JP2021021941A - Process cartridge and electrophotographic device - Google Patents

Abstract

To provide a process cartridge and an electrophotographic device that reduces fogging at a high level to reduce toner consumption.SOLUTION: A process cartridge is configured to be removably attached to a main body of an electrophotographic device, and has developing means that has toner and an electrophotographic photoreceptor. The toner has toner particles, and the toner particles each have polyvalent acid metal salt particles on its surface. The polyvalent acid metal salt particles each include, as a metal element, at least one metal element selected from metal elements included in group 3 to group 13. A surface layer of the electrophotographic photoreceptor contains at least one or more metal oxide particles from among aluminum oxide particles, silicon dioxide particles, and tin oxide particles.SELECTED DRAWING: None

Description

The present invention relates to process cartridges and electrophotographic devices.

In the electrophotographic process, in recent years, it has been desired to reduce the size of the electrophotographic apparatus and increase the number of printable sheets. Correspondingly, further reduction of toner consumption is required. In order to reduce the amount of toner consumed, it is required to reduce the fog that the toner develops in the non-image area.

Patent Document 1 discloses a toner having improved developability and durability by adhering inorganic fine particles composed of phosphoric acid-based anions and zirconium ions to the surface of the toner.
Patent Document 2 discloses a technique for suppressing fog by incorporating metal oxide particles in the surface layer of an electrophotographic photosensitive member.

Japanese Unexamined Patent Publication No. 2001-209207 Japanese Unexamined Patent Publication No. 2006-178412

According to the studies by the present inventors, the process cartridges described in Patent Documents 1 and 2 have been improved in terms of fog that can be visually confirmed on the image, but are further improved in terms of reducing toner consumption. Reduction of fog is required.

Therefore, an object of the present invention is to provide a process cartridge and an electrophotographic apparatus with highly reduced fog in order to reduce toner consumption.

The above object is achieved by the following invention. That is, the process cartridge according to one aspect of the present invention has a developing means having a toner and an electrophotographic photosensitive member, the toner has toner particles, and the toner particles have polyvalent acid metal salt particles on the surface. The surface layer of the electrophotographic photosensitive member is characterized by containing at least one or more metal oxide particles among aluminum oxide particles, silicon dioxide particles and tin oxide particles.

Further, the electrophotographic apparatus according to another aspect of the present invention is characterized by having the above-mentioned process cartridge.

According to the present invention, it is possible to provide a process cartridge and an electrophotographic apparatus with highly reduced fog in order to reduce toner consumption.

It is a figure which shows an example of the schematic structure of the electrophotographic apparatus provided with the process cartridge which concerns on this invention.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments.
In order to solve the above problems, it is a feature of the present invention to use a combination of a toner having polyvalent acid metal salt particles on the surface of the toner particles and an electrophotographic photosensitive member containing metal oxide particles on the surface layer. is there.

The present inventors infer the mechanism by which fog is improved by combining a toner satisfying the above characteristics and an electrophotographic photosensitive member as follows.

In the electrophotographic process, as an image forming method, a method of forming a toner image on an electrophotographic photosensitive member and then transferring the formed toner image onto an intermediate transfer body or paper is generally used.
Toners having polyvalent metal salt particles on their surface are likely to be negatively charged due to the polarization of the polyvalent metal salt particles, and are excellent in chargeability. Further, since the polyvalent acid metal salt particles have an appropriate resistance value, the electric charge is easily transferred.

On the other hand, an electrophotographic photosensitive member containing metal oxide particles in the surface layer is more likely to be positively charged than a toner having polyvalent acid metal salt particles on the surface.
Therefore, it is presumed that when a toner image is formed on the electrophotographic photosensitive member, a negative charge is supplied from the electrophotographic photosensitive member to the toner, so that the charge uniformity of the toner is improved and fog is reduced. ing.

[toner]
The toner has toner particles, and the surface of the toner particles has polyvalent acid metal salt particles.
The polyvalent acid contained in the polyvalent acid metal salt particles 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, terephthalic acid; citric acid, aconit Tricarboxylic acids such as acids and trimellitic anhydride.

Among them, it is preferable that the polyhydric acid contains at least one selected from the group consisting of the inorganic acids carbonic acid, sulfuric acid, and phosphoric acid because it reacts strongly with the metal element and does not easily absorb moisture. More preferably, the polyhydric acid contains phosphoric acid.

The polyvalent acid metal salt particles preferably contain at least one metal element selected from the metal elements contained in the Group 3 to Group 13 as the metal element. Since the salt composed of the metal element and the polyhydric acid contained in the 3rd to 13th groups has low water absorption, the effect of reducing fog can be stably obtained even in a high humidity environment.

Specific examples of the metal element contained in the polyvalent acid metal salt particles include titanium, zirconium, aluminum, zinc, indium, hafnium, iron, copper, silver and the like. Among them, as the metal element contained in the polyvalent acid metal salt particles, a metal having a valence of trivalent or higher is preferable. Specifically, titanium, zirconium, and aluminum are more preferable, and titanium is even more preferable.

Specific examples of the polyvalent acid metal salt particles in which the above metal and the above polyvalent acid are combined include a metal phosphate such as a titanium phosphate compound, a zirconium phosphate compound, an aluminum phosphate compound, and a copper phosphate compound, and titanium sulfate. Examples thereof include particles composed of compounds, metal sulfates such as zirconium sulfate compounds and aluminum sulfate compounds, metal carbonates such as titanium carbonate compounds, zirconium carbonate compounds and aluminum carbonate compounds, and metal oxalate salts such as titanium oxalate compounds. Among them, metal phosphate particles are preferable, and titanium phosphate compound particles are preferable because phosphate ions have high strength by cross-linking between metals and have excellent charge rising property due to having an ionic bond in the molecule. Is even more preferable.

The method for obtaining the polyvalent acid metal salt particles is not particularly limited, and a conventionally known method can be used. Above all, a method of reacting a metal compound serving as a metal source with a polyvalent acid ion in an aqueous medium to obtain polyvalent acid metal salt particles is preferable.

As a metal source for obtaining polyvalent acid metal salt particles by the above method, a conventionally known metal compound can be used without any particular limitation as long as it is a metal compound that gives polyvalent acid metal salt particles by reaction with polyvalent acid ions. Can be used.

Specific examples of the metal compound that gives polyvalent acid metal salt particles by reaction with polyvalent acid ions include titanium lactate, titanium tetraacetylacetonate, titanium lactate ammonium salt, titanium triethanolaminate, zirconium lactate, and zirconium. Examples thereof include metal chelates such as lactate ammonium salt, aluminum lactate, aluminum trisacetylacetonate and copper lactate, and metal alkoxides such as titanium tetraisopropoxide, titanium ethoxydo, zirconium tetraisopropoxide and aluminum trisisopropoxide. Of these, metal chelates are preferable because the reaction is easy to control and they react quantitatively with polyvalent acid ions. Further, a lactic acid chelate such as titanium lactate or zirconium lactate is more preferable from the viewpoint of solubility in an aqueous medium.

As the polyvalent acid ion when the polyvalent acid metal salt particles are obtained by the above method, the above-mentioned polyvalent acid ion can be used. As a form of addition to the aqueous medium, the polyhydric acid itself may be added, or a water-soluble polyvalent acid metal salt may be added to the aqueous medium and dissociated in the aqueous medium.

The number average particle size of the polyvalent acid metal salt particles is preferably 1.0 nm or more and 400 nm or less, more preferably 1.0 nm or more and 200 nm or less, and further preferably 1.0 nm or more and 60 nm or less. ..

By keeping the average particle size of the number of polyvalent metal salt particles within the above range, it is possible to suppress member contamination due to migration of polyvalent metal salt particles from the toner to the surface of the electrophotographic photosensitive member or other members. it can. This makes it easier to maintain the negative chargeability of the toner surface and the positive chargeability of the electrophotographic photosensitive member surface. Therefore, it becomes easier to obtain the effect of reducing fog.

The method of adjusting the number average particle size of the polyvalent acid metal salt particles within the above range is the amount of the compound containing the polyvalent acid and the metal element, which are the raw materials of the polyvalent acid metal salt particles, and when they react. A method of controlling the pH, temperature, etc. of the metal can be mentioned.

As a method for allowing a reaction product of a compound containing a polyhydric acid and a metal element to exist on the surface of the toner particles, for example, a reaction product of the compound containing a polyhydric acid and a metal element is used in a dispersion of toner mother particles. Examples thereof include a method of adhering to the surface of the toner matrix particles. In this case, when the toner matrix particles are produced in an aqueous medium, the aqueous medium containing the produced toner matrix particles may be used as it is as a dispersion liquid of the toner matrix particles. Further, a solution obtained by producing toner matrix particles in an aqueous medium, washing, filtering, and drying the toner matrix particles, and then redistributing the toner matrix particles in the aqueous medium may be used as a dispersion liquid of the toner matrix particles. On the other hand, when the toner matrix particles are produced by a dry method, the toner matrix particles may be dispersed in an aqueous medium by a known method to obtain a dispersion liquid of the toner matrix particles. In this case, in order to disperse the toner matrix particles in the aqueous medium, it is preferable that the aqueous medium contains a dispersion stabilizer.

<Detection method of polyvalent acid metal salt particles>
Polyvalent acid metal salt particles on the surface of toner particles can be detected by the following method using time-of-flight secondary ion mass spectrometry (TOF-SIMS).

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 can be confirmed that polyvalent acid metal salt particles are present on the toner surface.

The toner particles preferably have a toner mother particle containing a binder resin and an organosilicon polymer on the surface of the toner mother particle.

The organosilicon polymer is preferably present on the surface of the toner matrix particles as follows. That is, when a compound containing a polyhydric acid and a metal 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, the toner particles are produced. In, an organic silicon compound represented by the following formula (T-1) is used.
R _{a (n)} -Si-R _{b (4-n)} (T-1)
In the formula (T-1), _Ra represents a halogen atom, a hydroxy group or an alkoxy group, and R _b represents an alkyl group, an alkenyl group, an aryl group, an acyl group or a methacryloxyalkyl group. n represents an integer of 2 or more and 4 or less. When _a plurality of R _a and R _b exist, the plurality of _Ra and the plurality of R _b may be the same or different, respectively.
Hereinafter, R _a in the formula (T-1) is also referred to as _a functional group, and R _b is also referred to as a substituent.

By using the organosilicon compound represented by the formula (T-1), the reactant obtained by reacting the polyhydric acid with the compound containing a metal element is more firmly adhered to the toner particles and the surface is surfaced. It is made hydrophobic and the stability of triboelectric charging in a high humidity environment is further improved.

Specifically, first, the organosilicon compound represented by the formula (T-1) is hydrolyzed in advance or hydrolyzed in a dispersion of toner matrix particles.
Then, the obtained hydrolyzate of the organosilicon compound is condensed in a dispersion of toner mother particles to obtain a condensate.
The condensate migrates to the surface of the toner matrix particles. Since the condensate is viscous, a reaction product of a compound containing a polyhydric acid and a metal element can be brought into close contact with the surface of the toner particles, and the reaction product can be more firmly fixed to the toner particles.
Further, the condensate can also be transferred to the surface of the reactant to make the reactant hydrophobic and further improve the stability of triboelectric charging in a high humidity environment.

As the organosilicon compound represented by the formula (T-1), a known organosilicon compound can be used without particular limitation. Specific examples thereof include a bifunctional silane compound having two functional groups, a trifunctional silane compound having three functional groups, and a tetrafunctional silane compound having four functional groups, which are exemplified below.

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 , Hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, and other trifunctional silane compounds having an alkyl group as a substituent; vinyltrimethoxysilane, vinyl Trifunctional silane compound having an alkenyl group as a substituent such as triethoxysilane, allyltrimethoxysilane, allyltriethoxysilane; trifunctionalsilane compound having an aryl group as a substituent such as phenyltrimethoxysilane, 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.

The content of the condensate of at least one organosilicon compound selected from the group consisting of the organosilicon compounds represented by the formula (T-1) in the toner particles is 0.1% by mass or more and 20.0% by mass or less. It is preferable that it is 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 known suspension polymerization methods, dissolution suspension methods, emulsification and agglutination methods, pulverization methods and the like can be used.

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.
Dispersers include homogenizers, ball mills, colloid mills, or ultrasonic dispersers.

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 monomers exemplified below or 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.
Monovalent alcohols and aliphatic monocarboxylic acid esters such as behenyl behenyl, stearyl stearate, palmityl palmitate, or esters of monovalent carboxylic acid and aliphatic monoalcohol; dibehenyl sebacate, hexanediol dibehenate, etc. Divalent alcohol and aliphatic monocarboxylic acid ester, or divalent carboxylic acid and aliphatic monoalcoyl acid ester; trivalent alcohol such as glycerin tribehenate and aliphatic monocarboxylic acid ester, or 3 Esters of valent carboxylic acids and aliphatic monoalcohols; tetravalent alcohols and aliphatic monocarboxylic acid esters such as pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, or tetravalent carboxylic acids and aliphatic monoalcohols Estel; hexavalent alcohol and aliphatic monocarboxylic acid ester such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, or hexavalent carboxylic acid and aliphatic monocarboxylic acid ester; polyglycerin behenate etc. Polyvalent alcohols and aliphatic monocarboxylic acid esters, or polyvalent carboxylic acids and aliphatic monocarboxylic acid esters; natural ester waxes such as carnauba wax and rice wax; petroleum waxes such as paraffin wax, microcrystallin wax, and petrolatum. And derivatives thereof; hydrocarbon waxes and derivatives thereof according to the Fisher Tropsch 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 waxes.

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.

Various organic fine particles or inorganic fine particles may be externally added to the toner particles to the extent that the characteristics of the toner are not impaired. As the organic fine particles or the inorganic fine particles, for example, the following are used.
Liquidity-imparting agents: silica, alumina, titanium oxide, carbon black and carbon fluoride.
Abrasives: metal oxides (eg strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitrides (eg silicon nitride), carbides (eg silicon carbide), metal salts (eg calcium sulfate, etc. Barium sulfate, calcium carbonate).
Lubricants: Fluorine-based resin fine particles (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salts (for example, zinc stearate, calcium stearate).
Charge control particles: metal oxides (eg tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

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

<Structure of cross section of toner particles>
The toner particles have a toner mother particle containing a binder resin and a convex portion on the surface of the toner mother particle, and the convex portion preferably contains an organosilicon polymer.

The method of confirming the composition of the toner particles by observing the cross section of the toner particles with a transmission electron microscope will be described below.
First, the cross section of the toner particles observed with a transmission electron microscope (TEM) is analyzed using energy dispersive X-ray spectroscopy (EDX). An image of the toner mother particles and an image of the organosilicon polymer can be observed in the EDX mapping image of the constituent elements of the cross section of the toner particles thus obtained. Further, by confirming that the image of the organic silicon polymer forms a convex portion at a position corresponding to the surface of the toner mother particles in the image of the toner mother particles, the toner particles are organic on the surface of the toner mother particles. It can be confirmed that it has a convex portion containing a silicon polymer. The height H of the convex portion containing the organosilicon polymer that the toner particles have on the surface of the toner mother particles is preferably 30 nm or more and 300 nm or less.

<Calculation method of height H of convex part>
Using a transmission electron microscope (TEM), the cross section of the toner particles is observed by the following method.
First, the toner particles are sufficiently dispersed in a room temperature curable epoxy resin, and then cured in an atmosphere of 40 ° C. for 2 days.
A flaky sample having a thickness of 50 nm is cut out from the obtained cured product using a microtome (EM UC7: manufactured by Leica) equipped with a diamond blade.

This sample is magnified using a TEM (JEM2800 type: manufactured by JEOL Ltd.) at a magnification of 500,000 times under the conditions of an acceleration voltage of 200 V and an electron beam probe size of 1 mm, and the cross section of the toner particles is observed. At this time, the cross section of the toner particles is 0.9 times to 1.1 times the number average particle diameter (D1) when the same toner is measured according to the method for measuring the number average particle diameter (D1) of the toner particles described later. Select the one with double the maximum diameter. Subsequently, the constituent elements of the cross section of the obtained toner particles were analyzed using energy dispersive X-ray spectroscopy (EDX), and an EDX mapping image (256 × 256 pixels (2.2 nm / pixel), number of integrations). 200 times).

When a signal derived from a silicon element is observed on the surface of the toner mother particles in the prepared EDX mapping image, the signal is taken as an image of an organosilicon polymer. When an image of the organosilicon polymer is continuously observed on the surface of the toner matrix particles, the line segment connecting the end points of the image of the organosilicon polymer is used as the baseline. The portion where the intensity of the signal derived from silicon becomes equal to the intensity of silicon in the background is defined as the end point of the image of the organosilicon polymer.

For each baseline, a perpendicular line having the maximum length from the baseline to the image surface of the organosilicon polymer is searched for, and the maximum length is defined as the height of the convex portion. According to the above method, the cross sections of the 20 toner particles are analyzed, and the average value of the heights of the obtained convex portions is defined as the height H (nm) of the convex portions.

Regarding the toner, the metal element contained in the polyvalent acid metal salt particles is defined as the metal element M, and the ratio of the metal element M to the constituent element ratio of the toner particle surface obtained from the spectrum obtained by the X-ray photoelectron spectroscopic analysis of the toner particles is determined. Let it be M1 (atomic%). At this time, it is preferable that M1 is 1.0 (atomic%) or more and 10.0 (atomic%) or less.

Further, 1.0 g of toner is added to 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. Disperse. Subsequently, the toner obtained by performing the treatment (a) of shaking 300 times per minute using a shaker is used as the toner (a). Let M2 (atomic%) be the ratio of the metal element M in the ratio of the constituent elements on the surface of the toner particles obtained from the spectrum obtained by the X-ray photoelectron spectroscopy of the toner (a). At this time, it is preferable that both M1 and M2 are 1.0 or more and 10.0 or less, and M2 / M1 is 0.90 or more.

In the treatment (a), the polyhydric acid metal salt particles weakly attached to the toner surface can be removed. Specifically, the polyhydric acid metal salt particles attached to the toner mother particles by the dry method are easily removed by the above treatment (a). In this way, it is possible to evaluate the adhered state of the polyvalent acid metal salt particles and the organosilicon polymer existing on the toner surface by the treatment (a). The larger the ratio of M2 obtained after the treatment (a) to M1, the stronger the polyvalent acid metal salt particles are adhered to the toner matrix particles.

M1 and M2 represent the coating state of the toner surface by the polyvalent acid metal salt particles before and after each treatment. The coating state of the toner surface with the polyvalent acid metal salt particles contributes to chargeability and charge mobility.

M1 and M2 are preferably 1.0 (atomic%) or more and 10.0 (atomic%) or less. When M1 and M2 are within the above ranges, the negative charge property of the toner and the charge transfer property are improved, so that the charge transfer from the electrophotographic photosensitive member to the toner becomes smoother, and the effect of reducing fog is likely to be obtained. ..

M1 and M2 are more preferably 1.0 (atomic%) or more and 7.0 (atomic%) or less, and further preferably 1.5 (atomic%) or more and 5.0 (atomic%) or less.

M2 / M1 means the ratio at which the polyvalent acid metal salt particles do not peel off from the toner surface in the treatment (a) and remain. When M2 / M1 is 0.90 or more, the polyvalent metal salt particles are strongly adhered to the toner surface, so that the transfer of the polyvalent metal salt particles from the toner to the surface of the electrophotographic photosensitive member is suppressed. .. Therefore, it is possible to obtain a highly durable toner that can easily maintain the negative chargeability of the toner surface and the positive chargeability of the electrophotographic photosensitive member surface and can stably reduce fog even during long-term use. it can.
Further, it is more preferable that M2 / M1 is 0.95 or more.

<Method of forming convex parts containing organosilicon polymer>
The method for forming the convex portion containing the organosilicon polymer of the present invention is not particularly limited, and a conventionally known method can be used. For example, in an aqueous medium in which toner matrix particles are dispersed, a hydrolyzate of an organosilicon compound represented by the formula (T-1) (hereinafter, also simply referred to as an organosilicon compound) is condensed in a dispersion of toner matrix particles. , A method of forming a convex portion on the toner mother particle can be mentioned. Further, a method of adhering a convex portion containing an organosilicon polymer on a toner mother particle produced by a dry method or a wet method by a mechanical external force can be mentioned.

Above all, since it is possible to firmly fix the toner mother particles and the convex portions, the hydrolyzate of the organosilicon compound is condensed in the dispersion liquid of the toner mother particles in the aqueous medium in which the toner mother particles are dispersed. The method is preferred.

The above method will be described below.
When forming a convex portion on the toner mother particles by the above method, it is preferable to include the following steps 1 and 2. A step of dispersing the toner mother particles in an aqueous medium to obtain a toner mother particle dispersion liquid (step 1). The organosilicon compound (or its hydrolyzate) is mixed with the toner mother particle dispersion, and the organosilicon compound is condensed in the toner matrix dispersion to cause a convexity containing the organosilicon polymer on the toner matrix. A step of forming a portion (step 2).

In step 1, as a method of obtaining the toner mother particle dispersion liquid, a method of using the toner mother particle dispersion liquid produced in the aqueous medium as it is, and a method of charging the dried toner mother particles into the aqueous medium and mechanically dispersing them. There is a method of making the particles. When the dried toner matrix particles are dispersed in an aqueous medium, a dispersion aid may be used.

As the dispersion aid, known dispersion stabilizers, surfactants and the like can be used. Specifically, as dispersion stabilizers, the following tricalcium phosphate, hydroxyapatite, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, Inorganic dispersion stabilizers such as calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina, and organic dispersion stabilizers such as polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch. Can be mentioned. In addition, as surfactants, the following alkyl sulfate ester salts, alkylbenzene sulfonates, anionic surfactants such as fatty acid salts, nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxypropylene alkyl ethers, and alkylamine salts , Cationic surfactants such as quaternary ammonium salts. Among them, it is preferable to contain an inorganic dispersion stabilizer, and it is more preferable to contain a dispersion stabilizer containing a phosphate such as tricalcium phosphate, hydroxyapatite, magnesium phosphate, zinc phosphate and aluminum phosphate.

In step 2, the organosilicon compound may be added to the toner mother particle dispersion as it is, or may be added to the toner mother particle dispersion after hydrolysis. Above all, since the condensation reaction is easy to control and the amount of the organosilicon compound remaining in the toner mother particle dispersion can be reduced, it is preferable to add it after hydrolysis. Hydrolysis is preferably carried out in an aqueous medium whose pH has been adjusted using a known acid and base. It is known that the hydrolysis of an organosilicon compound is pH-dependent, and the pH at the time of hydrolysis is preferably changed as appropriate depending on the type of the organosilicon compound. For example, when methyltriethoxysilane is used as the organosilicon compound, the pH of the aqueous medium is preferably 2.0 or more and 6.0 or less.

Specific examples of the acid for adjusting the pH include hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chloric acid, chloric acid, perchloric acid, hypobromic acid, and the following acids. Inorganic acids such as bromine acid, bromic acid, perbromic acid, hypochlorous acid, iodic acid, iodic acid, periodic acid, sulfuric acid, nitrate, phosphoric acid, boric acid, acetic acid, citric acid, formic acid, gluconic acid , Lactic acid, oxalic acid, tartrate acid and other organic acids.

Specific examples of the base for adjusting the pH include hydroxides of alkali metals such as potassium hydroxide, sodium hydroxide, and lithium hydroxide, aqueous solutions thereof, and alkalis such as potassium carbonate, sodium carbonate, and lithium carbonate. Metal carbonates and their aqueous solutions, alkali metal sulfates such as potassium sulfate, sodium sulfate, lithium sulfate and their aqueous solutions, alkali metal phosphates such as potassium phosphate, sodium phosphate, lithium phosphate and theirs. Examples thereof include hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, aqueous solutions thereof, and amines such as ammonia and triethylamine.

The condensation reaction in step 2 is preferably controlled by adjusting the pH of the toner mother particle dispersion. It is known that the condensation reaction of an organosilicon compound is pH-dependent, and the pH at which the condensation reaction is carried out is preferably changed as appropriate depending on the type of the organosilicon compound. For example, when methyltriethoxysilane is used as the organosilicon compound, the pH of the aqueous medium is preferably 6.0 or more and 12.0 or less. By adjusting the pH, it is possible to control the height H and width W of the convex portion containing the organosilicon polymer that the toner particles have on the surface of the toner mother particles, and the effect of the present invention can be further obtained. It will be easier. As the acid and base for adjusting the pH, an acid and a base that can be used for the hydrolysis exemplified above can be used.

The method for measuring each physical property value is 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, Inc.) equipped with a 100 μm aperture tube by the pore electric resistance method is used. For the setting of measurement conditions and the analysis of measurement data, the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, one in which 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) 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).
By pressing the "threshold / noise level measurement button", the threshold and noise level are automatically set. Also, set the current to 1,600 μA, the gain to 2, and the electrolytic aqueous solution to ISOTON II, 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 their phases shifted by 180 degrees, and an ultrasonic disperser "Ultrasonic Dispersion System Tera150" (manufactured by Nikkaki Bios) with an electrical output of 120 W is prepared. 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 diameter (D4) and the number average particle diameter (D1) are calculated. The "average diameter" on the "analysis / volume statistic (arithmetic mean)" screen when graph / volume% is set with the dedicated software is the weight average particle size (D4), and the graph / volume is set with the dedicated software. The "average diameter" of the "analysis / number statistical value (arithmetic mean)" screen when the number% is set is the number average particle size (D1).

[Electrophotophotoreceptor]
<Surface layer>
In the present invention, the surface layer of the electrophotographic photosensitive member contains at least one of metal oxide particles among aluminum oxide particles, silicon dioxide particles and tin oxide particles.

In the case of the laminated photosensitive layer described later, the charge transport layer is the surface layer. In the case of a single-layer photosensitive layer, the single-layer photosensitive layer is a surface layer. Further, when a protective layer described later is provided on the upper layer of the photosensitive layer, the protective layer is a surface layer.

The content of the aluminum oxide particles in the surface layer is preferably 5.0 parts by mass or more and 100 parts by mass or less with respect to 100.0 parts by mass of the resin component of the surface layer. From the viewpoint of further improving the filming resistance, it is preferably 5.0 parts by mass or more, and more preferably 10.0 parts by mass or more. From the viewpoint of suppressing poor appearance due to the generation of solid foreign matter, the amount is preferably 100 parts by mass or less, and more preferably 40 parts by mass or less.

The average primary particle size of the aluminum oxide particles is preferably 0.1 μm or more and 2.0 μm or less. From the viewpoint of further improving the filming resistance, the average primary particle size of the particles is preferably 0.1 μm or more, and more preferably 0.3 μm or more. From the viewpoint of further suppressing the generation of transfer memory, the average primary particle size of the particles is preferably 2.0 μm or less, and more preferably 1.0 μm or less.

The content of the silicon dioxide particles in the surface layer is preferably 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin component. From the viewpoint of further improving the filming resistance, it is preferably 0.5 parts by mass or more, and more preferably 1.0 part by mass or more. From the viewpoint of suppressing poor appearance due to the generation of solid foreign matter, the amount is preferably 30 parts by mass or less, and more preferably 15 parts by mass or less.

The average primary particle size of the silicon dioxide particles is preferably 5.0 nm or more and 10 μm or less. From the viewpoint of further improving the filming resistance, the average primary particle size of the particles is preferably 10 nm or more, and more preferably 100 nm or more. From the viewpoint of further suppressing the generation of transfer memory, the average primary particle size of the particles is preferably 10.0 μm or less, and more preferably 5.0 μm or less.

The content of the tin oxide particles in the surface layer is preferably 30 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin component. From the viewpoint of further improving the filming resistance, it is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more. From the viewpoint of suppressing poor appearance due to the generation of solid foreign matter, the amount is preferably 150 parts by mass or less, and more preferably 100 parts by mass or less.

The average primary particle size of the tin oxide particles is preferably 1.0 nm or more and 300.0 nm or less. From the viewpoint of further improving the filming resistance, the average primary particle size of the particles is preferably 1.0 nm or more, and more preferably 3.0 nm or more. From the viewpoint of further suppressing the generation of the transfer memory, the average primary particle size of the particles is preferably 300 nm or less, more preferably 100 nm or less.

Each of the above mass parts can be verified from the mass of the surface layer, the mass obtained by decomposing the resin component of the surface layer, and the metal oxide particles extracted and detected.

Further, when the surface layer has a resin to be described later, the resin is referred to as a resin component. When a cured product obtained by polymerizing a composition containing a monomer having a polymerizable functional group is obtained, the cured product is referred to as a resin component. When a monomer having a polymerizable functional group has a cured product obtained by polymerizing using a material having a charge transporting ability, the cured product is called a resin component.

The average primary particle size of the metal oxide particles is measured by, for example, the following method. A plurality of metal oxide particles (powder) are used as the measurement sample. Measure the N ₂ adsorption isotherm of the measurement sample at -196 ° C. The obtained N ₂ adsorption isotherm is evaluated according to the methods of Brunauer, Emmett and Teller, and the t-curve method by De Boer. As a result, the specific surface area of the measurement sample is calculated. From the specific surface area of the obtained measurement sample, the particle size of the measurement sample is calculated according to the mathematical formula "d = 6 / ρS". In the formula, d indicates the particle size of the measurement sample, ρ indicates the density of the measurement sample, and S indicates the specific surface area of the measurement sample. The calculated particle size of the measurement sample is taken as the average primary particle size of the metal oxide particles.

As another method for measuring the average primary particle size of the metal oxide particles, there is also a method by image measurement. Specifically, an image of a considerable number of metal oxide particles is taken using a transmission electron microscope, and the primary particle size of each metal oxide particle in the image is measured. The average primary particle size of the metal oxide particles is calculated by dividing the sum of the measured primary particle sizes by the number of the measured metal oxide particles.

Examples of the method for producing the electrophotographic photosensitive member include a method in which a coating liquid for each layer, which will be described later, is prepared, applied in the order of desired layers, and dried. At this time, examples of the coating liquid coating method include immersion coating, spray coating, inkjet coating, roll coating, die coating, blade coating, curtain coating, wire bar coating, and ring coating. Among these, dip coating is preferable from the viewpoint of efficiency and productivity.

Hereinafter, each layer will be described.
<Support>
In the present invention, the electrophotographic photosensitive member has a support. In the present invention, the support is preferably a conductive support having conductivity. Further, examples of the shape of the support include a cylindrical shape, a belt shape, and a sheet shape. Above all, a cylindrical support is preferable. Further, the surface of the support may be subjected to an electrochemical treatment such as anodization, a blast treatment, a cutting treatment or the like.
As the material of the support, metal, resin, glass and the like are preferable.
Examples of the metal include aluminum, iron, nickel, copper, gold, stainless steel, and alloys thereof. Above all, it is preferable that the support is made of aluminum using aluminum.
Further, the resin or glass may be imparted with conductivity by a treatment such as mixing or coating a conductive material.

<Conductive layer>
In the present invention, a conductive layer may be provided on the support. By providing the conductive layer, it is possible to conceal scratches and irregularities on the surface of the support and control the reflection of light on the surface of the support.
The conductive layer preferably contains conductive particles and a resin.

Examples of the material of the conductive particles include metal oxides, metals, and carbon black.
Examples of the metal oxide include zinc oxide, aluminum oxide, indium oxide, silicon oxide, zirconium oxide, tin oxide, titanium oxide, magnesium oxide, antimony oxide, and bismuth oxide. Examples of the metal include aluminum, nickel, iron, nichrome, copper, zinc, silver and the like.
Among these, it is preferable to use a metal oxide as the conductive particles, and it is more preferable to use titanium oxide, tin oxide, and zinc oxide.
When a metal oxide is used as the conductive particles, the surface of the metal oxide may be treated with a silane coupling agent or the like, or the metal oxide may be doped with an element such as phosphorus, aluminum or niobium or its oxide. ..
The conductive particles may have a laminated structure having core material particles and a coating layer covering the particles. Examples of the core material particles include titanium oxide, barium sulfate, zinc oxide and the like. Examples of the coating layer include metal oxides such as tin oxide and titanium oxide.
When a metal oxide is used as the conductive particles, the volume average particle diameter thereof is preferably 1 nm or more and 500 nm or less, and more preferably 3 nm or more and 400 nm or less.

Examples of the resin include polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, and alkyd resin.
The conductive layer may further contain silicone oil, resin particles, a hiding agent such as titanium oxide, and the like.

The average film thickness of the conductive layer is preferably 1 μm or more and 50 μm or less, and particularly preferably 3 μm or more and 40 μm or less.

The conductive layer can be formed by preparing a coating liquid for a conductive layer containing each of the above-mentioned materials and a solvent, forming the coating film, and drying the coating film. Examples of the solvent used for the coating liquid include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and the like. Examples of the dispersion method for dispersing the conductive particles in the coating liquid for the conductive layer include a method using a paint shaker, a sand mill, a ball mill, and a liquid collision type high-speed disperser.

<Underlay layer>
In the present invention, an undercoat layer may be provided on the support or the conductive layer. By providing the undercoat layer, a charge injection blocking function can be imparted.

The undercoat layer preferably contains a resin. Further, an undercoat layer may be formed as a cured film by polymerizing a composition containing a monomer having a polymerizable functional group.

Resins include polyester resin, polycarbonate resin, polyvinyl acetal resin, acrylic resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinylphenol resin, alkyd resin, polyvinyl alcohol resin, polyethylene oxide resin, polypropylene oxide resin, and polyamide resin. , Polyamic acid resin, polyimide resin, polyamideimide resin, cellulose resin and the like.

The polymerizable functional group of the monomer having a polymerizable functional group includes an isocyanate group, a blocked isocyanate group, a methylol group, an alkylated methylol group, an epoxy group, a metal alkoxide group, a hydroxyl group, an amino group, a carboxyl group and a thiol group. Examples thereof include a carboxylic acid anhydride group and a carbon-carbon double bond group.

The undercoat layer may further contain an electron transporting substance, a metal oxide, a metal, a conductive polymer, or the like for the purpose of enhancing the electrical characteristics. Among these, it is preferable to use an electron transporting substance and a metal oxide.
Examples of the electron transporting substance include quinone compounds, imide compounds, benzimidazole compounds, cyclopentadienylidene compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, aryl halide compounds, silol compounds, and boron-containing compounds. .. An undercoat layer may be formed as a cured film by using an electron transporting substance having a polymerizable functional group as the electron transporting substance and copolymerizing it with the above-mentioned monomer having a polymerizable functional group.
Examples of the metal oxide include indium tin oxide, tin oxide, indium oxide, titanium oxide, zinc oxide, aluminum oxide, silicon dioxide and the like. Examples of the metal include gold, silver and aluminum.
The surface of the metal oxide may be treated with a silane coupling agent or the like, or the metal oxide may be doped with an element such as phosphorus, aluminum or niobium or an oxide thereof.
Further, the undercoat layer may further contain an additive.

The average film thickness of the undercoat layer is preferably 0.1 μm or more and 50 μm or less, more preferably 0.2 μm or more and 40 μm or less, and particularly preferably 0.3 μm or more and 30 μm or less.

The undercoat layer can be formed by preparing a coating liquid for an undercoat layer containing each of the above-mentioned materials and solvents, forming this coating film, and drying and / or curing. Examples of the solvent used for the coating liquid include alcohol solvents, ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and the like.

<Photosensitive layer>
The photosensitive layer of the electrophotographic photosensitive member is mainly classified into (1) a laminated photosensitive layer and (2) a single-layer photosensitive layer. (1) The laminated photosensitive layer has a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance. (2) The single-layer type photosensitive layer has a photosensitive layer containing both a charge generating substance and a charge transporting substance.

(1) Laminated Photosensitive Layer The laminated photosensitive layer has a charge generation layer and a charge transport layer.

(1-1) Charge generating layer The charge generating layer preferably contains a charge generating substance and a resin.

Examples of the charge generating substance include azo pigments, perylene pigments, polycyclic quinone pigments, indigo pigments, phthalocyanine pigments and the like. Among these, azo pigments and phthalocyanine pigments are preferable. Among the phthalocyanine pigments, oxytitanium phthalocyanine pigments, chlorogallium phthalocyanine pigments, and hydroxygallium phthalocyanine pigments are preferable.
The content of the charge generating substance in the charge generating layer is preferably 40% by mass or more and 85% by mass or less, and more preferably 60% by mass or more and 80% by mass or less with respect to the total mass of the charge generating layer. preferable.

As the resin, polyester resin, polycarbonate resin, polyvinyl acetal resin, polyvinyl butyral resin, acrylic resin, silicone resin, epoxy resin, melamine resin, polyurethane resin, phenol resin, polyvinyl alcohol resin, cellulose resin, polystyrene resin, polyvinyl acetate resin , Polyvinyl chloride resin and the like. Among these, polyvinyl butyral resin is more preferable.

Further, the charge generation layer may further contain additives such as an antioxidant and an ultraviolet absorber. Specific examples thereof include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, and benzophenone compounds.

The average film thickness of the charge generation layer is preferably 0.1 μm or more and 1.0 μm or less, and more preferably 0.15 μm or more and 0.4 μm or less.

The charge generation layer can be formed by preparing a coating liquid for a charge generation layer containing each of the above-mentioned materials and a solvent, forming the coating film, and drying the coating film. Examples of the solvent used for the coating liquid include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and the like.

(1-2) Charge Transport Layer The charge transport layer preferably contains a charge transport substance and a resin.

Examples of the charge transporting substance include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these substances. Be done. Among these, triarylamine compounds and benzidine compounds are preferable.
The content of the charge transporting substance in the charge transport layer is preferably 25% by mass or more and 70% by mass or less, and more preferably 30% by mass or more and 55% by mass or less, based on the total mass of the charge transport layer. preferable.

Examples of the resin include polyester resin, polycarbonate resin, acrylic resin, polystyrene resin and the like. Among these, polycarbonate resin and polyester resin are preferable. As the polyester resin, a polyarylate resin is particularly preferable.
The content ratio (mass ratio) of the charge transporting substance to the resin is preferably 4: 10 to 20:10, more preferably 5: 10 to 12:10.

Further, the charge transport layer may contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a leveling agent, a slipperiness imparting agent, and an abrasion resistance improving agent. Specific examples include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oils, fluororesin particles, polystyrene resin particles, polyethylene resin particles, alumina particles, and boron nitride particles. Be done.

The average film thickness of the charge transport layer is preferably 5 μm or more and 50 μm or less, more preferably 8 μm or more and 40 μm or less, and particularly preferably 10 μm or more and 17 μm or less.

The charge transport layer can be formed by preparing a coating liquid for a charge transport layer containing each of the above-mentioned materials and a solvent, forming the coating film, and drying the coating film. Examples of the solvent used for the coating liquid include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents. Among these solvents, ether-based solvents or aromatic hydrocarbon-based solvents are preferable.

When the charge transport layer is a surface layer, as described above, the charge transport layer contains at least one or more metal oxide particles among aluminum oxide particles, silicon dioxide particles, and tin oxide particles.

(2) Single-layer type photosensitive layer The single-layer type photosensitive layer is formed by preparing a coating liquid for a photosensitive layer containing a charge generating substance, a charge transporting substance, a resin and a solvent, forming this coating film, and drying the coating film. can do. The charge generating substance, the charge transporting substance, and the resin are the same as the examples of the materials in the above "(1) Laminated photosensitive layer".

When the single-layer type photosensitive layer is a surface layer, as described above, the single-layer type photosensitive layer contains at least one or more metal oxide particles among aluminum oxide particles, silicon dioxide particles, and tin oxide particles.

<Protective layer>
The protective layer preferably contains a charge transporting substance and a resin.
Examples of the resin include polyester resin, acrylic resin, phenoxy resin, polycarbonate resin, polystyrene resin, phenol resin, melamine resin, epoxy resin and the like. Of these, polycarbonate resin, polyester resin, and acrylic resin are preferable.
Examples of the charge transporting substance include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having a group derived from these substances. Among these, triarylamine compounds and benzidine compounds are preferable.

Further, the protective layer may form a resin film with a cured product by polymerizing a composition containing a monomer having a polymerizable functional group. Examples of the reaction at that time include a thermal polymerization reaction, a photopolymerization reaction, and a radiation polymerization reaction. Examples of the polymerizable functional group contained in the monomer having a polymerizable functional group include an acrylic group and a methacrylic group. As a monomer having a polymerizable functional group, a resin film may be formed from a cured product by polymerizing using a material having a charge transporting ability.

The protective layer may contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a leveling agent, a slipper-imparting agent, and an abrasion resistance improver. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oils, fluororesin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles. And so on.

The average film thickness of the protective layer is preferably 0.5 μm or more and 10 μm or less, and preferably 1 μm or more and 7 μm or less.

The protective layer can be formed by preparing a coating liquid for a protective layer containing each of the above-mentioned materials and solvents, forming this coating film, and drying and / or curing it. Examples of the solvent used for the coating liquid include alcohol-based solvents, ketone-based solvents, ether-based solvents, sulfoxide-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents.

When the electrophotographic photosensitive member has a protective layer, as described above, the protective layer contains at least one or more metal oxide particles among aluminum oxide particles, silicon dioxide particles, and tin oxide particles.

[Process cartridge, electrophotographic equipment]
The process cartridge according to the present invention has the developing means having the toner described above and the electrophotographic photosensitive member described above, and is characterized in that it is detachably attached to the main body of the electrophotographic apparatus. To do.
Further, the electrophotographic apparatus according to the present invention is characterized by having the above-mentioned process cartridge.

FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus having a process cartridge including an electrophotographic photosensitive member.
Reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is rotationally driven at a predetermined peripheral speed in the direction of an arrow about a shaft 2. The surface of the electrophotographic photosensitive member 1 is charged to a predetermined positive or negative potential by the charging means 3. Although the roller charging method using the roller type charging member is shown in the figure, a charging method such as a corona charging method, a proximity charging method, or an injection charging method may be adopted. The surface of the charged electrophotographic photosensitive member 1 is irradiated with exposure light 4 from an exposure means (not shown), and an electrostatic latent image corresponding to the target image information is formed. The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed with the toner contained in the developing means 5, and the toner image is formed on the surface of the electrophotographic photosensitive member 1. The toner image formed on the surface of the electrophotographic photosensitive member 1 is transferred to the transfer material 7 by the transfer means 6. The transfer material 7 to which the toner image is transferred is conveyed to the fixing means 8, undergoes the toner image fixing process, and is printed out of the electrophotographic apparatus. The electrophotographic apparatus may have a cleaning means 9 for removing deposits such as toner remaining on the surface of the electrophotographic photosensitive member 1 after transfer. Further, a so-called cleanerless system may be used in which the cleaning means 9 is not separately provided and the deposits are removed by the developing means 5 or the like. The electrophotographic apparatus may have a static elimination mechanism for statically eliminating the surface of the electrophotographic photosensitive member 1 with preexposure light 10 from a preexposure means (not shown). Further, in order to attach / detach the process cartridge 11 of the present invention to / from the main body of the electrophotographic apparatus, a guide means 12 such as a rail may be provided.

The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. 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>
(Preparation of aqueous 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. Further, 1.0 mol / L hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0, and an aqueous medium containing a dispersion stabilizer was prepared.

(Preparation of polymerizable monomer composition)
The following materials were prepared.
・ Styrene 60.0 parts ・ C.I. I. Pigment Blue 15: 3 6.3 parts These were 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.
Then, the following materials were prepared.
-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)
-Paraffin wax (trade name: HNP9, manufactured by Nippon Seiro Co., Ltd., melting point: 76 ° C)
6.0 parts These were added to the colorant dispersion. Then, the temperature was kept at 65 ° C. 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 with a high-speed stirrer as it was.

(Polymerization process)
Change the 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, and further 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 6.2 μm, and the weight average particle size (D4) was 6.9 μm.

<Production example of organosilicon compound solution>
The following materials were prepared.
-Ion-exchanged water 70.0 parts-Methyltriethoxysilane 30.0 parts These were 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 polyvalent acid metal salt particles>
The following materials were prepared.
-Ion-exchanged water 100.0 parts-Sodium phosphate (12-hydrate) 8.5 parts After mixing these, at room temperature, T.I. K. The following materials were added while stirring at 10,000 rpm using a homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.).
-Zirconium lactate ammonium salt (trade name: ZC-300, manufactured by Matsumoto Fine Chemicals Co., Ltd.) 60.0 parts (equivalent to 7.2 parts as zirconium lactate ammonium salt)
Further, 1.0 mol / L hydrochloric acid was added to adjust the pH to 7.0. 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 particles having a number average particle size of 124 nm.

<Manufacturing example of toner particles>
<Toner particle 1>
(Convex forming process)
The following samples were weighed in the reaction vessel and mixed using a propeller stirring blade.
-Toner mother particle dispersion 500.0 parts-Organosilicon compound liquid 35.0 parts Next, the pH of the obtained mixture was adjusted to 9.5 using a 1.0 mol / L NaOH aqueous solution and mixed. After the temperature of the liquid was adjusted to 50 ° C., the mixture was kept for 1.0 hour while mixing using a propeller stirring blade.

(Polyvalent acid metal salt particle adhesion process)
Subsequently, the following materials were prepared.
-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 After mixing these in a reaction vessel, the pH of the obtained mixed solution was adjusted to 9.5 using a 1.0 mol / L NaOH aqueous solution for 4.0 hours. Retained. 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. When the toner particles 1 were observed by TEM-EDX, convex portions containing an organosilicon polymer were observed on the surface of the toner particles, and it was confirmed that titanium was present on the surface of the convex portions. The height H of the convex portion was 60 nm. Further, by analyzing the toner particles 1 by TOF-SIMS, ions derived from titanium phosphate were detected.
The above-mentioned 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>
(Polyvalent acid metal salt particle 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 2.
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. When the toner particles 2 were observed by TEM-EDX, the organosilicon polymer was present on the surface of the toner particles, but the convex portions were not formed. It was also confirmed that titanium was present on the toner surface. Further, by analyzing the toner particles 2 by TOF-SIMS, ions derived from titanium phosphate were detected.
The above-mentioned 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 3>
In the production example of the toner particles 2, instead of 3.2 parts of a 44% aqueous solution of titanium lactate, 11.7 parts of a zirconium lactate ammonium salt (ZC-300, manufactured by Matsumoto Fine Chemical Co., Ltd.) (equivalent to 1.4 parts of a zirconium lactate ammonium salt). ) Was used. Other than that, the toner particles 3 were obtained in the same manner as in the production example of the toner particles 2.
The number average particle size (D1) of the toner particles 3 was 6.2 μm, and the weight average particle size (D4) was 6.9 μm. When the toner particles 3 were observed by TEM-EDX, the organosilicon polymer was present on the surface of the toner particles, but the convex portions were not formed. It was also confirmed that zirconium was present on the toner surface. Further, by analyzing the toner particles 3 by TOF-SIMS, ions derived from zirconium phosphate were detected.
The above-mentioned 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 4>
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 4.

<Toner particle 5>
In the production example of the toner particles 2, the toner particles 5 were obtained in the same manner as in the production example of the toner particles 2 except that the 44% aqueous solution of titanium lactate was not added.
The number average particle size (D1) of the toner particles 5 was 6.2 μm, and the weight average particle size (D4) was 6.9 μm. When the toner particles 5 were observed by TEM-EDX, the organosilicon polymer was present on the surface of the toner particles, but the convex portions were not formed. In addition, no metal element was present on the toner surface. Furthermore, when the toner particles 5 were analyzed by TOF-SIMS, no ions derived from the polyvalent acid metal salt were detected.

<Toner manufacturing method>
<Toner 1, 2, 3, 5>
Toner particles 1, 2, 3 and 5 were used as toners 1, 2, 3 and 5.

<Toner 4>
The following materials were prepared.
・ Toner particles 4 100.0 parts ・ Hydrophobic silica fine particles (hexamethyl disilazane treatment: number average particle size 12 nm) 1.0 parts ・ Polyvalent acid metal salt particles (zylconyl phosphate compound particles) 2.0 parts It was put into SUPERMIXER PICCOLO SMP-2 (manufactured by Kawata Co., Ltd.) and mixed at 3,000 rpm for 20 minutes. Then, the toner 4 was obtained by sieving with a mesh having an opening of 150 μm.
The number average particle size (D1) of the toner 4 was 6.2 μm, and the weight average particle size (D4) was 6.9 μm. When the toner 4 was observed by TEM-EDX, no organosilicon polymer was present on the surface of the toner particles. It was also confirmed that zirconium was present on the toner surface. When the toner 4 was analyzed by TOF-SIMS, ions derived from zirconium phosphate were detected.

<Calculation method of ratios M1 and M2 of metal element M using X-ray photoelectron spectroscopy>
・ Processing (a)
The following treatment (a) was performed on each of the toners 1 to 5 produced as described above to obtain a toner (a) corresponding to each toner.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) was added to 100 mL of ion-exchanged water and dissolved while boiling to prepare a 61.5% aqueous sucrose solution. 31.0 g of the above sucrose concentrate in a centrifuge tube and a 10 mass% aqueous solution of a neutral detergent for cleaning precision measuring instruments at pH 7 (trade name: Contaminon N, manufactured by Wako Pure Chemical Industries, Ltd., nonionic surfactant) A dispersion was prepared by adding 6 g of the agent, an anionic surfactant, and an organic builder. 1.0 g of the toner produced as described above was added to this dispersion, and the toner lumps were loosened with a spatula or the like. The centrifuge tube was shaken with a shaker at 300 spm (strokes per min) for 20 minutes. After shaking, the solution was replaced with a glass tube for a swing rotor (50 mL) and separated by a centrifuge at 3500 rpm for 30 minutes. It was visually confirmed that the toner and the aqueous solution were sufficiently separated, and the toner separated in the uppermost layer was collected with a spatula or the like. The collected toner was filtered through a vacuum filter and then dried in a dryer for 1 hour or longer. The dried product was crushed with a spatula to obtain a toner (a) corresponding to each toner.

The toners (a) corresponding to the toners 1 to 5 and the toners 1 to 5 produced as described above were measured by X-ray photoelectron spectroscopy under the following conditions, and the ratio of the metal element M was M1 (atomic%). And M2 (atomic%) were calculated.
-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: 0.125 eV
・ Analysis software: Multipak (PHI)
Here, for example, the peak of Ti 2p (BE 452-468eV) was used for calculating the quantitative value of the Ti atom. The quantitative value of the Ti element obtained here was defined as M1 (atomic%).

Table 1 shows the physical characteristics of the toners 1 to 5.

<Manufacturing of electrophotographic photosensitive member>
(Production example of electrophotographic photosensitive member 1)
An aluminum cylinder (JIS-A3003, aluminum alloy) having a diameter of 24 mm and a length of 257.5 mm was used as a support (conductive support).

(Formation of conductive layer)
Next, the following materials were prepared.
[Preparation of coating liquid for conductive layer]
(Coating liquid for conductive layer 1)
Next, the following materials were prepared.
-Titanium oxide (TiO ₂ ) particles coated with oxygen-deficient tin oxide (SnO ₂ ) as metal oxide particles 214 parts-Phenol resin (trade name: Pryofen J-325, made by DIC, resin) as a binding material Solid content: 60% by mass) 132 parts ・ 98 parts of 1-methoxy-2-propanol as a solvent Put these in a sand mill using 450 parts of glass beads with a diameter of 0.8 mm, rotation speed: 2000 rpm, dispersion treatment time: 4. A dispersion treatment was carried out for 5 hours under the condition of a set temperature of cooling water: 18 ° C. to obtain a dispersion liquid.
At this time, after removing the glass beads with a mesh (opening: 150 μm), filtration was performed using a filter having a pore diameter of 5 μm to obtain a dispersion liquid.
Further, silicone resin particles (trade name: Tospearl 120, manufactured by Momentive Performance Materials Japan, Inc., average particle size 2 μm) were added to the dispersion as a surface roughness-imparting agent. The amount of the silicone resin particles added at this time was set to be 10% by mass with respect to the total mass of the metal oxide particles and the binder material in the dispersion liquid after removing the glass beads. Further, silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning) as a leveling agent is dispersed so as to be 0.01% by mass with respect to the total mass of the metal oxide particles and the binder material in the dispersion liquid. A coating liquid for a conductive layer was prepared by adding to the liquid and stirring.
This coating liquid for a conductive layer was immersed and coated on the support, and the obtained coating film was dried at 150 ° C. for 30 minutes and thermoset to form a conductive layer having a film thickness of 30 μm.

(Formation of undercoat layer)
N-methoxymethylated 6-nylon resin: 15 parts of Tredin EF-30T (manufactured by Nagase ChemteX) and copolymerized nylon resin: 5 parts of Amylan CM8000 (manufactured by Toray) in a mixed solvent of 220 parts of methanol and 110 parts of 1-butanol It was dissolved to prepare a coating solution for the undercoat layer. This coating liquid for the undercoat layer was immersed and coated on the conductive layer, and this was heated at 100 ° C. for 10 minutes to form an undercoat layer having a film thickness of 0.65 μm.

(Formation of charge generation layer)
Next, the following materials were prepared.
-Bragg angles (2θ ± 0.2 °) of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28. in CuKα characteristic X-ray diffraction. Crystalline hydroxygallium phthalocyanine crystal with a peak at 3 ° (charge generator) 10 parts ・ Compound represented by structural formula (A) 0.1 part ・ Polyvinyl butyral (trade name: Eslek BX-1, Sekisui Chemical Industry Co., Ltd. ( (Manufactured by Co., Ltd.) 5 parts, 250 parts of cyclohexanone These were placed in a sand mill using glass beads having a diameter of 0.8 mm and subjected to dispersion treatment for 1.5 hours. Next, 250 parts of ethyl acetate was added thereto to prepare a coating liquid for a charge generation layer. The obtained coating liquid for a charge generating layer was immersed and coated on the undercoat layer and dried at 100 ° C. for 10 minutes to form a charge generating layer having a film thickness of 0.17 μm. The X-ray diffraction measurement was performed under the conditions shown below.

[Powder X-ray diffraction measurement]
Measuring machine used: X-ray diffractometer RINT-TTRII manufactured by Rigaku Denki Co., Ltd.
X-ray tube: Cu
Tube voltage: 50KV
Tube current: 300mA
Scan method: 2θ / θ scan Scan speed: 4.0 ° / min
Sampling interval: 0.02 °
Start angle (2θ): 5.0 °
Stop angle (2θ): 40.0 °
Attachment: Standard sample holder Filter: Not used Incident monochrome: Used Counter monochromator: Not used Divergence slit: Open Divergence vertical limiting slit: 10.00 mm
Scattering slit: Open Light receiving slit: Open Flat plate monochromator: Used Counter: Scintillation counter

(Formation of charge transport layer)
The following materials were prepared.
・ 4 parts of the compound represented by the structural formula (CTM-1) ・ 4 parts of the compound represented by the structural formula (CTM-2) ・ Bisphenol Z type polycarbonate (trade name: PCZ-400, manufactured by Mitsubishi Gas Chemical Company, Inc.) 10 parts A coating liquid for a hole transport layer (charge transport layer) was prepared by dissolving these in a mixed solvent of 40 parts of dimethoxymethane and 60 parts of chlorobenzene. The obtained coating liquid was immersed and coated on the charge generation layer and dried at 125 ° C. for 30 minutes to form a charge transport layer having a film thickness of 15 μm.

以上により電子写真感光体１を製造した。 (Formation of protective layer)
The following materials were prepared.
-Compound represented by structural formula (H-1) 43 parts by mass-Trimethylolpropane triacrylate (trade name: KAYARAD TMPTA, manufactured by Nippon Kayakusha) 21 parts by mass-Caprolactone-modified dipentaerythritol hexaacrylate (trade name: KAYARAD) DPCA-120, manufactured by Nippon Kayaku Co., Ltd.) 21 parts by mass, acrylic group-containing polyester-modified polydimethylsiloxane and propoxy-modified -2-neopentyl glycol diacrylate mixture (trade name: BYK-UV3570, manufactured by Big Chemie) 0.1 mass Part 1-Hydroxycyclohexylphenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) 4 parts by mass, aluminum oxide particles (trade name: Sumicorandom AA-03, manufactured by Sumitomo Chemical Industries, Ltd.)
4.25 parts by mass / phosphoric acid-based wet dispersant (trade name: Superdyne V201, Takemoto Oil & Fats Co., Ltd.) 1.0 parts by mass Dissolve these in 566 parts by mass of tetrahydrofuran to prepare a coating liquid 1 for a protective layer. did. The obtained coating liquid is immersed and coated on the charge transport layer, dried by natural drying for 20 minutes, and then a metal halide lamp: 160 W / cm, irradiation distance: 120 mm, irradiation intensity: 500 mW / cm ² , irradiation time: 60 seconds. Light irradiation was performed under the conditions to cure the coating film. Further drying was performed at 130 ° C. for 20 minutes to form a protective layer having a film thickness of 4.9 μm.

From the above, the electrophotographic photosensitive member 1 was manufactured.

(Production example of electrophotographic photosensitive members 2 to 5)
In the production example of the electrophotographic photosensitive member 1, the electrophotographic photosensitive members 2 to 5 were manufactured in the same manner as in the production example of the electrophotographic photosensitive member 1 except that the amount of aluminum oxide particles was changed as shown in Table 2.

(Production example of electrophotographic photosensitive member 6)
In the production example of the electrophotographic photosensitive member 1, the electrophotographic photosensitive member 6 was manufactured in the same manner as in the production example of the electrophotographic photosensitive member 1 except that the formation of the protective layer was changed as follows.

(Formation of a protective layer in the manufacture of the electrophotographic photosensitive member 6)
(Preparation of surface-treated metal oxide particles)
The following materials were prepared.
, Metal oxide particles as tin oxide particles (average primary particle diameter of 20 nm, volume resistivity 1.1 × 10 ⁵ Ω, CIK Nanotech Co., Ltd.) 100 parts by weight of methacrylic acid 3- (trimethoxysilyl) propyl 30 parts by weight thereof Was mixed with 150 parts by mass of toluene and 150 parts by mass of isopropyl alcohol, placed in a sand mill together with zirconia beads, and stirred at about 40 ° C. and a rotation speed of 1500 rpm. Further, the treated mixture was taken out, put into a Henschel mixer, stirred at a rotation speed of 1500 rpm for 15 minutes, and then dried at 120 ° C. for 3 hours to obtain surface-treated tin oxide particles.

Subsequently, the following materials were prepared.
-Surface-treated tin oxide particles 33 parts by mass-Compound 100 parts by mass represented by structural formula (H-2) -Compound 10 parts by mass represented by structural formula (CTM-3) -Polymerization initiator (trade name: Irgacure 819, (Manufactured by BASF Japan) 10 parts by mass, 2-mercaptobenzoxazole 10 parts by mass These were mixed and stirred in 320 parts by mass of 2-butanol and 80 parts by mass of tetrahydrofuran, and sufficiently dissolved and dispersed to prepare a coating liquid for a protective layer. .. The obtained coating liquid was immersed and coated on a charge transport layer and irradiated with ultraviolet rays for 1 minute using a metal halide lamp to form a protective layer having a dry film thickness of 3.0 μm to produce an electrophotographic photosensitive member 6.

(Production example of electrophotographic photosensitive members 7 to 10)
In the production example of the electrophotographic photosensitive member 6, the electrophotographic photosensitive members 7 to 10 were manufactured in the same manner as in the production example of the electrophotographic photosensitive member 6 except that the amount of the surface-treated tin oxide particles was changed as shown in Table 2. ..

(Production example of electrophotographic photosensitive member 11)
An aluminum cylinder (JIS-A3003, aluminum alloy) having a diameter of 24 mm and a length of 257.5 mm was used as a support (conductive support).
In addition, the following materials were prepared.
-X-type metal-free phthalocyanine (X-type crystal of metal-free phthalocyanine, x-H ₂ Pc) 3 parts by mass-Compound 50 parts by mass represented by the following structural formula (CTM-4) -With the following structural formula (ETM-1) The compound shown: 50 parts by mass, silicon dioxide particles (average primary particle size 0.012 μm, Rx200, manufactured by Nippon Aerodil Co., Ltd.) 0.5 parts by mass, bisphenol Z type polycarbonate (trade name: PCZ-400, Mitsubishi Gas Chemicals Co., Ltd.) (Manufactured by Co., Ltd.) 100 parts by mass These were mixed with 800 parts by mass of tetrahydrofuran, added to a ball mill, mixed for 50 hours, and subjected to dispersion treatment to prepare a coating liquid for a single-layer photosensitive layer. The obtained coating liquid for a single-layer photosensitive layer was dipped and coated on the support, and the obtained coating film was dried at 100 ° C. for 40 minutes to produce an electrophotographic photosensitive member 11 having a film thickness of 30 μm. ..

(Production example of electrophotographic photosensitive members 12 to 15)
In the production example of the electrophotographic photosensitive member 11, the electrophotographic photosensitive members 12 to 15 were manufactured in the same manner as in the production example of the electrophotographic photosensitive member 11 except that the amount of silicon dioxide particles was changed as shown in Table 2.

(Production example of electrophotographic photosensitive member 16)
In the production example of the electrophotographic photosensitive member 1, the electrophotographic photosensitive member 16 was manufactured in the same manner as in the production example of the electrophotographic photosensitive member 1 except that aluminum oxide particles were not used.

[Examples 1 to 18, Comparative Examples 1 to 3]
Evaluation was performed using the toners 1 to 5 and the electrophotographic photosensitive members 1 to 16 in the combinations shown in Table 3.
The evaluation method and evaluation criteria of the present invention will be described below.
As an image forming apparatus, a laser printer manufactured by Hewlett-Packard Company (Color LaserJet Enterprise M552 modified machine) was used. After removing the product toner from the inside of the cartridge and cleaning it with an air blow, the toner of the present invention was filled with 165 g, and the electrophotographic photosensitive member was replaced with the electrophotographic photosensitive member of the present invention.
The product toner was extracted from each of the yellow, magenta, and black stations, and the yellow, magenta, and black cartridges with the toner remaining amount detection mechanism disabled were inserted for evaluation.

<Evaluation of image fog>
A solid white image with a 0% print ratio was printed out in gloss paper mode (1/3 speed). For the printout, Letter size paper (trade name: HP Brochure Paper 200 g, Glossy, manufactured by Hewlett-Packard Company, basis weight 200 g / cm ² ) was used. Further, the Letter size paper was used by pasting a 75 mm × 75 mm paper (trade name: Post-it, manufactured by 3M Japan Ltd.) at the center position.
The pasted paper was removed from the printout image, and the whiteness was measured using "REFLECTMER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). The fog density (%) was calculated from the difference between the whiteness of the white part of the printout image and the whiteness of the transfer paper (the part from which the pasted paper was removed), and the image fog was evaluated. An amber filter was used as the filter.

The evaluation results are shown in Table 3.

1 Electrophotographic photosensitive member 2 axes 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

Claims (8)

A process cartridge that is removable from the main body of the electrophotographic device.
It has a developing means having toner and an electrophotographic photosensitive member.
The toner has toner particles, and the toner particles have polyvalent acid metal salt particles on the surface.
The polyvalent acid metal salt particles contain at least one metal element selected from the metal elements contained in Groups 3 to 13 as a metal element.
A process cartridge characterized in that the surface layer of the electrophotographic photosensitive member contains at least one metal oxide particle among aluminum oxide particles, silicon dioxide particles and tin oxide particles. The process cartridge according to claim 1, wherein the content of the aluminum oxide particles in the surface layer is 5.0 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin component. The process cartridge according to claim 1, wherein the content of the silicon dioxide particles in the surface layer is 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin component. The process cartridge according to claim 1, wherein the content of the tin oxide particles in the surface layer is 30 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin component. The process cartridge according to any one of claims 1 to 4, wherein the toner particles have a toner mother particle containing a binder resin and an organosilicon polymer on the surface of the toner mother particle. Any one of claims 1 to 5, wherein the toner particles have a toner mother particle containing a binder resin and a convex portion on the surface of the toner mother particle, and the convex portion contains an organosilicon polymer. The process cartridge described in the section. The process cartridge according to claim 6, wherein the height H of the convex portion is 30 nm or more and 300 nm or less. An electrophotographic apparatus comprising the process cartridge according to any one of claims 1 to 7.

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