine becomes 26 to 27 ° C. In addition, automatic focusing is performed at regular intervals, preferably using the following standard latex particles of 2 μm every two hours (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific Co., Ltd. is diluted with ion exchange water ).

The above-mentioned flow type particle image measuring device was used for measuring the circularity of toner particles, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as a sheath liquid. The dispersion adjusted according to the above procedure is introduced into the flow type particle image analyzer, and the concentration of the dispersion is readjusted and measured so that the concentration of toner particles at the time of measurement becomes about 5000 particles / μl. After measurement, using this data, the average circularity of toner in the range of equivalent circle diameter 2.00 μm or more and less than 40.02 μm is determined. The equivalent circle diameter is a value calculated as follows.
Circle equivalent diameter = (particle projected area / π) ^1/2 × 2

  The “FPIA-2100”, which is a measuring device used in the present invention, has a thinner sheath flow (7 μm → 4 μm) as compared to the “FPIA-1000” that was conventionally used to observe the shape of toner. And the magnification of the processed particle image is improved. In addition, the processing resolution of the captured image is improved (256 × 256 → 512 × 512), and the accuracy of the shape measurement of the toner is improved.

<Toner regulating member, the measuring method of the toner carrier 及 beauty friction factor of the toner>
The friction coefficient A of the intermediate transfer member and the toner is measured by using a sample moving device of a surface measuring apparatus HEIDON-14DR manufactured by Shinto Scientific Co., Ltd. Pin diameter 10mm alumina spherical pin (defined by ASTM D-1894) sample, so that the moving measuring the same direction of the terminal, further, the measurement surface is fixed to be horizontal. At the time of measurement, a load can be applied by placing a weight W of any weight on the tray.

  With the weight W not placed, adjust the weight and mounting position of the balancer weight so that the support bar becomes horizontal.

  The weight W of 500 g is placed on the tray, the photosensitive member 1 and the intermediate transfer belt sample S are brought into contact with each other, and the supporting rod 206 is adjusted horizontally by adjusting the fulcrum 207. Adjust the height of the load cell and connect with the support bar.

  As measurement conditions, 50 mm / min. Make a measurement of 100 mm at a speed of

  The coefficient of friction A is calculated from the force F [N] measured by the load cell and 0.98 [N] which is the measured load. The lowest value between 100 mm measurements is used as the measurement value.

The formula is shown below.
(Coefficient of friction A) = F / 0.98

  The measurement atmosphere is set to 23 ± 1 ° C., 60 ± 5% Rh, and the measurement sample is left in the same atmosphere for at least 8 hours in advance.

  In the toner of the present invention, although it is not an essential requirement, the effects described above are enhanced when various items described below are achieved, and various other properties are exhibited, which is preferable.

First, the toner of the present invention, it is preferable torque measured under pressure (2.0 kPa) using a circular flat plate of the toner is 10 ~ 20mNm.

The torque measured under pressure (2.0 kPa) using a circular flat plate of toner mimics the situation where the toner regulating member is pressed against the toner carrier and regulates the toner basis weight in the nonmagnetic one-component development method. ing. When this value is 10 to 20 mNm, it is possible to reduce the stress on the toner and make the charge amount appropriate.

  If the torque is smaller than 10 mNm, it is difficult to control the toner basis weight, so that the toner may be blown out and scattered to contaminate the inside of the main body. On the other hand, when the torque exceeds 20 mNm, the stress on the toner becomes large, so that the fluidity of the toner after printing on a large number of sheets may be deteriorated, which may cause image defects.

<Method of measuring toner torque>
In the present invention, the torque of the toner is measured by using a powder flowability analyzer powder rheometer FT-4 (made by Freeman Technology) (hereinafter sometimes abbreviated as FT-4).

Specifically, measurement is performed by the following operation. In all operations, the measuring terminal is a 48 mm diameter circular flat plate (A rotation axis exists in the normal direction at the center of a circular flat plate with a diameter of 48 mm, and the material is made of SUS. Hereinafter, it may be abbreviated as a circular flat plate) Use

  A cylindrical split container with a diameter of 50 mm and a volume of 160 ml dedicated to FT-4 measurement (Model number: C203. Height 82 mm from the bottom of the container to the split part. Material is glass. Hereinafter, may be abbreviated as container) 23 A toner powder layer is formed by adding 100 g of a toner which has been left in a 60% environment for 3 days or more.

  The toner torque is measured by gradually pushing the rotational speed of the circular flat plate 100 mm / sec downward with respect to the surface of the powder layer, and measuring the torque under the setting load.

  The above-described series of operations is repeated five times, excluding the upper and lower two points, and the average of the three median values is taken as the measured value. In the present invention, a pressure of 2.0 kPa is used.

In the present invention comprises a surface layer of the toner carrying member particles, frictional charging amount at 23 ° C. / 50% environment of the toner due to the particles is preferably -15 ~ -40mC / kg.

Triboelectric charge quantity of the toner by the particles contained in the surface layer of the toner carrying member, the charging property of particles added to the toner transportability improver in the front surface layer of the toner carrying member in a non-magnetic one-component developing method gives Is quantified. When this value is -15 to -40 mC / kg, an image with excellent uniformity can be obtained.

  When the absolute value of the triboelectric charge amount is smaller than -15 mC / kg, fogging to the white area tends to occur. On the other hand, when the absolute value of the frictional charge amount exceeds -40 mC / kg, it becomes difficult to separate from the toner carrier, resulting in coating unevenness and image defects such as vertical stripes may occur.

<Measurement of triboelectric charge>
The triboelectric charge of the toner by the particles contained in the surface layer of the toner carrier was measured based on the blow-off method. Also not a, the toner 2 parts by mass obtained in Toner Production Example, the toner prepared by mixing the particles 98 parts by mass which is contained in the surface layer of the measurement target toner carrying member, 20 ℃ / 50% RH Leave for 15 to 20 hours in a high temperature and high humidity environment. FIG. 4 is an explanatory view of an apparatus for measuring the amount of frictional charge. About 0.3 g of the toner that has been left is placed in a metal measuring container 32 having a screen 33 of 635 mesh on the bottom, and a metal lid 34 is placed. Release and measure the measuring container 32 total mass at this time is W1 (g). Next, in the suction unit 31 (at least the portion in contact with the measurement container 32 is an insulator), suction is performed from the suction port 37 and the air flow rate adjustment valve 36 is adjusted to make the pressure of the vacuum gauge 35 250 mmAq. In this state, suction is carried out sufficiently, preferably for 2 minutes, to suction and remove the toner . The potential of the electrometer 39 at this time is V (volt). Here, 38 is a capacitor, and its capacity is C (μF). Release and measure measuring container total mass after aspiration and W2 (g). The triboelectric charge (mC / kg) is defined as the following formula. The larger the absolute value, the larger the charge imparting ability of the particles contained in the surface layer of the toner carrier to the toner.
Triboelectric charge (mC / kg) = (C x V) / (W1-W2)

In the present invention, it is preferable that the external additive particles contain silica having a BET specific surface area of 250 to 450 m ² / g before the hydrophobization treatment. In addition, it is preferable to include an external additive that has been subjected to a hydrophobization treatment with silicone oil.

  In the non-magnetic one-component development method, the fluidity of the toner influences the uniformity of the image. It is preferable to add a relatively small particle size external additive, preferably silica in view of chargeability. Furthermore, it is better to include an external additive that has been hydrophobized with silicone oil from the viewpoint of environmental stability and component contamination.

<Toner BET specific surface area measurement method>
The measurement of the BET specific surface area of the toner is performed as follows.

  The BET specific surface area is determined by, for example, a multipoint BET method using nitrogen as an adsorption gas using a fully automatic gas adsorption amount measuring apparatus (Auto Soap 1) manufactured by Yuasa Ionics Co., Ltd. For sample pretreatment, degassing at 50 ° C. for 10 hours is performed.

An elastic layer on the outer periphery of the mandrel in the present invention, a toner carrying member having a surface layer containing at least a binder resin and particles on its outer periphery, is contained in the surface layer of the toner carrying particles The toner preferably has one peak in the volume particle size distribution, and the elastic modulus of the surface layer of the toner carrier is 1 × 10 ⁵ to 5 × 10 ⁷ Pa.

The particles contained in the surface layer of the toner carrier have one peak in the volume particle size distribution, and the elastic modulus of the surface layer of the toner carrier is 1 × 10 ⁵ to 5 × 10 ⁷ Pa. Stress can be reduced and the appropriate charge amount can be obtained.

When the elastic modulus of the surface layer of the toner carrier is smaller than 1 × 10 ⁵ Pa, the surface of the toner carrier becomes soft, so that toner deterioration can be prevented while the charge imparting ability is reduced and fogging of the white area tends to occur. There is a case. On the other hand, when the elastic modulus of the surface layer of the toner carrier exceeds 5 × 10 ⁷ Pa, the surface of the toner carrier becomes hard, and deterioration of the toner may be promoted to cause image defects.

Method of Measuring Viscoelasticity of Surface Layer of Toner Carrier
As a measuring device, a rotating plate type rheometer "ARES" (manufactured by TA INSTRUMENTS) is used.

As a measurement sample, the resin of the surface layer of the toner carrier is pressure-formed into a disc having a diameter of 7.9 mm and a thickness of 2.0 ± 0.3 mm using a tablet molding machine under an environment of 25 ° C. Use the sample you

  The sample is mounted on a parallel plate, heated from 25 ° C. to 100 ° C. for 15 minutes to adjust the shape of the sample, cooled to the measurement start temperature of viscoelasticity, and measurement is started. At this time, it is important to set the sample so that the initial normal force is zero. Also, as described below, in the subsequent measurement, the automatic tension adjustment (Auto Tension Adjustment ON) can cancel the influence of the normal force.

The measurement is performed under the following conditions.
(1) Use a parallel plate with a diameter of 7.9 mm.
(2) The frequency is 1.0 Hz.
(3) The applied strain initial value (Strain) is set to 0.1%.
(4) Measurement is performed at a temperature rising rate (Ramp Rate) of 2.0 ° C./min between 0 ° C. and 50 ° C. The measurement is performed under the following setting conditions of the automatic adjustment mode. Measure in the Auto Strain adjustment mode (Auto Strain).
(5) Set the maximum applied strain to 20.0%.
(6) The maximum torque (Max Allowed Torque) is 200.0 g · cm, and the minimum torque (Min Allowed Torque) 0.2 g · cm.
(7) The strain adjustment (Strain Adjustment) is set to 20.0% of the current strain. In measurement, an automatic tension adjustment mode (Auto Tension) is adopted.
(8) Set Auto Tension Direction as Compression.
(9) Set 10.0 g of Initial Static Force and 40.0 g of Auto Tension Sensitivity.
(10) The operating condition of the automatic tension (Auto Tension) is a sample modulus (Sample Modulus) of 1.0 × 10 ³ Pa or more.

In the present invention, a surface roughness S-Ra is 0.3 ~ 2.0 .mu.m with a laser microscope of the surface of the toner carrying member has a surface layer which the toner carrying member contains particles, the particles volume In the particle size distribution, when the peak particle size is C [μm] and the volume particle size distribution of the toner is D, the weight average particle size is preferably 2.0 ≦ C / D ≦ 5.0.

The C / D value depends on the basis weight of the toner conveyed to the toner carrier in the nonmagnetic one-component development method, and the larger the value, the more the particle diameter difference and the higher the toner conveyance power. When this value is 2.0-5.0, it is possible to optimize the toner grammage 及 beauty charge.

  If the value of C / D is smaller than 2.0, the toner conveying power is low, and it tends to be difficult to obtain a sufficient image density. On the other hand, when the C / D value exceeds 5.0, the toner basis weight increases, and charge distribution occurs in the toner particles to increase the toner of the opposite polarity. Therefore, adverse effects such as fogging may occur in a high temperature and high humidity environment.

  Here, the particle size distribution measuring method and the roughness measuring method of the present invention are shown below.

<Particle size distribution measurement method of particles contained in the surface layer of the toner 及 beauty toner carrier>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring apparatus, a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube and using a pore electrical resistance method is used. The setting of measurement conditions and the analysis of measurement data use the attached special software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with 25,000 channels of effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, a solution in which special grade sodium chloride is dissolved in ion exchange water so that the concentration is about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

In addition , before performing measurement and analysis, the dedicated software was set as follows.

  In the "Change Standard Measurement Method (SOM)" screen of the special software, set the total count number in the control mode to 50000 particles, set the number of measurements once, and the Kd value "standard particle 10.0 μm" (Beckman Coulter Inc. Make the obtained value. The threshold and noise level are automatically set by pressing the "Threshold / noise level measurement button". Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Aperture tube flush after measurement”.

  In the dedicated software “pulse to particle size conversion setting” screen, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Multisizer 3 placed the electrolytic solution about 200ml glass 250ml round-bottom beaker dedicated is set in a sample stand, carried out at 24 rotations / sec Stirring stirrer rod counterclockwise. Then, dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of special software.
(2) About 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat bottom beaker made of glass. Among them, “contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning consisting of organic builders as a dispersing agent, Wako Pure Chemical Industries, Ltd. Add about 0.3 ml of a diluted solution obtained by diluting about 3 times by mass with deionized water.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with 180 degrees of phase shift, and an ultrasonic dispersion device "Ultrasonic Dispensation System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 liters of ion exchange water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of said (2) is set to the beaker fixing hole of the said ultrasonic dispersion device, and an ultrasonic dispersion device is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, further, it continues for 60 seconds ultrasound dispersion treatment. In ultrasonic dispersion, the water temperature of the water tank is appropriately adjusted so as to be 10 ° C. or more and 40 ° C. or less.
(6) In the round bottom beaker of the above (1) placed in the sample stand, the electrolyte aqueous solution of the above (5) in which the toner is dispersed using a pipette is dropped to adjust the measurement concentration to about 5%. . Then, measurement is performed until the number of measurement particles reaches 50,000.
(7) performs the measurement data is analyzed with the dedicated software included with the apparatus to calculate the weight-average particle diameter (D4) 及 beauty number average particle diameter (D1). Incidentally, when set to graph /% by volume dedicated software is "analysis / volume statistics (arithmetic average)""averagediameter" is the weight average particle diameter of the screen (D4). The “average diameter” on the “Analysis / number statistics (arithmetic mean)” screen when the graph / number% is set by dedicated software is the number average particle diameter (D1).

<Measurement method of surface roughness Ra of the toner carrying member>
In the present invention, the surface roughness Ra of the toner carrier is based on JIS surface roughness "JIS B 0601 (2001)" using a surface roughness measuring device ("Surfcoder SE-30H" manufactured by Kosaka Laboratory Ltd.) Corresponds to the centerline average roughness measured.

  The method of producing the toner of the present invention is a method of directly producing a toner by using a suspension polymerization method; directly polymerizing in the presence of a water-soluble polymerization initiator which is soluble in monomers to produce toner particles Production of toner particles by an emulsion polymerization method represented by a soap-free polymerization method may, for example, be mentioned. In addition, production of interfacial polymerization method such as microcapsule production method, in situ polymerization method, coacervation method and the like can also be mentioned. Furthermore, there may be mentioned an interfacial association method in which a desired toner is obtained by aggregating at least one or more kinds of fine particles. Alternatively, the toner obtained by the pulverization method may be spheroidized by mechanical impact force.

  Among them, a suspension polymerization method which can easily obtain toner particles having a small particle size is particularly preferable. When suspension polymerization is used as a method of producing toner particles, it is possible to produce toner particles directly by the following production method.

A dispersion stabilizer is added to the monomer composition in which a colorant, a polymerization initiator, a crosslinking agent, and other additives are added to the monomer and uniformly dissolved or dispersed by a homogenizer, ultrasonic dispersion machine, etc. ordinary stirrer or homomixer in an aqueous medium and allowed to disperse by a homogenizer or the like. Preferably, the stirring speed and time are adjusted and granulated so that droplets of the monomer composition have the desired toner particle size. After that, stirring may be performed to maintain the particle state and prevent sedimentation of the particles by the action of the dispersion stabilizer. The polymerization is carried out by setting the polymerization temperature to 40 ° C. or higher, usually 50 to 80 ° C. (preferably 55 to 70 ° C.). The temperature may be raised in the latter half of the polymerization reaction, and the pH may be changed as necessary. In the present invention, in order to remove unreacted polymerizable monomers, by-products and the like that cause odor at the time of fixing of the toner, a part of the aqueous medium is distilled off after the reaction or in the end of the reaction. It is good. After completion of the reaction, the produced toner particles are collected by washing and filtration, and dried.

  The materials of the polymerized toner are described below.

  As a polymerizable monomer used when manufacturing the toner of the present invention by a polymerization method, a vinyl-based polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer is mainly used. In the present invention, the above-described monofunctional polymerizable monomers are used alone or in combination of two or more.

In the present invention, a water soluble initiator may be used in combination as an aid to the reaction. Further, in order to control the polymerization degree of the polymerizable monomer, it is also possible to further add and use a chain transfer agent, a polymerization inhibitor and the like.

  As the colorant used in the present invention, carbon black or a known yellow / magenta / cyan colorant as shown below is used.

  As yellow colorants, compounds represented by condensation azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I. I. Pigment yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 151, 154, 155, 168, 180, 185, etc. are preferred. Used for

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds are used. Specifically, C.I. I. Pigment red 2, 3, 5, 6, 7, 23, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 150, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.

  As a cyan colorant used in the present invention, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, etc. are particularly preferably used.

  The wax used in the present invention is not limited as the chemical structure, but as a preferred form, an ester wax (eg, monoester, diester, triester, tetraester, hexaester, oligoester, etc.) and graft compounds thereof, Derivatives such as blocking compounds are included.

  In a preferred embodiment of the present invention, residual raw materials such as liquid fatty acids and long chain alcohols, reaction residues and double products are previously purified and removed from these waxes. As the purification method, methods such as distillation, solvent washing, recrystallization and the like can be mentioned, and it is possible to adjust to the optimum range for the present invention by changing the process conditions of these methods.

  An antioxidant may be added to these waxes.

Furthermore , in the present invention, general-purpose waxes may be used in combination with the ester wax of the preferable form. However, in order to realize the effects of the present invention, it is preferable to add at least half the amount of the ester wax to the total added wax.

  As an additive of the toner which can be used in the present invention, inorganic fine particles of oil-treated silica, titania and the like are suitably used. In addition to oxides such as zirconium oxide and magnesium oxide, silicon carbide, silicon nitride, boron nitride, aluminum nitride, magnesium carbonate, organic silicon compounds and the like can be used in combination.

Silica is preferable in that the coalescence of the primary particles can be controlled to a certain extent optionally depending on the starting materials or the conditions of oxidation such as temperature. For example, such silica is fumed silica and alkoxides so-called dry process or generated called fumed silica, both of the so-called wet silica produced from water glass or the like can be used by the vapor-phase oxidation of a silicon halide or alkoxide It is. Surface and less silanol groups inside the silica fine powder, also, Na ₂ O, towards less dry silica with such manufacturing residue SO ₃ ^2-of is preferred. In the dry silica, in the manufacturing process, for example, aluminum chloride, by using a titanium other metal halide compounds chloride with silicon halogen compound, it is also possible to obtain complex fine powder of silica and other metal oxides Yes, they also include.

  Furthermore, it is preferable that the above-mentioned silica is hydrophobized to reduce the environmental dependence such as temperature and humidity of the toner charge amount and to prevent excessive release from the toner surface. Examples of the hydrophobizing agent include coupling agents such as silane coupling agents, titanium coupling agents and aluminum coupling agents. In particular, a silane coupling agent reacts with the remaining groups on the inorganic oxide fine particles or adsorbed water to achieve uniform processing, and is preferable in terms of stabilization of toner charge and imparting of fluidity.

The silane coupling agent has the following general formula Rm SiYn
R: an alkoxy group m: an integer of 1 to 3 Y: an alkyl group, a hydrocarbon group containing a vinyl group, a glycidoxy group or a methacryl group, n: an integer of 1 to 3, for example, vinyltrimethoxysilane, vinyl Triethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxy Silane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane etc. can be mentioned.

More _{preferably, C a H 2a + 1 -Si} (OC b H 2b + 1) 3 (a = 4~12, b = 1~3)
It is. Here, when a in the general formula is smaller than 4, processing is facilitated but hydrophobicity can not be sufficiently achieved. Furthermore, a although becomes sufficiently larger than hydrophobic 12, increases the coalescence of the particles, fluidity imparting capability is lowered.

  When b is larger than 3, the reactivity is lowered and the hydrophobization is not sufficiently performed. Accordingly, in the above general formula, a is 4 to 12, preferably 4 to 8, and b is 1 to 3, preferably 1 to 2.

  With regard to the oil treatment of silica, untreated silica may be treated directly with oil, or the above-mentioned hydrophobized silica may be further oil treated.

  As the oil, dimethylpolysiloxane, methylhydrogenpolysiloxane, paraffin, mineral oil and the like can be used, and among them, dimethylpolysiloxane excellent in environmental stability is preferable.

  In the toner of the present invention, other additives such as fluorocarbon resin powder, zinc stearate powder, lubricant powder such as polyvinylidene fluoride powder, cerium oxide powder, boron carbide powder, and the like within a range not causing a substantial adverse effect. Polishing agents such as strontium titanate powder, anti-caking agents such as aluminum oxide powder, or conductivity imparting agents such as carbon black powder, zinc oxide powder, tin oxide powder, and organic fine particles and inorganic fine particles of reverse polarity A small amount can also be used as a quality improver.

  Next, the image forming method of the present invention, an image forming apparatus for carrying out the method, and a process cartridge will be described.

  An image forming method to which the present invention can be applied will be described below with reference to the attached drawings.

(Non-magnetic one-component image forming apparatus)
(1) Example of Image Forming Apparatus FIG. 2 is a schematic block diagram of an example of the image forming apparatus according to the present invention. The image forming apparatus of this example, a tandem type arranged side by side a plurality of image bearing member photosensitive drum is (latent image carrier) up and down, is an electrophotographic color (multicolor image) printer over the intermediate transfer belt system .

  PY, PM, PC, and PBk respectively form first to fourth four image forming portions that form toner images of yellow (Y), magenta (M), cyan (C), and black (Bk), respectively (image formation Units), which are arranged in parallel from the bottom to the top in the image forming apparatus main body.

The first to fourth four image forming portions PY, PM, PC, PBk have the same configuration and electrophotographic imaging function except that the colors of toner images formed with one another are different as described above. There is. That is, first to fourth drum-type electrophotographic photosensitive member as the image forming portions respectively, the first image bearing member (photosensitive drum) 1, the charging roller over 2 as a primary charging means, as an exposure unit laser irradiation device 3, a toner developing device 4 as a developing means, a primary transfer roller over 5 as a primary transfer means, consisting of a blade cleaning device 6, etc. as a cleaning means. The first to fourth toner developing device 4 accommodated allowed to have toner yellow toner each of the image forming unit, a cyan toner, a magenta toner, a black toner. The toner of each color will be described later.

The image forming apparatus of this embodiment, the first to fourth image forming portions PY · PM · PC · PBk, respectively, as shown in FIG. 1, the photosensitive drum 1, the charging roller over 2, developing device 4, The four process devices of the blade cleaning device 6 are collectively formed as a process unit (process cartridge) which can be attached to and detached from the image forming apparatus main body.

In the present invention, the toner regulating means comprises a contact supporting surface resin or elastomer which is formed on a supporting member having a supporting abutment surfaces of the toner carrying member from the coating to a main material, the coating film is It is preferable to be conductive and to cover the support member at least from the contact support surface to the tip end surface.

13 is an intermediate transfer belt of the endless belt-shaped as a second image bearing member, the first to fourth four image forming portions PY · PM · PC · PBk photosensitive drum 1 side of the (printer over the front side ) in so Watarura the entire portion of the four image forming units, are disposed in the longitudinal direction Kakamawa is stretched between a plurality of support rollers over (not shown). In the first to the image forming section of the fourth primary transfer rollers over 5 are brought into pressure contact with the photosensitive drum 1 via the intermediate transfer belt 13, respectively. The contact portion between each photosensitive drum 1 and the intermediate transfer belt 13 is a primary transfer portion.

In the first to fourth image forming portions PY · PM · PC · PBk, the charging roller over 2 charging bias the photosensitive drum 1 is normally rotated in the rotation process from a power supply circuit (not shown) is applied to each Thus, the primary charging process is uniformly performed to a predetermined polarity and potential. Light image exposure LY · LM · LC · LBk according to each image pattern of yellow, magenta, cyan and black, which are color separation component images of a full color image, is performed by the LED array device 3 on the charged surface. . Then, electrostatic latent images of image information are formed on the respective photosensitive drums 1. The electrostatic latent images are each developed as a toner image by the developing device 4. The colors of yellow, magenta, cyan and black, which are color separation component images of a full color image by electrophotographic process respectively on the surface of each of the first to fourth four image forming portions PY, PM, PC and PBk A toner image is formed at a predetermined sequence control timing.

In each of the first to fourth image forming units PY, PM, PC, and PBk, yellow, magenta, cyan, and black color toner images formed on the surface of each photosensitive drum 1 are positive. First to fourth image forming portions PY, PM, PC, PBk with respect to the surface of the intermediate transfer belt 13 which is rotationally driven at substantially the same speed as the photosensitive drum 1 in the clockwise direction of the arrow in the forward direction. are sequentially superimposed and transferred in the primary transfer portion of the primary transfer roller over by a primary transfer bias applied from a power source circuit (not shown). As a result, an unfixed full-color toner image (mirror image) is synthetically formed on the surface of the intermediate transfer belt 13 which is rotationally driven.

  In each of the first to fourth image forming portions PY, PM, PC, PBk, the transfer residual toner remaining on each photosensitive drum 1 after the primary transfer of the toner image to the intermediate transfer belt 13 is removed by the cleaning blade of the blade cleaning device 6 It is removed and stored in the storage section 6 b in the device 6.

15 is a secondary transfer roller over. Opposed rollers Yes be disposed at the lower side of the intermediate transfer belt 13 inside the intermediate transfer belt, the secondary transfer roller over 15 between opposed intermediate by pinch the intermediate transfer belt 13 transferred between the roller belts 13 It is disposed in contact with the outer surface of the Contact portion between the secondary transfer roller over 15 and the intermediate transfer belt 13 is a secondary transfer portion.

A paper feed cassette 20 is disposed at the lower part of the main body of the image forming apparatus, and a transfer material as a final recording medium is stacked and accommodated. It drives the transport means (pickup roller over) 14 at a predetermined sequence control timing by one separate and feed the paper to the transfer material P of the paper feed cassette 20 is fed to the secondary transfer unit at a predetermined timing. Unfixed full-color toner image that is synthetically formed on the intermediate transfer belt 13, the surface of the transfer material P by a secondary transfer bias applied from a power source circuit (not shown) to the secondary transfer roller over 15 in the secondary transfer portion Will be transferred to the

  The transfer material having passed through the secondary transfer portion is separated from the surface of the intermediate transfer belt 13 and is sent to the fixing device 7 by the transport belt 18.

  The transfer residual toner remaining on the intermediate transfer belt 13 is removed by the cleaning blade of the blade cleaning device 16 and sent to the waste toner box 17 for storage.

Unfixed full-color toner image on the sent to the fixing device 7 the transfer material is added heat 及 beauty pressure is fused and fixed on the transfer material by a fixing device 7, distribution on the upper surface of the image forming apparatus main body through a sheet path The sheet is discharged as a color image formed article onto the provided sheet discharge tray 19.

The intermediate transfer belt 13 is made of PVDF having a thickness of 100 μm and a volume resistivity of 10 ¹⁰ Ωcm.

Secondary transfer counter roller over the distributed resistor 10 ⁴ Omega as a conductive agent of carbon in Al core metal, is used as the Φ25 coated with EPDM rubber thickness 1.5 mm.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited in any way.

Synthesis Example of Polar Resin (1)
The following raw materials are placed in a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas introduction pipe, and a catalytic amount of 0.5 mass% of titanium oxalate compound with respect to 100 parts by mass of the following raw materials I put it in. The temperature was raised gradually while stirring with nitrogen gas through a four-necked flask, reaction was carried out at 150 ° C. for 10 hours, the temperature was raised to 200 ° C. in the latter half of condensation polymerization reaction, and condensation polymerization reaction was promoted under reduced pressure. As a result, precursor polyester resin (1) (acid value 5 mg KOH / g) having a weight average molecular weight Mw of 11,000 was obtained.
-55 mol% of diol component represented by the general formula (1)

（式中、Ｒはエチレン又はプロピレン基を表し、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。本実施例では、Ｒはプロピレン基であり、ｘ＋ｙの平均値は３である。）
・イソフタル酸 ２０ｍｏｌ％
・テレフタル酸 ２５ｍｏｌ％
その後、前駆ポリエステル樹脂（１）の１００質量部を四口フラスコに入れ温度１５０℃に加熱する。無水トリメリット酸０．５質量部を加え、徐々に加熱して前駆ポリエステル樹脂（１）のポリマーの末端がトリメリット酸で変性された極性樹脂（１）を調製した。

(Wherein R represents an ethylene or propylene group, x and y each represent an integer of 1 or more, and the average value of x + y is 2 to 10. In this embodiment, R is a propylene group, x + y The average value of is 3.)
・ Isophthalic acid 20 mol%
-25 mol% of terephthalic acid
Thereafter, 100 parts by mass of the precursor polyester resin (1) is placed in a four-necked flask and heated to a temperature of 150.degree. 0.5 parts by mass of trimellitic anhydride was added and gradually heated to prepare a polar resin (1) in which the end of the polymer of the precursor polyester resin (1) was modified with trimellitic acid.

<Production of Carboxyl Group-Containing Styrene Resin 1>
300 parts by mass of xylene (boiling point 144 ° C.) is introduced into an autoclave equipped with a pressure reducing device, water separating device, nitrogen gas introducing device, temperature measuring device and stirring device, and the inside of the container is sufficiently purged with nitrogen while stirring The temperature was raised to reflux. Under this reflux,
Styrene 93.1 parts by mass Methyl methacrylate 2.5 parts by mass Methacrylic acid 1.8 parts by mass Methacrylic acid 2-hydroxyethyl copolymer 2.6 parts by mass Initiator di-tert-butyl peroxide 2 After adding .0 parts by mass of the mixed solution, polymerization was carried out for 5 hours with a polymerization temperature of 170.degree. C. and a reaction pressure of 0.150 MPa. Then, the solvent removal process was performed for 3 hours under reduced pressure, xylene was removed, and the carboxyl group-containing styrenic resin 1 was obtained by grinding.

  Hereinafter, production examples of the silica used in the present invention will be described.

<Production of silica 1>
10 parts by weight of hexamethyldisilazane 及 beauty dimethylpolysiloxane: hexane solution containing (trade name KF-96-100cs, Shin-Etsu Chemical Co., Ltd.) 20 parts by mass, an original obtained by the gas phase oxidation 及 beauty high temperature firing 100 parts by mass of body silica fine particles (trade name: Aerosil 380, manufactured by Nippon Aerosil Co., raw material BET specific surface area 380 m ² / g) was added and subjected to hydrophobization treatment at 350 ° C. Performs crushing process at a peripheral speed of 70m / sec by using a pin mill after processing, further, to adjust the particle size by performing a classifying process, silica 1 (average primary particle size 7 nm, the measured BET specific surface area of 300 meters ² / g Got).

<Production of Toner 1>
(Suspension polymerization method)
Three parts by mass of tricalcium phosphate is added to 900 parts by mass of ion-exchanged water heated to 65 ° C., and the mixture is stirred at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo) to obtain an aqueous medium. The

on the other hand,
Styrene 80 parts by mass n-butyl acrylate 20 parts by mass Polar resin (1) 5 parts by mass Carboxyl group-containing styrenic resin 1 5 parts by mass C. I. Pigment Blue 15: 3 10 parts by mass Charge control agent: Al compound of aromatic oxycarboxylic acid (aluminum compound of 3,5-di-tert-butyl salicylic acid [Bontron E 88: manufactured by Orient Chemical Co., Ltd.] 2.0 parts by mass The monomer composition was uniformly dispersed and mixed using a lighter (Mitsui Miike Kako Co., Ltd.) This monomer composition was heated to 65 ° C.
Paraffin wax (1) 10 parts by mass (DSC endothermic peak: 69 ° C., Mw: 700, Mn: 500)
Were mixed and dissolved, and 8 parts by mass of a polymerization initiator (t-butylperoxypivalate) was dissolved therein.

The polymerizable monomer system was charged into the aqueous medium, and the mixture was stirred at 10,000 rpm for 7 minutes with a TK homomixer under a N ₂ atmosphere at 65 ° C. for granulation for granulation. The mixture was then reacted at 75 ° C. for 4 hours while stirring with a paddle stirring blade. Finally, the solution temperature was raised to 85 ° C. and stirring was continued for further 3 hours. Hydrochloric acid was added to the suspension cooled to room temperature (25.degree. C.) to dissolve calcium phosphate and filtered and washed with water to obtain wet colored particles.

  Next, the particles were dried at 40 ° C. for 12 hours, and finally, 1.5 parts by mass of silica 1 and 100 parts by mass of the particles were subjected to the same hydrophobization treatment as silica 1 (average particles (average 0.2 parts by mass of a primary particle diameter of 30 nm) was added and externally added using a Henschel mixer to obtain a cyan toner 1 having a weight average particle diameter of 5.75 μm.

<Production of Toner 5>
(Emulsification aggregation method)
The cyan toner 5 was manufactured by the following emulsion aggregation method.

<< Preparation of Resin Particle Dispersion 1 >>
-Styrene 90 parts by mass-n-butyl acrylate 20 parts by mass-acrylic acid 3 parts by mass-dodecanethiol 6 parts by mass-carbon tetrabromide 1 part by mass or more mixed and dissolved into a nonionic surfactant (SANYO Made by dissolving 1.5 parts by mass of Kasei Co., Ltd .: Nonipole 400 and 2.5 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) in 140 parts by mass of ion-exchanged water Disperse in a flask and emulsify. 10 parts by mass of ion-exchanged water in which 1 part by mass of ammonium persulfate is dissolved is added to this while slowly mixing for 10 minutes, and after performing nitrogen substitution, the contents become 70 ° C. while stirring in the flask It heated with an oil bath and continued emulsion polymerization as it was for 5 hours. Thus, a resin particle dispersion 1 was prepared in which resin particles having an average particle diameter of 0.17 μm, a glass transition temperature of 57 ° C., and a weight average molecular weight (Mw) of 11,000 were dispersed.

<< Preparation of Resin Particle Dispersion 2 >>
-Styrene 75 parts by mass-n-butyl acrylate 25 parts by mass-Acrylic acid 2 parts by mass or more Mixed and dissolved, 1.5 parts by mass of nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Nonipole 400) And it disperse | distributes and emulsifies in what melt | dissolved 3 mass parts of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. product: Neogen SC) in 140 mass parts of ion-exchange water. 10 parts by mass of ion-exchanged water in which 0.8 parts by mass of ammonium persulfate is dissolved is added to this while slowly mixing for 10 minutes, and after performing nitrogen substitution, the contents are adjusted to 70 ° C. while stirring the inside of the flask The mixture is heated in an oil bath until the reaction is continued, and the emulsion polymerization is continued for 5 hours. A resin particle dispersion 2 was prepared by dispersing resin particles having an average particle diameter of 0.1 μm, a glass transition temperature of 61 ° C., and a weight average molecular weight (Mw) of 550,000.

<< Preparation of Releasing Agent Particle Dispersion >>
Ester-based wax (melting point 65 ° C.) 50 parts by mass Anionic surfactant 5 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd. product: Neogen SC)
-200 parts by mass of ion-exchanged water The above components are heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra-Turrax T50), and then dispersed using a pressure discharge type homogenizer to obtain an average particle diameter of 0.5 μm. A release agent particle dispersion obtained by dispersing the release agent is prepared.

<< Preparation of Colorant Particle Dispersion 1 >>
-Copper phthalocyanine 20 parts by mass-Anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd. product: Neogen SC)
Ion-exchanged water: 78 parts by mass or more were mixed and dispersed using a sand grinder mill. The particle size distribution of the colorant particle dispersion 1, a particle size analyzer (manufactured by Horiba, Ltd., LA-700) was measured using a mean particle diameter of the colorant particles contained is 0.2 [mu] m, also, 1 [mu] m No coarse particles above were observed.

<< Preparation of Charge Control Particle Dispersion >>
· Metal compound of di-alkyl-salicylic acid 20 parts by mass (charge control agent, Bontron E-88, manufactured by Orient Chemical Industries, Ltd.)
-Anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd. product: Neogen SC)
Ion-exchanged water: 78 parts by mass or more were mixed and dispersed using a sand grinder mill. The particle size distribution of the charge control particle dispersion, particle size analyzer (manufactured by Horiba, Ltd., LA-700) was measured using a mean particle diameter of the charge control particles contained is 0.2 [mu] m, also, a 1μm No coarse particles above were observed.

<Mixed liquid preparation>
-Resin particle dispersion 1 250 parts by mass-Resin particle dispersion 2 110 parts by mass-Colorant particle dispersion 1 50 parts by mass-Releasing agent particle dispersion 70 parts by mass or more, a stirrer, a cooling pipe, a thermometer The mixture was charged into a fitted 1-liter separable flask and stirred. The mixture was adjusted to pH = 5.2 with 1N potassium hydroxide.

<Agglomerated particle formation>
150 parts by mass of a 10% aqueous sodium chloride solution was added dropwise to the mixture as a coagulant, and the mixture was heated to 57 ° C. while stirring the inside of the flask in a heating oil bath. At this temperature, 3 parts by mass of the resin particle dispersion 2 and 10 parts by mass of the charge control agent particle dispersion were added. After holding at 50 ° C. for 1 hour, observation with an optical microscope confirmed that aggregated particles (A) having an average particle diameter of about 5.75 μm were formed.

<Fusing process>
Then, after adding 3 mass parts of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. product: Neogen SC) here, a stainless steel flask is sealed and it continues to 105 degreeC, continuing stirring using a magnetic seal. Heat and hold for 3 hours. After cooling, the reaction product is filtered, thoroughly washed with ion-exchanged water, and dried. Finally, 1.5 parts by mass of silica 1 and 100% by mass of the particles and the same hydrophobicity as silica 1 are used. 0.2 parts by mass of alumina particles (average primary particle diameter: 30 nm) subjected to the chemical conversion treatment were added, and external addition was performed using a Henschel mixer, to obtain a cyan toner 5.

<Production of Toner 9>
(Dry process)
The following materials are mixed in advance, melt-kneaded in a twin screw extruder, the cooled kneaded material is coarsely crushed in a hammer mill, the obtained pulverized material is classified, and a processing apparatus which applies mechanical impact is used. Finally, after spheroidizing, 1.5 parts by mass of silica 1 and hydrophobized in the same manner as silica 1 (an average primary particle diameter is 30 nm) is 0.2 at 100 parts by mass of particles. The toner was added by mass and externally added using a Henschel mixer to obtain cyan toner 9.
-Binder resin 100 parts by mass [Styrene-n-butyl acrylate copolymer resin (Mw = 30,000, Tg = 62 ° C)]
-Styrene resin (1) 10 parts by mass-C.I. I. Pigment Blue 15: 3 5 parts by mass Di - 3 parts by weight aluminum compound of tertiary butyl salicylic acid [manufactured by Orient Chemical Industries, Ltd.: Bontron E88]
-Ester wax 6.0 parts by mass (Behenyl behenate: maximum endothermic peak = 72 ° C, Mw = 700)

<Production of other toners>
The production method and the formulation were changed to obtain toners 2 to 4, 6 to 8 and 10 to 20 having physical properties shown in Table 1.

<Examples 1 to 27, Comparative Examples 1 to 12>
(Image evaluation)
The obtained toners 1 to 20 were used to perform image evaluation according to the following method.

As an image forming apparatus using the modified machine with different commercial laser over printer over showing a schematic manufactured by HP CLJ-CP3525 the process speed (HP Co.) to 350 mm / sec in FIG. Further, the cartridge (see FIG. 1) was used by modifying the one for CLJ-CP3525 as described later.

  Two types of evaluation were performed as evaluation methods of the present invention.

  First, 10000 sheets were printed by the continuous printing method described below in the single color mode using an image with a printing ratio of 1% in a high temperature and high humidity environment (30 ° C., 80% RH).

  Second, using an image with a printing ratio of 1% in a low temperature and low humidity environment (15 ° C., 10% RH), 10000 sheets were printed by the continuous printing method shown below in the single color mode.

  The image forming speed was set to the speed in the plain paper mode.

  Image evaluation was performed based on the following evaluation criteria using the initial and 10000th images. Tables 4 and 5 show the evaluation results.

The developing roller chromatography (toner carrying member) used to modify the developing unit was prepared using as follows.

(Method of Manufacturing Toner Carrier ( D-1 ) )
[Formation of elastic layer]
As the shaft core, nickel-plated SUS 8 mm 金 metal core, and further , primer DY35-051 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) was applied and baked. Next, the shaft core is disposed concentrically in a cylindrical mold having an inner diameter of 16 mm, and 100 parts by mass of liquid silicone rubber material SE6724A / B (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) is used as a carbon black talker. black # 7360SB (trade name, manufactured by Tokai carbon Co., Ltd.) 35 parts by weight, 0.2 parts by mass of silica powder as the heat-resistance imparting agent, the addition type silicone rubber composition obtained by mixing 0.1 part by weight 及 beauty platinum catalyst Was injected into the cavity formed in the mold. Subsequently, 0.99 ° C. The silicone rubber by heating the mold, and vulcanized for 15 minutes, after demolding, further, 200 ° C., to complete the heating 2 hours curing reaction, axial elastic layer having a thickness of 4mm It was placed around the body.

[Polyol synthesis]
As a binder resin component of the surface layer, 100 parts by mass of polytetramethylene glycol PTG 1000 SN (trade name, manufactured by Hodogaya Chemical Co., Ltd.), 20 parts by mass of an isocyanate compound Millionate MT (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) in MEK solvent The solution was mixed stepwise and reacted at 80.degree. C. for 7 hours under a nitrogen atmosphere to prepare a polyether polyol having a hydroxyl value of 20 mg KOH / g.

[Synthesis of isocyanate]
After heat-reacting 57 parts by mass of crude MDI with 100 parts by mass of polypropylene glycol having a number average molecular weight of 500 under a nitrogen atmosphere at 90 ° C. for 2 hours, butyl cellosolve is added so that the solid content becomes 70%. Obtained an isocyanate compound of 5.0%. Thereafter, 22 parts by mass of MEK oxime was added dropwise under the condition of a reaction product temperature of 50 ° C. to obtain a block polyisocyanate A.

[Preparation of paint for surface layer]
The block polyisocyanate A is mixed with the polyol prepared as described above such that the NCO / OH group ratio is 1.4, and carbon black (trade name: MA100) is used per 100 parts by mass of the binder resin solid content. , 20 parts by mass of Mitsubishi Chemical Co., Ltd., Ph = 3.5), dissolved and mixed in MEK such that the total solid content ratio is 35% by mass, and using a glass bead of 1.5 mm in particle diameter Dispersion was performed for 4 hours using a sand mill to prepare dispersion 1. Thereafter, 30 parts by mass of spherical urethane resin particles (volume average particle diameter 15.3 μm) is added to MEK of the same amount as the solid content of the binder resin component in the dispersion, and the dispersion is carried out by ultrasonic dispersion I got a liquid. The obtained spherical urethane resin particle dispersion was added to dispersion 1, and further dispersed for 30 minutes using a sand mill to obtain a paint for surface layer.

[Formation of surface layer on elastic layer]
The paint for the surface layer obtained as described above is dip coated on the elastic layer using an overflow coating dip coating device, dried, and heat treated at 150 ° C. for 2 hours. A surface layer (resin layer) having a thickness of 10 μm was provided on the layer surface to obtain a toner carrier ( D-1 ) .

<Production of Other Toner Carriers>
The manufacturing method and the formulation were changed, and toner carriers ( D-2 ) to ( D-13 ) having physical properties shown in Table 2 or Table 3 were obtained.

The toner regulating member used in the modified developing device is prepared as follows, was used.

(Method of manufacturing toner regulating member ( B-1 ) )
[ Manufacture of toner regulation member]
As a supporting member, a 0.1 mm thick phosphor bronze sheet (made by Harada Shinkosho Co., Ltd.) was inserted into an extrusion molding machine (made by Pla Giken Co., Ltd.). As a raw material of the blade member, using polyester elastomers in the main material, it was added sulfonate 1.0 parts by weight of a boron complex lithium to 100 parts by weight polyester elastomer. Thereafter, it was melted at 200 to 270 ° C., and the molten material was sequentially poured into the molding cavity while the support member in the extruder was run. The polyester elastomer was solidified, and the support member and the toner regulation member were integrated to obtain a sheet for a toner regulation member in which a film was formed on the contact support surface and the tip end surface of the support member. The film thickness of the member on the support member was adjusted by changing the extrusion amount of the resin, the feeding speed of the SUS sheet, and the size of the mold. The obtained sheet for toner regulating member was press-cut into dimensions of 200 mm in length and 23 mm in width, and used as a sample of the toner regulating member. Volume resistivity of the toner regulating member of this sample was measured in quasi Ji to JIS K6911, it was 2.3 × 10 ⁷ Ω.

(Method of manufacturing toner regulating member ( B-6 ) )
[ Manufacture of toner regulation member]
The material of the blade member used in the manufacturing method of the toner regulating member ( B-1 ) is injection molded into a mold finished at a mirror surface (Rz = 0.2 μm) and using a temperature of 40 ° C., and the width 5 mm, thickness 900 μm A plate-shaped molded product was produced. This plate-like molded product is adhered and fixed to one side of the contact support surface of a 0.1 mm thick phosphor bronze sheet (made by Harada Shinkosho Co., Ltd.), and the tip end surface is not covered in the longitudinal direction 200 mm long and 23 mm wide The toner regulation member ( B-6 ) was manufactured .

<Production of other toner regulating member>
The toner regulating members ( B-2 ) to ( B-5 ) , ( B-7 ) to ( B-8 ) and Comparative Examples 1 to 4 of the physical properties shown in Table 2 or Table 3 with the manufacturing method and formulation changed . The regulation member of

[Developability evaluation method] (measurement of fog)
The measurement of fog was measured using REFLECTOMETER MODEL TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.) and calculated by the following equation. The smaller the fog value, the better.

Evaluate after 30,000 sheets endurance.
Fog (reflectance;%) = (reflectance of standard paper;%)-(reflectance of white solid part of sample;%) A: 1.5% or less B: 1.5% or more and 2.0% or less C: more than 2.0% and 2.5% or less D: more than 2.5%

(Uneven toner carrier vertical direction)
The evaluation of the unevenness in the longitudinal direction of the toner carrier was made by visual observation and image of the surface of the toner carrier.

In the halftone image after printing 30,000 sheets, it was visually evaluated whether unevenness in density occurred between 1% printed image area and non-printed image area. Thereafter, the toner on the surface of the toner carrier was blown with air to observe the surface of the toner carrier.
A: There is no unevenness in density on the image, and the surface of the toner carrier is good. B: No unevenness in density on the image, but some filming is observed on the surface of the toner carrier.
C: Mild light and dark unevenness on the image D: Dark and light unevenness on the image (transfer efficiency)

Transfer efficiency, using the image forming apparatus shown in FIG. 2 the toner after 5,000 sheets of paper, N / N condition, following evaluation of the percentage of toner basis weight which is transferred onto the toner basis weight which is developed on the photosensitive member Evaluated based on the criteria.
A: 90% or more B: more than 80% and less than 90% C: more than 70% and less than 80% D: less than 70% (image density change)

Image density is measured by a Macbeth densitometer or a color reflection densitometer (e.g. Colorreflection densitometer X-RITE 404Amanufacturedby X- Rite Co.).

Evaluate the difference between the initial density and the density after 30,000 sheets endurance.
A: 10% or less B: 10% or more and 20% or less C: 20% or more and 30% or less D: 30% or more

(Toner regulation member on the filming)
Toner regulatory member on filming, to observe the surface of the toner regulating member visually further observes the image defect was evaluated based on the following evaluation criteria. Evaluate after 30,000 sheets endurance.
A: No defect was observed on the surface of the toner regulating member and the image.
B: In the second half of the endurance test, although some stains are observed on the surface of the toner regulating member, it does not appear in the image.
C: In the second half of the endurance test, some stains are observed on the surface of the toner regulating member, and some unevenness occurs in the image.
D: In the second half of the endurance test, the surface of the toner regulating member is heavily soiled, and the image is uneven. (White spots) White spots were observed by visual observation of the surface of the toner carrier , and image defects were observed and evaluated based on the following evaluation criteria. Evaluate after 30,000 sheets endurance.
A; toner responsible bearing member surface, defects in the image both can not be recognized at all.
B; durable late, the toner agglomerates on the surface of the toner charge of bearing member is slightly observed, does not appear in the image.
C; durable late, toner agglomerates is slightly observed on the surface of the toner charge of bearing member, some toner agglomerates in an image blank portion is produced.
D; durable late, badly toner agglomerates of the surface of the toner charge of bearing member is, toner agglomerates occurs in the image.

(Scattering letters)
Character scattering is (in the present invention, "conductive", "surprise") character of 5point also on the intermediate transfer member causes the developer transferred onto the transfer paper on the transfer material conveying member. Furthermore, it was visually observed 及 beauty loupe perform fixing at a temperature setting of 0.99 ° C., and evaluated based on the following evaluation criteria. Evaluate after 30,000 sheets endurance.
A: Even if checked with a loupe, the characters are not broken or missing.
B: Visually, letters are not broken or missing, but some missing letters are observed when checked with a loupe.
C: Some missing letters are recognized visually.
D: Missing letters are recognized visually, and the letters are clearly broken.

(Color shift)
Color shift, (in the present invention, "conductive", "surprise") character of 5point also on the intermediate transfer member causes the developer transferred onto the transfer the transfer material conveying member. Furthermore, it was visually observed 及 beauty loupe perform fixing at a temperature setting of 0.99 ° C., and evaluated based on the following evaluation criteria. Evaluate after 30,000 sheets endurance.
A: No color shift is observed even when checked with a loupe.
B: Although no color shift is observed visually, some color shifts are observed when checked with a loupe. C: A slight color shift is observed visually.
D: A color shift clearly occurs visually.

  Reference Signs List 1 photosensitive drum, 2 charging roller, 3 exposure device, 4 developing device, 5 primary transfer roller, 6 cleaning device, 7 fixing device, 8 waste toner container, 9 developing roller, 10 toner supply roller, 11 toner regulating blade, 12 toner Agitating blade, 13 intermediate transfer belt, 14 pickup roller, 15 secondary transfer roller, 16 intermediate transfer belt cleaning device, 17 waste toner box, 18 paper conveyance belt, 19 paper discharge unit, 20 paper feed cassette, 21 lower electrode, 22 Upper electrode, 24 ammeter, 25 constant voltage devices, 27 measurement samples, 28 guide rings, 31 suction machines, 32 measurement containers, 33 635 mesh screen, 34 lids, 35 vacuum gauges, 36 air flow control valves, 37 suction ports, 38 condenser, 39 electrometer

Claims (8)

An image forming method, comprising: carrying a toner on a toner carrier in order to develop an electrostatic latent image on an image carrier; conveying the toner; and regulating the toner by a toner regulating member,
The image forming method
The toner regulation member, and
Having a toner regulation step by toner regulation means having a resin material laminated on the surface of the toner regulation member;
The volume resistivity B of the resin material is 4.9 × 10 ^{6 to} 8.6 × 10 ⁸ Ωcm, and the relationship between the volume resistivity A of the toner and the volume resistivity B of the resin material is 5. Satisfy 2 × 10 ⁴ ≦ A / B ≦ 4.1 × 10 ⁸ ,
The dynamic friction coefficient μd of the toner carrier is 0.47 to 0.74,
The dynamic friction coefficient μb of the surface of the resin material is 0.16 to 0.21, and the difference (μd−μb) between the dynamic friction coefficient μd and the dynamic friction coefficient μb is 0.28 to 0.55,
The toner comprises toner particles and a hydrophobized external additive,
The addition amount of the hydrophobized external additive is 1.50 to 2.10 parts by mass with respect to 100 parts by mass of the toner particles,
The average circularity measured by the flow type particle image measuring device of the toner is 0.961 to 0.991,
The dynamic friction coefficient μt of the surface obtained by pelletizing the toner is 0.09 to 0.18, and the difference (μb−μt) between the dynamic friction coefficient μb and the dynamic friction coefficient μt is 0 to 0.1 An image forming method characterized by   The image forming method according to claim 1, wherein a torque measured using a circular flat plate under pressure (2.0 kPa) of the toner is 10 to 20 (mNm). The image formation according to claim 1 or 2 , wherein the toner contains, as the hydrophobized external additive, a hydrophobized silica having a BET specific surface area of 250 to 450 m ² / g of the pre-hydrophobized raw material. Method. The image forming method according to any one of claims 1 to 3 , wherein the hydrophobized external additive includes an external additive which is hydrophobized by silicone oil. The toner carrier has a surface layer containing particles,
The image forming method according to any one of claims 1 to 4, wherein a triboelectric charge amount of the particles in an environment of 23 ° C / 50% of the toner is -15 to -40 (mC / kg). The toner carrier includes an axial core, an elastic layer formed on the outer periphery of the axial core, and a surface layer formed on the outer periphery of the elastic layer;
The surface layer contains a binder resin and particles,
The particles contained in the surface layer have one peak in the volume particle size distribution, and the elastic modulus of the surface layer is 1 × 10 ^{5 to} 5 × 10 ⁷ Pa. The image forming method according to item 1. The surface roughness S-Ra of the surface of the toner carrier measured by a laser microscope is 0.3 to 2.0 μm,
Assuming that the peak particle size in the volume particle size distribution of the particles contained in the surface layer is C [μm] and the weight average particle size in the volume particle size distribution of the toner is D, 2.0 ≦ C / D ≦ 5 The image forming method according to claim 5 or 6 , wherein .0 is satisfied. The toner regulation means has a support member having an abutment support surface for supporting an abutment surface with the toner carrier, and a coating mainly made of a resin or an elastomer formed on the support member, The coating is conductive and
The image forming method according to any one of claims 1 to 7, wherein the coating covers the support member at least from the contact support surface to the tip end surface.

Images