JP5826212B2 - Method for producing electrophotographic photosensitive member - Google Patents

Description

The present invention relates to the production how the electronic photosensitive member.

  Currently, electrophotographic photoreceptors containing organic photoconductive substances are the mainstream as electrophotographic photoreceptors mounted on process cartridges and electrophotographic apparatuses. Since this electrophotographic photosensitive member has good film formability and can be produced by coating, it has an advantage that the productivity of the electrophotographic photosensitive member is high.

  An electrophotographic photoreceptor generally has a support and a photosensitive layer formed on the support. An undercoat layer is often provided between the support and the photosensitive layer for the purpose of suppressing charge injection from the support to the photosensitive layer side and suppressing the occurrence of image defects such as black spots. .

  In recent years, materials having higher sensitivity have been used as charge generating materials for electrophotographic photoreceptors.

  However, as the charge generating material becomes highly sensitive, there is a problem that the amount of generated charge increases, so that the charge tends to stay in the photosensitive layer and ghost is likely to occur. Specifically, in the output image, a phenomenon called so-called positive ghost, in which the density is increased only in a portion irradiated with light during the previous rotation, is likely to occur.

  As a technique for suppressing (reducing) such a ghost phenomenon, Patent Documents 1 and 2 disclose a technique in which an undercoat layer contains an electron transport material such as an imide compound.

JP 2001-83726 A JP 2003-345044 A

  In recent years, the demand for the quality of electrophotographic images has been increasing, and the allowable range for the above-mentioned positive ghost has become much stricter.

  As a result of the study by the present inventors, in the techniques disclosed in Patent Documents 1 and 2, the suppression of positive ghost may not be sufficiently improved, and further improvement is necessary.

  An object of the present invention is to provide an electrophotographic photosensitive member in which positive ghost is suppressed, and a method for producing the same. Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. Another object of the present invention is to provide a novel imide compound capable of suppressing positive ghost.

The present invention relates to a method for producing an electrophotographic photosensitive member having a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer.
The following (i), (ii) and (iii):
(I) Molecular weight having 3 to 6 groups selected from the group consisting of —NCO group and —NHCOX ¹ group (X ¹ is a group represented by any one of the following formulas (1) to (7)) (In the case of having -NHCOX ¹ group, it is a molecular weight calculated by removing X ¹ group.) Is an isocyanate compound of 200-1300,
(Ii) a resin having a repeating structural unit represented by the following formula (B), and (iii) a compound represented by the following formula (A1), a compound represented by the following formula (A2), and a following formula (A3). A compound represented by the following formula (A4), a compound represented by the following formula (A5), a compound represented by the following formula (A6), a compound represented by the following formula (A7), and a compound represented by the following formula (A8). At least one compound selected from the group consisting of compounds;
The present invention relates to a method for producing an electrophotographic photosensitive member , comprising a step of forming an undercoat layer containing a polymer obtained by polymerizing a composition containing.

In the formula (B), R ¹¹ represents a hydrogen atom or an alkyl group. Y represents a single bond or a phenylene group. W ¹ represents a hydroxy group, a thiol group, an amino group, or a carboxyl group.

In formulas (A1) to (A8), R ^{101 to} R ¹⁰⁶ , R ^{201 to} R ²¹⁰ , R ^{301 to} R ³⁰⁸ , R ^{401 to} R ⁴⁰⁸ , R ^{501 to} R ⁵¹⁰ , R ^{601 to} R ⁶⁰⁶ , R ^{701 to} R ⁷⁰⁸ and R ^{801 to} R ⁸¹⁰ 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 Represents a substituted or unsubstituted aryl group. However, at least one of R ^{101 to} R ¹⁰⁶ , at least one of R ^{201 to} R ²¹⁰ , at least one of R ^{301 to} R ³⁰⁸ , at least one of R ^{401 to} R ⁴⁰⁸ , at least one of R ^{501 to} R ⁵¹⁰ At least one of R ^{601 to} R ⁶⁰⁶ , at least one of R ^{701 to} R ⁷⁰⁸ , and at least one of R ^{801 to} R ⁸¹⁰ is a monovalent group represented by the following formula (A). One of the carbon atoms of the alkyl group may be replaced with O, S, NH, or NR ⁹⁰¹ (R ⁹⁰¹ is an alkyl group). The substituent of the substituted alkyl group is a group selected from the group consisting of an alkyl group, an aryl group, an alkoxycarbonyl group, and a halogen atom. The substituent of the substituted aryl group is a group selected from the group consisting of a halogen atom, a nitro group, a cyano group, an alkyl group, and a halogen group-substituted alkyl group. Z ²⁰¹ , Z ³⁰¹ , Z ⁴⁰¹ and Z ⁵⁰¹ each independently represent a carbon atom, a nitrogen atom or an oxygen atom. When Z ²⁰¹ is an oxygen atom, R ²⁰⁹ and R ²¹⁰ are not present, and when Z ²⁰¹ is a nitrogen atom, R ²¹⁰ is not present. When Z ³⁰¹ is an oxygen atom, R ³⁰⁷ and R ³⁰⁸ are not present, and when Z ³⁰¹ is a nitrogen atom, R ³⁰⁸ is not present. When Z ⁴⁰¹ is an oxygen atom, R ⁴⁰⁷ and R ⁴⁰⁸ are not present, and when Z ⁴⁰¹ is a nitrogen atom, R ⁴⁰⁸ is not present. If Z ⁵⁰¹ is an oxygen atom absent ^{R 509} and ^{R 510,} when ^{Z 501} is a nitrogen atom ^{R 510} is absent.

In formula (A), at least one of α, β, and γ is a group having a substituent, and the substituent is at least selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group. One kind of group. 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 an alkylene group having 1-6 atoms in the main chain, an alkylene group having 1-6 atoms in the main chain substituted with an alkyl group having 1-6 carbon atoms, or a main chain substituted with a benzyl group. An alkylene group having 1 to 6 atoms, an alkylene group having 1 to 6 atoms in the main chain substituted with an alkoxycarbonyl group, or an alkylene group having 1 to 6 atoms in the main chain substituted with a phenyl group These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group as a substituent. One of the carbon atoms in the main chain of the alkylene group may be replaced by O or S or NH or NR ¹⁹ (R ¹⁹ is an alkyl 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 are hydroxy groups as substituents , A thiol group, an amino group, and a carboxyl group may be included.

γ represents a hydrogen atom, an alkyl group having 1 to 6 atoms in the main chain, or an alkyl group having 1 to 6 atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms. May have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group as a substituent. One of the carbon atoms in the main chain of the alkyl group may be replaced with NR ⁹⁰² (R ⁹⁰² is an alkyl group).

Further, the present invention is a method for producing the electrophotographic photosensitive member, wherein the production method comprises:
Forming a coating film of an undercoat layer coating solution containing the isocyanate compound, a resin having a repeating structural unit represented by the formula (B), and a compound represented by any one of the formulas (A1) to (A8) And a process for forming the undercoat layer by heating and drying the coating film.

  Further, the present invention integrally supports the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means, and is detachable from the main body of the electrophotographic apparatus. It relates to a certain process cartridge.

  The present invention also relates to an electrophotographic apparatus comprising the electrophotographic photosensitive member, a charging unit, an exposure unit, a developing unit, and a transfer unit.

  Moreover, this invention relates to the imide compound shown by following formula (21)-(24).

  According to the present invention, it is possible to provide an electrophotographic photosensitive member in which positive ghost is suppressed and a method for manufacturing the same. Further, according to the present invention, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member can be provided. Moreover, according to this invention, the novel imide compound which can suppress a positive ghost can be provided.

1 is a diagram illustrating a schematic configuration of an electrophotographic apparatus having a process cartridge including the electrophotographic photosensitive member of the present invention. It is a figure explaining the printing for ghost evaluation used in the case of ghost image evaluation. It is a figure explaining a 1 dot Keima pattern image. It is a figure which shows an example of the layer structure of an electrophotographic photoreceptor.

  The present inventors speculate as follows why the electrophotographic photosensitive member having the undercoat layer of the present invention has an excellent effect of achieving positive ghost suppression at a high level.

The present invention has a molecular weight of 200 to 1300 having 3 to 6 groups selected from the group consisting of —NCO groups (hereinafter also referred to as isocyanate groups) and —NHCOX ¹ groups (hereinafter also referred to as blocked isocyanate groups). W ¹ of a resin having an isocyanate group of an isocyanate compound, a substituent of a compound represented by any one of formulas (A1) to (A8) (also referred to as an electron transport material), and a repeating structural unit represented by formula (B) And a polymer (cured product) is formed. By containing this polymer, the undercoat layer can transport electrons and can form an undercoat layer that is difficult to dissolve in a solvent.

  However, in the undercoat layer containing a polymer obtained by polymerizing a composition of a plurality of constituent materials (isocyanate compound, electron transport material, resin) in this way, constituent materials having the same structure are aggregated together. An uneven undercoat layer is easily formed. As a result, electrons tend to stay in the undercoat layer or at the interface between the undercoat layer and the photosensitive layer, and ghosts are easily generated. Therefore, the isocyanate compound of the present invention has 3 to 6 isocyanate groups and blocked isocyanate groups, so that the isocyanate groups are not adjacent to each other and have a moderately bulky and large volume. Thereby, when the isocyanate group or block isocyanate group of an isocyanate compound superposes | polymerizes with resin, it is thought that there exists an effect | action which pushes away the molecular chain of resin and suppresses aggregation (uneven distribution) of resin molecular chains. Furthermore, since the electron transport material is bound to the isocyanate compound that is bound to the molecular chain of the resin in which uneven distribution is suppressed, the electron transport material is uniformly present in the undercoat layer without being unevenly distributed. . As a result, it is believed that a polymer in which the structure derived from the isocyanate compound, the electron transport material, and the resin is uniformly present is obtained, the retention of electrons is greatly reduced, and a higher level of ghost suppression effect is obtained.

  On the other hand, in a polymer obtained by polymerizing a compound having an isocyanate group pendant on a polymer chain or a compound in which a site having an electron transporting ability is directly bonded to an isocyanate compound, the compound is contained in the polymer. Aggregation of the structure derived from is likely to occur. As a result, a high level of positive ghost suppression effect cannot be obtained sufficiently. In addition, when an isocyanate compound having two or less isocyanate groups is polymerized, there are few isocyanate groups contributing to the polymerization, and therefore, it is considered that the effect of pushing away the resin chain when the isocyanate group is polymerized with the resin is small. Accordingly, the effect of suppressing the uneven distribution of the electron transport material is reduced, and it is considered that a high level of ghost suppression effect cannot be obtained sufficiently.

  The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer. This photosensitive layer is preferably a laminated 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.

  FIGS. 4A and 4B are diagrams showing an example of the layer structure of the electrophotographic photosensitive member. In FIGS. 4A and 4B, 101 is a support, 102 is an undercoat layer, 103 is a photosensitive layer, 104 is a charge generation layer, and 105 is a charge transport layer.

  As a general electrophotographic photosensitive member, a cylindrical electrophotographic photosensitive member in which a photosensitive layer (charge generation layer, charge transport layer) is formed on a cylindrical support is widely used. It is also possible to have a shape of

[Support]
As the support, those having conductivity (conductive support) are preferable, and for example, a support made of a metal such as aluminum, nickel, copper, gold, iron, or an alloy can be used. A support in which a thin film of metal such as aluminum, silver, or gold is formed on an insulating support such as polyester resin, polycarbonate resin, polyimide resin, or glass, or a thin film of conductive material such as indium oxide or tin oxide is formed. A support is mentioned.

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

  A conductive layer may be provided between the support and the undercoat layer described below. The conductive layer can be obtained by forming a coating film of a coating liquid for conductive layer in which conductive particles are dispersed in a resin on a support and drying it. 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 resin, 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, more preferably 1 μm or more and 35 μm or less, and even more preferably 5 μm or more and 30 μm or less.

[Undercoat layer]
An undercoat layer is provided between the support or the conductive layer and the photosensitive layer.

  The undercoat layer contains a polymer obtained by polymerization of a composition containing (i) the isocyanate compound, (ii) the resin, and (iii) the electron transport material.

  The undercoating layer is formed by forming a coating film of a coating solution for an undercoating layer containing the above isocyanate compound, a resin having a repeating structural unit represented by the following formula (B), and an electron transport material. An undercoat layer is formed by heating and drying. Although these compounds are polymerized (cured) by a chemical reaction after the coating film is formed, the chemical reaction is accelerated and the polymerization is accelerated by heating at that time.

  Examples of the solvent used in the undercoat layer coating solution include an alcohol solvent, a sulfoxide solvent, a ketone solvent, an ether solvent, an ester solvent, and an aromatic hydrocarbon solvent.

In the formula (B), R ¹¹ represents a hydrogen atom or an alkyl group. Y represents a single bond or a phenylene group. W ¹ represents a hydroxy group, a thiol group, an amino group, or a carboxyl group.

In formulas (A1) to (A8), R ^{101 to} R ¹⁰⁶ , R ^{201 to} R ²¹⁰ , R ^{301 to} R ³⁰⁸ , R ^{401 to} R ⁴⁰⁸ , R ^{501 to} R ⁵¹⁰ , R ^{601 to} R ⁶⁰⁶ , R ^{701 to} R ⁷⁰⁸ and R ^{801 to} R ⁸¹⁰ 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 Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. However, at least one of R ^{101 to} R ¹⁰⁶ , at least one of R ^{201 to} R ²¹⁰ , at least one of R ^{301 to} R ³⁰⁸ , at least one of R ^{401 to} R ⁴⁰⁸ , at least one of R ^{501 to} R ⁵¹⁰ At least one of R ^{601 to} R ⁶⁰⁶ , at least one of R ^{701 to} R ⁷⁰⁸ , and at least one of R ^{801 to} R ⁸¹⁰ is a monovalent group represented by the following formula (A). One of the carbon atoms of the alkyl group may be replaced with O, S, NH, or NR ⁹⁰¹ (R ⁹⁰¹ is an alkyl group). The substituent of the substituted alkyl group is a group selected from the group consisting of an alkyl group, an aryl group, an alkoxycarbonyl group, and a halogen atom. The substituent of the substituted aryl group is a group selected from the group consisting of a halogen atom, a nitro group, a cyano group, an alkyl group, and a halogen group-substituted alkyl group. Z ²⁰¹ , Z ³⁰¹ , Z ⁴⁰¹ and Z ⁵⁰¹ each independently represent a carbon atom, a nitrogen atom or an oxygen atom. When Z ²⁰¹ is an oxygen atom, R ²⁰⁹ and R ²¹⁰ are not present, and when Z ²⁰¹ is a nitrogen atom, R ²¹⁰ is not present. When Z ³⁰¹ is an oxygen atom, R ³⁰⁷ and R ³⁰⁸ are not present, and when Z ³⁰¹ is a nitrogen atom, R ³⁰⁸ is not present. When Z ⁴⁰¹ is an oxygen atom, R ⁴⁰⁷ and R ⁴⁰⁸ are not present, and when Z ⁴⁰¹ is a nitrogen atom, R ⁴⁰⁸ is not present. If Z ⁵⁰¹ is an oxygen atom absent ^{R 509} and ^{R 510,} when ^{Z 501} is a nitrogen atom ^{R 510} is absent.

  In formula (A), at least one of α, β, and γ is a group having a substituent, and the substituent is at least selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group. One kind of group. 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 an alkylene group having 1-6 atoms in the main chain, an alkylene group having 1-6 atoms in the main chain substituted with an alkyl group having 1-6 carbon atoms, or a main chain substituted with a benzyl group. An alkylene group having 1 to 6 atoms, an alkylene group having 1 to 6 atoms in the main chain substituted with an alkoxycarbonyl group, or an alkylene group having 1 to 6 atoms in the main chain substituted with a phenyl group . These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group as a substituent. One of the carbon atoms in the main chain of the alkylene group may be replaced by O or S or NH or NR ¹⁹ (R ¹⁹ is an alkyl 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. These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group as a substituent.

γ represents a hydrogen atom, an alkyl group having 1 to 6 atoms in the main chain, or an alkyl group having 1 to 6 atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms. These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group as a substituent. One of the carbon atoms in the main chain of the alkyl group may be replaced with NR ⁹⁰² (R ⁹⁰² is an alkyl group).

  The content of the polymer is preferably 50% by mass or more and 100% by mass or less, and preferably 80% by mass or more and 100% by mass or less, based on the total mass of the undercoat layer, from the viewpoint of suppressing ghosts. More preferred.

  For the undercoat layer, in addition to the polymer, other resins, crosslinkers other than the isocyanate compounds, organic particles, inorganic particles, leveling agents, etc. in order to improve the film formability and electrical characteristics of the undercoat layer It may contain. However, their content in the undercoat layer is preferably less than 50% by mass and more preferably less than 20% by mass with respect to the total mass of the undercoat layer.

[Electron transport material]
The compound represented by any one of the above formulas (A1) to (A8) preferably has a molecular weight of 150 or more and 1000 or less. It is considered that the structure derived from the electron transport material is present more uniformly in the undercoat layer when the molecular weight is as described above.

  In addition, from the viewpoint of the uniformity of the structure derived from the electron transport material, the ratio of the molecular weight of the compound represented by any one of formulas (A1) to (A8) and the molecular weight of the isocyanate compound is 3/20 to 50 / 20 is preferable. More preferably, it is 12 / 20-28 / 20.

  Next, specific examples of the electron transport material are shown below. Table 1-1, Table 1-2, Table 1-3, and Table 1-4 show specific examples of the compound represented by the formula (A1). In the table, when γ is “−”, γ represents a hydrogen atom and is displayed in the column of α or β.

  Tables 2-1 and 2-2 show specific examples of the compound represented by the formula (A-2). In the table, when γ is “−”, γ represents a hydrogen atom and is displayed in the column of α or β.

  Tables 3-1 and 3-2 show specific examples of the compound represented by the formula (A-3). In the table, when γ is “−”, γ represents a hydrogen atom and is displayed in the column of α or β.

  Tables 4-1 and 4-2 show specific examples of the compound represented by the formula (A-4). In the table, when γ is “−”, γ represents a hydrogen atom and is displayed in the column of α or β.

  Tables 5-1 and 5-2 show specific examples of the compound represented by the above formula (A-5). In the table, when γ is “−”, γ represents a hydrogen atom and is displayed in the column of α or β.

  Table 6 shows specific examples of the compound represented by the above formula (A-6). In the table, when γ is “−”, γ represents a hydrogen atom and is displayed in the column of α or β.

  Tables 7-1 and 7-2 show specific examples of the compound represented by the formula (A-7). In the table, when γ is “−”, γ represents a hydrogen atom and is displayed in the column of α or β.

  Tables 8-1 and 8-2 show specific examples of the compound represented by the above formula (A-8). In the table, when γ is “−”, γ represents a hydrogen atom and is displayed in the column of α or β.

  In the above table, compound A124 (imide compound represented by formula (21)), A135 (imide compound represented by formula (22)), A153 (imide compound represented by formula (23)), A173 (formula (Imide compound represented by (24)) is a novel imide compound. This imide compound is a compound having an excellent positive ghost suppressing effect.

  Derivatives having the structure of (A1) (derivatives of electron transport materials) are disclosed in, for example, US Pat. No. 4,442,193, US Pat. No. 4,992,349, US Pat. No. 5,468,583, Chemistry of materials, Vol. 19, no. It is possible to synthesize using a known synthesis method described in 11, 2703-2705 (2007). Moreover, it can synthesize | combine by reaction with the naphthalene tetracarboxylic dianhydride and monoamine derivative which can be purchased from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd., and Johnson Matthey Japan Incorporated.

The compound represented by (A1) has a polymerizable functional group (hydroxy group, thiol group, amino group, and carboxyl group) that can be polymerized with the isocyanate group of the isocyanate compound. As a method of introducing these substituents into the derivative having the structure of (A1), a method of directly introducing a polymerizable functional group into the derivative having the structure of (A1), the polymerizable functional group, or the polymerizable functional group There is a method of introducing a structure having a functional group that can be a precursor of the above. As a method described later, for example, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base based on a halide of a naphthylimide derivative. For example, a method of introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base based on a halide of a naphthylimide derivative. For example, based on a halide of a naphthylimide derivative, 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. As a raw material for synthesizing a naphthylimide derivative, there is a method using the naphthalenetetracarboxylic dianhydride derivative or monoamine derivative having the polymerizable functional group or a functional group that can be a precursor of the polymerizable functional group.

  The derivative having the structure of (A2) can be purchased as a reagent from, for example, Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc. Further, based on phenanthrene derivatives or phenanthroline derivatives, Chem. Educator No. 6, 227-234 (2001), Journal of Synthetic Organic Chemistry, vol. 15, 29-32 (1957), Journal of Synthetic Organic Chemistry, vol. 15, 32-34 (1957). A dicyanomethylene group can also be introduced by reaction with malononitrile.

The compound represented by (A2) has a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the isocyanate group of the isocyanate compound. As a method for introducing these polymerizable functional groups into the derivative having the structure of (A2), for example, a method of directly introducing a polymerizable functional group into the derivative having the structure of the formula (A2), a polymerizable functional group or a polymerization There is a method of introducing a structure having a functional group that becomes a precursor of a functional functional group. As a method described later, for example, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base based on a halide of phenanthrenequinone. For example, based on a halide of phenanthrenequinone, a method of introducing a functional group-containing alkyl group using a cross-coupling reaction using an FeCl ₃ catalyst and a base. For example, based on a halide of phenanthrenequinone, 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.

  The derivative having the structure of (A3) can be purchased as a reagent from, for example, Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc. Also, based on phenanthrene derivatives or phenanthroline derivatives, Bull. Chem. Soc. Jpn. , Vol. 65, 1006-1011 (1992). A dicyanomethylene group can also be introduced by reaction with malononitrile.

The compound represented by (A3) has a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the isocyanate group of the isocyanate compound. Examples of the method for introducing these polymerizable functional groups into the derivative having the structure (A3) include a method for directly introducing a polymerizable functional group into the derivative having the structure (A3), a polymerizable functional group, or a polymerizable property. There is a method of introducing a structure having a functional group that serves as a precursor of a functional group. As a method described later, for example, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base based on a halide of phenanthroline quinone. For example, based on a halide of phenanthroline quinone, a functional group-containing alkyl group is introduced using a cross-coupling reaction using a FeCl ₃ catalyst and a base. For example, based on a halide of phenanthroline quinone, 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.

  The derivative having the structure of (A4) can be purchased as a reagent from, for example, Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc. Moreover, based on an acenaphthenequinone derivative | guide_body, it can also synthesize | combine with the synthesis | combining method of Tetrahedron Letters, 43 (16), 2991-2994 (2002), Tetrahedron Letters, 44 (10), 2087-2091 (2003). A dicyanomethylene group can also be introduced by reaction with malononitrile.

The compound represented by (A4) has a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the isocyanate group of the isocyanate compound. As a method for introducing these polymerizable functional groups into the derivative having the structure (A4), for example, a method for directly introducing a polymerizable functional group into the derivative having the structure (A4), a polymerizable functional group, or a polymerizable property. There is a method of introducing a structure having a functional group that serves as a precursor of a functional group. As a method to be described later, for example, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base based on a halide of acenaphthenequinone. For example, a method of introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base based on a halide of acenaphthenequinone. For example, based on a halide of acenaphthenequinone, 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.

  The derivative having the structure of (A5) can be purchased as a reagent from, for example, Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc. Further, it can be synthesized using a fluorenone derivative and malononitrile by the synthesis method described in US Pat. No. 4,562,132. Moreover, it can also synthesize | combine using the synthesis method as described in Unexamined-Japanese-Patent No. 5-279582 and Unexamined-Japanese-Patent No. 7-70038 using a fluorenone derivative and an aniline derivative.

The compound represented by (A5) has a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the isocyanate group of the isocyanate compound. As a method for introducing these polymerizable functional groups into the derivative having the structure (A5), for example, a method for directly introducing a polymerizable functional group into the derivative having the structure (A5), a polymerizable functional group, or a polymerizable property. There is a method of introducing a structure having a functional group that serves as a precursor of a functional group. As a method described later, for example, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base based on a halide of fluorenone. For example, a functional group-containing alkyl group is introduced using a cross coupling reaction using a FeCl ₃ catalyst and a base based on a halide of fluorenone. For example, based on a halide of fluorenone, 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.

  The derivative having the structure (A6) can be synthesized by using a synthesis method described in Chemistry Letters, 37 (3), 360-361 (2008), Japanese Patent Application Laid-Open No. 9-151157, for example. For example, it can be purchased as a reagent from Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc.

The compound represented by (A6) has a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the isocyanate group of the isocyanate compound. As a method of introducing these polymerizable functional groups into the derivative having the structure of (A6), there is a method of introducing a structure having a polymerizable functional group or a functional group serving as a precursor of the polymerizable functional group into a naphthoquinone derivative. . As this method, for example, based on a naphthoquinone halide, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base. For example, based on a naphthoquinone halide, a functional group-containing alkyl group is introduced using a cross-coupling reaction using a FeCl ₃ catalyst and a base. For example, based on a naphthoquinone halide, 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.

  Derivatives having the structure (A7) are disclosed in, for example, JP-A-1-206349, PPCI / Japan Hard Copy '98 Preliminary Collection p. 207 (1998). For example, a phenol derivative that can be purchased as a reagent from Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich Japan Co., Ltd. can be used as a raw material.

The compound represented by (A7) has a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the isocyanate group of the isocyanate compound. As a method of introducing these polymerizable functional groups into the derivative having the structure of (A7), there is a method of introducing a structure having a polymerizable functional group or a functional group serving as a precursor of the polymerizable functional group. As this method, for example, based on a halide of diphenoquinone, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base. For example, based on a halide of diphenoquinone, a method of introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base. For example, based on a diphenoquinone halide, there is a method of introducing a hydroxyalkyl group or a carboxyl group by allowing an epoxy compound or CO2 to act after lithiation.

  Derivatives having the structure (A8) are described in, for example, Journal of the American chemical society, Vol. 129, no. 49, 15259-78 (2007). Further, it can be synthesized by a reaction of perylenetetracarboxylic dianhydride, which can be purchased as a reagent from Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd. or Johnson Matthey Japan Inc., and a monoamine derivative. .

The compound represented by (A8) has a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the isocyanate group of the isocyanate compound. As a method for introducing these polymerizable functional groups into the derivative having the structure of (A8), in addition to the method of directly introducing a polymerizable functional group into the derivative having the structure of (A8), the polymerizable functional group or There is a method of introducing a structure having a functional group that can be a precursor of a polymerizable functional group. As a method to be described later, for example, a method using a cross-coupling reaction using a palladium catalyst and a base based on a halide of a perylene imide derivative. For example, there is a method using a cross coupling reaction using a FeCl ₃ catalyst and a base based on a halide of a perylene imide derivative. Further, as a raw material for synthesizing a perylene imide derivative, there is a method of using a perylene tetracarboxylic dianhydride derivative or a monoamine derivative having the polymerizable functional group or a functional group that can be a precursor of the polymerizable functional group.

[Isocyanate compound]
The isocyanate compound used in the present invention has a molecular weight of 200 to 1300 and has 3 to 6 groups selected from the group consisting of an isocyanate group (NCO group) and a blocked isocyanate group (NHCOX ¹ group). Any compound may be used. The isocyanate compounds used in the present invention are triisocyanatebenzene, 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-diisocyanate hexanoate, norbornane diisocyanate modified isocyanurate modified, biuret modified, allophanate modified, adduct with trimethylolpropane, etc. Is mentioned.

  The isocyanate compound of the present invention preferably has a cyclic structure. When it is a cyclic structure, the aggregation of resin molecular chains and the uneven distribution of the electron transport material are further suppressed, and the ghost suppression effect is excellent. More preferred is an isocyanurate structure, which is the structure shown below.

These isocyanate compounds may be compounds blocked with a blocking group (X ¹ ) of a blocked isocyanate group (—NHCOX ¹ group). X ¹ is a group represented by any of the following formulas (1) to (7).

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

  Moreover, as an isocyanate compound, Sumika Bayer Urethane Co., Ltd. product, BL3175, BL3475, BL3575, etc. can be used, for example.

〔resin〕
The resin having a repeating unit represented by the above formula (B) is a monomer having a polymerizable functional group (hydroxy group, thiol group, amino group, and carboxyl group) that can be purchased as a reagent from Sigma-Aldrich Japan, for example. It is obtained by polymerizing.

  Moreover, it is also possible to generally purchase as resin, and as a resin which can be purchased, Nippon Polyurethane Industry Co., Ltd. AQD-457, AQD-473, Sanyo Chemical Industries Co., Ltd. Sanniks GP-400, Polyether polyol resins such as GP-700, polyesters such as Hitachi Chemical Co., Ltd., Phthalkid W2343, DIC Corporation Watersol S-118, CD-520, Harima Kasei Co., Ltd. Halipip WH-1188 Polyol-based resins, polyacrylic polyol-based resins such as DIC's Vernock WE-300 and WE-304, polyvinyl alcohol-based resins such as Kuraray's Kuraray Poval PVA-203, Sekisui Chemical Co., Ltd. KW-1 and KW-3, BX-1, BM-1, KS-1, KS-5, etc. Vinyl acetal resins, polyamide compound resins such as Toray resin FS-350 manufactured by Nagase ChemteX Corporation, aqualic manufactured by Nippon Shokubai Co., Ltd., carboxyl group-containing resins such as Finelex SG2000 manufactured by Lead City Corporation, DIC ( Examples include polyamines such as Racamamide manufactured by Co., Ltd., and polythiols such as QE-340M manufactured by Toray Industries, Inc.

  Then, the specific example of resin which has a repeating unit shown by the said Formula (B) in Table 9 is shown.

  The compound according to the present invention was confirmed by the following method.

-Mass spectrometry The molecular weight was measured using a mass spectrometer (MALDI-TOF MS: ultraflex manufactured by Bruker Daltonics Co., Ltd.) under the conditions of acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: fullerene C60. It confirmed with the obtained peak top value.

・ NMR analysis ¹ H-NMR, ¹³ C-NMR analysis (FT-NMR: manufactured by JEOL Ltd.) in 1,1,2,2-tetrachloroethane (d2) or dimethyl sulfoxide (d6) at 120 ° C. The structure was confirmed by JNM-EX400 type).

-GPC analysis It measured with the gel permeation chromatography "HLC-8120" by Tosoh Corporation, and computed in polystyrene conversion.

  In addition, an undercoat layer obtained by forming a coating film of an undercoat layer coating solution containing an isocyanate compound, a resin, and an electron transport material, and heating and drying the coating film is immersed in cyclohexanone, before and after the immersion. The weight of the undercoat layer was confirmed. It was confirmed that the components of the undercoat layer were not dissolved by immersion, and were cured (polymerized).

(Photosensitive layer)
A photosensitive layer is provided on the undercoat layer.

  Charge generation materials include azo pigments, perylene pigments, anthraquinone derivatives, anthanthrone derivatives, dibenzpyrenequinone derivatives, pyranthrone derivatives, violanthrone derivatives, isoviolanthrone derivatives, indigo derivatives, thioindigo derivatives, metal phthalocyanines, metal-free phthalocyanines, etc. Phthalocyanine pigments and bisbenzimidazole derivatives. Among these, azo pigments or phthalocyanine pigments are preferable. Among the phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferable.

  When the photosensitive layer is a laminated photosensitive layer, the binder resin used for the charge generation layer includes vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene. Polymers and copolymers, polyvinyl alcohol resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, polysulfone resin, polyphenylene oxide resin, polyurethane resin, cellulose resin, phenol resin, melamine resin, silicon resin, epoxy resin, etc. It is done. Among these, polyester resin, polycarbonate resin, and polyvinyl acetal resin are preferable, and among these, polyvinyl acetal resin is more preferable.

  In the charge generation layer, the 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 in the range of 5/1 to 1/5. It is more preferable that The thickness of the charge generation layer is preferably 0.05 μm or more and 5 μm or less. 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.

  Examples of the charge transport material (hole transport material) include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, benzidine compounds, triarylamine compounds, and triphenylamine. Also included are polymers having groups derived from these compounds in the main chain or side chain.

  When the photosensitive layer is a laminated photosensitive layer, the binder resin used for the charge transport layer (hole transport layer) is a polyester resin, polycarbonate resin, polymethacrylate resin, polyarylate resin, polysulfone resin, polystyrene resin. Etc. Among these, polycarbonate resin and polyarylate resin are preferable. Moreover, it is preferable that these weight average molecular weights (Mw) are the range of 10,000-300,000.

  In the charge transport layer, the ratio of the charge transport material to the binder resin (charge transport material / binder resin) is preferably in the range of 10/5 to 5/10, and in the range of 10/8 to 6/10. It is more preferable that The thickness of the charge transport layer is preferably 5 μm or more and 40 μm or less.

  In addition, another layer such as a second undercoat layer not containing the polymer according to the present invention may be provided between the support and the undercoat layer or between the undercoat layer and the photosensitive layer. .

  Examples of the solvent used in the charge transport layer coating liquid include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

  Further, a protective layer (surface protective layer) containing conductive particles or a hole transport material and a binder resin may be provided on the photosensitive layer (charge transport layer). The protective layer may further contain an additive such as a lubricant. Further, the binder resin itself of the protective layer may have conductivity and hole transportability, and in that case, the protective layer may not contain conductive particles or hole transport materials other than the resin. Good. The binder resin of the protective layer may be a thermoplastic resin or a curable resin that is cured by heat, light, radiation (such as an electron beam), or the like.

  As a method for forming each layer constituting the electrophotographic photosensitive member such as an undercoat layer, a charge generation layer, and a charge transport layer, a coating solution obtained by dissolving and / or dispersing materials constituting each layer in a solvent is applied. To do. And the method of forming by drying and / or hardening the obtained coating film is preferable. Examples of the method for applying the coating liquid include a dip coating method (dip coating method), a spray coating method, a curtain coating method, and a spin coating method. Among these, the dip coating method is preferable from the viewpoints of efficiency and productivity.

[Process cartridge and electrophotographic apparatus]
FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus having a process cartridge provided with the electrophotographic photosensitive member of the present invention.

  In FIG. 1, reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is rotationally driven in a direction of an arrow about a shaft 2 at a predetermined peripheral speed. The surface (circumferential surface) of the electrophotographic photosensitive member 1 that is rotationally driven is uniformly charged to a predetermined positive or negative potential by a charging unit 3 (primary charging unit: charging roller or the like). Next, it receives exposure light (image exposure light) 4 from exposure means (not shown) such as slit exposure or laser beam scanning exposure. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the surface of the electrophotographic photosensitive member 1.

  The electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is then developed with toner contained in the developer of the developing means 5 to become a toner image. Next, the toner image formed and supported on the surface of the electrophotographic photosensitive member 1 is sequentially transferred onto a transfer material (such as paper) P by a transfer bias from a transfer unit (such as a transfer roller) 6. The transfer material P is taken out from the transfer material supply means (not shown) between the electrophotographic photoreceptor 1 and the transfer means 6 (contact portion) in synchronization with the rotation of the electrophotographic photoreceptor 1 and fed. Is done.

  The transfer material P that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member 1 and introduced into the fixing means 8 to receive the image fixing, and is printed out as an image formed product (print, copy). Is done.

  The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by receiving a developer (toner) remaining after transfer by a cleaning means (cleaning blade or the like) 7. Next, after being subjected to charge removal processing by pre-exposure light (not shown) from pre-exposure means (not shown), it is repeatedly used for image formation. As shown in FIG. 1, when the charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not necessarily required.

  A plurality of the above-described electrophotographic photosensitive member 1, charging means 3, developing means 5, transfer means 6 and cleaning means 7 are housed in a container and integrally combined as a process cartridge. This process cartridge is electrophotographic. You may comprise so that attachment or detachment with respect to an apparatus main body is possible. In FIG. 1, an electrophotographic photosensitive member 1, a charging unit 3, a developing unit 5 and a cleaning unit 7 are integrally supported to form a cartridge, and an electrophotographic apparatus is provided using a guide unit 10 such as a rail of the electrophotographic apparatus main body. The process cartridge 9 is detachable from the main body.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “part” means “part by mass”. First, a synthesis example of the electron transport material according to the present invention is shown.

(Synthesis Example 1)
To 200 parts of dimethylacetamide, 5.4 parts of naphthalenetetracarboxylic dianhydride, 4 parts of 2-methyl 6-ethylaniline and 3 parts of 2-amino 1-butanol are added under nitrogen atmosphere and stirred at room temperature for 1 hour. A solution was prepared. After preparing the solution, the mixture was refluxed for 8 hours. The precipitate was filtered off and recrystallized from ethyl acetate to obtain 1.0 part of Compound A101.

(Synthesis Example 2)
In a nitrogen atmosphere, 5.4 parts of naphthalenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 parts of 2-aminobutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to 200 parts of dimethylacetamide. And stirred at room temperature for 1 hour to prepare a solution. After preparing the solution, the mixture was refluxed for 8 hours, and the precipitate was filtered off and recrystallized from ethyl acetate to obtain 4.6 parts of Compound A128.

(Synthesis Example 3)
200 parts of dimethylacetamide, 5.4 parts of naphthalenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2,6 diethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.5 under a nitrogen atmosphere Part and 4-aminobenzenethiol 4 parts were added and stirred at room temperature for 1 hour to prepare a solution. After preparing the solution, the mixture was refluxed for 8 hours. The precipitate was filtered off and recrystallized from ethyl acetate to obtain 1.3 parts of Compound A114.

(Synthesis Example 4)
2-Aminobenzyl alcohol (Tokyo Chemical Industry Co., Ltd.) in 200 parts of dimethylacetamide and 1.8 parts of naphthalenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) over 2 hours at room temperature in a nitrogen atmosphere. 2.5 parts) and 50 parts of dimethylacetamide were added. Thereafter, the mixture was stirred at 40 ° C. for 1 hour and at 120 ° C. for 1 hour, and then refluxed for 8 hours. Dimethylacetamide was removed by distillation under reduced pressure, 100 parts of a methanol / water = 1/1 solution was added, and crystals were precipitated, followed by filtration. The crystals were dissolved in a mixed solution of ethyl acetate / THF and separated by silica gel column chromatography (developing solvent: ethyl acetate). After separation, the fraction containing the desired product was concentrated, and the obtained crystal was recrystallized with a mixed solution of ethyl acetate / THF to obtain 1.6 parts of compound A124 (imide compound represented by formula (21)). It was.

(Synthesis Example 5)
200 parts of dimethylacetamide and 2.7 parts of naphthalenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.6 parts of phenylalaninol (manufactured by Tokyo Chemical Industry Co., Ltd.) and dimethyl under a nitrogen atmosphere 50 parts of acetamide was added. Thereafter, the mixture was stirred at 120 ° C. for 3 hours and then refluxed for 5 hours. After removing dimethylacetamide by distillation under reduced pressure, 100 parts of water was added to precipitate crystals, followed by filtration. Recrystallization from ethanol gave 3.1 parts of Compound A135 (an imide compound represented by the formula (22)).

(Synthesis Example 6)
2.8 parts of 4- (hydroxymethyl) phenylboronic acid (manufactured by Aldrich) and phenanthrenequinone (manufactured by Sigma-Aldrich Japan Co., Ltd.) were added in a Chem. Educator No. 6, 227-234 (2001), 7.4 parts of 3,6-dibromo-9,10-phenanthrene range was synthesized. To a mixed solvent of 100 parts of toluene and 50 parts of ethanol, 7.4 parts of 3,6-dibromo-9,10-phenanthrene dione is added, and 100 parts of 20% aqueous sodium carbonate solution is added dropwise, followed by tetrakis (triphenylphosphine) palladium. After adding 0.55 parts of (0), the mixture was refluxed for 2 hours. After the reaction, the organic phase was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography to obtain 3.2 parts of Compound A216.

(Synthesis Example 7)
2,7-Dibromo-9,10-phenanthroline was prepared in the same manner as in Synthesis Example 6 except that 2.8 parts of 3-aminophenylboronic acid monohydrate and phenanthroline quinone (manufactured by Sigma-Aldrich Japan Co., Ltd.) were used. 7.4 parts of quinone were synthesized. 7.4 parts of 2,7-dibromo-9,10-phenanthrolinequinone was added to a mixed solvent of 100 parts by mass of toluene and 50 parts by mass of ethanol. To this was added dropwise 100 parts of a 20% aqueous sodium carbonate solution, 0.55 parts of tetrakis (triphenylphosphine) palladium (0) was added, and the mixture was refluxed for 2 hours. After the reaction, the organic phase was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography to obtain 2.2 parts of Compound A316.

(Synthesis Example 8)
200 parts of dimethylacetamide, under a nitrogen atmosphere, 7.4 parts of perylenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4 parts of 2,6 diethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 4 parts of 2-aminophenylethanol was added and stirred at room temperature for 1 hour to prepare a solution. After preparing the solution, the mixture was refluxed for 8 hours, and the precipitate was filtered off and recrystallized from ethyl acetate to obtain 5.0 parts of Compound A803.

(Synthesis Example 11)
Under a nitrogen atmosphere, 5.4 parts of naphthalenetetracarboxylic dianhydride, 2.6 parts of leucinol and 2.7 parts of 2- (2-aminoethylthio) ethanol are added to 200 parts of dimethylacetamide at room temperature for 1 hour. After stirring, the mixture was refluxed for 7 hours. Dimethylacetamide was removed from the resulting black brown solution by distillation under reduced pressure, and then dissolved in a mixed solution of ethyl acetate / toluene.

After separation by silica gel column chromatography (developing solvent: ethyl acetate / toluene), the fraction containing the target compound was concentrated, and the resulting crystals were recrystallized with a toluene / hexane mixed solution to obtain compound A173 (formula (23)). 2.5 parts of the imide compound shown) was obtained (Synthesis Example 10).
To 200 parts of dimethylacetamide, 5.4 parts of naphthalenetetracarboxylic dianhydride and 5.2 parts of leucinol were added under a nitrogen atmosphere, stirred at room temperature for 1 hour, and then refluxed for 7 hours. After removing dimethylacetamide by distillation under reduced pressure, recrystallization was performed with ethyl acetate to obtain 5.0 parts of Compound A157 (imide compound represented by the formula (24)).

  Next, an electrophotographic photoreceptor was produced and evaluated as follows.

Example 1
An aluminum cylinder (JIS-A3003, aluminum alloy) having a length of 260.5 mm and a diameter of 30 mm was used as a support (conductive support).

  Next, 50 parts of titanium oxide particles coated with oxygen-deficient tin oxide (powder resistivity: 120 Ω · cm, tin oxide coverage: 40%), phenol resin (Pryofen J-325, Dainippon) Ink Chemical Industry Co., Ltd., resin solid content: 60%.) 40 parts and 40 parts of methoxypropanol were placed in a sand mill using glass beads with a diameter of 1 mm and dispersed for 3 hours, thereby applying a coating solution for a conductive layer. (Dispersion) was prepared. The conductive layer coating solution was dip-coated on a support, and the resulting coating film was dried and thermally cured at 145 ° C. for 30 minutes to form a conductive layer having a thickness of 16 μm.

  The average particle diameter of the titanium oxide particles coated with oxygen-deficient tin oxide in the coating liquid for the conductive layer was measured using a particle size distribution meter (trade name: CAPA700) manufactured by Horiba, Ltd., and tetrahydrofuran as a dispersion medium. , And measured by centrifugal sedimentation at a rotational speed of 5000 rpm. As a result, the average particle size was 0.33 μm.

  Next, 8 parts of compound A101, 10 parts of isocyanate compound (I-1) blocked with a group represented by formula (1), 0.1 part of zinc octylate (II) as a catalyst, and resin B1 (2 parts) ) Was dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an undercoat layer coating solution. This undercoat layer coating solution is dip-coated on the conductive layer, and the resulting coating film is heated at 160 ° C. for 30 minutes and cured (polymerized) to form an undercoat layer having a thickness of 0.5 μm. did.

  Next, hydroxygallium phthalocyanine crystal (7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 ° of Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction, 10 parts, 5 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 260 parts of cyclohexanone having a diameter of 1 mm have strong peaks at 25.1 ° and 28.3 °. The mixture was placed in a sand mill using glass beads and dispersed for 1.5 hours. Next, 240 parts of ethyl acetate was added thereto to prepare a charge generation layer coating solution. This charge generation layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 95 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.

  Next, 7 parts of an amine compound (hole transport material) represented by the following formula (15) and 10 parts of a polyester resin D (repeating structural unit represented by the following formula (16-1), and the following formula (16-2) ) Is dissolved in a mixed solvent of 30 parts of dimethoxymethane and 70 parts of chlorobenzene to dissolve the coating composition for the charge transport layer. Was prepared. The charge transport layer coating solution was dip coated on the charge generation layer, and the resulting coating film was dried at 120 ° C. for 60 minutes to form a charge transport layer having a thickness of 15 μm.

  Thus, an electrophotographic photosensitive member having a conductive layer, an undercoat layer, a charge generation layer, and a charge transport layer on a support was produced.

  The manufactured electrophotographic photoreceptor is mounted on a modified laser beam printer (trade name: LBP-2510) manufactured by Canon Inc. in an environment of a temperature of 15 ° C. and a humidity of 10% RH. Measurements and output image evaluation were performed. Details are as follows.

  For the measurement of the surface potential, a cyan process cartridge for the laser beam printer was modified, and a potential probe (model 6000B-8: manufactured by Trek Japan Co., Ltd.) was mounted at the development position. Further, the potential of the central portion of the electrophotographic photosensitive member was measured using a surface potentiometer (model 344: manufactured by Trek Japan Co., Ltd.). The surface potential of the drum was set such that the initial dark portion potential (Vd) was −500 V and the initial bright portion potential (Vl) was −100 V.

  Subsequently, the manufactured electrophotographic photosensitive member was attached to the cyan process cartridge of the laser beam printer, and the process cartridge was attached to a cyan process cartridge station to output an image. First, image output was successively performed in the order of one solid white image, five ghost evaluation images, one solid black image, and five ghost evaluation images. Next, 10,000 full-color images (character images with a color printing rate of 1%) are output on A4 size plain paper, and then one solid white image, five ghost evaluation images, and a solid black image. Image output was successively performed in the order of one image and five ghost evaluation images.

  As shown in FIG. 2, the ghost evaluation image has a “solid image” of a square in a “white image” at the head of the image, and then a “halftone image of 1-dot Keima pattern” shown in FIG. It was created. In FIG. 2, the “ghost” portion is a portion where a ghost attributed to the “solid image” may appear.

  The positive ghost was evaluated by measuring the density difference between the halftone image density of the 1-dot Keima pattern and the image density of the ghost portion. A spectral densitometer (trade name: X-Rite 504/508, manufactured by X-Rite Co., Ltd.) was used to measure 10 density differences in one ghost evaluation image. This operation was performed on all 10 ghost evaluation images, the average of 100 points in total was calculated, and the Macbeth density difference (initial) at the time of initial image output was evaluated. Next, the difference (change) between the Macbeth density difference after output of 10,000 sheets and the Macbeth density difference at the time of initial image output was calculated to obtain the fluctuation amount of the Macbeth density difference. The smaller the Macbeth density difference, the more positive ghost is suppressed. The smaller the difference between the Macbeth density difference after outputting 10,000 sheets and the Macbeth density difference when outputting the initial image, the smaller the change in the positive ghost. The results are shown in Table 10.

(Examples 2-122)
Tables 10 and 11 show the types and contents of the isocyanate compound (compound I, blocking group X ¹ ), the resin (resin B) having the repeating structural unit represented by the formula (B), and the electron transport material (compound A). An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the above was changed. Similarly, positive ghost was evaluated. The results are shown in Tables 10 and 11.

(Example 123)
An electrophotographic photosensitive member was produced in the same manner as in Example 112 except that the conductive layer of Example 112 was changed as follows, and positive ghost was evaluated in the same manner. The results are shown in Tables 10 and 11.

207 parts of metal oxide particles (titanium oxide (TiO ₂ ) particles coated with tin oxide (SnO ₂ ) doped with phosphorus (P)), phenol resin as a binder resin (trade name: Pryofen J-325, manufactured by Dainippon Ink and Chemicals, Inc., resin solid content: 60% by mass.) 144 parts and 98 parts of 1-methoxy-2-propanol as a solvent were added to glass beads 450 having a diameter of 0.8 mm. Dispersion treatment was carried out by putting in a sand mill using a part to obtain a dispersion. Dispersion conditions were controlled at a rotational speed of 2000 rpm, a dispersion treatment time of 4.5 hours, and a cooling water set temperature of 18 ° C. Glass beads were removed from this dispersion with a mesh (aperture: 150 μm).

  Silicone resin particles as a surface roughening agent (trade name: Tospearl 120, Momentive Performance Materials (so that the total mass of metal oxide particles and binder resin in the dispersion liquid is 15% by mass) Co., Ltd., average particle size 2 μm) was added to the dispersion. In addition, silicone oil as a leveling agent (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.) so that the total mass of the metal oxide particles and the binder resin in the dispersion is 0.01% by mass. ) Was added to the dispersion and stirred to prepare a coating solution for the conductive layer. The conductive layer coating solution was dip-coated on a support, and the resulting coating film was dried and thermally cured at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 30 μm.

(Example 124)
An electrophotographic photosensitive member was produced in the same manner as in Example 112 except that the conductive layer of Example 112 was changed as follows, and positive ghost was evaluated in the same manner. The results are shown in Tables 10 and 11.

Metal oxide particles (titanium oxide (TiO ₂ ) particles coated with oxygen-deficient tin oxide (SnO ₂ )) 214 parts, phenol resin as a binder resin (trade name: Pryofen J-325) 132 And 98 parts of 1-methoxy-2-propanol as a solvent were placed in a sand mill using 450 parts of glass beads having a diameter of 0.8 mm, and dispersion treatment was performed to obtain a dispersion. Dispersion conditions were controlled at a rotational speed of 2000 rpm, a dispersion treatment time of 4.5 hours, and a cooling water set temperature of 18 ° C. Glass beads were removed from this dispersion with a mesh (aperture: 150 μm).

  Silicone resin particles (trade name: Tospearl 120) as a surface roughening agent were added to the dispersion 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. Further, a silicone oil (trade name: SH28PA) as a leveling agent is added to the dispersion so as to be 0.01% by mass with respect to the total mass of the metal oxide particles and the binder resin in the dispersion, followed by stirring. By doing this, the coating liquid for conductive layers was prepared. The conductive layer coating solution was dip-coated on a support, and the resulting coating film was dried and thermally cured at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 30 μm.

(Example 125)
The preparation of the coating solution for the charge transport layer in Example 112 was changed as follows. 9 parts of a charge transport material having a structure represented by the above formula (8), 1 part of a charge transport material having a structure represented by the following formula (18), polyester resin E (a repeating structural unit represented by the following formula (26)) It has a repeating structural unit represented by the following formula (25) at a ratio of 7: 3, 3 parts of weight average molecular weight 90,000) and 7 parts of polyester resin D in a mixed solvent of 30 parts of dimethoxymethane and 50 parts of orthoxylene. By dissolving, a coating solution for a charge transport layer was prepared. In addition, in polyester resin E, content of the repeating structural unit shown by following formula (24) is 10 mass%, and content of the repeating structural unit shown by following formula (25), (26) is 90 mass. %Met.

  The charge transport layer coating solution was dip-coated on the charge generation layer and dried at 120 ° C. for 60 minutes to form a charge transport layer having a thickness of 15 μm. It was confirmed that the formed charge transport layer contained a domain structure containing the polyester resin E in a matrix containing the charge transport material and the polyester resin D.

(Example 126)
The adjustment of the coating liquid for the charge transport layer in Example 112 was changed as follows.

  9 parts of a charge transport material having a structure represented by the above formula (8), 1 part of a charge transport material having a structure represented by the above formula (18), and a polycarbonate resin F having a repeating structure represented by the following formula (29) ( 10 parts by weight average molecular weight 70,000), a repeating structural unit represented by the following formula (29), a repeating structural unit represented by the following formula (30), and at least one of the terminals represented by the following formula (31) A coating solution for a charge transport layer was prepared by dissolving 0.3 part of polycarbonate resin G (weight average molecular weight 40,000) having the structure shown in 30 parts of dimethoxymethane and 50 parts of orthoxylene. The total mass of the structures represented by the following formulas (30) and (31) in the polycarbonate resin G was 30% by mass. The charge transport layer coating solution was dip-coated on the charge generation layer and dried at 120 ° C. for 60 minutes to form a charge transport layer having a thickness of 15 μm.

(Example 127)
In the preparation of the charge transport layer coating solution of Example 126, a charge transport layer coating solution was prepared in the same manner as in Example 126 except that 10 parts of the polyester resin D was used instead of 10 parts of the polycarbonate resin F. The body was manufactured.

In Table 10-12, "Compound A / crosslinker" refers to a ratio of Compound A molecular weight of the molecular weight and the isocyanate compound of (electron transport material) (molecular weight calculated with the exception of blocking groups X ^1).

(Comparative Example 1)
In Example 1, as an isocyanate compound, an isocyanate compound having a unit represented by the following formula (C-1) (a copolymer described in JP 2008-250082 A (unit represented by the following formula (C-1)) The copolymer represented by the formula (C-1) is an electrophotographic photoreceptor in the same manner as in Example 1 except that the unit represented by the formula (C-1) is 5 mol% and the weight average molecular weight Mw is 42000). The ghost was similarly evaluated. The Macbeth density difference at the time of initial image output was 0.035, and the difference (change) between the Macbeth density difference after output of 10,000, 10,000 sheets and the Macbeth density difference at the time of initial image output was 0.042.

(Comparative Example 2)
An electrophotographic photoreceptor is produced in the same manner as in Example 1 except that an undercoat layer is formed using hexamethylene diisocyanate and a compound represented by the following formula (11) (configuration of Example 1 of JP-A-2007-148293). In the same manner, the ghost was evaluated. The Macbeth density at the initial image output was 0.034, and the difference (change) between the Macbeth density difference after outputting 10,000 sheets and the Macbeth density difference at the initial image output was 0.051.

(Comparative Example 3)
Electrophotography as in Example 1 except that an undercoat layer was formed using a blocked isocyanate compound, a butyral resin, and a compound represented by the following formula (12) (configuration of Example 2 of JP-A-2008-65173). Photoconductors were manufactured and ghosts were similarly evaluated. The Macbeth density at the time of initial image output was 0.052, and the difference (change) between the Macbeth density difference after output of 10,000 sheets and the Macbeth density difference at the time of initial image output was 0.055.

(Comparative Example 4)
In Example 1, electrophotographic photosensitization was performed in the same manner as in Example 1 except that the block copolymer represented by the following structural formula (the copolymer described in JP-T-2009-505156) was used from Example Compound A101. The body was manufactured and evaluated. The Macbeth density difference at the initial image output was 0.040, and the difference (change) between the Macbeth density difference after outputting 10,000 sheets and the Macbeth density difference at the initial image output was 0.055.

DESCRIPTION OF SYMBOLS 1 Electrophotographic photosensitive member 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Cleaning means 8 Fixing means 9 Process cartridge 10 Guide means P Transfer material 101 Support body 102 Undercoat layer 103 Photosensitive layer 104 Charge generation layer 105 Charge Transport layer

Claims (8)

In a method for producing an electrophotographic photoreceptor having a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer,
The following (i), (ii) and (iii):
(I) Molecular weight having 3 to 6 groups selected from the group consisting of —NCO group and —NHCOX ¹ group (X ¹ is a group represented by any one of the following formulas (1) to (7)) (In the case of having -NHCOX ¹ group, it is a molecular weight calculated by removing X ¹ group.) Is an isocyanate compound of 200-1300,
(Ii) a resin having a structural unit represented by the following formula (B), and (iii) a compound represented by the following formula (A1), a compound represented by the following formula (A2), a compound represented by the following formula (A3) , A compound represented by the following formula (A4), a compound represented by the following formula (A5), a compound represented by the following formula (A6), a compound represented by the following formula (A7), and a compound represented by the following formula (A8) At least one electron transport material selected from the group consisting of:
A process for producing an electrophotographic photosensitive member , comprising a step of forming an undercoat layer containing a polymer obtained by polymerizing a composition comprising a polymer .

(In formula (B), R ¹¹ represents a hydrogen atom or an alkyl group. Y represents a single bond or a phenylene group. W ¹ represents a hydroxy group, a thiol group, an amino group, or a carboxyl group.)

(Formula (A1) ~ (A8) ^{in, R 101 ~R 106, R 201} ~R 210, R 301 ~R 308, R 401 ~R 408, R 501 ~R 510, R 601 ~R 606, R 701 ~ R ⁷⁰⁸ and R ^{801 to} R ⁸¹⁰ 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, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, provided that at least one of R ^{101 to} R ¹⁰⁶ , at least one of R ^{201 to} R ²¹⁰ , and at least one of R ^{301 to} R ³⁰⁸ 1, at least one of R ^{401 to} R ⁴⁰⁸ , at least one of R ^{501 to} R ⁵¹⁰ , at least one of R ^{601 to} R ⁶⁰⁶ , At least one of R ^{701 to} R ⁷⁰⁸ and at least one of R ^{801 to} R ⁸¹⁰ is a monovalent group represented by the following formula (A): one of the carbon atoms of the alkyl group is O, S, NH, NR ⁹⁰¹ (R ⁹⁰¹ is an alkyl group) may be replaced with a group selected from the group consisting of an alkyl group, an aryl group, an alkoxycarbonyl group and a halogen atom. The substituent of the substituted aryl group is a group selected from the group consisting of a halogen atom, a nitro group, a cyano group, an alkyl group, and a halogen group-substituted alkyl group: Z ²⁰¹ , Z ³⁰¹ , Z ⁴⁰¹ and Z ⁵⁰¹ are each independently if ^{.Z 201} showing a carbon atom, a nitrogen atom or oxygen atom, is an oxygen atom absent ^{R 209} and ^{R 210, 201} is not present is ^{R 307} and ^{R 308} when a ^{.Z 301} is oxygen ^{atom R 210} is absent when a nitrogen ^{atom, .Z} if ^{Z 301} is a nitrogen atom ^{R 308} is absent ⁴⁰¹ there absent ^{R 407} and ^{R 408} when an oxygen ^atom, if ^{Z 401} is a nitrogen atom if ^{.Z 501} not present ^{R 408} is an oxygen atom absent ^{R 509} and ^{R 510} In the case where Z ⁵⁰¹ is a nitrogen atom, R ⁵¹⁰ is not present.)

(In Formula (A), l and m are each independently 0 or 1, and the sum of l and m is 0 or more and 2 or less. When l = 1 and m = 1, α, β, And at least one of γ has a substituent, and when l = 1 and m = 0, at least one of α and γ has the substituent, and when l = 0 and m = 1, β and γ At least one has the substituent, and when 1 = 0 and m = 0, γ has the substituent, and the substituent is selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group Is at least one group.
α is an alkylene group having 1-6 atoms in the main chain, an alkylene group having 1-6 atoms in the main chain substituted with an alkyl group having 1-6 carbon atoms, or a main chain substituted with a benzyl group. An alkylene group having 1 to 6 atoms, an alkylene group having 1 to 6 atoms in the main chain substituted with an alkoxycarbonyl group, or an alkylene group having 1 to 6 atoms in the main chain substituted with a phenyl group These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group as a substituent. One of the carbon atoms in the main chain of the alkylene group may be replaced by O or S or NH or NR ¹⁹ (R ¹⁹ is an alkyl 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 are hydroxy groups as substituents , At least one group selected from the group consisting of a thiol group, an amino group, and a carboxyl group.
γ represents a hydrogen atom, an alkyl group having 1 to 6 atoms in the main chain, or an alkyl group having 1 to 6 atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms. May have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group as a substituent. ) In the formula (A),
α is an alkylene group having 1-6 atoms in the main chain, an alkylene group having 1-6 atoms in the main chain substituted with an alkyl group having 1-6 carbon atoms, or a main chain substituted with a benzyl group. An alkylene group having 1 to 6 atoms, an alkylene group having 1 to 6 atoms in the main chain substituted with an alkoxycarbonyl group, or an alkylene group having 1 to 6 atoms in the main chain substituted with a phenyl group ,
2. The electrophotographic image according to claim 1, wherein one of carbon atoms in the main chain of the alkylene group may be replaced by O, NH, or NR ¹⁹ (R ¹⁹ is an alkyl group). A method for producing a photoreceptor. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the isocyanate compound has a cyclic structure. The method for producing an electrophotographic photosensitive member according to claim 3, wherein the cyclic structure is an isocyanurate structure. The method for producing an electrophotographic photosensitive member according to any one of claims 1 to 4, wherein the resin having the structural unit represented by the formula (B) is a polyvinyl acetal resin. 6. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the molecular weight of the electron transport material is 150 or more and 1000 or less. The method for producing an electrophotographic photosensitive member according to any one of claims 1 to 6, wherein a ratio of a molecular weight of the isocyanate compound to a molecular weight of the electron transport material is 3/20 to 50/20. Forming the undercoat layer comprises:
A step of forming a coating film of a coating liquid for an undercoat layer containing the isocyanate compound, a resin having a structural unit represented by the formula (B), and the electron transport material; and heating and drying the coating film The method for producing an electrophotographic photosensitive member according to claim 1, further comprising a step of forming the undercoat layer.

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