JP2021021943A - Process cartridge and electrophotographic device - Google Patents

Abstract

To provide a process cartridge and an electrophotographic device that reduces fogging 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 includes toner and an electrophotographic photoreceptor. The toner is a toner having toner particles, and the toner particles each have a polyvalent acid metal salt on at least part of its surface. The polyvalent acid metal salt includes, 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 a resin including a siloxane portion.SELECTED DRAWING: Figure 1

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 of incorporating a siloxane-modified resin having a siloxane structure in a molecular chain into the surface layer of an electrophotographic photosensitive member in contact with various members.

Japanese Unexamined Patent Publication No. 2001-209207 JP-A-2007-199688

According to the studies by the present inventors, the process cartridges described in Patent Documents 1 and 2 are improved in terms of reduction of fog visually confirmed on the image. However, it has become clear that further reduction of fog is desired in terms of reducing toner consumption.

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

The above object is achieved by the following invention.
That is, the process cartridge according to the present invention has a developing means containing toner and an electrophotographic photosensitive member, and the toner is a toner having toner particles, and the toner is present on at least a part of the surface of the toner particles. It has a valent acid metal salt, and the polyvalent acid metal salt contains at least one metal element selected from the metal elements contained in Groups 3 to 13 as a metal element, and the electrophotographic photosensitive member thereof. The surface layer of the body is a process cartridge containing a resin containing a siloxane moiety.

Further, the electrophotographic apparatus according to the present invention is an electrophotographic apparatus having the above process cartridge.

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

It is a figure which shows an example of the schematic structure of the electrophotographic apparatus which has a process cartridge provided with an electrophotographic photosensitive member.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments.
In order to solve the above problems, a configuration in which a toner having a polyvalent acid metal salt on at least a part of the surface of the toner particles and an electrophotographic photosensitive member containing a resin containing a siloxane moiety in the surface layer are combined. Is a feature of the process cartridge and electrophotographic apparatus of the present invention.

The present inventors speculate as follows about the mechanism by which fog is reduced by combining a toner satisfying these characteristics with an electrophotographic photosensitive member.
In the electrophotographic process, image formation is generally performed by forming a toner image on an electrophotographic photosensitive member and transferring the toner image onto an intermediate transfer body or paper.
A toner having a polyvalent acid metal salt on at least a part of the surface of the toner particles tends to be negatively charged due to the polarization of the polyvalent acid metal salt, and is excellent in chargeability. Further, since the polyvalent acid metal salt has an appropriate resistance value, the electric charge is easily transferred. A negative charge is supplied to the polyvalent acid metal salt on the surface of the toner particles from the resin containing the siloxane moiety contained in the surface layer of the electrophotographic photosensitive member. This is because the contact between the polyvalent acid metal salt on the surface of the toner particles and the resin containing the siloxane portion of the surface layer of the electrophotographic photosensitive member causes the transfer of electric charges by the charged trains between the constituent materials. it is conceivable that. 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, the charge uniformity of the toner is improved, and fog is reduced.

[toner]
The toner in the present invention is a toner having toner particles, and is characterized by having a polyvalent acid metal salt on at least a part of the surface of the toner particles.
The polyhydric acid metal salt is composed of a combination of the polyhydric acid and a metal element.

The polyvalent acid may be any acid as long as it is a divalent or higher acid. Specific examples include the following acids. Examples of the inorganic acid include phosphoric acid, carbonic acid and sulfuric acid. Examples of the organic acid include a dicarboxylic acid and a tricarboxylic acid. Specifically, the dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. Can be mentioned. Examples of the tricarboxylic acid include citric acid, aconitic acid and trimellitic acid.
Among the polyhydric acids, it is preferable to contain at least one acid selected from phosphoric acid, carbonic acid, and sulfuric acid because the metal element reacts strongly with the polyhydric acid and the polyvalent acid metal salt does not easily absorb moisture. Furthermore, the polyhydric acid preferably contains phosphoric acid.

The metal element constituting the polyvalent acid metal salt preferably contains at least one metal element selected from the metal elements contained in Groups 3 to 13. Since the salt composed of the metal element and the polyhydric acid contained in the 3rd to 13th groups has low hygroscopicity, the effect of stably reducing fog can be obtained even in a high humidity environment.
Specific examples of the metal element include titanium, zirconium, aluminum, zinc, indium, hafnium, iron, copper, silver and the like. Among them, a metal having a valence of 3 or more is preferable. More specifically, titanium, zirconium, and aluminum are more preferable, and titanium is even more preferable.

Examples of the polyvalent acid metal salt are preferably a metal phosphate, a metal sulfate, a metal carbonate, and a metal oxalate. Examples of the metal phosphate salt include a titanium phosphate compound, a zirconium phosphate compound, an aluminum phosphate compound, and a copper phosphate compound. Examples of metal sulfates include titanium sulfate compounds, zirconium sulfate compounds, and aluminum sulfate compounds. Examples of metal carbonates include titanium carbonate compounds, zirconium carbonate compounds, and aluminum carbonate compounds. Examples of metal oxalate salts include titanium oxalate compounds. Among them, a metal phosphate salt is preferable, and a titanium phosphate compound is preferable because the phosphate ion has high strength by cross-linking between metals and has an ionic bond in the molecule and is excellent in charge rising property. More preferred.

The method for producing the polyvalent acid metal salt is not particularly limited, and a conventionally known method can be used. A method of reacting a metal compound containing a metal element with a polyvalent acid ion in an aqueous medium to obtain a polyvalent acid metal salt is preferable. As long as it is a metal compound that gives a polyvalent acid metal salt by reaction with a polyvalent acid ion, a conventionally known metal compound can be used without particular limitation, and examples thereof include a metal chelate and a metal alkoxide.

Examples of the metal chelate include titanium lactate, titanium tetraacetylacetonate, titanium lactate ammonium salt, titanium triethanolaminate, zirconium lactate, zirconium lactate ammonium salt, aluminum lactate, aluminum trisacetylacetonate, and copper lactate. Examples of the metal alkoxide include titanium tetraisopropoxide, titanium ethoxyde, zirconium tetraisopropoxide, and aluminum trisisopropoxide. Of these, a metal chelate is preferable because the reaction is easy to control and it reacts quantitatively with polyvalent acid ions. Further, from the viewpoint of solubility in an aqueous medium, a lactic acid chelate such as titanium lactate or zirconium lactate is more preferable.

As the polyvalent acid ion when the polyvalent acid metal salt is obtained by the above-mentioned preparation 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 diameter of the polyvalent acid metal salt is preferably 1 nm or more and 400 nm or less, more preferably 1 nm or more and 200 nm or less, and further preferably 1 nm or more and 60 nm or less.

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

Methods for adjusting the number average particle size of the polyvalent acid metal salt to the above range include the amount of the compound containing the polyvalent acid and the metal element, which are the raw materials of the particles, the pH at the time of the reaction, and the temperature at the time of the reaction. ..

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 formula (T-1) is used. It is preferable to use the indicated organosilicon compounds in combination.

By using the organosilicon compound in combination, the obtained reactant is more firmly adhered to the toner particles, the surface is hydrophobized, and the environmental stability is further improved.

Specifically, 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 to obtain a condensate. The condensate migrates to the surface of the toner particles. Since the condensate is viscous, the reactant of the compound containing the polyhydric acid and the metal element can be brought into close contact with the surface of the toner particles, and the reactant can be more firmly fixed to the toner particles. In addition, the condensate can be transferred to the surface of the reactant to make the reactant hydrophobic and further improve the environmental stability.
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 2-4. However, when a plurality of _Ra and R _b exist, the plurality of _Ra and the plurality of R _b may be the same or different, respectively.

As the organosilicon compound represented by the formula (T-1), a known organosilicon compound can be used without particular limitation. Specific examples thereof include the following bifunctional silane compounds in which n is 2, trifunctional silane compounds in which n is 3, and tetrafunctional silane compounds in which n is 4.

Examples of the bifunctional silane compound include dimethyldimethoxysilane and dimethyldiethoxysilane.

The trifunctional silane compound, trifunctional silane compound having an alkyl group as R _b, trifunctional silane compound having an alkenyl group as R _b, trifunctional silane compound having an aryl group as R _b, methacryloxy alkyl group as R _b Examples thereof include trifunctional silane compounds having. _Examples of the trifunctional silane compound having an alkyl group as _Rb include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and propyltrimethoxysilane. Examples thereof include propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane and decyltriethoxysilane. Examples of the trifunctional silane compound having an alkenyl group as R _b include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane. _Examples of the trifunctional silane compound having an aryl group as R _b include phenyltrimethoxysilane and phenyltriethoxysilane. Examples of the trifunctional silane compound having a methacryloxyalkyl group as _Rb include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldiethoxymethoxysilane, and γ-methacryloxypropylethoxy. Dimethoxysilane can be mentioned.

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. It is preferably 0.5% by mass or more, and more preferably 15.0% by mass or less.

The method for producing the toner matrix particles is not particularly limited, and a known suspension polymerization method, dissolution suspension method, emulsion aggregation method, pulverization method and the like can be used.

When a reactant of a compound containing a polyhydric acid and a metal element is present on the surface of the toner particles, or when the toner matrix particles are produced in an aqueous medium, the toner matrix particles may be used as they are as a dispersion liquid of the toner matrix particles. .. Further, after washing, filtering, and drying, the toner may be redispersed in an aqueous medium to prepare a dispersion of toner matrix particles.

On the other hand, when the toner mother particles are produced by a dry method, they may be dispersed in an aqueous medium by a known method to prepare a dispersion liquid of the toner mother particles. In order to disperse the toner matrix particles in the aqueous medium, it is preferable that the aqueous medium contains a dispersion stabilizer.

Hereinafter, an example of producing toner matrix particles using the suspension polymerization method will be specifically described.
First, a polymerizable monomer capable of producing a binder resin and various additives, if necessary, are mixed, and a disperser is used to prepare a polymerizable monomer composition in which the material is dissolved or dispersed. ..
Examples of various additives include colorants, waxes, charge control agents, polymerization initiators, and chain transfer agents.
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 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 toner mother particles (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 binder resin include the following resins or polymers.
Specific examples of the resin include vinyl-based resin, polyester resin, polyamide resin, furan resin, epoxy resin, xylene resin, and silicone resin. Of these, vinyl-based resins are preferable. Examples of the vinyl resin include the following monomer polymers or copolymers thereof. Styrene-based monomers such as styrene and α-methylstyrene. Unsaturated carboxylic acid esters such as methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate. Unsaturated carboxylic acids such as acrylic acid and methacrylic acid. Unsaturated dicarboxylic acids such as maleic acid. Unsaturated dicarboxylic acid anhydrides such as maleic anhydride. Examples thereof include nitrile vinyl monomers such as acrylonitrile. Halogen-containing vinyl monomer such as vinyl chloride. Nitro-based vinyl monomer such as nitrostyrene. Of these, a copolymer using a styrene-based monomer and an unsaturated carboxylic acid ester as a monomer is preferable.

As the colorant, the following black pigments, yellow pigments, magenta pigments, and cyan pigments are used.
Examples of the black pigment include carbon black.

Examples of the yellow pigment include monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, isoindolin compounds, benzimidazolone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185.

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 and 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.

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, and ferrite; metals typified by iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, berylium, etc. Examples thereof include alloys with metals such as bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium and mixtures thereof.

As the wax, for example, a monovalent alcohol and an aliphatic monocarboxylic acid ester such as behenyl behenate, stearyl stearate, and palmityl palmitate, or an ester of a monovalent carboxylic acid and an aliphatic monoalcohol; dibehenyl sebacate. , Divalent alcohols and aliphatic monocarboxylic acid esters such as hexanediol dibehenate, or esters of divalent carboxylic acids and aliphatic monoalcohols; trivalent alcohols and fats such as glycerin tribehenate. Group monocarboxylic acid esters, or trivalent carboxylic acids and aliphatic monoalcohol esters: tetravalent alcohols and aliphatic monocarboxylic acid esters such as pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, or 4 Esters of valent carboxylic acids and aliphatic monoalcohols: hexavalent alcohols and aliphatic monocarboxylic acid esters such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, or hexavalent carboxylic acids and aliphatics Monoalcohol esters; polyvalent alcohols and aliphatic monocarboxylic acid esters such as polyglycerin behenate, or polyvalent carboxylic acids and aliphatic monocarboxylic acid esters; natural ester waxes such as carnauba wax and rice wax; Petroleum waxes and derivatives such as paraffin wax, microcrystalin wax, petrolatum; hydrocarbon waxes and derivatives thereof by Fishertropus method; polyolefin waxes such as polyethylene wax, polypropylene wax and derivatives thereof; higher aliphatic alcohols; stearic acid , Carboxylic acids such as palmitic acid; acid amide wax.

The wax content is preferably 0.5 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner may be supplemented with various organic particles or inorganic particles to the extent that the characteristics or effects are not impaired. Organic or inorganic particles include, for example, silica, alumina, titanium oxide, carbon black and carbon fluoride as fluidity modifiers; metal oxides (strontium titanate, cerium oxide, alumina, magnesium oxide, as abrasives, Chromide oxide), nitride (silicon nitride), carbide (silicon carbide), metal salts (calcium sulfate, barium sulfate, calcium carbonate); as lubricants, fluororesin particles (vinylidene fluoride, polytetrafluoroethylene), fatty acid metal Salts (zinc stearate, calcium stearate); as charge control particles, metal oxides (tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

The organic particles or the inorganic particles may be hydrophobized. Treatment agents for hydrophobizing organic particles and / or inorganic particles include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, and other organic substances. Examples include silicon compounds and organotitanium compounds. These treatment agents may be used alone or in combination.

<Structure of cross section of toner particles>
Hereinafter, a preferable form when the cross section of the toner particles constituting the toner in the present invention is observed with a transmission electron microscope will be described.

By comparing the cross section of the toner particles observed with a transmission electron microscope with the EDX mapping image of the constituent elements of the cross section of the toner particles obtained by analysis using energy dispersive X-ray spectroscopy (EDX). , It can be confirmed that the organic silicon polymer forms a convex portion at a position corresponding to the surface of the toner matrix particles. When the height of the convex portion of the toner particles constituting the toner of the present invention is the convex height H, the convex height H is preferably 30 nm or more and 300 nm or less. The method of calculating the convex height H will be described later.

In the toner of the present invention, the metal element contained in the polyvalent acid metal salt is the metal element M, and 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 spectroscopic analysis of the toner particles. When the ratio of is M1 (atm%), it is preferable that M1 is 1.0 (atm%) or more and 10.0 (atm%) or less.

Further, 1 g of toner is dispersed in a mixed aqueous solution consisting of 31 g of a 61.5% sucrose aqueous solution and 6 g of a 10% neutral detergent aqueous solution for cleaning a precision measuring instrument composed of a nonionic surfactant and an anionic surfactant. The toner obtained by performing the treatment (a) of shaking 300 times per minute using a shaker is used as the toner (a). When 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) is M2 (atm%), both M1 and M2 are 1.0. It is preferably (atm%) or more and 10.0 (atm%) or less, and M1 and M2 satisfy the following formula (ME-1).
0.90 ≤ M2 / M1 (ME-1)

In the treatment (a), the polyvalent metal salt weakly attached to the surface of the toner particles can be removed. Specifically, the polyvalent acid metal salt attached to the toner matrix particles by the dry method is easily removed by the treatment (a). Therefore, it is possible to evaluate the fixed state of the polyvalent acid metal salt existing on the surface of the toner particles by the treatment (a), and the smaller the change in each parameter due to the treatment (a), the more the polyvalent acid metal salt becomes. Indicates that it is strongly adhered to the toner parameters.

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

When both M1 and M2 are 1.0 (atm%) or more and 10.0 (atm%) or less, the negative charge property and charge transfer property of the toner are good, so that the electrophotographic photosensitive member is transferred to the toner. Charge transfer becomes smoother, and it is easy to obtain the effect of reducing fog. M1 and M2 are more preferably 1.0 (atm%) or more and 7.0 (atm%) or less, and further preferably 1.5 (atm%) or more and 5.0 (atm%) or less. ..

The formula (ME-1) means the ratio at which the polyvalent acid metal salt does not peel off from the surface of the toner particles in the treatment (a) and remains. When M2 / M1 is 0.90 or more, the polyvalent metal salt is strongly adhered to the surface of the toner particles, so that the transfer of the polyvalent acid metal salt from the toner to the surface of the photoconductor is suppressed. Therefore, such a toner tends to maintain the negative chargeability on the surface of the toner particles and the positive chargeability on the surface of the photoconductor, and can stably reduce fog even during long-term use, and is excellent in durability. .. Further, it is more preferable that M2 / M1 is 0.95 or more.

<Method of forming convex parts containing organosilicon polymer>
There is no particular limitation on the method for forming the convex portion of the toner particles containing the organosilicon polymer, and a conventionally known method can be used. Specifically, a method of condensing the compound shown in the section of organosilicon compound in an aqueous medium in which the toner matrix particles are dispersed to form a convex portion on the toner matrix particle, or a dry or wet method on the toner matrix particle. Examples thereof include a method of attaching the convex portion containing the organosilicon polymer by a mechanical external force.

Above all, since it is possible to firmly fix the toner mother particles and the convex portions, the compounds shown in the section of organosilicon compounds are condensed in an aqueous medium in which the toner mother particles are dispersed, and the protrusions are projected on the toner mother particles. The method of forming the portion is preferable. The details will be described below.

When forming a convex portion on the toner mother particle by the above method, the step (step 1) of dispersing the toner mother particle in an aqueous medium to obtain a toner mother particle dispersion liquid and the organosilicon compound (or its hydrolyzate) are performed. It may include a step (step 2) of forming a convex portion containing an organosilicon polymer on the toner matrix particles by mixing it with the toner matrix particle dispersion and subjecting the organosilicon compound to a condensation reaction in the toner matrix particle dispersion. preferable.

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 way to make it. 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. Specific dispersion stabilizers include tricalcium phosphate, hydroxyapatite, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and calcium metasilicate. , Inorganic dispersion stabilizers such as calcium sulfate, barium sulfate, bentonite, silica, alumina, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salts of carboxymethyl cellulose, organic dispersion stabilizers such as starch. Be done. In addition, examples of the surfactant include anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates and fatty acid salts, nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxypropylene alkyl ethers, and alkyls. Cationic surfactants such as amine salts and quaternary ammonium salts can be mentioned. Among them, it is preferable to contain an inorganic dispersion stabilizer, and it is more preferable to include 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.

Acids for adjusting pH include hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chloric acid, chloric acid, perchloric acid, hypobromic acid, bromine acid, bromic acid, Inorganic acids such as perbromic acid, hypochlorous acid, subiodic acid, iodic acid, periodic acid, sulfuric acid, nitrate, phosphoric acid, boric acid, acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, Examples include organic acids such as tartrate.

Bases for adjusting pH include hydroxides of alkali metals such as potassium hydroxide, sodium hydroxide and lithium hydroxide and aqueous solutions thereof, and carbonates of alkali metals such as potassium carbonate, sodium carbonate and lithium carbonate. Salts 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 aqueous solutions, 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 convex height H and the convex width W of the convex portion of the present invention, and the effect of the present invention can be more easily obtained. As the acid and base for adjusting the pH, the acid and base exemplified in the section of hydrolysis can be used.

<Measuring method of weight average particle size (D4) and number average particle size (D1) of toner particles>
The weight average particle size (D4) and the number average particle size (D1) of the toner particles are calculated as follows.
As the measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark) (manufactured by Beckman Coulter Co., Ltd.) equipped with a 100 μm aperture tube by the pore electric resistance method is used. 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 Co., Ltd.) is used. The measurement is performed with 25,000 effective measurement channels.
The electrolytic aqueous solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration becomes 1.0%, for example, "ISOTON II" (trade name) (manufactured by Beckman Coulter, Inc.). ) 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" (trade name). ) (Made by Beckman Coulter Co., Ltd.) to set the value obtained.
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" (trade name) (nonionic surfactant, anionic surfactant, 10% aqueous solution of neutral detergent for cleaning a precision measuring instrument with pH 7 consisting of an organic builder, Wako Pure Chemicals Add 0.3 mL of a diluted solution obtained by diluting Kogyo Co., Ltd. with ion-exchanged water 3 times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with their phases shifted by 180 degrees, and an ultrasonic disperser with an electrical output of 120 W "Ultrasonic Dispersion System Tera150" (trade name) (Nikkaki Bios Co., Ltd.) (Made). Put 3.3 L of ion-exchanged water in the water tank of the ultrasonic disperser, and add 2.0 mL of contaminantin N to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner particles are added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the electrolytic aqueous solution of (5) in which toner particles are dispersed is dropped onto the round-bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to 5%. .. Then, the measurement is performed until the number of particles to be measured reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) and the number average particle size (D1) are calculated. The "average diameter" on the "analysis / volume 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]
In the present invention, the electrophotographic photosensitive member is characterized by containing a resin containing a siloxane moiety in the surface layer.
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 method of the coating liquid 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. 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 anodizing, a blasting treatment, a cutting treatment or the like.
The material of the support is preferably metal, resin, or glass.
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>
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 and silver.
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 particle, the surface of the metal oxide is treated with a material such as a silane coupling agent, or the metal oxide is doped with an element such as phosphorus, aluminum, niobium or its oxide. You may.
The conductive particles may have a laminated structure having core material particles and a coating layer that coats the core material particles. Examples of the core material particles include titanium oxide, barium sulfate, and zinc oxide. 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, its volume average particle diameter 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 a masking agent such as silicone oil, resin particles, titanium oxide.

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 a coating film, and drying the coating film. Examples of the solvent used for the coating liquid include alcohol-based solvents, sulfoxide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents. 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>
An undercoat layer may be provided on the support or the conductive layer. By providing the undercoat layer, the adhesive function between the layers is enhanced, and the 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.

As the resin, 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, polyamide resin , Polyamic acid resin, polyimide resin, polyamideimide resin, cellulose resin.

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, and a conductive polymer for the purpose of enhancing electrical properties. Among these, it is preferable to use an electron transporting substance and a metal oxide.

Examples of the electron transporting substance include a quinone compound, an imide compound, a benzimidazole compound, a cyclopentadienylidene compound, a fluorenone compound, a xanthone compound, a benzophenone compound, a cyanovinyl compound, an aryl halide compound, a silol compound, and a boron-containing compound. 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 a 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, and silicon dioxide. Examples of the metal include gold, silver and aluminum.

The surface of the metal oxide may be treated with a material such as a silane coupling agent, 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 a coating film, and drying and / or curing. 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.

<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, and phthalocyanine pigments. 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 is 60% by mass or more and 80% by mass or less with respect to the total mass of the charge generating layer. Is more 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 can be mentioned. 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 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 a coating film, and drying the coating film. Examples of the solvent used for the coating liquid include alcohol-based solvents, sulfoxide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents.

(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 a group derived from these substances. Among these, a triarylamine compound and a benzidine compound 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 is 30% by mass or more and 55% by mass or less with respect to the total mass of the charge transport layer. Is more preferable.

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

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 a 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, an ether solvent or an aromatic hydrocarbon solvent is preferable.

(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 a coating film, and drying the coating film. be able to. 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".

<Surface layer>
The surface layer in the present invention indicates a charge transport layer when the photosensitive layer is a laminated photosensitive layer, and indicates a photosensitive layer when the photosensitive layer is a single-layer photosensitive layer. When a protective layer is provided on the photosensitive layer, the surface layer in the present invention indicates a protective layer.

The electrophotographic photosensitive member of the present invention is characterized by containing a resin containing a siloxane moiety in the surface layer.
The resin containing a siloxane moiety in the present invention is a resin having a siloxane moiety in the structure constituting the resin. Therefore, when the surface layer is a photosensitive layer, the resin for the charge transport layer includes a resin having a siloxane moiety.

As the resin containing a siloxane moiety, any resin containing a siloxane moiety can be applied. Among them, the resin containing a siloxane moiety is preferably a polycarbonate resin containing a siloxane moiety or a polyester resin containing a siloxane moiety.

式（Ａ）中のｎは、括弧内の構造の繰り返し数の平均値を示し、１０以上、１２０以下である。ｎは２０以上、８０以下であることが電子写真感光体の繰り返し使用時の耐久性の維持の観点で好ましい。

式（Ｂ）中のａ、ｂおよびｃは、それぞれ独立に括弧内の構造の繰り返し数の平均値を示し、ａおよびｂは１以上、１０以下であり、ｃは、２０以上、２００以下である。ａおよびｂは１以上、５以下であることが好ましく、ｃは、２０以上、８０以下であることが電子写真感光体の繰り返し使用時の耐久性の維持の観点で好ましい。

式（Ｃ）中のｄは、括弧内の構造の繰り返し数の平均値を示し、１０以上、１２０以下である。Ｚは炭素数３以下のアルキレン基を示す。ｄは２０以上、８０以下であることが電子写真感光体の繰り返し使用時の耐久性の維持の観点で好ましい。 The siloxane moiety of the polycarbonate resin containing the siloxane moiety or the polyester resin containing the siloxane moiety shall be the structure represented by the formula (A), the structure represented by the formula (B), or the structure represented by the formula (C). Is preferable.

N in the formula (A) indicates the average value of the number of repetitions of the structure in parentheses, and is 10 or more and 120 or less. It is preferable that n is 20 or more and 80 or less from the viewpoint of maintaining the durability of the electrophotographic photosensitive member during repeated use.

A, b and c in the formula (B) independently indicate the average value of the number of repetitions of the structure in parentheses, a and b are 1 or more and 10 or less, and c is 20 or more and 200 or less. is there. It is preferable that a and b are 1 or more and 5 or less, and c is 20 or more and 80 or less from the viewpoint of maintaining durability of the electrophotographic photosensitive member during repeated use.

D in the formula (C) indicates the average value of the number of repetitions of the structure in parentheses, and is 10 or more and 120 or less. Z represents an alkylene group having 3 or less carbon atoms. It is preferable that d is 20 or more and 80 or less from the viewpoint of maintaining the durability of the electrophotographic photosensitive member during repeated use.

式（Ｂ）で示される構造を有するシロキサン部位を含むポリカーボネート樹脂の具体例としては、式（Ｂ−ＰＣ）で示される構造単位を有する樹脂である。

式（Ｃ）で示される構造を有するシロキサン部位を含むポリカーボネート樹脂の具体例としては、式（Ｃ−ＰＣ）で示される構造単位を有する樹脂である。

Hereinafter, the resin containing the siloxane moiety will be specifically described.
A specific example of a polycarbonate resin containing a siloxane moiety having a structure represented by the formula (A) is a resin having a structural unit represented by the formula (A-PC).

A specific example of a polycarbonate resin containing a siloxane moiety having a structure represented by the formula (B) is a resin having a structural unit represented by the formula (B-PC).

A specific example of a polycarbonate resin containing a siloxane moiety having a structure represented by the formula (C) is a resin having a structural unit represented by the formula (C-PC).

式（ＰＣ）中、Ｒ^１〜Ｒ^４は、それぞれ独立に水素原子、またはメチル基を示す。Ｙ^１は、置換基としてアルキル基、またはフェニル基を有してもよいメチレン基、シクロヘキシリデン基、酸素原子、または単結合を示す。 The polycarbonate resin containing a siloxane moiety has a structural unit represented by the formula (A-PC) or the formula (B-PC) or a structural unit represented by the formula (C-PC) at the end, but with other structural units. It may be a copolymer resin of. Examples of other structural units include structural units represented by the formula (PC).

In the formula (PC), R ^{1 to} R ⁴ independently represent a hydrogen atom or a methyl group, respectively. Y ¹ represents a methylene group, a cyclohexylidene group, an oxygen atom, or a single bond which may have an alkyl group or a phenyl group as a substituent.

中でも、式（ＰＣ−１）、（ＰＣ−５）、（ＰＣ−７）、（ＰＣ−８）、（ＰＣ−９）で示される構造単位であることが好ましく、特に式（ＰＣ−７）で示される構造単位であることが好ましい。 Specific examples of the structural unit represented by the formula (PC) are given below.

Of these, structural units represented by the formulas (PC-1), (PC-5), (PC-7), (PC-8), and (PC-9) are preferable, and the formula (PC-7) is particularly preferable. It is preferably a structural unit indicated by.

The polycarbonate resin containing the siloxane moiety is a polycarbonate resin obtained by combining a plurality of structural units from the structural unit represented by the formula (A-PC) or the formula (B-PC) and the structural unit represented by the formula (PC). May be good.

When the polycarbonate resin containing the siloxane moiety has a structural unit represented by the formula (PC) in addition to the structural unit represented by the formula (A-PC) or the structural unit represented by the formula (B-PC), the polycarbonate resin contains the siloxane moiety. The total content of the structural unit represented by the formula (A-PC) and the structural unit represented by the formula (B-PC) is preferably 6% by mass or more and 40% by mass or less with respect to the total mass of the polycarbonate resin. .. Further, the content of the structural unit represented by the formula (PC) with respect to the total mass of the polycarbonate resin containing the siloxane moiety is preferably 60% by mass or more and 94% by mass or less. More preferably, the total content of the structural unit represented by the formula (A-PC) and the structural unit represented by the formula (B-PC) with respect to the total mass of the polycarbonate resin containing the siloxane moiety is 10% by mass or more and 20% by mass. The content of the structural unit represented by the formula (PC) with respect to the total mass of the polycarbonate resin containing the siloxane moiety is 60% by mass or more and 90% by mass or less.

When the polycarbonate resin containing the siloxane moiety has a structural unit represented by the formula (A-PC) or a structural unit represented by the formula (B-PC) and a structural unit represented by the formula (PC), the siloxane moiety is used. The polycarbonate resin contained is a copolymer containing a structural unit represented by the formula (A-PC) or a structural unit represented by the formula (B-PC) and a structural unit represented by the formula (PC). The copolymerization form may be any form such as block copolymerization, random copolymerization, and alternate copolymerization.

The polycarbonate resin containing the siloxane moiety may be a resin having a structure represented by the formula (C-PC) at the end of the polycarbonate resin in which a plurality of structures are combined from the structural unit represented by the formula (PC).

When the polycarbonate resin containing the siloxane moiety has a structural unit represented by the formula (C-PC) at the end of the polycarbonate resin containing the structure represented by the formula (PC), the formula is based on the total mass of the polycarbonate resin containing the siloxane moiety. The content of the structural unit represented by (C-PC) is preferably 0.5% by mass or more and 3% by mass or less. Further, it is preferably 0.8% by mass or more and 2% by mass or less.

The weight average molecular weight of the polycarbonate resin containing the siloxane moiety is preferably 30,000 or more and 200,000 or less. Further, it is more preferably 40,000 or more and 150,000 or less. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured according to a conventional method, specifically by the method described in JP-A-2007-79555.

The copolymerization ratio of the polycarbonate resin containing the siloxane moiety can be confirmed by the conversion method based on the peak area ratio of hydrogen atoms (hydrogen atoms constituting the resin) by ¹ H-NMR measurement of the resin, which is a general method. it can.

Tables 1 to 3 exemplify the polycarbonate resin containing the siloxane moiety of the present invention.

Table 1 exemplifies a polycarbonate resin containing a structural unit represented by the formula (A-PC) and a structural unit represented by the formula (PC). In Table 1, n represents the value of n in the formula (A-PC). (PC) shows a specific example of the structural unit represented by the above formula (PC). (A-PC) / (PC) indicates the copolymerization ratio (mass ratio) of the structural unit represented by the formula (A-PC) and the structural unit represented by the formula (PC). Mw indicates the weight average molecular weight.

表２には、式（Ｂ−ＰＣ）で示される構造単位と式（ＰＣ）で示される構造単位を含むポリカーボネート樹脂を例示する。表２中、ａ、ｂおよびｃは、式（Ｂ−ＰＣ）中のａの値、ｂの値およびｃの値を示す。（ＰＣ）は、上記式（ＰＣ）で示される構造単位の具体例を示す。（Ｂ−ＰＣ）／（ＰＣ）は、式（Ｂ−ＰＣ）で示される構造単位と式（ＰＣ）で示される構造単位の共重合比（質量比）を示す。Ｍｗは、重量平均分子量を示す。

Table 2 exemplifies a polycarbonate resin containing a structural unit represented by the formula (B-PC) and a structural unit represented by the formula (PC). In Table 2, a, b and c represent the value of a, the value of b and the value of c in the formula (B-PC). (PC) shows a specific example of the structural unit represented by the above formula (PC). (B-PC) / (PC) indicates the copolymerization ratio (mass ratio) of the structural unit represented by the formula (B-PC) and the structural unit represented by the formula (PC). Mw indicates the weight average molecular weight.

表３には、式（Ｃ−ＰＣ）で示される構造単位と式（ＰＣ）で示される構造単位を含むポリカーボネート樹脂を例示する。表３中、ｄは、式（Ｃ−ＰＣ）中のｄの値を示す。Ｚの値は、アルキレン基を構成する炭素数を示す。（ＰＣ）は、ポリカーボネート樹脂の主鎖を構成する構造単位を示す。Ｍｗは、重量平均分子量を示す。

Table 3 exemplifies a polycarbonate resin containing a structural unit represented by the formula (C-PC) and a structural unit represented by the formula (PC). In Table 3, d indicates the value of d in the formula (C-PC). The value of Z indicates the number of carbon atoms constituting the alkylene group. (PC) indicates a structural unit constituting the main chain of the polycarbonate resin. Mw indicates the weight average molecular weight.

Among them, the polycarbonate resin is (A-PC-1), (A-PC-2), (A-PC-3), (B-PC-1), (B-PC-2), (B-PC). -3), (C-PC-1) and (C-PC-2) are preferable, and (A-PC-2), (B-PC-2) and (C-PC-2) are particularly preferable.

式（Ａ−Ｅ）中、Ｘ^１は、ｍ−フェニレン基、ｐ−フェニレン基、または２つのｐ−フェニレン基が酸素原子を介して結合した２価の基を示す。 A specific example of a polyester resin containing a siloxane moiety having a structure represented by the formula (A) is a resin having a structural unit represented by the formula (AE).

In formula (AE), X ¹ represents a divalent group in which an m-phenylene group, a p-phenylene group, or two p-phenylene groups are bonded via an oxygen atom.

式（Ｂ−Ｅ）中、Ｘ^２は、ｍ−フェニレン基、ｐ−フェニレン基、または２つのｐ−フェニレン基が酸素原子を介して結合した２価の基を示す。 A specific example of a polyester resin containing a siloxane moiety having a structure represented by the formula (B) is a resin having a structural unit represented by the formula (BE).

In formula (BE), X ² represents a divalent group in which an m-phenylene group, a p-phenylene group, or two p-phenylene groups are bonded via an oxygen atom.

式（Ｃ−Ｅ）中、Ｘ^３は、ｍ−フェニレン基、ｐ−フェニレン基、または２つのｐ−フェニレン基が酸素原子を介して結合した２価の基を示す。 A specific example of a polycarbonate resin containing a siloxane moiety having a structure represented by the formula (C) is a resin having a structural unit represented by the formula (CE) at the end.

In formula (CE), X ³ represents a divalent group in which an m-phenylene group, a p-phenylene group, or two p-phenylene groups are bonded via an oxygen atom.

式（Ｅ）中、Ｒ^５〜Ｒ^８は、それぞれ独立に水素原子、またはメチル基を示す。Ｙ^２は、置換基としてアルキル基を有してもよいメチレン基、シクロヘキシリデン基、酸素原子または単結合を示す。Ｘ^４は、ｍ−フェニレン基、ｐ−フェニレン基、または２つのｐ−フェニレン基が酸素原子を介して結合した２価の基を示す。 The polyester resin containing a siloxane moiety has a structural unit represented by the formula (AE) or the formula (BE) or a structural unit represented by the formula (CE) at the end, but is different from other structural units. It may be a copolymerized resin of. Examples of other structural units include structural units represented by the formula (E).

In formula (E), R ^{5 to} R ⁸ each independently represent a hydrogen atom or a methyl group. Y ² represents a methylene group, a cyclohexylidene group, an oxygen atom or a single bond which may have an alkyl group as a substituent. X ⁴ represents a m- phenylene group, p- phenylene group, or a bivalent group having two p- phenylene groups bonded via an oxygen atom.

Specific examples of the structural unit represented by the formula (E) are given below.

Of these, structural units represented by the formulas (E-1), (E-7), (E-13), (E-14), and (E-18) are preferable, and in particular, the formula (E-). It is preferably a structural unit represented by 1) and (E-7).

The polyester resin containing the siloxane moiety is a polyester obtained by combining a plurality of structural units from the structural unit represented by the formula (AE) or the structural unit represented by the formula (BE) and the structural unit represented by the formula (E). It may be a resin.

When the polyester resin containing the siloxane moiety has a structural unit represented by the formula (AE) or a structural unit represented by the formula (BE) in addition to the structural unit represented by the formula (E), the polyester resin contains the siloxane moiety. The total content of the structural unit represented by the formula (AE) and the structural unit represented by the formula (BE) is preferably 6% by mass or more and 40% by mass or less with respect to the total mass of the polyester resin. Further, the content of the structural unit represented by the formula (E) with respect to the total mass of the polyester resin containing the siloxane moiety is preferably 60% by mass or more and 94% by mass or less. More preferably, the total content of the structural unit represented by the formula (AE) and the structural unit represented by the formula (BE) with respect to the total mass of the polyester resin containing the siloxane moiety is 10% by mass or more and 20% by mass. The content of the structural unit represented by the formula (E) with respect to the total mass of the polyester resin including the siloxane moiety is 60% by mass or more and 90% by mass or less.

When the polyester resin containing the siloxane moiety has a structural unit represented by the formula (AE) or a structural unit represented by the formula (BE) and a structural unit represented by the formula (E), the siloxane moiety is used. The polyester resin contained is a copolymer containing a structural unit represented by the formula (AE) or a structural unit represented by the formula (BE) and a structural unit represented by the formula (E). The copolymerization form may be any form such as block copolymerization, random copolymerization, and alternate copolymerization.

The polyester resin containing the siloxane moiety may be a resin having a structural unit represented by the formula (CE) at the end of the polyester resin obtained by combining a plurality of structures from the structural unit represented by the formula (E).

When the polyester resin containing the siloxane moiety has the structural unit represented by the formula (CE) at the end of the polyester resin containing the structural unit represented by the formula (E), the total mass of the polyester resin containing the siloxane moiety is increased. The content of the structural unit represented by the formula (CE) is preferably 0.5% by mass or more and 3% by mass or less. Further, it is preferably 0.8% by mass or more and 2% by mass or less.

The weight average molecular weight of the polyester resin containing the siloxane moiety is preferably 50,000 or more and 150,000 or less. Further, it is more preferably 60,000 or more and 120,000 or less. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured according to a conventional method, specifically by the method described in JP-A-2007-79555.

The copolymerization ratio of the polyester resin containing the siloxane moiety can be confirmed by the conversion method based on the peak area ratio of hydrogen atoms (hydrogen atoms constituting the resin) by ¹ H-NMR measurement of the resin, which is a general method. it can.

表４には、式（Ａ−Ｅ）で示される構造単位と式（Ｅ）で示される構造単位を含むポリエステル樹脂を例示する。表４中、ｎおよびＸ^１は、式（Ａ−Ｅ）中のｎの値およびＸ^１を構成する構造を示す。（Ｅ）は、上記式（Ｅ）で示される構造単位の具体例および共重合比（質量比）を示す。（Ａ−Ｅ）／（Ｅ）は、式（Ａ−Ｅ）で示される構造単位と式（Ｅ）で示される構造単位の共重合比（質量比）を示す。Ｍｗは、重量平均分子量を示す。 Tables 4 to 6 exemplify polyester resins containing the siloxane moiety of the present invention.

Table 4 exemplifies a polyester resin containing a structural unit represented by the formula (AE) and a structural unit represented by the formula (E). In Table 4, n and X ¹ indicate the value of n in the formula (AE) and the structure constituting X ¹ . (E) shows a specific example of the structural unit represented by the above formula (E) and a copolymerization ratio (mass ratio). (AE) / (E) indicates the copolymerization ratio (mass ratio) of the structural unit represented by the formula (AE) and the structural unit represented by the formula (E). Mw indicates the weight average molecular weight.

表５には、式（Ｂ−Ｅ）で示される構造単位と式（Ｅ）で示される構造単位を含むポリエステル樹脂を例示する。表５中、ａ、ｂ、ｃおよびＸ^２は、式（Ｂ−Ｅ）中のａの値、ｂの値およびｃの値並びにＸ^２を構成する構造を示す。（Ｅ）は、上記式（Ｅ）で示される構造単位の具体例を示す。（Ｂ−Ｅ）／（Ｅ）は、式（Ｂ−Ｅ）で示される構造単位と式（Ｅ）で示される構造単位の共重合比（質量比）を示す。Ｍｗは、重量平均分子量を示す。

Table 5 exemplifies a polyester resin containing a structural unit represented by the formula (BE) and a structural unit represented by the formula (E). In Table 5, a, b, c and X ² show the value of a, the value of b and the value of c in the formula (BE) and the structures constituting X ² . (E) shows a specific example of the structural unit represented by the above formula (E). (BE) / (E) indicates the copolymerization ratio (mass ratio) of the structural unit represented by the formula (BE) and the structural unit represented by the formula (E). Mw indicates the weight average molecular weight.

表６には、式（Ｃ−Ｅ）で示される構造単位と式（Ｅ）で示される構造単位を含むポリエステル樹脂を例示する。表６中、ｄは、式（Ｃ−Ｅ）中のｄの値およびを示す。Ｚの値は、アルキレン基を構成する炭素数を示す。Ｘ^３は、式（Ｃ−Ｅ）中のＸ^３を構成する構造を示す。（Ｅ）は、ポリエステル樹脂の主鎖を構成する構造単位を示す。Ｍｗは、重量平均分子量を示す。

Table 6 exemplifies a polyester resin containing a structural unit represented by the formula (CE) and a structural unit represented by the formula (E). In Table 6, d indicates the value and value of d in the formula (CE). The value of Z indicates the number of carbon atoms constituting the alkylene group. X ³ represents a structure constituting ^{X 3} in the formula (C-E). (E) indicates a structural unit constituting the main chain of the polyester resin. Mw indicates the weight average molecular weight.

Among them, the polyester resin is preferably (AE-2), (BE-2), or (CE-2).

In the present invention, the siloxane moiety is a moiety containing silicon atoms at both ends constituting the siloxane portion, a group bonded to them, an oxygen atom sandwiched between silicon atoms at both ends, a silicon atom, and a group bonded to them. is there. Specifically, in the present invention, the siloxane moiety is a moiety surrounded by a broken line of the structure represented by the formula (AS) in the case of the structure represented by the formula (A).

Further, in the case of the structure represented by the formula (B), it is the portion surrounded by the broken line of the structure represented by the formula (BS).

Further, in the case of the structure represented by the formula (C), it is the portion surrounded by the broken line of the structure represented by the formula (CS).

In the present invention, the surface layer of the electrophotographic photosensitive member contains a resin containing a siloxane moiety, but a resin containing no siloxane moiety may be mixed. Such a resin is optional, but a polycarbonate resin containing no siloxane moiety or a polyester resin containing no siloxane moiety is preferable from the viewpoint of maintaining durability with repeated use of the electrophotographic photosensitive member.

The polycarbonate resin containing no siloxane moiety preferably has a structural unit represented by the formula (PC). Similarly, the polyester resin containing no siloxane moiety preferably has a structural unit represented by the formula (E). The weight average molecular weight (Mw) of the polycarbonate resin containing no siloxane moiety or the polyester resin containing no siloxane moiety is preferably 60,000 or more and 160,000 or less from the viewpoint of maintaining durability, and further 80, It is preferably 000 or more and 140,000 or less.

When a resin containing a siloxane moiety and a resin other than the resin containing a siloxane moiety are mixed and used in the surface layer, the content of the resin containing the siloxane moiety is 0.1% by mass or more with respect to the total mass of the constituent components in the surface layer. It is preferably 10% by mass or less from the viewpoint of the effect of reducing fog of the present invention. Further, it is preferably 0.3% by mass or more and 8% by mass or less.

[Process cartridge, electrophotographic equipment]
The process cartridge of the present invention is characterized by having a developing means containing toner and an electrophotographic photosensitive member described above and being removable from the main body of the electrophotographic apparatus.
Further, the electrophotographic apparatus of the present invention is characterized by having a toner and an electrophotographic photosensitive member.

FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus having a process cartridge including an electrophotographic photosensitive member.
The cylindrical electrophotographic photosensitive member 1 is rotationally driven at a predetermined peripheral speed in the direction of the arrow about the axis 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 make the process cartridge 11 of the present invention removable from the main body of the electrophotographic apparatus, a guide means 12 such as a rail may be provided.

The electrophotographic photosensitive member of the present invention can be used in a laser beam printer, an LED printer, a copier, and the like.

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 added to a reaction vessel containing 390.0 parts of ion-exchanged water to prepare an aqueous sodium phosphate solution, and the mixture was kept warm at 65 ° C. for 1.0 hour while purging nitrogen. did. While stirring the sodium phosphate aqueous solution at 12,000 rpm using a stirrer (trade name: TK Homomixer, manufactured by Tokushu Kagaku Kogyo Co., Ltd.), 7.4 parts to 10.0 parts of ion-exchanged water. An aqueous solution of calcium chloride in which calcium chloride (dihydrate) was dissolved was put into a reaction vessel all at once to prepare an aqueous medium containing a dispersion stabilizer. Further, 1.0 mol / L hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0 to prepare an aqueous medium.

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

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

(Polymerization process)
By changing from a stirrer to a stirrer equipped with a propeller stirring blade, polymerizing at 70 ° C. for 5.0 hours while stirring at 200 rpm, and further raising the temperature to 85 ° C. and heating for 2.0 hours. A polymerization reaction was carried out. 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>
-Ion-exchanged water 70.0 parts-Methyltriethoxysilane 30.0 parts The above materials 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 fine particles>
-Ion-exchanged water 100.0 parts-Sodium phosphate (12-hydrate) 8.5 parts After mixing the above materials, at room temperature, a stirrer (trade name: TK Homomixer, Tokushu Kagaku Kogyo Co., Ltd.) (Product), while stirring at 10,000 rpm, add 60.0 parts of zirconium lactate ammonium salt (trade name: ZC-300, Matsumoto Fine Chemical Co., Ltd.) (equivalent to 7.2 parts as zirconium lactate ammonium salt). did. 1.0 mol / L hydrochloric acid was added to the reaction solution to adjust the pH to 7.0. The temperature of the reaction solution 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 fine particles of a zirconium phosphate compound having a number average particle size of 124 nm.

<Manufacturing example of toner particles>
<Toner particle 1>
(Convex formation process)
The following samples were weighed in the reaction vessel and mixed using a propeller stirring blade to obtain a mixed solution.
-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 adhesion process)
-Titanium lactate 44% aqueous solution (trade name: TC-310, manufactured by Matsumoto Fine Chemicals Co., Ltd.) 3.2 parts (equivalent to 1.4 parts as titanium lactate)
10.0 parts of organosilicon compound solution Subsequently, after mixing the above materials 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. It was held for 4.0 hours. After lowering the temperature to 25 ° C., the pH was adjusted to 1.5 with 1.0 mol / L hydrochloric acid, the mixture was stirred for 1.0 hour, and then filtered while being washed with ion-exchanged water. The obtained powder was dried in a constant temperature bath and then classified by a wind power classifier to obtain toner particles 1. The number average particle size (D1) of the toner particles 1 was 6.2 μm, and the weight average particle size (D4) was 6.9 μm. When the toner particles 1 were analyzed and observed by a transmission electron microscope and energy dispersive X-ray spectroscopy (TEM-EDX), convex portions containing an organic silicon polymer were observed on the surface of the toner particles, and titanium was observed on the surface of the convex portions. Was confirmed to exist. The convex height H was 60 nm. Further, the toner particles 1 were analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS analysis) to detect ions derived from titanium phosphate.
The titanium phosphate compound is a reaction product of titanium lactate and a phosphate ion derived from sodium phosphate or calcium phosphate derived from an aqueous medium.

<Toner particle 2>
(Polyvalent acid metal salt adhesion process)
The following samples were weighed in the reaction vessel and mixed using a propeller stirring blade to obtain a mixed solution.
-Toner mother particle dispersion 500.0 parts-Titanium lactate 44% aqueous solution (trade name: TC-310, manufactured by Matsumoto Fine Chemicals Co., Ltd.) 3.2 parts (equivalent to 1.4 parts 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 surface of the toner particles. Further, the toner particles 2 were subjected to TOF-SIMS analysis to detect ions derived from titanium phosphate.
The titanium phosphate compound is a reaction product of titanium lactate and a phosphate ion derived from sodium phosphate or calcium phosphate derived from an aqueous medium.

<Toner particle 3>
In the production example of the toner particles 2, instead of 3.2 parts of titanium lactate 44% aqueous solution (trade name: TC-310, manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium lactate ammonium salt (trade name: ZC-300, manufactured by Matsumoto Fine Chemical Co., Ltd.) ) 11.7 parts (equivalent to 1.4 parts as a zirconium lactate ammonium salt) was added to obtain toner particles 3 in the same manner as in the production example of 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 surface of the toner particles. Further, the toner particles 3 were subjected to TOF-SIMS analysis to detect ions derived from zirconium phosphate.
The zirconium phosphate compound is a reaction product of a zirconium lactate ammonium salt and a phosphate ion derived from sodium phosphate or calcium phosphate derived from 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 a 44% aqueous solution of titanium lactate (trade name: TC-310, manufactured by Matsumoto Fine Chemical Co., Ltd.) 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. Further, no metal element was present on the surface of the toner particles. Further, when the toner particles 5 were subjected to TOF-SIMS analysis, 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>
・ 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 fine particles 2.0 parts SUPERMIXER PICCOLO SMP-2 ( It was put into (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 surface of the toner particles. When the toner 4 was subjected to TOF-SIMS analysis, ions derived from zirconium phosphate were detected.
Table 7 shows the physical characteristics of the toners 1 to 5.

<Calculation method of convex height H>
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 (trade name: EM UC7, manufactured by Leica) equipped with a diamond blade.
This sample is magnified using a TEM (trade name: 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 convex height. According to the above method, the cross sections of the 20 toner particles are analyzed, and the average value of the obtained convex heights is defined as the convex height H (nm).

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

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

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

<Manufacturing of electrophotographic photosensitive member>
(Manufacturing Example 1 of Electrophotographic Photoreceptor)
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.

(Metal oxide particles 1)
As the metal oxide particles 1, titanium oxide coated with niobium-doped titanium oxide produced by the following production method was used.
Titanium dioxide as a core material can be produced by a known sulfuric acid method. That is, a solution containing titanium sulfate, titanyl sulfate or the like is heated and hydrolyzed to prepare a metatitanic acid slurry, and the metatitanic acid slurry is dehydrated and fired.
As the core material particles, anatase-type titanium oxide particles having an average primary particle size of 200 nm were used. 33.7g of titanium in terms of TiO _2, niobium was prepared Chitan'niobu sulfuric acid solution containing 2.9g calculated as _Nb 2 _{O 5.} 100 g of core material particles were dispersed in pure water to form a 1 L suspension, which was heated to 60 ° C. The titaniumniobium sulfuric acid solution and 10 mol / L sodium hydroxide were added dropwise over 3 hours so that the pH of the suspension became 2-3. After dropping the whole amount, the pH was adjusted to near neutral, and a flocculant was added to precipitate the solid content. The supernatant was removed, filtered and washed, and dried at 110 ° C. to obtain an intermediate containing 0.1 wt% of organic matter derived from the flocculant in terms of C. This intermediate was calcined in nitrogen gas at 750 ° C. for 1 hour, the temperature was lowered to 450 ° C., and then calcined in oxygen gas for 1 hour to prepare metal oxide particles 1.

[Preparation of coating liquid for conductive layer]
(Coating liquid for conductive layer 1)
80 parts of phenol resin (monomer / oligomer of phenol resin) (trade name: Pryofen J-325, manufactured by DIC, resin solid content: 60%, density after curing: 1.3 g / cm ³ ) as a binder material , A solution was obtained by dissolving in 60 parts of 1-methoxy-2-propanol as a solvent.
160 parts of metal oxide particles 1 were added to this solution, and the mixture was placed in a vertical sand mill using 200 parts of glass beads having an average particle size of 1.0 mm as a dispersion medium, and the dispersion liquid temperature was 23 ± 3 ° C. and the rotation speed was 1500 rpm ( A dispersion treatment was carried out for 2 hours under the condition of a peripheral speed of 5.5 m / s) to obtain a dispersion solution. Glass beads were removed from this dispersion with a mesh. The dispersion after removing the glass beads was pressure-filtered using a PTFE filter paper (trade name: PF060, manufactured by Advantech Toyo). In the dispersion liquid after pressure filtration, 0.015 parts of silicone oil (trade name: SH28 PAINT ADDITIVE, manufactured by Toray Dow Corning) as a leveling agent, and silicone resin particles (trade name: Tospearl 120) as a surface roughness imparting material. , Momentive Performance Materials Co., Ltd., average particle size 2 μm) 15 parts was added and stirred to prepare a coating liquid 1 for a conductive layer.
This coating liquid for a conductive layer was immersed and coated on a support and heated at 150 ° C. for 30 minutes to form a conductive layer having a film thickness of 25.0 μm.

(Formation of undercoat layer)
The following materials were prepared.
Electron transport material represented by the following formula (ET-1) 4 parts Block isocyanate (trade name: Duranate SBN-70D, manufactured by Asahi Kasei Chemicals Co., Ltd.) 5.5 parts Polyvinyl butyral resin (trade name: Eslek KS-5Z, Sekisui) (Manufactured by Chemical Industry Co., Ltd.) 0.3 parts Zinc (II) hexanoate as a catalyst (manufactured by Mitsuwa Chemical Co., Ltd.) 0.05 parts These are 50 parts of tetrahydrofuran and 50 parts of 1-methoxy-2-propanol. A coating solution for the undercoat layer was prepared by dissolving in the mixed solvent of. This coating liquid for the undercoat layer was immersed and coated on the conductive layer, and this was heated at 170 ° C. for 30 minutes to form an undercoat layer having a film thickness of 0.7 μm.

(Formation of charge generation layer)
Next, in the chart obtained from CuKα characteristic X-ray diffraction, 10 parts of crystalline hydroxygallium phthalocyanine having peaks at the positions of 7.5 ° and 28.4 ° and polyvinyl butyral resin (trade name: Eslek BX-1, 5 copies (manufactured by Sekisui Chemical Co., Ltd.) were prepared. These are added to 200 parts of cyclohexanone, dispersed in a sand mill device using glass beads having a diameter of 0.9 mm for 6 hours, and 150 parts of cyclohexanone and 350 parts of ethyl acetate are further added and diluted to dilute the coating liquid for the charge generation layer. Got The obtained coating liquid was immersed and coated on the undercoat layer and dried at 95 ° C. for 10 minutes to form a charge generation layer having a film thickness of 0.20 μm. The X-ray diffraction measurement was performed under the following conditions.

[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

この電荷輸送層用塗布液を電荷発生層上に浸漬塗布して塗膜を形成し、塗膜を３０分間１２０℃で乾燥させることによって、膜厚が１６μｍの電荷輸送層を形成した。 (Formation of charge transport layer)
Next, the following materials were prepared.
Compound represented by formula (CTM-1) (charge transporting substance (hole transporting compound)) 9 parts Compound represented by formula (CTM-2) (charge transporting substance (hole transporting compound)) Part 1 siloxane site 1 part of the resin (A-PC-1) shown in Table 8 as a resin containing siloxane 9 parts of a resin having a structural unit represented by the formula (PC-7) shown in Table 8 as a resin containing no siloxane site. A coating solution for a charge transport layer was prepared by dissolving 25 parts of xylene / 15 parts of methyl benzoate / 35 parts of dimethoxymethane in a mixed solvent.

The coating liquid for the charge transport layer was immersed and coated on the charge generation layer to form a coating film, and the coating film was dried at 120 ° C. for 30 minutes to form a charge transport layer having a film thickness of 16 μm.

In this way, the electrophotographic photosensitive member of Production Example 1 having a cylindrical shape (drum shape) having a support, an undercoat layer, a charge generation layer, and a charge transport layer in this order was manufactured.

In Table 8, the content rate indicates the content rate (mass%) of the resin containing the siloxane moiety with respect to the total mass of the constituent components in the surface layer. Mw indicates the weight average molecular weight of the resin having no siloxane moiety.

(Production Examples 2-34 of Electrophotographic Photoreceptors)
In the production of the electrophotographic photosensitive members 2-34, the electrophotographic photosensitive member was produced in the same manner as in Production Example 1 except that the composition of the resin contained in the surface layer was changed as shown in Table 8.

(Production Example 35 of Electrophotographic Photoreceptor)
In the production of the electrophotographic photosensitive member 35, the formation of the charge generation layer was carried out in the same manner as in Production Example 1 of the electrophotographic photosensitive member.
The following materials were prepared as materials for the coating liquid for the charge transport layer.
Compound represented by formula (CTM-1) (charge transporting substance (hole transporting compound)) 9 parts Compound represented by formula (CTM-2) (charge transporting substance (hole transporting compound)) 1 part formula ( A coating solution for a charge transport layer was prepared by dissolving 10 parts of a resin having the structural unit shown in PC-7) in a mixed solvent of 25 parts of o-xylene / 15 parts of methyl benzoate / 35 parts of dimethoxymethane.
The coating liquid for the charge transport layer was immersed and coated on the charge generation layer to form a coating film, and the coating film was dried at 120 ° C. for 30 minutes to form a charge transport layer having a film thickness of 16 μm.
In this way, the electrophotographic photosensitive member of Production Example 35 having a cylindrical shape (drum shape) having a support, a conductive layer, an undercoat layer, a charge generation layer, and a charge transport layer in this order was manufactured.

[Examples 1 to 34 and Comparative Examples 1 to 5]
Using the toners 1 to 5 and the electrophotographic photosensitive members of Production Examples 1 to 35, the following evaluation was performed with the combinations shown in Table 9. The evaluation results are shown in Table 9.

The evaluation method and evaluation criteria of the present invention will be described.
As an image forming device, a commercially available laser printer (trade name: LBP-712Ci, manufactured by Canon) is connected to an external high-voltage power supply, modified so that an arbitrary potential difference can be provided between the charging blade and the charging roller, and the process speed is 200 mm. A modified machine with / sec and a commercially available process cartridge were used. The product toner was removed from the inside of the cartridge, cleaned by air blowing, and then filled with 165 g of the toner 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>
In gloss paper mode (1/3 speed), use Letter size HP Brochure Paper 200g, Glossy (basis weight 200g / cm ² ), and use 75mm x 75mm paper (Post-it 3M Japan Ltd.) at the center position. It was pasted and a solid white image with a 0% print ratio was printed out.
Remove the pasted paper from the printout image, and use "REFLECTOMTER MODEL TC-6DS" (trade name) (manufactured by Tokyo Denshoku Co., Ltd.) to measure the whiteness of the white background of the printout image and the whiteness of the transfer paper. The fog density (%) was calculated from the difference between the two, and the image fog was evaluated. An amber filter was used as the filter.

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 (7)

A process cartridge that is removable from the main body of the electrophotographic device.
It has a developing means containing toner and an electrophotographic photosensitive member.
The toner is a toner having toner particles, and has a polyvalent acid metal salt on at least a part of the surface of the toner particles.
The polyhydric acid metal salt contains at least one metal element selected from the metal elements contained in Groups 3 to 13 as a metal element.
A process cartridge in which the surface layer of the electrophotographic photosensitive member contains a resin containing a siloxane moiety. Claim 1 in which the resin containing a siloxane moiety is a polycarbonate resin containing a siloxane moiety or a polyester resin containing a siloxane moiety, and the siloxane moiety has a structure represented by the formula (A) or a structure represented by the formula (B). The process cartridge described in.

(In the formula (A), n indicates the average value of the number of repetitions of the structure in parentheses, which is 10 or more and 120 or less.)

(In the formula (B), a, b and c independently indicate the average value of the number of repetitions of the structure in parentheses, a and b are 1 or more and 10 or less, and c is 20 or more and 200 or less. is there.) The process cartridge according to claim 1, wherein the resin containing a siloxane moiety is a polycarbonate resin containing a siloxane moiety or a polyester resin containing a siloxane moiety, and the siloxane moiety has a structure represented by the formula (C). ..

(D in the formula (C) indicates the average value of the number of repetitions of the structure in parentheses, which is 10 or more and 120 or less. Z indicates an alkylene group having 3 or less carbon atoms.) According to any one of claims 1 to 3, the content of the resin containing the siloxane moiety with respect to the total mass of the constituents in the surface layer of the electrophotographic photosensitive member is 0.1% by mass or more and 10% by mass or less. The described process cartridge. The ratio M1 of the metal element M contained in the polyvalent acid metal salt to the component ratio of the surface of the toner particles obtained from the spectrum obtained by the X-ray photoelectron spectroscopic analysis of the toner is 1.0 (atm%) or more. The process cartridge according to any one of claims 1 to 4, which is 10.0 (atm%) or less. The process cartridge according to claim 5, wherein the metal element M is titanium. An electrophotographic apparatus having the process cartridge according to any one of claims 1 to 6.

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