JP2021021797A - Process cartridge and image forming apparatus - Google Patents

Abstract

To provide a process cartridge and an image forming apparatus that can prevent the charge-up of toner and stably perform peeling-off of a toner on a developing roller, regulation of the thickness of a toner layer, and removal of a toner on a photoconductor drum.SOLUTION: A process cartridge comprises: a rotating body that carries developer; and a contact member that is in contact with the rotating body. The developer includes toner particles containing a binder resin, and the surface of each of the toner particles has a reactant of polyacid and a compound containing a group 4 element.SELECTED DRAWING: Figure 3

Description

The present invention relates to an image forming apparatus for developing an electrostatic latent image formed on an image carrier, a process cartridge attached to and detachable from the image forming apparatus, and a developer used for these.
Here, the process cartridge is an integral cartridge of an image carrier and a developing device that acts on the image carrier.

Conventionally, in an electrophotographic image forming apparatus, an image carrier (hereinafter referred to as a photosensitive drum) is charged and then exposed according to image information to form an electrostatic latent image. Then, a developer (hereinafter referred to as toner) is supplied to the photosensitive drum by a developing means according to the electrostatic latent image to obtain a toner image (developer image). Then, after the toner image is transferred to a recording material such as a recording paper or an OHP sheet by a transfer means, the toner image is fixed to the recording material by a fixing means to obtain a recorded image.
In recent years, in this image forming apparatus, in order to achieve image stability when a large number of images having a low print density are printed, a toner in which the phenomenon that the amount of charge continues to increase (charge up) is suppressed is required. .. Numerous studies have been conducted to achieve this performance. Patent Document 1 discloses a toner whose chargeability is stable for a long period of time by using calcium phosphate-based compound particles and silica particles in combination. Patent Document 2 discloses a toner capable of stably controlling the amount of charge by using a resin charge control agent and hydrophobic titanium oxide in combination.

Japanese Unexamined Patent Publication No. 2012-208409 Japanese Unexamined Patent Publication No. 2006-072199

The toner of Patent Document 1 has improved chargeability by using calcium phosphate-based compound particles.
However, in the study by the present inventors, the hygroscopicity of the calcium phosphate-based compound may reduce the chargeability in a high humidity environment.

The toner described in Patent Document 2 uses a charge control resin in which a sulfonic acid base-containing monomer, an aromatic monomer having an electron-withdrawing group, and an acrylic acid ester monomer and / or a methacrylic acid ester monomer are used in combination. The charge control resin improves environmental stability while ensuring chargeability. At the same time, the charge-up is suppressed by using hydrophobized titanium oxide fine particles having a water-soluble component content of 0.2% by weight or more.
However, in the study by the present inventors, the amount of charge may decrease in a high humidity environment.
It is considered that this is due to the hygroscopicity of the water-soluble component of the titanium oxide fine particles at the same time that the hygroscopicity of the sulfonic acid base of the charge control resin could not be completely controlled.
In particular, the water-soluble component of the titanium oxide fine particles is an essential component for setting the resistance of titanium oxide low. Therefore, it is presumed that there is a trade-off relationship between the suppression of charge-up achieved by lowering the resistance and the decrease in the amount of charge in a high-humidity environment due to the absorption of water-soluble components, and it is difficult to achieve both. To.

If titanium oxide fine particles that have been hydrophobized by reducing the amount of water-soluble components are used in order to give priority to environmental stability, the charge-up suppressing effect is reduced and the amount of charge of the toner continues to increase. As a result, the mirror image power of the toner is increased, and the toner strongly adheres to the developer carrier (hereinafter, referred to as a developing roller) constituting the developing means. As a result, there is a possibility that the toner cannot be completely stripped even by the developer stripping member (hereinafter referred to as the stripping roller) that strips the developed toner from the developing roller. Insufficient toner stripping can lead to ghost images. This ghost image is a phenomenon in which the history of the image developed in the previous round of the developing roller appears as density unevenness in a uniform halftone image with a phase difference of the developing roller period after the next round. Further, when the mirror image power of the toner is increased, there is a possibility that the toner cannot be regulated even by a developer regulating member (hereinafter referred to as a regulating blade) that regulates the amount of toner coated on the developing roller to a constant layer thickness. If the toner is not sufficiently regulated, the amount of toner coated increases, and it may become difficult for the developing roller to support the toner. Similarly, when the mirror image power of the toner is increased, the toner adheres strongly to the photosensitive drum, and there is a possibility that the toner cannot be completely removed even by the cleaning member that cleans the photosensitive drum after transfer.

In view of the above, an object of the present invention is to suppress toner charge-up regardless of the printing environment, to remove toner from the developing roller, to regulate the toner layer thickness, and to stably remove toner on the photosensitive drum. It is to provide a process cartridge and an image forming apparatus.

In order to achieve the above object, the process cartridge in the present invention is
A process cartridge including a rotating body carrying a developer and an abutting member that comes into contact with the rotating body.
The developer has toner particles containing a binder resin and has
The surface of the toner particles is characterized by having a reactant of a polyhydric acid and a compound containing a Group 4 element.

Further, in order to achieve the above object, the image forming apparatus in the present invention is used.
An image forming device that forms an image on a recording material.
With the device body
The apparatus main body is provided with the above-mentioned process cartridge that can be attached and detached.

As described above, according to the present invention, toner charge-up is suppressed regardless of the printing environment, toner stripping from the developing roller, regulation of toner layer thickness, and toner removal on the photosensitive drum are stable. It is possible to provide a process cartridge and an image forming apparatus that can be used.

Schematic cross-sectional view of the toner according to this embodiment Schematic configuration diagram of the image forming apparatus according to this embodiment Schematic sectional view of the process cartridge according to this embodiment Schematic cross-sectional view of the developing apparatus according to this embodiment Explanatory drawing of mirror image force acting on toner which concerns on this Example Cross-sectional view of another embodiment of the regulation blade according to this embodiment Cross-sectional view of toner particles according to this embodiment

Hereinafter, embodiments for carrying out the present invention will be described in detail exemplarily based on examples with reference to the drawings. However, the dimensions, materials, shapes, and relative arrangements of the components described in this embodiment should be appropriately changed depending on the configuration of the apparatus to which the invention is applied and various conditions. That is, it is not intended to limit the scope of the present invention to the following embodiments. Further, the materials, shapes, and the like of the members once described in the following description are the same as those in the first description in the later description unless otherwise specified.

(Example)
<Image forming device>
The configuration of the entire image forming apparatus will be described with reference to FIGS. 2 and 3. FIG. 2 is a cross-sectional view showing a schematic configuration of an image forming apparatus according to an embodiment of the present invention. In addition, in FIG. 2, each configuration is briefly shown. FIG. 3 is a schematic cross-sectional view of the process cartridge according to the embodiment of the present invention.
The image forming apparatus 100 according to the present embodiment includes four process cartridges 10a, 10b, 10c, and 10d (hereinafter, appropriately referred to as cartridges 10) that are detachably attached to the apparatus main body. The cartridge 10a is a yellow cartridge, the cartridge 10b is a magenta cartridge, the cartridge 10c is a cyan cartridge, and the cartridge 10d is a black cartridge. As shown in FIG. 3, each cartridge 10 includes a photosensitive drum 11 (image carrier) as an example of a rotating body. Around the photosensitive drum 11, there are a charging roller 12 for charging the surface of the photosensitive drum 11 and a contact member that comes into contact with the surface of the photosensitive drum 11, and a cleaning member for cleaning the surface of the photosensitive drum 11. 14 is provided. Further, a developing device 20 for developing an electrostatic latent image formed on the surface of the photosensitive drum 11 with toner is also provided. An opening 13 is also provided in order to secure a path for the laser beam from the exposure device 101 that irradiates the surface of the photosensitive drum 11.

<Image formation process>
Next, the process of image formation will be described. When the image formation starts, the photosensitive drum 11 rotates in the direction of arrow A in FIG. 3, and the charging roller 12 follows the rotation of the photosensitive drum 11 and rotates in the direction of arrow B. Then, the surface of the photosensitive drum 11 is uniformly charged by the charging roller 12. After that, the surface of the photosensitive drum 11 is irradiated with laser light from the exposure device 101 to form an electrostatic latent image. On the other hand, in the developing device 20, after the rotation of the photosensitive drum 11 starts, the developing roller 23 separated from the photosensitive drum 11 moves in the direction of contact with the photosensitive drum 11. Subsequently, the developing roller 23 starts rotating in the direction of arrow C in FIG. 3, and the stripping roller 24 starts rotating in the direction of arrow D. Then, the electrostatic latent image formed on the photosensitive drum 11 is developed by the developing device 20. The developed toner image is first transferred to the intermediate transfer body 104 that is in contact with the toner image due to the potential difference with the primary transfer roller 103.

The above process is sequentially performed by the cartridge 10a, the cartridge 10b, the cartridge 10c, and the cartridge 10d, and all the toner images are superimposed on the intermediate transfer body 104. After that, the toner image is transferred to a recording medium (recording material) such as paper by the potential difference with the secondary transfer roller 105. The recording medium on which the toner image is transferred is conveyed to the fixing device 106 to be heated and pressurized. As a result, the toner image is fixed on the recording medium. After that, the recording medium is discharged to the outside of the image forming apparatus 100. After passing through the intermediate transfer body 104, the toner remaining on the photosensitive drum 11 without being transferred is stripped off by the cleaning member 14. After that, the above process is repeated again.
The cleaning member 14 is composed of a rubber portion 14a and a sheet metal portion 14b, and the rubber portion 14a comes into contact with the surface of the photosensitive drum 11.

<Developer>
The developing apparatus 20 will be described in more detail with reference to FIG. The developing device 20 includes a developing container 21 having an opening at a position facing the photosensitive drum 11. The developing container 21 contains toner, which is a developing agent. Further, the developing apparatus 20 includes a developing roller 23, which is an example of a rotating body different from the photosensitive drum 11 described above, and a stripping roller 24, which is a contact member that comes into contact with the developing roller 23. The developing roller 23 plays a role of transporting toner as a developer carrier to the electrostatic latent image on the photosensitive drum 11 while supporting the toner. The stripping roller 24 has a surface layer 24b made of a foaming material that slides on the surface of the developing roller 23. The stripping roller 24 serves as a developer stripping member that strips the toner on the developing roller 23 that has been collected in the developing container 21 without being developed. On the other hand, the stripping roller 24 also plays a role of supplying the toner in the developing container 21 to the developing roller 23. Further, the developing apparatus 20 regulates the toner adhering to the developing roller 23 before development, regulates the toner coating amount to a certain layer thickness, and also plays a role of imparting charge to the toner by rubbing with the toner. It also has a blade 25 (developer regulating member). Since the regulating blade 25 abuts on the developing roller 23 and regulates the amount of toner coat carried on the surface of the developing roller 23 to a constant layer thickness, it can be said that it is a contact member different from the above-mentioned stripping roller 24. .. That is, the developing apparatus 20 in this embodiment is provided with two contact members, a stripping roller 24 and a regulation blade 25, with respect to the developing roller 23 which is a developer carrier.
The developing roller 23 is composed of a core metal 23a having a diameter of 6 mm, which is a conductive support, and an elastic body layer 23b provided on the outer periphery of the core metal 23a. The elastic body layer 23b in this embodiment is composed of a 2.75 mm-thick silicon rubber layer provided on the outer periphery of the core metal 23a and a 10 μm-thick urethane resin layer provided on the outer periphery of the silicon rubber layer. .. The diameter of the entire roller is 11.5 mm.

The stripping roller 24 is composed of a core metal 24a having a diameter of 5 mm, which is a conductive support, and a surface layer 24b made of a foam material provided on the outer periphery of the core metal 24a. The surface layer 24b in this embodiment is made of urethane foam. The foam cell of this urethane foam is a continuous foam so that toner can enter and exit the urethane, and the diameter of the entire roller including the urethane foam is 13 mm. The axial center of the stripping roller 24 is located at a position 11.05 mm away from the developing roller 23. Therefore, the stripping roller 24 is compressed and deformed by a maximum of 1.2 mm along the developing roller 23 at the contact portion with the developing roller 23, and is in the same direction as the rotating direction (arrow C) of the developing roller 23 (arrow D). Rotate to. That is, the abutting portions of both rollers have velocities in opposite directions, and friction occurs. Therefore, the stripping roller 24 strips the toner on the surface of the developing roller 23 at the contact portion with the developing roller 23, and the urethane foam is compressed at the time of contact with the developing roller 23 toward the developing roller 23. It plays the role of discharging and supplying toner.

The regulation blade 25 is composed of a support sheet metal 25a obtained by bending a 1 mm thick SUS plate into an L shape, and a blade 25b made of a 100 μm thick SUS plate joined to the support sheet metal 25a by laser welding.

<Toner>
The toner as a developer used in the present invention is a toner having toner particles containing a binder resin, and the surface of the toner particles is a compound containing a polyhydric acid and a Group 4 element as shown in FIG. It is characterized by having a reaction product with. The inventors are a process cartridge and image forming that can suppress toner charge-up regardless of the printing environment, strip toner from the developing roller, regulate toner layer thickness, and stably remove toner on the photosensitive drum. We earnestly considered providing the device. Among them, as the toner, a toner having toner particles containing a binder resin and having a reaction product of a polyhydric acid and a compound containing a Group 4 element on the surface of the toner particles is used. It has been found that by doing so, the rising property of charging, the environmental stability, and the charge-up suppressing performance are improved.

The mechanism is not clear, but the present inventors speculate as follows.
The polyvalent acid receives an electron pair and tends to be negatively charged. Therefore, the reaction product of the polyhydric acid and the compound containing the Group 4 element is also easily negatively charged and has excellent chargeability. Furthermore, Group 4 elements are most stable when the oxidation number is +4. Therefore, it is possible to form a crosslinked structure with the polyvalent acid, promote the movement of electrons by the crosslinked structure, improve the rising property of charging, and suppress the charge-up. Further, the reaction product of the polyhydric acid and the compound containing the Group 4 element has good environmental stability by blocking water molecules by the crosslinked structure.

As described above, it is only possible to use a compound containing another polyhydric acid or a compound containing another Group 4 element for the first time when the polyvalent acid and the compound containing a Group 4 element become a reactant. Performance that cannot be achieved can be achieved.

On the other hand, titanium oxide (TiO ₂ ), which has been conventionally used, is an extremely stable compound, so that it cannot form a reactant with a polyhydric acid and has low chargeability. In addition, charge-up suppression is also insufficient. In addition, polyvalent acid salts other than Group 4 elements, for example, polyvalent acid salts of alkaline earth metals, were insufficient to suppress the adsorption of water.

Hereinafter, a specific configuration of the toner used in the present invention will be described.
The polyvalent acid may be any acid having a divalent value or higher. Specific examples include the following.
Inorganic acids such as phosphoric acid, carbonic acid and sulfuric acid; organic acids such as dicarboxylic acids and tricarboxylic acids. Specific examples of organic acids include the following.
Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. Tricarboxylic acids such as citric acid, aconitic acid, trimellitic anhydride.
Among them, it is preferable that the polyhydric acid contains at least one selected from the group consisting of carbonic acid, sulfuric acid, and phosphoric acid because it reacts strongly with the Group 4 element and is difficult to absorb moisture. More preferably, the polyhydric acid contains phosphoric acid.
As the polyhydric acid, the polyhydric acid may be used as it is, or an alkali metal salt of the polyhydric acid and sodium, potassium, lithium or the like; an alkaline earth metal salt of magnesium, calcium, strontium, barium or the like; or , May be used as an ammonium salt of a polyhydric acid.

The compound containing the Group 4 element is not particularly limited as long as it is a compound containing the Group 4 element, and any compound may be used.
Examples of Group 4 elements include titanium, zirconium, and hafnium.
Among them, the Group 4 element preferably contains at least one of titanium and zirconium.
Specific examples of the compound containing titanium include the following.
Titanium alkoxides such as tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.
Titanium diisopropoxybis acetylacetonate, titanium tetraacetylacetonate, titanium diisopropoxybis (ethylacetacetate), titanium di-2-ethylhexoxybis 2-ethyl-3-hydroxyhexoxide, titanium diisopropoxy Titanium chelates such as bisethylacetacetate, titanium lactate, titanium lactate ammonium salt, titanium diisopropoxybistriethanol amine, titanium isostearate, titanium aminoethylaminoetanolate, titanium triethanol aminate.
Of these, titanium chelate is preferable because it easily reacts with polyhydric acid. Further, titanium lactate and titanium lactate ammonium salt are more preferable.

Specific examples of the zirconium-containing compound include the following.
Zirconium alkoxides such as zirconium tetrapropoxide and zirconium tetrabutoxide.
Zirconium chelates such as zirconium tetraacetylacetone, zirconium tributoxymonoacetylacetone, zirconium dibutoxybis (ethylacetacetate), zirconium lactate, zirconium lactate ammonium salt.
Of these, zirconium chelate is preferable because it easily reacts with polyhydric acid. Further, zirconium lactate and zirconium lactate ammonium salt are more preferable.

Specific examples of the hafnium-containing compound include the following.
Hafnium chelate such as hafnium lactate, hafnium lactate ammonium salt.

What is meant by the state that the surface of the toner particles has a reactant of the polyhydric acid and the compound containing the Group 4 element? For example, the surface of the toner particles contains the polyhydric acid and the Group 4 element. A state in which a reaction product with the containing compound is present can be mentioned.
As a method for allowing a reaction product of a polyhydric acid and a compound containing a Group 4 element to exist on the surface of the toner particles, various conventionally known methods can be used, and for example, there are the following methods.

A method in which a compound containing a polyhydric acid and a Group 4 element is reacted in a dispersion of toner mother particles, and the obtained reactant is adhered to the surface of the toner mother particles to obtain toner particles.
For example, by adding and mixing a compound containing a polyhydric acid and a Group 4 element to a dispersion of toner matrix particles, the polyhydric acid and a compound containing a Group 4 element are reacted to obtain a reactant. At the same time, there is a method of obtaining the toner particles by adhering them to the surface of the toner mother particles by stirring the dispersion liquid.

Further, for example, a polyhydric acid is reacted with a compound containing a Group 4 element to prepare fine particles containing a reactant, and the reactant is contained on the surface of the toner matrix particle by mixing with the toner matrix particle. Examples thereof include a method of obtaining toner particles by adhering fine particles.
Specifically, the toner matrix particles and the fine particles of the reaction product are mixed using a high-speed stirrer that applies shearing force such as FM mixer, mechano hybrid (manufactured by Nippon Coke), super mixer, and Nobilta (manufactured by Hosokawa Micron). It is good to do.

The reaction product of the polyhydric acid and the compound containing the Group 4 element can be obtained by reacting the polyhydric acid and the compound containing the Group 4 element in a solvent. Any solvent may be used. Specific examples of the solvent include the following.
Hexene, benzene, toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran, acetone, acetonitrile, N, N-dimethylformamide, 1-butanol, 1-propanol, 2-propanol, methanol, ethanol, water.

The type of reaction product of the polyhydric acid and the compound containing the Group 4 element is not particularly limited. However, from the viewpoint of suppressing image deterioration during printing of a large number of sheets, it is preferable to contain at least one selected from the group consisting of titanium sulfate, titanium carbonate, titanium phosphate, zirconium sulfate, zirconium carbonate, and zirconium phosphate. .. More preferably, it contains at least one of titanium phosphate and zirconium phosphate.

The number average particle size of the fine particles containing the reaction product of the polyhydric acid and the compound containing the Group 4 element is preferably 1 nm or more and 400 nm or less, more preferably 1 nm or more and 200 nm or less, and 1 nm or more and 60 nm. The following is more preferable. By setting the number average particle diameter of the fine particles within the above range, it is possible to suppress member contamination due to desorption of the fine particles.
The method for adjusting the number average particle size of the fine particles within the above range is the amount of the compound containing the polyhydric acid and the Group 4 element, which are the raw materials of the fine particles, the pH at which they react, and the temperature at the time of reaction. And so on. The content of the reaction product of the polyhydric acid and the compound containing the Group 4 element in the toner particles is preferably 0.01% by mass or more and 5.00% by mass or less, and 0.02% by mass or more and 3. It is more preferably 00% by mass or less.

In the toner in this embodiment, when a metal salt is used together with the polyhydric acid, the metal element contained in the metal salt is the metal element M. Then, when the ratio of the metal element M in the constituent element ratio of the toner surface obtained from the spectrum obtained by the X-ray photoelectron spectroscopy of the toner is M1 (at%), M1 is 1.0 (at%) or more. It is preferably 10.0 (at%) or less.

Further, 1 g of the toner (1 g of the developer) in this example, 31 g of a 61.5% sucrose aqueous solution, and a 10% neutral detergent for cleaning a precision measuring instrument composed of a nonionic surfactant and an anionic surfactant. Disperse in a mixed aqueous solution consisting of 6 g of the aqueous solution. Next, the toner obtained by performing the treatment (a) of shaking 300 times per minute using a shaker is used as the toner (a). Then, the ratio of the metal element M in the constituent element ratio of the toner surface obtained from the spectrum obtained by the X-ray photoelectron spectroscopy analysis of the toner (a) is defined as M2 (at%). At this time, it is preferable that both M1 and M2 are 1.0 or more and 10.0 or less, and M1 and M2 satisfy the following relational expression (ME-1).
0.90 ≤ M2 / M1 (ME-1)

In the above treatment (a), the polyvalent metal salt that is weakly adhered to the toner surface can be removed. Specifically, the polyhydric acid metal salt attached to the toner matrix particles by the dry method is easily removed by the above treatment (a). In this way, it is possible to evaluate the polyvalent acid metal salt present on the toner surface by the above treatment (a). The smaller the change in each parameter due to the above treatment (a), the stronger the polyvalent acid metal salt is adhered to the toner matrix particles.
The above M1 and M2 represent the coating state of the toner surface with the polyvalent acid metal salt before and after each treatment. The state of coating the toner surface with the polyvalent acid metal salt contributes to chargeability and charge mobility.

The M1 and M2 are preferably 1.0 (at%) or more and 10.0 (at%) or less. When the above M1 and M2 are in the above range, the negative charge property and the charge mobility of the toner are further improved.
The M1 and M2 are more preferably 1.0 (at%) or more and 7.0 (at%) or less, and further preferably 1.5 (at%) or more and 5.0 (at%) or less. ..
The above formula (ME-1) means the ratio at which the polyvalent acid metal salt does not peel off from the toner surface in the above treatment (a) and remains. When the above formula (ME-1) is 0.90 or more, the polyvalent metal salt is strongly adhered to the toner surface, so that the transfer of the polyvalent metal salt from the toner to the member is suppressed. Therefore, it is possible to obtain a toner that is stable even during long-term use and has excellent durability.

When a polyhydric acid is reacted with a compound containing a Group 4 element in a dispersion of toner mother particles and the obtained reactant is adhered to the surface of the toner mother particles to obtain toner particles, the following formula (1) is used. It is preferable to use the organosilicon compound shown by. By using the organosilicon compound in combination, the obtained reactant is firmly adhered to the toner particles by the organosilicon polymer produced by the polymerization of the organosilicon compound, and the polyvalent acid and the Group 4 element are combined. The reaction product with the containing compound is hydrophobized, and the environmental stability is further improved.
Specifically, first, the organosilicon compound represented by the following formula (1) is hydrolyzed in advance or hydrolyzed in a dispersion of toner matrix particles. Then, the obtained hydrolyzate of the organosilicon compound is condensed to obtain a condensate. The condensate migrates to the surface of the toner particles. Since the condensate is viscous, the reactant of the polyhydric acid and the compound containing the Group 4 element can be brought into close contact with the surface of the toner particles, and the reactant can be more firmly fixed to the toner particles.
In addition, the condensate can also migrate to the surface of the reactant, making the reactant hydrophobic and further improving environmental stability.

Ra (n) -Si-Rb (4-n) (1)
In the formula (1), Ra represents a halogen atom, a hydroxy group or an alkoxy group, and Rb represents an alkyl group, an alkenyl group, an aryl group, an acyl group or a methacryloxyalkyl group. n represents an integer of 2-4. However, when a plurality of Ra and Rb are present, the substituents of the plurality of Ra and the plurality of Rb may be the same or different, respectively.

Hereinafter, Ra in the formula (1) will be referred to as a functional group, and Rb will be referred to as a substituent. As the organosilicon compound represented by the formula (1), a known organosilicon compound can be used without particular limitation. Specific examples thereof include the following bifunctional silane compounds having two functional groups, trifunctional silane compounds having three functional groups, and tetrafunctional silane compounds having four functional groups.

Examples of the bifunctional silane compound include dimethyldimethoxysilane and dimethyldiethoxysilane.
Examples of the trifunctional silane compound include the following.
Methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane , A trifunctional silane compound having an alkyl group as a substituent such as hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane;
A trifunctional silane compound having an alkenyl group as a substituent such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane;
A trifunctional silane compound having an aryl group as a substituent such as phenyltrimethoxysilane and phenyltriethoxysilane;
Trifunctional silane having a methacryloxyl group as a substituent such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldiethoxymethoxysilane, γ-methacryloxypropylethoxydimethoxysilane Compounds etc.
Examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

As the organosilicon polymer, conventionally known organosilicon polymers can be used without particular limitation. Above all, it is preferable to use an organosilicon polymer having a structure represented by the following formula (I).
R-SiO3 / 2 formula (I)
In formula (I), R is an alkyl group (preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms), preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms). An alkenyl group, an acyl group (preferably 1 to 6 carbons, more preferably 1 to 4 carbons), an aryl group (preferably 6 to 14 carbons, more preferably 6 to 10 carbons) or a methacrylate alkyl Indicates a group.
The formula (I) represents that the organosilicon polymer has an organic group and a silicon polymer portion. As a result, in the organic silicon polymer containing the structure represented by the formula (I), the organic group has an affinity with the toner mother particles or the toner particles, so that the organic groups are strongly adhered to the toner mother particles or the toner particles, and the silicon Since the polymer portion has an affinity for the reactant of the polyvalent acid and the compound containing the Group 4 element, the polymer portion strongly adheres to the reactant of the polyvalent acid and the compound containing the Group 4 element.
As described above, the organosilicon polymer has a function of adhering the toner particles to the reaction product of the compound containing the polyhydric acid and the Group 4 element, so that the organosilicon polymer is made more robust through the organosilicon polymer. A reaction product of a polyhydric acid and a compound containing a Group 4 element can be fixed to the toner particles.
Further, the formula (I) represents that the organosilicon polymer is crosslinked. Since the organosilicon polymer has a crosslinked structure, the strength of the organosilicon polymer is increased, and the remaining silanol groups are reduced, so that the hydrophobicity is increased. Therefore, it is possible to obtain a toner that is more durable and exhibits stable performance even in a high humidity environment.
In the formula (I), R is preferably an alkyl group having 1 or more and 6 or less carbon atoms such as a methyl group, a propyl group, and a normal hexyl group, a vinyl group, a phenyl group, and a methacryloxypropyl group, and preferably has 1 or more carbon atoms and 6 or less carbon atoms. It is more preferably the following alkyl group or vinyl group.
Since the organosilicon polymer having the above structure has both hardness and flexibility by controlling the molecular motion of the organic group, deterioration of the toner is suppressed even when it is used for a long period of time, and it exhibits excellent performance. ..
The content of the organosilicon polymer obtained by polymerizing at least one organosilicon compound selected from the group consisting of the organosilicon compounds represented by the formula (1) in the toner particles is 0.1% by mass or more and 20. It is preferably 0.0% by mass or less. Further, it is more preferably 0.5% by mass or more and 15.0% by mass or less.

The method for producing the toner matrix particles is not particularly limited, and a known suspension polymerization method, dissolution suspension method, emulsification / aggregation method, pulverization method, or the like can be used.
When a reaction product of a polyhydric acid and a compound containing a Group 4 element is present on the surface of the toner particles, or when the toner matrix particles are produced in an aqueous medium, they are used as they are as a dispersion liquid of the toner matrix particles. May be good. Further, after washing, filtering, and drying, the toner may be redispersed in an aqueous medium to prepare a dispersion of toner matrix particles.
On the other hand, when the toner mother particles are produced by a dry method, they may be dispersed in an aqueous medium by a known method to prepare a dispersion liquid of the toner mother particles. In order to disperse the toner matrix particles in the aqueous medium, it is preferable that the aqueous medium contains a dispersion stabilizer.

Hereinafter, an example of producing toner matrix particles using the suspension polymerization method will be specifically described.
First, a polymerizable monomer capable of producing a binder resin and various additives, if necessary, are mixed, and a disperser is used to prepare a polymerizable monomer composition in which the material is dissolved or dispersed. To do. Examples of various additives include colorants, waxes, charge control agents, polymerization initiators, chain transfer agents and the like. Examples of the disperser include a homogenizer, a ball mill, a colloid mill, and an ultrasonic disperser.
Next, the polymerizable monomer composition is put into an aqueous medium containing poorly water-soluble inorganic fine particles, and the polymerizable monomer composition is prepared using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser. Prepare droplets (granulation step).
Then, the polymerizable monomer in the droplet is polymerized to obtain a toner mother particle (polymerization step). The polymerization initiator may be mixed when preparing the polymerizable monomer composition, or may be mixed in the polymerizable monomer composition immediately before forming droplets in the aqueous medium.
Further, it can be added in a state of being dissolved in a polymerizable monomer or another solvent, if necessary, during the granulation of the droplet or after the completion of the granulation, that is, immediately before the start of the polymerization reaction. After polymerizing the polymerizable monomer to obtain resin particles, it is advisable to perform solvent removal treatment as necessary to obtain a dispersion of toner mother particles.

Examples of the binding resin include the following resins or polymers.
Vinyl-based resin; polyester resin; polyamide resin; furan resin; epoxy resin; xylene resin; silicone resin.
Among these, vinyl-based resins are preferable. Examples of the vinyl resin include polymers of the following monomers and copolymers thereof. Of these, a copolymer of a styrene-based monomer and an unsaturated carboxylic acid ester is preferable.
Styrene-based monomers such as styrene and α-methylstyrene; unsaturated carboxylic acids such as methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate and 2-ethylhexyl methacrylate. Estel; unsaturated carboxylic acid such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acid such as maleic acid; unsaturated dicarboxylic acid anhydride such as maleic acid anhydride; nitrile vinyl monomer such as acrylonitrile; vinyl chloride and the like Halogen-containing vinyl monomer; Nitro-based vinyl monomer such as nitrostyrene.

As the colorant, the following black pigments, yellow pigments, magenta pigments, cyan pigments and the like are used.
Examples of the black pigment include carbon black and the like.
Examples of the yellow pigment include monoazo compounds; disazo compounds; condensed azo compounds; isoindolinone compounds; isoindolin compounds; benzimidazolone compounds; anthraquinone compounds; azometal complexes; methine compounds; allylamide compounds. Specifically, C.I. I. Pigment Yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185 and the like.
Examples of magenta pigments include monoazo compounds; condensed azo compounds; diketopyrrolopyrrole compounds; anthraquinone compounds; quinacridone compounds; basic dye lake compounds; naphthol compounds: benzimidazolone compounds; thioindigo compounds; perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19 and the like.
Examples of the cyan pigment include copper phthalocyanine compounds and derivatives thereof; anthraquinone compounds; and basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
Further, various dyes conventionally known as colorants may be used in combination with the pigment. 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 parts by mass of the binder resin.

The toner may contain a magnetic substance to be a magnetic toner. In this case, the magnetic material can also serve as a colorant. Magnetic materials include iron oxide typified by magnetite, hematite, ferrite, etc .; metals typified by iron, cobalt, nickel, etc. or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, Examples thereof include alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

Wax is illustrated below.
A monohydric alcohol and an aliphatic monocarboxylic acid ester such as behenyl behenyl, stearyl stearate, and palmityl palmitate, or an ester of a monohydric carboxylic acid and an aliphatic monoalcohol; dibehenyl sebacate, hexanediol dibehenate, etc. Divalent alcohol and aliphatic monocarboxylic acid ester, or divalent carboxylic acid and aliphatic monoalcohol ester; trihydric alcohol such as glycerin tribehenate and aliphatic monocarboxylic acid ester, or 3 Esters of valent carboxylic acids and aliphatic monoalcohols; tetravalent alcohols such as pentaerythritol tetrastearate, pentaerythritol tetrapalmitate and aliphatic monocarboxylic acid esters, or tetravalent carboxylic acids and aliphatic monoalcohols. Esters; hexahydric alcohols such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate and aliphatic monocarboxylic acid esters, or 6
Esters of valent carboxylic acids and aliphatic monoalcohols; esters of polyhydric alcohols such as polyglycerin behenate and aliphatic monocarboxylic acids, or esters of polyvalent carboxylic acids and aliphatic monoalcohols; carnauba wax, rice wax, etc. Natural ester waxes; petroleum waxes such as paraffin wax, microcrystallin wax, petrolatum and derivatives thereof; hydrocarbon waxes and derivatives thereof by Fishertropus method; polyolefin waxes such as polyethylene wax and polypropylene wax and derivatives thereof; higher aliphatic alcohols Fatty acids such as stearic acid and palmitic acid; acid amide wax.
The wax content is preferably 0.5 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

As the toner, various organic or inorganic fine particles may be externally added to the toner particles to the extent that the characteristics or effects are not impaired. As the organic or inorganic fine particles, for example, the following are used.
(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black and carbon fluoride.
(2) Abrasive: Metal oxide (eg, strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (eg, silicon nitride), carbide (eg, silicon carbide), metal salt (eg, eg) Calcium sulphate, barium sulphate, calcium carbonate).
(3) Lubricants: Fluorine-based resin fine particles (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salts (for example, zinc stearate, calcium stearate).
(4) Charge control particles: metal oxides (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

Organic or inorganic fine particles can also be hydrophobized. Examples of the treatment agent for hydrophobizing organic or inorganic fine particles include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organic substances. Examples include titanium compounds. These treatment agents may be used alone or in combination.

The method of measuring each physical property value of the toner in this example will be described below.
<Measuring method of weight average particle size (D4) and number average particle size (D1) of toner particles>
The weight average particle size (D4) and the number average particle size (D1) of the toner particles are calculated as follows.
As the measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter Co., Ltd.) equipped with a 100 μm aperture tube by the pore electric resistance method is used. The attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter Co., Ltd.) is used for setting the measurement conditions and analyzing the measurement data. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes 1.0%, for example, "ISOTON II" (manufactured by Beckman Coulter Co., Ltd.) can be used. ..

Before performing measurement and analysis, set the dedicated software as follows.
On the "Change standard measurement method (SOMME)" screen of the dedicated software, set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter. Set the value obtained using Coulter Co., Ltd.
By pressing the "threshold / noise level measurement button", the threshold and noise level are automatically set. Further, the current is set to 1,600 μA, the gain is set to 2, and the electrolytic aqueous solution is ISOTON I.
Set to I and check "Flash of aperture tube after measurement".
On the "Pulse to particle size conversion setting" screen of the dedicated software, set the bin spacing to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Put 200.0 mL of the electrolytic aqueous solution in a 250 mL round bottom beaker made of glass dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "flash of the aperture tube" function of the dedicated software.
(2) Put 30.0 mL of the electrolytic aqueous solution in a 100 mL flat bottom beaker made of glass. Among them, as a dispersant, "Contaminone N" (a 10% aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, Wako Pure Chemical Industries, Ltd. Is diluted 3 times by mass with ion-exchanged water, and 0.3 mL of the diluted solution is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and an ultrasonic disperser "Ultrasonic Dispersion System Tera150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W is prepared. To do. Put 3.3 L of ion-exchanged water in the water tank of the ultrasonic disperser, and add 2.0 mL of contaminantin N to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner particles are added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the electrolytic aqueous solution of (5) in which toner particles are dispersed is dropped onto the round-bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to 5%. .. Then, the measurement is performed until the number of particles to be measured reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) and the number average particle size (D1) are calculated. The "average diameter" on the "analysis / volume statistical value (arithmetic mean)" screen when the graph / volume% is set by the dedicated software indicates the weight average particle diameter (D4). Further, the "average diameter" of the "analysis / number statistical value (arithmetic mean)" screen when the graph / number% is set by the dedicated software indicates the number average particle size (D1).

<Measurement method of glass transition temperature (Tg) of toner particles>
The glass transition temperature (Tg) of the toner particles is measured using a differential scanning calorimeter (hereinafter, also referred to as “DSC”).
The glass transition temperature is measured by DSC in accordance with JIS K 7121 (international standard is ASTM D3418-82).
In this measurement, "Q1000" (manufactured by TA Instruments) is used, the melting points of indium and zinc are used for the temperature correction of the device detection unit, and the heat of fusion of indium is used for the correction of the calorific value.
For the measurement, 10 mg of the measurement sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference.
In the first temperature raising process, the measurement is performed while raising the temperature of the measurement sample from 20 ° C. to 200 ° C. at 10 ° C./min. Then, after holding at 200 ° C. for 10 minutes, a cooling process of cooling from 200 ° C. to 20 ° C. at 10 ° C./min is performed.

Further, after holding at 20 ° C. for 10 minutes, the temperature is raised again from 20 ° C. to 200 ° C. at 10 ° C./min in the second temperature raising process. The glass transition temperature is the midpoint glass transition temperature. In the DSC curve in the second heating process obtained by the above-mentioned measurement conditions, it is defined as follows. That is, the temperature at the point where the straight line equidistant in the vertical axis direction from the extended straight line of each baseline on the low temperature side and the high temperature side of the stepwise change of the glass transition temperature and the curve of the stepwise change portion intersect with the glass transition temperature Let it be temperature (Tg).
When toner particles are produced in an aqueous medium or the like, a part of the toner particles is sampled, and the non-toner particles are washed and dried before the DSC is measured.

<Calculation method of ratios M1 and M2 of metal element M using X-ray photoelectron spectroscopy>
・ Processing (a)
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved while boiling to prepare a 61.5% sucrose aqueous solution. A neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of 31.0 g of the above sucrose concentrate in a centrifuge tube and Contaminone N (trade name) (nonionic surfactant, anionic surfactant, and organic builder). Add 6 g of a 10% by mass aqueous solution of Wako Pure Chemical Industries, Ltd. to prepare a dispersion. 1.0 g of toner is added to this dispersion, and the toner lumps are loosened with a spatula or the like. The centrifuge tube is shaken with a shaker at 300 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced with a glass tube for a swing rotor (50 mL) and separated by a centrifuge at 3500 rpm for 30 minutes. Visually confirm that the toner and the aqueous solution are sufficiently separated, and collect the separated toner in the uppermost layer with a spatula or the like. After filtering the collected toner with a vacuum filter, it is dried in a dryer for 1 hour or more. The dried product is crushed with a spatula to obtain toner (a).

The toner in this example and the toner (a) are measured as follows using X-ray photoelectron spectroscopy, and M1 and M2 are calculated.
The ratio of the metal element M The ratio of M1 and M2 is calculated by measuring the toner under the following conditions.
-Measuring device: X-ray photoelectron spectrometer: Quantum2000 (manufactured by ULVACPHI Co., Ltd.)
・ X-ray source: Monochrome Al Kα
-Xray Setting: 100 μmφ (25 W (15 KV))
・ Photoelectron extraction angle: 45 degrees ・ Neutralization condition: Combined use of neutralization gun and ion gun ・ Analysis area: 300 × 200 μm
-Pass Energy: 58.70 eV
-Step size: 0.1.25 eV
-Analysis software: Maltipak (PHI)
Here, for example, the peak of Ti 2p (BE 452 to 468 eV) is used for calculating the quantitative value of the Ti atom. Let the quantitative value of the Ti element obtained here be M1 (at%).
Using the above method, the toner in this example and the toner (a) are measured, and the ratio of the metal element M of each toner is set to M1 (at%) and M2 (at%), respectively.

<Detection method for polyvalent acid metal salts>
Using time-of-flight secondary ion mass spectrometry (TOF-SIMS), polyvalent acid metal salts on the toner surface are detected by the following methods.
The toner sample is analyzed using TOF-SIMS (TRIFTIV: manufactured by ULVAC-PHI) under the following conditions.
・ Primary ion species: Gold ion (Au ⁺ )
・ Primary ion current value: 2pA
・ Analysis area: 300 × 300 μm ²
-Number of pixels: 256 x 256 pixels
・ Analysis time: 3min
-Repeat frequency: 8.2 kHz
・ Charge neutralization: ON
-Secondary ion polarity: Positive
-Secondary ion mass range: m / z 0.5 to 1850
Sample substrate: Indium above conditions was analyzed, secondary ions containing the metal ion and the polyvalent ion (for example, in the case of titanium phosphate _{TiPO 3 (m / z 127)} , TiP 2 O 5 (m / z When a peak derived from 207), etc.) is detected, it is assumed that a polyvalent metal salt is present on the surface of the toner.

The toner and the method for manufacturing the toner will be described below. Unless otherwise specified, "parts" and "%" in Examples and Comparative Examples are all based on mass.

<Production example of toner mother particle dispersion>
(Production example of water-based medium)
11.2 parts of sodium phosphate (12-hydrate) was put into a reaction vessel containing 390.0 parts of ion-exchanged water, and the mixture was kept warm at 65 ° C. for 1.0 hour while purging with nitrogen. T. K. The mixture was stirred at 12,000 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.). While maintaining stirring, an aqueous solution of calcium chloride in which 7.4 parts of calcium chloride (dihydrate) was dissolved in 10.0 parts of ion-exchanged water was put into the reaction vessel all at once to prepare an aqueous medium containing a dispersion stabilizer. did. Further, 1.0 mol / L hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0 to prepare an aqueous medium.

(Preparation of polymerizable monomer composition)
・ 60.0 parts of styrene ・ C. I. Pigment Blue 15: 3 6.3 parts The above material was put into an attritor (manufactured by Nippon Coke Industries, Ltd.) and further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5.0 hours to disperse the pigment. A colorant dispersion was prepared.
Next, the following materials were added to the colorant dispersion.
-Styrene 10.0 parts-N-butyl acrylate 30.0 parts-Polyester resin 5.0 parts (condensation polymer of terephthalic acid and 2 mol adduct of propylene oxide of bisphenol A, weight average molecular weight Mw = 10, 000, acid value: 8.2 mgKOH / g)
-HNP9 (melting point: 76 ° C, manufactured by Nippon Seiro Co., Ltd.) 6.0 parts The above material was kept warm at 65 ° C, and T.I. K. A polymerizable monomer composition was prepared by uniformly dissolving and dispersing at 500 rpm using a homomixer.

(Granulation process)
8. While maintaining the temperature of the aqueous medium at 70 ° C. and the rotation speed of the stirrer at 12,000 rpm, the polymerizable monomer composition was charged into the aqueous medium, and the polymerization initiator, t-butylperoxypivalate 8. 0 parts were added. Granulation was carried out for 10 minutes while maintaining 12,000 rpm in the stirrer as it was.

(Polymerization process)
Change from a high-speed stirrer to a stirrer equipped with a propeller stirring blade, carry out polymerization at 70 ° C. for 5.0 hours while stirring at 200 rpm, then raise the temperature to 85 ° C. and heat for 2.0 hours. The polymerization reaction was carried out in. Further, the residual monomer is removed by raising the temperature to 98 ° C. and heating for 3.0 hours, and ion-exchanged water is added to adjust the concentration of the toner matrix particles in the dispersion to 30.0%. A toner mother particle dispersion liquid in which the mother particles were dispersed was obtained.
The number average particle size (D1) of the toner mother particles was 6.1 μm, and the weight average particle size (D4) was 6.6 μm.

<Production example of organosilicon compound solution>
-Ion-exchanged water 70.0 parts-Methyltriethoxysilane 30.0 parts The above material was weighed in a 200 mL beaker and the pH was adjusted to 3.5 with 10% hydrochloric acid. Then, the mixture was stirred for 1.0 hour while heating at 60 ° C. in a water bath to prepare an organosilicon compound solution.

<Production example of a reaction product of a compound containing a polyhydric acid and a Group 4 element>
・ 100.0 parts of ion-exchanged water ・ 8.5 parts or more of sodium phosphate (12-hydrate) After mixing, at room temperature, T.I. K. Stir at 10,000 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.). At the same time as stirring, 60.0 parts of zirconium lactate ammonium salt (ZC-300, Matsumoto Fine Chemical Co., Ltd.) (equivalent to 7.2 parts as zirconium lactate ammonium salt) was added. The pH was adjusted to 7.0 by adding 1.0 mol / L hydrochloric acid. The temperature was adjusted to 25 ° C., and the reaction was carried out for 1 hour while maintaining stirring.
Then, the solid content was taken out by centrifugation. Subsequently, the process of redispersing in ion-exchanged water and taking out the solid content by centrifugation was repeated three times to remove ions such as sodium. It was dispersed again in ion-exchanged water and dried by spray drying to obtain zirconium phosphate compound fine particles containing zirconium phosphate, which is a reaction product of a compound containing a polyhydric acid having a number average particle size of 124 nm and a Group 4 element. It was.

<Manufacturing example of toner particles>
<Toner particle 1>
(Polyvalent acid metal salt adhesion process)
The following samples were weighed in the reaction vessel and mixed using a propeller stirring blade.
-Toner mother particle dispersion 500.0 parts-Titanium lactate 44% aqueous solution (TC-310: manufactured by Matsumoto Fine Chemicals Co., Ltd.)
3.2 copies (equivalent to 1.4 copies as titanium lactate)
10.0 parts of organosilicon compound solution Next, the pH of the obtained mixed solution was adjusted to 9.5 using a 1.0 mol / L NaOH aqueous solution and maintained for 5.0 hours. After lowering the temperature to 25 ° C., the pH was adjusted to 1.5 with 1.0 mol / L hydrochloric acid, the mixture was stirred for 1.0 hour, and then filtered while being washed with ion-exchanged water. The obtained powder was dried in a constant temperature bath and then classified by a wind power classifier to obtain toner particles 1. The number average particle size (D1) of the toner particles 1 was 6.2 μm, and the weight average particle size (D4) was 6.9 μm. Ions derived from titanium phosphate were detected by TOF-SIMS analysis of the toner particles 1.
The titanium phosphate compound is a reaction product of titanium lactate and a phosphate ion derived from sodium phosphate or calcium phosphate in an aqueous medium.

<Toner particle 2>
The method for producing the toner particles 2 is the same as that of the toner particles 1 except for the following two points. The first is that it was replaced with 3.2 parts of a 44% aqueous solution of titanium lactate (TC-310: manufactured by Matsumoto Fine Chemicals Co., Ltd.). The second point is that 11.7 parts of zirconium lactate ammonium salt (ZC-300, Matsumoto Fine Chemical Co., Ltd.) (equivalent to 1.4 parts as zirconium lactate ammonium salt) was added. The number average particle size (D1) of the toner particles 2 was 6.2 μm, and the weight average particle size (D4) was 6.9 μm. Toner particles 2 are TOF-SIM
Ions derived from zirconium phosphate were detected by S analysis. The zirconium phosphate compound is a reaction product of a zirconium lactate ammonium salt and a phosphate ion derived from sodium phosphate or calcium phosphate in an aqueous medium.

<Toner particle 3>
The following samples were weighed in the reaction vessel and mixed using a propeller stirring blade.
-Toner mother particle dispersion 500.0 parts Next, while maintaining the temperature at 25 ° C, adjust the pH to 1.5 with 1.0 mol / L hydrochloric acid, stir for 1.0 hour, and then use ion-exchanged water. It was filtered while washing. The obtained powder was dried in a constant temperature bath and then classified by a wind power classifier to obtain toner particles 3.

<Toner manufacturing method>
<Toner 1, 2>
Toner particles 1 and 2 were used as toners 1 and 2.

<Toner 3>
・ Toner particles 3 100.0 parts ・ Hydrophobic silica fine particles (hexamethyl disilazane treatment: number average particle size 12 nm) 1.0 parts ・ Zirconium phosphate compound fine particles 2.0 parts SUPERMIXER PICCOLO SMP-2 (stock) It was put into (manufactured by Kawata Co., Ltd.) and mixed at 3,000 rpm for 20 minutes. Then, the toner 3 was obtained by sieving with a mesh having an opening of 150 μm. The number average particle size (D1) of the toner 3 was 6.2 μm, and the weight average particle size (D4) was 6.9 μm. When the toner 3 was subjected to TOF-SIMS analysis, ions derived from zirconium phosphate were detected.

<Toner 4>
In the production example of the toner 3, 2.0 parts of titanium oxide fine particles having a number average particle diameter of 28 nm are mixed with FM mixer (manufactured by Nippon Coke Industries Co., Ltd.) instead of the zirconium phosphate compound fine particles to obtain the toner 4. Obtained. When the toner 4 was subjected to TOF-SIMS analysis, no ions derived from the polyvalent acid metal salt were detected.

<Toner 5>
In the production example of the toner 3, 2.0 parts of tricalcium phosphate fine particles having a number average particle size of 482 nm are mixed with FM mixer (manufactured by Nippon Coke Industries Co., Ltd.) instead of the zirconium phosphate compound fine particles. I got 5. When the toner 5 was subjected to TOF-SIMS analysis, ions derived from tricalcium phosphate were detected.

Table 1 shows the physical property values of the toners 1 to 5.

<Charge retention mechanism on the toner surface>
The estimation of the charge retention mechanism of the toner 3 will be described with reference to FIG. FIG. 1A is a cross section of the toner 3 and shows a state in which an electric charge is retained on the surface. The toner 3 charged by the regulation blade 25 is supported on the developing roller 23 and the photosensitive drum 11 while holding the electric charge on the surface thereof. Here, as shown in FIG. 7, the surface of the toner 3 has a reactant 3b of a compound containing a polyhydric acid and a group 4 element, and the structure thereof is a crosslinked structure. In this crosslinked structure, the reactants have a continuous connection with each other and cover the surface of the toner mother particles 3a of the toner 3, so that the electrons 32, which are the carriers of electric charges, easily move on the surface of the toner 3. ing. Since the charges that have become easy to move on the surface of the toner 3 have the same polarity, they try to keep the distance between the charges equal due to their repulsive forces. Therefore, as shown in FIG. 1A, the electric charges applied from the regulation blade 25 can be easily arranged substantially uniformly without being unevenly distributed on the surface of the toner 1.
This mechanism is considered to be the same for toner 1 and toner 2 which have a reaction product of a polyhydric acid and a compound containing a Group 4 element on the surface of the toner and whose structure is a crosslinked structure.

On the other hand, as a comparative example, the case of the toner 4 having no crosslinked structure on the surface as in this embodiment will be described with reference to FIG. 1 (b). FIG. 1B is a cross section of the toner 4, showing a state in which electric charges are retained on the surface. The electric charge given from the regulation blade 25 is in a state where the electric charge is unevenly distributed on the surface of the toner 4 due to the contact opportunity between the toner 4 and the regulation blade 25 and the variation in contact strength. At this time, since there is no reactant of the polyhydric acid and the compound containing the group 4 element on the surface of the toner and the toner 4 having no crosslinked structure has an electron 32 which is a carrier of the electric charge, the electric charge is unevenly distributed. The condition is hard to resolve.
Similarly, even in the toner 5 which does not have a reactant of the polyhydric acid and the compound containing the group 4 element on the surface of the toner and does not have a crosslinked structure, it is difficult to eliminate the unevenly distributed state of the electric charge.

<Mechanism of suppressing mirror image force>
With reference to FIG. 5, the speculation of the mirror image force suppression mechanism due to the charge retention state on the toner surface will be described. Since the mirror image force acting on the toner is proportional to the square of the amount of charge, it acts more strongly on the portion of the toner surface where the charge density is high. Therefore, the portion having a high charge density is likely to be supported in contact with the surface of the developing roller 23 or the photosensitive drum 11. Further, since the mirror image force acting on the toner is inversely proportional to the square of the distance, it acts even more strongly when the charge density of the contact portion is large.
The state in which the toner is supported on the developing roller 23 is shown in FIGS. 5 (a) and 5 (b) for the toner 3 of the present invention and the toner 4 of the comparative example, respectively. Since the surface charge density of the toner 3 is substantially uniform, the portion having a high charge density does not come into contact with the developing roller 23. On the other hand, since the toner 4 tends to have a portion having a high surface charge density, this portion comes into contact with the developing roller 23. Therefore, when the mirror image force Fm1 acting on the toner 3 and the mirror image force Fm2 acting on the toner 4 are compared, Fm1 <Fm2, and the toner 3 can suppress the mirror image force.
This mechanism is considered to be the same for the toner 1 and the toner 2 in which the structure of the toner surface is a crosslinked structure. In particular, in the toners 1 and 2 in which the charge mobility is good and the transfer of the polyvalent acid metal salt from the toner to the member is suppressed, the uneven distribution of the electric charge is less likely to occur, so that the mirror image force can be further suppressed.

<Toner stripping effect of stripping roller>
The toner stripping effect of the stripping roller 24 using the toner 3 of the present invention will be described with reference to FIG. The toner 3 on the developing roller 23 collected in the developing container 21 without being developed comes into contact with the stripping roller 24 in a state of being supported by the mirror image force on the developing roller 23. At this time, the mirror image force acting on the toner 3 is suppressed to a small value as described in the above-mentioned "charge retention mechanism on the toner surface" and "mechanism for suppressing the mirror image force", so that the stripping roller 24 is sufficient for peeling. You can take it.

Here, the results of comparative studies using toners 1 to 5 will be described. For comparison, a developing device 20 containing each toner was prepared. Each developing device 20 was attached to the image forming device 100, and an image evaluation test was performed. The image used for the evaluation is a 1 cm square solid black patch printed with a length of one circumference of the developing roller 23, and then a vertical band having a halftone density printed. The image evaluation results are shown in Table 2. The ghost evaluation was made by outputting a ghost image and visually judging according to the following criteria.
A: The shadow of the patch is almost invisible on the second lap of rotation of the developing roller B: The shadow of the patch is slightly visible on the second lap of rotation of the developing roller C: The shadow of the patch is clearly visible on the second lap of rotation of the developing roller

The stripping roller 24 also plays a role of supplying the toner 3 to the developing roller 23. Therefore, when it is desired to increase the amount of toner supplied, an electric field in the direction in which the toner 3 moves from the stripping roller 24 to the developing roller 23 may be applied by a voltage applying device (not shown). When an electric field is applied, a Coulomb force acts in addition to the mirror image force, so that the toner is more difficult to peel off. However, since the toner 3 of the present invention can suppress the mirror image force, it is sufficient even when an electric field is applied. Can be stripped off.
As described above, in the toner of the present invention, a reaction product of a polyhydric acid and a compound containing a Group 4 element forms a crosslinked structure, so that the toner charge-up is not deteriorated in a high humidity environment. Can be suppressed, so that toner can be stably stripped from the top of the developing roller 23.

<Toner regulation effect of regulation blade>
The toner regulation effect of the regulation blade 25 using the toner 3 of the present invention will be described with reference to FIG. The toner 3 supplied from the stripping roller 24 onto the developing roller 23 comes into contact with the regulating blade 25 in a state of being supported by the mirror image force on the developing roller 23. At this time, the mirror image force acting on the toner 3 is suppressed to be small as described in the above-mentioned "charge retention mechanism on the toner surface" and "mechanism for suppressing the mirror image force". As a result, it is possible to prevent the regulating blade 25 from taking in the toner 3 excessively, and the toner coating amount can be regulated to a constant layer thickness.
Here, the results of comparative studies using toners 1 to 5 will be described. For comparison, a developing device 20 containing each toner was prepared. Each developing apparatus 20 was attached to the image forming apparatus 1000, and a toner coating amount evaluation test was conducted. The evaluation results are shown in Table 3. The evaluation of the toner coating amount was made by examining the change in the weight of the toner carried on the developing roller 23 after passing 1000 sheets of paper, and judging by the following criteria.
A: Toner weight change less than 5% on the 1st and 1000th sheets of paper B: Toner weight change of 5% or more and less than 10% on the 1st and 1000th sheets of paper C: 1st and 1000th sheets of paper 10% or more change in toner weight on the first sheet

The toners 1 to 3 of this embodiment can regulate the toner coating amount to a certain layer thickness, and the toners 1 and 2 are particularly effective. On the other hand, in the toners 4 and 5, the toner coating amount could not be regulated to a constant layer thickness.
The shape of the blade 25b of the regulation blade 25 is not limited to the flat plate shape as shown in FIG. 4, and the tip may have a rectangular cross section as shown in FIG. As described above, in the toner of the present invention, a reaction product of a polyhydric acid and a compound containing a Group 4 element forms a crosslinked structure, so that the toner charge-up is not deteriorated in a high humidity environment. Therefore, the toner layer thickness on the developing roller 23 can be stably regulated.

<Toner stripping effect of cleaning member>
The toner stripping effect of the cleaning member 14 using the toner 3 of the present invention will be described with reference to FIG. The toner 3 that remains on the photosensitive drum 11 without being transferred comes into contact with the rubber portion 14a of the cleaning member 14 in a state of being supported by the mirror image force on the photosensitive drum 11. At this time, since the mirror image force of the toner 3 is suppressed to be small as described in the above-mentioned "charge retention mechanism of the toner surface" and "mechanism of suppressing the mirror image force", the cleaning member 14 can sufficiently peel off the toner 3. ..
Here, the results of comparative studies using toners 1 to 5 will be described. For comparison, a developing device 20 containing each toner was prepared. Each developing device 20 was attached to the image forming device 100, and an image evaluation test was performed. The image used for evaluation is a solid white image. The image evaluation results are shown in Table 4. The evaluation of cleaning was made by visually observing a solid white image after passing 1000 sheets of paper, and judging by the presence or absence of vertical streaks due to poor cleaning.
A: Vertical streaks are almost invisible on the image B: Vertical streaks are slightly visible on the image C: Vertical streaks are clearly visible on the image

The toners 1 to 3 of this example could be sufficiently peeled off by the cleaning member 14. On the other hand, the toners 4 and 5 could not be sufficiently peeled off. As described above, in the toner of the present invention, a reaction product of a polyhydric acid and a compound containing a Group 4 element forms a crosslinked structure, so that the toner charge-up is not deteriorated in a high humidity environment. Can be suppressed, so that the toner on the photosensitive drum 11 can be stably removed.

10 ... Process cartridge, 11 ... Photosensitive drum, 14 ... Cleaning member, 23 ... Development roller, 25 ... Regulatory blade, 3 ... Toner

Claims (8)

A process cartridge including a rotating body carrying a developer and an abutting member that comes into contact with the rotating body.
The developer has toner particles containing a binder resin and has
A process cartridge characterized in that the surface of the toner particles has a reactant of a polyhydric acid and a compound containing a Group 4 element. When a metal salt is used together with the polyhydric acid in the reactant,
When the metal element contained in the metal salt is the metal element M,
The ratio M1 of the metal element M to the constituent element ratio of the reactant having on the surface of the toner particles obtained from the spectrum obtained by the X-ray photoelectron spectroscopy of the developer is 1.0 (at%) or more. The process cartridge according to claim 1, wherein the process cartridge is 0.0 (at%) or less. 1 g of the developer is dispersed in a mixed aqueous solution consisting of 31 g of a 61.5% sucrose aqueous solution and 6 g of a 10% neutral detergent aqueous solution for cleaning a precision measuring instrument composed of a nonionic surfactant and an anionic surfactant. The developer obtained by performing the treatment (a) of shaking 300 times per minute using a shaker was used as the toner (a).
The ratio of the metal element M to the constituent element ratio of the reactant having on the surface of the toner particles constituting the toner (a) obtained from the spectrum obtained by the X-ray photoelectron spectroscopy of the toner (a) is M2. (At%)
Both M1 and M2 are 1.0 or more and 10.0 or less.
The process cartridge according to claim 2, wherein the M1 and M2 satisfy the following relational expression (ME-1).

0.90 ≤ M2 / M1 (ME-1)
The process cartridge according to any one of claims 1 to 3, wherein the developer contains an organosilicon polymer on the surface of the toner particles containing a binder resin. The process cartridge according to any one of claims 1 to 4, wherein the rotating body is a developer carrier, and the contact member is a developer stripping member. The process cartridge according to any one of claims 1 to 4, wherein the rotating body is a developer carrier and the abutting member is a developer regulating member. The process cartridge according to any one of claims 1 to 4, wherein the rotating body is an image carrier and the contact member is a cleaning member. An image forming device that forms an image on a recording material.
With the device body
An image forming apparatus comprising the process cartridge according to any one of claims 1 to 7 that can be attached to and detached from the apparatus main body.

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