JP6762799B2 - Image formation method, process cartridge and electrophotographic equipment - Google Patents

Description

The present invention relates to an image forming method, a process cartridge and an electrophotographic apparatus. More specifically, the present invention relates to an image forming method using a specific electrophotographic photosensitive member and a specific toner, and a process cartridge and an electrophotographic apparatus including the specific electrophotographic photosensitive member and the specific toner.

As a general electrophotographic process, which is an image forming method, an electrical latent image is formed on an image carrier (electrophotographic photosensitive member, hereinafter also referred to as “photoreceptor”), and toner is supplied to the latent image. A method is known in which a toner image is visualized and transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat or pressure to obtain a recorded image (copy, printed matter, etc.).

After the transfer step, cleaning is performed to remove the toner remaining on the electrophotographic photosensitive member. The most widely used cleaning method is blade cleaning. Blade cleaning is a method in which an elastic blade-like member such as rubber is pressed against the surface of an electrophotographic photosensitive member to scrape off toner.

In blade cleaning, it is important to suppress as much as possible cleaning defects in which toner slips through the contact nip between the blade and the electrophotographic photosensitive member. When cleaning failure occurs, the toner that has slipped through adheres to the charged member, causing contamination of the charged member. In the region where the charging member is contaminated, the charging process of the photoconductor is not performed normally, and the image quality is impaired. Further, once the toner slips through, the toner easily passes through the gap between the blade and the electrophotographic photosensitive member caused by the slipping, and the contamination of the charged member becomes worse. For this reason, unless the occurrence of cleaning defects is suppressed, it is necessary to provide a mechanism for removing the toner adhering to the charged member, which complicates the mechanism, increases the size of the process cartridge and the electrophotographic apparatus, and increases the cost. Or become.

The cause of poor cleaning is that the amount of inclusions (retention layer) due to toner or the like remaining on the contact nip between the blade and the photoconductor is small, and the friction applied to the blade becomes uneven, so the stick of the blade -It is considered that one of the causes is that the slip motion tends to be unstable.

In order to stabilize the stick-slip motion of the blade, an attempt has been made to stabilize the stick-slip motion by discharging toner to the blade nip during non-image formation and increasing the amount of inclusions (retention layer). However, this method takes an extra time during non-image formation, and has problems such as a decrease in paper output productivity.

In addition, cleaning defects are often likely to occur even in the initial stage of using a new process cartridge or electrophotographic apparatus. This is partly because the amount of inclusions (retention layer) due to toner or the like remaining near the contact nip between the blade and the photoconductor is small in the initial stage of use of a new process cartridge or electrophotographic apparatus. Conceivable. If the amount of inclusions in the vicinity of the abutting nip portion is small, the friction applied to the blade becomes non-uniform, so that the stick-slip motion of the blade tends to be unstable, and toner tends to slip through.

In order to stabilize the stick-slip movement of the blade from the initial stage of using a new process cartridge or electrophotographic device, toner, carbon fluoride, or oxidation is applied to the edge of the cleaning blade during the manufacture of the process cartridge or electrophotographic device. Attempts have been made to apply particles such as cerium, titanium oxide, silica, and tospearl (registered trademark) as lubricants. However, since the countermeasure by applying the lubricant to the blade leads to the complexity of the manufacturing process, there is a demand for a means for suppressing the occurrence of cleaning failure without applying the lubricant.

As another countermeasure for suppressing poor cleaning, for example, an attempt has been made to increase the linear pressure at which the edge portion of the blade is pressed against the surface of the photoconductor to prevent the toner from slipping through. However, this countermeasure measure by simply increasing the linear pressure may cause problems such as promotion of chipping of the blade edge portion, generation of abnormal noise due to chatter vibration of the blade, and promotion of wear of the photoconductor.

Patent Document 1 proposes a method of suppressing poor cleaning by using non-spherical and irregularly shaped large particle size silica particles as an external additive for toner. However, the use of a large particle size inorganic external additive may impair the low temperature fixability of the toner. As a result, the power consumption in the fixing process may increase.

Japanese Unexamined Patent Publication No. 2007-279702

In recent years, improvement in image output productivity has been required, and the waiting time has been shortened. As a result, the number of times the toner is ejected to the contact nip portion between the blade and the photoconductor has been reduced. In particular, under low printing conditions and the like, the retention layer is not sufficiently formed at the time of image formation, and there is a possibility that cleaning failure is likely to occur. Above all, high printing after repeated use under low printing conditions tends to lead to poor cleaning. Therefore, in order to suppress cleaning defects and obtain good image quality, there is a need for a means for stabilizing the stick-slip motion of the blade in a state where toner ejection during non-image formation is reduced.

Further, with the evolution of the electrophotographic process, the pre-rotation time from starting a new process cartridge or an electrophotographic device to a printable standby state has been shortened. As a result, even if the toner is discharged from the developing unit during the forward rotation, it is difficult to obtain a time for the toner to be sufficiently evenly distributed in the vicinity of the contact nip portion between the blade and the photoconductor. If the uneven distribution of toner is not sufficiently evened in the vicinity of the contact nip, image formation is performed before the retention layer is sufficiently formed, and the stick-slip motion of the blade becomes unstable, which may lead to poor cleaning. The sex is coming out. Therefore, in order to suppress cleaning defects and obtain good image quality, the stick-slip motion of the blade is performed even if the retention layer is insufficiently formed in the initial stage of use of a new process cartridge or electrophotographic apparatus. There is a need for a means for stabilizing the temperature and then uniformly forming the retention layer in a short time.

An object of the present invention is to provide an image forming method, a process cartridge, and an electrophotographic apparatus that solve the above problems. That is, it is an object of the present invention to provide an image forming method, a process cartridge, and an electrophotographic apparatus capable of reducing the number of times of toner ejection, having good cleaning property, and suppressing deterioration of image quality due to contamination of charged members. Another object of the present invention is to provide an image forming method, a process cartridge and an electrophotographic apparatus capable of suppressing the occurrence of cleaning defects and obtaining good image quality even in the initial stage of using a new process cartridge or an electrophotographic apparatus. ..

The present invention comprises a charging step of contacting an electrophotographic photosensitive member to charge the electrophotographic photosensitive member, a developing step of developing the electrophotographic photosensitive member with toner to form a toner image, and an electrophotographic photosensitive member. In an image forming method comprising a transfer step of transferring the toner image to a transfer material and a cleaning step of bringing a blade into contact with the electrophotographic photosensitive member and removing the toner on the electrophotographic photosensitive member.
The surface layer of the electrophotographic photosensitive member satisfies the following conditions (i) or (ii).
(I) Polyarylate resin A and polycarbonate having a polysiloxane structure represented by the formula (1) (ii) containing fluororesin particles and at least one resin selected from the group consisting of polyarylate resin and polycarbonate resin. Contains at least one resin selected from the group consisting of resin B
(In the formula (1), R ¹¹ and R ¹² each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. N represents an integer of 10 or more and 200 or less.)
The polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the following formula (2) at least at least a part of the terminals.
(In the formula (2), R ^{21 to} R ²⁴ independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Z represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. n represents an integer of 10 or more and 200 or less. M represents an integer of 1 or more and 3 or less.)
The toner is to have a toner particle containing resin C and styrene acrylic resins having a isosorbide units represented by the formula (14) in its surface,
The content of the styrene acrylic resin in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 50.0% by mass or more and 99.0% by mass or less.
The resin C contains 0.10 mol% or more and 30.00 mol% or less of the isosorbide unit represented by the above formula (14) as a constituent component.
The present invention relates to an image forming method , wherein the content of the resin C in the toner with respect to a total resin having a number average molecular weight of 1500 or more is 1.0% by mass or more and 35.0% by mass or less .

The present invention is a process cartridge that is detachably attached to the main body of the electrophotographic apparatus.
The process cartridge is a charging means for contacting the electrophotographic photosensitive member and the electrophotographic photosensitive member to charge the electrophotographic photosensitive member, and a developing means for developing the electrophotographic photosensitive member with toner to form a toner image. And a cleaning means for contacting the blade with the electrophotographic photosensitive member and removing the toner on the electrophotographic photosensitive member.
The surface layer of the electrophotographic photosensitive member satisfies the following conditions (i) or (ii).
(I) Polyarylate resin A and polycarbonate having a polysiloxane structure represented by the formula (1) (ii) containing fluororesin particles and at least one resin selected from the group consisting of polyarylate resin and polycarbonate resin. Contains at least one resin selected from the group consisting of resin B
The polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the following formula (2) at least at least a part of the terminals.
(In the formula (2), R ^{21 to} R ²⁴ each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Z represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. n represents an integer of 10 or more and 200 or less. M represents an integer of 1 or more and 3 or less.)
The toner is to have a toner particle containing resin C and styrene acrylic resins having a isosorbide units represented by the formula (14) in its surface,
The content of the styrene acrylic resin in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 50.0% by mass or more and 99.0% by mass or less.
The resin C contains 0.10 mol% or more and 30.00 mol% or less of the isosorbide unit represented by the above formula (14) as a constituent component.
The present invention relates to a process cartridge characterized in that the content of the resin C in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 1.0% by mass or more and 35.0% by mass or less .

Further, the present invention comprises an electrophotographic photosensitive member, a charging means for contacting the electrophotographic photosensitive member to charge the electrophotographic photosensitive member, and a developing process for forming a toner image on the electrophotographic photosensitive member by developing with toner. It has means, a transfer means for transferring the toner image on the electrophotographic photosensitive member to a transfer material, and a cleaning means for abutting the blade on the electrophotographic photosensitive member to remove the toner on the electrophotographic photosensitive member. In the image forming apparatus
The surface layer of the electrophotographic photosensitive member satisfies the following conditions (i) or (ii).
(I) Polyarylate resin A and polycarbonate having a polysiloxane structure represented by the formula (1) (ii) containing fluororesin particles and at least one resin selected from the group consisting of polyarylate resin and polycarbonate resin. Contains at least one resin selected from the group consisting of resin B
The polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the following formula (2) at least at least a part of the terminals.
(In the formula (2), R ^{21 to} R ²⁴ each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Z represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. n represents an integer of 10 or more and 200 or less. M represents an integer of 1 or more and 3 or less.)
The toner is to have a toner particle containing resin C and styrene acrylic resins having a isosorbide units represented by the formula (14) in its surface,
The content of the styrene acrylic resin in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 50.0% by mass or more and 99.0% by mass or less.
The resin C contains 0.10 mol% or more and 30.00 mol% or less of the isosorbide unit represented by the above formula (14) as a constituent component.
The present invention relates to an electrophotographic apparatus , wherein the content of the resin C in the toner with respect to a total resin having a number average molecular weight of 1500 or more is 1.0% by mass or more and 35.0% by mass or less .

According to the present invention, the number of times of toner ejection can be reduced and good cleaning property can be obtained. In addition, good cleanability can be obtained even in the initial stage of use of a new process cartridge or electrophotographic apparatus. This makes it possible to provide an image forming method, a process cartridge, and an electrophotographic apparatus capable of suppressing deterioration of image quality due to contamination of the charged member.

It is a figure which shows an example of the schematic structure of the image forming apparatus used in the image forming method of this invention. It is a figure which shows the relationship between the solubility parameter and the adhesion energy.

The image forming method of the present invention includes a charging step of contacting the electrophotographic photosensitive member to charge the electrophotographic photosensitive member, a developing step of developing the electrophotographic photosensitive member with toner to form a toner image, and the electron. It includes a transfer step of transferring the toner image on the photographic photosensitive member to a transfer material, and a cleaning step of bringing a blade into contact with the electrophotographic photosensitive member to remove the toner on the electrophotographic photosensitive member.

In addition, the electrophotographic photosensitive member has the following features. That is, the surface layer of the electrophotographic photosensitive member satisfies the following conditions (i) or (ii).
(I) Polyarylate resin A and polycarbonate having a polysiloxane structure represented by the formula (1) (ii) containing fluororesin particles and at least one resin selected from the group consisting of polyarylate resin and polycarbonate resin. Contains at least one resin selected from the group consisting of resin B
(In the formula (1), R ¹¹ and R ¹² each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. N represents an integer of 10 or more and 200 or less.)
The polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the following formula (2) at least at least a part of the terminals.
(In the formula (2), R ^{21 to} R ²⁴ each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Z represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. n represents an integer of 10 or more and 200 or less. M represents an integer of 1 or more and 3 or less.)
The toner is to have a toner particle containing resin C and styrene acrylic resins having a isosorbide units represented by the formula (14) in its surface,
The content of the styrene acrylic resin in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 50.0% by mass or more and 99.0% by mass or less.
The resin C contains 0.10 mol% or more and 30.00 mol% or less of the isosorbide unit represented by the above formula (14) as a constituent component.
The content of the resin C in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 1.0% by mass or more and 35.0% by mass or less.

<Toner>
The toner used in the present invention will be described in more detail. The toner particles contained in the toner of the present invention have a resin. The resin contained in the toner particles contains a resin C (hereinafter, also referred to as “resin C”) containing an isosorbide unit represented by the formula (14) as a constituent component.

The resin C having the isosorbide unit described in the present invention is preferably a polyester resin using isosorbide as an alcohol component. When the resin C is a polyester resin, the resin C contains a dibasic acid or an anhydride thereof and an isosorbide represented by the following formula (17) and a divalent alcohol in a nitrogen atmosphere in a composition ratio in which a carboxyl group remains. It can be prepared by a method such as dehydration condensation at a reaction temperature of 180 to 260 ° C. Further, if necessary, a trifunctional or higher polybasic acid or an anhydride thereof, a monobasic acid, a trifunctional or higher alcohol, a monohydric alcohol, or the like can be used.

Examples of the divalent alcohol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3.3) -2,2-bis (4-hydroxy). Phenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis ( Alkylene oxide adducts of bisphenol A such as 4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2- Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, Alipylene diols such as dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol;

Examples of trihydric or higher alcohols include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, and the like. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene. Be done.

On the other hand, examples of the acid component such as the dibasic acid include the following.
Aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; aliphatic polyvalent carboxylic acids such as fumaric acid, maleic acid, adipic acid, succinic acid; dodecenyl succinic acid, An aliphatic polyvalent carboxylic acid of succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms such as octenyl succinic acid; an anhydride of those acids and an alkyl (carbon) of those acids. Numbers 1-8) Ester. Among them, a polyester resin obtained by polycondensing a bisphenol derivative as an alcohol component and a divalent or higher carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof as an acid component can be preferably used. ..

In the present invention, it is preferable that the resin C contains the isosorbide unit represented by the formula (14) in an amount of 0.10 mol% or more as a constituent component from the viewpoint of effectively exhibiting good cleaning properties. Further, from the viewpoint of stability of the charge amount of the toner, it is more preferably 30.00 mol% or less. That is, it is more preferable that the resin C contains the isosorbide unit represented by the formula (14) in an amount of 0.10 mol% or more and 30.00 mol% or less. Further, it is more preferably contained in an amount of 0.50 mol% or more and 20.0 mol% or less.

The composition of the resin C can be confirmed by a 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.

In the present invention, the acid value of the resin C is preferably 0.5 mgKOH / g or more and 25.0 mgKOH / g or less from the viewpoint of maintaining a good charge amount of the toner. Further, it is more preferably 1.5 mgKOH / g or more and 20.0 mgKOH / g or less. The acid value (mgKOH / g) of the resin C can be controlled by the monomer composition ratio at the time of polymerization and the like.

In the present invention, as the resin, a conventionally known styrene acrylic resin, styrene resin, acrylic resin, or polyester resin may be used in combination with the resin C. When a resin other than the resin C is used in combination, the content of the resin C in the toner with respect to the total resin having a number average molecular weight (Mn) of 1500 or more is 1.0% by mass or more and 35.0% by mass or less. preferable. It is preferable that the content of the resin C is 1.0% by mass or more from the viewpoint of effectively obtaining good cleaning properties. Further, the content of the resin C is preferably 35.0% by mass or less from the viewpoint of suppressing the hygroscopic characteristics of the toner.

In the toner of the present invention, the content of the resin C is expressed as a ratio (mass%) with respect to the total resin having a number average molecular weight (Mn) of 1500 or more in the toner as described above. That is, the content of the resin C in the present invention is represented by the following formula.
(Formula) Resin C content (mass%) = 100 × {resin C (mass) / total resin (mass) having a number average molecular weight (Mn) of 1500 or more in toner}
Similarly, when a resin other than the resin C is used in combination, the content of the resin other than the resin C is expressed as a ratio (mass%) with respect to the total resin having a number average molecular weight (Mn) of 1500 or more in the toner.

In the present invention, the resin C is more preferably used in combination with the styrene acrylic resin. Further, when the content of the styrene acrylic resin in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 50.0% by mass or more and 99.0% by mass or less, the chargeability of the toner is good. It is particularly preferable because it can be used. More preferably, it is 60% by mass or more and 80% by mass or less.

Specifically, the charge amount of the toner can be optimized by the configuration, and the charge amount distribution of the toner can be sharpened. As a result, when the toner of the present invention is used in a one-component developing method or the like, it is possible to provide an image in which the image density is good and the generation of fog is suppressed. It is considered that the resistance value of the toner is optimized by allowing both the low resistance resin C and the high resistance styrene acrylic resin to exist in the optimum amounts, and as a result, the charge amount distribution of the toner becomes sharp. ing.

The styrene acrylic resin preferable to be used in combination with the resin C of the present invention is a copolymer of a styrene monomer and an acrylic monomer. Examples of acrylic monomers include acrylic acid and methacrylic acid; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, and methacrylic acid. Octyl, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, Examples thereof include acrylic acid ester-based monomers such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate; and methacrylic acid ester-based monomers.

Further, an aromatic vinyl monomer other than the styrene monomer may be used in combination with the styrene monomer and the acrylic monomer. Examples of the aromatic vinyl monomer include o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, and p-ethylstyrene. , 2,4-Dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, Examples thereof include styrene derivatives such as pn-dodecylstyrene.

In the present invention, a cross-linking agent may be used in order to increase the mechanical strength of the toner and control the molecular weight of the styrene acrylic resin.

The cross-linking agent includes divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol diacrylate as bifunctional cross-linking agents. , 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # Examples of 600 diacrylates, dipropylene glycol diacrylates, polypropylene glycol diacrylates, polyester type diacrylates (MANDA, manufactured by Nippon Kayaku Co., Ltd.), and the above diacrylates replaced with dimethacrylate can be mentioned.

On the other hand, examples of the polyfunctional cross-linking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and its methacrylate, and 2,2-bis (4-methacryloxy). Polyethoxyphenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate and the like can be mentioned.

In the present invention, the peak molecular weight (Mp) of the styrene acrylic resin is preferably 5,000 or more and 30,000 or less, and more preferably 8,000 or more and 27,000 or less. When the peak molecular weight (Mp) of the styrene acrylic resin is less than 5000, the molecular movement of the molecular chain of the resin C coexisting with the styrene acrylic resin tends to be large, and the moisture absorption in a high humidity environment tends to be high. The charge amount of the toner tends to decrease. Further, when the peak molecular weight (Mp) exceeds 30,000, the compatibility between the styrene acrylic resin and the resin C tends to decrease, a large domain of the resin C is likely to be formed in the toner, and the charge amount distribution of the toner is broad. It is easy to become.
The peak molecular weight (Mp) of the resin can be measured using an existing device such as gel permeation chromatography (GPC).

The toner of the present invention may contain a colorant. As the colorant, known ones can be used.

Examples of the black colorant include those toned in each color using carbon black, a magnetic material, and the following yellow, magenta, and cyan colorants.

Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, Examples thereof include 155, 168, 180, 185 and 214.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221 238, 254, 269, C.I. I. Pigment Bio Red 19 and the like can be exemplified.

Examples of the cyan colorant include a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like can be exemplified.

These colorants can be used alone or in admixture, and even in the form of a solid solution. The colorant is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner. The amount of the colorant added is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin.

In the toner of the present invention, it is also possible to contain a magnetic material to obtain a magnetic toner. In this case, the magnetic material can also serve as a colorant.

Examples of the magnetic material include the following iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc and antimony. Examples thereof include alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

The magnetic material is preferably surface modified. When the magnetic toner is prepared by the suspension polymerization method, it is preferable that the magnetic toner is hydrophobized with a surface modifier which is a substance that does not inhibit polymerization. Examples of such a surface modifier include a silane coupling agent and a titanium coupling agent.

The magnetic material preferably has a number average particle diameter of 2 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. The content in the toner is preferably 20 parts by mass or more and 200 parts by mass or less, and more preferably 40 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin.

The toner of the present invention may contain wax. Examples of the wax include the following.
Petroleum waxes such as paraffin wax, microcrystallin wax, petrolactam and derivatives thereof; Montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof by Fishertropus method; polyolefin waxes such as polyethylene wax and polypropylene wax and derivatives thereof; Natural waxes such as carnauba wax and candelilla wax and their derivatives. Examples of the derivative include oxides, block copolymers with vinyl-based monomers, and graft-modified products. Further, the following can be mentioned. Higher fatty alcohols; fatty acids such as stearic acid and palmitic acid; acid amide waxes; ester waxes; hardened castor oil and its derivatives; plant waxes; animal waxes. Of these, ester wax and hydrocarbon wax are particularly preferable from the viewpoint of excellent mold releasability. More preferably, a compound having the same total carbon number of 50% by mass or more and 95% by mass or less is contained in the wax, which has high wax purity and is preferable from the viewpoint of developability.

The content of the wax is preferably 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin. More preferably, it is 3 parts by mass or more and 25 parts by mass or less. When the wax content is 1 part by mass or more and 40 parts by mass or less, the bleeding property of the wax can be appropriately obtained when the toner is heated and pressed, so that the wrapping resistance at high temperature is improved. Further, even if the toner is stressed during development or transfer, the wax is less exposed on the toner surface, and uniform chargeability of each toner can be obtained.

The toner of the present invention preferably has inorganic fine particles externally added to the toner particles for the purpose of improving fluidity and the like.
The inorganic fine particles externally added to the toner particles preferably contain at least silica fine particles. The number average particle size of the primary particles of the silica fine particles is preferably 4 nm or more and 80 nm or less. When the number average particle size of the primary particles of the silica fine particles is in the above range, the fluidity of the toner is improved and the storage stability of the toner is also improved.
The number average particle diameter of the primary particles of the inorganic fine particles is determined by observing with a scanning electron microscope, measuring the particle diameter of 100 primary particles of the inorganic fine particles in the visual field, and calculating the arithmetic mean.

As the inorganic fine particles, silica fine particles and fine particles of titanium oxide, alumina or a compound oxide thereof can be used in combination. Titanium oxide is preferable as the inorganic fine particles used in combination.

The silica fine particles include both fine particles of dry silica produced by vapor phase oxidation of a silicon halide or dry silica called fumed silica, and wet silica produced from water glass. As silica, less silanol groups on the inner surface and the silica, also Na 2 _O, who SO ₃ ^2-less dry silica of production residue is preferable. In addition, dry silica can also obtain composite fine particles of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the manufacturing process. .. Silica also includes them.

Inorganic fine particles are also added to homogenize the triboelectricity of the toner. By hydrophobizing the inorganic fine particles, it is possible to impart functions such as adjusting the triboelectric charge of the toner, improving environmental stability, and improving the characteristics in a high humidity environment. It is preferable to use fine particles. When the inorganic fine particles externally attached to the toner particles absorb moisture, the triboelectric charge amount of the toner tends to decrease, and the developability and transferability tend to decrease.

Examples of the treatment agent for the hydrophobic treatment of the inorganic fine particles include the following.
Unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, organic titanium compounds. These treatment agents may be used alone or in combination.

Among them, inorganic fine particles treated with silicone oil are preferable. More preferably, the hydrophobic treated inorganic fine particles treated with silicone oil at the same time as the hydrophobic treatment with the coupling agent or after the hydrophobic treatment with the coupling agent rub the toner particles even in a high humidity environment. It is good in that the charge amount can be maintained high and the selective developability can be reduced.

The amount of the inorganic fine particles added is usually 0.01 parts by mass or more and 10 parts by mass or less, and preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the toner particles.

The method for producing the toner of the present invention is not particularly limited, and conventionally known methods such as a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and a pulverization method can be used. Among the above, the suspension polymerization method can easily control the presence state of the resin C in the vicinity of the toner surface by utilizing the polar balance between water and the toner material. Therefore, the suspension polymerization method is a more preferable form in order to improve the chargeability of the toner.

The method for producing toner particles using the suspension polymerization method will be described below.
First, a polymerizable monomer composition containing a resin C, a polymerizable monomer that produces a resin other than the resin C if necessary, and other components such as a colorant, if necessary, is water-based. Granulate in a medium and polymerize the polymerizable monomer contained in the polymerizable monomer composition. The particles obtained by the polymerization may be converted into toner particles through filtration, washing, and drying steps.

A dispersant may be added to the aqueous medium in order to uniformly disperse the polymerizable monomer composition and granulate the droplets of the polymerizable monomer composition.

When a styrene acrylic resin is used, in the suspension polymerization method, a styrene monomer and an acrylic monomer may be used as the polymerizable monomer as a method for adjusting the content of the styrene acrylic resin in the toner. Styrene acrylic resin may be added in advance to adjust the turbid polymerization.

The polymerization initiator used in the suspension polymerization method may be added at the same time when other additives are added to the polymerizable monomer, or the polymerizable monomer composition is granulated in an aqueous medium. It may be mixed immediately before. Further, immediately after granulation and before starting the polymerization reaction, a polymerizable monomer or a polymerization initiator dissolved in a solvent may be added.

Examples of the polymerization initiator include the following.
2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichloro Peroxide-based polymerization initiators such as benzoyl peroxide, lauroyl peroxide, and tert-butyl-peroxypivalate.

The amount of these polymerization initiators used varies depending on the desired degree of polymerization, but is generally 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the above-mentioned polymerizable monomer. preferable. The type of polymerization initiator is slightly different depending on the purpose, but is selected with reference to the 10-hour half-life temperature, and is used alone or in combination.

As the dispersant for dispersing the polymerizable monomer composition in the aqueous medium, known inorganic and organic dispersants can be used.

Examples of the inorganic dispersant include the following.
Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina ..

On the other hand, examples of the organic dispersant include the following.
Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch.

Further, as a dispersant for dispersing the polymerizable monomer composition in an aqueous medium, a commercially available nonionic, anionic or cationic surfactant can also be used. Examples of such a surfactant include the following.
Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.

Among the dispersants for dispersing the above-mentioned polymerizable monomer composition in an aqueous medium, an inorganic poorly water-soluble dispersant is preferable, and an acid-soluble poorly water-soluble inorganic dispersant is used. It is more preferable to use it.

The amount of the dispersant used is preferably 0.2 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Further, the aqueous medium is preferably prepared by using 300 parts by mass or more and 3,000 parts by mass or less of water with respect to 100 parts by mass of the polymerizable monomer composition.

In the present invention, when preparing an aqueous medium in which the above-mentioned poorly water-soluble inorganic dispersant is dispersed, a commercially available dispersant may be used as it is for dispersion. Further, in order to obtain particles of the dispersant having a fine and uniform particle size, a poorly water-soluble inorganic dispersant may be produced and prepared in an aqueous medium under high-speed stirring. For example, when tricalcium phosphate is used as a dispersant, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high-speed stirring to form tricalcium phosphate fine particles.

<Electrophotophotoreceptor>
The electrophotographic photosensitive member used in the present invention will be described in more detail.
As the electrophotographic photosensitive member, generally, a cylindrical electrophotographic photosensitive member in which a photosensitive layer (charge generation layer, charge transport layer) is formed on a cylindrical support is widely used, but a belt-shaped or sheet It is also possible to make it into a shape such as a shape.

As the support, a support having conductivity (conductive support) is preferable, and a metal support such as aluminum, an aluminum alloy, or stainless steel can be used. In the case of a support made of aluminum or an aluminum alloy, it has an ED tube (Extrusion Drawing), an EI tube (Extrusion Ironing), and cutting and electrolytic compound polishing (electrolytic and polishing action by an electrode having an electrolytic action and an electrolyte solution). Polishing with a grindstone), wet or dry honing supported supports can also be used. Further, a metal support or a resin support on which an aluminum, an aluminum alloy or an indium oxide-tin oxide alloy is formed by vacuum vapor deposition can also be used. The surface of the support may be subjected to cutting treatment, roughening treatment, alumite treatment, or the like.
Further, a support obtained by impregnating a resin or the like with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, and silver particles, or a plastic having a conductive resin can also be used.

A conductive layer may be provided between the support and the undercoat layer or the charge generation layer described later for the purpose of suppressing interference fringes due to scattering of laser light or the like and covering scratches on the support. This is a layer formed by using a coating liquid for a conductive layer in which conductive particles are dispersed in a resin. Examples of the conductive particles include carbon black, acetylene black, metal powders such as aluminum, nickel, iron, dichrome, copper, zinc, and silver, and metal oxide powders such as conductive tin oxide and ITO. Can be mentioned.
Examples of the resin used for the conductive layer include polyarylate resin, polycarbonate resin, polyvinyl butyral resin, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin and alkyd resin.
Examples of the solvent of the coating liquid for the conductive layer include an ether solvent, an alcohol solvent, a ketone solvent and an aromatic hydrocarbon solvent.
The film thickness of the conductive layer is preferably 0.2 μm or more and 40 μm or less, more preferably 1 μm or more and 35 μm or less, and further preferably 5 μm or more and 30 μm or less.

In the electrophotographic photosensitive member used in the present invention, an undercoat layer may be provided between the support or the conductive layer and the charge generation layer.
The undercoat layer can be formed by applying a resin-containing undercoat layer coating liquid onto a support or a conductive layer and drying or curing the undercoat layer.
Examples of the resin used for the undercoat layer include polyacrylic acids, methyl cellulose, ethyl cellulose, polyamide resin, polyimide resin, polyamide imide resin, polyamic acid resin, melamine resin, epoxy resin, polyurethane resin, and polyolefin resin.
The film thickness of the undercoat layer is preferably 0.05 μm or more and 7 μm or less, and more preferably 0.1 μm or more and 2 μm or less.
Further, the undercoat layer may contain semi-conductive particles, an electron transporting substance, or an electron accepting substance.

A charge generation layer is provided on the support, the conductive layer or the undercoat layer.
Examples of the charge generating substance used in the charge generating layer include azo pigments, phthalocyanine pigments, indigo pigments and perylene pigments. Only one kind of these charge generating substances may be used, or two or more kinds may be used. Among these, metal phthalocyanines such as oxytitanium phthalocyanine, hydroxygallium phthalocyanine, and chlorogallium phthalocyanine are particularly preferable because of their high sensitivity.
Examples of the resin used for the charge generation layer include polycarbonate resin, polyarylate resin, butyral resin, polyvinyl acetal resin, acrylic resin, vinyl acetate resin and urea resin. Among these, butyral resin is particularly preferable. These can be used alone, mixed or as a copolymer of one or more.
The charge generation layer can be formed by applying a coating liquid for a charge generation layer obtained by dispersing a charge generation substance together with a resin and a solvent, and drying the obtained coating film. Further, the charge generation layer may be a vapor deposition film of a charge generation substance.

Examples of the dispersion method include a method using a homogenizer, ultrasonic waves, a ball mill, a sand mill, an attritor, and a roll mill.
The ratio of the charge generating substance to the resin is preferably in the range of 1:10 to 10: 1 (mass ratio), and more preferably in the range of 1: 1 to 1: 1 (mass ratio).
Examples of the solvent used in the coating liquid for the charge generation layer include alcohol-based solvents, sulfoxide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, aromatic hydrocarbon solvents, and the like.
The film thickness of the charge generation layer is preferably 0.01 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 2 μm or less.
Further, various sensitizers, antioxidants, ultraviolet absorbers, plasticizers and the like can be added to the charge generation layer as needed. Further, in order to prevent the flow of charges from being blocked in the charge generation layer, the charge generation layer may contain an electron transporting substance or an electron accepting substance.

A charge transport layer is provided on the charge generation layer. When the charge transport layer is the outermost surface, the charge transport layer is the surface layer. Further, when the charge transport layers are laminated and used, the charge transport layer located on the outermost surface becomes the surface layer. Further, a protective layer may be provided on the charge transport layer, in which case the protective layer becomes a surface layer.

In the present invention, the surface layer is at least one selected from the group consisting of a polyarylate resin A having a polysiloxane structure represented by the formula (1) and a polycarbonate resin B having a polysiloxane structure represented by the formula (1). Contains seed resin.

Further, in the present invention, it contains fluororesin particles and at least one resin selected from the group consisting of polyarylate resin and polycarbonate resin.

The surface layer having such a structure has good cleanability. The present inventors consider that there are mainly the following three reasons for improving the cleanability.

The first is considered to be that the toner having the isosorbide unit is hard to adhere to the surface layer of the fluororesin particles or the electrophotographic photosensitive member having a polysiloxane structure. When the present inventors searched for factors that affect the adhesive force between resins, they found that the adhesion energy between resins correlates with the solubility parameter (SP value) of the resins. FIG. 2 is a graph in which the adhesion energy between various resins and urethane rubber is measured, the SP value of each resin is taken on the horizontal axis, and the adhesion energy between the resin and urethane rubber is plotted on the vertical axis. From this, it can be seen that the larger the difference in SP value between the resin and the urethane rubber, the smaller the adhesion energy. In the present invention, the surface layer of the electrophotographic photosensitive member has fluororesin particles or polysiloxane structure having a low SP value, and the surface of the toner has an isosorbide unit having a high SP value, so that the electrophotographic photosensitive member does not have these. It is considered that the adhesive force between the solids is weakened because the SP values are separated from each other as compared with the body and the toner.

If the toner does not easily adhere to the surface layer of the electrophotographic photosensitive member, the toner does not adhere to the surface of the photoconductor at the contact nip portion between the cleaning blade and the photoconductor, and easily spreads over the entire vicinity of the contact nip portion (initial stage). The toner that was unevenly distributed in the above is easily leveled in the longitudinal direction of the cleaning blade), so that a uniform retention layer is easily formed. Further, since the toner becomes slippery on the surface of the photoconductor, the force of rotating the toner exerted by the surface of the photoconductor to be rubbed and the cleaning blade in the vicinity of the contact nip portion is less likely to be transmitted to the toner (with respect to the toner). It becomes difficult for the force in the direction of rotation to act). It is considered that when the rolling of the toner in the vicinity of the abutting nip portion is suppressed, it becomes difficult for the cleaning blade to be pushed up by the rotational force of the toner, and the toner can be prevented from slipping through the abutting nip.

The second reason is that the isosorbide unit contained in the toner exhibits hydrophilicity, which is considered to be due to an appropriate interaction between the toners. By having an appropriate interaction between the toners, even if the amount of toner existing near the contact nip between the blade and the photoconductor is small, the function to dam the transfer residual toner and the external additive that are carried. It is thought that it will be easier to fulfill.

The third reason is that the presence of fluororesin particles and polysiloxane structure in the surface layer of the electrophotographic photosensitive member can stabilize the stick-slip motion of the blade due to the low friction effect of the fluororesin particles and polysiloxane. it is conceivable that. As a result, even if the amount of toner present in the vicinity of the abutting nip portion is small, chatter vibration of the blade does not occur, and it is considered that the retention layer is formed quickly.

Due to the synergistic effect of the above mechanisms, it is considered that the image forming method, the process cartridge and the electrophotographic apparatus of the present invention have good cleanability and can suppress deterioration of image quality due to contamination of the charged member.

Next, a polyarylate resin A (hereinafter, also referred to as "polyarylate resin A") whose surface layer has a polysiloxane structure represented by the formula (1), and a polycarbonate resin B having a polysiloxane structure represented by the formula (1). A configuration containing at least one resin selected from the group consisting of (hereinafter, also referred to as “polycarbonate resin B”) will be described in detail.

The content of the polysiloxane structure represented by the formula (1) in the polyarylate resin A and the polycarbonate resin B is preferably 5.0% by mass or more and 60% by mass or less. The content is preferably 5.0% by mass or more from the viewpoint of obtaining good cleanability. Further, it is preferable that the content is 60% by mass or less from the viewpoint that the effect of improving the cleanability can be stably obtained. Further, the content is more preferably 10% by mass or more and 50% by mass or less. The content of the structure represented by the formula (1) contained in the polyarylate resin A and the polycarbonate resin B is a hydrogen atom (hydrogen constituting the resin) measured by ¹ H-NMR of the resin, which is a general method. It can be confirmed by a conversion method based on the peak area ratio of (atom).

The degree of presence of the silicon-containing compound on the outermost surface of the electrophotographic photosensitive member can be known by measuring the abundance ratio of the silicon element to the constituent elements on the outermost surface. In the present invention, the abundance ratio of silicon element to the constituent elements on the outermost surface of the surface layer of the electrophotographic photosensitive member obtained by using X-ray photoelectron spectroscopy (ESCA) is 3.0 atomic% or more. Is preferable. When the abundance ratio of the silicon element is 3.0 atomic% or more, better cleaning property can be obtained. Furthermore, it is more preferable that the abundance ratio of the silicon element is 5.0 atomic% or more. Further, it is preferable that the abundance ratio of the silicon element is 30 atomic% or less because good cleanability can be obtained more stably.

In the present invention, the measurement of the abundance ratio of the silicon element to the constituent elements on the outermost surface of the surface layer of the electrophotographic photosensitive member by X-ray photoelectron spectroscopy (ESCA) was performed as follows.
Equipment used:
Quantum 2000 Scanning ESCA Microprobe manufactured by PHI (Physical Electronics Industries, INC.)
Measurement condition:
Excited X-ray: Al Kα
Photoelectron escape angle: 45 °
X-ray: 100 μm 25 W 15 kV
Raster: 300 μm x 200 μm
Electronic neutralization gun: 20μA, 1V
Ion neutralization gun: 7mA, 10V
Pass Energy: 58.70eV
Step Size: 0.125eV
Sweep: F (10 times), C (10 times), O (10 times), Si (30 times), N (30 times)
From the peak intensity of each element measured under the above conditions, the surface atomic concentration (atomic%) was calculated using the relative sensitivity factor provided by PHI, and the abundance ratio of silicon element to the constituent elements on the outermost surface of the surface layer was calculated. To do.

In the present invention, the polysiloxane structure of the polyarylate resin A and the polycarbonate resin B is preferably a polysiloxane structure represented by the following formula (15) because the effects of the present invention can be more easily obtained. This is because the polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the formula (15), so that the polyarylate resin A and the polycarbonate resin B are easily localized to the outermost surface of the surface layer, and the outermost surface is easily localized. It is considered that the abundance of polysiloxane in is increased.
R ^{151 to} R ¹⁵⁴ in the formula (15) each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Further, R ^{151 to} R ¹⁵⁴ in the formula (15) are preferably a methyl group or a phenyl group.
Z in formula (15) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
N in the formula (15) represents an integer of 10 or more and 200 or less.

Further, in the present invention, the polyarylate resin A or the polycarbonate resin B is a polyarylate resin having a polysiloxane structure represented by the following formula (2) at least at least a part of the end, or at least a part of the following formula (2). It is preferable that the polycarbonate resin has the polysiloxane structure shown by. In a polyarylate resin having a polysiloxane structure represented by the formula (2) at least a part of the terminal, the structural unit constituting the main chain to which the polysiloxane structure represented by the formula (2) is bonded to the terminal will be described later. Equations (9) and (10) can be mentioned. In the polycarbonate resin represented by the formula (2) at least a part of the terminal, the structural unit constituting the main chain to which the polysiloxane structure represented by the formula (2) is bonded to the terminal is the structural unit described later in the formula (11). And (12).

Further, the polyarylate resin A or the polycarbonate resin B is a polyarylate resin having at least one of the structural units represented by the following formulas (3) to (5), or is represented by the following formulas (6) to (8). It is preferably a polycarbonate resin having at least one structural unit. From the viewpoint of more effectively obtaining the effects of the present invention, a polyarylate resin having a polysiloxane structure represented by the formula (2) at least a part of the terminal or a poly represented by the formula (2) at least a part of the terminal. It is more preferable that it is either a polycarbonate resin having a siloxane structure, a polyarylate resin having a structural unit represented by the formula (5), or a polycarbonate resin having a structural unit represented by the formula (8). This is a polyarylate resin A having a polysiloxane structure represented by the formula (2) at least a part of the terminal, or having a structural unit represented by the formula (5) or a structural unit represented by the formula (8). In addition to being easily localized to the outermost surface of the surface layer of the polycarbonate resin B, the polysiloxane structure in the resin localized on the outermost surface is likely to be oriented toward the outermost surface, so that the polysiloxane on the outermost surface is easily localized. It is thought that this is because the abundance is further increased.

The polyarylate resin A and the polycarbonate resin B may be used alone or in combination of two or more.

The structures represented by the formulas (2) to (8) will be described in detail below.
Formula (2) is a monovalent group, and R ^{21 to} R ²⁴ in the formula (2) independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, an alkyl group or a phenyl group is preferable, and a methyl group or a phenyl group is more preferable.
Z in the formula (2) represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.
N in the formula (2) indicates the number of repetitions of the structure in parentheses, and is an integer of 10 or more and 200 or less from the viewpoint of achieving both good cleanability and electrical characteristics.
M in the equation (2) indicates the number of repetitions of the structure in parentheses, and is an integer of 1 or more and 3 or less.

Specific examples of the structure represented by the formula (2) are shown below, but the present invention is not limited thereto.

Among these, the structures represented by the formulas (2-1), (2-2), (2-5), (2-7), (2-11) or (2-13) are preferable. Further, the above structure may be used alone or in combination.
R ^{31 to} R ³⁴ in the formula (3) independently represent a hydrogen atom, an alkyl group, a fluoroalkyl group, or a substituent represented by the following formula (3-A), and among R ^{31 to} R ³⁴ . At least one is a substituent represented by the formula (3-A).
X ³ in the formula (3) shows a m- phenylene group, p- phenylene, or two p-2 monovalent group phenylene groups bonded via an oxygen atom.
Y ³ is single bond in the formula (3), a methylene group, an ethylidene group, a propylidene group or a phenyl ethylidene group.

Specific examples of the structural unit represented by the formula (3) are shown below, but the present invention is not limited thereto. In formulas (3-1) to (3-14), A represents formula (3-A).

Among these, the formulas (3-1), (3-2), (3-3), (3-4), (3-5), (3-6), (3-7) or (3-3) The structural unit shown in 11) is preferable. Further, the above structural units may be used alone or in combination.
R ^{311 to} R ³¹⁴ in the formula (3-A) each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, an alkyl group or a phenyl group is preferable, and a methyl group is more preferable.
Z in the formula (3-A) represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.
N in the formula (3-A) indicates the number of repetitions of the structure in parentheses. From the viewpoint of achieving both good cleanability and electrical characteristics, the average value of n is 10 or more and 200 or less. Further, it is preferable that each value of the number of repetitions n of the structure in parentheses is within ± 10% of the value indicated by the average value of n, from the viewpoint that the effect of the present invention can be stably obtained.
M in the formula (3-A) indicates the number of repetitions of the structure in parentheses. The average value of m is 0 or more and 5 or less.

Specific examples of the groups represented by the formula (3-A) are shown below, but the present invention is not limited thereto.

Among these, structural units represented by the formulas (3-A-1), (3-A-2), (3-A-4) or (3-A-7) are preferable. Further, the above structural units may be used alone or in combination.
R ^{41 to} R ⁴⁴ in the formula (4) independently represent a hydrogen atom, an alkyl group, or a fluoroalkyl group, respectively. Of these, a hydrogen atom or a methyl group is preferable.
R ⁴⁵ in the formula (4) represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, a hydrogen atom, a methyl group or a phenyl group is preferable.
X ⁴ in the formula (4) shows a m- phenylene group, p- phenylene, or two p-2 monovalent group phenylene groups bonded via an oxygen atom.
V in the formula (4) represents at least one of the structures represented by the following formulas (4-A) and (4-B).

Specific examples of the structural unit represented by the formula (4) are shown below, but the present invention is not limited thereto. In formulas (4-1) to (4-12), V represents formula (4-A) or (4-B).

Among these, the structural unit represented by the formulas (4-1), (4-2), (4-3), (4-4), (4-5) or (4-6) is preferable. Further, the above structural units may be used alone or in combination.
R ^{411 to} R ⁴¹⁴ in the formula (4-A) each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, a methyl group is preferable.
Z in the formula (4-A) represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.

N in the formula (4-A) indicates the number of repetitions of the structure in parentheses. From the viewpoint of achieving both good cleanability and electrical characteristics, the average value of n is 10 or more and 200 or less. Furthermore, the average value of n is preferably 10 or more and 100 or less. Further, it is preferable that each value of the number of repetitions n of the structure in parentheses is within ± 10% of the value indicated by the average value of n, from the viewpoint that the effect of the present invention can be stably obtained.

M in the formula (4-A) indicates the number of repetitions of the structure in parentheses. From the viewpoint of obtaining good cleanability, the average value of m is 3 or more and 20 or less. Further, it is preferable that the difference between the maximum value and the minimum value of the number of repetitions m of the structure in parentheses is 0 or more and 3 or less from the viewpoint that the effect of the present invention can be stably obtained.

R ^{421 to} R ⁴²⁸ in the formula (4-B) each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, a methyl group is preferable.
Z ¹ and Z ² in the formula (4-B) independently represent an alkyl group having 1 to 4 carbon atoms or a phenyl group.

N ¹ and n ² in the formula (4-B) indicate the number of repetitions of the structure in parentheses. From the viewpoint of achieving both good cleanability and electrical characteristics, the average value of n ^{1 and} the average value of n ² are independently 10 or more and 200 or less, and the average value of n ^{1 and} the average value of n ² are the same. The total value is 20 or more and 250 or less. Further, it is preferable that the average value of n ^{1 and} the average value of n ² are independently 10 or more and 100 or less. Further, it is found that the individual values of the number of repetitions n ¹ and n ² of the structure in parentheses are within ± 10% of the values indicated by the average value of n ^{1 and} the average value of n ² , respectively. It is preferable in that the effect of the invention can be stably obtained.

M in the formula (4-B) indicates the number of repetitions of the structure in parentheses. From the viewpoint of obtaining good cleanability, the average value of m is 3 or more and 20 or less. Further, it is preferable that the difference between the maximum value and the minimum value of the number of repetitions m of the structure in parentheses is 0 or more and 3 or less from the viewpoint that the effect of the present invention can be stably obtained.

X ⁵ in the formula (5) 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.
M ¹ and m ² in the formula (5) indicate the number of repetitions of the structure in parentheses. The average value of m ^{1 and} the average value of m ² are independently 1 or more and 3 or less.
W in the formula (5) shows the structure represented by the following formula (5-A).

Specific examples of the structural unit represented by the formula (5) are shown below, but the present invention is not limited thereto. In formulas (5-1) to (5-6), W represents formula (5-A).

Among these, the structural unit represented by the formula (5-1), (5-2) or (5-3) is preferable. Further, the above structural units may be used alone or in combination.

R ^{511 to} R ⁵²⁰ in the formula (5-A) each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, a methyl group is preferable.
Z in the formula (5-A) represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.

N in the formula (5-A) indicates the number of repetitions of the structure in parentheses. From the viewpoint of achieving both good cleanability and electrical characteristics, the average value of n is 10 or more and 200 or less. Furthermore, the average value of n is preferably 10 or more and 150 or less. Further, it is preferable that each value of the number of repetitions n of the structure in parentheses is within ± 10% of the value indicated by the average value of n, from the viewpoint that the effect of the present invention can be stably obtained.

K and l in the formula (5-A) indicate the number of repetitions of the structure in parentheses. The average value of k and the average value of l are independently 1 or more and 10 or less. Further, it is preferable that the difference between the maximum value and the minimum value of the number of repetitions k and l of the structure in parentheses is 0 or more and 3 or less independently.

R ^{61 to} R ⁶⁴ in the formula (6) independently represent a hydrogen atom, an alkyl group, a fluoroalkyl group, a phenyl group, or a substituent represented by the following formula (6-A), and are R ^{61 to} R. ^At least one of ⁶⁴ is a substituent represented by the formula (6-A).
Y ⁶ in the formula (6) represents a single bond, a methylene group, ethylidene group, propylidene group, a phenyl ethylidene group, a cyclohexylidene group, or an oxygen atom.

Specific examples of the structural unit represented by the formula (6) are shown below, but the present invention is not limited thereto. In formulas (6-1) to (6-9), A represents formula (6-A).

Among these, the structural units represented by the formulas (6-1), (6-3), (6-5), (6-6) or (6-8) are preferable. Further, the above structural units may be used alone or in combination.

R ^{611 to} R ⁶¹⁴ in the formula (6-A) each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, an alkyl group or a phenyl group is preferable, and a methyl group is more preferable.
Z in the formula (6-A) represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.
N in the formula (6-A) indicates the number of repetitions of the structure in parentheses. From the viewpoint of achieving both good cleanability and electrical characteristics, the average value of n is 10 or more and 200 or less. Further, it is preferable that each value of the number of repetitions n of the structure in parentheses is within ± 10% of the value indicated by the average value of n, from the viewpoint that the effect of the present invention can be stably obtained.
M in the formula (6-A) indicates the number of repetitions of the structure in parentheses. The average value of m is 0 or more and 5 or less.

Specific examples of the structure represented by the formula (6-A) are the same as those of the formulas (3-A-1) to (3-A-9). However, it is not limited to these. Further, the above structure may be used alone or in combination.

R ^{71 to} R ⁷⁴ in the formula (7) independently represent a hydrogen atom, an alkyl group, a fluoroalkyl group, or a phenyl group, respectively. Of these, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group is preferable.
R ⁷⁵ in the formula (7) represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, a hydrogen atom or a methyl group is preferable.
V in the formula (7) represents at least one of the structures represented by the following formulas (7-A) and (7-B).

Specific examples of the structural unit represented by the formula (7) are shown below, but the present invention is not limited thereto. In formulas (7-1) to (7-4), V represents formula (7-A) or (7-B).

Among these, the structural unit represented by the formula (7-1) or (7-2) is preferable. Further, the above structural units may be used alone or in combination.

R ^{711 to} R ⁷¹⁴ in the formula (7-A) each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, a methyl group is preferable.
Z in the formula (7-A) represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.

N in the formula (7-A) indicates the number of repetitions of the structure in parentheses. From the viewpoint of achieving both good cleanability and electrical characteristics, the average value of n is 10 or more and 200 or less. Furthermore, the average value of n is preferably 10 or more and 100 or less. Further, it is preferable that each value of the number of repetitions n of the structure in parentheses is within ± 10% of the value indicated by the average value of n, from the viewpoint of stably obtaining the effect of the present invention.

M in the formula (7-A) indicates the number of repetitions of the structure in parentheses. From the viewpoint of obtaining good cleanability, the average value of m is 3 or more and 20 or less. Further, it is preferable that the difference between the maximum value and the minimum value of the number of repetitions m of the structure in parentheses is 0 or more and 3 or less from the viewpoint that the effect of the present invention can be stably obtained.

R ^{721 to} R ⁷²⁸ in the formula (7-B) each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, a methyl group is preferable.
Z ¹ and Z ² in the formula (7-B) each independently represent an alkyl group having 1 to 4 carbon atoms or a phenyl group.

N ¹ and n ² in the formula (7-B) indicate the number of repetitions of the structure in parentheses. From the viewpoint of achieving both good cleanability and electrical characteristics, the average value of n ^{1 and} the average value of n ² are independently 10 or more and 200 or less, and the average value of n ^{1 and} the average value of n ² are the same. The total value is 20 or more and 250 or less. Further, it is preferable that the average value of n ^{1 and} the average value of n ² are independently 10 or more and 100 or less. Further, it is found that the individual values of the number of repetitions n ¹ and n ² of the structure in parentheses are within ± 10% of the values indicated by the average value of n ^{1 and} the average value of n ² , respectively. It is preferable in that the effect of the invention can be stably obtained.

M in the formula (7-B) indicates the number of repetitions of the structure in parentheses. From the viewpoint of obtaining good cleanability, the average value of m is 3 or more and 20 or less. Further, it is preferable that the difference between the maximum value and the minimum value of the number of repetitions m of the structure in parentheses is 0 or more and 3 or less from the viewpoint that the effect of the present invention can be stably obtained.

M ¹ and m ² in the formula (8) indicate the number of repetitions of the structure in parentheses. The average value of m ^{1 and} the average value of m ² are independently 1 or more and 3 or less.
W in the formula (8) shows the structure represented by the following formula (8-A).

Specific examples of the structural unit represented by the formula (8) are shown below, but the present invention is not limited thereto. In formulas (8-1) to (8-2), W represents formula (8-A).

Among these, the structural unit represented by the formula (8-1) is preferable. Further, the above structural units may be used alone or in combination.

R ^{811 to} R ⁸²⁰ in the formula (8-A) each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Of these, a methyl group is preferable.
Z in the formula (8-A) represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.

N in the formula (8-A) indicates the number of repetitions of the structure in parentheses. From the viewpoint of achieving both good cleanability and electrical characteristics, the average value of n is 10 or more and 200 or less. Furthermore, the average value of n is preferably 10 or more and 150 or less. Further, it is preferable that each value of the number of repetitions n of the structure in parentheses is within ± 10% of the value indicated by the average value of n, from the viewpoint that the effect of the present invention can be stably obtained.

K and l in the formula (8-A) indicate the number of repetitions of the structure in parentheses. The average value of k and the average value of l are independently 1 or more and 10 or less. Further, it is preferable that the difference between the maximum value and the minimum value of the number of repetitions k and l of the structure in parentheses is 0 or more and 3 or less independently.

In the present invention, the polyarylate resin A and the polycarbonate resin B may have structural units other than the structural units represented by the formulas (3) to (8) on the main chain skeleton. As the structural unit other than the structural units represented by the formulas (3) to (8), the structural units represented by the following formulas (9) to (12) are preferable.

In formula (9), R ^{91 to} R ⁹⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, respectively. Of these, a hydrogen atom or a methyl group is preferable. X ⁹ 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. Y ⁹ represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. Of these, a single bond or a divalent organic group having 1 to 3 carbon atoms is preferable.

In formula (10), R ^{101 to} R ¹⁰⁴ each independently represent a methyl group, an ethyl group, or a phenyl group. X ¹⁰ 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. n indicates the number of repetitions in parentheses. The average value of n is preferably 10 or more and 150 or less.

In formula (11), R ^{111 to} R ¹¹⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, respectively. Of these, a hydrogen atom or a methyl group is preferable. Y ¹¹ represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. Of these, a single bond, a divalent organic group having 1 to 3 carbon atoms, a phenylethylidene group, a cyclohexylidene group, or an oxygen atom is preferable.

In formula (12), R ^{121 to} R ¹²⁴ each independently represent a methyl group, an ethyl group, or a phenyl group. n indicates the number of repetitions in parentheses. The average value of n is preferably 10 or more and 150 or less.

Specific examples of the structural units represented by the formulas (9) to (12) are shown below, but the present invention is not limited thereto.

When structural units other than the structural units represented by the above formulas (3) to (8) are used in the polyarylate resin A and the polycarbonate resin B, they may be used alone or in combination.

Further, the polyarylate resin A and the polycarbonate resin B may contain a linear polysiloxane structure in the main chain instead of the polysiloxane structure represented by the formula (15). Specific examples thereof include a polyarylate resin having a structural unit represented by the formula (10) and a polycarbonate resin having a structural unit represented by the formula (12). Of these, polyarylate resins having structural units represented by the formulas (10-1) to (10-3) or polycarbonate resins having structural units represented by (12-1) are preferable. Further, the above structural units may be used alone or in combination.

The viscosity average molecular weight (Mv) of the polyarylate resin A and the polycarbonate resin B is preferably 1,000 or more and 200,000 or less. Further, it is preferably 5,000 or more and 100,000 or less from the viewpoint of synthesis and film forming property.

The polyarylate resin A and the polycarbonate resin B used in the present invention can be appropriately selected and synthesized from known methods such as a transesterification method, an interfacial polymerization method, and a direct polymerization method.

In the present invention, the surface layer of the electrophotographic photosensitive member is selected from the group consisting of a polyarylate resin A having a polysiloxane structure represented by the formula (1) and a polycarbonate resin B having a polysiloxane structure represented by the formula (1). Although it contains at least one resin, other resins may be used in combination as long as the effects of the present invention are not impaired. In that case, the total content of the polyarylate resin A and the polycarbonate resin B in the surface layer may be 0.1% by mass or more and 50% by mass or less with respect to the total mass of the total solid content contained in the surface layer. preferable. Further, when the polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the formula (2) at least a part of the terminals, the polyarylate in the surface layer can obtain good electrical characteristics of the photoconductor. The total content of the resin A and the polycarbonate resin B is more preferably 0.1% by mass or more and 20% by mass or less with respect to the total mass of the total solid content contained in the surface layer.

Examples of the resin that can be used together include acrylic resin, acrylonitrile resin, allyl resin, alkyd resin, epoxy resin, silicone resin, phenol resin, phenoxy resin, butyral resin, polyacrylamide resin, polyacetal resin, polyamideimide resin, and polyamide resin. Polyallyl ether resin, polyallylate resin, polyimide resin, polyurethane resin, polyester resin, polyethylene resin, polycarbonate resin, polystyrene resin, polysulfone resin, polyvinyl butyral resin, polyphenylene oxide resin, polybutadiene resin, polypropylene resin, methacrylic resin, urea resin, Examples thereof include vinyl chloride resin and vinyl acetate resin. In particular, polyester resin, polyarylate resin, and polycarbonate resin are preferable. Further, a polyarylate resin having a structural unit represented by the formula (9) or a polycarbonate resin having a structural unit represented by the formula (11) is more preferable. Specific examples of the structural unit represented by the formula (9) and the structural unit represented by the formula (11) are as described above. The resin that can be used in combination with the polyarylate resin A or the polycarbonate resin B can be used alone, as a mixture, or as a copolymer of one or more.

In the electrophotographic photosensitive member of the present invention, in addition to at least one resin selected from the group consisting of polyarylate resin A and polycarbonate resin B, polydimethylsiloxane represented by the following formula (16) is mixed and used. , It is preferable because it can exhibit more good cleaning property. It is considered that by further mixing the polydimethylsiloxane, the abundance ratio of the polysiloxane structure on the outermost surface of the electrophotographic photosensitive member is further increased, and the effect of reducing the adhesive force to the toner and the effect of reducing the friction with the cleaning blade are improved.
(In equation (16), n represents a positive integer of 10 or more and 200 or less.)
The mixing ratio of the polydimethylsiloxane represented by the formula (16) is 3.0% by mass or more and 20.0% by mass or less with respect to the polyarylate resin A and the polycarbonate resin B contained in the charge transport layer. preferable. When it is 3.0% by mass or more, the effect of improving the cleanability by mixing the polydimethylsiloxane can be easily obtained. Further, when it is 20.0% by mass or less, deterioration of electrophotographic characteristics due to an increase in residual potential can be suppressed.
It is particularly preferable that n in the formula (16) is 10 or more and 100 or less.

When polydimethylsiloxane is added alone, the residual potential tends to increase remarkably even with a small amount of addition, and the image density decreases due to the decrease in sensitivity and memory images such as ghosts tend to occur. However, by mixing at least one resin selected from the group consisting of the polyarylate resin A and the polycarbonate resin B according to the present invention with polydimethylsiloxane in the above range, it is difficult for the residual potential to increase, which is good. Excellent image quality can be obtained.

The surface layer may contain a charge transport material. Examples of the charge transporting substance include triarylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, stilben compounds, butadiene compounds, and enamine compounds. Only one kind of these charge transporting substances may be used, or two or more kinds thereof may be used.

Specific examples of charge transporting substances are shown below, but the present invention is not limited to these.

When the surface layer is a charge transport layer, it is formed by at least one resin selected from the group consisting of polyarylate resin A and polycarbonate resin B, and a coating liquid of a coating liquid obtained by dissolving a charge transport substance in a solvent. be able to. Further, as described above, a resin other than the polyarylate resin A and the polycarbonate resin B may be used in combination.

Further, the charge transport layer may have a laminated structure, and in that case, at least the charge transport layer on the outermost surface side contains at least one resin selected from the group consisting of polyarylate resin A and polycarbonate resin B.

The ratio of the charge-transporting substance to the total resin in the charge-transporting layer is preferably in the range of 3: 10 to 20:10 (mass ratio), and more preferably in the range of 5: 10 to 12:10 (mass ratio).

Examples of the solvent used for the coating liquid for the charge transport layer include a ketone solvent, an ester solvent, an ether solvent and an aromatic hydrocarbon solvent. These solvents may be used alone or in combination of two or more. Among these solvents, it is preferable to use an ether solvent or an aromatic hydrocarbon solvent from the viewpoint of resin solubility.

The film thickness of the surface layer is preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 35 μm or less.

Next, a case where the surface layer contains fluororesin particles and at least one resin selected from the group consisting of polyarylate resin and polycarbonate resin will be described in detail.

When an electrophotographic photosensitive member whose surface layer contains fluororesin particles and at least one resin selected from the group consisting of polyallylate resin and polycarbonate resin is repeatedly used, it is present on the outermost surface by rubbing with a cleaning blade. The soft fluororesin particles are spread (stretched) on the electrophotographic photosensitive member, and the area where the fluororesin is present on the electrophotographic photosensitive member is increased. Due to this spreading effect, even if the amount of the fluororesin particles contained in the surface layer is small, the above-mentioned cleaning property improving effect is likely to be exhibited. Further, the better the dispersibility of the fluororesin particles existing in the surface layer, the larger the area where the fluororesin exists due to the spreading effect, and the greater the effect of improving the cleanability.

The polyarylate resin used in the present invention is preferably a resin having a structural unit represented by the following formula (9).
In formula (9), R ^{91 to} R ⁹⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, respectively. Of these, a hydrogen atom or a methyl group is preferable. X ⁹ 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. Y ⁹ represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. Of these, a single bond or a divalent organic group having 1 to 3 carbon atoms is preferable.
Specific examples of the structural unit represented by the formula (9) are as described above.

Next, the polycarbonate resin used in the present invention will be described. The polycarbonate resin used in the present invention is preferably a resin having a structural unit represented by the following formula (11).
In formula (11), R ^{111 to} R ¹¹⁸ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, respectively. Of these, a hydrogen atom or a methyl group is preferable. Y ¹¹ represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. Of these, a single bond, a divalent organic group having 1 to 3 carbon atoms, a phenylethylidene group, a cyclohexylidene group, or an oxygen atom is preferable.
Specific examples of the structural unit represented by the formula (11) are as described above.

Next, the fluororesin particles used in the present invention will be described. The fluororesin particles used in the present invention are tetrafluoroethylene resin particles, trifluoroethylene resin particles, tetrafluoroethylene hexafluoropropylene resin particles, vinyl fluoride resin particles, vinylidene fluoride resin particles, and difluoride. Ethylene dichloride resin particles are preferred. Moreover, the particles of those copolymers are preferable. Among these, tetrafluoroethylene resin particles are more preferable.

The primary particle size of the fluororesin particles is preferably 0.05 μm to 1.0 μm, more preferably 0.1 μm to 0.6 μm. Better cleaning performance can be easily obtained when the particles are fine to some extent and uniformly dispersed in the surface layer. As a result, it is preferable that the fluororesin particles in the surface layer are dispersed in a secondary volume average particle size of 0.2 μm to 1.0 μm from the viewpoint of obtaining better cleaning performance.

A dispersion aid can be used to uniformly disperse the fluororesin particles in the surface layer. As the dispersion aid for the fluororesin particles, existing ones can be used, but it has both a site having an affinity for the fluororesin particles and a site having an affinity for the polyarylate of the surface layer or the polycarbonate resin. It is preferably a compound.
These fluororesin particle dispersion aids are also generally available for purchase. Examples of the resin that can be purchased include the Modiper series (manufactured by NOF Corporation) and the surflon series (manufactured by AGC Seimi Chemical Co., Ltd.).

In the present invention, in order to more uniformly disperse the fluororesin particles in the surface layer, a compound having the following structural units is more preferable as the dispersion aid.
(In formula (18), R ¹ represents a hydrogen or methyl group; R ² represents a single bond or a divalent group; Rf represents a monovalent group having at least one of a fluoroalkyl group and a fluoroalkylene group. In formula (19), R ³ represents a hydrogen or methyl group. Y represents a divalent organic group. Z represents a polymer unit.)

Further, a diorganopolysiloxane represented by the following formula (20) is also preferable as a dispersion aid.
(In formula (20), R ^{11 to} R ¹⁶ represent a substituted or unsubstituted hydrocarbon group, B represents a substituted or unsubstituted organic group having a perfluoroalkyl group, and D is a terminal-blocked polymerization. Indicates a group having a substituted or unsubstituted polystyrene chain having a degree of 3 or more, E ¹ and E ² indicate a group selected from R ^{11 to} R ¹⁶ , B and D, and l indicates an integer of 0 to 1000. , M and n represent integers from 1 to 1000.)

These compounds can be produced according to the procedures disclosed in JP-A-58-164656 and JP-A-2001-249481. Since the compound produced in this manner has both a site having an affinity for the fluororesin particles and a site having an affinity for the polyarylate of the surface layer or the polycarbonate resin, the dispersibility of the fluororesin particles is more uniform. Is obtained, which is preferable.

Specific examples of the structural units represented by the formulas (18) and (19) and the compounds represented by the formula (20) are shown below, but the present invention is not limited thereto.

Specific example of the structure unit represented by the formula (18)

Specific example of the structural unit represented by the formula (19) Y in the formula (19) is
The structure shown by is mentioned, and Y ¹ and Y ² each independently represent an alkylene group. It is preferably a methyl group or a hydroxyl group.

Z in the formula (19) is a polymer unit, and if it is a polymer unit, the structure is arbitrary, but the following formulas (19-b1) and (19-b2)
It is preferably a polymer unit having a repeating structural unit indicated by. R ²⁰¹ and R ²⁰² represent an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group or a nonyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. Alternatively, a hexyl group or the like is preferable.

The end of the polymer unit represented by Z may use a terminal terminator or may have a hydrogen atom.

Specific Examples of Compounds Represented by Formula (20)

Compared with other dispersant structures, the compound represented by the above formula (20) is structurally more likely to be oriented toward the PTFE surface if it is an alkyl fluoride side chain on the siloxane chain, while it is more likely to be oriented to the PTFE surface on the styrene side chain side. It is preferable because it is easily compatible with each other and more uniform dispersibility is enhanced. Of these, the compounds represented by the above formulas (20-11), (20-14), and (20-18) are more preferable.

These repeating structural units may be either random or block copolymer type. The content of the fluoropolymer in the polymer having the repeating structural units represented by the above formulas (18) and (19) or the polymer represented by the above formula (20) is 1 with respect to the total mass of the compound. It is preferably 9.0% by mass to 60.0% by mass, and particularly preferably 5.0% by mass to 40.0% by mass from the viewpoint of good dispersibility of the fluororesin particles.

The molecular weight (Mw) of the polymer having the repeating structural units represented by the above formulas (18) and (19) or the polymer represented by the above formula (20) is 10,000 to 200,000. Is preferable.

The polymer having the repeating structural units represented by the above formulas (18) and (19) or the polymer represented by the above formula (20) is used as a constituent component of the coating liquid for the surface layer together with the fluororesin particles. By manufacturing the electrophotographic photosensitive member, the fluororesin particles can be dispersed to a particle size close to that of the primary particles.

Therefore, according to the present invention, it is possible to obtain an electrophotographic photosensitive member having a surface layer in which fluorine atom-containing resin particles are appropriately dispersed, and as a result, uniform fluororesin particles are formed on the surface layer of the photoconductor even after repeated use. By being present, excellent cleaning performance can be exhibited.

In the present invention, it is preferable that the surface layer contains 3.0% by mass to 10.0% by mass of fluororesin particles in order to exhibit a higher effect in cleaning performance after repeated use. When it is 3.0% by mass or more, the area of the fluororesin on the electrophotographic photosensitive member is sufficiently increased due to the above-mentioned spreading effect, and better cleaning property can be obtained, which is preferable. When it is 10.0% by mass or less, it is preferable in that better photoconductor characteristics can be obtained. With respect to the mass of these fluororesin particles, the polymer having the repeating structural units represented by the above formulas (18) and (19) or the polymer represented by the above formula (20) is 2.0% by mass or more. It is preferable that the fluororesin particles are contained in the range of 10.0% by mass from the viewpoint of achieving both the dispersibility of the fluororesin particles and the characteristics of the photoconductor.

As a method of dispersing the fluororesin particles in the surface layer coating liquid, if necessary, disperse the fluororesin particles by a method such as a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor, roll mill, and liquid collision type high-speed disperser. Can be done.

The average particle size of the fluorine atom-containing resin particles is determined by the ultracentrifugal particle size distribution measuring device "CAPA-700" (manufactured by HORIBA, Ltd.) or the laser diffraction / scattering type particle size distribution measuring device "LA-750". It can be measured by (HORIBA, Ltd.). For example, the method for measuring the average particle size is as follows. Fluorine atom-containing resin particles are added, and the average particle size is measured by a liquid phase precipitation method before mixing the dispersion liquid immediately after dispersion with the coating liquid for the surface layer. When using the ultracentrifugation automatic particle size distribution measuring device (CAPA700) manufactured by HORIBA, Ltd., dilute with the solvent that is the main component of the coating liquid for the surface layer according to the conditions of the instruction manual, and adjust the average particle size. Measure.

The surface layer may contain a charge transport material. Examples of the charge transporting substance include triarylamine compounds, hydrazone compounds, styryl compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, stilben compounds, butadiene compounds, and enamine compounds. Only one kind of these charge transporting substances may be used, or two or more kinds thereof may be used.
Specific examples of the charge transport material are as described above.

The surface layer contains fluororesin particles and at least one resin selected from the group consisting of polyarylate resin and polycarbonate resin. It can be formed by a coating film of a surface layer obtained by dissolving and dispersing at least one resin selected from the group consisting of a polyarylate resin and a polycarbonate resin, and fluororesin particles in a solvent. Further, as described above, a resin other than the polyarylate resin and the polycarbonate resin may be used in combination.

Further, the charge transport layer may have a laminated structure, and in that case, at least the charge transport layer on the outermost surface side contains at least one resin selected from the group consisting of the polyarylate resin D and the polycarbonate resin E. Further, fluororesin particles are contained.

The ratio of the charge-transporting substance to the total resin in the charge-transporting layer is preferably in the range of 3: 10 to 20:10 (mass ratio), and more preferably in the range of 5: 10 to 12:10 (mass ratio).

Examples of the solvent used for the coating liquid for the charge transport layer include a ketone solvent, an ester solvent, an ether solvent and an aromatic hydrocarbon solvent. These solvents may be used alone or in combination of two or more. Among these solvents, it is preferable to use an ether solvent or an aromatic hydrocarbon solvent from the viewpoint of resin solubility.

The film thickness of the charge transport layer is preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 35 μm or less.

Various additives can be added to each layer of the electrophotographic photosensitive member. Examples of the additive include deterioration inhibitors such as antioxidants, ultraviolet absorbers and light-resistant stabilizers, and particles such as organic particles and inorganic particles. Examples of the deterioration inhibitor include a hindered phenol-based antioxidant, a hindered amine-based light-resistant stabilizer, a sulfur atom-containing antioxidant, and a phosphorus atom-containing antioxidant. Examples of the organic particles include polymer resin particles such as polystyrene resin particles and polyethylene resin particles. Examples of the inorganic particles include metal oxide particles such as silica and alumina. Further, silicone oil or the like may be added as a leveling agent as needed.

When applying the coating liquid for each of the above layers, a coating method such as a dip coating method (immersion coating method), a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method, or a blade coating method can be used. ..

<Image formation method>
The image forming method of the present invention includes a charging step of contacting the electrophotographic photosensitive member to charge the electrophotographic photosensitive member, a developing step of developing the electrophotographic photosensitive member with toner to form a toner image, and the electron. It has a transfer step of transferring the toner image on the photographic photosensitive member to a transfer material, and a cleaning step of bringing a blade into contact with the electrophotographic photosensitive member to remove the toner on the electrophotographic photosensitive member, and electrophotographic photosensitive member. The above-mentioned <electrophotographic photosensitive member> is used as the body, and the above-mentioned <toner> is used as the toner.

The image forming method of the present invention will be further described by using an electrophotographic apparatus as an example of an image forming apparatus to which the image forming method of the present invention can be applied.

FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member and toner.
In FIG. 1, reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is rotationally driven at a predetermined peripheral speed in the direction of an arrow about a shaft 2. The surface of the rotationally driven electrophotographic photosensitive member 1 is uniformly charged to a predetermined positive or negative potential by the charging means (primary charging means: charging roller or the like) 3 in contact with the electrophotographic photosensitive member 1 in the rotation process. It is charged (charging process). Next, the exposure light (image exposure light) 4 output from an exposure means (not shown) such as slit exposure or laser beam scanning exposure is received. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the surface of the electrophotographic photosensitive member 1 (electrostatic latent image forming step).

The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed with the toner T contained in the developing means 5 to become a toner image (development step). Next, the toner image formed and supported on the surface of the electrophotographic photosensitive member 1 is sequentially transferred to the transfer material (paper or the like) P by the transfer bias from the transfer means (transfer roller or the like) 6 (transfer step). .. The transfer material P is taken out from the transfer material supply means (not shown) in synchronization with the rotation of the electrophotographic photosensitive member 1 and supplied between the electrophotographic photosensitive member 1 and the transfer means 6 (contact portion). Will be sent.

The transfer material P to which the toner image has been transferred is separated from the surface of the electrophotographic photosensitive member 1 and introduced into the fixing means 8 to receive image fixing, and is discharged to the outside of the apparatus as an image forming product (print, copy). Toner.

The surface of the electrophotographic photosensitive member 1 after the toner image transfer is rubbed by a cleaning means (cleaning blade or the like) 7 and is cleaned by removing the developer (transfer residual toner) remaining on the transfer (cleaning step). ). Since the specific electrophotographic photosensitive member and the specific toner are used in the present invention, the occurrence of cleaning defects is suppressed even in the initial stage of use of a new process cartridge or electrophotographic apparatus, and good image quality is obtained. be able to.

Next, it is statically eliminated by pre-exposure light (not shown) from the pre-exposure means (not shown), and then used for repeated image formation. As shown in FIG. 1, when the charging means 3 is a contact charging means using a charging roller or the like, pre-exposure is not always necessary.

As described above, the present invention comprises an electrophotographic photosensitive member 1, a charging means 3, a developing means 5, a cleaning means 7, and if necessary, other components, for example, housed in a container and integrally bonded. It is a process cartridge. This process cartridge is detachably attached to the main body of an electrophotographic apparatus such as a copier or a laser beam printer. In FIG. 1, the electrophotographic photosensitive member 1 is integrally supported by the charging means 3, the developing means 5, and the cleaning means 7 to form a cartridge, and the electrophotographic apparatus is formed by using a guiding means 10 such as a rail of the electrophotographic apparatus main body. The process cartridge 9 is removable from the main body.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited thereto.

An example of manufacturing the resin C and the toner used in the present invention is shown below. The present invention is not limited by the production example.

[Production Example 1 of Resin C]
100 parts by mass of a mixture in which raw material monomers other than trimellitic anhydride were mixed in the amounts shown in Table 1 and 0.52 parts by mass of di (2-ethylhexanoic acid) tin as a catalyst were added to a nitrogen introduction tube, a dehydration tube, and the like. The mixture was placed in a 6-liter four-mouthed flask equipped with a stirrer and a thermocouple, and reacted at 200 ° C. for 6 hours under a nitrogen atmosphere. Further, trimellitic anhydride was added at 210 ° C., and the reaction was carried out under a reduced pressure of 40 kPa, and the reaction was continued until the weight average molecular weight (Mw) reached 12000. The obtained resin C is designated as resin C1.

[Production Examples 2 to 4 of Resin C]
The resin C was produced in the same manner as in Production Example 1 except that the amounts of the acid component and the alcohol component charged were changed as shown in Table 1. The obtained resin C is designated as resins C2 to C4.

* The notation of the monomer composition indicates the molar ratio when the total number of moles of the alcohol component is 100.
TPA: Terephthalic acid IPA: Isophthalic acid TMA: Trimellitic acid BPA (PO): 3 mol adduct of propylene oxide of bisphenol A BPA (EO): 2 mol adduct of ethylene oxide of bisphenol A

[Toner Manufacturing Example 1]
Toner 1 was manufactured by the following procedure.
Was added 0.1mol / _L-Na 3 PO ₄ aqueous solution 850 parts by weight in a container equipped with a high speed stirrer CLEARMIX (manufactured by M Technique Co., Ltd.) to adjust the rotational speed to 15000 rpm, was heated to 60 ° C. .. 68 parts by mass of a 1.0 mol / L-CaCl ₂ aqueous solution was added thereto to prepare an aqueous medium containing a minute water-insoluble dispersant Ca ₃ (PO ₄ ) ₂ .
Further, the following materials were dissolved at 100 r / min with a propeller type stirrer to prepare a solution.
-Styrene 75.0 parts by mass-Acrylic monomer (n-butyl acrylate) 25.0 parts by mass-Resin C1 3.8 parts by mass Next, the following materials were added to the above solution.
・ C. I. Pigment Blue 15: 3 6.5 parts by mass ・ Hydrocarbon wax 9.0 parts by mass (Maximum endothermic peak temperature is 77 ° C, HNP-51, manufactured by Nippon Seiro Co., Ltd.)

Then, after heating the mixed solution to a temperature of 60 ° C., it was stirred at 9000 r / min with a TK homomixer (manufactured by Primix (former: Tokushu Kagaku Kogyo)) to dissolve and disperse.
10.0 parts by mass of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved therein to prepare a polymerizable monomer composition. The above-mentioned polymerizable monomer composition was put into the above-mentioned aqueous medium, and the clear mix was granulated for 15 minutes while rotating at 15,000 rpm at a temperature of 60 ° C.

Then, the mixture was transferred to a propeller type stirrer and stirred at 100 r / min, reacted at a temperature of 70 ° C. for 5 hours, then heated to a temperature of 80 ° C. and further reacted for 5 hours to produce toner particles. After completion of the polymerization reaction, the slurry containing the particles was cooled, washed with 10 times the amount of water of the slurry, filtered and dried, and then the particle size was adjusted by classification to obtain toner particles.

Hydrophobic silica fine particles (primary particles) that are treated with dimethyl silicone oil (20% by mass) as a fluidity improver with respect to 100 parts by mass of the toner particles and are frictionally charged to the same polarity (negative value) as the toner particles. Number Average particle size: 10 nm, BET specific surface area: 170 m ^{2 /} g) 2.0 parts by mass is mixed with a Henschel mixer (manufactured by Nippon Coke Industries (formerly Mitsui Miike)) at 3000 r / min for 15 minutes to add toner 1. Obtained.

When the surface composition of the toner 1 was analyzed using TOF-SIMS, it was confirmed that a fragment derived from the isosorbide unit was present. Therefore, it was found that the toner 1 was in a state where the isosorbide unit was exposed on the surface.

[Toner Production Examples 2 and 3]
In Toner Production Example 1, the toner was produced in the same manner as in Toner Production Example 1 except that the addition amount and type in Table 2 were followed. The obtained toners are referred to as toner 2 and toner 3.
When the surface compositions of the toner 2 and the toner 3 were analyzed using TOF-SIMS, it was confirmed that fragments derived from the isosorbide unit were present. Therefore, it was found that the toner 2 and the toner 3 were in a state where the isosorbide unit was exposed on the surface.

[Toner Manufacturing Example 4]
Toner was produced by the dissolution suspension method according to the following procedure.
First, an aqueous medium and a solution were prepared according to the following procedure to prepare a toner.
An aqueous medium was prepared by mixing and stirring 660 parts by mass of water and 25 parts by mass of an aqueous solution of 48.5% by mass of sodium dodecyldiphenyl ether disulfonate, and stirring at 10000 r / min using a TK homomixer (manufactured by Primix). ..
Further, the following materials were put into 500 parts by mass of ethyl acetate and dissolved at 100 r / min with a propeller type stirrer to prepare a solution.
100.0 parts by mass of styrene-n-butyl acrylate copolymer (copolymerization mass ratio: styrene / n-butyl acrylate = 75/25, Mp = 17000)
-Resin C1 3.8 parts by mass-C. I. Pigment Blue 15: 3 6.5 parts by mass, hydrocarbon wax 9.0 parts by mass (peak temperature of maximum endothermic peak is 77 ° C, HNP-51, manufactured by Nippon Seiro Co., Ltd.)

Next, 150 parts by mass of the aqueous medium was placed in a container, stirred using a TK homomixer (manufactured by Primix Corporation) at a rotation speed of 12000 rpm, 100 parts by mass of the above solution was added thereto, and the mixture was mixed for 10 minutes to form an emulsified slurry. Was prepared.

After that, 100 parts by mass of the emulsified slurry was placed in a flask in which a degassing pipe, a stirrer and a thermometer were set, and the solvent was removed at 30 ° C. for 12 hours under reduced pressure while stirring at a stirring peripheral speed of 20 m / min to 45 ° C. The mixture was aged for 4 hours to obtain a solvent-free slurry. After the solvent-free slurry was filtered under reduced pressure, 300 parts by mass of ion-exchanged water was added to the obtained filtered cake, mixed and redispersed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered. The obtained filtered cake was dried at 45 ° C. for 48 hours in a dryer, and sieved toner particles were obtained with a mesh having a mesh size of 75 μm.

Hydrophobic silica fine particles (primary particles) that are treated with dimethyl silicone oil (20% by mass) as a fluidity improver with respect to 100 parts by mass of the toner particles and are frictionally charged to the same polarity (negative electrode property) as the toner particles. Number average particle size: 10 nm, BET specific surface area: 170 m ^{2 /} g) 2.0 parts by mass was mixed with a Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd.) at 3000 r / min for 15 minutes to obtain toner 4.

When the surface composition of the toner 4 was analyzed using TOF-SIMS, it was confirmed that a fragment derived from the isosorbide unit was present. Therefore, it was found that the toner 4 was in a state where the isosorbide unit was exposed on the surface.

[Toner Production Example 5]
Toner was produced by the pulverization method according to the following procedure.
-Resin C1 100.0 parts by mass-C. I. Pigment Blue 15: 3 5.0 parts by mass, Fischer-Tropsch wax 5.0 parts by mass (peak temperature of maximum endothermic peak is 105 ° C)
-0.5 parts by mass of 3,5-di-t-butylsalicylate aluminum compound After mixing the above materials with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industries, Ltd.), a twin-screw kneader (PCM-30 type, It was kneaded at Ikegai Corp. (formerly manufactured by Ikegai Iron Works Co., Ltd.) under the conditions of a rotation speed of 3.3 s- ¹ and a kneading resin temperature of 110 ° C.

The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed product. The obtained pyroclastic material was finely pulverized with a mechanical crusher (T-250, manufactured by Freund Turbo Co., Ltd. (former: Turbo Industry Co., Ltd.)). Further, the obtained finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect to obtain negative triboelectric toner particles having a weight average particle size of 7.0 μm.

100 parts by mass of the obtained toner particles were surface-treated with 15% by mass of isobutyltrimethoxysilane, 1.0 part by mass of titanium oxide fine particles having a primary average particle size of 50 nm, and 20% by mass of hexamethyldisilazane. 0.8 parts by mass of hydrophobic silica fine particles having a particle size of 16 nm were added and mixed with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industries Co., Ltd.) to obtain toner 5.

When the surface composition of the toner 5 was analyzed using TOF-SIMS, it was confirmed that a fragment derived from the isosorbide unit was present. Therefore, it was found that the toner 5 was in a state where the isosorbide unit was exposed on the surface.

[Toner Manufacturing Example 6]
In the toner production example 1, the toner was produced in the same manner as in the toner production example 1 except that the acrylic monomer was not used and the addition amount and type in Table 2 were followed. The obtained toner is referred to as toner 6.

When the surface composition of the toner 6 was analyzed using TOF-SIMS, it was confirmed that a fragment derived from the isosorbide unit was present. Therefore, it was found that the toner 6 was in a state where the isosorbide unit was exposed on the surface.

[Toner Manufacturing Example 7]
In Toner Production Example 1, the toner was produced in the same manner as in Toner Production Example 1 except that the addition amount and type in Table 2 were followed. The obtained toner is referred to as toner 7.

When the surface composition of the toner 7 was analyzed using TOF-SIMS, it was confirmed that a fragment derived from the isosorbide unit was present. Therefore, it was found that the toner 7 was in a state where the isosorbide unit was exposed on the surface.

[Production Example 1 of Comparative Toner]
In the production example of the toner 1, the resin C1 was not added, and the toner was produced in the same manner as in the production example 1 of the toner except for the addition. The obtained toner is designated as the comparative toner 1.

When the surface composition of Comparative Toner 1 was analyzed using TOF-SIMS, no fragment derived from the isosorbide unit was present.

Table 3 shows the resin C (type, content) contained in the toner, the resin other than the resin C (type, content), and the toner manufacturing method for the toners 1 to 7 and the comparative toner 1.

Next, a synthesis example of the polyarylate resin A and the polycarbonate resin B is shown below. The present invention is not limited by the synthesis example.

[Synthesis Example A1]
An acid halide solution was prepared by dissolving 3.3 g of isophthalic acid chloride and 3.3 g of terephthalic acid chloride in dichloromethane. In addition to the acid halide solution, 4.2 g of the siloxane derivative represented by the following formula (a-1), 6.8 g of the diol represented by the following formula (a-2), and the following formula (a-3) are represented. 3.6 g of the diol was dissolved in a 10% aqueous sodium hydroxide solution. Further, tributylbenzylammonium chloride was added as a polymerization catalyst and stirred to prepare a diol compound solution.

Next, the acid halide solution was added to the diol compound solution with stirring to initiate polymerization. The polymerization reaction was carried out for 3 hours with stirring while keeping the reaction temperature at 25 ° C. or lower. Then, the polymerization reaction was terminated by adding acetic acid, and washing with water was repeated until the aqueous phase became neutral. Subsequently, this liquid phase was added dropwise to methanol, and the precipitate was filtered and dried to obtain a white polymer (resin A1).
The viscosity average molecular weight of the obtained resin A1 was 21,000. The viscosity average molecular weight was calculated as follows. 0.5 g of the sample is dissolved in 100 ml of dichloromethane, and the specific viscosity at 25 ° C. is measured using an Ubbelohde type viscometer. The calculated intrinsic viscosity from specific viscosity, Mark - Houwink (Mark-Houwink) viscosity equation of K (proportional constant part) and a the (exponent; sometimes denoted by alpha) respectively 1.23 × 10 ^{- The} viscosity average molecular weight was calculated as ⁴ and 0.83.
Further, when the content of the portion corresponding to the structure represented by the formula (1) contained in the resin A1 was analyzed by the above method, it was 20% by mass.

[Synthesis Examples A2 to A8]
Synthesis Examples Resins A2 to A8 were synthesized by using the synthesis method described in Example A1 and using the raw materials corresponding to the structures shown in Table 4. The viscosity average molecular weight of the resins A2 to A8 was controlled by adjusting the time from the start of polymerization to the end of polymerization.
Table 4 shows the composition and viscosity average molecular weight of the resins A1 to A8.

“Equation (2)” in Table 4 shows the structure represented by the equation (2). The “content of the formula (1)” in Table 4 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Formula (9)” in Table 4 indicates a structural unit represented by the formula (9). When the structural units represented by the formula (9) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Formula (10)” in Table 4 indicates a structural unit represented by the formula (10). When the structural units represented by the formula (10) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “N in equation (10)” in Table 4 means the average value of the number of repetitions n of the structure in parentheses in the structural unit represented by equation (10).

[Synthesis Example B1]
12.0 g of the diol represented by the following formula (b-1) was dissolved in a 10% aqueous sodium hydroxide solution. Dichloromethane was added to this solution and stirred, and 15 g of phosgene was blown into the solution over 1 hour while keeping the solution temperature at 10 ° C. or higher and 15 ° C. or lower. When about 70% of phosgene was blown in, 4.2 g of the siloxane derivative represented by the formula (a-1) and 4.0 g of the diol represented by the formula (a-3) were added to the solution. After the introduction of phosgene was completed, the reaction solution was emulsified with vigorous stirring, triethylamine was added, and the mixture was stirred for 1 hour. Then, the dichloromethane phase was neutralized with phosphoric acid, and washing with water was repeated until the pH became about 7. Subsequently, this liquid phase was added dropwise to isopropanol, and the precipitate was filtered and dried to obtain a white polymer (resin B1).
The viscosity average molecular weight of the obtained resin B1 was 18,000. The content of the portion of the resin B1 corresponding to the structure represented by the formula (1) was 10% by mass.

[Synthesis Examples B2 to B9]
The resins B2 to B9 were synthesized by using the synthesis method described in Synthesis Example B1 and using the raw materials corresponding to the structures shown in Table 5. The viscosity average molecular weight of the resins B2 to B9 was controlled by adjusting the time from the start of polymerization to the end of polymerization.
Table 5 shows the composition and viscosity average molecular weight of the resins B1 to B9.

“Equation (2)” in Table 5 shows the structure represented by the equation (2). The “content of the formula (1)” in Table 5 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Equation (11)” in Table 5 indicates a structural unit represented by the equation (11). When the structural units represented by the formula (11) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Equation (12)” in Table 5 indicates a structural unit represented by the equation (12). “N in equation (12)” in Table 5 means the average value of the number of repetitions n of the structure in parentheses in the structural unit represented by equation (12).

[Synthesis Example A9]
Using the siloxane derivative represented by the following formula (a-4) and the diol represented by the formula (a-2), the resin A9 having the structure shown in Table 6 was synthesized according to the method of Synthesis Example A1. The viscosity average molecular weight of the obtained resin A9 was 22,000. Moreover, the content of the portion corresponding to the structure represented by the formula (1) contained in the resin A9 was 20% by mass.
The siloxane derivative represented by the formula (a-4) is, for example, a compound that can be obtained by a hydrosilylation reaction between a bisphenol having a carbon-carbon double bond in the side chain and a polysiloxane having a one-terminal Si—H structure. ..

[Synthesis Examples A10 to A14]
Synthesis Examples Resins A10 to A14 were synthesized using the synthesis method described in Example A1 and the raw materials corresponding to the structures shown in Table 6. The viscosity average molecular weight of the resins A10 to A14 was controlled by adjusting the time from the start of polymerization to the end of polymerization.
Table 6 shows the composition and viscosity average molecular weight of the resins A9 to A14.

“Equation (3)” in Table 6 indicates a structural unit represented by the equation (3). When the structural units represented by the formula (3) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Formula (3-A)” in Table 6 shows the structure represented by the formula (3-A). The “content of the formula (1)” in Table 6 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Formula (9)” in Table 6 indicates a structural unit represented by the formula (9). When the structural units represented by the formula (9) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Formula (10)” in Table 6 indicates a structural unit represented by the formula (10). When the structural units represented by the formula (10) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “N in equation (10)” in Table 6 means the average value of the number of repetitions n of the structure in parentheses in the structural unit represented by equation (10).

[Synthesis Example B10]
Using the siloxane derivative represented by the formula (a-4) and the diol represented by the formula (b-1), a resin B10 having the structure shown in Table 7 was synthesized according to the method of Synthesis Example B1. The viscosity average molecular weight of the obtained resin B10 was 19,000. Moreover, the content of the portion corresponding to the structure represented by the formula (1) contained in the resin B10 was 20% by mass.

[Synthesis Examples B11 to B16]
Using the synthesis method described in Synthesis Example B1, resins B11 to B16 were synthesized using the raw materials corresponding to the structures shown in Table 7. The viscosity average molecular weight of the resins B11 to B16 was controlled by adjusting the time from the start of polymerization to the end of polymerization.
Table 7 shows the composition and viscosity average molecular weight of the resins B10 to B16.

“Equation (6)” in Table 7 indicates a structural unit represented by the equation (6). “Formula (6-A)” in Table 7 indicates the structure represented by the formula (6-A). The "content of the formula (1)" in Table 7 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Formula (11)” in Table 7 indicates a structural unit represented by the formula (11). When the structural units represented by the formula (11) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Formula (12)” in Table 7 indicates a structural unit represented by the formula (12). “N in equation (12)” in Table 7 means the average value of the number of repetitions n of the structure in parentheses in the structural unit represented by equation (12).

[Synthesis Example A15]
Using the siloxane derivative represented by the following formula (a-5) and the diol represented by the formula (a-2), the resin A15 having the structure shown in Table 8 was synthesized according to the method of Synthesis Example A1. The viscosity average molecular weight of the obtained resin A15 was 23,000. Moreover, the content of the portion corresponding to the structure represented by the formula (1) contained in the resin A15 was 20% by mass.
The siloxane derivative represented by the formula (a-5) is, for example, a compound that can be obtained by a hydrosilylation reaction between a bisphenol having a carbon-carbon double bond at a substituent of the central skeleton and a polysiloxane having a one-terminal Si—H structure. Is.

[Synthesis Examples A16 to A21]
Using the synthesis method described in Synthesis Example A1, resins A16 to A21 were synthesized using the raw materials corresponding to the structures shown in Tables 8 and 9. The viscosity average molecular weight of the resins A16 to A21 was controlled by adjusting the time from the start of polymerization to the end of polymerization.
The configurations and viscosity average molecular weights of the resins A15 to A21 are shown in Tables 8 and 9.

“Formula (4)” in Tables 8 and 9 indicates the structural unit represented by the formula (4). When the structural units represented by the formula (4) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Formula (4-A)” in Table 8 shows the structure represented by the formula (4-A). “Formula (4-B)” in Table 9 shows the structure represented by the formula (4-B). The "content of the formula (1)" in Tables 8 and 9 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Formula (9)” in Tables 8 and 9 indicates the structural unit represented by the formula (9). When the structural units represented by the formula (9) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Formula (10)” in Table 8 indicates a structural unit represented by the formula (10). When the structural units represented by the formula (10) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “N in equation (10)” in Table 8 means the average value of the number of repetitions n of the structure in parentheses in the structural unit represented by equation (10).

[Synthesis Example B17]
Using the siloxane derivative represented by the formula (a-5) and the diol represented by the formula (b-1), a resin B17 having the structure shown in Table 10 was synthesized according to the method of Synthesis Example B1. The viscosity average molecular weight of the obtained resin B17 was 18,000. Moreover, the content of the portion corresponding to the structure represented by the formula (1) contained in the resin B17 was 20% by mass.

[Synthesis Examples B18 to B22]
Using the synthesis method described in Synthesis Example B1, resins B18 to B22 were synthesized using the raw materials corresponding to the structures shown in Tables 10 and 11. The viscosity average molecular weight of the resins B18 to B22 was controlled by adjusting the time from the start of polymerization to the end of polymerization.
The composition and viscosity average molecular weight of the resins B17 to B22 are shown in Tables 10 and 11.

“Formula (7)” in Tables 10 and 11 indicates a structural unit represented by the formula (7). “Formula (7-A)” in Table 10 indicates the structure represented by the formula (7-A). “Formula (7-B)” in Table 11 shows the structure represented by the formula (7-B). The "content of the formula (1)" in Tables 10 and 11 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Formula (11)” in Tables 10 and 11 indicates a structural unit represented by the formula (11). When the structural units represented by the formula (11) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Formula (12)” in Table 10 indicates a structural unit represented by the formula (12). “N in equation (12)” in Table 10 means the average value of the number of repetitions n of the structure in parentheses in the structural unit represented by equation (12).

[Synthesis Example A22]
Using the siloxane derivative represented by the following formula (a-6) and the diol represented by the formula (a-2), the resin A22 having the structure shown in Table 12 was synthesized according to the method of Synthesis Example A1. The viscosity average molecular weight of the obtained resin A22 was 40,000. Moreover, the content of the portion corresponding to the structure represented by the formula (1) contained in the resin A22 was 20% by mass.

[Synthesis Examples A23 to A26]
Using the synthesis method described in Synthesis Example A1, resins A23 to A26 were synthesized using the raw materials corresponding to the structures shown in Table 12. The viscosity average molecular weight of the resins A23 to A26 was controlled by adjusting the time from the start of polymerization to the end of polymerization.
Table 12 shows the composition and viscosity average molecular weight of the resins A22 to A26.

“Formula (5)” in Table 12 indicates a structural unit represented by the formula (5). When the structural units represented by the formula (5) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Formula (5-A)” in Table 12 shows the structure represented by the formula (5-A). The “content of the formula (1)” in Table 12 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Formula (9)” in Table 12 indicates a structural unit represented by the formula (9). When the structural units represented by the formula (9) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Formula (10)” in Table 12 indicates a structural unit represented by the formula (10). When the structural units represented by the formula (10) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “N in equation (10)” in Table 12 means the average value of the number of repetitions n of the structure in parentheses in the structural unit represented by equation (10).

[Synthesis Example B23]
Using the siloxane derivative represented by the formula (a-6) and the diol represented by the formula (b-1), the resin B23 having the structure shown in Table 13 was synthesized according to the method of Synthesis Example B1. The viscosity average molecular weight of the obtained resin B23 was 31,000. Moreover, the content of the portion corresponding to the structure represented by the formula (1) contained in the resin B23 was 20% by mass.

[Synthesis Examples B24 to B31]
Resins B24 to B31 were synthesized using the synthesis method described in Synthesis Example B1 and the raw materials corresponding to the structures shown in Table 13. The viscosity average molecular weight of the resins B24 to B31 was controlled by adjusting the time from the start of polymerization to the end of polymerization.
Table 13 shows the composition and viscosity average molecular weight of the resins B23 to B31.

“Formula (8)” in Table 13 indicates a structural unit represented by the formula (8). “Formula (8-A)” in Table 13 indicates the structure represented by the formula (8-A). The “content of the formula (1)” in Table 13 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Formula (11)” in Table 13 indicates a structural unit represented by the formula (11). When the structural units represented by the formula (11) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “Formula (12)” in Table 13 indicates a structural unit represented by the formula (12). “N in equation (12)” in Table 13 means the average value of the number of repetitions n of the structure in parentheses in the structural unit represented by equation (12).

[Synthesis Example A27]
Synthesis Example A1 except that the siloxane derivative represented by the formula (a-1) was not used and the siloxane derivative represented by the formula (a-3) was changed to the siloxane derivative represented by the following formula (a-7). The resin A27 having the structure shown in Table 14 was synthesized according to the method of. The viscosity average molecular weight of the obtained resin A27 was 31,000. Moreover, the content of the portion corresponding to the structure represented by the formula (1) contained in the resin A27 was 20% by mass.

[Synthesis Examples A28-32]
Synthesis Examples Resins A28 to A32 were synthesized using the synthesis method described in Example A1 and the raw materials corresponding to the structures shown in Table 14. The viscosity average molecular weight of the resins A28 to A32 was controlled by adjusting the time from the start of polymerization to the end of polymerization.
Table 14 shows the composition and viscosity average molecular weight of the resins A27 to A32.

“Equation (10)” in Table 14 shows the structure represented by the equation (10). When the structural units represented by the formula (10) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown. “N in equation (10)” in Table 14 means the average value of the number of repetitions n of the structure in parentheses in the structural unit represented by equation (10). The “content of the formula (1)” in Table 14 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Equation (9)” in Table 14 indicates a structural unit represented by the equation (9). When the structural units represented by the formula (9) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown.

[Synthesis Example B32]
Synthesis Example B1 except that the siloxane derivative represented by the formula (a-1) was not used and the siloxane derivative represented by the formula (a-3) was changed to the siloxane derivative represented by the formula (a-7). According to the method, a resin B32 having the structure shown in Table 15 was synthesized. The viscosity average molecular weight of the obtained resin B32 was 25,000. Moreover, the content of the portion corresponding to the structure represented by the formula (1) contained in the resin B32 was 20% by mass.

[Synthesis Examples B33 to B35]
Using the synthesis method described in Synthesis Example B1, resins B33 to B35 were synthesized using the raw materials corresponding to the structures shown in Table 15. The viscosity average molecular weight of the resins B33 to B35 was controlled by adjusting the time from the start of polymerization to the end of polymerization.
Table 15 shows the composition and viscosity average molecular weight of the resins B32 to B35.

“Equation (12)” in Table 15 shows the structure represented by the equation (12). “N in equation (12)” in Table 15 means the average value of the number of repetitions n of the structure in parentheses in the structural unit represented by equation (12). The “content of the formula (1)” in Table 15 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Formula (11)” in Table 15 indicates a structural unit represented by the formula (11). When the structural units represented by the formula (11) are mixed and used, the type of the structural unit and the mixing ratio (mass standard) are shown.

[Synthesis Example A33]
Using the siloxane derivative represented by the formula (a-1), the siloxane derivative represented by the formula (a-6), and the diol represented by the formula (a-2), the structures shown in Table 16 are followed according to the method of Synthesis Example A1. Resin A33 having the above was synthesized. The viscosity average molecular weight of the obtained resin A33 was 30,000. Further, the content of the structure represented by the formula (1) contained in the resin A33 was 10% by mass.

“Equation (2)” in Table 16 indicates a structural unit represented by the equation (2). “Formula (5)” in Table 16 indicates the type of structural unit represented by the formula (5) and the mixing ratio (mass basis). “Formula (5-A)” in Table 16 indicates the structure represented by the formula (5-A). The “content of the formula (1)” in Table 16 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Formula (9)” in Table 16 indicates the type of structural unit represented by the formula (9) and the mixing ratio (mass basis).

[Synthesis Example B36]
Using the siloxane derivative represented by the formula (a-1), the siloxane derivative represented by the formula (a-6), and the diol represented by the formula (b-1), the structures shown in Table 17 are used according to the method of Synthesis Example B1. Resin B36 having the above was synthesized. The viscosity average molecular weight of the obtained resin B36 was 25,000. Further, the content of the structure represented by the formula (1) contained in the resin B36 was 5% by mass.

“Formula (2)” in Table 17 indicates a structural unit represented by the formula (2). “Formula (8)” in Table 17 indicates a structural unit represented by the formula (8). “Formula (8-A)” in Table 17 indicates the structure represented by the formula (8-A). The “content of the formula (1)” in Table 17 means the content (mass%) of the structure represented by the formula (1) contained in the resin. “Formula (11)” in Table 17 indicates a structural unit represented by the formula (11).

An example of manufacturing the electrophotographic photosensitive member of the present invention is shown below. The present invention is not limited by the production example.

[Production Example 1 of Photoreceptor]
An aluminum cylinder having a diameter of 24 mm and a length of 257 mm was used as a support (conductive support).

Next, 214 parts of titanium oxide (TiO ₂ ) particles coated with oxygen-deficient tin oxide (SnO ₂ ) as metal oxide particles, and a phenol resin (monomer / oligomer of phenol resin) as a binder material (trade name: Pryofen J-325, DIC Co., Ltd. (former: Dainippon Ink and Chemicals Co., Ltd., resin solid content: 60% by mass) 132 parts, and 98 parts of 1-methoxy-2-propanol as a solvent. Put it in a sand mill using 450 parts of glass beads with a diameter of 0.8 mm, and perform dispersion treatment under the conditions of rotation speed: 2000 rpm, dispersion treatment time: 4.5 hours, and set temperature of cooling water: 18 ° C. to obtain a dispersion liquid. It was. Glass beads were removed from this dispersion with a mesh (opening: 150 μm).

Silicone resin particles as a surface roughening material (trade name: Tospearl 120,) so as to be 10% by mass with respect to the total mass of the metal oxide particles and the binder material in the dispersion liquid after removing the glass beads. Momentive Performance Materials Co., Ltd., average particle size (2 μm) was added to the dispersion. Further, silicone oil as a leveling agent (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.) so as to be 0.01% by mass with respect to the total mass of the metal oxide particles and the binder material in the dispersion liquid. ) Was added to the dispersion and stirred to prepare a coating liquid for a conductive layer.
This coating liquid for a conductive layer was immersed and coated on a support, and the obtained coating film was dried and thermoset at 150 ° C. for 30 minutes to form a conductive layer having a film thickness of 30 μm.

Next, 5 parts of the electron transporting substance represented by the following formula (d-1), 8.6 parts of a blocked isocyanate compound (trade name: SBN-70D, manufactured by Asahi Kasei Chemicals Co., Ltd.), and a polyvinyl acetal resin (commodity). Name: KS-5Z, manufactured by Sekisui Chemical Industry Co., Ltd. 0.6 parts, zinc hexanoate (II) (trade name: zinc hexanoate (II), manufactured by Mitsuwa Chemical Co., Ltd.) 0.15 parts , 1-methoxy-2-propanol 45 parts and tetrahydrofuran 45 parts dissolved in a mixed solvent. To the obtained solution, 3.3 parts of a slurry in which silica particles were dispersed in isopropanol (trade name: IPA-ST-UP, silica ratio: 15% by mass, manufactured by Nissan Chemical Co., Ltd.) was added and stirred. This coating liquid for the undercoat layer is immersed and coated on the conductive layer, and the obtained coating film is heated at 170 ° C. for 20 minutes and cured (polymerized) to form an undercoat layer having a film thickness of 0.6 μm. did.

Next, strong peaks at 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° of Bragg angles 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction. 10 parts of crystalline hydroxygallium phthalocyanine (charge generator) having the above was prepared. In addition, 250 parts of cyclohexanone and 5 parts of polyvinyl butyral resin (trade name: Eslek BX-1, manufactured by Sekisui Chemical Co., Ltd.) are mixed, and a sand mill device using glass beads with a diameter of 1 mm is used in an atmosphere of 23 ± 3 ° C. Time dispersed. After dispersion, 250 parts of ethyl acetate was added to prepare a coating liquid for a charge generation layer. The coating liquid for the charge generating layer was immersed and coated on the undercoat layer, and the obtained coating film was dried at 100 ° C. for 10 minutes to form a charge generating layer having a film thickness of 0.26 μm.

Next, as the charge transporting substance, 8 parts of the compound represented by the formula (13-1) and 2 parts of the compound represented by the formula (13-8), and as the resin, the resin A1 synthesized in Synthesis Example A1 was 0.4. 9.6 parts of polyallylate resin (viscosity average molecular weight: 40,000) containing parts and structural units represented by the formula (9-1) and structural units represented by the formula (9-2) in a ratio of 5: 5. Was dissolved in a mixed solvent consisting of 40 parts of dimethoxymethane, 60 parts of o-xylene and 5 parts of methyl benzoate to prepare a coating liquid for a charge transport layer. The coating liquid for the charge transport layer was immersed and coated on the charge generation layer, and the obtained coating film was dried at 120 ° C. for 1 hour to form a charge transport layer having a film thickness of 16 μm.

In this way, the photoconductor 1 having the charge transport layer as the surface layer was produced. Table 18-1 shows the configurations of the charge-transporting substance and the resin contained in the charge-transporting layer of the photoconductor 1. Table 18-1 shows the abundance ratio of the silicon element to the constituent elements on the outermost surface of the surface layer of the photoconductor 1.

[Production Example 2 of Photoreceptor]
In the photoconductor 1, the resin A1 in the charge transport layer was changed to the resin A2, and 0.04 part of polydimethylsiloxane (average value of n: 40) represented by the formula (16) was added to the photoconductor 1. The photoconductor 2 was produced in the same manner as in the above. Table 18-1 shows the configurations of the charge-transporting substance, the resin, and the polydimethylsiloxane contained in the charge-transporting layer of the photoconductor 2. Table 18-1 shows the abundance ratio of the silicon element to the constituent elements on the outermost surface of the photoconductor 2.

[Production Examples 3 to 96, 102, 103 of Photoreceptor]
In the photoconductor 2, the charge transporting substances, the resin, and the polydimethylsiloxane in the charge transporting layer were changed as shown in Tables 18-1 and 18-2, but the photoconductors 3 to 3 were similar to the photoconductor 2. 96, 102 and 103 were prepared. The configurations of the charge-transporting substance, the resin and the polydimethylsiloxane contained in the charge-transporting layers of the photoconductors 3 to 96, 102 and 103 are shown in Tables 18-1 and 18-2. Tables 18-1 and 18-2 show the abundance ratio of the silicon element to the constituent elements on the outermost surfaces of the photoconductors 3 to 96, 102, and 103.

“Charge transport material” in Table 18-1 and Table 18-2 indicates the type and number of copies of the charge transport material. “Resin A, resin B” in Tables 18-1 and 18-2 indicate the resins shown in Tables 4 to 17. “Other resins” in Tables 18-1 and 18-2 indicate structural units of resins other than resin A or resin B contained in the charge transport layer. When structural units are mixed and used, the type of structural unit and the mixing ratio (mass standard) are shown. “Polydimethylsiloxane mixing ratio” in Tables 18-1 and 18-2 indicates the mixing ratio (mass%) of polydimethylsiloxane to the total amount of resin A and resin B contained in the charge transport layer. “Polydimethylsiloxane n” in Tables 18-1 and 18-2 means the average value of the number of repetitions n of the structure in parentheses of polydimethylsiloxane contained in the charge transport layer. The “ratio of resin A and resin B” in Tables 18-1 and 18-2 means the content (mass%) of resin A or resin B with respect to the total solid content in the charge transport layer. “Silicon element ratio” in Tables 18-1 and 18-2 means the abundance ratio (atomic%) of silicon element to the constituent elements on the outermost surface of the charge transport layer as measured by using ESCA.

[Production Example 97 of Photoreceptor]
In the photoconductor 2, the photoconductor 97 was produced in the same manner as the photoconductor 2 except that the method for producing the undercoat layer was changed as follows.
That is, for the undercoat layer, a coating liquid for the undercoat layer was prepared by dissolving 3 parts of N-methoxymethylated nylon and 3 parts of copolymerized nylon in a mixed solvent of 65 parts of methanol / 30 parts of n-butanol. The undercoat layer coating liquid was immersed and coated on the conductive layer and dried at 100 ° C. for 10 minutes to form an undercoat layer having a film thickness of 0.7 μm.

Table 19 shows the configurations of the charge transporting substance, the resin and the polydimethylsiloxane contained in the charge transporting layer of the photoconductor 97. Table 19 shows the abundance ratio of the silicon element to the constituent elements on the outermost surface of the photoconductor 97.

[Production Examples of Photoreceptors 98, 99]
In the photoconductor 97, the photoconductors 98 and 99 were prepared in the same manner as the photoconductor 97 except that the charge transport material, the resin and the polydimethylsiloxane in the charge transport layer were changed as shown in Table 19. Table 19 shows the configurations of the charge transporting substance, the resin and the polydimethylsiloxane contained in the charge transporting layers of the photoconductors 98 and 99. Table 19 shows the abundance ratio of the silicon element to the constituent elements on the outermost surfaces of the photoconductors 98 and 99.

[Production Example 100 of Photoreceptor]
In the photoconductor 98, the photoconductor 100 was produced in the same manner as the photoconductor 98 except that the method for producing the conductive layer was changed as follows and the undercoat layer was eliminated.
That is, 100 parts of zinc oxide particles (specific surface area: 19 m ² / g, powder resistance: 4.7 × 10 ⁶ Ω · cm) as a metal oxide are stirred and mixed with 500 parts of toluene, and a silane coupling agent (silane coupling agent) is added thereto. Compound name: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, trade name: KBM602, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.8 parts was added, and the mixture was stirred for 6 hours. Then, toluene was distilled off under reduced pressure, and the mixture was heated and dried at 130 ° C. for 6 hours to obtain surface-treated zinc oxide particles.

Next, as polyol resin, 15 parts of butyral resin (trade name: BM-1, manufactured by Sekisui Chemical Industry Co., Ltd.) and blocked isocyanate (trade name: Sumijour 3175, Sumika Bayer Urethane Co., Ltd. (former: Sumitomo Bayer)) (Urethane) 15 parts) was dissolved in a mixed solution of 73.5 parts of methyl ethyl ketone and 73.5 parts of 1-butanol. 80.64 parts of the surface-treated zinc oxide particles and 0.8 parts of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to this solution, and these are glass beads having a diameter of 0.8 mm. The particles were dispersed for 3 hours in an atmosphere of 23 ± 3 ° C. with a sand mill device using the above. After dispersion, 0.01 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone), crosslinked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER SSX-102, manufactured by Sekisui Plastics Co., Ltd.) , Average primary particle size (2.5 μm) was added in 5.6 parts and stirred to prepare a coating liquid for a conductive layer.
The coating liquid for the conductive layer was immersed and coated on the support to form a coating film, and the coating film was heated and dried at 160 ° C. for 40 minutes to form a conductive layer having a film thickness of 18 μm.

Table 19 shows the configurations of the charge transporting substance, the resin and the polydimethylsiloxane contained in the charge transporting layer of the photoconductor 100. Table 19 shows the abundance ratio of the silicon element to the constituent elements on the outermost surface of the photoconductor 100.

[Production Example 101 of Photoreceptor]
In the photoconductor 100, the photoconductor 101 was produced in the same manner as the photoconductor 100, except that the charge transporting substance, the resin, and the polydimethylsiloxane in the charge transport layer were changed as shown in Table 19. Table 19 shows the configurations of the charge transporting substance, the resin and the polydimethylsiloxane contained in the charge transporting layer of the photoconductor 101. Table 19 shows the abundance ratio of the silicon element to the constituent elements on the outermost surface of the photoconductor 101.

“Charge transporting substance” in Table 19 indicates the type and number of copies of the charge transporting substance. “Resin A, Resin B” in Table 19 indicates the resins shown in Tables 4 to 17. “Other resins” in Table 19 indicate structural units of resins other than resin A or resin B contained in the charge transport layer. When structural units are mixed and used, the type of structural unit and the mixing ratio (mass standard) are shown. “Polydimethylsiloxane mixing ratio” in Table 19 indicates the mixing ratio (mass%) of polydimethylsiloxane to the total amount of resin A and resin B contained in the charge transport layer. “Polydimethylsiloxane n” in Table 19 means the average value of the number of repetitions n of the structure in parentheses of polydimethylsiloxane contained in the charge transport layer. The “ratio of resin A and resin B” in Table 19 means the content (mass%) of resin A or resin B with respect to the total solid content in the charge transport layer. The "silicon element ratio" in Table 19 means the abundance ratio (atomic%) of the silicon element to the constituent elements on the outermost surface of the charge transport layer, which was measured using ESCA.

[Production Example 1 of Comparative Photoreceptor]
A comparative photoconductor 1 was produced in the same manner as the photoconductor 4 except that the resin A2 in the charge transport layer was not used in the photoconductor 4. Table 20 shows the configurations of the charge-transporting substance and the resin contained in the charge-transporting layer of the comparative photoconductor 1. Further, the abundance ratio of the silicon element to the constituent elements on the outermost surface of the comparative photoconductor 1 was 0.0 atomic%.

“Charge transporting substance” in Table 20 indicates the type and number of copies of the charge transporting substance. “Resin A, Resin B” in Table 20 indicates the resins shown in Tables 4 to 17. “Other resins” in Table 20 indicate structural units of resins other than resin A or resin B contained in the charge transport layer. “Polydimethylsiloxane n” in Table 20 means the average value of the number of repetitions n of the structure in parentheses of polydimethylsiloxane contained in the charge transport layer. The “ratio of resin A and resin B” in Table 20 means the content (mass%) of resin A or resin B with respect to the total solid content in the charge transport layer. The “silicon element ratio” in Table 20 means the abundance ratio (atomic%) of the silicon element to the constituent elements on the outermost surface of the charge transport layer, which was measured using ESCA.

[Production Example 104 of Photoreceptor]
In the photoconductor 1, the photoconductor 104 was produced in the same manner as the photoconductor 1 except that the method for producing the charge transport layer was changed as follows.
That is, as the charge transporting substance, 9 parts of the compound represented by the above formula (13-1), 1 part of the above formula (13-8), and as the resin, a polycarbonate resin (trade name: Iupilon Z400, Mitsubishi Engineering Plastics Co., Ltd.) The mixture was dissolved in a mixed solvent of 10 parts of the above formula (11-1), viscosity average molecular weight Mv = 40,000), 60 parts of o-xylene and 50 parts of dimethoxymethane.
Next, 5 parts of tetrafluoroethylene resin particles (trade name: Lubron L2, manufactured by Daikin Industries, Ltd.), 5 parts of polycarbonate resin composed of the repeating structural unit of the above formula (11-1), and 70 parts of o-xylene. Was mixed. Further, 0.25 parts of the polymer (EA, Mw = 22,000) produced in Production Example (E-1) described in Japanese Patent No. 4436456 was added as a dispersion aid to prepare a liquid. This liquid is passed twice at a pressure of 49 MPa (500 kg / cm ² ) with a high-speed liquid collision type disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA) to contain tetrafluoroethylene resin particles. The liquid was dispersed under high pressure. The average particle size of the tetrafluoroethylene resin particles after dispersion was 0.32 μm. The tetrafluoroethylene resin particle dispersion prepared in this manner was mixed with the coating liquid containing the charge transporting substance to prepare a coating liquid for the surface. The added amount is such that the mass ratio of the tetrafluoroethylene resin particles to the total solid content (charge transport substance, binder resin and tetrafluoroethylene resin particles) in the coating liquid is 5.0% by mass. did. The coating liquid for the surface layer prepared as described above is dipped and coated on the charge generating layer and dried at a temperature of 125 ° C. for 20 minutes to form a surface layer having an average film thickness of 17 μm at a position 130 mm from the upper end of the support. did.
In this way, the photoconductor 104 was produced.

[Production Examples 105, 107, 113-117 of Photoreceptor]
In Production Example 104 of the photoconductor, the dispersion aid was synthesized by the method described in JP-A-2001-249481, changed to the polymer (Mw = 100,000) represented by the above formula (20-8), and Table 21 Photoconductors 105, 107, 113 to 117 were produced in the same manner as in Production Example 104 with the material composition and ratio shown in 1.

[Production Examples 106, 108 to 112 of Photoreceptor]
In the production example 104 of the photoconductor, the photoconductors 106 and 108 to 112 were produced in the same manner as in the production example 104 except that the dispersion aid type was not changed and the material composition and ratio shown in Table 21 were changed.

[Production Examples of Photoreceptors 118-120]
In Production Example 104 of the photoconductor, fluorine oil (trade name: Modiper F210, manufactured by NOF CORPORATION) was used as a dispersion aid, and the photosensitivity was the same as in Production Example 104 except that the composition and ratio were changed to those shown in Table 21. Body 118-120 was made.

[Production Example 121 of Photoreceptor]
In Production Example 104 of the photoconductor, 0.25 parts of the polymer (EB, Mw = 20,000) produced in Production Example (E-2) described in Japanese Patent No. 4436456 as a dispersion aid was used, and Table 21 Photoreceptor 121 was produced in the same manner as in Production Example 104 except that the material composition and ratio of the above were used.

[Production Example 122 of Photoreceptor]
In Production Example 104 of the photoconductor, 0.25 parts of the polymer (EC, Mw = 23,000) produced in Production Example (E-3) described in Japanese Patent No. 4436456 as a dispersion aid was used, and Table 21 The photoconductor 122 was produced in the same manner as in Production Example 104 except that the material composition and ratio of the above were used.

[Production Example 123 of Photoreceptor]
In Production Example 104 of the photoconductor, 0.25 parts of the polymer (ED, Mw = 22,600) produced in Production Example (E-4) described in Japanese Patent No. 4436456 as a dispersion aid was used, and Table 21 Photoreceptor 123 was produced in the same manner as in Production Example 104 except that the material composition and ratio of the above were used.

[Production Example 124 of Photoreceptor]
In Production Example 104 of the photoconductor, the dispersion aid was synthesized by the method described in JP-A-2001-249481, changed to the polymer (Mw = 85,000) represented by the above formula (20-3), and Table 21 Photoreceptor 124 was produced in the same manner as in Production Example 104 with the material composition and ratio shown in 1.

[Production Example 125 of Photoreceptor]
In Production Example 104 of the photoconductor, the dispersion aid was synthesized by the method described in JP-A-2001-249481, changed to the polymer (Mw = 105,000) represented by the above formula (20-6), and Table 21 Photoreceptor 125 was produced in the same manner as in Production Example 104 with the material composition and ratio shown in 1.

[Production Example 126 of Photoreceptor]
In Production Example 104 of the photoconductor, the dispersion aid was synthesized by the method described in JP-A-2001-249481, changed to the polymer (Mw = 90,000) represented by the above formula (20-7), and Table 21 Photoreceptor 126 was produced in the same manner as in Production Example 104 with the material composition and ratio shown in 1.

[Production Example 127 of Photoreceptor]
In Production Example 104 of the photoconductor, the dispersion aid was synthesized by the method described in JP-A-2001-249481, changed to the polymer (Mw = 80,000) represented by the above formula (20-11), and Table 21 Photoreceptor 127 was produced in the same manner as in Production Example 104 with the material composition and ratio shown in 1.

[Production Example 128 of Photoreceptor]
In Production Example 104 of the photoconductor, the dispersion aid was synthesized by the method described in JP-A-2001-249481, changed to the polymer (Mw = 40,000) represented by the above formula (20-18), and Table 21 Photoreceptor 128 was produced in the same manner as in Production Example 104 with the material composition and ratio shown in 1.

[Production Example 129 of Photoreceptor]
In Production Example 104 of the photoconductor, the dispersion aid was synthesized by the method described in JP-A-2001-249481, changed to the polymer (Mw = 50,000) represented by the above formula (20-19), and Table 21 Photoreceptor 129 was produced in the same manner as in Production Example 104 with the material composition and ratio shown in 1.

[Production Example 2 of Comparative Photoreceptor]
In Production Example 104 of the photoconductor, the comparative photoconductor 2 was produced in the same manner as the photoconductor 104 except that the surface layer was made of a charge transporting substance and a resin without using tetrafluoroethylene resin particles.

“Charge transporting substance” in Table 21 indicates the type and number of copies of the charge transporting substance. “Resin” refers to a resin having a repeating unit represented by the formula. "Resin viscosity average molecular weight" indicates the viscosity average molecular weight (Mv) of the resin. The "fluororesin particle amount" indicates the ratio (mass%) of the fluororesin particles to the total mass of the surface layer. "Amount of dispersion aid" indicates the ratio (mass%) of the dispersion aid to the mass of the fluororesin particles. "Fluororesin particle size" indicates the average particle size (μm) of the fluororesin particles immediately after dispersion.

[Example 1]
<Manufacturing of process cartridge>
A toner cartridge (Cartridge 311 Cyan; manufactured by Canon Inc.) was used. The cleaning blade was thoroughly wiped with a cloth impregnated with ethanol and allowed to air dry for 1 day to eliminate concerns that deposits on the cleaning blade would affect the evaluation. Further, in order to evaluate whether cleaning is possible without increasing the linear pressure of pressing the edge portion of the cleaning blade onto the surface of the photoconductor, the amount of penetration of the cleaning blade into the surface of the photoconductor is 0.8 mm (cleaning blade). The state in which the cleaning blade is in contact with the surface of the photoconductor at zero linear pressure is defined as "penetration amount 0.0 mm", and from there, the cleaning blade is pushed in 0.8 mm in the direction perpendicular to the surface of the photoconductor). The photoconductor 1 was used as the photoconductor, and the developing container was filled with toner 1. In this way, a process cartridge having the photoconductor 1 and the toner 1 was obtained.

<Evaluation>
As the evaluation device, a developing device (Satera LBP5300; manufactured by Canon Inc.) of a one-component contact developing system was used. In consideration of the evolution of the electrophotographic system in the future, the pre-rotation time from the insertion of the new cartridge into the developing device to the ready state for printing was modified to be 5 seconds. The evaluation was performed in a low temperature and low humidity environment (10 ° C./14% RH) where cleaning becomes more severe. It is considered that the reason why cleaning becomes strict under low temperature and low humidity is that the hardness of the cleaning blade increases and the followability to the photoconductor decreases.

(1) Image evaluation Under a low-temperature and low-humidity environment (10 ° C / 14% RH), 20 consecutive charts with a solid image portion formed on the entire surface of printing paper in cyan monochromatic mode are output continuously and evaluated according to the following criteria. did. The evaluation results are shown in Table 22.
A: No white streaky vertical lines are seen in any of the 20 images.
B: Among the 20 images, there is an image in which one or two white streaky vertical lines are thinly seen.
C: Among the 20 images, there is an image in which clear white streaky vertical lines are seen, or three or more thin vertical lines are seen.

(2) Contamination of charged members After the above image evaluation was performed, the charged members in the cartridge were collected, visually confirmed whether or not stains due to toner adhesion were observed, and evaluated according to the following criteria. The evaluation results are shown in Table 22.
A: No dirt is seen.
B: Some dirt is seen.
C: Dirt is noticeable.

[Examples 2 to 103]
In Example 1, a process cartridge was produced in the same manner as in Example 1 except that the photoconductor 1 and the toner 1 were changed to the photoconductor and the toner shown in Table 22, and image evaluation and evaluation of charge member contamination were performed. It was. The results are shown in Table 22.

[Examples 104 and 105]
In Examples 12 and 78, the process cartridge was used in the same manner as in Examples 12 and 78, except that the pre-rotation time from inserting the new cartridge into the developing device to the printable standby state was changed to 20 seconds. It was prepared and evaluated for image and contamination of charged members. The results are shown in Table 22.

[Comparative Examples 1 to 5]
In Example 1, a process cartridge was produced in the same manner as in Example 1 except that the photoconductor 1 and the toner 1 were changed to the photoconductor and the toner shown in Table 23, and image evaluation and evaluation of charge member contamination were performed. It was. The results are shown in Table 23.

[Example 106]
<Manufacturing of process cartridge>
The evaluation device used a developing device (Satera LBP5300; manufactured by Canon) of a one-component contact developing system, and was adjusted so as not to discharge toner during non-image formation. The evaluation was performed in a low temperature and low humidity environment (10 ° C./14% RH) where cleaning becomes more severe. It is considered that the reason why cleaning becomes strict under low temperature and low humidity is that the hardness of the cleaning blade increases and the elastic modulus decreases, so that the followability to the photoconductor decreases.
The photoconductor 104 was used as the photoconductor, and the developing container was filled with toner 1. In this way, the image evaluation and the contamination of the charged member were evaluated using the process cartridge having the photoconductor 104 and the toner 1.

(3) Image evaluation Under a low temperature and low humidity environment (10 ° C / 14% RH), after enduring 10,000 sheets using a test chart with a printing rate of 1%, the entire surface of the paper is covered with a solid black image in cyan monochromatic mode. Twenty charts forming the above were output in succession and evaluated according to the following criteria. The evaluation results are shown in Table 24.
A: No white streaky vertical lines are seen in any of the 20 images.
B: Among the 20 images, there is an image in which one or two white streaky vertical lines are thinly seen.
C: Among the 20 images, there is an image in which clear white streaky vertical lines are seen, or three or more thin vertical lines are seen.

(4) Contamination of charged members After the above image evaluation was performed, the charged members in the cartridge were collected, and it was visually confirmed whether or not stains due to the adhesion of the external additive were observed, and the evaluation was performed according to the following criteria. The evaluation results are shown in Table 24.
A: No white stains can be seen.
B: Some white stains can be seen.
C: White stains are noticeable.

[Examples 107 to 157]
In Example 106, a process cartridge was produced in the same manner as in Example 106 except that the photoconductor 104 and the toner 1 were changed to the photoconductor and the toner shown in Table 24, and image evaluation and evaluation of charge member contamination were performed. .. The results are shown in Table 24.

[Comparative Examples 6 to 11]
In Example 106, a process cartridge was produced in the same manner as in Example 106 except that the photoconductor 104 and the toner 1 were changed to the photoconductor and the toner shown in Table 25, and image evaluation and evaluation of charge member contamination were performed. .. The results are shown in Table 25.

From the comparison between the examples and the comparative examples, in the comparative examples, the effect of suppressing the contamination of the charged members is not sufficiently obtained, and the image quality is deteriorated due to the contamination of the charged members. Further, when the evaluated electrophotographic photosensitive member was taken out from the cartridge and the vicinity of the portion where the cleaning blade was in contact was observed, a retention layer uniform in the longitudinal direction of the photosensitive member was formed on the photosensitive member used in the examples. Although lines were formed, the lines of the retention layer on the photoconductor used in the comparative example were interrupted (non-uniform). In the above examples, examples other than Examples 1, 2, 3, 5, 8, and 9 are reference examples.

From the above evaluation, it was shown that a uniform retention layer can be formed by the image forming method, the process cartridge and the electrophotographic apparatus of the present invention. The image forming method, the process cartridge, and the electrophotographic apparatus of the present invention have been shown to be superior in that they can exhibit good cleanability and suppress deterioration of image quality due to contamination of charged members.

1 Electrophotographic photosensitive member 2 axes 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Cleaning means 8 Fixing means 9 Process cartridge 10 Guide means P Transfer material T Toner

Claims (9)

A charging step of contacting the electrophotographic photosensitive member to charge the electrophotographic photosensitive member, a developing step of developing the electrophotographic photosensitive member with toner to form a toner image, and the toner image on the electrophotographic photosensitive member. In an image forming method including a transfer step of transferring the toner to the transfer material and a cleaning step of contacting the blade with the electrophotographic photosensitive member and removing the toner on the electrophotographic photosensitive member.
The surface layer of the electrophotographic photosensitive member satisfies the following conditions (i) or (ii).
(I) Polyarylate resin A and polycarbonate having a polysiloxane structure represented by the formula (1) (ii) containing fluororesin particles and at least one resin selected from the group consisting of polyarylate resin and polycarbonate resin. Contains at least one resin selected from the group consisting of resin B
(In the formula (1), R ¹¹ and R ¹² each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. N represents an integer of 10 or more and 200 or less.)
The polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the following formula (2) at least at least a part of the terminals.
(In the formula (2), R ^{21 to} R ²⁴ independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Z represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. n represents an integer of 10 or more and 200 or less. M represents an integer of 1 or more and 3 or less.)
The toner is to have a toner particle containing resin C and styrene acrylic resins having a isosorbide units represented by the formula (14) in its surface,
The content of the styrene acrylic resin in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 50.0% by mass or more and 99.0% by mass or less.
The resin C contains 0.10 mol% or more and 30.00 mol% or less of the isosorbide unit represented by the above formula (14) as a constituent component.
An image forming method , wherein the content of the resin C in the toner with respect to a total resin having a number average molecular weight of 1500 or more is 1.0% by mass or more and 35.0% by mass or less . The abundance ratio of the silicon element to the constituent elements on the outermost surface of the surface layer obtained by using X-ray photoelectron spectroscopy (ESCA) is 3.0 atomic% or more.
The image forming method according to claim 1, wherein the resin C contains 0.10 mol% or more of the isosorbide unit represented by the formula (14) as a constituent component. The content of the structure represented by the formula (1) in the polyarylate resin A and the polycarbonate resin B is 5.0% by mass or more and 60% by mass or less.
The image forming method according to claim 1, wherein the resin C contains 0.10 mol% or more of the isosorbide unit represented by the formula (14) as a constituent component. The image forming method according to claim 1, wherein the polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the following formula (15).
(In formula (15), R ^{151 to} R ¹⁵⁴ independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Z is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or Indicates a substituted or unsubstituted aryl group. N indicates an integer of 10 or more and 200 or less.) The polyarylate resin A, an image forming method according to claim 1, characterized by having a structural unit represented by the following following formula (5).
(In formula (5), X ⁵ 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. M ¹ and m ² are parentheses. Indicates the number of repetitions of the structure in, and the average value of m ^{1 and} the average value of m ² are independently 1 or more and 3 or less. W indicates the structure represented by the following formula (5-A).)
(In the formula (5-A), R ^{511 to} R ⁵²⁰ each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Z represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. Shown. N indicates the number of repetitions of the structure in parentheses, and the average value of n is 10 or more and 200 or less. K and l indicate the number of repetitions of the structure in parentheses, and the average value of k and the average of l. The values are independently 1 or more and 10 or less.) The image forming method according to claim 1, wherein the surface layer contains a polydimethylsiloxane represented by the following formula (16).
(In equation (16), n represents an integer of 10 or more and 200 or less.) The content of the polydimethylsiloxane represented by the formula (16) contained in the surface layer is 3.0% by mass or more with respect to the polyarylate resin A and the polycarbonate resin B contained in the surface layer. 20.0% by mass or less,
The image forming method according to claim 6 , wherein the resin C contains 0.10 mol% or more of the isosorbide unit represented by the formula (14) as a constituent component. A process cartridge that is detachably attached to the main body of the electrophotographic apparatus.
The process cartridge is a charging means for contacting the electrophotographic photosensitive member and the electrophotographic photosensitive member to charge the electrophotographic photosensitive member, and a developing means for developing the electrophotographic photosensitive member with toner to form a toner image. And a cleaning means for contacting the blade with the electrophotographic photosensitive member and removing the toner on the electrophotographic photosensitive member.
The surface layer of the electrophotographic photosensitive member satisfies the following conditions (i) or (ii).
(I) Polyarylate resin A and polycarbonate having a polysiloxane structure represented by the formula (1) (ii) containing fluororesin particles and at least one resin selected from the group consisting of polyarylate resin and polycarbonate resin. Contains at least one resin selected from the group consisting of resin B
(In the formula (1), R ¹¹ and R ¹² each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. N represents an integer of 10 or more and 200 or less.)
The polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the following formula (2) at least at least a part of the terminals.
(In the formula (2), R ^{21 to} R ²⁴ independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Z represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. n represents an integer of 10 or more and 200 or less. M represents an integer of 1 or more and 3 or less.)
The toner is to have a toner particle containing resin C and styrene acrylic resins having a isosorbide units represented by the formula (14) in its surface,
The content of the styrene acrylic resin in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 50.0% by mass or more and 99.0% by mass or less.
The resin C contains 0.10 mol% or more and 30.00 mol% or less of the isosorbide unit represented by the above formula (14) as a constituent component.
A process cartridge characterized in that the content of the resin C in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 1.0% by mass or more and 35.0% by mass or less . An electrophotographic photosensitive member, a charging means for contacting the electrophotographic photosensitive member to charge the electrophotographic photosensitive member, a developing means for developing a toner image on the electrophotographic photosensitive member with toner, and the electrophotographic photosensitive member. In an image forming apparatus having a transfer means for transferring the toner image on the photoconductor to a transfer material, and a cleaning means for abutting the blade against the electrophotographic photosensitive member and removing the toner on the electrophotographic photosensitive member.
The surface layer of the electrophotographic photosensitive member satisfies the following conditions (i) or (ii).
(I) Polyarylate resin A and polycarbonate having a polysiloxane structure represented by the formula (1) (ii) containing fluororesin particles and at least one resin selected from the group consisting of polyarylate resin and polycarbonate resin. Contains at least one resin selected from the group consisting of resin B
(In the formula (1), R ¹¹ and R ¹² each independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. N represents an integer of 10 or more and 200 or less.)
The polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the following formula (2) at least at least a part of the terminals.
(In the formula (2), R ^{21 to} R ²⁴ independently represent an alkyl group, a fluoroalkyl group, or a phenyl group. Z represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. n represents an integer of 10 or more and 200 or less. M represents an integer of 1 or more and 3 or less.)
The toner is to have a toner particle containing resin C and styrene acrylic resins having a isosorbide units represented by the formula (14) in its surface,
The content of the styrene acrylic resin in the toner with respect to the total resin having a number average molecular weight of 1500 or more is 50.0% by mass or more and 99.0% by mass or less.
The resin C contains 0.10 mol% or more and 30.00 mol% or less of the isosorbide unit represented by the above formula (14) as a constituent component.
An electrophotographic apparatus characterized in that the content of the resin C in the toner with respect to a total resin having a number average molecular weight of 1500 or more is 1.0% by mass or more and 35.0% by mass or less .