JP2020079899A - Developing device, image formation device, and process cartridge - Google Patents

Abstract

To provide a developing device, an image formation device, and a process cartridge that can reduce their sizes.SOLUTION: In a conveyance path for conveying a developer from a developer container to a storage part of a frame body supporting a developer regulating member and a developer regulating member, a first conveyance member for conveying the developer by rotating and a second conveyance member for conveying the developer by rotating downstream of the first conveyance member are arranged. The second conveyance member has a drive receiving part for receiving the rotational force from the first conveyance member. The developer contains a toner having a toner particle and a compound containing silicon present on the surface of the toner particle. The adhesion ratio of the compound containing silicon to the surface of the toner particle is between 87% to 100%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an image forming apparatus, a developing device, and a process cartridge that form an image on a recording material (sheet) by using an electrophotographic method, and particularly to supply a developer (toner) to a developing means. The present invention relates to a developing device including the toner transport path. Here, the electrophotographic image forming apparatus (hereinafter, also simply referred to as “image forming apparatus”) is an apparatus that forms an image on a recording material (recording medium) using an electrophotographic image forming method. Examples of the image forming apparatus include a copying machine, a printer (laser beam printer, LED printer, etc.), a facsimile machine, a word processor, and a multifunction machine (multifunction printer) of these.

  In recent years, the size of the main body of the image forming apparatus (hereinafter referred to as the main body) has been reduced, but with the reduction in size of each unit inside the main body, the space that can be arranged in the book is limited. It Therefore, there is a case where the arrangement of the toner cartridge is restricted, and the toner transport path connects the toner cartridge and the developing unit. As a toner transport device for such a toner transport path, a toner transport member including a screw made of plastic, a coil spring made of metal, or the like may be provided. For example, Patent Document 1 discloses a screw-type toner conveying member. When the toner conveying member rotates, a blade tooth surface spirally provided on the toner conveying member moves toner in a path. By pushing out, the toner is conveyed to the developing means.

  In the configuration in which toner is supplied using the toner carrying member, a certain amount of space is required to arrange the toner carrying path including the toner carrying member. Therefore, for example, when it is attempted to linearly extend the toner transport path in the arrangement direction (opposite direction) of the toner cartridge and the developing means, the toner transport path including the toner transport member is provided between the toner cartridge and the developing means. It is necessary to provide a predetermined interval for providing That is, when such a configuration is adopted, it is necessary to sacrifice the toner storage amount by, for example, reducing the size of the toner cut ridge in order to secure the space of the toner transport path.

JP, 2010-20227, A

  An object of the present invention is to provide a developing device, an image forming apparatus, and a process cartridge that can reduce the size of the apparatus.

In order to achieve the above object, the developing device in the present invention comprises:
A developing device used in an image forming apparatus,
A developer carrying member carrying a developer for developing the latent image formed on the image carrying member;
A regulating member for regulating the developer carried on the developer carrier,
A frame body that supports the developer carrier and the regulation member, and has a developer accommodating portion,
A developer container containing the developer,
A conveyance path for supplying the developer from the developer container to the housing portion of the frame,
A first transport member that transports the developer by rotating and a second transport member that transports the developer by rotating are arranged in the transport path.
The second transport member has a drive receiving portion that receives a rotational force from the first transport member,
The developer contains a toner having toner particles and a silicon-containing compound present on the surface of the toner particles,
The adhesion rate of the silicon-containing compound on the surface of the toner particles is 87% or more and 100% or less.
In order to achieve the above object, the image forming apparatus of the present invention,
An image carrier on which a latent image is formed,
A developer carrying member carrying a developer for developing the latent image formed on the image carrying member;
A regulating member for regulating the developer carried on the developer carrier,
A frame body that supports at least the developer carrying member and the regulating member, and has a housing portion for the developer,
A developer container containing the developer,
A conveyance path for supplying the developer from the developer container to the housing portion of the frame,
A first transport member that transports the developer by rotating and a second transport member that transports the developer by rotating are arranged in the transport path.
The second transport member has a drive receiving portion that receives a rotational force from the first transport member,
The developer contains a toner having toner particles and a silicon-containing compound present on the surface of the toner particles,
The adhesion rate of the silicon-containing compound on the surface of the toner particles is 87% or more and 100% or less.
In order to achieve the above object, the process cartridge according to the present invention,
A process cartridge used in an image forming apparatus,
A developer carrying member carrying a developer for developing the latent image formed on the image carrying member;
A regulating member for regulating the developer carried on the developer carrier,
A frame body that supports the developer carrier and the regulation member, and has a developer accommodating portion,
A developer container containing the developer,
A conveyance path for supplying the developer from the developer container to the housing portion of the frame,
A first transport member that transports the developer by rotating and a second transport member that transports the developer by rotating are arranged in the transport path.
The second transport member has a drive receiving portion that receives a rotational force from the first transport member,
The developer contains a toner having toner particles and a silicon-containing compound present on the surface of the toner particles,
The adhesion rate of the silicon-containing compound on the surface of the toner particles is 87% or more and 100% or less.

  According to the present invention, it is possible to suppress the occurrence of an image defect in image formation while reducing the size of the device.

The schematic diagram of the connection part of the conveyance member in Embodiment 1 of this invention. 1 is a schematic diagram of an image forming apparatus according to Embodiment 1 of the present invention. Explanatory drawing of the toner cartridge in Embodiment 1 of the present invention Explanatory drawing of a toner cartridge and a main body conveyance path in the embodiment of the present invention Explanatory drawing of a toner cartridge, a main body conveyance path, and a process cartridge in Embodiment 1 of the present invention Schematic diagram of a toner having a surface layer containing an organosilicon polymer in Embodiment 1 of the present invention Schematic diagram of an image forming apparatus according to a second embodiment of the present invention Explanatory drawing of the toner cartridge in Embodiment 2 of the present invention Explanatory drawing of a toner cartridge and a main body conveyance path in Embodiment 2 of the present invention Explanatory drawing of a toner cartridge and a process cartridge in Embodiment 3 of the present invention Explanatory drawing of a toner cartridge and a process cartridge in Embodiment 4 of the present invention

Hereinafter, embodiments or examples of the present invention will be illustratively described in detail with reference to the drawings. However, the dimensions, materials, shapes, relative positions, etc. of the components described in the embodiments or examples are appropriately changed depending on the configuration of the device to which the invention is applied and various conditions, Unless otherwise stated, the scope of the invention is not intended to be limited thereto.
In the embodiment according to the present invention, the toner container is provided with a toner transport path from the toner container to the developing unit, and one of the plurality of transport members in the transport path is driven by receiving the rotational force from the other. The toner contained in the toner has a fixing rate of 87% or more and 100% or less.
In the present invention, the description such as “more than or equal to XX and less than or equal to XX” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit, which are endpoints, unless otherwise specified.

<Developer>
In the present invention, the developer contains toner having toner particles and a compound containing silicon present on the surface of the toner particles.
Further, the toner preferably has toner particles and inorganic silicon fine particles present on the surfaces of the toner particles.
Further, it is preferable that the toner has toner particles and an organosilicon polymer coating the surfaces of the toner particles.

The toner particles may contain a binder resin as a constituent component.
Examples of the binder resin include polyester resin, vinyl resin, epoxy resin, and polyurethane resin.
The polyester resin may be produced by a generally known method of polycondensing an alcohol component and an acid component.
Examples of vinyl resins include styrene and its derivatives; unsaturated monoolefins; unsaturated polyenes; α-methylene aliphatic monocarboxylic acid esters; acrylic acid esters; vinyl ketones; acrylonitrile, methacrylonitrile, acrylamide, etc. It may be produced by polymerizing a polymerizable monomer such as acrylic acid or methacrylic acid derivative.

The toner particles may contain a release agent. The release agent is not limited as long as it can enhance the releasability, and examples thereof include the following.
Aliphatic hydrocarbon wax such as polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax.
The content of the release agent is preferably 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer that forms the binder resin, It is more preferably 5.0 parts by mass or more and 25.0 parts by mass or less.

The toner may be either a magnetic one-component toner or a non-magnetic one-component toner, but a non-magnetic one-component toner is preferable.
Examples of the colorant when used as the non-magnetic one-component toner include various conventionally known dyes and pigments.

Examples of the black colorant include carbon black and those toned in black using the yellow, magenta, and cyan colorants shown below.
Examples of the yellow colorant include monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds.
Examples of magenta colorants include monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds.
Examples of cyan colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds.
The content of the colorant is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer that forms the binder resin.

As the inorganic silicon fine particles used in the present invention, silica fine particles such as wet process silica fine particles and dry process silica fine particles, and the silica fine particles are surface-treated with a silane coupling agent, a titanium coupling agent, or silicone oil. Hydrophobized silica fine particles may be mentioned.
The dry-process silica fine particles are produced, for example, by utilizing the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame, and the basic reaction formula is as follows.
SiCl ₄ +2H ₂ +O ₂ →SiO ₂ +4HCl
In this manufacturing process, it is possible to obtain composite fine particles of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds, and these are also used as the inorganic silicon fine particles. Include.
The number average particle diameter (D1) of the primary particles of the inorganic silicon fine particles is preferably 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, and 500 nm or less, 400 nm or less, 300 nm or less, 250 nm or less. , 200 nm or less is preferable. The numerical ranges can be combined arbitrarily.
The content of the inorganic silicon fine particles is preferably 0.1 part by mass or more and 10.0 parts by mass or less, and 1.0 part by mass or more and 5.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles. Is more preferable.

In the present invention, the fixing rate of the inorganic silicon fine particles on the surface of the toner particles is 87% or more and 100% or less, and preferably 90% or more and 100% or less.
When the fixing rate is within the above range, even if the toner is subjected to a strong shearing force in the conveying path by the conveying member, the inorganic silicon fine particles are hard to come off and the aggregation of the inorganic silicon fine particles can be suppressed. it can. As a result, since the aggregates of the inorganic silicon fine particles do not grow large, image defects such as streak images are unlikely to occur.
The fixing rate can be adjusted to the above range by adjusting the impact force or the shearing force due to the high speed contact with the mixture of the toner particles and the inorganic silicon fine particles.

In the present invention, the coverage of the inorganic silicon fine particles on the surface of the toner particles is preferably 80% or more, 85% or more, 90% or more, and preferably 100% or less. The above numerical ranges can be combined arbitrarily.
When the coverage is within the above range, even if the toner is subjected to a strong shearing force by the conveying member in the conveying path, the inorganic silicon fine particles are hard to come off and the aggregation of the inorganic silicon fine particles can be suppressed. it can. As a result, the aggregates of the inorganic silicon fine particles do not grow significantly, so that image defects such as streak images are less likely to occur.
The above-mentioned coverage can be adjusted within the above range by the addition amount of the inorganic silicon fine particles.

<Method of measuring the sticking rate of the inorganic silicon fine particles on the surface of the toner particles>
Toner before washing: Using the produced various toners as they are, the amount of silicon in the silicon compound existing on the surface of the toner particles before washing is determined by the following method.
Toner after cleaning:
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved with a water bath to prepare a concentrated sucrose solution. In a centrifuge tube (volume 50 mL), 31 g of the above concentrated sucrose solution, Contaminone N (a nonionic surfactant, an anionic surfactant, and an organic builder, pH 7 precision measuring instrument) 6% of a mass% aqueous solution, manufactured by Wako Pure Chemical Industries, Ltd. is added to prepare a dispersion liquid. To this dispersion, 1.0 g of toner is added, and a lump of toner is loosened with a spatula or the like.
The centrifuge tube is shaken with a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube for swing rotor (capacity: 50 mL), and separated by a centrifuge (H-9R, manufactured by Kokusan Co., Ltd.) under conditions of 3500 rpm and 30 minutes. Visually confirm that the toner and the aqueous solution are sufficiently separated, and collect the toner separated in the uppermost layer with a spatula or the like. The collected aqueous solution containing the toner is filtered with a vacuum filter and then dried with a dryer for 1 hour or more. The dried product is crushed with a spatula, and the amount of silicon present on the surface of the toner particles after washing is determined by the following method.
Then, (the amount of silicon present on the surface of the toner particles after washing/the amount of silicon present on the surface of the toner particles before washing)×100 is defined as the sticking rate (%).

The measurement using fluorescent X-rays of silicon conforms to JIS K 0119-1969, and specifically is as follows.
As a measuring device, a wavelength dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and attached dedicated software "SuperQ ver. 4.0F" (manufactured by PANalytical) for performing measurement condition setting and measurement data analysis ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds. Moreover, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).
As a measurement sample, about 1 g of toner before or after washing was put into a dedicated aluminum ring for press with a diameter of 10 mm and flattened to flatten it, and a tablet molding compressor "BRE-32" (Maekawa Testing Machine Manufacturing Co., Ltd. (Manufactured by Mfg. Co., Ltd.) is used and pressure is applied at 20 MPa for 60 seconds, and pellets molded to a thickness of about 2 mm are used.
The measurement is performed under the conditions, the element is identified based on the obtained X-ray peak position, and the concentration is calculated from the count rate (unit: cps) which is the number of X-ray photons per unit time.

On the other hand, to 100 parts by mass of the toner particles, for example, silica (SiO ₂ ) fine powder is added so as to be 0.5 parts by mass and sufficiently mixed using a coffee mill. Similarly, fine silica powder is mixed with toner particles so as to be 2.0 parts by mass and 5.0 parts by mass, respectively, and these are used as a sample for a calibration curve.

For each sample, pellets of the sample for the calibration curve were prepared as described above using the tablet molding compressor, and when PET was used for the dispersive crystal, it was observed at the diffraction angle (2θ)=109.08°. The Si-Kα ray count rate (unit: cps) is measured. At this time, the acceleration voltage and the current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the obtained X-ray count rate as the vertical axis and the addition amount of SiO ₂ in each calibration curve sample as the horizontal axis.
Next, the count rate of Si-Kα ray of the above-mentioned pellet to be analyzed is measured. Then, each amount of silicon is obtained using the above calibration curve.

<Method of measuring the coverage of the inorganic silicon fine particles on the surface of the toner particles>
For the coverage of the surface of the toner particles of the inorganic silicon fine particles, the toner particle surface image photographed by Hitachi Ultra High Resolution Field Emission Scanning Electron Microscope S-4800 (Hitachi High Technologies Co., Ltd.) is used as the image analysis software Image- Pro Plus ver. Calculated by analysis with 5.0 (Nippon Roper Co., Ltd.). The image capturing conditions of S-4800 are as follows.
(1) Sample Preparation A sample table (aluminum sample table 15 mm×6 mm) is thinly coated with a conductive paste, and toner is sprayed onto the sample. Further, air blow is performed to remove excess toner from the sample table and dry it sufficiently. The sample table is set on the sample holder, and the sample table height is adjusted to 36 mm by the sample height gauge.
(2) S-4800 Observation Condition Setting The above coverage is calculated using the image obtained by the backscattered electron image observation of S-4800. Since the backscattered electron image has less charge-up of inorganic fine particles than the secondary electron image, the coverage can be measured with high accuracy.
Liquid nitrogen is poured into the anti-contamination trap attached to the housing of S-4800 until it overflows, and it is left for 30 minutes. The "PC-SEM" of S-4800 is started and flushing (cleaning of the FE chip which is the electron source) is performed. Click the accelerating voltage display area on the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Execute after confirming that the flushing strength is 2. Confirm that the emission current due to flashing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel and move the sample holder to the observation position.
Click the acceleration voltage display area to open the HV setting dialog, and set the acceleration voltage to [0.8 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select the SE detector [Up (U)] and [+BSE], and select [+BSE] in the selection box to the right. L. A. 100] is selected and the mode is set to observe with a backscattered electron image. Similarly, in the [Basic] tab of the operation panel, set the probe current of the electron optical system condition block to [Normal], the focus mode to [UHR], and the WD to [3.0 mm]. Press the [ON] button on the acceleration voltage display of the control panel to apply the acceleration voltage.
(3) Calculation of number average particle diameter (D1) of toner Drag inside the magnification display area of the control panel to set the magnification to 5000 (5k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. The STIGMA/ALIGNMENT knobs (X, Y) on the operation panel are rotated to move the displayed beam to the center of the concentric circles.
Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it so that the movement becomes the minimum. Close the aperture dialog and use auto focus to focus. Repeat this operation twice more to focus.
Then, the particle size of 300 toners is measured to obtain the number average particle size (D1). The particle size of each particle is the maximum size when the toner particles are observed.
(4) Focus adjustment For the particles of number average particle diameter (D1) of ±0.1 μm obtained in (3), adjust the inside of the magnification display section of the control panel with the midpoint of the maximum diameter aligned with the center of the measurement screen. Drag to set the magnification to 10,000 (10k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. The STIGMA/ALIGNMENT knobs (X, Y) on the operation panel are rotated to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it so that the movement becomes the minimum. Close the aperture dialog and use auto focus to focus. After that, the magnification is set to 50,000 (50k) times, focus adjustment is performed using the focus knob and STIGMA/ALIGNMENT knob in the same manner as above, and focus is adjusted again by autofocus. Repeat this operation again to focus. Here, if the angle of inclination of the observation surface is large, the measurement accuracy of the coverage rate tends to be low, so by selecting one that simultaneously focuses on the entire observation surface when adjusting the focus, select a surface with as little inclination as possible. And analyze.
(5) Image storage Brightness matching is performed in ABC mode, and a picture is taken with a size of 1280 x 960 pixels and saved. The following analysis is performed using this image file. One photograph is taken for each toner particle, and an image is obtained for at least 30 toner particles.
(6) Image Analysis In the present invention, the coverage is calculated by binarizing the image obtained by the above-mentioned method using the following analysis software. At this time, the above-mentioned one screen is divided into 12 squares and analyzed.
Image analysis software Image-Pro Plus ver. The analysis conditions of 5.0 are as follows.
Select "Count/Size" then "Option" from the "Measure" on the toolbar and set the binarization conditions. Select 8 concatenation in the object extraction options and set smoothing to 0. In addition, selection of lines, filling of holes, and comprehensive lines are not selected in advance, and “exclude boundary lines” is set to “none”.
Select "Measurement item" from "Select" on the toolbar and enter 2 to 10 ⁷ in the area selection range.
The coverage is calculated by surrounding a square area. At this time, the area (C) of the area is set to 24000 to 26000 pixels. "Processing"-Automatic binarization by binarization to calculate the total area (D) of the regions without inorganic fine particles.
From the area C of the square area and the total area D of the areas without the inorganic silicon fine particles, the coverage of the inorganic silicon fine particles can be calculated by the following formula.
Inorganic silicon fine particle coverage (%)=100−(D/C×100)
The above-described calculation of the coverage is performed on 30 or more toner particles. The arithmetic average value of all the obtained data is defined as the coverage (%) on the surface of the toner particles of the inorganic silicon fine particles in the invention.

On the other hand, when the surface of the toner particle is coated with the organosilicon polymer, it has a surface layer which is a layer existing on the outermost surface of the toner particle. That is, the toner particles have a surface layer containing the organosilicon polymer. This means that the toner has toner particles and a silicon-containing compound present on the surface of the toner particles. The surface layer may have a part where the surface layer is not formed on a part of the surface of the toner particles.
In the present invention, the fixing rate of the organosilicon polymer on the surface of the toner particles is 87% or more and 100% or less, and preferably 90% or more and 100% or less.
When the sticking ratio is within the above range, the organosilicon polymer is less likely to come off and the aggregation of the organosilicon polymer is suppressed even if the toner is subjected to a strong shearing force by the carrying member in the carrying path. be able to. As a result, aggregates of the organosilicon polymer do not grow significantly, so that image defects such as streak images are less likely to occur.

In order to obtain the fixing rate, it is preferable to form a surface layer containing an organosilicon polymer having a structure represented by the following formula (1) on the toner particles.
Further, the fixing rate of the organosilicon polymer depends on the type and amount of the organosilicon compound used for forming the organosilicon polymer, the method for producing toner particles during the formation of the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH. Can be controlled.
R-SiO _3/2 formula (1)
(The R represents a hydrocarbon group having 1 to 6 carbon atoms.)

In the organosilicon polymer having the structure of formula (1), one of the four valences of the Si atom is bonded to R and the remaining three are bonded to O atom. Each of the O atoms has a valence of 2 and is bonded to Si, that is, a siloxane bond (Si-O-Si).
Considering Si atoms and O atoms as the organosilicon polymer, two Si atoms have three O atoms, and thus they are expressed as —SiO _3/2 .
It is considered that the -SiO _3/2 structure of this organosilicon polymer has properties similar to silica (SiO ₂ ) composed of many siloxane bonds. Therefore, the hardness of the toner can be set higher than that of the organic resin and lower than that of the inorganic silicon fine particles because of the structure closer to that of the inorganic substance as compared with the toner formed on the surface layer of the conventional organic resin.

In the partial structure represented by the formula (1), R is a hydrocarbon group having 1 to 6 carbon atoms. This makes it easy to stabilize the charge amount. Particularly, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a phenyl group, which is excellent in environmental stability, is preferable.
Further, it is more preferable that R is an aliphatic hydrocarbon group having 1 to 3 carbon atoms in order to further improve chargeability and fog prevention. When the chargeability is good, the transferability is good and the transfer residual toner is small, so that the contamination of the drum, the charging member and the transfer member is improved.
Preferred examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and a vinyl group. From the viewpoint of environmental stability and storage stability, R is more preferably a methyl group.

  As a production example of the organosilicon polymer, the sol-gel method is preferable. The sol-gel method is a method in which a liquid raw material is used as a starting raw material for hydrolysis and condensation polymerization, and a gel is formed through a sol state, and is used for synthesizing glass, ceramics, organic-inorganic hybrids, and nanocomposites. By using this manufacturing method, it is possible to manufacture functional materials having various shapes such as surface layers, fibers, bulk bodies, and fine particles from a liquid phase at a low temperature.

Specifically, the organosilicon polymer is preferably produced by hydrolysis and condensation polymerization of a silicon compound represented by alkoxysilane.
By coating the surface of the toner particles with the organosilicon polymer, the sticking rate of the organosilicon polymer on the surface of the toner particles can be improved. Further, by coating the surface of the toner particles with the organosilicon polymer, the environmental stability of the toner is improved, and the performance of the toner is less likely to deteriorate during long-term use, and a toner having excellent storage stability is obtained. be able to.

  Furthermore, since the sol-gel method starts from a liquid and forms the material by gelling the liquid, various fine structures and shapes can be formed. In particular, when the toner particles are manufactured in an aqueous medium, the hydrophilicity of a hydrophilic group such as a silanol group of the organosilicon compound facilitates precipitation on the surface of the toner particles. The fine structure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH and the kind and amount of the organometallic compound.

  The organosilicon polymer is preferably a polycondensation product of an organosilicon compound having a structure represented by the following formula (Z).

（式（Ｚ）中、Ｒ_１は、炭素数が１以上、６以下の炭化水素基を表し、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、アセトキシ基、又は、アルコキシ基を表す。）

(In the formula (Z), R ₁ represents a hydrocarbon group having 1 or more and 6 or less carbon atoms, and R ₂ , R ₃ and R ₄ are each independently a halogen atom, a hydroxy group, an acetoxy group, Or represents an alkoxy group.)

The hydrocarbon group (preferably an alkyl group) of R ₁ can improve hydrophobicity, and toner particles excellent in environmental stability can be obtained. Further, an aryl group which is an aromatic hydrocarbon group, for example, a phenyl group can be used as the hydrocarbon group. When R ₁ has a large hydrophobicity, the charge amount tends to increase in various environments. Therefore, in view of environmental stability, R ₁ is preferably a hydrocarbon group having 1 to 3 carbon atoms, It is more preferably a methyl group.

R ₂ , R ₃ and R ₄ are each independently a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group (hereinafter, also referred to as a reactive group). These reactive groups are hydrolyzed, addition-polymerized and polycondensed to form a crosslinked structure, and a toner excellent in member contamination resistance and development durability can be obtained. Hydrolyzability is mild at room temperature, and an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable, from the viewpoints of depositability on the surface of toner particles and coverage. preferable. The hydrolysis, addition polymerization and condensation polymerization of R ₂ , R ₃ and R ₄ can be controlled by the reaction temperature, reaction time, reaction solvent and pH.

In order to obtain the organosilicon polymer, an organosilicon compound having _three reactive groups (R ₂ , R ₃ and R ₄ ) in one molecule excluding R ₁ in the above formula (Z) (hereinafter, referred to as three (Also referred to as a functional silane) may be used alone or in combination.
The following is mentioned as said formula (Z).
Methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyl Triacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxy Trifunctional methylsilanes such as hydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane.
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional such as methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane Silane.
Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltrihydroxysilane.
Further, an organosilicon polymer obtained by using the following together with the organosilicon compound having the structure represented by the formula (Z) may be used to the extent that the effects of the present invention are not impaired. Organosilicon compound having four reactive groups in one molecule (tetrafunctional silane), organosilicon compound having two reactive groups in one molecule (difunctional silane) or organosilicon compound having one reactive group ( Monofunctional silane).

The content of the organosilicon polymer in the toner particles is preferably 0.5% by mass or more and 10.5% by mass or less.
When the content of the organosilicon polymer is 0.5% by mass or more, the surface free energy of the surface layer can be further reduced, the fluidity can be improved, and member contamination and fogging can be suppressed. .. When the content is 10.5% by mass or less, it is possible to make charge-up less likely to occur.
The content of the organosilicon polymer is controlled by the kind and amount of the organosilicon compound used for forming the organosilicon polymer, the method for producing toner particles during the formation of the organosilicon polymer, the reaction temperature, the reaction time, the reaction solvent and the pH. can do.
It is preferable that the surface layer containing the organosilicon polymer and the toner particles are in contact with each other without a gap.

<Method of manufacturing toner particles>
As a method for producing the toner particles, known means can be used, and a kneading and pulverizing method or a wet production method can be used. From the viewpoint of making the particle diameter uniform and controlling the shape, the wet production method can be preferably used. Further, examples of the wet manufacturing method include a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method.
Here, the suspension polymerization method will be described. In the suspension polymerization method, first, a polymerizable monomer for forming a binder resin, and if necessary, a colorant and other additives are added using a disperser such as a ball mill or an ultrasonic disperser. Then, these are uniformly dissolved or dispersed to prepare a polymerizable monomer composition (step of preparing the polymerizable monomer composition). At this time, a polyfunctional monomer, a chain transfer agent, a wax as a release agent, a charge control agent, a plasticizer, and the like can be appropriately added, if necessary.

Next, the polymerizable monomer composition is put into an aqueous medium prepared in advance, and a droplet made of the polymerizable monomer composition is desired by a stirrer or a disperser having a high shearing force. To the size of the toner particles (granulating step).
It is preferable that the aqueous medium in the granulation step contains a dispersion stabilizer in order to control the particle size of the toner particles, sharpen the particle size distribution, and suppress coalescence of the toner particles in the manufacturing process. The dispersion stabilizer is generally classified into a polymer that exhibits a repulsive force due to steric hindrance and a poorly water-soluble inorganic compound that stabilizes the dispersion by electrostatic repulsive force. Since the fine particles of the poorly water-soluble inorganic compound are dissolved by an acid or an alkali, they can be easily dissolved and removed by washing with an acid or an alkali after the polymerization, and thus are preferably used.
After the granulation step or while performing the granulation step, the temperature is preferably set to 50° C. or higher and 90° C. or lower to polymerize the polymerizable monomer contained in the polymerizable monomer composition to obtain a toner. A particle dispersion is obtained (polymerization step).

In the polymerization step, it is preferable to carry out a stirring operation so that the temperature distribution in the container becomes uniform. When the polymerization initiator is added, it can be carried out at an arbitrary timing and required time. In addition, the temperature may be raised in the latter half of the polymerization reaction for the purpose of obtaining a desired molecular weight distribution. After that, part of the aqueous medium may be distilled off by a distillation operation. The distillation operation can be performed under normal pressure or reduced pressure.

  From the viewpoint of obtaining a high-definition and high-resolution image, the weight average particle diameter of the toner is preferably 3.0 μm or more and 10.0 μm or less. The weight average particle diameter of the toner can be measured by the pore electrical resistance method. For example, it can be measured using "Coulter Counter Multisizer 3" (manufactured by Beckman Coulter, Inc.). The toner particle dispersion liquid thus obtained is sent to a filtration step for solid-liquid separating the toner particles and the aqueous medium.

  Solid-liquid separation for obtaining toner particles from the obtained toner particle dispersion liquid can be carried out by a general filtration method, and thereafter, in order to remove foreign substances that could not be completely removed from the toner particle surface, reslurry or washing water is used. Further washing is preferably carried out by washing with water. After sufficient washing is performed, solid-liquid separation is performed again to obtain a toner cake. After that, it is dried by a known drying means, and if necessary, a group of particles having a particle diameter outside the predetermined range is separated by classification to obtain toner particles. The particles having a particle size outside the predetermined range may be reused in order to improve the final yield.

  When forming a surface layer having an organosilicon polymer, when forming the toner particles in an aqueous medium, the hydrolysis solution of the organosilicon compound is added as described above while performing the polymerization step in an aqueous medium. The surface layer can be formed. You may use the dispersion liquid of the toner particle after superposition|polymerization as a core particle dispersion liquid, and add the hydrolysis liquid of an organosilicon compound and form the said surface layer. Further, in the case of other than an aqueous medium such as a kneading and pulverizing method, the obtained toner particles are dispersed in an aqueous medium and used as a core particle dispersion liquid, and a hydrolyzed liquid of an organosilicon compound is added to the surface layer as described above. Can be formed.

When forming the surface layer having an organosilicon polymer, the following method is particularly preferable.
First, core particles of toner particles are manufactured and dispersed in an aqueous medium to obtain a core particle dispersion liquid.
The concentration at this time is preferably such that the solid content of the core particles is 10% by mass or more and 40% by mass or less based on the total amount of the core particle dispersion liquid. The temperature of the core particle dispersion liquid is preferably adjusted to 35°C or higher. Further, the pH of the core particle dispersion liquid is preferably adjusted to a pH at which condensation of the organosilicon compound does not easily proceed. Since the pH at which condensation of the organosilicon polymer is difficult to proceed differs depending on the substance, it is preferably within ±0.5 around the pH at which the reaction is most difficult to proceed.

  On the other hand, it is preferable to use a hydrolyzed organosilicon compound. For example, the organosilicon compound is hydrolyzed in a separate container as a pretreatment. When the amount of the organosilicon compound is 100 parts by mass, the charged concentration of hydrolysis is preferably 40 parts by mass or more and 500 parts by mass or less of water obtained by removing ion components such as ion-exchanged water and RO water, and more preferably 100 parts by mass of water. It is above 400 parts by mass. As conditions for hydrolysis, the pH is preferably 2 to 7, the temperature is 15° C. to 80° C., and the time is 30 minutes to 600 minutes.

  By mixing the obtained hydrolyzed liquid and the core particle dispersion liquid and adjusting the pH (preferably 6 to 12, or 1 to 3, and more preferably 8 to 12) suitable for condensation, the organosilicon compound is removed. A surface layer can be formed on the surface of the core particles of the toner particles while being condensed. Condensation and surface coating are preferably performed at 35° C. or higher for 60 minutes or longer. The surface macrostructure can be adjusted by adjusting the time of holding at 35° C. or higher before adjusting to a pH suitable for condensation, but in order to easily obtain a specific Martens hardness, 3 minutes or more and 120 minutes The following are preferred.

  By the means as described above, it is possible to reduce the reaction residues, form irregularities on the surface layer, and further form a network structure between the protrusions, so that the toner particles having the above-mentioned specific sticking ratio can be obtained. It is easy to get hit.

<Measurement of particle size of toner (particles)>
A precise particle size distribution measuring device (trade name: Coulter Counter Multisizer 3) by a pore electric resistance method and dedicated software (trade name: Beckman Coulter Multisizer 3 Version 3.51, manufactured by Beckman Coulter, Inc.) were used. The aperture diameter was 100 μm, the number of effective measurement channels was 25,000, and the measurement data was analyzed and calculated. As the electrolytic aqueous solution for measurement, a solution in which special grade sodium chloride was dissolved in ion-exchanged water so that the concentration became about 1% by mass, and ISOTON II (trade name) manufactured by Beckman Coulter, Inc. was used. Before the measurement and analysis, the dedicated software was set as follows.
On the "Change standard measurement method (SOM) screen" of the dedicated software, set the total count number in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to (standard particles 10.0 μm, Beckman Coulter, Inc. The value obtained by using the product was set. The threshold and noise level were automatically set by pressing the threshold/noise level measurement button. Further, the current was set to 1600 μA, the gain was set to 2, and the electrolytic solution was set to ISOTON II (trade name), and the flash of the aperture tube after the measurement was checked.
In the dedicated software “pulse to particle size conversion setting screen”, the bin interval was set to logarithmic particle size, the particle size bin was set to 256 particle size bin, and the particle size range was set to 2 μm to 60 μm.
The specific measuring method is as follows.
(1) About 200 mL of the electrolytic aqueous solution was placed in a glass 250 mL round-bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 rotations/second. Then, the dirt and air bubbles in the aperture tube were removed by the "flush aperture tube" function of the analysis software.
(2) About 30 mL of the electrolytic aqueous solution was placed in a 100 mL flat-bottom beaker made of glass. Diluted solution of Contaminone N (trade name) (10% by mass aqueous solution of neutral detergent for cleaning precision measuring instruments, manufactured by Wako Pure Chemical Industries, Ltd.) 3 times by mass with deionized water was added to this solution. 3 mL was added.
(3) An ultrasonic disperser (trade name: Ultrasonic Dispersion System Tetra 150, manufactured by Nikkaki Bios Co., Ltd.) that has two oscillators with an oscillating frequency of 50 kHz and a phase shift of 180 degrees and has an electric output of 120 W. About 2 mL of a predetermined amount of ion-exchanged water and Contaminone N (trade name) were added to the water tank.
(4) The beaker of (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker was maximized.
(5) About 10 mg of toner (particles) was added little by little to the electrolytic aqueous solution in the beaker of the above (4) while being irradiated with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion treatment was continued for another 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank was appropriately adjusted to be 10°C or higher and 40°C or lower.
(6) To the round-bottom beaker of (1) installed in the sample stand, drop the electrolytic solution of (5) in which the toner (particles) is dispersed using a pipette so that the measured concentration is about 5%. Adjusted to. Then, the measurement was performed until the number of measured particles reached 50,000.
(7) The measurement data was analyzed by the dedicated software attached to the apparatus to calculate the weight average particle diameter (D4). The “average diameter” on the analysis/volume statistical value (arithmetic mean) screen when the graph/volume% is set with the dedicated software is the weight average particle diameter (D4). The number average particle size (D1) is the "average diameter" of the "Analysis/number statistical value (arithmetic mean)" screen when graph/number% is set with dedicated software.

(Method for preparing THF-insoluble matter of toner particles for NMR measurement)
Tetrahydrofuran (THF) insoluble matter of the toner particles was prepared as follows.
10.0 g of the toner particles are weighed, put into a cylindrical filter paper (No. 86R manufactured by Toyo Roshi Kaisha, Ltd.), and put on a Soxhlet extractor. 200 mL of THF was used as a solvent for extraction for 20 hours, and the filter cake in the cylindrical filter paper was vacuum dried at 40° C. for several hours to obtain the THF-insoluble content of the toner particles for NMR measurement.

When the surface of the toner particles is treated with an external additive or the like, the external additive is removed by the following method to obtain toner particles.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved with a water bath to prepare a concentrated sucrose solution. Centrifuge tube (capacity: 50 mL) containing 31 g of the concentrated sucrose solution and Contaminone N (a nonionic surfactant, anionic surfactant, an organic builder, pH 7 precision measuring instrument) 6% of a mass% aqueous solution, manufactured by Wako Pure Chemical Industries, Ltd. is added to prepare a dispersion liquid. To this dispersion, 1.0 g of toner is added, and a lump of toner is loosened with a spatula or the like.
The centrifuge tube is shaken with a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube for a swing rotor (volume: 50 mL), and separated by a centrifuge (H-9R Kokusan Co., Ltd.) under conditions of 3500 rpm and 30 minutes. By this operation, the toner particles and the detached external additive are separated. Visually confirm that the toner and the aqueous solution are sufficiently separated, and collect the toner separated in the uppermost layer with a spatula or the like. The collected toner is filtered with a vacuum filter and then dried with a dryer for 1 hour or more to obtain toner particles. This operation is performed multiple times to secure the required amount.

<<Method for confirming structure represented by formula (1)>>
The following method is used to confirm the structure represented by the formula (1) in the organosilicon polymer contained in the toner particles.
The hydrocarbon group represented by R in the formula (1) was confirmed by ¹³ C-NMR.

<< ¹³ C-NMR (solid) measurement conditions>>
Device: JEOL RESONANCE JNM-ECX500II
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran particles insoluble in toner particles for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP/MAS
Measurement nuclear frequency: 123.25MHz ( ^13C )
Reference substance: Adamantane (external standard: 29.5 ppm)
Sample rotation speed: 20 kHz
Contact time: 2ms
Delay time: 2s
Total number of times: 1024

At this method, a methyl group _(Si-CH 3) bonded to the silicon atom, an ethyl group _{(Si-C 2 H 5)} , propyl _{(Si-C 3 H 7)} , butyl group _{(Si-C 4} H ₉ ), a pentyl group (Si—C ₅ H ₁₁ ), a hexyl group (Si—C ₆ H ₁₃ ), a phenyl group (Si—C ₆ H ₅ —), etc. depending on the presence or absence of a signal, the formula (1) The hydrocarbon group represented by R was confirmed.

<<Calculation Method of Ratio of Peak Areas Assigned to Structure of Formula (1) in Organosilicon Polymer Contained in Toner Particles>>
²⁹ Si-NMR (solid) measurement of the THF insoluble matter of the toner particles is performed under the following measurement conditions.
<< ²⁹ Si-NMR (solid) measurement conditions>>
Device: JEOL RESONANCE JNM-ECX500II
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran particles insoluble in toner particles for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP/MAS
Measurement nuclear frequency: 97.38 MHz ( ²⁹ Si)
Reference substance: DSS (external standard: 1.534 ppm)
Sample rotation speed: 10 kHz
Contact time: 10 ms
Delay time: 2s
Total number of times: 2000-8000 times

After the above measurement, a plurality of silane components having different substituents and bonding groups, which are insoluble in tetrahydrofuran of the toner particles, are peak-separated into the following X1 structure, X2 structure, X3 structure, and X4 structure by curve fitting. Calculate the area.
X1 structure: (Ri)(Rj)(Rk)SiO _1/2 (2)
X2 structure: (Rg)(Rh)Si(O _1/2 ) ₂ (3)
X3 structure: RmSi(O _1/2 ) ₃ (4)
X4 structure: Si(O _1/2 ) ₄ (5)

(Ri, Rj, Rk, Rg, Rh, and Rm in formulas (2), (3), and (4) are organic groups such as hydrocarbon groups having 1 to 6 carbon atoms, which are bonded to silicon, and halogen atoms. , Hydroxy group, acetoxy group or alkoxy group.)
When the structure represented by the above formula (1) needs to be confirmed in more detail, it may be identified by the measurement result of ¹ H-NMR together with the measurement result of ¹³ C-NMR and ²⁹ Si-NMR.

<Measurement of Content of Organosilicon Polymer in Toner Particles>
The content of the organosilicon polymer is measured by a wavelength dispersive X-ray fluorescence analyzer “Axios” (manufactured by PANalytical) and dedicated software “SuperQ ver. 4.” attached for setting measurement conditions and analyzing measurement data. 0F” (manufactured by PANalytical) is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. When measuring a light element, a proportional counter (PC) is used, and when measuring a heavy element, a scintillation counter (SC) is used.
As a measurement sample, 4 g of toner particles were placed in a dedicated aluminum ring for pressing and flattened, and a tablet molding compressor "BRE-32" (manufactured by Maekawa Testing Machine Co., Ltd.) was used at 60 MPa at 60 MPa. Pellets that are pressed for 2 seconds and molded into a thickness of 2 mm and a diameter of 39 mm are used.
To 100 parts by mass of toner particles containing no organosilicon polymer, 0.5 parts by mass of silica (SiO ₂ ) powder is added and sufficiently mixed using a coffee mill. Similarly, fine silica powder is mixed with toner particles in an amount of 5.0 parts by mass and 10.0 parts by mass, and these are used as a sample for a calibration curve.
For each sample, pellets of the sample for the calibration curve were prepared as described above using the tablet molding compressor, and when PET was used for the dispersive crystal, it was observed at the diffraction angle (2θ)=109.08°. The Si-Kα ray count rate (unit: cps) is measured. At this time, the acceleration voltage and current value of the X-ray generator were set to 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the obtained X-ray count rate as the vertical axis and the addition amount of SiO ₂ in each calibration curve sample as the horizontal axis.
Next, the toner particles to be analyzed are pelletized by using a tablet molding compressor as described above, and the Si-Kα ray count rate is measured. Then, the organosilicon polymer content in the toner particles is determined from the above calibration curve.

<Method for measuring the sticking rate of the organosilicon polymer on the surface of the toner particles>
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved with a water bath to prepare a concentrated sucrose solution. In a centrifuge tube (volume 50 mL), 31 g of the above concentrated sucrose solution, Contaminone N (a nonionic surfactant, an anionic surfactant, and an organic builder, pH 7 precision measuring instrument) 6% of a mass% aqueous solution, manufactured by Wako Pure Chemical Industries, Ltd. is added to prepare a dispersion liquid. To this dispersion, 1.0 g of toner is added, and a lump of toner is loosened with a spatula or the like.

The centrifuge tube is shaken with a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution was replaced with a glass tube for swing rotor (capacity: 50 mL), and a centrifuge (H-9R manufactured by Kokusan Co., Ltd.) was operated at 3500 rp.
Separation under the condition of m, 30 minutes. Visually confirm that the toner particles and the aqueous solution are sufficiently separated, and collect the toner particles separated in the uppermost layer with a spatula or the like. The collected aqueous solution containing toner particles is filtered with a vacuum filter and then dried with a dryer for 1 hour or more. The dried product is disintegrated with a spatula and the amount of silicon is measured by fluorescent X-ray. The sticking rate (%) is calculated from the element amount ratio of the toner particles after the treatment with the concentrated sucrose solution and the toner particles before the treatment.
The measurement of the fluorescent X-ray of each element conforms to JIS K 0119-1969, and specifically is as follows.
As a measuring device, a wavelength dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and attached dedicated software "SuperQ ver. 4.0F" (manufactured by PANalytical) for performing measurement condition setting and measurement data analysis ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds. When measuring a light element, a proportional counter (PC) is used, and when measuring a heavy element, a scintillation counter (SC) is used.
As a measurement sample, about 1 g of the toner particles after washing and the initial toner particles were put into a dedicated aluminum ring for press with a diameter of 10 mm and flattened, and the tablet molding compressor “BRE-32” (Maekawa Test Machine Co., Ltd. (Manufactured by K.K.) is used to press at 20 MPa for 60 seconds, and pellets molded to a thickness of about 2 mm are used.
The measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the concentration is calculated from the count rate (unit: cps), which is the number of X-ray photons per unit time.

As a quantification method in the toner particles, for example, silica is added in an amount of 0.5 parts by mass with respect to 100 parts by mass of the toner particles, and silica (SiO ₂ ) fine powder is sufficiently added using a coffee mill. Mix. Similarly, fine silica powder is mixed with toner particles so as to be 2.0 parts by mass and 5.0 parts by mass, respectively, and these are used as a sample for a calibration curve.
For each sample, pellets of the sample for the calibration curve were prepared as described above using the tablet molding compressor, and when PET was used for the dispersive crystal, it was observed at the diffraction angle (2θ)=109.08°. The Si-Kα ray count rate (unit: cps) is measured. At this time, the acceleration voltage and the current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the obtained X-ray count rate as the vertical axis and the addition amount of SiO ₂ in each calibration curve sample as the horizontal axis.

Next, the toner particles to be analyzed are pelletized by using a tablet molding compressor as described above, and the Si-Kα ray count rate is measured. Then, the amount of silicon in the toner particles is obtained from the above calibration curve.
Then, (the amount of silicon present on the surface of the toner particles after the sucrose treatment/the amount of silicon present on the surface of the toner particles before the sucrose treatment)×100 is defined as the sticking rate (%).

[External additive]
The toner particles can be used as a toner without externally adding an external additive, but in order to improve fluidity, charging property, cleaning property, etc., so-called external additives such as a fluidizing agent and a cleaning aid are used. May be added to obtain a toner.

  As the external additive, for example, inorganic oxide fine particles made of alumina fine particles, titanium oxide fine particles, etc., inorganic stearate compound fine particles such as aluminum stearate fine particles, zinc stearate fine particles, or strontium titanate, zinc titanate, etc. Inorganic titanate compound fine particles and the like. These can be used alone or in combination of two or more.

These inorganic fine particles are preferably surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil or the like in order to improve the heat resistant storage property and the environmental stability. The BET specific surface area of the external additive is preferably 10 m ² /g or more and 450 m ² /g or less.

The BET specific surface area can be determined by the low temperature gas adsorption method by the dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, by using a specific surface area measuring device (trade name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the surface of the sample, and measurement is performed using the BET multipoint method. The BET specific surface area (m ² /g) can be calculated.

  The total amount of these various external additives added is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass with respect to 100 parts by mass of the toner particles. It is below the mass part. Further, various external additives may be used in combination.

<<Embodiment 1>>
<Outline of image forming apparatus>
The overall configuration of the electrophotographic image forming apparatus according to the first embodiment of the present invention will be described with reference to FIG. FIG. 2 is a schematic sectional view of the image forming apparatus 1 according to the first embodiment of the present invention. Examples of the image forming apparatus to which the present invention can be applied include a copying machine and a printer using an electrophotographic method. Here, the image forming apparatus 1 of the present embodiment is a full-color image forming apparatus using a tandem method and an intermediate transfer method. A case where the present invention is applied to a laser beam printer will be described.

  As shown in FIG. 2, in the image forming apparatus 1, a photosensitive drum 5 is arranged as an image carrier so as to be rotatable and driven. Around the photoconductor drum 5, a charging roller 6 as a charging means for uniformly charging the surface of the photoconductor drum 5, a laser based on image information is irradiated with a laser, and an electrostatic image (electrostatic latent image) is formed on the photoconductor drum. A laser scanner unit 90 (exposure device) as an exposure unit for forming an image is formed. Further, around the photosensitive drum 5, a developing device for developing an electrostatic image as a toner image (developer image), and a cleaning unit for removing transfer residual toner remaining on the surface of the photosensitive drum 5 after transfer. The cleaning member 8 is disposed.

  The developing unit (developing device) 45 uses a toner of non-magnetic one-component developer (one-component toner) as a developer, a developing roller 7 as a developer carrying member, and a developing process for toner coating on the developing roller 7. It has a developing blade 9 as an agent regulating member. The image forming apparatus according to the present exemplary embodiment is a contact developing method in which the developing roller 7 is brought into contact with the photosensitive drum 5 to perform reversal development. That is, by attaching the negatively charged toner carried by the developing roller 7 to the portion (image portion, exposed portion) of which the charge is attenuated by the exposure on the photosensitive drum 5, an electrostatic image on the photosensitive drum 5 is obtained. Is developed into a toner image (developer image).

  The image forming apparatus 1 according to the present embodiment is configured such that the process means such as the photosensitive drum 5 is integrated as a process cartridge 4 and is attachable to and detachable from the apparatus body of the image forming apparatus 1. In the main assembly of the image forming apparatus 1, four process cartridges 4 are provided for each color of yellow, magenta, cyan, and black, and are arranged in a line. That is, the process cartridges 4y, 4m, 4c, and 4k are arranged in a line in the apparatus main body of the image forming apparatus 1. Further, each process cartridge 4 includes a photosensitive drum 5 (5y, 5m, 5c, 5k) which is an image bearing member, a charging roller 6 (6y, 6m, 6c, 6k), a developing roller 7 (7y, 7m, 7c, 7k), the developing blade 9 (9y, 9m, 9c, 9k), the drum cleaning member 8 (8y, 8m, 8c, 8k) and the like.

The posture of the image forming apparatus 1 in FIG. 1 shows a state in which the image forming apparatus is installed on a horizontal plane as a normal installation state (installation state during operation). It corresponds substantially to the direction of gravity (vertical direction), and the left-right direction of the paper surface corresponds substantially to the horizontal direction.
In addition, here, the subscripts of y, m, c, and k are described for each color of yellow, magenta, cyan, and black. The description is omitted.

The toner cartridges 20 (developer containers) are attachable to and detachable from the main body of the image forming apparatus 1, and four toner cartridges 20 (developer containers) are provided corresponding to each of the yellow, magenta, cyan, and black process cartridges 4. That is, the toner cartridges 20y, 20m, 20c and 20k are arranged to supply toner to the process cartridges 4y, 4m, 4c and 4k, respectively. The process cartridges 4y, 4m, 4c, and 4k are provided with toner storage portions 44y, 44m, 44c, and 44k, respectively, and store the toners supplied from the toner cartridges 20y, 20m, 20c, and 20k, respectively.
More specifically, the process cartridge 4 is divided into a drum unit 46 and a developing unit 45, and is configured to be attachable to and detachable from the main body of the image forming apparatus 1 either integrally or individually. The drum unit 46 integrally supports the photoconductor drum 5, the charging roller 6, the drum cleaning member 8, and the waste toner containing the residual toner scraped off the photoconductor drum 5 by the drum cleaning member 8. It is a cartridge in which a frame having a housing portion is integrated. The developing unit 45 includes a developing roller 7 as a developer carrying member, a toner supply roller, a developing blade 9 as a regulating member, and a frame body (developing container) that integrally supports them and has a toner storage portion 44. And is an integrated cartridge.
In this embodiment, the toner cartridges 20 are arranged so as to be aligned with the developing unit 45 in a substantially horizontal direction and below the drum unit 46 in a substantially vertical direction.
Details of the toner transport path for the process cartridge 4 will be described later.

In the present embodiment, the toner cartridge 20 as a developer container, the developing unit 45 as a developing unit in which the developing roller 7 and the like are arranged, and the toner are supplied from the toner cartridge 20 to the developing unit 45 (toner accommodating portion 44). A developing device of the present invention is configured by a toner transport path (described later) that includes a toner transport means for performing the above.
In the present embodiment, the toner cartridge 20 and the developing unit 45 are provided as separate bodies and are detachably attached to the apparatus body of the image forming apparatus 1, thereby improving maintainability.
That is, while the image forming process means is integrally configured as the process cartridge 4 so as to be attachable to and detachable from the apparatus main body, the developer container for containing the developer used in the image forming process is provided independently of the process cartridge 4. The toner cartridge 20 is attachable to and detachable from the main body of the apparatus. Further, the toner conveying path is arranged in the apparatus main body 1 to reduce the size of the cartridge.

  The intermediate transfer unit 17 includes a primary transfer roller 10 (10y, 10m, 10c, 10k), an intermediate transfer belt 11, a drive roller 12, a tension roller 13, a secondary transfer counter roller 14a, and a cleaning device 30. The intermediate transfer belt 11 is an endless cylindrical belt, and is stretched around a drive roller 12, a tension roller 13, and a secondary transfer counter roller 14a. The toner picked up by the cleaning device 30 is collected in the waste toner box 40 as a waste toner container.

  At the time of image formation, when a control unit (not shown) issues a print signal, the feeding roller 3 sends out the sheets stacked and stored in the sheet stacking unit 2.

On the other hand, the surface of the photosensitive drum 5 is charged by the charging roller 6. Then, the laser scanner unit 90 emits a laser beam from a light source (not shown) provided inside, and irradiates the photosensitive drum 5 with the laser beam. As a result, an electrostatic latent image is formed on the surface of the photosensitive drum 5. By developing this electrostatic latent image with the toner (developer) carried by the developing roller 7, a toner image (developer image) is formed on the photosensitive drum 5. The toner image formed on the photosensitive drum 5 of each process cartridge 4 is primarily transferred to the intermediate transfer belt 11. The intermediate transfer belt 11 rotates in the direction of arrow A when the drive roller 12 receives a rotational force from a drive source such as a motor (not shown). The primary-transferred toner image reaches the secondary transfer portion formed by the secondary transfer counter roller 14a and the secondary transfer roller 14b, which is downstream in the rotation direction by the rotation of the intermediate transfer belt 11, and the toner image is transferred here. Transferred to the sheet.
The sheet on which the toner image is transferred is sent to the fixing device 15, heated and pressed to fix the toner image on the sheet, and then is conveyed by the discharge roller 16 and discharged to a discharge portion (paper discharge tray). ..

<Developing blade>
The developing blade 9 is arranged so as to face the counter direction with respect to the rotation of the developing roller 7, and is a member that regulates the amount of toner carried on the developing roller 7. Further, the toner is frictionally charged by the sliding friction between the developing blade 9 and the developing roller 7 to be given an electric charge, and at the same time, the layer thickness is regulated. The developing blade 9 has one end in the short side direction fixed to the developing container by a fastener such as a screw, and the other end is a free end.

  In this embodiment, as the developing blade 9, a thin plate of SUS304-1/2H having a leaf spring-like elasticity and having a free length of 8 mm in the lateral direction and a thickness of 0.08 mm is used. The free end of the blade was brought into contact with the surface of the developing roller 7 with a pressing force of 25 N/m of linear pressure.

<Developing roller>
As the developing roller 7, a roller coated with an elastic rubber layer was used. The hardness of the elastic rubber layer is preferably 20 to 50° in MD1 hardness in order to keep the contact state with the photosensitive drum 5 uniform. In the embodiment, a rubber having a hardness of 38° was used. The rubber hardness was measured with a MD-1 hardness meter (pressing needle shape: type A) manufactured by Kobunshi Keiki Co., Ltd. The surface roughness is set to 0.2 to 2.0 μm in terms of center line average roughness Ra, and a required amount of toner is retained on the surface. If Ra is less than 0.2, the desired toner amount cannot be obtained and the density becomes low. Further, when Ra is larger than 2.0, it is difficult to give sufficient charge to each toner, and the so-called “fog” that toner adheres to the non-image area is likely to occur. In the embodiment, Ra=1.0 μm was used. The center line average roughness Ra was measured by "Surfcoder SE3500" manufactured by Kosaka Laboratory Ltd.

<Toner transport>
As shown in FIGS. 3A, 3</b>B, and 3</b>C, the toner cartridge 20 is provided with a toner outlet 24 and a toner conveying screw 23. 3A is a schematic perspective view of the toner cartridge 20, FIG. 3B is a schematic sectional view of the toner cartridge 20 taken along the dotted line A in FIG. 3A, and FIG. 3A is a schematic cross-sectional view of the toner cartridge 20 taken along the dotted line B in FIG.

  The internal space of the toner cartridge 20 includes a toner storage chamber 201 in which the toner 40 is stored, and a toner transport chamber 202 in which the toner transport screw 23 as a developer transport member is disposed. The toner cartridge 20 has a connecting portion 203 that is connected to a conveying path forming member 70 that forms a toner conveying path on the main body side, which will be described later. And communicate with the outside of the toner cartridge 20.

The connecting portion 203 is further projected downstream from the side surface facing the downstream side in the mounting direction of the toner cartridge 20 in the image forming apparatus main body (the inner side of the housing portion of the toner cartridge 20 in the apparatus main body) in the mounting direction. It is provided. When the toner cartridge 20 is attached to the main body of the image forming apparatus, the toner discharge port 24 of the connecting portion 203 is at a position where the toner can be transferred to the transport path forming member 70 (a toner receiving port 71 of the transport path forming member 70 described later). It is located at a position where they can communicate with each other.

  In the toner storage chamber 201, a stirring blade 22 as a stirring/transporting member for stirring the stored toner 40 and transporting it to the toner transporting chamber 202 is provided rotatably around the stirring shaft 21. The toner 40, which the stirring blades 22 have jumped up in accordance with the rotation of the stirring shaft 21, is delivered to the toner transport chamber 202 in which the toner transport screw 23 is arranged. Then, by the rotation of the toner transport screw 23, the toner is transported in the toner transport chamber 202 toward the toner discharge port 24 and discharged from the toner discharge port 24.

FIG. 4A is a schematic perspective view in a state where the toner cartridge 20 is mounted on the main body 1, and FIG. 4B is a toner cartridge 20 and a main body transport path forming section along a dotted line C in FIG. 4A. A schematic cross-sectional view of 70 is shown.
5A is a schematic perspective view of the configuration around the main body transport path forming member 70 in a state where the toner cartridge 20 and the process cartridge 4 are mounted in the main body 1, and FIG. A schematic cross-sectional view taken along the dotted line H in FIG.
The toner discharged from the toner cartridge 20 is delivered to the toner receiving port 71 of the main body transport path forming member 70 by its own weight. Then, it is conveyed in the direction of arrow D by the rotation of the conveying screw 36.

  The transport path forming member 70 is a duct-shaped hollow member, and the hollow inner space thereof constitutes a toner transport path. The conveyance path forming member 70 includes a first conveyance section 701 and a second conveyance section 702, which have different toner conveyance directions, and the connection section 203 of the toner cartridge 20 is provided on the upstream side of the first conveyance section 701. A connecting portion 703 is provided to connect the toner transport path between the two. A toner receiving port 71 for receiving the toner falling from the toner discharging port 24 of the toner cartridge 20 is provided on the upper surface of the connecting portion 703. The first transport unit 701 forms a transport path extending in the mounting direction of the toner cartridge 20 in the apparatus main body 1, and the second transport unit 702 is connected downstream thereof. The second transport unit 702 has a transport path extending in the mounting direction of the toner cartridge 20 in the apparatus main body 1 by the first transport unit 701 in parallel to the alignment direction of the toner cartridge 20 and the process cartridge 4 (developing unit 45). Change direction. A toner discharge port 72 that opens below the transport path is provided on the downstream side of the transport path of the second transport unit 702. The toner transport path extending from the toner cartridge 20 through the first transport unit 701 and the second transport unit 702 extends from the toner discharge port 72 to the toner receiving port 41 provided in the connection unit 43 of the process cartridge 4 (developing unit 45). It is connected to the toner storage unit 44 via the. The connecting portion 43 of the process cartridge 4 further projects downstream from the side facing the downstream side in the mounting direction of the process cartridge 4 in the apparatus main body 1 (the inner side of the accommodating portion of the process cartridge 4 in the apparatus main body). It is provided to do. When the process cartridge 4 is mounted on the main body of the image forming apparatus, the toner receiving port 41 opening on the upper surface of the connecting portion 43 on the downstream side in the mounting direction is located at a position where the toner discharged from the transport path forming member 70 can be received (toner). It is arranged at a position (overlapping so as to communicate with the discharge port 72).

  In this embodiment, the path of the toner carrying path is detoured in a direction different from the direction in which the process cartridge 4 and the toner cartridge 20 are arranged, and the direction of the carrying path is changed in a substantially U-shape. .. With such a configuration, the process cartridge 4 and the toner cartridge 20 can be arranged as close to each other as possible, the size of the apparatus can be reduced, and a route required for disposing a screw as a toner conveying unit. The length can be arbitrarily secured. The configuration of the toner transport path is not limited to that shown here.

  FIG. 1 is a schematic perspective view showing a joint portion (driving force transmission portion) of a toner conveying screw 36 as a first conveying member and a toner discharging screw 37 as a second conveying member provided in a conveying path forming member 70. It is a figure.

The toner carrying screw 36 is arranged in the first carrying unit 701, and carries the toner sent from the toner cartridge 20 into the first carrying unit 701 via the connecting unit 703 toward the second carrying unit 702. The toner conveying screw 36 has a rotating shaft 36k at its center, and a screw portion (spiral blade) having a first blade tooth surface 36g spirally provided on the outer peripheral surface thereof so as to convey the toner in the rotating shaft 36k direction. ) Is provided. Then, a rotational force is applied from a drive source (not shown) such as a motor by a drive gear (drive receiving means) (not shown) provided at the end of the rotary shaft 36k of the toner carrying screw 36, and the rotational force is applied in the direction of arrow E in FIG. Rotate.
The toner discharge screw 37 may directly receive a rotational force from a drive source such as a motor (not shown), and the toner transport screw 36 may receive the rotational force from the toner discharge screw 37 and be driven to rotate.

  The toner that has come into contact with the toner carrying screw 36 is carried in the rotation axis direction (arrow D direction) by the first blade tooth surface 36g that moves as the toner carrying screw 36 rotates. Then, the toner is discharged in a direction (arrow D direction) toward the upstream end of the toner discharging screw 37 provided downstream of the toner carrying screw 36 in the toner carrying direction, and starts to come into contact with the toner discharging screw 37.

  The toner discharging screw 37 is arranged in the second conveying unit 702, and the toner sent by the toner conveying screw 36 from the first conveying unit 701 to the second conveying unit 702 is directed toward the connecting portion 43 of the process cartridge 4. Transport. The toner discharge screw 37 includes a rotating shaft 37k, and a screw portion having an outer peripheral surface having a second blade tooth surface 37g spirally provided so as to convey the toner in the rotating shaft 37k direction (arrow G direction). Equipped with (spiral blade). Further, it is provided in a direction substantially orthogonal to the toner carrying screw 36 for downsizing of the apparatus. Further, the toner discharging screw 37 has a drive receiving portion 50 for receiving a rotational force from the toner carrying screw 36, and rotates in the arrow F direction following the rotation of the toner carrying screw 36. The drive receiving portion 50 is configured in such a manner that a force for rotating the toner discharging screw 37 from the rotating toner conveying screw 36 acts by the contact with the first blade tooth surface 36g of the toner conveying screw 36. When the drive receiving portion 50 receives the rotational force from the toner carrying screw 36, the toner is sandwiched and rubbed between the toner carrying screw 36 and the drive receiving portion 50.

The toner in contact with the toner discharge screw 37 is directed toward the toner discharge port 72 provided near the downstream end of the toner discharge screw 37 by the second blade tooth surface 37g that moves with the rotation of the toner discharge screw 37 (arrow). It is conveyed in the form of being extruded in the G direction). After that, the toner is discharged from the toner discharge port 72 by its own weight and delivered to the receiving port 41 of the process cartridge 4. Toner is supplied to the process cartridge 4 by being conveyed into the process cartridge 4 by the conveying screw 42.
The rotary shaft 36k of the toner transport screw 36 and the rotary shaft 37k of the toner discharge screw 37 are in a positional relationship offset from each other in a direction orthogonal to the two (the vertical direction in FIG. 5). Therefore, the moving area of the first blade tooth surface 36g of the toner carrying screw 36 (the space area where the blade tooth surface directly carries (contacts) the toner carrying operation) and the second blade tooth surface of the toner discharging screw 37. The moving areas of the surface 37g also have a positional relationship that is offset from each other. Therefore, the hollow space of the transport path forming member 70, the hollow space of the first transport unit 701, and the hollow space of the second transport unit 702 correspond to the displacements of the moving regions of the tooth flanks of the respective screws. It is preferable to have a configuration that is displaced in a direction orthogonal to the rotation axis of the screw. That is, the heights of the bottom surface and the ceiling of the toner transport path are vertically displaced between the first transport section 701 and the second transport section 702. As described above, it is preferable that the gap between each screw and the hollow inner wall surface of the transport path forming member 70 is set to be suitable for toner transport to enhance the toner transport efficiency.
Note that, in FIG. 4, the first transporting section 701 and the second transporting section 702 are formed at the same height, but the respective internal spaces have been described above, for example, by changing the thickness of the wall. As described above, the blade tooth surfaces may be displaced from each other in accordance with the displacement of the moving area of the blade tooth surfaces. Alternatively, if the wall thickness is made uniform in the entire conveyance path forming member 70, the height of the upper surface and the lower surface of each of the first conveyance unit 701 and the second conveyance unit 702 is vertically displaced as the external configuration in FIG. Such a configuration may be adopted.
Thus, changing the configuration of the transport path forming member according to the height shift of the moving region of the blade tooth surface may be similarly applied to the configurations of other embodiments.

<Toner>
The toner used in this embodiment will be described below. Hereinafter, all “parts” of each material are based on mass unless otherwise specified.

(Preparation process of aqueous medium 1)
To 1000.0 parts of ion-exchanged water in the reaction vessel, 14.0 parts of sodium phosphate (12 hydrate manufactured by Lhasa Kogyo Co., Ltd.) was charged, and the temperature was kept at 65° C. for 1.0 hour while purging with nitrogen.
T. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12000 rpm, an aqueous solution of calcium chloride in which 9.2 parts of calcium chloride (dihydrate) was dissolved in 10.0 parts of ion-exchanged water was collected. Then, an aqueous medium containing the dispersion stabilizer was prepared. Furthermore, 10 mass% hydrochloric acid was added to the aqueous medium to adjust the pH to 5.0, and thus an aqueous medium 1 was obtained.

(Process for preparing polymerizable monomer composition)
-Styrene: 60.0 parts-C.I. I. Pigment Blue 15:3: 6.5 parts The above material was put into an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.) and further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5.0 hours to prepare a pigment. A dispersion was prepared. The following materials were added to the pigment dispersion.
-Styrene: 20.0 parts-n-butyl acrylate: 20.0 parts-Crosslinking agent (divinylbenzene): 0.3 parts-Saturated polyester resin: 5.0 parts (Propylene oxide-modified bisphenol A (2 mol addition product) Polycondensate of terephthalic acid (molar ratio 10:12), glass transition temperature Tg=68° C., weight average molecular weight Mw=10000, molecular weight distribution Mw/Mn=5.12)
Fischer-Tropsch wax (melting point 78° C.): 7.0 parts This was kept warm at 65° C. K. A homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to uniformly dissolve and disperse at 500 rpm to prepare a polymerizable monomer composition.

(Granulation process)
The temperature of the aqueous medium 1 is 70° C. K. While maintaining the rotation speed of the homomixer at 12000 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 9.0 parts of t-butylperoxypivalate as a polymerization initiator was added. Granulation was performed for 10 minutes while maintaining 12,000 rpm with the stirring device.

(Polymerization process)
After the granulation step, the stirrer was changed to a propeller stirring blade to carry out polymerization for 5.0 hours while maintaining 70°C while stirring at 150 rpm, and the polymerization reaction was performed by heating to 85°C and heating for 2.0 hours. To obtain toner particles. When the temperature of the slurry was cooled to 55° C. and the pH was measured, it was pH=5.0.

(Washing and drying process)
After the completion of the polymerization process, the toner particle slurry is cooled, hydrochloric acid is added to the toner particle slurry to adjust the pH to 1.5 or less, and the mixture is left to stir for 1 hour, followed by solid-liquid separation with a pressure filter to obtain a toner cake. Got This was reslurried with ion-exchanged water to form a dispersion again, and then solid-liquid separation was performed with the above-mentioned filter. The reslurry and solid-liquid separation were repeated until the electric conductivity of the filtrate became 5.0 μS/cm or less, and finally solid-liquid separation was performed to obtain a toner cake.
The obtained toner cake was dried using a flash jet dryer, a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and fine coarse powder was cut using a multi-division classifier utilizing the Coanda effect to obtain toner particles 1. The drying conditions were such that the blowing temperature was 90° C., the dryer outlet temperature was 40° C., and the toner cake supply rate was adjusted so that the outlet temperature did not deviate from 40° C. according to the water content of the toner cake.

(External process)
In this example, inorganic silicon fine particles were externally added to the obtained toner particles 1 to prepare a toner.
2.0 parts by mass to 5.0 parts by mass of silica fine particles are dry-mixed with 100 parts by mass of the toner particles by a Henschel mixer (FM-10C, manufactured by Mitsui Mining Co., Ltd.) for 10 minutes to 30 minutes to obtain toners A to E. Got

  A plurality of toners having different sticking rates were realized by changing the mixing time of the Henschel mixer. The toner is as shown in Table 1.

In the image forming apparatus 1 according to this embodiment, the obtained toner was used and printing was performed at a printing rate of 2%. Image evaluation when a solid image was output at the time of 50,000 sheets and observation of the surface of the developing roller 7 were performed. The toner supply from the toner container to the developing container was set to 8 g/1000 sheets, which is almost the same as the printed toner amount.
(Vertical streak image)
◯: No occurrence of vertical stripe-like density unevenness over the entire image △: Slight occurrence of slight vertical stripe-like density unevenness, but no problem in use ×: Occurrence in part or all of the image Vertical stripe-shaped density unevenness (developing roller streaks)
◯: No occurrence of scratches by visual observation after cleaning the developing roller △: Slight occurrence Occurrence of slight scraping by visual observation after cleaning of the developing roller
No problem in use x: Occurrence There is a scratch mark by visual observation after cleaning the developing roller.

(Evaluation results)
Table 2 shows the results of image evaluation using the toner shown in Table 1 and observation of the surface of the developing roller.

In the toner D and the toner E, at the contact position between the developing blade 9 and the developing roller 7 in the streak generating portion, there was a portion where an aggregate of silica fine particles was sandwiched. It is considered that this is because the silica fine particles are detached and aggregated by receiving a strong shearing force in the vicinity of the drive receiving portion in the toner conveying path.
After that, if the agglomerates of the silica fine particles supplied onto the developing roller 7 are small, a streak image will not be formed by passing through the developing blade 9 and developing, but the silica fine particles as in the case of the toner D. When the agglomerates of the toner become large and stay in the contact nip with the developing blade 9 and the upstream side thereof, uneven toner coating on the developing roller 7 may occur, leading to image streaks.
Further, when the aggregate of silica fine particles further grows large, as in the case of the toner E, it may be pinched in the contact nip with the developing blade 9 and its upstream side, and rubs against the surface of the developing roller 7. As a result, the developing roller 7 may be stripped.

In particular, in the toner E, streaking of the developing roller 7 has occurred, which suggests that agglomerates of silica fine particles have grown significantly in the vicinity of the drive receiving portion in the toner transport path.
On the contrary, in toners A, B, and C, since the aggregate of silica fine particles did not grow significantly, streak images did not occur.

In this embodiment, a toner having a fixing rate of inorganic silicon fine particles of 87% to 93% is used.
By using a toner having a high sticking rate of the inorganic silicon fine particles, the silica fine particles are hard to come off even if the composition is subjected to a strong shearing force in the transportation route as in the example, and the formation of aggregates of the silica fine particles is suppressed. be able to. The meaning of the sticking rate represents the degree of difficulty in removing the silica fine particles, as can be understood from the method of measuring the sticking rate described above.

  As described above, even if one of the plurality of conveying members in the conveying path is driven by receiving a rotational force from the other, the toner of the present invention has vertical stripes caused by the growth of aggregates of silica fine particles. The image can be suppressed.

<<Embodiment 2>>
In the present embodiment, parts different from the first embodiment will be described in detail, and detailed description of the same parts as the first embodiment will be omitted.

<Image forming device>
FIG. 7 is a simplified diagram of the main body 1 in this embodiment. The difference from the first embodiment is that the toner cartridge 25 is arranged below the frame of the developing unit 45, which is the developing container portion housing the developing roller 7, and is arranged substantially horizontally with the drum unit 46. That is the point. By arranging the toner cartridge 25 in this way, there is an advantage that, for example, the toner conveying path to the developing unit 45 is shortened and the main body configuration can be simplified.

<Toner transport>
FIG. 8 is a schematic perspective view showing an external configuration of the toner cartridge 25. The toner cartridge 25 according to the present exemplary embodiment has a configuration in which the configuration of the toner cartridge 20 according to the first exemplary embodiment is laterally reversed. That is, the toner discharging structure of the toner cartridge 25 is the same as that of the toner cartridge 20, and the description thereof is omitted.

FIG. 9A is a schematic perspective view of the configuration around the main body transport path forming member 80 when the toner cartridge 25 and the process cartridge 4 are mounted on the main body 1. FIG. 9B is a schematic sectional view taken along the dotted line H in FIG. 9A.
The toner discharged from the toner discharge port 24 of the connecting portion 253 of the toner cartridge 25 (having the same configuration as the connecting portion 203 of the toner cartridge 20 of the first embodiment) is self-weighted to the receiving port 81 of the main body conveyance path forming member 80. Delivered by.

  The transport path forming member 80 is a duct-shaped hollow member, like the transport path forming member 70, and its hollow internal space constitutes a toner transport path. The conveyance path forming member 80 includes a first conveyance section 801 and a second conveyance section 801 having different conveyance directions from the connection portion 253 of the toner cartridge 25 on the upstream side of the toner conveyance path to the connection portion 43 of the process cartridge 4 on the downstream side. It has a transport unit 802 and a third transport unit 803. A toner conveying screw 86 is arranged in the second conveying portion 802, and a toner discharging screw 87 is arranged in the third conveying portion 803.

  The above-described receiving port 81 is provided on the upper surface of the first transporting unit 801, and the inclined surface 85 for moving the toner entering from the receiving port 81 toward the downstream of the toner transporting path by its own weight. Are formed on the bottom surface of the toner transport path. The inclined surface 85 is provided so that the angle with respect to the horizontal plane is larger than the repose angle of the toner in order to promote the movement of the toner.

  The toner that has moved from the first transport unit 801 to the lower portion (upstream side) of the second transport path 802 by the action of the inclined surface 85 comes into contact with the toner transport screw 86 arranged in the second transport unit 802. The toner in contact with the toner carrying screw 86 is carried upward in the direction of arrow J from the upstream end of the toner carrying screw 86 toward the downstream end thereof by the rotation of the toner carrying screw 86.

  The toner carried by the toner carrying screw 86 to the downstream side (upper side) of the toner carrying path of the second carrying unit 802 comes into contact with the toner discharging screw 87 arranged in the third carrying unit 803. The toner in contact with the toner discharging screw 87 is conveyed in the arrow K direction (substantially horizontal direction) in the toner conveying path of the third conveying portion 803 by the rotation of the toner discharging screw 87.

Here, the toner carrying screw 86 rotates following the rotation of the toner discharging screw 87 when the drive receiving portion 50 receives the rotational force from the toner discharging screw 87. The toner discharge screw 87 receives a rotational force from a drive source (not shown) such as a motor by a drive gear (drive receiving means) (not shown) provided at the end of the rotation shaft, and rotates to rotate the toner in the direction of arrow K. To transport. When the drive receiving portion 50 receives the rotational force, the toner is sandwiched and rubbed between the toner conveying screw 86 and the drive receiving portion 50.
The toner transport screw 86 may directly receive a rotational force from a drive source such as a motor (not shown), and the toner discharge screw 87 may receive the rotational force from the toner transport screw 86 and be driven to rotate.

  The toner carried to the downstream of the toner carrying path of the third carrying unit 803 is discharged by its own weight from the toner discharge port 82 provided on the lower surface of the third carrying unit 803, and then to the receiving port 41 of the connecting unit 43 of the process cartridge 4. Delivered. Toner is supplied to the process cartridge 4 (toner accommodating portion 44 of the developing unit 45) by being conveyed by the conveying screw 42 into the process cartridge 4.

  The transport path forming member 70 of the first embodiment has a configuration in which the toner transport path is laid in a substantially U-shape in the mounting direction of the process cartridge 4 and the drum cartridge 20 in the apparatus main body. On the other hand, in the transport path forming member 80 of the second embodiment, the toner transport path is formed in a substantially U-shape in the direction substantially parallel to the arrangement direction (opposing direction) of the process cartridge 4 and the drum cartridge 25 on the inner side. It is a crawling structure and is a more excellent structure in terms of device miniaturization.

The present embodiment is characterized in that the toner carrying screw 86 for carrying the toner upward is driven by the rotation of the toner carrying screw 87, and the drive receiving portion 50 is rotated by receiving the rotational force.
According to the inventors' earnest study, in this configuration, the toner is repeatedly subjected to the shearing force in the drive receiving portion 50, and the external additive that is dislodged from the toner easily stays. It was found that the agglomerates of were easy to grow.

  The effects of the toners shown in Table 3 below were confirmed by the method of Embodiment 1 using the image forming apparatus described in this embodiment.

(Evaluation results)
Table 4 shows the results of image evaluation using the toner shown in Table 3 and observation of the developing roller surface.

In the toner D and the toner E, at the contact position between the developing blade 9 and the developing roller 7 in the streak generating portion, there was a portion where an aggregate of silica fine particles was sandwiched. It is considered that this is because the silica fine particles are detached and aggregated by receiving a strong shearing force in the vicinity of the drive receiving portion in the toner conveying path. On the other hand, in the toner C, the agglomerates of the silica fine particles are sandwiched, but the agglomerates do not grow as large as the toner D and the toner E, and slight vertical stripe-like density unevenness is present in a part of the image. Although it occurred, it was judged that there was no problem in use.
The difference from the first embodiment is that the toner conveying screw 86 conveys the toner upward. According to the inventors' earnest study, the toner nipped by the drive receiving portion is immediately received by the toner discharging screw 87 and spills from the toner discharging screw 87, and falls between the toner conveying screw 86 and the wall of the conveying path. I found out that there are things. As a result, the toner that is nipped by the drive receiving portion is repeatedly generated. Therefore, it is considered that the sticking rate required to suppress the formation of aggregates of the external additive is increased.
As a result of further study, it was found that the condition under which the toner spills from the toner discharge screw 87 is that the angle of the rotation axis of the toner discharge screw 87 is equal to or greater than the repose angle of the toner with respect to the horizontal plane.

  Here, the angle of repose of the toner will be described. The angle of repose of the toner means the inclination angle of the ridge line of the mountain of the toner formed on the flat surface when the toner is dropped on the flat surface. In the present embodiment, the powder tester PT-S (manufactured by Hosokawa Micron) was used to measure the angle of repose. 150 g of toner is placed on a mesh having an opening of 250 μm, and vibration is applied to deposit the toner on a circular table having a diameter of 8 cm through a funnel. At this time, the toner is deposited to the extent that the toner overflows from the end of the table. The angle of repose was determined by measuring the angle formed between the ridgeline of the toner deposited on the table and the circular table surface at this time.

  In the present embodiment, the toner conveying screw 86 on the upstream side of the drive receiving portion conveys upward, but even if the toner discharging screw 87 on the downstream side of the drive receiving portion conveys upward, Since the toner spills to the upstream side of the portion and is repeatedly nipped by the repeated drive receiving portion, the same effect as this embodiment can be obtained.

  Further, particularly in the toner D and the toner E, streaking of the developing roller 7 has occurred, which suggests that the aggregate of silica fine particles has grown significantly in the vicinity of the drive receiving portion in the toner transport path. .. On the contrary, in toners A to C, since the aggregates of silica fine particles did not grow significantly, streak images that would cause problems in use were not generated.

As described above, one of the plurality of transport members in the transport path is driven by receiving the rotational force from the other, and at least one of the transport members is arranged to transport the toner upward. However, if the toner has a fixing rate of the inorganic silicon fine particles of 87% or more, it is possible to suppress the vertical stripe image due to the growth of the aggregate of the silica fine particles. Further, more preferably, a toner in which the fixing rate of the inorganic silicon fine particles is 90% or more can further suppress the vertical stripe image due to the growth of the aggregate of silica fine particles.

Further, in this embodiment, a toner having toner particles and an organosilicon polymer coating the surface of the toner particles as shown in FIG. 6 is used (in FIG. 6, the toner 25 is the toner particle 25a and the toner particle 25a is the surface thereof). Has a surface layer 25b containing an organosilicon polymer).
Also in the toner coated with the surface layer containing the organosilicon polymer, the same effects as those described in the above embodiment can be obtained. That is, in the present embodiment, it is possible to prevent the organosilicon polymer from coming off and forming an aggregate even when a strong shearing force is applied in the toner conveying path.

  Next, the manufacturing conditions of the toner used will be described.

[Toner K]
(Preparation process of aqueous medium 1)
To 1000.0 parts of ion-exchanged water in the reaction vessel, 14.0 parts of sodium phosphate (12 hydrate manufactured by Lhasa Kogyo Co., Ltd.) was charged, and the temperature was kept at 65° C. for 1.0 hour while purging with nitrogen.
T. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12000 rpm, an aqueous solution of calcium chloride in which 9.2 parts of calcium chloride (dihydrate) was dissolved in 10.0 parts of ion-exchanged water was collected. Then, an aqueous medium containing the dispersion stabilizer was prepared. Furthermore, 10 mass% hydrochloric acid was added to the aqueous medium to adjust the pH to 5.0, and thus an aqueous medium 1 was obtained.

(Hydrolysis step of organosilicon compound for surface layer)
60.0 parts of ion-exchanged water was weighed in a reaction vessel equipped with a stirrer and a thermometer, and the pH was adjusted to 3.0 using 10% by mass of hydrochloric acid. This was heated with stirring to bring the temperature to 70°C. Thereafter, 40.0 parts of methyltriethoxysilane, which is an organosilicon compound for the surface layer, was added and stirred for 2 hours or more for hydrolysis. The end point of the hydrolysis was visually confirmed by the fact that the oil and water did not separate to form a single layer, and it was cooled to obtain a hydrolyzed solution of the organosilicon compound for the surface layer.

(Process for preparing polymerizable monomer composition)
-Styrene: 60.0 parts-C.I. I. Pigment Blue 15:3: 6.5 parts The above material was put into an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.) and further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5.0 hours to prepare a pigment. A dispersion was prepared. The following materials were added to the pigment dispersion.
-Styrene: 20.0 parts-n-butyl acrylate: 20.0 parts-Crosslinking agent (divinylbenzene): 0.3 parts-Saturated polyester resin: 5.0 parts (Propylene oxide-modified bisphenol A (2 mol addition product) Polycondensate of terephthalic acid (molar ratio 10:12), glass transition temperature Tg=68° C., weight average molecular weight Mw=10000, molecular weight distribution Mw/Mn=5.12)
Fischer-Tropsch wax (melting point 78° C.): 7.0 parts The pigment dispersion liquid containing the above materials was kept warm at 65° C. K. A homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to uniformly dissolve and disperse at 500 rpm to prepare a polymerizable monomer composition.

(Granulation process)
The temperature of the aqueous medium 1 is 70° C. K. While maintaining the rotation speed of the homomixer at 12000 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 9.0 parts of t-butylperoxypivalate as a polymerization initiator was added. Granulation was performed for 10 minutes while maintaining 12,000 rpm with the stirring device.

(Polymerization process)
After the granulation step, the stirrer was changed to a propeller stirring blade to carry out polymerization for 5.0 hours while maintaining 70°C while stirring at 150 rpm, and the polymerization reaction was performed by heating to 85°C and heating for 2.0 hours. To obtain core particles. When the temperature of the slurry was cooled to 55° C. and the pH was measured, it was pH=5.0. While continuing stirring at 55° C., 20.0 parts of the hydrolyzed liquid of the organosilicon compound for the surface layer was added to start the formation of the surface layer of the toner particles. After maintaining as such for 30 minutes, the pH of the slurry was adjusted to 9.0 for completion of condensation using an aqueous solution of sodium hydroxide, and the slurry was further maintained for 300 minutes to form a surface layer.

(Washing and drying process)
After the completion of the polymerization process, the toner particle slurry is cooled, hydrochloric acid is added to the toner particle slurry to adjust the pH to 1.5 or less, and the mixture is left to stir for 1 hour, followed by solid-liquid separation with a pressure filter to obtain a toner cake. Got This was reslurried with ion-exchanged water to form a dispersion again, and then solid-liquid separation was performed with the above-mentioned filter. The reslurry and solid-liquid separation were repeated until the electric conductivity of the filtrate became 5.0 μS/cm or less, and finally solid-liquid separation was performed to obtain a toner cake.

  The obtained toner cake was dried with a flash dryer, a jet jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and fine coarse powder was cut using a multi-division classifier utilizing the Coanda effect to obtain toner particles K. The drying conditions were such that the blowing temperature was 90° C., the dryer outlet temperature was 40° C., and the toner cake supply rate was adjusted so that the outlet temperature did not deviate from 40° C. according to the water content of the toner cake.

  It was confirmed that silicon atoms were present in the surface layer by performing silicon mapping in cross-sectional TEM observation of the toner particles K. Also in the following toner production examples, it was confirmed by the same silicon mapping that the surface layer containing the organic silicon polymer had silicon atoms in the surface layer. In this production example, the obtained toner particles K were used as the toner K as it was without external addition.

The method of evaluating the toner K will be described below.
<Method of measuring sticking rate>
The measurement was carried out by the method described in "Method for measuring sticking rate of organosilicon polymer on surface of toner particles".

[Toner L]
Toner L was manufactured in the same manner as Toner K, except that the conditions for adding the hydrolysis liquid in the (polymerization step) and the holding time after addition were changed as shown in Table 5. The pH of the slurry was adjusted with hydrochloric acid and sodium hydroxide aqueous solution. Table 5 shows the measurement results of the obtained toner L.

[Toner M]
Toner M was prepared in the same manner as Toner K except that the conditions for adding the hydrolyzed liquid in the (polymerization step) and the holding time after addition were changed as shown in Table 5. The pH of the slurry was adjusted with hydrochloric acid and sodium hydroxide aqueous solution. Table 5 shows the evaluation results of the obtained toner M.

[Toner N]
(Hydrolysis step of organosilicon compound for surface layer) was not performed. Instead, 30 parts of methyltriethoxysilane, which is an organosilicon compound for the surface layer, was added as a monomer (step of preparing a polymerizable monomer composition).
In the (polymerization step), after cooling to 70° C. and measuring the pH, the hydrolysis solution was not added. While continuing stirring at 70° C., the pH of the slurry was adjusted to 9.0 for completion of condensation with an aqueous sodium hydroxide solution, and the slurry was further held for 300 minutes to form a surface layer. Table 5 shows the evaluation results of the obtained toner N.

(Evaluation results)
Table 6 shows the results of image evaluation using the toner shown in Table 5 and observation of the surface of the developing roller.

  As shown in Table 6, in the modified examples of the toner shown in Table 5, the same phenomenon as that of the toner shown in Table 3 was confirmed. In the toner N, at the contact position between the developing blade 9 and the developing roller 7 in the streak generating portion, there was a portion where the aggregate of the organosilicon compound was sandwiched. Further, streaking of the developing roller 7 occurs, which means that the organic silicon compound is detached and aggregated by the strong shearing force in the vicinity of the drive receiving portion in the toner conveying path, and further grows larger. Conceivable. On the contrary, in toner K, toner L, and toner M, since the aggregate of the organosilicon compound does not significantly grow, streak images are not generated.

As described above, one of the plurality of transport members in the transport path is driven by receiving the rotational force from the other, and at least one of the transport members is arranged to transport the toner upward. Even if the toner has a fixing rate of the organosilicon polymer of 90% or more, it is possible to suppress the vertical streak image resulting from the growth of the organosilicon polymer aggregate.

<<Embodiment 3>>
The present embodiment is different from the first embodiment in that the conveyance path forming member 70 provided in the apparatus main body 1 is integrated with the toner cartridge 20 and is detachable from the apparatus main body 1.

FIG. 10 is a schematic perspective view of the process cartridge 4 and the toner cartridge 26 in this embodiment.
The toner cartridge 26 of the third exemplary embodiment is provided with the transport path forming portion 27 on the side surface on the downstream side in the mounting direction to the apparatus main body.
The transport path forming unit 27 is configured by a duct-shaped hollow member similar to the transport path forming member 70, and the hollow inner space thereof constitutes a toner transport path. The toner transport path formed by the transport path forming unit 27 communicates between the internal space of the toner cartridge 26 and the internal space of the connecting portion 43 of the process cartridge 4. The transport path forming unit 27 includes a first transport unit 271, a second transport unit 272, and a third transport unit 273 that have different transport directions from the upstream toner cut ridge 26 side to the downstream process cartridge 4 coupling unit 43 side. Have
The internal structure of the toner cartridge 26 is similar to that of the toner cartridge 20 of the first embodiment, and the tip of the toner carrying screw 26 extends to the inside of the first carrying section 271 of the carrying path forming section 27. Therefore, the toner is carried into the upper part of the first carrying part 271 by the toner carrying screw 26 and falls inside the first carrying part 271. Subsequent toner conveyance is performed by a toner conveyance screw and a toner discharge screw (not shown) disposed inside the second conveyance section 272 and the third conveyance section 273, respectively, as with the conveyance path forming member 70 of the first embodiment. ..

By providing the toner cartridge 26 with the transport path, the number of parts to be transferred between the transfer paths of the toner is reduced, so that the number of parts of the toner leakage prevention member (not shown) in the transfer part can be reduced.
The setting conditions used in the description of this embodiment are examples, and the present invention is not limited to these.

<<Embodiment 4>>
The present embodiment is different from the first embodiment in that the toner conveyance path 70 provided in the apparatus body 1 is integrated with the process cartridge 4 and is attachable to and detachable from the apparatus body 1.

FIG. 11 is a perspective view of the process cartridge 4 and the toner cartridge 20 in this embodiment.
In the process cartridge 4 of the fourth embodiment, the conveyance path forming portion 47 is provided on the side surface on the downstream side in the mounting direction of the apparatus main body.
The toner cartridge 20 has the same configuration as that of the first embodiment.
The transport path forming unit 47 is configured by a duct-shaped hollow member similar to the transport path forming member 70, and the hollow inner space thereof constitutes a toner transport path. The toner transportation path by the transportation path forming unit 47 communicates between the internal space of the toner cartridge 20 and the internal space of the process cartridge 4 (the toner storage unit 44 of the developing unit 45). The transport path forming unit 47 includes a first transport unit 471, a second transport unit 472, a third transport unit 473, a third transport unit 473, and a third transport unit 473, which have different transport directions from the upstream toner cartridge 20 side to the downstream internal space side of the process cartridge 4. It has four transport units 474.
Toner transport screws (not shown) are respectively arranged in the second transport unit 472, the third transport unit 473, and the fourth transport unit 474, and are sequentially connected so that the rotational driving force is transmitted in series.

By providing the process cartridge 4 with the carrying path, the number of parts for delivering the toner between the carrying paths is reduced, so that the number of parts of the toner leakage prevention member (not shown) in the delivering part can be reduced.
The setting conditions used in the description of this embodiment are examples, and the present invention is not limited to these.

  DESCRIPTION OF SYMBOLS 1... Image forming apparatus, 4... Process cartridge, 20... Toner cartridge, 21... Stirring shaft, 22... Stirring blade, 23... Toner conveying screw, 24... Discharge port, 25... Toner, 25a... Toner particles, 25b... Organosilicon Surface layer containing polymer, 36... Toner conveying screw, 36g... First blade tooth surface, 36k... Rotating shaft, 37... Toner discharging screw, 37g... Second blade tooth surface, 37k... Rotating shaft, 41... Toner receiving port , 70... Main body conveyance path forming member, 71... Toner receiving port, 72... Toner discharging port

Claims (21)

A developing device used in an image forming apparatus,
A developer carrying member carrying a developer for developing the latent image formed on the image carrying member;
A regulating member for regulating the developer carried on the developer carrier,
A frame body that supports the developer carrying member and the regulating member, and has a developer accommodating portion;
A developer container containing the developer,
A conveyance path for supplying the developer from the developer container to the housing portion of the frame,
A first transport member that transports the developer by rotating and a second transport member that transports the developer by rotating are arranged in the transport path.
The second transport member has a drive receiving portion that receives a rotational force from the first transport member,
The developer contains a toner having toner particles and a silicon-containing compound present on the surface of the toner particles,
A developing device, wherein the adhesion rate of the compound containing silicon on the surface of the toner particles is 87% or more and 100% or less. The rotation axis of one of the first transport member and the second transport member, which is located downstream in the transport path, is arranged to be larger than the repose angle of the developer with respect to the horizontal plane during operation. Has been done,
The developing device according to claim 1, wherein the fixing rate is 90% or more and 100% or less.   The developing device according to claim 1, wherein the first transport member and the second transport member are screws having a rotation shaft and a spiral blade provided on the outer periphery of the rotation shaft.   The developing device according to claim 1, wherein the toner has toner particles and inorganic silicon fine particles present on the surfaces of the toner particles.   The developing device according to claim 1, wherein the toner includes toner particles and an organic silicon polymer that coats surfaces of the toner particles.   6. The transport path extends from the developer container to the accommodating portion of the frame by bypassing in a direction different from the facing direction of the frame and the developer container. The developing device according to item 1. The developer carrying body, the regulating member, and the frame body are attachable to and detachable from the apparatus body of the image forming apparatus as a first cartridge,
The developer container is detachable from the main assembly of the image forming apparatus as a second cartridge separately from the first cartridge.
The transport path is provided in the apparatus main body,
The developing device according to claim 1. An image carrier on which a latent image is formed,
A developer carrying member carrying a developer for developing the latent image formed on the image carrying member;
A regulating member for regulating the developer carried on the developer carrier,
A frame body that supports at least the developer carrying member and the regulating member, and has a housing portion for the developer,
A developer container containing the developer,
A conveyance path for supplying the developer from the developer container to the housing portion of the frame,
A first transport member that transports the developer by rotating and a second transport member that transports the developer by rotating are arranged in the transport path.
The second transport member has a drive receiving portion that receives a rotational force from the first transport member,
The developer contains a toner having toner particles and a silicon-containing compound present on the surface of the toner particles,
An image forming apparatus characterized in that the adhesion rate of the compound containing silicon on the surface of the toner particles is 87% or more and 100% or less. The rotation axis of one of the first transport member and the second transport member, which is located downstream in the transport path, is arranged to be larger than the repose angle of the developer with respect to the horizontal plane during operation. Has been done,
The image forming apparatus according to claim 8, wherein the fixation ratio is 90% or more and 100% or less.   The image forming apparatus according to claim 8, wherein the first transport member and the second transport member are screws having a rotation shaft and a spiral blade provided on the outer periphery of the rotation shaft.   The image forming apparatus according to claim 8, wherein the toner has toner particles and inorganic silicon fine particles present on the surfaces of the toner particles.   The image forming apparatus according to claim 8, wherein the toner includes toner particles and an organosilicon polymer that coats surfaces of the toner particles.   13. The transport path extends from the developer container to the accommodating portion of the frame by bypassing in a direction different from the facing direction of the frame and the developer container. The image forming apparatus according to item 1. The developer carrying member, the regulating member, and the frame body are configured to be detachable separately from the developer container as a first cartridge, the developer container as a second cartridge, and the first cartridge. Further equipped with a device body,
The transport path is provided in the apparatus main body,
The image forming apparatus according to any one of claims 8 to 13. A process cartridge used in an image forming apparatus,
A developer carrying member carrying a developer for developing the latent image formed on the image carrying member;
A regulating member for regulating the developer carried on the developer carrier,
A frame body that supports the developer carrying member and the regulating member, and has a developer accommodating portion;
A developer container containing the developer,
A conveyance path for supplying the developer from the developer container to the housing portion of the frame,
A first transport member that transports the developer by rotating and a second transport member that transports the developer by rotating are arranged in the transport path.
The second transport member has a drive receiving portion that receives a rotational force from the first transport member,
The developer contains a toner having toner particles and a silicon-containing compound present on the surface of the toner particles,
A process cartridge, wherein a sticking rate of the compound containing silicon on the surface of the toner particles is 87% or more and 100% or less. The rotation axis of one of the first transport member and the second transport member, which is located downstream in the transport path, is arranged to be larger than the repose angle of the developer with respect to the horizontal plane during operation. Has been done,
The process cartridge according to claim 15, wherein the fixing rate is 90% or more and 100% or less.   The process cartridge according to claim 15 or 16, wherein each of the first transport member and the second transport member is a screw having a rotation shaft and a spiral blade provided on the outer periphery of the rotation shaft.   18. The process cartridge according to claim 15, wherein the toner has toner particles and inorganic silicon fine particles present on the surfaces of the toner particles.   18. The process cartridge according to claim 15, wherein the toner has toner particles and an organosilicon polymer that coats surfaces of the toner particles.   20. The transport path extends from the developer container to the accommodating portion of the frame by detouring in a direction different from a facing direction of the frame body and the developer container. The process cartridge according to item 1. The developer carrying body, the regulating member, and the frame body are attachable to and detachable from the apparatus body of the image forming apparatus as a first cartridge,
The developer container is detachable from the main assembly of the image forming apparatus as a second cartridge separately from the first cartridge.
The transport path is provided in the apparatus main body,
The process cartridge according to any one of claims 15 to 20.

Images