JP2016218370A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method with which an image can be stably obtained for a long period, the image having good image density stability, image density uniformity, and thin line reproducibility irrespective of environment, and preventing image defects, such as fogging and ghost.SOLUTION: There is provided an image forming method including a charging step of charging an electrophotographic photoreceptor and a development step of developing an electrostatic latent image with a toner to form a toner image, where the toner is a toner having a core-shell structure in which a shell layer containing a polyester resin A is formed; the content of the polyester resin A is 0.10 parts by mass or more and 40.0 parts by mass or less; the dielectric loss tangent of the polyester resin A is 0.007 or more and 0.014 or less; the volume resistivity of an undercoat layer of the electrophotographic photoreceptor is 1×10Ω cm or more and 1×10Ω cm or less; and the undercoat layer contains an organic electron transport compound.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrophotographic image forming method for developing an electrostatic latent image.

  In an electrophotographic image forming method, an electrophotographic photosensitive member is charged to form an electrostatic latent image, and the electrostatic latent image is developed with charged toner particles to form an image. In recent years, there has been a demand for higher definition and higher image quality in image forming apparatuses, and along with this, improvements in image quality against image density fluctuations, image defects, and the like are increasing.

  In order to further improve the image quality, there is a technique for improving the sharp charge distribution and the rising characteristics of the toner that reaches the charge distribution and suppressing fogging in the initial stage of use. Patent Documents 1 and 2 describe a method of improving toner charge-up characteristics by adding a charge control agent to toner particles or externally adding inorganic fine particles to improve toner fluidity. ing.

  On the other hand, in the electrophotographic photoreceptor, there is a technique for improving the ghost by suppressing the staying of charges in the photosensitive layer in order to further improve the image quality. Patent Documents 3 and 4 describe that an undercoat layer formed between a support and a photosensitive layer contains an organic electron transporting compound such as an imide compound.

JP 2006-71970 A JP 2014-52646 A JP 2001-83726 A JP 2003-345044 A

  However, as a result of investigations by the present inventors, the toners described in Patent Documents 1 and 2 impart a high charge amount to the toner, and therefore, fogging derived from excessively charged toner when printing is advanced. There was a need to improve the suppression of Toner that is excessively charged (charged up) easily adheres electrostatically to the charge imparting member, tends to impede charge imparting to the toner, and tends to cause fog. Such a phenomenon is more remarkable in a low-temperature and low-humidity environment where toner charge-up is promoted.

  In addition, as in Patent Documents 1 and 2, when the charge rising characteristics of the toner are improved, it becomes easy to inject charges from the toner to the electrophotographic photosensitive member, and the surface potential of the electrophotographic photosensitive member may be disturbed. . As a result, charges are more likely to stay at the interface between the photosensitive layer and the undercoat layer, and ghosts are likely to occur.

  For the above reasons, it is possible to achieve a high image quality by combining both the sharp charge distribution of the toner and the rising characteristics of the toner charge leading to the charge distribution and the suppression of charge retention in the photosensitive layer of the electrophotographic photoreceptor. In reality, there is a demand for an image forming method that achieves the above.

  An object of the present invention is an image that has good image density stability, image density uniformity, fine line reproducibility regardless of the environment, and can obtain a stable image for a long time without image defects such as fogging and ghosting. A forming method is provided.

The present invention relates to a charging step for charging an electrophotographic photosensitive member,
An electrostatic latent image forming step of forming an electrostatic latent image on the charged electrophotographic photosensitive member,
A developing step of developing the electrostatic latent image with toner to form a toner image; and a transferring step of transferring the toner image to a transfer material with or without an intermediate transfer member;
An image forming method comprising:
The toner is a toner containing core-shell toner particles in which a shell layer containing polyester resin A is formed on a core containing a resin and a colorant;
The content of the polyester resin A is 0.10 parts by mass or more and 40.0 parts by mass or less with respect to 100.0 parts by mass of the resin.
The dielectric tangent of Polyester resin A at 25 ° C. and 10,000 Hz is 0.007 or more and 0.014 or less,
The polyester resin A contains 0.10 mol% or more and 20.0 mol% or less of units represented by the following formula (1) based on all monomer units constituting the polyester resin A,
The electrophotographic photoreceptor has a support, an undercoat layer formed on the support, a photosensitive layer formed on the undercoat layer,
The volume resistivity of the undercoat layer is 1 × 10 ¹¹ Ω · cm or more and 1 × 10 ¹⁶ Ω · cm or less,
The present invention relates to an image forming method, wherein the undercoat layer contains an organic electron transporting compound.

  According to the present invention, image density stability, image density uniformity, and fine line reproducibility are good regardless of the environment, and a stable image can be obtained for a long time without image defects such as fogging and ghosting. An image forming method can be provided.

1 is a schematic cross-sectional view of an image forming apparatus of the present invention. It is a figure which shows schematic sectional drawing of a process cartridge. (A) is a top view for demonstrating the method of measuring the volume resistivity of an undercoat layer, (B) It is sectional drawing for demonstrating the method of measuring the volume resistivity of an undercoat layer.

  The image forming method of the present invention will be described.

  As one of the structures of the present invention, a toner including core-shell structure toner particles in which a shell layer is formed on a core containing a resin and a colorant is used. The present inventors diligently studied about a toner having a core-shell structure, which has a sharp charge distribution and a good charge rising property of the toner leading to the charge distribution. As a result, it has been found that a toner that solves the above-mentioned problems can be obtained by using the polyester resin forming the shell with the structure and physical properties described in detail below. Specifically, the polyester resin A is contained in the shell layer, and the content of the polyester resin A is 0.10 parts by mass or more and 40.0 parts by mass or less with respect to 100.0 parts by mass of the resin. Furthermore, the dielectric loss tangent of the polyester resin A at 25 ° C. and 10,000 Hz is 0.007 or more and 0.014 or less. Polyester resin A contains 0.10 mol% or more and 20.0 mol% or less of units represented by the following formula (1) based on all monomer units constituting polyester resin A.

  The toner particles according to the present invention may be toner particles having the above-described configuration, and can be produced using a known pulverization method and polymerization method. Among them, it is preferable to produce by a suspension polymerization method, a solution suspension polymerization method, or an emulsion aggregation method that can easily form and control the core-shell structure. In particular, it is easy to obtain a toner particle having a core-shell structure, which is easy to reduce the particle size, has a nearly spherical shape and has little surface irregularity, and has a sharp charge distribution and a good charge rising property of the toner leading to the charge distribution. Toner particles produced by a polymerization method are preferred.

  For example, in the suspension polymerization method, toner particles are produced by adding a polar resin to a polymerizable monomer composition containing a polymerizable monomer that produces a resin and, if necessary, a colorant and a wax. This makes it possible to obtain toner particles having a core-shell structure in which a core formed from a resin, a colorant, and if necessary, a wax is covered with a shell layer formed from a polar resin.

  In the present invention, the above-mentioned polyester resin A is contained as a polar resin for forming a shell layer of toner particles.

  In the polyester resin A, the unit represented by the formula (1) is 0.10 mol% or more and 20.0 mol% or less, preferably 1.30 mol% or more and 15.0 mol%, based on all monomer units constituting the polyester resin A. Contains the following.

  When the content of the unit represented by the formula (1) (hereinafter also referred to as an isosorbide unit) is within the above range, it is possible to improve the sharp charge distribution of the toner and the rising characteristics of the toner leading to the charge distribution. it can. The reason is presumed to be due to the following effects.

  Since the isosorbide unit has a cyclic structure having an ether group in the molecule, the polyester resin A containing the isosorbide unit has the same charge generation as that of the conventional polyester resin, and has a moderately large dielectric loss tangent. Therefore, by including the polyester resin A in the shell layer of the toner particles having the core-shell structure, the exchange of charges between the toner particles can be improved within a limited number of toner contacts. As a result, it is speculated that the sharp charge distribution of the toner and the rising characteristics of the toner leading to the charge distribution are improved, and the high image quality can be maintained over a long period of time.

  Conventionally, improving the sharp charge distribution of the toner and the rising characteristics of the charge of the toner that leads to the charge distribution speeds up the transfer of charge between toner particles, making it easier to inject charge from the toner to the electrophotographic photoreceptor. The surface potential of the electrophotographic photosensitive member may be disturbed. However, even if the toner of the present invention is used, if the electrophotographic photoreceptor of the present invention described later is used, the effect of preventing disturbance of the surface potential of the electrophotographic photoreceptor due to the injection of charge from the toner can be exhibited. all right. As a result, image density stability, image density uniformity, and fine line reproducibility are good regardless of the environment, and high-quality images can be stably obtained over a long period without image defects such as fogging and ghosting. became.

  The polyester resin A of the present invention uses isosorbide as an alcohol component, but the following materials can be used in combination as other alcohol components.

  Examples of the dihydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl). ) Propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4) -Alkylene oxide adducts of bisphenol A such as 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, neope Fats such as til glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Group-based diols; bisphenol A such as bisphenol A and hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Is mentioned.

  Moreover, the following are mentioned as an acid component used in order to form the polyester resin A. For example, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; carbons such as fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid Aliphatic polycarboxylic acids such as succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms; anhydrides of these acids and alkyls of these acids (1 to 8 carbon atoms) Examples include esters.

  Among them, in particular, a polyester obtained by polycondensation using a bisphenol derivative as an alcohol component and a divalent or higher carboxylic acid or acid anhydride thereof or a lower alkyl (carbon number 1 to 8) ester thereof as an acid component. Resin A can be preferably used.

  The dielectric loss tangent of polyester resin A at 25 ° C. and 10,000 Hz is 0.007 or more and 0.014 or less. Preferably it is 0.008 or more and 0.012 or less. When the dielectric loss tangent is 0.007 or more and 0.014 or less, the charge transfer between the toner particles is good, and the sharp charge distribution of the toner and the rising characteristic of the toner charge leading to the charge distribution are improved. When it is larger than 0.014, the toner charge leakage increases, and developability such as fogging in a high humidity environment may be deteriorated. Furthermore, charge injection from the toner into the electrophotographic photosensitive member is increased, and the surface potential of the electrophotographic photosensitive member is likely to be disturbed, which may cause fogging, image density stability, and image defects. On the other hand, if it is smaller than 0.007, the charge transfer between the toner particles becomes insufficient, and it is impossible to obtain the desired charge sharpness distribution of the toner and the rising characteristic of the toner charge that leads to the charge distribution. In order to make the dielectric loss tangent within the above range, the content of the isosorbide unit, the alcohol component and the acid component exemplified above can be adjusted. In the present invention, for example, in addition to the isosorbide unit, a component having an ether structure such as ethylene glycol can be added and the content can be adjusted to adjust the dielectric loss tangent. Especially, it is preferable to adjust a dielectric loss tangent in the said range by adjusting content of an isosorbide unit.

  The reason why it is preferable to adjust the content of the isosorbide unit is presumed to be due to the following effects. Since the isosorbide unit has an ether bond in the cyclic structure, the influence on the dielectric loss tangent per unit is not so large as compared with a unit having an ether bond such as ethylene glycol, and is moderate. Therefore, it is assumed that the dielectric loss tangent is not partially increased as the polyester resin, and an appropriate dielectric loss tangent can be imparted to the polyester resin A.

  The acid value of the polyester resin A is preferably 0.5 mgKOH / g or more and 25.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or more and 15.0 mgKOH / g or less.

  When the acid value of the polyester resin A is within the above range, the shell layer is sufficiently formed, and the heat resistant storage stability and developability are improved. Further, when the acid value of the polyester resin A is within the above range, the particle size distribution is good when the toner particles are produced by the suspension polymerization method, and the developability is improved.

  The acid value of the polyester resin A can be adjusted to the above range by adjusting the type and blending amount of monomers used for the resin. Specifically, it can be controlled by adjusting the alcohol monomer component ratio / acid monomer component ratio and molecular weight during resin production.

  The weight average molecular weight (Mw) of the polyester resin A is preferably 5000 or more and 30000 or less, and more preferably 7000 or more and 20000 or less. Within the above range, the strength of the shell layer becomes appropriate, and both low-temperature fixability, heat-resistant storage stability, and developability are improved.

  The weight average molecular weight (Mw) of the polyester resin A can be controlled by adjusting the reaction time and the amount of catalyst added.

  In the toner of the present invention, the amount of the polyester resin A is 0.10 parts by mass or more and 40.0 parts by mass or less with respect to 100.0 parts by mass of the resin forming the core. More preferably, they are 1.0 mass part or more and 20.0 mass parts or less, More preferably, they are 1.5 mass parts or more and 10.0 mass parts or less. If it is within the above range, the thickness of the shell layer becomes appropriate, and good toner can be obtained while maintaining good heat storage stability and developability.

  In the present invention, a conventionally known polyester resin may be used in combination with the binder resin and the polyester resin A.

  Next, the toner and the toner production method of the present invention will be described in detail.

  The weight average particle diameter (D4) of the toner of the present invention is preferably 4.0 μm or more and 9.0 μm or less. More preferably, it is 5.0 μm or more and 7.5 μm or less.

  When the weight average particle diameter of the toner is 4.0 μm or more, the fluidity of the toner is maintained, the charge rising property and the charge distribution are improved, and it is difficult to cause problems such as fogging, scattering, and low image density. In addition, the cleaning performance of the transfer residual toner remaining on the electrophotographic photosensitive member or the intermediate transfer member is maintained, and image defects due to contamination of the image carrier, the intermediate transfer member, and the charge imparting member are less likely to occur. When it is 9.0 μm or less, it becomes difficult to cause deterioration of fine line reproducibility of minute characters and image scattering.

  Hereinafter, the toner particles produced by the suspension polymerization method, which is a preferred production method of the toner particles of the present invention, will be described in detail.

  Toner particles produced by the suspension polymerization method are produced, for example, as follows. A polymerizable monomer composition is prepared by mixing a colorant (colorant composition), a wax, a polymerization initiator, and the like, if necessary, with the polymerizable monomer that forms the resin. Next, the polymerizable monomer composition is dispersed in an aqueous medium to form (granulate) particles of the polymerizable monomer composition. Then, the polymerizable monomer in the particles of the polymerizable monomer composition is polymerized in an aqueous medium to obtain toner particles.

  As the polymerizable monomer, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Examples of the monofunctional polymerizable monomer include the following.

  Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n- Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n -Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl Phosphate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl Vinyl ethers such as ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone;

  The following are mentioned as a polyfunctional polymerizable monomer. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2 '-Bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-bu Lenglycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2,2′-bis ( 4- (methacryloxy polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether.

  A monofunctional polymerizable monomer is used individually or in combination of 2 or more types or in combination with a polyfunctional polymerizable monomer. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

  The polymerizable monomer composition in the above step is prepared by mixing a dispersion in which a colorant is dispersed in the first polymerizable monomer with the second polymerizable monomer. Is preferred. That is, after sufficiently dispersing the colorant with the first polymerizable monomer, the colorant is mixed with the second polymerizable monomer together with the other toner materials, so that the colorant is in a better dispersed state. It can be present in the toner particles.

  As a polymerization initiator used in the polymerization of the polymerizable monomer, an oil-soluble initiator and / or a water-soluble initiator is used. Examples of oil-soluble initiators include the following. 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4 -Pigment dispersants such as methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t- Butyl peroxy-2-ethylhexanoate, benzoyl peroxide, t-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroper Kisaido, di -t- butyl peroxide, peroxide initiators such as cumene hydroperoxide.

  The following are mentioned as a water-soluble initiator. Ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) Hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

  In order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor or the like can be further added and used.

  As for the density | concentration of the said polymerization initiator, 0.1-20 mass parts is preferable with respect to 100 mass parts of polymerizable monomers, More preferably, it is 0.1-10 mass parts. The kind of the polymerizable initiator is slightly different depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  Furthermore, in the present invention, a crosslinking agent can be used during the synthesis of the vinyl polymer in order to increase the stress resistance of the toner particles and to control the molecular weight of the constituent molecules of the toner particles.

  As the crosslinking agent, a compound having two or more polymerizable double bonds is used. Specifically, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; two compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, and 1,3-butanediol dimethacrylate. Examples thereof include carboxylic acid esters having two heavy bonds; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

  These cross-linking agents are preferably in the range of 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts with respect to 100 parts by mass of the polymerizable monomer in terms of toner fixing property and offset resistance. Used in the range of parts by mass.

  The polymerizable monomer and the crosslinking agent are preferably used alone or by appropriately mixing the monomers so that the theoretical glass transition temperature (Tg) is in the range of 40 to 75 ° C. When the theoretical glass transition temperature is 40 ° C. or higher, there is little problem in terms of storage stability and stress resistance of the toner, while when it is 75 ° C. or lower, transparency and low-temperature fixability in the case of toner full-color image formation. Does not drop.

  The aqueous medium used in the suspension polymerization method preferably contains a dispersion stabilizer. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used. Examples of inorganic dispersion stabilizers include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate, bentonite, silica, alumina and the like.

  Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. Nonionic, anionic and cationic surfactants can also be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like can be mentioned.

  Among the dispersion stabilizers, in the present invention, it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in acid. In the present invention, when preparing a water-based dispersion medium using a hardly water-soluble inorganic dispersion stabilizer, these dispersion stabilizers are added in an amount of 0.2 to 2 to 100 parts by mass of the polymerizable monomer. It is preferable to use it in a proportion that is in the range of 0.0 part by mass. This is because by using in such a range, the droplet stability of the polymerizable monomer composition in the aqueous medium is improved. Moreover, in this invention, it is preferable to prepare an aqueous medium using the water of the range of 300-3000 mass parts with respect to 100 mass parts of polymerizable monomer compositions.

  In the present invention, when preparing an aqueous medium in which the poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is. However, in order to obtain dispersion stabilizer particles having a fine uniform particle size, it is preferable to prepare by preparing the above hardly water-soluble inorganic dispersion stabilizer under high speed stirring in water. For example, when calcium phosphate is used as a dispersion stabilizer, a preferable dispersion stabilizer can be obtained by mixing a sodium phosphate aqueous solution and a calcium chloride aqueous solution under high speed stirring to form calcium phosphate fine particles.

  In the suspension polymerization method, a polar resin containing polyester resin A is added to the polymerizable monomer composition to produce toner particles. As a result, it is possible to obtain a toner having a core-shell structure in which a resin mainly forming a core and a wax added as necessary are coated with a polar resin (shell) containing the polyester resin A.

  For this reason, these polymerized toners contain wax in a toner well, so that even if a relatively large amount of wax is contained, exposure to the surface of the toner is small and toner deterioration in continuous printing is suppressed. Can do.

  As the colorant of the toner of the present invention, the following black, yellow, magenta and cyan pigments and, if necessary, dyes can be used.

  Examples of the black colorant include carbon black. Moreover, the following yellow / magenta / cyan colorants are mixed and adjusted to black. Although there is no restriction | limiting in particular as carbon black, For example, carbon black obtained by manufacturing methods, such as a thermal method, an acetylene method, a channel method, a furnace method, a lamp black method, can be used. The average primary particle size of the carbon black used in the present invention is not particularly limited, but the average primary particle size is preferably 14 to 80 nm, more preferably 25 to 50 nm. When the average primary particle size is 14 nm or more, the toner does not exhibit a reddish color and is preferable as black for forming a full-color image. When the average primary particle size of carbon black is 80 nm or less, it is preferable that the carbon black is well dispersed and the coloring power is not too low. The carbon black may be used alone or in combination of two or more. These may be crude pigments, or may be prepared pigment compositions as long as they do not significantly inhibit the effect of the pigment dispersant of the present invention.

  As the pigment-based yellow colorant, compounds represented by condensed polycyclic pigments, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191: 1, 191, 192, 193 199.

  Examples of the dye-based yellow colorant include C.I. I. solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. Disperse Yellow 42, 64, 201, 211 are listed.

  As the magenta colorant, condensed polycyclic pigments, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, 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 Violet 19 is exemplified.

  As the cyan colorant, phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds are used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  The colorants can be used alone or mixed and further used in the form of a solid solution. In the present invention, the colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, transparency of the OHP image, and dispersibility in the toner. The addition amount of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin forming the core.

  The toner of the present invention preferably contains one or more waxes. The total amount of wax contained in the toner is preferably 2.5 to 25.0 parts by mass in 100 parts by mass of toner particles. Further, the total amount of wax contained in the toner is more preferably 4.0 parts by mass or more and 20 parts by mass or less, and further preferably 6.0 parts by mass or more and 18.0 parts by mass or less.

  Examples of the wax include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, Fischer-Tropsch wax, paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof ; Waxes mainly composed of fatty acid esters such as carnauba wax and montanic acid ester wax, and deoxidized part or all of fatty acid esters such as deoxidized carnauba wax; palmitic acid, stearic acid, montanic acid, etc. Saturated linear fatty acids; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, merisyl Saturated alcohols such as alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide; Saturated fatty acid bisamides such as hexamethylene bisstearic acid amide; unsaturated fatty acids such as ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N ′ dioleyl sebacic acid amide Amides; aromatic bisamides such as m-xylene bis-stearic acid amide and N, N ′ distearyl isophthalic acid amide; fats such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate Metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and polyhydric alcohols Partially esterified products: methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

  In the toner of the present invention, it is preferable to use a charge control agent in order to keep the charging property of the toner stable regardless of the environment.

  Examples of negatively charged charge control agents include the following. Monoazo metal compound, acetylacetone metal compound, aromatic oxycarboxylic acid, aromatic dicarboxylic acid, oxycarboxylic acid and dicarboxylic acid-based metal compound, aromatic oxycarboxylic acid, aromatic mono- and polycarboxylic acid and metal salt thereof, Examples include anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and charge control resins.

  Examples of the positive charge control agent include the following. Nigrosine-modified products of nigrosine and fatty acid metal salts, etc .; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Phosphonium salts and other onium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid Acid, ferricyanide, ferrocyanide, etc.); metal salt of higher fatty acid; diorganotin oxide such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; DOO, dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate; and the charge control resin. These can be used alone or in combination of two or more.

  Among these, the charge control resin is preferable, and the pKa of the charge control resin is more preferably 6.0 or more and 9.0 or less. In particular, the pKa of the charge control resin is preferably 7.0 or more and 8.5 or less. By setting the pKa of the charge control resin within the above range, moisture adsorption of the toner is suppressed, the toner exhibits excellent charging characteristics in a high temperature and high humidity environment, and developability such as fog is improved.

  The charge control resin may be any resin as long as it satisfies the above pKa (acid dissociation constant). In particular, the charge control resin preferably has a structure represented by the formula (2) in the side chain as a molecular structure.

(R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms. N represents an integer of 0 to 3; when n is 2 or 3, R ¹ May be the same or different, * is a binding site in the charge control resin.)

  The structure represented by the above formula (2) is more preferably a structure represented by the following formula (3).

(R ² represents an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms. R ³ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or Represents an alkoxyl group having 1 to 18 carbon atoms, g represents an integer of 1 to 3, h represents an integer of 0 to 3, and when h is 2 or 3, R ² is the same. Or may be different. * Is a binding site in the charge control resin.)

Examples of the alkyl group in R ² and R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. Examples of the alkoxyl group in R ² and R ³ include methoxy group, ethoxy group, propoxy group and the like.

  The main chain structure of the charge control resin having a structure represented by the formula (2) in the side chain is not particularly limited. For example, a vinyl polymer, a polyester polymer, a polyamide polymer, a polyurethane polymer, a poly Examples thereof include ether polymers, etc. Considering ease of production in producing the charge control resin, cost merit, etc., polyester polymers or vinyl polymers are preferable.

  The charge control resin containing Formula (2) and Formula (3) may be a single polymer or a copolymer with another polymerizable monomer. Specific examples of the polymerizable monomer that can be used as the copolymer are as follows. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n -Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-buty methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, Diethyl phosphate ethyl methacrylate, dibutyl phosphate Such methacrylic polymerizable monomers of methacrylate are exemplified.

  It does not specifically limit as a manufacturing method of the said charge control resin, It can manufacture by a well-known method. As an example, polymerization may be performed using a polymerizable monomer (a compound represented by the formula (4)) having a structure represented by the formula (2) and a polymerization initiator.

(In Formula (4), R ⁶ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms. R ⁷ represents a hydrogen atom, a hydroxy group, or 1 to 18 carbon atoms. The following alkyl group or an alkoxyl group having 1 to 18 carbon atoms is shown, m is an integer of 1 to 3, and n is an integer of 0 to 3. When n is 2 or 3, R ⁶ may be the same or different.)

  Specific examples of the compound represented by the formula (4) are shown below.

  The content of the structure a represented by the formula (2) contained in the charge control resin is preferably 50 μmol / g or more and 1000 μmol / g or less. By setting it to 50 μmol / g or more and 1000 mol / g or less, good chargeability and durability can be exhibited. Further, moisture adsorption to the toner can be suppressed in a high temperature and high humidity environment.

  When a charge control resin having a structure represented by formula (2) in the side chain is used, a charge generated by frictional charging can be stably imparted. In addition, moisture adsorption to the toner is suppressed in a high-temperature and high-humidity environment, so that excellent charging characteristics are exhibited and developability such as fog is improved.

  Although the measuring method of pKa (acid dissociation constant) is mentioned later, it can obtain | require from a neutralization titration result.

  The content of the charge control agent is preferably 0.01 parts by mass to 20.0 parts by mass, more preferably 0.05 parts by mass to 10.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer. It is.

  In addition to the polyester resin A, the toner of the present invention may use a polar resin that forms a shell layer. Examples of the polar resin are given below, but other resins may be used.

  Examples of the polar resin include polyester resin, polycarbonate resin, phenol resin, epoxy resin, polyamide resin, and cellulose resin. More preferably, a polyester resin is desired because of the variety of materials. The polar resin is preferably 0.5 parts by mass or more and 20.0 parts by mass or less, more preferably 1.0 parts by mass per 100 parts by mass of the resin forming the core in order to obtain the above-described detailed effect of the polyester resin A. Part to 10.0 parts by weight.

  The toner of the present invention may contain a crystalline polyester in the core for the purpose of improving the low-temperature fixability.

  Examples of the crystalline polyester include a resin obtained by polycondensation of an aliphatic dicarboxylic acid and an aliphatic diol.

  Aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, peric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecane Dicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, cyclohexanedicarboxylic acid, anhydrides or lower alkyl esters of these acids, etc. Is mentioned.

  Moreover, although crystalline polyester uses the aliphatic dicarboxylic acid as mentioned above as a main component, you may use trivalent or more polyvalent carboxylic acid other than said component.

  Trivalent or higher polyvalent carboxylic acid components include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, Examples thereof include 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, and derivatives such as acid anhydrides or lower alkyl esters thereof.

  These may be used alone or in combination of two or more.

  Specific examples of the aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, and pentamethylene. Examples include glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol, 1,4-butadiene glycol and the like.

  In addition, the above-mentioned aliphatic diol is used as the main component of the crystalline polyester. In addition to the above components, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A, 1,4-cyclohexanedimethanol, etc. Dihydric alcohol, aromatic alcohol such as 1,3,5-trihydroxymethylbenzene, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol Trivalent alcohols such as glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and the like may be used.

  These may be used alone or in combination of two or more.

  In the toner of the present invention, inorganic fine particles may be externally added to the surface of the toner particles. The inorganic fine particles are added to and mixed with the toner particles in order to improve the fluidity of the toner and make the charge uniform, and the added inorganic fine particles are present in a state of being uniformly attached to the surface of the toner particles.

  The inorganic fine particles preferably have a number average particle diameter (D1) of primary particles of 4 nm to 500 nm.

  As the inorganic fine particles, inorganic fine particles selected from silica, alumina, titania, or composite oxides thereof can be used. Examples of the composite oxide include silica alumina composite oxide, silica titania composite oxide, strontium titanate fine powder, and the like. These inorganic fine particles are preferably used after the surface is hydrophobized.

  Furthermore, other additives may be used in the toner used in the present invention as long as no substantial adverse effect is caused. For example, abrasives such as Teflon (registered trademark) powder, zinc stearate powder, polyvinylidene fluoride powder, abrasive powder such as cerium oxide powder, silicon carbide powder, anti-caking agent, and organic and / or inorganic of reverse polarity Examples include developability improvers that are fine particles. These additives can also be used after hydrophobizing the surface.

[Electrophotographic photoconductor]
Next, the electrophotographic photoreceptor of the present invention will be described.

The electrophotographic photoreceptor of the present invention has a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer. The volume resistivity of the undercoat layer is 1 × 10 ¹¹ Ω · cm or more and 1 × 10 ¹⁶ Ω · cm or less, and the undercoat layer contains an organic electron transporting compound.

  With the undercoat layer having the above characteristics, the charge movement in the undercoat layer and at the interface between the undercoat layer and the photosensitive layer is accelerated, and charge transfer due to injection of charge from the toner to the electrophotographic photosensitive member is accelerated. It is possible to eliminate the stay. Thereby, it is considered that fluctuation / decrease (attenuation) of the surface potential of the electrophotographic photosensitive member is suppressed.

When the volume resistivity of the undercoat layer is less than 1 × 10 ¹¹ Ω · cm, the surface potential is likely to decrease, and image defects due to charge injection from the toner are likely to occur. For this reason, fogging may deteriorate, or image density stability and image density uniformity may decrease. On the other hand, if it is larger than 1 × 10 ¹⁶ Ω · cm, electrons cannot move sufficiently before development after exposure, so that sufficient development contrast cannot be obtained and image density is lowered.

  In this way, a combination of a toner having a specific core-shell structure and an electrophotographic photosensitive member containing an organic electron transporting compound that controls the undercoat layer, synergistically stabilizes high-quality images over a long period of time. It is thought that it will be possible to output automatically.

  The photosensitive layer is preferably a stacked type (functional separation type) photosensitive layer separated into a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material. Furthermore, from the viewpoint of electrophotographic characteristics, the multilayer photosensitive layer is preferably a normal photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order from the support side.

[Support]
As the support, for example, a conductive support formed of a metal or alloy such as aluminum, nickel, copper, gold, or iron can be used. A support formed by a thin film of aluminum, silver or gold metal on an insulating support such as polyester resin, polycarbonate resin, polyimide resin or glass, or a support formed by a thin film of conductive material such as indium oxide or tin oxide. Can be mentioned.

  The surface of the support may be subjected to electrochemical treatment such as anodic oxidation, wet honing treatment, blast treatment, or cutting treatment in order to improve electrical characteristics and suppress interference fringes.

[Conductive layer]
A conductive layer may be provided between the support and the undercoat layer. The conductive layer is a layer formed using a conductive layer coating liquid in which conductive particles are dispersed in a resin. Examples of the conductive particles include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, and metal oxide powder such as conductive tin oxide and ITO. Can be mentioned.

  Examples of the resin include polyester resin, polycarbonate resin, polyvinyl butyral, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, and alkyd resin.

Examples of the solvent for the conductive layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents. The thickness of the conductive layer is preferably 0.2 μm or more and 40 μm or less. It is more preferably 1 μm or more and 35 μm or less, and further preferably 5 μm or more and 35 μm or less.

[Undercoat layer]
The undercoat layer is provided on the support or the conductive layer. The undercoat layer has a volume resistivity of 1 × 10 ¹¹ or more and 1 × 10 ¹⁶ Ω · cm or less and contains an organic electron transporting compound.

  The organic electron transporting compound preferably has a polymerizable functional group selected from a hydroxy group, a thiol group, an amino group, and a carboxy group. More preferably, it is a polymer of a composition comprising an organic electron transporting compound having a polymerizable functional group, a resin having a polymerizable functional group, and a crosslinking agent.

  The undercoat layer may contain conductive particles as long as the volume resistivity of the undercoat layer is within the above range. Examples of the conductive particles include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, and metal oxide powder such as conductive tin oxide and ITO. Can be mentioned. The content of the organic electron transporting compound is more preferably 30% by mass or more and 70% by mass or less with respect to the total mass of the composition.

  Examples of the organic electron transporting compound include quinone compounds, imide compounds, benzimidazole compounds, and cyclopentadienylidene compounds. Below, the compound shown by either of following formula (A-1)-(A-11) is shown as a specific example of an organic electron transport compound.

(Formula (A1) in ^{~ (A11), R 11 ~R} 16, R 21 ~R 30, R 31 ~R 38, R 41 ~R 48, R 51 ~R 60, R 61 ~R 66, R 71 ~ R ⁷⁸ , R ^{81 to} R ⁹⁰ , R ^{91 to} R ⁹⁸ are R ^{101 to} R ¹¹⁰ , R ^{111 to} R ¹²⁰ are each independently a monovalent group represented by the following formula (A), a hydrogen atom, A cyano group, a nitro group, a halogen atom, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic ring, and CH _{2 in} the main chain of the alkyl group. One may be replaced by O, S, NH or NR ¹²¹ (R ¹²¹ is an alkyl group), at least one of R ^{11 to} R ¹⁶ , at least one of R ^{21 to} R ³⁰ , and R ^{31 to} R ³⁸ . Small Both one ^and at least one of R 41 ^{to R 48,} at least one of R 51 ^{to R 60,} at least one of R 61 ^{to R 66,} at least one of R 71 ^{to R 78,} the R 81 ^{to R 90} At least one, at least one of R ^{91 to} R ⁹⁸ , at least one of R ^{101 to} R ¹¹⁰ , and at least one of R ^{111 to} R ¹²⁰ have a monovalent group represented by the formula (A).

  The substituent of the substituted alkyl group is an alkyl group, an aryl group, a halogen atom, or an alkoxycarbonyl group. The substituent of the substituted aryl group and the substituent of the substituted heterocyclic group are a halogen atom, a nitro group, a cyano group, an alkyl group, a halogen-substituted alkyl group, and an alkoxy group.

Z ²¹ , Z ³¹ , Z ⁴¹ and Z ⁵¹ each independently represent a carbon atom, a nitrogen atom or an oxygen atom. When Z ²¹ is an oxygen atom, R ²⁹ and R ³⁰ do not exist, and when Z ²¹ is a nitrogen atom, R ³⁰ does not exist. When Z ³¹ is an oxygen atom, R ³⁷ and R ³⁸ do not exist, and when Z ³¹ is a nitrogen atom, R ³⁸ does not exist. If Z ⁴¹ is an oxygen atom ^{R 47} and ^{R 48} are ^absent, when ^{Z 41} is a nitrogen atom ^{R 48} is absent. When Z ⁵¹ is an oxygen atom, R ⁵⁹ and R ⁶⁰ do not exist, and when Z ⁵¹ is a nitrogen atom, R ⁶⁰ does not exist. )

  (In Formula (A), at least one of α, β, and γ is a group having a polymerizable functional group, and the polymerizable functional group includes a hydroxy group, a thiol group, an amino group, a carboxyl group, and a methoxy group. And at least one group selected from the group, wherein l and m are each independently 0 or 1, and the sum of l and m is 0 or more and 2 or less.

α is derived by replacing one of CH _{2 in} the main chain of an alkylene group having 1 to 6 carbon atoms in the main chain and a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms in the main chain with an oxygen atom. Group, a group derived by replacing one of CH _{2 in} the main chain of a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms in the main chain with a sulfur atom, or a substitution having 1 to 6 carbon atoms in the main chain Alternatively, one of CH _{2 in} the main chain of the unsubstituted alkylene group represents a group derived by replacing NR ¹⁹ , and R ¹⁹ represents a hydrogen atom or an alkyl group.

  The substituent of the substituted alkylene group is an alkyl group having 1 to 6 carbon atoms, a benzyl group, an alkoxycarbonyl group, or a phenyl group. These groups may have the polymerizable functional group.

  β represents a phenylene group, an alkyl group-substituted phenylene group having 1 to 6 carbon atoms, a nitro group-substituted phenylene group, a halogen group-substituted phenylene group, or an alkoxy group-substituted phenylene group, and these groups represent the polymerizable functional group. You may have.

  γ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms in the main chain, or an alkyl group having 1 to 6 carbon atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms. May have the polymerizable functional group.

  Specific examples of the electron transporting substance having a polymerizable functional group are shown below. In the table, Aa is represented by the same structural formula as A, and specific examples of the monovalent group are shown in the columns of A and Aa. In the table, when γ is “−”, it indicates a hydrogen atom, and the hydrogen atom of γ is included in the structure shown in the column of α or β.

  Derivatives having a structure of any one of (A2) to (A6) and (A9) (derivatives of organic electron transport compounds) are Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd., and Johnson Matthey Japan Incorporated. It can be purchased from DE. The derivative having the structure of (A1) can be synthesized by reaction of naphthalene tetracarboxylic dianhydride, which can be purchased from Tokyo Chemical Industry Co., Ltd. or Johnson Matthey Japan Incorporated, and a monoamine derivative. The derivative having the structure (A7) can be synthesized using a phenol derivative that can be purchased from Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Japan Co., Ltd. as a raw material. The derivative having the structure of (A8) can be synthesized by reaction of perylenetetracarboxylic dianhydride that can be purchased from Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich Japan Co., Ltd. and a monoamine derivative. The derivative having the structure (A10) is obtained by oxidizing a phenol derivative having a hydrazone structure with an appropriate oxidizing agent such as potassium permanganate in an organic solvent using a known synthesis method described in Japanese Patent No. 3717320, for example. Can be synthesized. Derivatives having the structure of (A11) are naphthalenetetracarboxylic dianhydride, monoamine derivative and hydrazine, which can be purchased from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd. or Johnson Matthey Japan Incorporated. It can be synthesized by the reaction of

The compound represented by any of (A1) to (A11) has a polymerizable functional group (hydroxy group, thiol group, amino group, carboxyl group, and methoxy group) that can be polymerized with a crosslinking agent. As a method for synthesizing a compound represented by any of (A1) to (A11) by introducing a polymerizable functional group into a derivative having any one of the structures (A1) to (A11), the following method is used. Is mentioned. For example, there is a method of directly introducing a polymerizable functional group after synthesizing a derivative having any one of the structures (A1) to (A11). There is also a method of introducing a structure having a polymerizable functional group or a functional group that can be a precursor of the polymerizable functional group. As a method to be described later, based on the halide of the derivative having any one of the structures (A1) to (A11), for example, a cross-coupling reaction using a palladium catalyst and a base is used to form an aryl group having a functional group. There is a way to introduce. Further, there is a method of introducing an alkyl group having a functional group using a cross-coupling reaction using a FeCl ₃ catalyst and a base based on a halide of a derivative having any one of the structures (A1) to (A11). is there. Further, there is a method of introducing a hydroxyalkyl group or a carboxyl group by allowing an epoxy compound or CO ₂ to act after lithiation based on a halide of a derivative having any one of the structures (A1) to (A11). .

  From the viewpoint of high solvent resistance and forming a strong cross-linked structure, the organic electron transporting compound preferably has two or more polymerizable functional groups in the same molecule.

[Crosslinking agent]
Next, the crosslinking agent having a polymerizable functional group will be described.

  As a crosslinking agent, the compound normally used as a crosslinking agent can be used. Specifically, compounds described in Shinzo Yamashita and Tosuke Kaneko “Crosslinking Agent Handbook” published by Taiseisha (1981) and the like can be used.

  The crosslinking agent used in the present invention is preferably an isocyanate compound or an amino compound.

  The isocyanate compound used in the present invention preferably has two or more isocyanate groups or blocked isocyanate groups. More preferably, it has 3 to 6 isocyanate groups or blocked isocyanate groups. For example, triisocyanatebenzene, triisocyanatemethylbenzene, triphenylmethane triisocyanate, lysine triisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, methyl-2,6-diisocyanatohexanoate, norbornane diisocyanate modified isocyanurate modified, biuret modified, allophanate modified, adduct modified with trimethylolpropane or pentaerythritol Various modified products such as

  The blocked isocyanate group takes the form of -NHCOX (X is a protecting group). X may be any protecting group that can be introduced into an isocyanate group, but groups represented by the following (H1) to (H6) are more preferred.

  Below, the specific example of an isocyanate compound is shown.

  The undercoat layer of the present invention may further contain a resin having a polymerizable functional group. As the resin having a polymerizable functional group, a resin having a structural unit represented by the following formula (D) is preferable.

In formula (D), R ₁ represents a hydrogen atom or an alkyl group. Y ¹ represents a single bond, an alkylene group or a phenylene group. W ¹ represents a hydroxy group, a thiol group, an amino group, a carboxyl group, or a methoxy group.

  Examples of the resin having the structural unit represented by the formula (D) include an acetal resin, a polyolefin resin, a polyester resin, a polyether resin, and a polyamide resin. The structural unit represented by the above formula (D) may be included in the following characteristic structure, or may be included other than the characteristic structure. Characteristic structures are shown in (E-1) to (E-5) below. (E-1) is a structural unit of an acetal resin. (E-2) is a structural unit of polyolefin resin. (E-3) is a structural unit of a polyester resin. (E-4) is a structural unit of a polyether resin. (E-5) is a structural unit of polyamide resin.

In the above ^formula, R 201 ^{to R 205} each independently represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ^{206 to} R ²¹⁰ each independently represent a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group. When R ²⁰¹ is C ₃ H ₇ (propyl group), (E-1) represents butyral.

  Resin having a structural unit represented by the formula (D) (hereinafter also referred to as resin D) is, for example, a polymerizable functional group (hydroxy group, thiol) that can be purchased from Sigma-Aldrich Japan Co., Ltd. or Tokyo Chemical Industry Co., Ltd. Group, amino group, carboxyl group, or methoxy group).

  The resin D can also be generally purchased. Examples of the resin that can be purchased include polyether polyol resins such as AQD-457 and AQD-473 manufactured by Nippon Polyurethane Industry Co., Ltd., Sannics GP-400 and GP-700 manufactured by Sanyo Chemical Industries, Ltd., and Hitachi Chemical. Industrial Co., Ltd., Phthalkid W2343, DIC Corporation, Watersol S-118, CD-520, Beckolite M-6402-50, M-6201-40IM, Harima Chemicals Co., Ltd., Hollidip WH-1188, Japan Polyester polyol resins such as Eupica ES3604 and ES6538, Polyacrylic polyol resins such as DIC Corporation, Bernock WE-300 and WE-304, and polyvinyl alcohols such as Kuraray Kuraraypoval PVA-203 Resin, BX-1, BM-1 manufactured by Sekisui Chemical Co., Ltd. Which polyvinyl acetal resin, polyamide resin such as Toraysin FS-350 manufactured by Nagase ChemteX Corporation, aqualic manufactured by Nippon Shokubai Co., Ltd., carboxyl group-containing resin such as Finelex SG2000 manufactured by Lead City, DIC ( Co., Ltd., polyamine resins such as racamide, and polythiol resins such as Toray Co., Ltd. QE-340M. Among these, polyvinyl acetal resins, polyester polyol resins and the like are more preferable from the viewpoints of polymerizability and uniformity of the electron transport layer.

  The weight average molecular weight (Mw) of the resin D is more preferably in the range of 5000 to 400,000.

  Table 12 below shows specific examples of the resin D.

  The thickness of the undercoat layer is preferably from 0.3 μm to 15 μm, and more preferably from 0.5 μm to 5.0 μm.

(Charge generation layer)
A charge generation layer is formed on the undercoat layer.

  Examples of charge generating materials include azo pigments, perylene pigments, anthraquinone derivatives, anthanthrone derivatives, dibenzpyrenequinone derivatives, pyranthrone derivatives, violanthrone derivatives, isoviolanthrone derivatives, indigo derivatives, thioindigo derivatives, phthalocyanine pigments, and bisbenzimidazoles. Derivatives. Among these, phthalocyanine pigments are preferable, and oxytitanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferable.

  Examples of the binder resin used for the charge generation layer include polymers and copolymers of vinyl compounds, polyvinyl alcohol resins, polyvinyl acetal resins, polycarbonate resins, polyester resins, polysulfone resins, polyphenylene oxide resins, polyurethane resins, and cellulose. Resins, phenol resins, melamine resins, silicon resins, and epoxy resins can be used. Among these, polyester resin, polycarbonate resin, and polyvinyl acetal resin are preferable, and polyvinyl acetal is more preferable.

  The charge generation layer is preferably formed by forming a coating film of a coating solution for a charge generation layer obtained by dispersing a charge generation material together with a binder resin and a solvent, and drying the obtained coating film. The charge generation layer may be a vapor generation film of a charge generation material.

  In the charge generation layer, the mass ratio of the charge generation material to the binder resin (charge generation material / binder resin) is preferably in the range of 10/1 to 1/10, and is preferably 5/1 to 1/5. A range is more preferable. Examples of the solvent used in the charge generation layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents. The thickness of the charge generation layer is preferably 0.05 μm or more and 5 μm or less.

(Hole transport layer)
A hole transport layer is formed on the charge generation layer.

  Examples of the hole transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, benzidine compounds, triarylamine compounds, and triphenylamine. Alternatively, examples of the hole transport material include polymers having groups derived from these compounds in the main chain or side chain. Among these, a triarylamine compound, a benzidine compound, and a styryl compound are preferable.

  Examples of the binder resin used for the hole transport layer include polyester resins, polycarbonate resins, polymethacrylate resins, polyarylate resins, polysulfone resins, and polystyrene resins. Among these, polycarbonate resin and polyarylate resin are preferable. Moreover, as these molecular weights, weight average molecular weight (Mw) = 10,000-300,000 is preferable.

  In the hole transport layer, the mass ratio of the hole transport material to the binder resin (hole transport material / binder resin) is preferably 10/5 to 5/10, and more preferably 10/8 to 6/10. .

  The thickness of the hole transport layer is preferably 3 μm or more and 40 μm or less, and more preferably 5 μm or more and 16 μm or less. Examples of the solvent used in the hole transport layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

  A protective layer may be formed on the hole transport layer. The protective layer preferably contains conductive particles or a charge transport material and a binder resin. The protective layer may further contain an additive such as a lubricant. In addition, the binder resin itself may have conductivity and charge transport property, and in that case, the protective layer may not contain conductive particles or a charge transport material in addition to the binder resin. The binder resin of the protective layer may be a thermoplastic resin or a curable resin obtained by polymerization with heat, light, or radiation (electron beam). The thickness of the protective layer is preferably 1 μm or more and 10 μm or less.

  As a method of forming each layer, a coating film obtained by dissolving and / or dispersing materials constituting each layer in a solvent is applied to form a coating film, and the resulting coating film is dried and / or cured. The method of forming by making it preferable is preferable. Examples of the method for applying the coating solution include a dip coating method (dip coating method), a spray coating method, a curtain coating method, and a spin coating method.

  The toner and the electrophotographic photosensitive member of the present invention can sufficiently exhibit the above-described effects when used in an image forming method described in detail below.

  Examples of the image forming method of the present invention include an image forming method including a developing step of forming a toner image from an electrostatic latent image formed on an electrophotographic photosensitive member using toner in a developing device.

  An example of an image forming apparatus using an image forming method to which the present invention is applied will be described below. This is shown in FIG. 1 and the configuration of the present invention will be described in more detail. However, this does not limit the present invention in any way. Absent.

  FIG. 1 is a schematic sectional view of an image forming apparatus 100 using an image forming method to which the present invention is applied. The image forming apparatus 100 is a full-color laser printer that employs an inline method and an intermediate transfer method. The image forming apparatus 100 can form a full-color image on a recording material (for example, recording paper, plastic sheet, cloth, etc.) according to the image information.

  The image forming apparatus 100 includes, as a plurality of image forming units, first, second, and third images for forming yellow (Y), magenta (M), cyan (C), and black (K) images, respectively. And fourth image forming units SY, SM, SC, and SK. The first to fourth image forming units SY, SM, SC, and SK are arranged in a line in a direction that intersects the vertical direction.

  In the following example, the configurations and operations of the first to fourth image forming units SY, SM, SC, and SK are substantially the same except that the colors of images to be formed are different. Therefore, in the following, unless there is a particular distinction, the subscripts Y, M, C, and K given to the reference numerals to indicate that they are elements provided for any color are omitted, and generally explain.

  In this embodiment, the image forming apparatus 100 includes four drum-type electrophotographic photosensitive members 1 arranged in parallel in a direction intersecting the vertical direction as a plurality of image carriers. The electrophotographic photosensitive member 1 is rotationally driven by a driving means (driving source) (not shown) in the direction indicated by an arrow A (clockwise). Around the electrophotographic photoreceptor 1, a charging roller 2 as a charging means for uniformly charging the surface of the electrophotographic photoreceptor 1, a laser is irradiated on the basis of image information, and an electrostatic latent image is formed on the electrophotographic photoreceptor 1. A scanner unit (exposure device) 3 is disposed as an exposure unit for forming an image. Further, around the electrophotographic photosensitive member 1, a developing unit 4 as a developing unit that develops the electrostatic latent image as a toner image, and toner (transfer residual toner) remaining on the surface of the electrophotographic photosensitive member 1 after transfer. A cleaning member 6 is disposed as a cleaning means to be removed. Further, an intermediate transfer belt 5 as an intermediate transfer member for transferring the toner image on the electrophotographic photosensitive member 1 to a transfer material (recording material) 12 is disposed opposite to the four electrophotographic photosensitive members 1. Yes.

  In the present invention, the developing unit 4 preferably uses toner of a non-magnetic one-component developer as the developer. The developing unit 4 performs reversal development by bringing a developing roller as a developer carrying member into contact with the electrophotographic photosensitive member 1. That is, the developing unit 4 is a portion where the charge is attenuated by exposure on the electrophotographic photosensitive member 1 (an image portion, an image portion, a toner charged to the same polarity as the charging polarity of the electrophotographic photosensitive member 1 (negative polarity in this embodiment)). The electrostatic image is developed by adhering to the exposed portion.

  In the present invention, the electrophotographic photoreceptor 1 and the charging roller 2, the developing unit 4 and the cleaning member 6 as process means acting on the electrophotographic photoreceptor 1 are integrated, that is, integrated into a cartridge. The process cartridge 7 is preferably used. The process cartridge 7 can be attached to and detached from the image forming apparatus 100 via mounting means such as a mounting guide and a positioning member provided in the image forming apparatus main body 100A. The process cartridges 7 for the respective colors all have the same shape, and the process cartridges 7 for the respective colors have yellow (Y), magenta (M), cyan (C), and blank (K) colors, respectively. Toner is contained.

  The intermediate transfer belt 5 that is an intermediate transfer member is in contact with all the electrophotographic photosensitive members 1 and circulates (rotates) in the direction of arrow B (counterclockwise) in the figure. The intermediate transfer belt 5 is wound around a driving roller 51, a secondary transfer counter roller 52, and a driven roller 53 as a plurality of support members.

  On the inner peripheral surface side of the intermediate transfer belt 5, four primary transfer rollers 8 as primary transfer means are arranged in parallel so as to face each electrophotographic photosensitive member 1. The primary transfer roller 8 presses the intermediate transfer belt 5 toward the electrophotographic photosensitive member 1 to form a primary transfer portion N1 where the intermediate transfer belt 5 and the electrophotographic photosensitive member 1 come into contact with each other. A bias having a polarity opposite to the normal charging polarity of the toner is applied to the primary transfer roller 8 from a primary transfer bias power source (high voltage power source) as a primary transfer bias applying unit (not shown). As a result, the toner image on the electrophotographic photoreceptor 1 is transferred (primary transfer) onto the intermediate transfer belt 5.

  In addition, a secondary transfer roller 9 as a secondary transfer unit is disposed at a position facing the secondary transfer counter roller 52 on the outer peripheral surface side of the intermediate transfer belt 5. The secondary transfer roller 9 is pressed against the secondary transfer counter roller 52 via the intermediate transfer belt 5 to form a secondary transfer portion N2 where the intermediate transfer belt 5 and the secondary transfer roller 9 come into contact. A bias having a polarity opposite to the normal charging polarity of the toner is applied to the secondary transfer roller 9 from a secondary transfer bias power source (high voltage power source) as a secondary transfer bias applying unit (not shown). As a result, the toner image on the intermediate transfer belt 5 is transferred (secondary transfer) to the transfer material 12.

  At the time of image formation, first, the surface of the electrophotographic photosensitive member 1 is uniformly charged by the charging roller 2. Next, the surface of the charged electrophotographic photosensitive member 1 is scanned and exposed by laser light corresponding to the image information emitted from the scanner unit 3, and an electrostatic latent image according to the image information is formed on the electrophotographic photosensitive member 1. (Electrostatic latent image forming step). Next, the electrostatic latent image formed on the electrophotographic photoreceptor 1 is developed as a toner image by the developing unit 4. The toner image formed on the electrophotographic photosensitive member 1 is transferred (primary transfer) onto the intermediate transfer belt 5 by the action of the primary transfer roller 8.

  For example, when forming a full-color image, the above-described process is sequentially performed in the first to fourth image forming units SY, SM, SC, and SK, and the toner images of the respective colors are next superimposed on the intermediate transfer belt 5. The primary transfer. Thereafter, the transfer material 12 is conveyed to the secondary transfer portion N2 in synchronization with the movement of the intermediate transfer belt 5. The four-color toner images on the intermediate transfer belt 5 are secondarily transferred onto the transfer material 12 collectively by the action of the secondary transfer roller 9 that is in contact with the intermediate transfer belt 5 via the transfer material 12.

  The transfer material 12 onto which the toner image has been transferred is conveyed to a fixing device 10 as a fixing unit. By applying heat and pressure to the transfer material 12 in the fixing device 10, the toner image is fixed to the transfer material 12.

  Further, the primary transfer residual toner remaining on the electrophotographic photosensitive member 1 after the primary transfer step is removed and collected by the cleaning member 6. The secondary transfer residual toner remaining on the intermediate transfer belt 5 after the secondary transfer process is cleaned by the intermediate transfer belt cleaning device 11.

  Next, the overall configuration of the process cartridge 7 attached to the image forming apparatus 100 will be described. In the present invention, it is preferable to use a process cartridge 7 having substantially the same configuration and operation except for the type (color) of toner contained therein.

  FIG. 2 is a schematic cross-sectional view (main cross-sectional view) of the process cartridge 7 as viewed along the longitudinal direction (rotational axis direction) of the electrophotographic photosensitive member 1. The posture of the process cartridge 7 in FIG. 2 is a posture in a state where the process cartridge 7 is mounted on the image forming apparatus main body. When the positional relationship and direction of each member of the process cartridge are described below, the positional relationship and direction in this posture are described below. Etc.

  The process cartridge 7 is formed by integrating an electrophotographic photosensitive member unit 13 including the electrophotographic photosensitive member 1 and the developing unit 4 including a developing roller 17 and the like.

  The electrophotographic photoreceptor unit 13 has a cleaning frame 14 as a frame that supports various elements in the electrophotographic photoreceptor unit 13. In the electrophotographic photosensitive member 1, the driving force of a driving motor (not shown) as a driving means (driving source) is transmitted to the electrophotographic photosensitive member unit 13, so that an arrow A direction (clockwise) shown in the drawing corresponds to an image forming operation. Is driven to rotate. In addition, the cleaning member 6 and the charging roller 2 are disposed in the electrophotographic photosensitive member unit 13 so as to contact the peripheral surface of the electrophotographic photosensitive member 1. The transfer residual toner removed from the surface of the electrophotographic photosensitive member 1 by the cleaning member 6 falls and is stored in the cleaning frame 14. The charging roller 2 as charging means is driven to rotate by bringing the roller portion of conductive rubber into pressure contact with the image carrier 1.

  Here, a predetermined DC voltage is applied to the core of the charging roller 2 to the electrophotographic photosensitive member 1 as a charging step, whereby a uniform dark portion is formed on the surface of the electrophotographic photosensitive member 1. A potential (Vd) is formed. The spot pattern of the laser beam emitted corresponding to the image data by the laser beam from the scanner unit 3 described above exposes the electrophotographic photosensitive member 1, and the exposed portion is exposed on the surface by the carrier from the charge generation layer. The charge disappears and the potential drops. As a result, an electrostatic latent image is formed on the electrophotographic photosensitive member 1 with a predetermined bright portion potential (Vl) at the exposed portion and a predetermined dark portion potential (Vd) at the unexposed portion.

  On the other hand, the developing unit 4 has a developing chamber 15 in which a developing roller 17 as a toner carrier for carrying toner 80 and a toner supply roller 20 as a toner supply member for supplying toner to the developing roller 17 are arranged. doing. Further, the toner supply roller 20 forms an abutting portion N (a portion where the toner is sandwiched between the development roller 17 and the toner supply roller 20) between the development roller 17 and rotates in the same direction. A stirring and conveying member 22 is provided in the toner storage chamber 18. The agitating / conveying member 22 agitates the toner accommodated in the toner accommodating chamber 18 and also conveys the toner toward the upper portion of the toner supply roller 20 in the direction of arrow G in the figure.

  The developing blade 21 is disposed below the developing roller 17 and is in contact with the developing roller at a counter, and regulates the coating amount of toner supplied by the toner supply roller 20 and applies a charge. The developing blade 21 is, for example, a thin plate made of SUS made of a leaf spring having a thickness of 0.1 mm. The developing blade 21 uses the spring elasticity of the thin plate to form a contact pressure, and its surface is in contact with the toner and the developing roller 17. The Here, the developing blade is not limited to this, and may be a thin metal plate such as phosphor bronze or aluminum. Alternatively, the surface of the developing blade 21 may be coated with a thin film such as polyamide elastomer, urethane rubber, or urethane resin.

  The toner is triboelectrically charged by rubbing between the developing blade 21 and the developing roller 17 to be charged, and at the same time the layer thickness is regulated. In the present invention, it is preferable to stabilize the toner coat layer by applying a predetermined voltage to the developing blade 21 from a blade bias power source (not shown).

  The developing roller 17 and the electrophotographic photosensitive member 1 rotate so that the surfaces of the developing roller 17 and the electrophotographic photosensitive member 1 move in the same direction (the direction from the bottom to the top in FIG. 2).

  In FIG. 2, the developing roller 17 is disposed in contact with the electrophotographic photosensitive member 1, but the developing roller 17 is disposed close to the electrophotographic photosensitive member 1 with a predetermined interval. There may be.

  In the present invention, the toner charged negatively by frictional charging with respect to the predetermined DC bias applied to the developing roller 17 in the developing portion where it contacts the electrophotographic photoreceptor 1, from the potential difference, the bright portion potential portion. The electrostatic latent image is visualized by transferring only to.

  In the present invention, it is preferable that the surfaces of the toner supply roller 20 and the developing roller 17 rotate in the same direction at the contact portion N. Further, the rotation directions of the developing roller 17 and the toner supply roller 20 are directions in which the respective surfaces move in the same direction at the contact portion, and the amount of penetration of the toner supply roller 20 into the development roller 17 at the contact portion is 0. It is preferable that it is 3 mm or more and 1.5 mm or less. Further, the peripheral speed at the contact portion of the toner supply roller 20 is preferably 110% or more and 250% or less with respect to the peripheral speed at the contact portion of the developing roller 17. When the image forming method has a configuration in which the rotation directions of the developing roller 17 and the toner supply roller 20 are the directions in which the respective surfaces move in the same direction at the contact portion, the developing is performed more than in the configuration in which the developing roller 17 and the toner supply roller 20 move in the opposite directions. There is little toner deterioration due to sliding between the roller 17 and the toner supply roller 20. On the other hand, there is a case where the recoverability (peelability) of the toner from the developing roller 17 after development by the toner supply roller 20 is weak, and when the speed is further increased, the toner brought to the developing roller is easily charged up. There is room for improvement. However, when the toner of the present invention is used, since it has a shell containing the polyester resin A, it has excellent charge rise characteristics, and even when the speed is increased, it does not charge up gradually or suddenly. . Therefore, charge injection into the electrophotographic photosensitive member due to toner charge-up is also suppressed. Furthermore, since the electrophotographic photosensitive member of the present invention is hardly affected by the charge from the toner, a high-quality image can be obtained over a long period of time. Therefore, the toner of the present invention can sufficiently exhibit the synergistic effect of the toner and the image carrier described in detail when the image forming method is used.

  In FIG. 2, the toner supply roller 20 rotates in the direction of the arrow E (clockwise) and the developing roller 17 rotates in the direction of the arrow D (counterclockwise). As a result, the load on the toner can be reduced, and high image quality can be maintained even during long-term use. The toner supply roller 20 is, for example, an elastic sponge roller in which a foam layer is formed on the outer periphery of a conductive metal core. The toner supply roller 20 and the developing roller 17 are in contact with each other with a predetermined intrusion amount, that is, the recess amount ΔE in which the toner supply roller 20 is recessed by the developing roller 17.

  In the present invention, the intrusion amount is preferably 0.3 mm or more and 1.5 mm or less, and preferably 0.7 mm or more and 1.2 mm or less, in consideration of the balance between the peelability of the development residual toner and the load on the toner. More preferred.

  The toner supply roller 20 and the developing roller 17 are rotated with a peripheral speed difference in the same direction at the abutting portion N. With this operation, the toner supply roller 20 and the toner supply to the developing roller 17 are separated from each other. Is going. At this time, the toner supply amount to the developing roller can be adjusted by adjusting the potential difference between the toner supply roller and the developing roller.

  In the present invention, the peripheral speed of the supply roller (supply member) at the contact portion is preferably 110% or more and 250% or less with respect to the peripheral speed of the developing roller (toner carrier), and is 150% or more and 200%. The following is more preferable. A DC bias may be applied to the toner supply roller.

  Hereinafter, details of the toner supply roller preferably used in the present invention will be described.

  The toner supply roller 20 in FIG. 2 includes, for example, a conductive support and a foam layer supported by the conductive support. Specifically, a foamed urethane layer 20b is provided as a foam layer composed of a cored bar electrode 20a as a conductive support and an open cell body (open cell) in which bubbles are connected to the periphery thereof, It rotates in the direction of E in the figure. A large amount of toner can enter the inside of the toner supply roller 20 by using urethane on the surface layer as an open cell body. The surface cell diameter of the toner supply roller 20 is preferably 50 μm to 1000 μm.

  Next, it describes regarding the measuring method of each physical property which concerns on this invention.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1) of toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels. As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows. On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked. In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4), and the graph / volume in the dedicated software is graph / When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Acid value of polyester resin A>
The acid value of the polyester resin A in the present invention is determined by the following operation.

  The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the polyester resin A was measured according to JIS K 0070-1992. Specifically, it measured according to the following procedures.

(1) Preparation of Reagent 1.0 g of phenolphthalein was dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water was added to make 100 ml to obtain a phenolphthalein solution.

  7 g of special grade potassium hydroxide was dissolved in 5 ml of water, and ethyl alcohol (95 vol%) was added to make 1 l. In order to avoid contact with carbon dioxide, etc., it was placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution was stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. It calculated | required from the quantity of the potassium solution. The 0.1 mol / l hydrochloric acid was prepared according to JIS K 8001-1998.

(2) Operation (A) Main test 2.0 g of the pulverized polyester resin A sample was precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene: ethanol (2: 1) was added and dissolved over 5 hours. . Next, several drops of the phenolphthalein solution were added as indicators and titrated with the potassium hydroxide solution. The end point of the titration was when the light red color of the indicator lasted for about 30 seconds.

(B) Blank test Titration was performed in the same manner as described above, except that no sample was used (that is, only a mixed solution of toluene: ethanol (2: 1) was used).

(3) The acid value was calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Weight average molecular weight of polyester resin A>
After 0.03 g of polyester resin A is dispersed and dissolved in 10 ml of o-dichlorobenzene, the mixture is shaken with a shaker at 135 ° C. for 24 hours, filtered through a 0.2 μm filter, and the filtrate is used as a sample. Analyze.

[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene Mobile phase flow rate: 1.0 ml / min.
Sample concentration: about 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71
In calculating the molecular weight of the sample, standard polystyrene resin (TSO standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

<Dielectric loss tangent of polyester resin A>
Using a 4284A Precision LCR meter (manufactured by Hewlett-Packard Company), the dielectric loss tangent (tan δ = ε ″ / ε ′) is calculated from the measured value of the complex dielectric constant at a frequency of 10,000 Hz.

0.3 to 0.7 g of polyester resin A coarsely pulverized in a mortar is weighed, and a load of 350 Kgf / cm ² is molded for 2 minutes to obtain a disk-shaped measurement sample having a diameter of 25 mm and a thickness of 1 mm or less. Using this measurement sample, ARES (manufactured by Rheometric Scientific F.E.) equipped with a dielectric constant measuring jig (electrode) having a diameter of 25 mm, a load of 350 g was applied at 25 ° C. Measure three times in the frequency range of 100,000 Hz. And it obtains by calculating the average value of the measured value in 10000Hz of each measurement.

<PKa of charge control resin>
A measurement sample of charge control resin (0.100 g) is precisely weighed in a 250 ml tall beaker, 150 ml of THF is added and dissolved over 30 minutes. A pH electrode is placed in this solution, and the pH of the sample THF solution is read. Thereafter, 10 μl of 0.1 mol / l potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.) is added, and the pH is read and titrated each time. A 0.1 mol / l potassium hydroxide ethyl alcohol solution is added until the pH becomes 10 or more and there is no change in pH even when 30 μl is added. From the obtained results, the pH is plotted against the addition amount of 0.1 mol / l potassium hydroxide ethyl alcohol solution to obtain a titration curve. From the obtained titration curve, the place where the slope of the pH change is the greatest is taken as the neutralization point, and the acid value (mgKOH / g) is calculated from the amount of added potassium hydroxide. Since pKa is the same value as the pH in half of the 0.1 mol / l potassium hydroxide ethyl alcohol solution required up to the neutralization point, the pH in half is read from the titration curve.

<Method for measuring volume resistivity of undercoat layer of electrophotographic photoreceptor>
A method for measuring the volume resistivity of the undercoat layer will be described. FIG. 3A is a top view for explaining a method for measuring the volume resistivity of the undercoat layer, and FIG. 3B is a diagram for explaining a method for measuring the volume resistivity of the undercoat layer. FIG.

  The volume resistivity of the undercoat layer is measured under a normal temperature and normal humidity environment (temperature 23 ° C. ± 3 ° C., humidity 50% ± 5% RH). A copper tape 203 (manufactured by Sumitomo 3M Co., Ltd., model No. 1181) is attached to the surface of the undercoat layer 202, and this is used as an electrode on the surface side of the undercoat layer 202. In addition, the support (conductive support) 201 is used as an electrode on the back side of the undercoat layer 202. A power source 206 for applying a voltage between the copper tape 203 and the support 201 and a current measuring device 207 for measuring a current flowing between the copper tape 203 and the support 201 are installed. In order to apply a voltage to the copper tape 203, first, the copper wire 204 is placed on the copper tape 203. And the copper tape 205 similar to the copper tape 203 is stuck on the copper wire 204 so that the copper wire 204 does not protrude from the copper tape 203, and the copper wire 204 is fixed to the copper tape 203. A voltage is applied to the copper tape 203 using a copper wire 204.

The background current value when no voltage is applied between the copper tape 203 and the support 201 is I ₀ (A), and the current value when a voltage of only a DC voltage (DC component) is applied by −1 V is I ( A). The film thickness d (cm) of the undercoat layer 202 and the area of the electrode (copper tape 203) on the surface side of the undercoat layer 202 are S (cm ² ). And let the value represented by following formula (3) be the volume resistivity (rho) (ohm * cm) of the undercoat layer 202. FIG.
ρ = 1 / (I−I ₀ ) × S / d (Ω · cm) (3)
In this measurement, in order to measure a minute current amount of 1 × 10 ⁻⁶ A or less in absolute value, it is preferable to use a device capable of measuring a minute current as the current measuring device 207. Examples of such a device include a pA meter (trade name: 4140B) manufactured by Yokogawa Hewlett-Packard and a high resistance meter (trade name: 4339B) manufactured by Agilent Technologies.

  The volume resistivity of the undercoat layer may be measured with a sample in which only the undercoat layer is formed on the support, or each layer on the undercoat layer is peeled off from the electrophotographic photosensitive member to obtain a support. Similar values are obtained even when measured with a configuration in which only the undercoat layer is left on the top.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but this does not limit the present invention in any way. Unless otherwise specified, all parts and% in the examples and comparative examples are based on mass. Hereinafter, a method for producing a resin and a toner will be described.

<Example of production of polyester resin 1>
100 parts by mass of a mixture of raw material monomers mixed in the charging ratio shown in Table 13 and 0.55 parts by mass of di (2-ethylhexanoic acid) tin as a catalyst were equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. Placed in a liter four-necked flask. Then, it was made to react over 6 hours at 200 degreeC by nitrogen atmosphere. Furthermore, trimellitic anhydride was added at 210 ° C., and the reaction was carried out under reduced pressure of 40 kPa, and the reaction was continued until the weight average molecular weight (Mw) became 12,000. The obtained polyester resin A is designated as polyester resin 1. A composition analysis of the polyester resin 1 was performed, and the results of the isosorbide unit ratio are shown in Table 13. Moreover, the acid value of the obtained polyester resin 1 was as shown in Table 13.

The composition analysis of the polyester resin 1 was performed by 1-NMR. The specific measurement method is as follows.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times Measurement temperature: 30 ° C
A sample of 50 mg is put into a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl 3) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. to prepare a measurement sample. It measured on the said conditions using the said measurement sample.

<Production Examples 2 to 16 of polyester resin>
Polyester resins 2 to 16 were produced in the same manner as in the production example of polyester resin 1 except that the charged amounts of the acid component and alcohol component were changed as shown in Table 13. Table 13 shows the physical properties of the polyester resins 2 to 16.

<Production Examples 17-22 of polyester resin>
In the manufacture example of the polyester resin 1, it reacted similarly except having adjusted the reaction time and changing the weight average molecular weight (Mw), and manufactured the polyester resins 17-22. Table 13 shows the physical properties of the polyester resins 17-22.

  In Table 13, TPA: terephthalic acid, TMA: trimellitic acid, BPA (PO): bisphenol A propylene oxide 2-mole adduct, EG: ethylene glycol.

  Next, a synthesis example of the charge control resin used as an example and a manufacturing example of a toner including the same will be described below.

<Synthesis Example of Polymerizable Monomer M-3>
(Process 1)
100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were heated and mixed at 50 ° C. To this mixed solution, 144 g of tert-butyl alcohol was added and stirred at 50 ° C. for 30 minutes. Thereafter, 144 g of tert-butyl alcohol was added to this mixed solution, and the mixture was stirred for 30 minutes three times. The reaction solution was cooled to room temperature and poured slowly into 1 kg of ice water. The precipitate was filtered, washed with water, and then washed with hexane. This precipitate was dissolved in 200 mL of methanol and reprecipitated in 3.6 L of water. After filtration, it was dried at 80 ° C. to obtain 74.9 g of a salicylic acid intermediate represented by the following formula (10).

(Process 2)
25.0 g of the salicylic acid intermediate represented by the above formula (10) was dissolved in 150 mL of methanol, 36.9 g of potassium carbonate was added, and the mixture was heated to 65 ° C. To this reaction solution, a mixed solution of 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol was added dropwise, and reacted at 65 ° C. for 3 hours. The reaction solution was cooled and then filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dispersed in 1.5 L of water at pH = 2 and extracted by adding ethyl acetate. Thereafter, it was washed with water and dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and purified by recrystallization from toluene and ethyl acetate to obtain 20.1 g of the polymerizable monomer M-3.

<Synthesis Example of Polymerizable Monomer M-8>
Except for changing the salicylic acid intermediate of the formula (10) to 18 g of 2,4-dihydroxybenzoic acid, the above polymerizable monomer M- was prepared in the same manner as the synthesis of the polymerizable monomer M-3 (step 2). 8 was obtained.

<Synthesis Example of Polymerizable Monomer M-9>
Except for changing the salicylic acid intermediate of formula (10) to 18 g of 2,3-dihydroxybenzoic acid, in the same manner as the synthesis of the polymerizable monomer M-3 (step 2), the polymerizable monomer M- 9 was obtained.

<Synthesis Example of Polymerizable Monomer M-10>
Except for changing the salicylic acid intermediate of formula (10) to 18 g of 2,6-dihydroxybenzoic acid, in the same manner as the synthesis of polymerizable monomer M-3 (step 2), the polymerizable monomer M- 10 was obtained.

<Synthesis Example of Charge Control Resin 1>
The polymerizable monomer M-3 (9.9 g) and styrene (60.1 g) were dissolved in dimethylformamide (42.0 ml), stirred for 1 hour while bubbling nitrogen, and then heated to 110 ° C. To this reaction solution, a mixture of tert-butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) and 42 ml of toluene was added dropwise as an initiator. Furthermore, it reacted at 110 degreeC for 4 hours. Then, it cooled and it was dripped at methanol 1L, and the deposit was obtained. The obtained precipitate was dissolved in 120 ml of tetrahydrofuran and then added dropwise to 1.80 L of methanol to precipitate a white precipitate, which was filtered and dried at 90 ° C. under reduced pressure to obtain 57.6 g of charge control resin 1. It was. NMR and acid value of the obtained charge control resin 1 were measured, and the content of components derived from the polymerizable monomer M-3 was confirmed.

<Synthesis Example of Charge Control Resins 2-6>
Charge control resin 2 to charge control resin 6 were obtained in the same manner as in the synthesis example of charge control resin 1 except that the amount of raw material charged was changed as shown in Table 14.

<Synthesis Example of Charge Control Resin 7>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.

Next, the following materials were mixed and added dropwise to the reaction vessel with stirring for 10 hours.
5-vinyl salicylic acid 9.0 parts Styrene 75.0 parts 2-Ethylhexyl acrylate 16.0 parts Dimethyl-2,2'-azobis (2-methylpropionate) 5.0 parts Thereafter, the solvent is distilled by distillation. And dried at 40 ° C. under reduced pressure to obtain a charge control resin 7.

<Synthesis Example of Charge Control Resins 8-9>
Of the synthesis examples of the charge control resin 7, the synthesis was performed in the same manner except for the following changes.

  A charge control resin 8 was obtained in the same manner as in the synthesis example of the charge control resin 7 except that 9.0 parts of 5-vinylsalicylic acid was changed to 5.3 parts of 1 vinyl phthalate.

  A charge control resin 9 was obtained in the same manner as in the synthesis example of the charge control resin 7, except that 9.0 parts of 5-vinylsalicylic acid was changed to 10.9 parts of 1-vinylnaphthalene-2-carboxylic acid.

<Synthesis Example of Charge Control Resin 10>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 200 parts by mass of xylene and refluxed under a nitrogen stream. Next, the following materials were mixed and added dropwise to the reaction vessel with stirring for 10 hours.
2-acrylamido-2-methylpropanesulfonic acid 6.0 parts styrene 72.0 parts 2-ethylhexyl acrylate 18.0 parts Thereafter, distillation is performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to charge control resin 10 Got.

<Synthesis Example of Charge Control Resin 11>
The following materials are mixed in a reaction vessel equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple, a polycondensation reaction is performed at 230 ° C. for 8 hours, and the polycondensation reaction is continued at 8 kPa for 1 hour. did.
Bisphenol A propylene oxide 2 mol adduct 500 parts terephthalic acid 154 parts fumaric acid 45 parts tin octylate 2 parts Thereafter, the polyester resin was formed by cooling to 160 ° C, and then acrylic acid 10 at a temperature of 160 ° C. Parts, mix and hold for 15 minutes,
Styrene 142 parts n-butyl acrylate 35 parts Polymerization initiator (di-t-butyl peroxide) 10 parts of the mixture was added dropwise by a dropping funnel over 1 hour, followed by addition polymerization for 1 hour while maintaining the temperature at 160 ° C. After carrying out the reaction, the temperature was raised to 200 ° C. and held at 10 kPa for 1 hour to obtain the charge control resin 11.

  In Table 14, St: styrene, 2EHA: 2-ethylhexyl acrylate, a content: means the content of a component derived from the polymerizable monomer used in each charge control resin.

<Production Example of Toner 1>
For 100 parts of styrene monomer, C.I. I. 16.5 parts of Pigment Blue 15: 3 and 3.0 parts of an aluminum compound of di-tertiary butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Industries)] were prepared. These were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.) and stirred at 200 rpm at 25 ° C. for 180 minutes using zirconia beads (140 parts by mass) with a radius of 1.25 mm to prepare a master batch dispersion 1. .

On the other hand, 450 parts of 0.1M Na ₃ PO ₄ aqueous solution was added to 710 parts of ion-exchanged water and heated to 60 ° C., then 67.7 parts of 1.0M CaCl ₂ aqueous solution was gradually added to form a calcium phosphate compound. An aqueous medium containing was obtained.
・ Master batch dispersion 1 40 parts ・ Styrene monomer 49.5 parts ・ N-butyl acrylate monomer 16.5 parts ・ Hydrocarbon wax (Fischer-Tropsch wax, peak temperature of maximum endothermic peak = 78 ° C., Mw = 750) 9 parts. Charge control resin 1 0.3 part. Polyester resin 1 4 parts. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), it was uniformly dissolved and dispersed at 5,000 rpm. In this, 7.1 mass part of 70% toluene solution of polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition is charged into the aqueous medium, and the temperature is 65 ° C. in an N ₂ atmosphere. K. The mixture was stirred with a homomixer at 12,000 rpm for 10 minutes to granulate the polymerizable monomer composition. Thereafter, the temperature was raised to 67 ° C. while stirring with a paddle stirring blade. When the polymerization conversion rate of the polymerizable vinyl monomer reached 90%, a 0.1 mol / liter sodium hydroxide aqueous solution was added. The pH of the aqueous dispersion medium was adjusted to 9. Furthermore, it heated up at 80 degreeC with the temperature increase rate of 40 degreeC / h, and was made to react for 4 hours. After completion of the polymerization reaction, the residual monomer of the replenishing toner particles was distilled off under reduced pressure. After cooling the aqueous medium, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 6 hours to dissolve the calcium phosphate salt. The toner particles were separated by filtration and washed with water, and then dried at a temperature of 40 ° C. for 48 hours. The obtained dried product was strictly classified and removed at the same time with a multi-division classifier (elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.) to obtain a cyan color having a weight average particle diameter (D4) of 6.3 μm. Toner particles 1 were obtained.

  For 100 parts of toner particles 1, 1.2 parts of hydrophobic silica particles RY200 (Nippon Aerosil Co., Ltd.) and 0.4 parts of titanium oxide fine powder JMT-150AO (Taika Co., Ltd.) Cyan toner 1 was obtained by dry-mixing for 5 minutes with a mixer (Mitsui Miike Chemical Co., Ltd.).

<Production example of toners 2 to 11>
Toner 1 to toner 11 were obtained in the same manner as in the production example of toner 1 except that polyester 1 was changed as shown in Table 15.

<Production Example of Toners 12 to 17>
Toners 12 to 17 were obtained in the same manner as in Production Example of Toner 1 except that the addition amount of Polyester 1 was changed as shown in Table 15.

<Production Example of Toners 18 to 28>
Toner 1 was produced in the same manner as in Production Example 1 except that polyester 1 was changed as shown in Table 15.

<Production Example of Toners 29 to 38>
In the production example of the toner 1, the same procedure was performed except that the charge control resin 1 was changed as shown in Table 14, and toners 29 to 38 were obtained.

  Next, a specific method for producing an electrophotographic photoreceptor will be described.

<Example of production of electrophotographic photoreceptor (d-1)>
An aluminum cylinder (JIS-A3003) having a diameter of 30 mm was used as a support.

Next, a conductive layer was formed on the support. The conductive layer is 214 parts of titanium oxide (TiO ₂ ) particles coated with oxygen-deficient tin oxide (SnO ₂ ) as metal oxide particles, and a phenol resin (trade name: Pryofen J-325 as a binder resin). ) 132 parts, 40 parts of methanol, and 58 parts of 1-methoxy-2-propanol were put into a sand mill using 450 parts of glass beads having a diameter of 0.8 mm, the rotation speed: 2000 rpm, and the dispersion treatment time: 4.5 hours. Then, a dispersion treatment was performed under the condition of a set temperature of cooling water: 18 ° C. to obtain a dispersion. Glass beads were removed from this dispersion with a mesh (aperture: 150 μm). After removing the glass beads, silicone resin particles as a surface-roughening agent (Tospearl 120, manufactured by Momentive Co., Ltd.) are used so as to be 10% by mass with respect to the total mass of the metal oxide particles and the binder resin in the dispersion. ) Was added to the dispersion. Furthermore, silicone oil as a leveling agent (SH28PA, manufactured by Toray Dow Corning Co., Ltd.) is added to the dispersion so that the total mass of the metal oxide particles and the binder resin in the dispersion is 0.01% by mass. did. A conductive layer coating solution was prepared by stirring the dispersion. This conductive layer coating solution was dip-coated on a support, and the resulting coating film was dried and thermally cured at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 30.2 μm.

  Next, as an undercoat layer coating solution, 3.0 parts of an organic electron transporting compound represented by the following formula (Y-1), 3.5 parts of a copolymer nylon resin (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.) Is mixed with 25.0 parts of methanol (manufactured by Kishida Chemical Co., Ltd., special grade) and 6.5 parts of n-butanol (manufactured by Kishida Chemical Co., Ltd., special grade), and dissolved by stirring to apply an undercoat layer. The liquid was adjusted.

  An undercoat layer coating solution is dip-coated on the conductive layer to form a coating film, and the resulting coating film is dried at a temperature of 120 ° C. for 20 minutes to form an undercoat layer having a thickness of 1.0 μm. did.

  Next, the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction are 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 °. A crystalline form of hydroxygallium phthalocyanine crystal (charge generating material) having a strong peak was prepared. Disperse 10 parts of this hydroxygallium phthalocyanine crystal, 5 parts of polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 250 parts of cyclohexanone in a sand mill using 0.8 mm diameter glass beads. Treatment time: The dispersion treatment was performed under the condition of 3 hours. Next, 250 parts of ethyl acetate was added to prepare a coating solution for charge generation layer. This charge generation layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.15 μm.

  Next, 4 parts each of a compound represented by the following formula (9-1) and a compound represented by the following formula (9-2), and a bisphenol Z-type polycarbonate (trade name: Z400, Mitsubishi Engineering Plastics Co., Ltd.) )) Was dissolved in a mixed solvent of 50 parts of dimethoxymethane and 50 parts of o-xylene to prepare a coating solution for a hole transport layer. This hole transport layer coating solution is dip-coated on the charge generation layer to form a coating film, and the resulting coating film is dried at a temperature of 120 ° C. for 40 minutes, thereby transporting a hole with a thickness of 15 μm. A layer was formed.

In this way, an electrophotographic photoreceptor was prepared in which a support, a conductive layer, an undercoat layer, a charge generation layer, and a hole transport layer were laminated in this order. Moreover, when the volume resistivity of the undercoat layer was measured by the above-mentioned method, it was 3.0 × 10 ¹⁵ Ω · cm.

<Example of production of electrophotographic photoreceptor (d-2)>
The electrophotographic photosensitive member d-1 was prepared in the same manner as the image carrier d-1, except that the undercoat layer was changed as follows.

  For undercoat layer, 4.0 parts of organic electron transport compound represented by formula (A101) and 5.0 parts of formula (B1: protecting group H5) as a crosslinking agent are dissolved in a mixed solvent of 50 parts of dimethylacetamide and 50 parts of methyl ethyl ketone. A coating solution was prepared.

The undercoat layer coating solution is applied onto the conductive layer by dip coating, and the resulting coating film is heated at 160 ° C. for 40 minutes to evaporate the solvent and harden it, thereby reducing the film thickness to 0.5 μm. A layer was formed. When the volume resistivity of the undercoat layer was measured by the method described above, it was 1.2 × 10 ¹⁵ Ω · cm.

<Example of production of electrophotographic photoreceptor (d-3)>
The electrophotographic photosensitive member d-1 was prepared in the same manner as the electrophotographic photosensitive member d-1, except that the undercoat layer was changed as follows.

  4.0 parts of an organic electron transport compound represented by formula (A101), 5.0 parts of formula (B1: protecting group H5) as a crosslinking agent, 0.5 parts of formula (D25) as a resin, 50 parts of dimethylacetamide and 50 parts of methyl ethyl ketone The coating solution for undercoat layer was prepared.

The undercoat layer coating solution is applied onto the conductive layer by dip coating, and the resulting coating film is heated at 160 ° C. for 40 minutes to evaporate the solvent and harden it, thereby reducing the film thickness to 0.7 μm. A layer was formed. When the volume resistivity of the undercoat layer was measured by the method described above, it was 1.0 × 10 ¹⁵ Ω · cm.

<Example of production of electrophotographic photoreceptor (d-4)>
The electrophotographic photosensitive member d-1 was prepared in the same manner as the electrophotographic photosensitive member d-1, except that the undercoat layer was changed as follows.

  4.0 parts of an organic electron transport compound represented by formula (A117), 5.5 parts of formula (B1: protecting group H1) as a crosslinking agent, 0.5 parts of formula (D25) as a resin, 50 parts of THF and 1-methoxy-2 -A coating solution for undercoat layer was prepared by dissolving in 50 parts of a mixed solvent of propanol and stirring.

The undercoat layer coating solution is applied onto the conductive layer by dip coating, and the resulting coating film is heated at 160 ° C. for 40 minutes to evaporate the solvent and harden it, thereby reducing the film thickness to 0.7 μm. A layer was formed. When the volume resistivity of the undercoat layer was measured by the method described above, it was 3.8 × 10 ¹⁴ Ω · cm.

<Example of production of electrophotographic photoreceptor (d-5)>
The electrophotographic photosensitive member d-1 was prepared in the same manner as the electrophotographic photosensitive member d-1, except that the undercoat layer was changed as follows.

  4.0 parts of the organic electron transport compound represented by the formula (A107) and 5.5 parts of the formula (B1: protecting group H1) as a crosslinking agent were dissolved in a mixed solvent of 50 parts of THF and 50 parts of 1-methoxy-2-propanol. . A mixture was prepared by adding 5.0 parts of titanium oxide (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.) and 25 parts of glass beads having a diameter of 0.8 mm. This mixed solution was subjected to a dispersion treatment with a paint shaker for 16 hours to remove the glass beads, thereby obtaining an undercoat layer coating solution.

The undercoat layer coating solution is applied onto the conductive layer by dip coating, and the resulting coating film is heated at 160 ° C. for 40 minutes to evaporate the solvent and harden it, thereby reducing the film thickness to 1.3 μm. A layer was formed. When the volume resistivity of the undercoat layer was measured by the method described above, it was 4.1 × 10 ¹² Ω · cm.

<Example of production of electrophotographic photosensitive member (d-6)>
The electrophotographic photosensitive member d-1 was prepared in the same manner as the electrophotographic photosensitive member d-1, except that the undercoat layer was changed as follows.

  4.0 parts of an organic electron transport compound represented by formula (A107), 5.5 parts of formula (B1: protecting group H1) as a crosslinking agent, 0.5 parts of formula (D25) as a resin, 50 parts of THF and 1-methoxy-2 -Dissolved in 50 parts of a mixed solvent of propanol. A mixture was prepared by adding 5.0 parts of titanium oxide (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.) and 25 parts of glass beads having a diameter of 0.8 mm. This mixed solution was subjected to a dispersion treatment with a paint shaker for 16 hours to remove the glass beads, thereby obtaining an undercoat layer coating solution.

The coating solution for the undercoat layer is dip-coated on the conductive layer, and the resulting coating film is heated at 160 ° C. for 40 minutes to evaporate the solvent and harden it, thereby reducing the film thickness to 0.6 μm. A layer was formed. When the volume resistivity of the undercoat layer was measured by the method described above, it was 2.3 × 10 ¹² Ω · cm.

<Example of production of electrophotographic photoreceptor (d-7)>
The electrophotographic photosensitive member d-1 was prepared in the same manner as the electrophotographic photosensitive member d-1, except that the undercoat layer was changed as follows.

  3.0 parts of an organic electron transport compound represented by the above formula (Y-1), N-methoxymethylated nylon (trade name: Toresin EF-30T, manufactured by Nagase ChemteX Corporation (former Teikoku Chemical Industry Co., Ltd.) ) 4.5 parts are mixed with 25.0 parts of methanol (made by Kishida Chemical Co., Ltd., special grade) and 6.5 parts of n-butanol (made by Kishida Chemical Co., Ltd., special grade), and dissolved by stirring. The undercoat layer coating solution was prepared.

This undercoat layer coating solution was applied onto the conductive layer by dip coating, and the resulting coating film was heated at 100 ° C. for 40 minutes to evaporate the solvent, thereby forming an undercoat layer having a thickness of 1.1 μm. When the volume resistivity of the undercoat layer was measured by the method described above, it was 6.5 × 10 ¹¹ Ω · cm.

<Example of production of electrophotographic photoreceptor (d-8)>
The electrophotographic photosensitive member d-1 was prepared in the same manner as the electrophotographic photosensitive member d-1, except that the undercoat layer was changed as follows.

  4.0 parts of the organic electron transport compound represented by the formula (A107) and 5.5 parts of the formula (B1: protecting group H1) as a crosslinking agent were dissolved in a mixed solvent of 50 parts of THF and 50 parts of 1-methoxy-2-propanol. Further, 9.0 parts of titanium oxide (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.) and 25 parts of glass beads having a diameter of 0.8 mm were added to obtain a mixed solution. This mixed solution was subjected to a dispersion treatment with a paint shaker for 16 hours to remove the glass beads, thereby obtaining an undercoat layer coating solution.

This undercoat layer coating solution is applied onto the conductive layer by dip coating, and the resulting coating film is heated at 160 ° C. for 40 minutes to evaporate the solvent and harden it, thereby undercoating the film thickness to 1.4 μm. A layer was formed. When the volume resistivity of the undercoat layer was measured by the method described above, it was 7.2 × 10 ¹¹ Ω · cm.

<Example of production of electrophotographic photoreceptor (d-9)>
The electrophotographic photosensitive member d-1 was prepared in the same manner as the electrophotographic photosensitive member d-1, except that the undercoat layer was changed as follows.

  Copolymerized nylon resin (trade name: Amilan CM8000) 4.5 parts methanol (Kishida Chemical Co., Ltd., special grade) 25.0 parts and n-butanol (Kishida Chemical Co., Ltd., special grade) 6.5 The mixture was mixed and stirred to dissolve. Further, 2.0 parts of titanium oxide (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.) and 25 parts of glass beads having a diameter of 0.8 mm were added to obtain a mixed solution. This mixed solution was subjected to a dispersion treatment with a paint shaker for 16 hours to remove the glass beads, thereby obtaining an undercoat layer coating solution.

The undercoat layer coating solution was applied onto the conductive layer by dip coating, and the resulting coating film was heated at 100 ° C. for 40 minutes to evaporate the solvent and form an undercoat layer having a thickness of 1.0 μm. When the volume resistivity of the undercoat layer was measured by the method described above, it was 7.1 × 10 ¹² Ω · cm.

<Example of production of electrophotographic photoreceptor (d-10)>
The electrophotographic photosensitive member d-1 was prepared in the same manner as the electrophotographic photosensitive member d-1, except that the undercoat layer was changed as follows.

  25 parts of an organic electron transport compound represented by the above formula (Y-1) and 4.5 parts of N-methoxymethylated nylon (trade name: Toresin EF-30T) are methanol (made by Kishida Chemical Co., Ltd., special grade) 25 0.0 parts and 6.5 parts of n-butanol (manufactured by Kishida Chemical Co., Ltd., special grade) were mixed and stirred to dissolve. Furthermore, 5.0 parts of titanium oxide (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.) and 25 parts of glass beads having a diameter of 0.8 mm were added to obtain a mixed solution. This mixed solution was subjected to a dispersion treatment with a paint shaker for 16 hours to remove the glass beads, thereby obtaining an undercoat layer coating solution.

The undercoat layer coating solution was applied onto the conductive layer by dip coating, and the resulting coating film was heated at 100 ° C. for 40 minutes to evaporate the solvent, thereby forming an undercoat layer having a thickness of 1.3 μm. When the volume resistivity of the undercoat layer was measured by the method described above, it was 4.5 × 10 ¹⁰ Ω · cm.

<Example of production of electrophotographic photosensitive member (d-11)>
The electrophotographic photosensitive member d-1 was prepared in the same manner as the electrophotographic photosensitive member d-1, except that the undercoat layer was changed as follows.

  4.5 parts of N-methoxymethylated nylon (trade name: Toresin EF-30T) 25.0 parts of methanol (made by Kishida Chemical Co., Ltd., special grade) and n-butanol (made by Kishida Chemical Co., Ltd., special grade) ) 6.5 parts mixed and stirred to dissolve. Furthermore, 5.0 parts of titanium oxide (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.) and 25 parts of glass beads having a diameter of 0.8 mm were added to obtain a mixed solution. This mixed solution was subjected to a dispersion treatment with a paint shaker for 16 hours to remove the glass beads, thereby obtaining an undercoat layer coating solution.

The undercoat layer coating solution was applied onto the conductive layer by dip coating, and the resulting coating film was heated at 100 ° C. for 40 minutes to evaporate the solvent, thereby forming an undercoat layer having a thickness of 1.3 μm. When the volume resistivity of the undercoat layer was measured by the method described above, it was 6.2 × 10 ¹⁰ Ω · cm.

[Example 1]
Image evaluation was performed using A4 color laser copier paper (manufactured by Canon, 80 g / m ² ) at a temperature of 23 ° C. and a relative humidity of 50% using cyan toner 1 as a developer. As the image forming apparatus, a commercially available laser printer LBP-7700C (manufactured by Canon) and a modified cartridge of a toner cartridge 323 (cyan) (manufactured by Canon) which is a process cartridge were used.

  This modified cartridge was modified so that the toner supply roller moved in the same direction at the contact portion with the toner carrying roller by changing / adding the gear inside the cartridge. The peripheral speed of the toner supply roller on the basis of the toner carrying roller was adjusted to 160%. Further, the amount of penetration of the cleaning blade into the electrophotographic photosensitive member was adjusted to 0.8 mm. The product toner was extracted from the inside of the cartridge, the inside was cleaned by air blow, and 160 g of the toner according to the present invention was filled for evaluation. In addition, the product toner was extracted from each of the magenta, yellow, and black stations, and evaluation was performed by inserting magenta, yellow, and black cartridges in which the toner remaining amount detection mechanism was disabled.

  The toner was evaluated by performing a durability test using the modified machine described above.

  The conditions of the durability test are as follows. Under a high-temperature and high-humidity environment (30 ° C., 80% RH) and a low-temperature low-humidity environment (15 ° C., 10% RH), an original image with a printing ratio of 1% was printed out 1000 sheets per day. In addition, after printing out 1000 sheets per day, it was left in each environment for 1 week, and then the next 1000 sheets were printed out per day for a total of 13000 printouts. In addition, the evaluation timing was performed according to each evaluation standard by outputting an image for each evaluation at the beginning and the end of each evaluation day for every 1000 sheets. Detailed results are shown in Table 17.

<Evaluation>
(1) Image fog image fog was evaluated by the following method from the viewpoint of image quality (environmental charge stability, charge distribution and charge rising property).

  At the time of each evaluation, a solid white image was output, and the following evaluation criteria were used. The paper was A4 plain paper (GF-C081A4: manufactured by Canon Marketing Japan).

  Using “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the white background portion of the standard paper and the printout image was measured, and the fog (reflectance:%) was calculated by the following formula. The filter was measured with a blue filter attached.

In addition, the evaluation criteria judged the worst value through durability with the following criteria.
Fog (reflectance;%) = (reflectance of standard paper;%) − (reflectance of sample;%)
A: The fog is less than 0.8%.
B: The fog is 0.8% or more and less than 1.6%.
C: The fog is 1.6% or more and less than 2.1%.
D: The fog is 2.1% or more.

(2) Image Density Stability Image density stability was evaluated by the following method from the viewpoint of image quality (environmental charge stability, charge distribution, and charge rising property).

A solid black image was output at each evaluation. The image density was measured at the center of a solid black image using a color reflection densitometer (X-RITE 404 Amanufactured by X-Rite Co.). In the image output test under the above-mentioned high temperature and high humidity environment (30 ° C., 80% RH) and low temperature and low humidity environment (15 ° C., 10% RH), one solid image every time before and after leaving for one week. Each image was output and the density of each image was measured. Of the obtained image densities, the difference between the maximum density and the minimum density was determined and shown based on the following evaluation criteria.
A: The image density difference is 0.3 or less.
B: The image density difference is greater than 0.3 and 0.5 or less.
C: Image density difference is larger than 0.5.

(3) Evaluation of image uniformity From the viewpoint of image quality (transferability, charge distribution, and charge rising property), image uniformity was evaluated by the following method. Immediately after 12,000 sheets of the durability test were output, a solid image was output, and the uniformity of the image was visually evaluated.
A: The image density is uniform and uniform.
B: Image density is slightly uneven.
C: Image density is uneven.

(4) Evaluation of ghost From the viewpoint of image quality (charge distribution and charge rising property), ghost was evaluated by the following method in a low temperature and low humidity environment.

  In an image output test under a low-temperature and low-humidity environment, a solid black of 15 mm square was printed at the leading end within one sheet and then a halftone image was printed on the entire surface before and after being left for one week. Then, the density unevenness of the developer carrying roller period appearing in the halftone portion was visually evaluated, and the ghost was evaluated according to the following criteria.

[L / L image damage assessment]
A: Ghost is not recognized.
B: Extremely slight ghost is recognized.
C: A remarkable ghost is recognized.

  When the toner 1 was evaluated under the above conditions, the toner 1 showed very good results in all the evaluation items. Detailed results are shown in Table 17.

(5) Fine line reproducibility (image quality)
The fine line reproducibility was evaluated from the viewpoint of image quality. In the above image output, after outputting 4600 images, an image (print area ratio 4%) in which a grid pattern with a line width of 3 pixels was printed on the entire surface of A4 paper was printed, and the fine line reproducibility was evaluated. The line width of 3 pixels is theoretically 127 μm. The line width of the image is measured with a microscope VK-8500 (manufactured by Keyence). The line width is measured by selecting 5 points at random, and the following L is defined as the fine line reproducibility index when the average value of 3 points excluding the minimum value and the maximum value is d (μm).
L (μm) = | 127−d |
L defines the difference between the theoretical line width of 127 μm and the line width d on the output image. Since d may be larger than 127 or smaller than 127, it is defined as the absolute value of the difference. Smaller L indicates better fine line reproducibility.

(Evaluation criteria)
A: L is 0 μm or more and less than 5 μm.
B: L is 5 μm or more and less than 15 μm.
C: L is 15 μm or more and less than 30 μm.

[Examples 2 to 32, Comparative Examples 1 to 9]
In Example 1, the toner and / or the electrophotographic photosensitive member were changed as shown in Table 16 and evaluated in the same manner as in Example 1. Detailed results are shown in Table 17.

Example 31
In Example 1, the evaluation was performed in the same manner except that the amount of penetration of the supply member into the toner carrier at the contact portion of the evaluation machine (modified machine) was 0.3 mm. The evaluation results are shown in Table 17.

[Example 32]
In Example 1, the evaluation was performed in the same manner except that the amount of penetration of the supply member into the toner carrier at the contact portion of the evaluation machine (modified machine) was 1.5 mm. The evaluation results are shown in Table 16.

Example 33
In Example 1, the evaluation was performed in the same manner except that the peripheral speed of the contact portion of the supply member of the evaluation machine (modified machine) was 110% with respect to the peripheral speed of the contact portion of the toner carrier. went. The evaluation results are shown in Table 17.

Example 34
In Example 1, the evaluation was performed in the same manner except that the peripheral speed of the contact portion of the supply member of the evaluation machine (modified machine) was 250% with respect to the peripheral speed of the contact portion of the toner carrier. went. The evaluation results are shown in Table 17.

[Examples 35 and 36]
In Example 1, the evaluation was performed in the same manner except that the intrusion amounts of the supply member into the toner carrier at the contact portion of the evaluation machine (modified machine) were 0.2 mm and 1.8 mm, respectively. The evaluation results are shown in Table 17.

Examples 37 and 38
In Example 1, the peripheral speed of the contact portion of the supply member of the evaluation machine (modified machine) is 90% and 300% with respect to the peripheral speed of the contact portion of the toner carrier, respectively. And evaluated. The evaluation results are shown in Table 17.

Example 39
In Example 1, the evaluation was performed in the same manner except that the gear of the evaluation machine main body, the software, and the gear of the cartridge were changed and the rotation direction of the developer carrying roller was changed to the opposite direction. The evaluation results are shown in Table 17.

[Examples 40 to 49]
In Example 1, the toner and / or the electrophotographic photosensitive member were changed as shown in Table 16 and evaluated in the same manner as in Example 1. Detailed results are shown in Table 17.

Claims (11)

A charging step for charging the electrophotographic photosensitive member,
An electrostatic latent image forming step of forming an electrostatic latent image on the charged electrophotographic photosensitive member,
A developing step of developing the electrostatic latent image with toner to form a toner image, and a transferring step of transferring the toner image to a transfer material with or without an intermediate transfer member;
An image forming method comprising:
The toner is a toner containing core-shell toner particles in which a shell layer containing polyester resin A is formed on a core containing a resin and a colorant;
The content of the polyester resin A is 0.10 parts by mass or more and 40.0 parts by mass or less with respect to 100.0 parts by mass of the resin.
The dielectric tangent of Polyester resin A at 25 ° C. and 10,000 Hz is 0.007 or more and 0.014 or less,
The polyester resin A contains 0.10 mol% or more and 20.0 mol% or less of an isosorbide unit represented by the following formula (1) based on all monomer units,
The electrophotographic photoreceptor has a support, an undercoat layer formed on the support, a photosensitive layer formed on the undercoat layer,
The volume resistivity of the undercoat layer is 1 × 10 ¹¹ Ω · cm or more and 1 × 10 ¹⁶ Ω · cm or less,
An image forming method, wherein the undercoat layer contains an organic electron transporting compound.

The organic electron transporting compound has a polymerizable functional group;
The image forming method according to claim 1, wherein the undercoat layer contains a polymer of a composition containing the organic electron transporting compound and a crosslinking agent. The image forming method according to claim 1, wherein the organic electron transporting compound is a compound represented by any one of the following formulas (A1) to (A11).

(Formula (A1) in ^{~ (A11), R 11 ~R} 16, R 21 ~R 30, R 31 ~R 38, R 41 ~R 48, R 51 ~R 60, R 61 ~R 66, R 71 ~ R ⁷⁸ , R ^{81 to} R ⁹⁰ , R ^{91 to} R ⁹⁸ are R ^{101 to} R ¹¹⁰ , R ^{111 to} R ¹²⁰ are each independently a monovalent group represented by the following formula (A), a hydrogen atom, A cyano group, a nitro group, a halogen atom, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic ring, and CH _{2 in} the main chain of the alkyl group. One may be replaced by O, S, NH or NR ¹²¹ (R ¹²¹ is an alkyl group), at least one of R ^{11 to} R ¹⁶ , at least one of R ^{21 to} R ³⁰ , and R ^{31 to} R ³⁸ . Small Both one ^and at least one of R 41 ^{to R 48,} at least one of R 51 ^{to R 60,} at least one of R 61 ^{to R 66,} at least one of R 71 ^{to R 78,} the R 81 ^{to R 90} At least one, at least one of R ^{91 to} R ⁹⁸ , at least one of R ^{101 to} R ¹¹⁰ , and at least one of R ^{111 to} R ¹²⁰ have a monovalent group represented by the formula (A).
The substituent of the substituted alkyl group is an alkyl group, an aryl group, a halogen atom, or an alkoxycarbonyl group. The substituent of the substituted aryl group and the substituent of the substituted heterocyclic group are a halogen atom, a nitro group, a cyano group, an alkyl group, a halogen-substituted alkyl group, and an alkoxy group.
Z ²¹ , Z ³¹ , Z ⁴¹ and Z ⁵¹ each independently represent a carbon atom, a nitrogen atom or an oxygen atom. When Z ²¹ is an oxygen atom, R ²⁹ and R ³⁰ do not exist, and when Z ²¹ is a nitrogen atom, R ³⁰ does not exist. When Z ³¹ is an oxygen atom, R ³⁷ and R ³⁸ do not exist, and when Z ³¹ is a nitrogen atom, R ³⁸ does not exist. If Z ⁴¹ is an oxygen atom ^{R 47} and ^{R 48} are ^absent, when ^{Z 41} is a nitrogen atom ^{R 48} is absent. When Z ⁵¹ is an oxygen atom, R ⁵⁹ and R ⁶⁰ do not exist, and when Z ⁵¹ is a nitrogen atom, R ⁶⁰ does not exist. )

(In Formula (A), at least one of α, β, and γ is a group having a polymerizable functional group, and the polymerizable functional group includes a hydroxy group, a thiol group, an amino group, a carboxyl group, and a methoxy group. And at least one group selected from the group, wherein l and m are each independently 0 or 1, and the sum of l and m is 0 or more and 2 or less.
α is derived by replacing one of CH _{2 in} the main chain of an alkylene group having 1 to 6 carbon atoms in the main chain and a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms in the main chain with an oxygen atom. Group, a group derived by replacing one of CH _{2 in} the main chain of a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms in the main chain with a sulfur atom, or a substitution having 1 to 6 carbon atoms in the main chain Alternatively, one of CH _{2 in} the main chain of the unsubstituted alkylene group represents a group derived by replacing NR ¹⁹ , and R ¹⁹ represents a hydrogen atom or an alkyl group.
The substituent of the substituted alkylene group is an alkyl group having 1 to 6 carbon atoms, a benzyl group, an alkoxycarbonyl group, or a phenyl group. These groups may have the polymerizable functional group.
β represents a phenylene group, an alkyl group-substituted phenylene group having 1 to 6 carbon atoms, a nitro group-substituted phenylene group, a halogen group-substituted phenylene group, or an alkoxy group-substituted phenylene group, and these groups represent the polymerizable functional group. You may have.
γ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms in the main chain, or an alkyl group having 1 to 6 carbon atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms. May have the polymerizable functional group.   The image forming method according to any one of claims 1 to 3, wherein the acid value of the polyester resin A is 0.5 mgKOH / g or more and 25.0 mgKOH / g or less.   The image forming method according to any one of claims 1 to 4, wherein the polyester resin A has a weight average molecular weight (Mw) of 5,000 or more and 30,000 or less.   The toner particles are formed by forming particles of a polymerizable monomer composition containing a polyester resin A, a colorant, and a polymerizable monomer in an aqueous medium, and forming the particles of the polymerizable monomer composition on the particles. The image forming method according to claim 1, wherein the toner particles are obtained by polymerizing the polymerizable monomer contained therein. The toner particles further contain a charge control resin;
The image forming method according to claim 1, wherein the charge control resin has a pKa (acid dissociation constant) of 6.0 or more and 9.0 or less.   The image forming method according to claim 7, wherein the charge control resin has a pKa of 7.0 or more and 8.5 or less. 9. The image forming method according to claim 7, wherein the charge control resin has a structure represented by the following formula (2) in a side chain.

(R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms. N represents an integer of 0 to 3; when n is 2 or 3, R ¹ May be the same or different, and * is a binding site in the charge control resin.) The image forming method according to claim 9, wherein the structure represented by the formula (2) is a structure represented by the following formula (3).

(R ² represents an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms. R ³ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or Represents an alkoxyl group having 1 to 18 carbon atoms, g represents an integer of 1 to 3, h represents an integer of 0 to 3, and when h is 2 or 3, R ² is the same. Or may be different. * Is a binding site in the charge control resin.) The developing step is a step of forming a toner image using the toner inside a developing device;
The developing device includes:
A developing chamber having a toner carrier, and a toner supply member arranged to form a contact portion with the toner carrier;
A toner storage chamber,
The rotation direction of the toner carrier and the toner supply member is the same in each contact surface of the surface,
The amount of penetration of the toner supply member into the toner carrier at the contact portion is 0.3 mm or more and 1.5 mm or less,
11. The image forming method according to claim 1, wherein a peripheral speed of the toner supply member at the contact portion is 110% or more and 250% or less with respect to a peripheral speed of the toner carrier.

Images