JP5879817B2 - Novel reactive compound, charge transport film and photoelectric conversion device - Google Patents

Description

  The present invention relates to a novel reactive compound, a charge transporting film, and a photoelectric conversion device.

  The cured film having charge transportability is used in various fields, for example, photoelectric conversion devices such as electrophotographic photosensitive members, organic electroluminescence (electroluminescence) elements, memory elements, and wavelength conversion elements.

  For example, in an electrophotographic image forming apparatus, the surface of the electrophotographic photosensitive member is charged to the polarity and potential determined by the charging device, and the surface of the electrophotographic photosensitive member after charging is selectively neutralized by image exposure. To form an electrostatic latent image. Next, the latent image is developed as a toner image by attaching toner to the electrostatic latent image by a developing device, and the toner image is transferred to a recording medium by a transfer unit, and discharged as an image formed product.

  As an electrophotographic photoreceptor, it has been proposed to provide a protective layer on the surface from the viewpoint of improving strength. Examples of the material system for forming the protective layer include a material in which conductive powder is dispersed in a phenol resin (for example, see Patent Document 1), an organic-inorganic hybrid material (for example, see Patent Document 2), an alcohol-soluble charge transport material, and the like. The thing by a phenol resin (for example, refer patent document 3) etc. are disclosed. Further, a cured film of an alkyl etherified benzoguanamine / formaldehyde resin and an electron-accepting carboxylic acid or an electron-accepting polycarboxylic acid anhydride (see, for example, Patent Document 4), iodine, an organic sulfonic acid compound, or a second chloride is added to the benzoguanamine resin. A cured film doped with iron or the like (see, for example, Patent Document 5), a cured film of a specific additive and a phenol resin, melamine resin, benzoguanamine resin, siloxane resin, or urethane resin (for example, see Patent Document 6) is disclosed. ing.

  In recent years, a protective layer made of an acrylic material has attracted attention. For example, a film obtained by applying and curing a liquid containing a photocurable acrylic monomer (see, for example, Patent Document 7), a monomer having a carbon-carbon double bond, a charge transfer material having a carbon-carbon double bond, and a binder Disclosed is a film formed by reacting a resin mixture with a carbon-carbon double bond of the monomer and a carbon-carbon double bond of the charge transfer material by heat or light energy (see, for example, Patent Document 8). Has been.

Furthermore, a film made of a compound obtained by polymerizing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule is disclosed (for example, see Patent Document 9). In addition, a technique of using a polymer of a charge transport material having a chain polymerizable functional group for a protective layer is disclosed (for example, see Patent Document 10).
These acrylic materials are strongly affected by curing conditions, curing atmospheres, and the like, and are formed, for example, by a film formed by heating after irradiation with radiation in a vacuum or an inert gas (see, for example, Patent Document 11) or inert. A film (for example, see Patent Document 12) cured by heating in a gas is disclosed.
In addition, a cross-linked product of a charge transporting compound in which a styrene skeleton is linked with an ether group as a chain polymerizable group is disclosed (Patent Documents 13 and 14).

Japanese Patent No. 3287678 JP 2000-019749 A JP 2002-82469 A Japanese Patent Laid-Open No. 62-251757 Japanese Patent Laid-Open No. 7-146564 JP 2006-84711 A JP-A-5-40360 JP-A-5-216249 JP 2000-206715 A JP 2001-175016 A Japanese Patent Laid-Open No. 2004-12986 Japanese Patent Laid-Open No. 7-72640 Japanese Patent No. 2546739 Japanese Patent No. 2852464

  An object of the present invention is to provide a novel compound capable of obtaining a charge transporting film in which variation in mobility is suppressed even when used repeatedly.

  The above object is achieved by the following means.

The invention of claim 1 is a reactive compound represented by the following general formula ( II ).

(In the general formula ( II ), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, and Ar ⁵ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group. . D is below in formula (III) a group represented .c1 to c5 represents a 2 an integer 0 or more, respectively, the sum of c1 to c5 is 2 to 8 integer .k is 0 or 1 in is.)

(In General Formula (III), L is a divalent linking group formed by combining —C (═O) —O— and — (CH ₂ ) n— (where n is an integer of 1 or more and 10 or less). )

The invention according to claim 2 is the reactive compound according to claim 1, wherein the group represented by the general formula (III) is a group represented by the following general formula (IV).

(In general formula (IV), p represents an integer of 0 or more and 4 or less.)

The invention according to claim 3 is the reactive compound according to claim 2 , wherein the group represented by the general formula (IV) is a group represented by the following general formula (V).

(In general formula (V), p represents an integer of 0 or more and 4 or less.)

Invention of Claim 4 is a reactive compound as described in any one of Claims 1-3 whose sum total of c1 thru | or c5 in the said general formula (II) is an integer of 2-6.

The invention according to claim 5 is the reactive compound according to claim 4 , wherein the total of c1 to c5 in the general formula (II) is an integer of 3 or more and 6 or less.

The invention according to claim 6 is the reactive compound according to claim 5 , wherein the total of c1 to c5 in the general formula (II) is an integer of 4 or more and 6 or less.
The invention according to claim 7 is a reactive compound represented by the following general formula (II).

(In the general formula (II), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group. Ar ⁵ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group. D is a group represented by the following general formula (IV), c1 to c5 each represents 0 or 1, and the sum of c1 to c5 is 1. k is 0 or 1.)

(In general formula (IV), p represents an integer of 0 or more and 4 or less.)
The invention according to claim 8 is the reactive compound according to claim 7, wherein the group represented by the general formula (IV) is a group represented by the following general formula (V).

(In general formula (V), p represents an integer of 0 or more and 4 or less.)

  The invention according to claim 9 is a charge transport film comprising the reactive compound according to any one of claims 1 to 8 or a structure derived from the reactive compound.

  The invention according to claim 10 is a charge transport film comprising a polymerized or cured film of a composition containing the reactive compound according to any one of claims 1 to 8.

  An eleventh aspect of the invention is a photoelectric conversion device having the charge transporting film according to the ninth or tenth aspect.

According to the first and seventh aspects of the present invention, a reactive compound can be obtained in which a charge transporting film can be obtained in which fluctuations in mobility are suppressed even when it is used repeatedly as compared with the case where the compound is not represented by the general formula (II). Is provided.
According to the invention of claim 2 , mobility variation is suppressed even when the group represented by the general formula (III) is not a group represented by the general formula (IV) repeatedly. Reactive compounds that provide charge transport membranes are provided.
According to the third and eighth aspects of the present invention, fluctuation in mobility is suppressed even when the group represented by the general formula (IV) is not a group represented by the general formula (V) repeatedly. There is provided a reactive compound from which a charge transporting membrane is obtained.
According to the inventions of claims 4 , 5 and 6 , compared to the case where the sum of c1 to c5 in the general formula (II) is not within the above range, the charge whose mobility is suppressed even when used repeatedly. Reactive compounds that provide transportable membranes are provided.

1 is a schematic partial cross-sectional view showing an electrophotographic photosensitive member according to an embodiment. 1 is a schematic partial cross-sectional view showing an electrophotographic photosensitive member according to an embodiment. 1 is a schematic partial cross-sectional view showing an electrophotographic photosensitive member according to an embodiment. It is IR spectrum of compound 1-7. It is IR spectrum of compound I-15. It is IR spectrum of compound I-17. It is IR spectrum of compound I-23. It is IR spectrum of compound I-25. It is IR spectrum of compound I-27. It is IR spectrum of compound I-30. It is IR spectrum of compound 1-43. It is IR spectrum of compound I-46. It is IR spectrum of compound I-53.

  The present invention will be described below with reference to the accompanying drawings as appropriate.

[Reactive compound]
The novel reactive compound according to this embodiment is a reactive compound represented by the following general formula (I).

  In general formula (I), F represents a charge transporting skeleton, and D represents a group represented by the following general formula (III). m represents an integer of 1 or more and 8 or less.

  In general formula (III), L represents a divalent linking group containing one or more —C (═O) —O— groups.

The reactive compound according to the present embodiment has a styrene skeleton having a structure in which a vinyl group (—CH═CH ₂ ) is directly connected to a benzene ring as a chain polymerizable group, and an aryl group that is a main skeleton of a charge transport agent; It has good compatibility, and cured films using it can suppress fluctuations in mobility even after repeated use by suppressing aggregation of charge transport structures due to film shrinkage and curing and chain polymerizable group peripheral structures. Conceivable. Furthermore, in the reactive compound of the present embodiment, the charge transporting skeleton and the styrene skeleton are linked via a linking group containing a —C (═O) —O— group, whereby the ester group and the charge are It is considered that the strength of the cured film is further improved by the interaction with the nitrogen atom in the transporting skeleton or the interaction between the ester groups.

The reactive compound of this embodiment is preferably a compound represented by the following general formula (II) from the viewpoint of excellent charge transportability.

In general formula (II), Ar ^{1 to} Ar ⁴ each independently represent a substituted or unsubstituted aryl group. Ar ⁵ represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylene group. D has the same meaning as D in formula (I). c1 to c5 each represents an integer of 0 to 2, and the sum of c1 to c5 is an integer of 1 to 8. k is 0 or 1.

In addition, L in the general formula (III) is a divalent linking group formed by combining —C (═O) —O— and — (CH ₂ ) _n — (wherein n is 1 or more and 10 or less. Is an integer).
Specifically, the group represented by the general formula (III) is desirably a group represented by the following general formula (IV), and more desirably a group represented by the following general formula (V).

  In general formula (IV), p represents an integer of 0 or more and 4 or less.

  In general formula (V), p represents an integer of 0 or more and 4 or less.

  Further, m in the general formula (I) or the sum of c1 to c5 in the general formula (II) is preferably an integer of 2 or more and 6 or less, and an integer of 3 or more and 6 or less. More desirably, it is an integer of 4 or more and 6 or less.

[Electrophotographic photoreceptor]
Hereinafter, an electrophotographic photoreceptor will be described as a specific example to which the reactive compound according to the present embodiment is applied.

By making the surface of the electrophotographic photosensitive member a cured film, the mechanical strength of the photosensitive member by repeated use is improved, but the image quality itself and the stability of the image quality by repeated use are not sufficient. The cause is not clear, but by curing, the intermolecular distance and conformation of the chemical structure responsible for charge transport properties change from the state before curing, or by curing, the chain polymerizable group It is considered that the peripheral chemical structure and the chemical structure responsible for charge transporting are aggregated to change the film state before curing. Moreover, in addition to the charge transporting material having a chain polymerizable functional group, when the film containing the binder resin is cured, the structure of the charge transporting material and the compatibility of the binder resin are reduced by curing. It is considered as a factor.
Thus, it is important to achieve both mechanical strength and image quality with the aim of extending the life of the electrophotographic photosensitive member.

The electrophotographic photoreceptor according to the exemplary embodiment (hereinafter may be simply referred to as “photoreceptor”) includes at least a conductive substrate and a photosensitive layer provided on the conductive substrate, and is an outermost surface layer. As described above, the compound represented by the general formula (I), that is, a structure in which one or more charge transporting skeletons and one or more styrene skeletons not conjugated to the charge transporting skeleton are linked in the same molecule. And a compound having a charge transporting property containing a —C (═O) —O— group (that is, an ester group) in a linking group for linking the charge transporting skeleton and the styrene skeleton (as appropriate “ A layer (Oc) made of a polymerized or cured film of a composition containing the charge transporting material (A) ”.
According to the above-described embodiment, an electrophotographic photosensitive member is provided that is less likely to be scratched even when used repeatedly, has little image quality degradation, and has less occurrence of depletion.

Although the cause of the effect of the photoconductor of the present embodiment has not been clarified, the cause of little deterioration in image quality due to repeated use is estimated as follows. It is considered that a photoreceptor having a polymerized or cured film as the outermost surface causes film shrinkage due to polymerization or curing, and aggregation of the structure around the charge transport structure and the chain polymerizable group. Therefore, if the surface of the photoreceptor is subjected to mechanical stress by repeated use, the film itself is worn out or the chemical structure in the molecule is cut, and the above-mentioned film contraction and aggregation state change greatly, and as a photoreceptor The electrical characteristics of the image will change, causing image quality degradation.
On the other hand, in this embodiment, a styrene skeleton is used as the chain polymerizable group, and is compatible with the aryl group that is the main skeleton of the charge transport agent, and the charge transport structure due to film shrinkage and curing, around the chain polymerizable group It is considered that the aggregation of the structure is suppressed and the image quality deterioration due to repeated use is suppressed.

Furthermore, in this embodiment, the charge transporting skeleton and the styrene skeleton are linked via a linking group containing a —C (═O) —O— group, so that the ester group and the charge transporting skeleton are contained in the charge transporting skeleton. It is considered that the strength in the polymerized or cured film is further improved by the interaction between the nitrogen atoms and the ester groups.
The ester group contained in the linking group is attributed to its polarity and hydrophilicity, and may cause deterioration in image quality under charge transportability and high humidity conditions, but in this embodiment, as a chain polymerizable group. Since a styrene skeleton having a higher hydrophobicity than (meth) acryl or the like is used, image quality deterioration such as the above-described deterioration of charge transportability and depression is suppressed.

The photoreceptor according to the exemplary embodiment includes at least a conductive substrate and a photosensitive layer provided on the conductive substrate, and the outermost surface layer is a reactive compound represented by the general formula (I). As long as a layer (Oc) composed of a polymerized or cured film of a composition containing a certain charge transporting material (A) is provided, the layer structure and the like are not particularly limited.
The photosensitive layer according to the present embodiment may be a function-integrated type photosensitive layer having both charge transport capability and charge generation capability, or a function-separated type photosensitive layer including a charge transport layer and a charge generation layer. Also good. Furthermore, other layers such as an undercoat layer may be provided.

Hereinafter, the configuration of the photoreceptor according to the present embodiment will be described with reference to FIGS. 1 to 3, but the present embodiment is not limited to FIGS. 1 to 3.
FIG. 1 is a schematic view showing an example of the layer structure of the photoreceptor according to the present embodiment. The photoreceptor shown in FIG. 1 has a layer structure in which an undercoat layer 4, a charge generation layer 2A, a charge transport layer 2B-1, and a charge transport layer 2B-2 are laminated on a substrate 1 in this order. 2 is composed of three layers, a charge generation layer 2A and charge transport layers 2B-1 and 2B-2 (first embodiment). In the photoreceptor shown in FIG. 1, the charge transport layer 2B-2 corresponds to the layer (Oc) of this embodiment containing the reactive compound represented by the general formula (I). Hereinafter, the layer of the present embodiment in the first aspect is referred to as a layer (Oc1) of the present embodiment. The charge transport layer 2B-2 serving as the outermost surface layer also functions as a protective layer for protecting the charge transport layer 2B-1.

  FIG. 2 is a schematic view showing another example of the layer structure of the photoreceptor according to this embodiment. 2 has a layer structure in which an undercoat layer 4, a charge generation layer 2A, and a charge transport layer 2B are laminated in this order on a substrate 1, and the photosensitive layer 2 includes the charge generation layer 2A and the charge transport layer. It is composed of two layers 2B (second embodiment). In the photoreceptor shown in FIG. 2, the charge transport layer 2B corresponds to the layer (Oc) of this embodiment containing the reactive compound represented by the general formula (I). Hereinafter, the layer of this embodiment in the second aspect is referred to as a layer (Oc2) of this embodiment.

  FIG. 3 is a schematic view showing another example of the layer structure of the photoreceptor according to this embodiment. 3 has a layer structure in which an undercoat layer 4 and a photosensitive layer 6 are laminated in this order on a substrate 1, and the photosensitive layer 6 includes a charge generation layer 2A and a charge transport layer shown in FIG. This is a layer in which the functions of 2B are integrated (third mode). In the photoreceptor shown in FIG. 3, the function-integrated photosensitive layer 6 corresponds to the layer (Oc) of this embodiment containing the reactive compound represented by the general formula (I). The layer of the present embodiment is referred to as a layer (Oc3) of the present embodiment.

  Hereinafter, each of the first to third aspects will be described as an example of the photoreceptor according to the present exemplary embodiment.

-Conductive substrate-
Any conductive substrate may be used as long as it is conventionally used. For example, thin films (eg, metals such as aluminum, nickel, chromium, stainless steel, and films of aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, indium tin oxide (ITO), etc.) And a plastic film coated or impregnated with a conductivity-imparting agent, a plastic film coated or impregnated with a conductivity-imparting agent, and the like. The shape of the substrate is not limited to a cylindrical shape, and may be a sheet shape or a plate shape.
The conductive base particles preferably have conductivity with a volume resistivity of less than 10 ⁷ Ω · cm, for example.

  When a metal pipe is used as the conductive substrate, the surface may be left as it is, and processing such as mirror cutting, etching, anodizing, rough cutting, centerless grinding, sand blasting, wet honing has been performed in advance. May be.

-Undercoat layer-
The undercoat layer is provided as necessary for the purpose of preventing light reflection on the surface of the conductive substrate and preventing inflow of unnecessary carriers from the conductive substrate to the photosensitive layer.

The undercoat layer includes, for example, a binder resin and, if necessary, other additives.
As the binder resin contained in the undercoat layer, acetal resins such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, Known polymer resin compounds such as polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol resin, phenol-formaldehyde resin, melamine resin, urethane resin, and charge transporting group Examples thereof include charge transporting resins having a conductive resin such as polyaniline. Among these, resins that are insoluble in the upper coating solvent are preferably used, and phenol resins, phenol-formaldehyde resins, melamine resins, urethane resins, epoxy resins, and the like are particularly preferably used.

  The undercoat layer may contain a metal compound such as a silicon compound, an organic zirconium compound, an organic titanium compound, or an organic aluminum compound.

  The ratio between the metal compound and the binder resin is not particularly limited, and is set within a range in which desired electrophotographic photoreceptor characteristics can be obtained.

  In the undercoat layer, resin particles may be added to the undercoat layer in order to adjust the surface roughness. Examples of the resin particles include silicone resin particles and cross-linked polymethyl methacrylate (PMMA) resin particles. The surface may be polished after forming the undercoat layer for adjusting the surface roughness. As a polishing method, buffing, sandblasting, wet honing, grinding, or the like is used.

Here, the constitution of the undercoat layer includes a constitution containing at least a binder resin and conductive particles. Note that the conductive particles preferably have conductivity with a volume resistivity of less than 10 ⁷ Ω · cm, for example.

Examples of the conductive particles include metal particles (particles such as aluminum, copper, nickel, and silver), conductive metal oxide particles (particles such as antimony oxide, indium oxide, tin oxide, and zinc oxide), and conductive substance particles. (Carbon fiber, carbon black, particles of graphite powder) and the like. Among these, conductive metal oxide particles are preferable. You may mix and use 2 or more types of electroconductive particle.
In addition, the conductive particles may be subjected to a surface treatment with a hydrophobizing agent (for example, a coupling agent) or the like to adjust the resistance.
The content of the conductive particles in the undercoat layer is, for example, desirably from 10% by mass to 80% by mass, and more desirably from 40% by mass to 80% by mass with respect to the binder resin.

In forming the undercoat layer, an undercoat layer forming coating solution in which the above components are added to a solvent is used.
In addition, as a method of dispersing particles in the coating solution for forming the undercoat layer, a media dispersing machine such as a ball mill, a vibrating ball mill, an attritor, a sand mill, a horizontal sand mill, a stirring, an ultrasonic dispersing machine, a roll mill, a high-pressure homogenizer, etc. Medialess dispersers are used. Here, examples of the high-pressure homogenizer include a collision method in which the dispersion liquid is dispersed by liquid-liquid collision or liquid-wall collision in a high-pressure state, and a penetration method in which a fine flow path is dispersed in a high-pressure state. .

  Examples of the method for applying the coating solution for forming the undercoat layer onto the conductive substrate include dip coating, push-up coating, wire bar coating, spray coating, blade coating, knife coating, and curtain coating. It is done.

  The thickness of the undercoat layer is preferably 15 μm or more, and more preferably 20 μm or more and 50 μm or less.

  Here, although not shown, an intermediate layer may be further provided between the undercoat layer and the photosensitive layer. As the binder resin used for the intermediate layer, acetal resins such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl In addition to polymer resins such as acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, melamine resin, zirconium, titanium, aluminum, manganese, silicon atom, etc. An organometallic compound containing These compounds may be used alone or as a mixture or polycondensate of a plurality of compounds. Among these, an organometallic compound containing zirconium or silicon is preferable in that it has a low residual potential, a small potential change due to the environment, and a small potential change due to repeated use.

  In forming the intermediate layer, a coating solution for forming an intermediate layer in which the above components are added to a solvent is used. As the coating method for forming the intermediate layer, usual methods such as a dip coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, a knife coating method, and a curtain coating method are used.

  In addition to improving the coatability of the upper layer, the intermediate layer also serves as an electrical blocking layer, but if the film thickness is too large, the electrical barrier becomes too strong and the potential increases due to desensitization or repetition. May cause. Therefore, when forming the intermediate layer, it is preferable to set the film thickness within the range of 0.1 μm to 3 μm. In this case, the intermediate layer may be used as the undercoat layer.

-Charge generation layer-
The charge generation layer includes, for example, a charge generation material and a binder resin. Examples of such a charge generating material include phthalocyanine pigments such as metal-free phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, dichlorotin phthalocyanine, and titanyl phthalocyanine. Chlorogallium phthalocyanine crystal having strong diffraction peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 °, at least 7.7 Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-ray Metal-free phthalocyanine crystals having strong diffraction peaks at °, 9.3 °, 16.9 °, 17.5 °, 22.4 ° and 28.8 °, Bragg angle with respect to CuKα characteristic X-ray (2θ ± 0.2 °) at least 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, Hydroxygallium phthalocyanine crystal having strong diffraction peaks at 5.1 ° and 28.3 °, Bragg angle (2θ ± 0.2 °) to CuKα characteristic X-ray of at least 9.6 °, 24.1 ° and 27.2 A titanyl phthalocyanine crystal having a strong diffraction peak at 0 ° can be mentioned. In addition, examples of the charge generation material include quinone pigments, perylene pigments, indigo pigments, bisbenzimidazole pigments, anthrone pigments, quinacridone pigments, and the like. These charge generation materials may be used alone or in combination of two or more.

Examples of the binder resin constituting the charge generation layer include polycarbonate resin such as bisphenol A type or bisphenol Z type, acrylic resin, methacrylic resin, polyarylate resin, polyester resin, polyvinyl chloride resin, polystyrene resin, acrylonitrile-styrene. Copolymer resin, acrylonitrile-butadiene copolymer, polyvinyl acetate resin, polyvinyl formal resin, polysulfone resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride Examples thereof include resins, silicone resins, phenol-formaldehyde resins, polyacrylamide resins, polyamide resins, poly-N-vinylcarbazole resins. These binder resins may be used alone or in combination of two or more.
The mixing ratio of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10, for example.

  When forming the charge generation layer, a coating solution for forming a charge generation layer in which the above components are added to a solvent is used.

  As a method for dispersing particles (for example, charge generation material) in the coating solution for forming the charge generation layer, a media dispersion machine such as a ball mill, a vibration ball mill, an attritor, a sand mill, a horizontal sand mill, an agitation, an ultrasonic dispersion machine, a roll mill, etc. Medialess dispersers such as high-pressure homogenizers are used. Examples of the high-pressure homogenizer include a collision method in which the dispersion liquid is dispersed by liquid-liquid collision or liquid-wall collision in a high-pressure state, and a penetration method in which a fine flow path is dispersed in a high-pressure state.

  Examples of the method for applying the charge generation layer forming coating liquid on the undercoat layer include dip coating, push-up coating, wire bar coating, spray coating, blade coating, knife coating, and curtain coating. It is done.

  The thickness of the charge generation layer is desirably set in the range of 0.01 μm to 5 μm, more desirably 0.05 μm to 2.0 μm.

-Charge transport layer 2B-1 (in the case of the first embodiment)-
The charge transport layer 2B-1 is the case of the first embodiment, and is configured to include a charge transport material and, if necessary, a binder resin.
Examples of the charge transport material include oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1- [ Pyrazoline derivatives such as pyridyl- (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline, triphenylamine, N, N′-bis (3,4-dimethylphenyl) biphenyl- Aromatic tertiary amino compounds such as 4-amine, tri (p-methylphenyl) aminyl-4-amine, dibenzylaniline, N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine Aromatic tertiary diamino compounds such as 3- (4'-dimethylaminophenyl) -5,6-di- (4'-methoxyphenyl) -1,2,4 1,2,4-triazine derivatives such as triazine, hydrazone derivatives such as 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, quinazoline derivatives such as 2-phenyl-4-styryl-quinazoline, 6-hydroxy-2,3- Benzofuran derivatives such as di (p-methoxyphenyl) benzofuran, α-stilbene derivatives such as p- (2,2-diphenylvinyl) -N, N-diphenylaniline, enamine derivatives, carbazole derivatives such as N-ethylcarbazole, poly -Hole transport materials such as -N-vinylcarbazole and its derivatives, quinone compounds such as chloranil and broanthraquinone, tetraanoquinodimethane compounds, 2,4,7-trinitrofluorenone, 2,4,5,7 -Fluorenone such as tetranitro-9-fluorenone Examples thereof include an electron transport material such as a compound, a xanthone compound, and a thiophene compound, and a polymer having a group consisting of the above-described compounds in a main chain or a side chain. These charge transport materials may be used alone or in combination of two or more.

As the binder resin constituting the charge transport layer 2B-1, for example, polycarbonate resin such as bisphenol A type or bisphenol Z type, acrylic resin, methacrylic resin, polyarylate resin, polyester resin, polyvinyl chloride resin, polystyrene resin, Acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene copolymer resin, polyvinyl acetate resin, polyvinyl formal resin, polysulfone resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinyl acetate -Insulating resins such as maleic anhydride resin, silicone resin, phenol-formaldehyde resin, polyacrylamide resin, polyamide resin, chlorine rubber, and polyvinylcarbazole, polyvinyl Anthracene, organic photoconductive polymers such as polyvinyl pyrene, and the like. These binder resins may be used alone or in combination of two or more.
The mixing ratio between the charge transport material and the binder resin is preferably 10: 1 to 1: 5, for example.

  The charge transport layer 2B-1 is formed using a coating liquid for forming the charge transport layer 2B-1 in which the above components are added to a solvent.

As a method of applying the coating liquid for forming the charge transport layer 2B-1 on the charge generation layer, dip coating method, push-up coating method, wire bar coating method, spray coating method, blade coating method, knife coating method, curtain coating method Ordinary methods such as are used.
The film thickness of the charge transport layer 2B-1 is desirably set in the range of 5 μm or more and 50 μm or less, more desirably 10 μm or more and 40 μm or less.

-Charge transport layer 2B-2 (corresponding to the layer (Oc1) of the present embodiment in the first mode)-
The layer (Oc1) of the present embodiment has a structure in which one or more charge transporting skeletons and one or more styrene skeletons are linked in the same molecule, and the charge transporting skeletons and the styrene skeletons. Is a layer formed of a polymerized or cured film of a composition containing a charge transporting material (A) containing one or more —C (═O) —O— groups in a linking group for linking.

The styrene skeleton contained in the charge transport material (A) of the present embodiment has a structure in which a vinyl group (—CH═CH ₂ ) is directly connected to a benzene ring, but is substituted instead of the hydrogen atom of the benzene ring. It may have a group. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and the like, but it is desirable that there is no substituent.

Hereinafter, the composition for forming the charge transport layer 2B-2 will be described.
Examples of the charge transporting skeleton in the charge transport material (A) of the present embodiment include those described in the charge transport layer 2B-1. The charge transporting skeleton preferably includes an arylamine skeleton, and more preferably includes a triarylamine skeleton.

  Hereinafter, a more desirable structure of the charge transporting material (A) of this embodiment is represented by the general formula (II).

In general formula (II), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylene group, D is a group represented by the general formula (III). In General Formula (III), L represents a divalent linking group containing one or more —C (═O) —O— groups.
C1 to c5 in the general formula (II) each represents an integer of 0 or more and 2 or less, and may be different from each other. However, the sum total of c1 to c5 in the formula (II) is an integer of 1 to 8. k is 0 or 1.

The total number of styrene skeletons in the general formula (I) corresponds to m. The total number of styrene skeletons in the general formula (II) corresponds to a value of c1 + c2 + k × (c3 + c4) + c5.
The lower limit of the total number of styrene skeletons in the general formulas (I) and (II) is preferably 2 or more, more preferably 3 or more, and still more preferably, from the viewpoint of obtaining a stronger crosslinked film (cured film). 4 or more. Also, if the number of chain polymerizable groups in one molecule is too large, as the polymerization (crosslinking) reaction proceeds, the molecules become difficult to move and the chain polymerization reactivity decreases, and the proportion of unreacted chain polymerizable groups increases. Therefore, the upper limit of the total number of styrene skeletons in the general formula (II) is preferably 7 or less, and more preferably 6 or less.

D in the general formula (II) is a group represented by the general formula (III), and L represents a divalent linking group containing one or more —C (═O) —O— groups.
L in the general formula (III) shown as D in the general formula (II) is not particularly limited as long as it is a divalent linking group containing the ester group. For example, the ester group and a saturated hydrocarbon Specific examples include a divalent group formed by arbitrarily combining a residue of an aromatic hydrocarbon (including any of linear, branched, and cyclic) and an oxygen atom. L is preferably formed by arbitrarily combining the ester group and a linear saturated hydrocarbon residue.
The total number of carbon atoms contained in L in the general formula (II) is preferably from 1 to 20 and more preferably from 2 to 10 from the viewpoints of the density of the styrene skeleton in the molecule and the chain polymerization reactivity.

In general formula (II), Ar ^{1 to} Ar ⁴ each independently represent a substituted or unsubstituted aryl group. Ar ^{1 to} Ar ⁴ may be the same or different. Here, as a substituent in the substituted aryl group, a substituent other than D is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. A phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, a halogen atom, and the like.

Ar ^{1 to} Ar ⁴ are preferably any one of the following structural formulas (1) to (7). The following structural formulas (1) to (7) are shown together with “-(D) c” that can be connected to each of Ar ^{1 to} Ar ⁴ . Here, “-(D) c” has the same meaning as “-(D) c1 to (D) c4” in the general formula (II), and the same applies to desirable examples.

In the structural formula (1), R ⁰¹ is a phenyl group substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. , An unsubstituted phenyl group, and one selected from the group consisting of an aralkyl group having 7 to 10 carbon atoms.
In the structural formulas (2) and (3), R ^{02 to} R ⁰⁴ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 or more carbon atoms. 1 type selected from the group consisting of a phenyl group substituted with 4 or less alkoxy groups, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom. M represents an integer of 1 or more and 3 or less. In the structural formula (7), Ar represents a substituted or unsubstituted arylene group.
Here, as Ar in Formula (7), what is shown by following Structural formula (8) or (9) is desirable.

In the structural formulas (8) and (9), R ⁰⁵ and R ⁰⁶ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 or more carbon atoms. 1 represents one selected from the group consisting of a phenyl group substituted with 4 or less alkoxy groups, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, and q is 1 to 3 Represents an integer.

  In the structural formula (7), Z ′ represents a divalent organic linking group, and is preferably represented by any one of the following structural formulas (10) to (17). P represents 0 or 1.

In the structural formulas (10) to (17), R ⁰⁷ and R ⁰⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 or more carbon atoms. 1 represents one selected from the group consisting of a phenyl group substituted with 4 or less alkoxy groups, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, and W represents a divalent group. , R and s each independently represents an integer of 1 to 10, and t represents an integer of 1 to 3.

  W in the structural formulas (16) to (17) is preferably any one of divalent groups represented by the following (18) to (26). However, in formula (25), u represents an integer of 0 or more and 3 or less.

In general formula (II), Ar ⁵ is a substituted or unsubstituted aryl group when k is 0, and this aryl group is the same as the aryl group exemplified in the description of Ar ^{1 to} Ar ^4. Can be mentioned. Ar ⁵ is a substituted or unsubstituted arylene group when k is 1, and the arylene group includes a hydrogen atom at a target position from the aryl group exemplified in the description of Ar ^{1 to} Ar ^4. An arylene group excluding one may be mentioned.

  Specific examples of the compound represented by the general formula (I) are shown below. In addition, the compound shown by general formula (I) is not limited at all by these.

  First, as specific examples of the charge transporting skeleton F in the case where the total number of D in the general formula (I) is 1, “(1) -1” to “(1) -25” are shown, but are not limited thereto. is not. In addition, the part of * in each structure shows connecting with D in general formula (I).

Next, as specific examples of the charge transporting skeleton F in the case where the total number of D in the general formula (I) is 2, “(2) -1” to “(2) -29” are shown, but are not limited thereto. It is not a thing.
In addition, the part of * in each structure shows connecting with D in general formula (I).

Next, specific examples of the charge transporting skeleton F in the case where the total number of D in the general formula (I) is 3 are “(3) -1” to “(3) -29”, but are not limited thereto. It is not a thing.
In addition, the part of * in each structure shows connecting with D in general formula (I).

  Next, specific examples of the charge transporting skeleton F in the case where the total number of D in the general formula (I) is 4 or more include “(4) -1” to “(4) -31”. It is not something that can be done. In addition, the part of * in each structure shows connecting with D in general formula (I).

Next, “(III) -1” to “(III) -11” are shown as specific examples of D in the general formula (I) or the general formula (II), that is, the group represented by the formula (III). In addition, it shows that the part of * in each structure connects with the charge transporting skeleton F in the general formula (I) or Ar ^{1 to} Ar ⁵ in the general formula (II).

  Next, as specific examples of the reactive compound represented by the general formula (I), “(I) -1” to “(I) -60” are shown below, but this embodiment is not limited thereto. Absent. In addition, the CTM skeleton structure in the table below corresponds to the charge transporting skeleton F in the general formula (I).

  Next, the synthesis route of the reactive compound of this embodiment is shown below as an example.

  Two or more kinds of the charge transport material (A) of this embodiment may be used in the composition for forming the charge transport layer 2B-2. For example, in the charge transport material (A) of the present embodiment, a compound having a total number of styrene skeletons in one molecule of 4 or more and a compound having a total number of styrene skeletons in one molecule of 1 to 3 are included. When used in combination, the strength of the polymerized or cured film can be adjusted without reducing the charge transport performance. In that case, a compound in which the total number of styrene skeletons in one molecule is 4 or more in the charge transporting material (A) of the present embodiment with respect to the total content of the charge transporting material (A) of the present embodiment. Is preferably 5% by mass or more, and more preferably 20% by mass or more.

  The content of the charge transport material (A) of the present embodiment is preferably 40% by mass or more, preferably 50% by mass or more, based on the total solid content of the composition for forming the charge transport layer 2B-2. 60 mass% or more is more desirable.

  Next, components other than the charge transport material (A) of the present embodiment among the components constituting the composition for forming the charge transport layer 2B-2 will be described.

  The composition for forming the charge transport layer 2B-2 may contain a charge transport agent (B) having a chain polymerizable functional group other than the charge transport material (A) of the present embodiment. Examples of the charge transfer agent (B) include compounds described in paragraphs [0060] to [0099] of JP-A-2000-206715, and paragraphs [0066] to [0080] of JP-A-2011-70023. And the like. The content of the charge transport agent (B) is usually 0% by mass or more and 40% by mass or less, and 0% by mass or more and 30% by mass with respect to the total solid content of the composition for forming the charge transport layer 2B-2. The following is desirable, and more preferably 0% by mass or more and 20% by mass or less.

  The composition for forming the charge transport layer 2B-2 may include the charge transport material and the binder resin mentioned in the description of the charge transport layer 2B-1. The content is usually 0% by mass or more and 40% by mass or less, and preferably 0% by mass or more and 30% by mass or less, based on the total solid content of the composition for forming the charge transport layer 2B-2. More preferably, the content is 0% by mass to 20% by mass.

The composition for forming the charge transport layer 2B-2 may contain the following surfactant from the viewpoint of ensuring film forming properties.
Examples of the surfactant include (A) a structure formed by polymerizing an acrylic monomer having a fluorine atom, (B) a structure having a carbon-carbon double bond and a fluorine atom, (C) an alkylene oxide structure, and (D) carbon. -A surfactant containing in the molecule thereof one or more types of structures having a carbon triple bond and a hydroxyl group.
This surfactant needs to contain 1 or more types of the structure of (A) thru | or (D) in the molecule | numerator, and may contain 2 or more types.

  Hereinafter, the structures (A) to (D) and the surfactant having the structure will be described.

(A) Structure formed by polymerizing an acrylic monomer having a fluorine atom (A) The structure formed by polymerizing an acrylic monomer having a fluorine atom is not particularly limited, but an acrylic monomer having a fluoroalkyl group is polymerized. The structure is preferably a structure obtained by polymerizing an acrylic monomer having a perfluoroalkyl group.

  Specific examples of the surfactant having the structure (A) include Polyflow KL-600 (manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF-351, EF-352, EF-801, EF-802, and EF- 601 (manufactured by JEMCO).

(B) Structure having a carbon-carbon double bond and a fluorine atom (B) The structure having a carbon-carbon double bond and a fluorine atom is not particularly limited, but in the following structural formulas (B1) and (B2) It is desirable that the group be at least one of them.

As the surfactant having the structure (B), a compound having a group represented by at least one of the structural formulas (B1) and (B2) in the side chain of the acrylic polymer, or the following structural formulas (B3) to (B3) to The compound represented by any one of (B5) is desirable.
When the surfactant having the structure (B) is a compound having at least one of the structural formulas (B1) and (B2) in the side chain of the acrylic polymer, the acrylic structure and the other components in the composition Since it has the property of being easily adapted, an outermost surface layer that is nearly uniform can be formed.
In addition, when the surfactant having the structure (B) is a compound represented by any one of the structural formulas (B3) to (B5), it tends to prevent repelling during coating. Defects can be suppressed.

In the structural formulas (B3) to (B5), v and w each independently represent an integer of 1 or more, R ′ represents a hydrogen atom or a monovalent organic group, and Rf each independently represents a structural formula (B1). Or represents the group shown by (B2).
In the structural formulas (B3) to (B5), examples of the monovalent organic group represented by R ′ include an alkyl group having 1 to 30 carbon atoms and a hydroxyalkyl group having 1 to 30 carbon atoms.

The following are mentioned as a commercial item of surfactant which has the structure of (B).
For example, as a compound represented by any one of structural formulas (B3) to (B5), the following are possible: 100, 100C, 110, 140A, 150, 150CH, AK, 501, 250, 251, 222F, FTX-218, 300, 310, 400SW, 212M, 245M, 290M, FTX-207S, FTX-211S, FTX-220S, FTX-230S, FTX-209F, FTX-213F, FTX-222F, FTX-233F, FTX-245F, FTX- 208G, FTX-218G, FTX-230G, FTX-240G, FTX-204D, FTX-280D, FTX-212D, FTX-216D, FTX-218D, FTX-220D (manufactured by Neos Corporation), etc. It is done.
Moreover, as a compound which has at least one of Structural formula (B1) and (B2) in the side chain of an acrylic polymer, KB-L82, KB-L85, KB-L97, KB-L109, KB-L110, KB-F2L , KB-F2M, KB-F2S, KB-F3M, KB-FaM (manufactured by Neos Corporation) and the like.

-(C) alkylene oxide structure (C) As an alkylene oxide structure, an alkylene oxide and a polyalkylene oxide are included. Specific examples of the alkylene oxide include ethylene oxide and propylene oxide, and the alkylene oxide may be a polyalkylene oxide having a repeating number of 2 to 10,000.
Examples of the surfactant (C) having an alkylene oxide structure include polyethylene glycol, polyether antifoaming agent, and polyether-modified silicone oil.
The polyethylene glycol preferably has an average molecular weight of 2000 or less, and the polyethylene glycol having an average molecular weight of 2000 or less includes polyethylene glycol 2000 (average molecular weight 2000), polyethylene glycol 600 (average molecular weight 600), polyethylene glycol 400 (average molecular weight). 400), polyethylene glycol 200 (average molecular weight 200), and the like.
In addition, PE-M, PE-L (above, manufactured by Wako Pure Chemical Industries, Ltd.), antifoam No. 1. Antifoaming agent No. 1 Polyether antifoaming agents such as 5 (above, manufactured by Kao Corporation) are also suitable examples.

(C) As the surfactant containing a fluorine atom in the molecule in addition to the alkylene oxide structure, those having an alkylene oxide or polyalkylene oxide in the side chain of the polymer having a fluorine atom, and alkylene oxide or polyalkylene oxide Examples thereof include those in which the terminal is substituted with a substituent containing a fluorine atom.
(C) Specific examples of surfactants containing a fluorine atom in the molecule in addition to the alkylene oxide structure include, for example, Megafac F-443, F-444, F-445, F-446 (and above, Dainippon Ink, Inc.). Chemical Industry Co., Ltd.), Footgent 250, 251, 222F (above, manufactured by Neos), POLY FOX PF636, PF6320, PF6520, PF656 (above, made by Kitamura Chemical Co., Ltd.).

  (C) Specific examples of the surfactant containing a silicone structure in the molecule in addition to the alkylene oxide structure include KF351 (A), KF352 (A), KF353 (A), KF354 (A), KF355 (A ), KF615 (A), KF618, KF945 (A), KF6004 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF4440, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460 (manufactured by GE Toshiba Silicon Corporation), BYK- 300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 341, 344, 345, 346, 347, 348, 370, 375, 377, 378, UV3500, UV3510, UV3570, etc. (above, Kkukemi Japan Co., Ltd.) and the like.

-(D) Structure having a carbon-carbon triple bond and a hydroxyl group (D) The structure having a carbon-carbon triple bond and a hydroxyl group is not particularly limited, and examples of the surfactant having this structure include the following compounds. It is done.
(D) Examples of the surfactant having a structure having a carbon-carbon triple bond and a hydroxyl group include compounds having a triple bond and a hydroxyl group in the molecule. Specifically, for example, 2-propyn-1-ol, 1-butyn-3-ol, 2-butyn-1-ol, 3-butyn-1-ol, 1-pentyn-3-ol, 2-pentyn-1-ol, 3-pentyn-1-ol, 4- Pentyn-1-ol, 4-pentyn-2-ol, 1-hexyn-3-ol, 2-hexyn-1-ol, 3-hexyn-1-ol, 5-hexyn-1-ol, 5-hexyne- 3-ol, 1-heptin-3-ol, 2-heptin-1-ol, 3-heptin-1-ol, 4-heptin-2-ol, 5-heptin-3-ol, 1-octin-3- All, 1-o Chin-3-ol, 3-octyn-1-ol, 3-nonin-1-ol, 2-decyn-1-ol, 3-decyn-1-ol, 10-undecin-1-ol, 3-methyl- 1-butyn-3-ol, 3-methyl-1-penten-4-in-3-ol, 3-methyl-1-pentyn-3-ol, 5-methyl-1-hexyn-3-ol, 3- Ethyl-1-pentyn-3-ol, 3-ethyl-1-heptin-3-ol, 4-ethyl-1-octin-3-ol, 3,4-dimethyl-1-pentyn-3-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3,6-dimethyl-1-heptin-3-ol, 2,2,8,8-tetramethyl-3,6-nonadiin-5-ol, 4,6 -Nonadecadiin-1-ol, 10,12-pe Tacosadin-1-ol, 2-butyne-1,4-diol, 3-hexyne-2,5-diol, 2,4-hexadiyne-1,6-diol, 2,5-dimethyl-3-hexyne-2, 5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, (+)-1,6-bis (2-Chlorophenyl) -1,6-diphenyl-2,4-hexadiyne-1,6-diol, (-)-1,6-bis (2-chlorophenyl) -1,6-diphenyl-2,4-hexadiyne -1,6-diol, 2-butyne-1,4-diol bis (2-hydroxyethyl), 1,4-diacetoxy-2-butyne, 4-diethylamino-2-butyn-1-ol, 1,1-diphenyl -2-propyne 1-ol, 1-ethynyl-1-cyclohexanol, 9-ethynyl-9-fluorenol, 2,4-hexadiindiyl-1,6-bis (4-phenylazobenzenesulfonate), 2-hydroxy-3- Butynoic acid, 2-hydroxy-3-butynoic acid ethyl ester, 2-methyl-4-phenyl-3-butyn-2-ol, methyl propargyl ether, 5-phenyl-4-pentyn-1-ol, 1-phenyl- 1-propyn-3-ol, 1-phenyl-2-propyne-1-ol, 4-trimethylsilyl-3-butyn-2-ol, 3-trimethylsilyl-2-propyne-1-ol and the like can be mentioned.
Moreover, the compound (For example, Surfynol 400 series (made by Shin-Etsu Chemical Co., Ltd.) etc.) which alkylene oxides, such as ethylene oxide, added to a part or all of the hydroxyl group of said compound are mentioned.

  (D) As the surfactant having a structure having a carbon-carbon triple bond and a hydroxyl group, a compound represented by any one of the following general formulas (D1) and (D2) is desirable.

In the general formulas (D1) and (D2), R ^a , R ^b , R ^c , and R ^d each independently represent a monovalent organic group, and x, y, and z are each independently An integer of 1 or more is shown.
Among the compounds represented by the general formula (D1) or (D2), those in which R ^a , R ^b , R ^c and R ^d are alkyl groups are preferable. More preferably, at least one of R ^a and R ^b and at least one of R ^c and R ^d are branched alkyl groups. Furthermore, z is preferably 1 or more and 10 or less. x and y are each preferably 1 or more and 500 or less.

  Surfinol 400 series (made by Shin-Etsu Chemical Co., Ltd.) is mentioned as a commercial item of the compound shown by general formula (D1) or (D2).

The surfactants having the structures (A) to (D) described above may be used singly or in combination of two or more. In the case of using a mixture of a plurality of types, a surfactant having a structure different from the surfactant having the structure of (A) to (D) may be used in combination as long as the effect is not impaired.
Examples of the surfactant that can be used in combination include the following surfactants having a fluorine atom and surfactants having a silicone structure.
That is, as the surfactant having a fluorine atom that can be used in combination with the surfactant having the structure of (A) to (D), perfluoroalkylsulfonic acid (for example, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, etc.) ), Perfluoroalkyl carboxylic acids (for example, perfluorobutane carboxylic acid, perfluoro octane carboxylic acid, etc.), and perfluoroalkyl group-containing phosphate esters. Perfluoroalkylsulfonic acids and perfluoroalkylcarboxylic acids may be salts thereof and amide-modified products thereof.
Examples of commercially available perfluoroalkyl sulfonic acids include Megafac F-114 (manufactured by Dainippon Ink & Chemicals, Inc.), F-top EF-101, EF102, EF-103, EF-104, EF-105, and EF. -112, EF-121, EF-122A, EF-122B, EF-122C, EF-123A (JEMCO) As mentioned above, the Neos company) etc. are mentioned.
Examples of commercially available perfluoroalkylcarboxylic acids include Megafac F-410 (Dainippon Ink Chemical Co., Ltd.), F-Top EF-201, EF-204 (above, JEMCO).
As commercial products of perfluoroalkyl group-containing phosphates, MegaFac F-493, F-494 (above, manufactured by Dainippon Ink & Chemicals, Inc.) F-top EF-123A, EF-123B, EF-125M, EF -132 (above, manufactured by JEMCO).

  In addition, the surfactant having a fluorine atom that can be used in combination with the surfactant having the structure of (A) to (D) is not limited to the above, and for example, a fluorine atom-containing betaine structure compound (for example, Factent 400SW, Neos) and surfactants having amphoteric ion groups (for example, Footent SW (manufactured by Neos)) are also preferably used.

  Examples of the surfactant having a silicone structure that can be used in combination with the surfactant having the structure of (A) to (D) include general silicone oils such as dimethyl silicone, methylphenyl silicone, diphenyl silicone, and derivatives thereof. Can be mentioned.

The content of the surfactant is desirably 0.01% by mass or more and 1% by mass or less, more desirably 0.02% by mass or more, based on the total solid content of the composition for forming the charge transport layer 2B-2. 0.5% by mass or less. When the content of the surfactant is less than 0.01% by mass, the coating film defect preventing effect tends to be insufficient. Further, when the content of the surfactant exceeds 1% by mass, a polymerized or cured film obtained by separating the surfactant from the curing component (a compound represented by the general formula (I), other monomers, oligomers, etc.) The strength of the steel tends to decrease.
The surfactant having the structures (A) to (D) is preferably contained in an amount of 1% by mass or more, and more preferably 10% by mass or more.

In addition, the composition used for forming the charge transport layer 2B-2 has no charge transport ability for the purpose of controlling the viscosity, film strength, flexibility, smoothness, cleaning property, etc. of the composition. A radical polymerizable monomer, oligomer or the like may be added.
Examples of the monofunctional radical polymerizable monomer include isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, 2-hydroxy acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate , Phenoxypolyethyleneglycol Lumpur acrylate, phenoxy polyethylene glycol methacrylate, hydroxyethyl o- phenylphenol acrylate, and the like o- phenylphenol glycidyl ether acrylate.

  Examples of the bifunctional radical polymerizable monomer include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 2-n-butyl-2-ethyl- 1,3-propanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dioxane glycol diacrylate, polytetramethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane Examples include methanol diacrylate, tricyclodecane methanol dimethacrylate, divinylbenzene, and diallylpropyl isocyanurate.

  Examples of the tri- or more functional radical polymerizable monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol acrylate, trimethylolpropane EO-added triacrylate, glycerin PO-added triacrylate, and trisacryloyloxyethylphosphine. Fate, pentaerythritol tetraacrylate, ethoxylated isocyanuric triacrylate, triallyl isocyanuric acid, trivinylcyclohexane, trivinylbenzene, and the like.

  Moreover, as a radically polymerizable oligomer, an epoxy acrylate type, a urethane acrylate type, and a polyester acrylate type oligomer are mentioned, for example.

  The radically polymerizable monomer or oligomer having no charge transporting ability is preferably contained in an amount of 0 to 50% by mass, more preferably 0 to 40% by mass, based on the total solid content of the composition. More preferably, the content is from 0 to 30% by mass.

Here, the cured film (crosslinked film) constituting the charge transport layer 2B-2 can be obtained by curing the composition containing the above components by various methods such as heat, light, and electron beam. If necessary, a thermal polymerization initiator and a photopolymerization initiator may be added to the composition.
In order to balance characteristics such as mechanical strength, thermosetting is desirable. Usually, when curing a general acrylic paint or the like, an electron beam that cures without a catalyst and photopolymerization that cures in a short time are preferably used. However, in the electrophotographic photosensitive member, since the photosensitive layer which is the surface of the outermost layer contains a photosensitive material, it is difficult to damage the photosensitive material, and in order to improve the surface properties of the obtained cured film, It is desirable to perform thermosetting that allows the reaction to proceed. Thermal curing may be performed without a catalyst, but it is desirable to use a thermal radical initiator as a catalyst.

  The thermal radical initiator is not particularly limited, but is preferably one having a 10-hour half-life temperature of 40 ° C. or higher and 110 ° C. or lower in order to suppress damage to the photosensitive material in the photosensitive layer during formation of the charge transport layer 2B-2. .

Commercially available products of thermal radical initiators include V-30 (10-hour half-life temperature: 104 ° C.), V-40 (same: 88 ° C.), V-59 (same: 67 ° C.), V-601 (same as above: 66 ° C), V-65 (same: 51 ° C), V-70 (same: 30 ° C), VF-096 (same: 96 ° C), Vam-110 (same: 111 ° C), Vam-111 (same: 111 ° C.), VE-073 (same as above: 73 ° C.) (Wako Pure Chemical Industries, Ltd.), OTAZO-15 (same as 61 ° C.), OTAZO-30 (same as 57 ° C.), AIBN (same as 65 ° C.) Azo initiators such as AMBN (same: 67 ° C.), ADVN (same: 52 ° C.), ACVA (same: 68 ° C.) (above, manufactured by Otsuka Chemical Co., Ltd.);
Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Perbutyl H, Park Mill H, Park Mill P, Permenta H, Per Octa H, Perbutyl C, Perbutyl D, Perhexyl D, Parroyl IB, Parroyl 355, Parroyl L , Parroyl SA, Niper BW, Niper BMT-K40 / M, Parroyl IPP, Parroyl NPP, Parroyl TCP, Parroyl OPP, Parroyl SBP, Parkmill ND, Perocta ND, Perhexyl ND, Perbutyl ND, Perbutyl NHP, Perhexyl PV, Perbutyl PV, Perhexa 250, Perocta O, Perhexyl O, Perbutyl O, Perbutyl L, Perbutyl 355, Perhexyl I, Perbutyl I, Perbutyl E, Perhexa 5Z, perbutyl A, perhexyl Z, perbutyl ZT, perbutyl Z (manufactured by NOF Chemical Co., Ltd.), Kayaketal AM-C55, Trigonox 36-C75, Laurox, Parkardox L-W75, Percadox CH-50L, Trigonox TMBH, Kayakumen H, Kayabutyl H-70, Percadox BC-FF, Kaya Hexa AD, Parka Dox 14, Kaya Butyl C, Kaya Butyl D, Kaya Hexa YD-E85, Perkadox 12-XL25, Perkadox 12-EB20, Trigonox 22-N70, Trigonox 22-70E, Trigonox DT50, Trigonox 423-C70, Kayaester CND-C70, Kayaester CND-W50, Trigonox 23-C70, Trigonox 23-W5 N, Trigonox 257-C70, Kayaester P-70, Kayaester TMPO-70, Trigonox 121, Kayaester O, Kayaester HTP-65W, Kayaester AN, Trigonox42, Trigonox F-C50, Kayabutyl B, Kayacarboxyl EH- C70, Kaya-Carbon EH-W60, Kaya-Carbon I-20, Kaya-Carbon BIC-75, Trigonox 117, Kayalen 6-70 (manufactured by Kayaku Akzo), Luperox LP (same: 64 ° C.), Ruperox 610 (same: 37 ° C. ), Lupelox 188 (same: 38 ° C), Lupelox 844 (same: 44 ° C), Lupelox 259 (same: 46 ° C), Lupelox 10 (same: 48 ° C), Lupelox 701 (same: 53 ° C), Lupelox 11 ( Same: 58 ℃) Rox 26 (same: 77 ° C), Lupelox 80 (same: 82 ° C), Lupelox 7 (same: 102 ° C), Lupelox 270 (same: 102 ° C), Lupelox P (same: 104 ° C), Lupelox 546 (same: 46 ° C), Lupelox 554 (same: 55 ° C), Lupelox 575 (same: 75 ° C), Lupelox TANPO (same: 96 ° C), Lupelox 555 (same: 100 ° C), Lupelox 570 (same: 96 ° C), Lupelox TAP (same as above: 100 ° C.), Luperox TBIC (same as above: 99 ° C.), Luperlocks TBEC (same as above: 100 ° C.), Luperlocks JW (same as above: 100 ° C.), Lupelox TAIC (same as above: 96 ° C.), Luperox TAEC (same as 99 ° C), Luperox DC (same as 117 ° C), Luperox 101 (same as 120 ° C) Lupelox F (same as 116 ° C), Lupelox DI (same as 129 ° C), Lupelox 130 (same as 131 ° C), Lupelox 220 (same as 107 ° C), Lupelox 230 (same as 109 ° C), Lupelox 233 (same as above) : 114 ° C.), Ruperox 531 (same as 93 ° C.) (above, manufactured by Arkema Yoshitomi).

  The thermal radical initiator is preferably contained in an amount of 0.001% by mass to 10% by mass with respect to the reactive compound in the composition, more preferably 0.01% by mass to 5% by mass. It is more desirable to contain 1 mass% or more and 3 mass% or less.

Moreover, when forming charge transport layer 2B-2 by photocuring, a well-known thing is used as a photoinitiator. Examples of the photo radical initiator include an intramolecular open type and a hydrogen abstraction type.
Examples of the intramolecular open type include benzyl ketal, alkylphenone, aminoalkylphenone, phosphine oxide, titanocene, and oxime.
Specifically, 2,2-dimethoxy-1,2-diphenylethane-1-one is mentioned as the benzyl ketal system. Examples of alkylphenones include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl] -2. -Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane- Examples include 1-one, acetophenone, and 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone. Examples of aminoalkylphenones include p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1 -Butanone and the like. Examples of the phosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Examples of the titanocene include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Examples of oximes include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (0-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl]-, 1- (0-acetyloxime) and the like.

Examples of the hydrogen abstraction type include benzophenone series, thioxanthone series, benzyl series, and Michler ketone series.
Specifically, examples of the benzophenone series include 2-benzoylbenzoic acid, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl 4′-methyldiphenyl sulfide, p, p′-bisdiethylaminobenzophenone, and the like. It is done. Examples of the thioxanthone series include 2,4-diethylthioxanthen-9-one, 2-chlorothioxanthone, and 2-isopropylthioxanthone. Examples of the benzyl type include benzyl, (±) -camphorquinone, p-anisyl and the like.

  The photo radical initiator is preferably contained in an amount of 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, based on the reactive compound in the composition. It is more desirable to contain 1 mass% or more and 3 mass% or less.

  In addition, the composition used for forming the charge transport layer 2B-2 is added with a phenol resin, for the purpose of effectively suppressing oxidation by the discharge generated gas by adding the discharge generated gas so as not to adsorb too much. You may add other thermosetting resins, such as a melamine resin and a benzoguanamine resin.

Further, the composition used for forming the charge transport layer 2B-2 further includes a coupling agent, a hard coat for the purpose of adjusting the film formability, flexibility, lubricity, and adhesiveness of the film. An agent and a fluorine-containing compound may be added. Specifically, various silane coupling agents and commercially available silicone hard coat agents are used as these additives.
As the silane coupling agent, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane and the like are used.

Commercially available hard coat agents include KP-85, X-40-9740, X-8239 (manufactured by Shin-Etsu Silicone), AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Etc.) are used.
Further, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (hepta) for imparting water repellency and the like. Fluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyl Fluorine-containing compounds such as triethoxysilane may be added.
Although the silane coupling agent is used in an arbitrary amount, the amount of the fluorine-containing compound should be 0.25 times or less in terms of mass ratio with respect to the compound not containing fluorine from the viewpoint of the film formability of the crosslinked film. Is desirable.

The composition used to form the charge transport layer 2B-2 includes discharge gas resistance, mechanical strength, scratch resistance, torque reduction, wear amount control, pot life extension, etc. of the charge transport layer 2B-2, A thermoplastic resin may be added for the purpose of particle dispersibility and viscosity control.
Polyvinyl butyral resin, polyvinyl formal resin, polyvinyl acetal resin such as partially acetalized polyvinyl acetal resin in which a part of butyral is modified with formal, acetoacetal or the like (for example, Sleksui Chemical Co., Ltd. ESREC B, K etc.), polyamide resin, cellulosic -Resin, polyvinyl phenol resin and the like. In particular, polyvinyl acetal resin and polyvinyl phenol resin are desirable in terms of electrical characteristics. The resin preferably has a weight average molecular weight of 2,000 to 100,000, and more preferably 5,000 to 50,000. If the molecular weight of the resin is less than 2,000, the effect due to the addition of the resin tends to be insufficient, and if it exceeds 100,000, the solubility is reduced and the addition amount is limited. It tends to cause defects. The amount of the resin added is preferably 1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and further preferably 5% by mass or more and 20% by mass or less. If the addition amount of the resin is less than 1% by mass, the effect of the addition of the resin tends to be insufficient. If the addition amount exceeds 40% by mass, the temperature is high under high humidity (for example, 28 ° C., 85% RH). Image blur is likely to occur.

An antioxidant is added to the composition used for forming the charge transport layer 2B-2 for the purpose of preventing deterioration due to an oxidizing gas such as ozone generated in the charging device of the charge transport layer 2B-2. Is desirable. When the mechanical strength of the surface of the photoconductor is increased and the photoconductor has a long life, the photoconductor is in contact with the oxidizing gas for a long time, and therefore, stronger oxidation resistance is required than before.
Antioxidants are preferably hindered phenols or hindered amines, organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, benzimidazole antioxidants. , Etc., may be used. The addition amount of the antioxidant is preferably 20% by mass or less, and more preferably 10% by mass or less.
Examples of the hindered phenol antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, N, N′-hexamethylene bis (3,5-di). -T-butyl-4-hydroxyhydrocinnamide, 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 2,4-bis [(octylthio) methyl] -o-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol) 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,5-di-t-amylhydroquinone, 2-t-butyl-6- (3-butyl-2-hydro Xyl-5-methylbenzyl) -4-methylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), and the like.

Furthermore, various particles may be added to the composition used for forming the charge transport layer 2B-2 for the purpose of lowering the residual potential of the charge transport layer 2B-2 or improving the strength.
An example of the particles is silicon-containing particles. The silicon-containing particles are particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone particles. The colloidal silica used as the silicon-containing particles is obtained by dispersing silica having an average particle diameter of 1 nm or more and 100 nm or less, preferably 10 nm or more and 30 nm or less in an organic solvent such as an acidic or alkaline aqueous dispersion, alcohol, ketone, or ester. A commercially available product may be used. The solid content of colloidal silica in the charge transport layer 2B-2 is not particularly limited, but the total solid content of the charge transport layer 2B-2 is determined from the viewpoint of film forming properties, electrical characteristics, and strength. As a reference, it is used in the range of 0.1 to 50% by mass, desirably 0.1 to 30% by mass.
The silicone particles used as the silicon-containing particles are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and those commercially available are generally used. These silicone particles are spherical, and the average particle size is desirably 1 nm or more and 500 nm or less, and more desirably 10 nm or more and 100 nm or less. Silicone particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain more sufficient properties is low, the electron does not hinder the crosslinking reaction. The surface properties of the photographic photoreceptor are improved. In other words, it is improved in lubricity and water repellency on the surface of the electrophotographic photosensitive member in a state of being taken in without a variation in a strong cross-linked structure, and has good wear resistance and contamination resistance adhesion over a long period of time. Maintained.
The content of the silicone particles in the charge transport layer 2B-2 is desirably 0.1% by mass or more and 30% by mass or less, more desirably 0.5% by mass based on the total amount of the total solid content of the charge transport layer 2B-2. It is 10 mass% or less.

Other particles include fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, and vinylidene fluoride, as shown in the 8th Polymer Materials Forum Lecture Proceedings p89. As shown, particles made of a resin obtained by copolymerizing a fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO ₂ —TiO ₂ , ZnO Examples thereof include semiconductive metal oxides such as —TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. For the same purpose, an oil such as silicone oil may be added. Silicone oils include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane; amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, mercapto-modified poly Reactive silicone oils such as siloxane and phenol-modified polysiloxane; cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; 1,3,5- Trimethyl-1.3.5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclo Cyclic methylphenylcyclosiloxanes such as tetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane; cyclic phenylcyclosiloxanes such as hexaphenylcyclotrisiloxane Fluorine-containing cyclosiloxanes such as (3,3,3-trifluoropropyl) methylcyclotrisiloxane; hydrosilyl group-containing cyclosiloxanes such as methylhydrosiloxane mixtures, pentamethylcyclopentasiloxane, and phenylhydrocyclosiloxane; penta And vinyl group-containing cyclosiloxanes such as vinylpentamethylcyclopentasiloxane.

  Moreover, you may add a metal, a metal oxide, carbon black, etc. to the composition used in order to form charge transport layer 2B-2. Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, or those obtained by depositing these metals on the surface of plastic particles. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. . These may be used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed, or may be in the form of a solid solution or fusion. The average particle diameter of the conductive particles is preferably 0.3 μm or less, particularly preferably 0.1 μm or less, from the viewpoint of the transparency of the charge transport layer 2B-2.

The composition used to form the charge transport layer 2B-2 is preferably prepared as a coating solution for forming the charge transport layer 2B-2, and this coating solution may be solventless or necessary. Aromatic hydrocarbons such as toluene, xylene and chlorobenzene; alcohols such as methanol, ethanol, propanol, butanol, cyclopentanol and cyclohexanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran, diethyl Ethers such as ether, diisopropyl ether and dioxane; solvents such as esters such as ethyl acetate, npropyl acetate, nbutyl acetate and ethyl lactate may be contained.
Such solvents are used singly or in combination of two or more, and preferably have a boiling point of 100 degrees or less.
Moreover, you may contain a polymerization inhibitor in order to improve the storage stability of the coating liquid for charge transport layer 2B-2 formation. Known polymerization inhibitors are used. The hindered phenol type or hindered amine type listed as specific examples of the above-mentioned antioxidant is advantageous because it functions also as a polymerization inhibitor.

A coating liquid for forming a charge transport layer 2B-2 containing a composition used for forming the charge transport layer 2B-2 is formed on the charge transport layer 2B-1 by a blade coating method, a wire bar coating method, or a spray coating method. It is applied by a usual method such as a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, etc., and polymerized by heating at a temperature of 100 ° C. or more and 170 ° C. or less as necessary. Alternatively, a cured film is obtained. As a result, a charge transport layer 2B-2 (corresponding to the layer (Oc1) of the present embodiment in the first mode) made of this polymerized or cured film is obtained.
In addition, the oxygen concentration during curing of the coating liquid for forming the charge transport layer 2B-2 is desirably 1% or less, more desirably 1000 ppm or less, and further desirably 500 ppm or less.

  The coating liquid for forming the charge transport layer 2B-2 is used for, for example, an antistatic film such as a fluorescent coloring paint, a glass surface, a plastic surface, etc. in addition to the use as a photoreceptor. When this coating solution is used, a film having excellent adhesion to the lower layer is formed, and performance deterioration due to repeated use over a long period is suppressed.

-Charge transport layer 2B (corresponding to the layer (Oc2) of the present embodiment in the second mode)
The charge transport layer 2B may have the same configuration as that of the charge transport layer 2B-2 in the first embodiment. As a composition for forming the charge transport layer 2B and a method for forming the composition, the charge transport layer 2B-2 is used. Is the same as

-Single-layer type photosensitive layer 6 (corresponding to the layer (Oc3) of the present embodiment in the third mode)-
As described above, the example of the function separation type is described as the electrophotographic photosensitive member. However, the content of the charge generation material in the single-layer type photosensitive layer 6 (charge generation / charge transport layer) shown in FIG. It is about 85% by mass or less, desirably 20% by mass or more and 50% by mass or less. In addition, the content of the charge transport material is desirably 5% by mass or more and 50% by mass or less.
The formation method of the single-layer type photosensitive layer 6 (charge generation / charge transport layer) is the same as the formation method of the charge generation layer 2A and the charge transport layer 2B-2. The film thickness of the single-layer type photosensitive layer (charge generation / charge transport layer) 6 is preferably about 5 μm to 50 μm, and more preferably 10 μm to 40 μm.

  Moreover, although the said embodiment demonstrated the form in which the outermost surface layer (charge transport film | membrane) which consists of a polymerized or cured film of the composition containing the said charge transport material (A) is a charge transport layer or a photosensitive layer. When the protective layer is provided as the outermost surface layer on the charge transporting layer or the photosensitive layer, the protective layer may be constituted by polymerization or a cured film of a composition containing the charge transporting material (A).

  In the present embodiment described above, a polymerized or cured film (charge transport film) of the composition containing the charge transport material (A) of the present embodiment is applied as the outermost surface layer of the electrophotographic photosensitive member. Although the embodiment has been described, the polymerized or cured film containing the charge transporting material (A) of the present embodiment is not limited thereto. The cured film containing the charge transport material (A) of this embodiment is applied to, for example, an organic electroluminescence (electroluminescence, EL) element, a memory element, a wavelength conversion element, and the like. And since the cured film according to the present embodiment is considered to be formed without impairing the charge transport property, there is no change in the morphology due to Joule heat as seen in the conventional charge transport film, and when the layers are laminated. The film has excellent film forming properties. As a result, it is useful for the above applications.

[Photoelectric conversion device]
The photoelectric conversion device according to this embodiment includes the above-described charge transport film according to this embodiment.
As described above, since the charge transport film according to this embodiment is excellent in both mechanical strength and charge transport performance, it can be suitably applied to a layer that requires mechanical strength in a photoelectric conversion device.

Examples of the photoelectric conversion device according to this embodiment include an electrophotographic photosensitive member, an organic EL device, an organic transistor, and an organic solar battery.
Specifically, for example, the organic EL device is composed of a pair of electrodes, at least one of which is transparent or translucent, and one or a plurality of organic compound layers sandwiched between the electrodes. The charge transport film of the present invention can be used for at least one layer of the organic compound layer, and the layer structure is not particularly limited. Specifically, the above-described charge transport film according to this embodiment is applied as the light emitting layer, the hole transport layer, and the hole injection layer.
Further, for example, the organic thin film transistor includes an organic semiconductor layer that is in contact with both the source electrode and the drain electrode that are provided to face each other, a gate electrode that is separated from both the source electrode and the drain electrode, and the organic semiconductor layer and the gate electrode. It has an insulating layer disposed between them. The charge transport film of the present invention can be used for at least one layer of the organic semiconductor layer, and the layer structure is not particularly limited.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

<Synthesis Example 1>
—Synthesis of Charge Transfer Agent I-7 of the Present Invention—
To a 500 ml three-necked flask, 32.6 g of 3,4-dimethylacetanilide, 56.0 g of 4-iodobiphenyl, 30.4 g of potassium carbonate, 1.5 g of copper sulfate pentahydrate, and 50 ml of n-tridecane were added. The mixture was stirred for 20 hours while heating at 220 ° C. while flowing. Thereafter, the temperature was lowered to 120 ° C., 50 ml of ethylene glycol and an aqueous potassium hydroxide solution (15.7 g of potassium hydroxide / 20 ml of water) were added, and the mixture was further stirred for 6 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 20 g of sodium sulfate was added and stirred for 10 minutes, and then sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 42.1 g of I-7a (yield 77%).

  To a 500 ml three-necked flask was added 41.0 g of I-15a, 43.5 g of methyl 3- (4-iodophenyl) propionate, 22.8 g of potassium carbonate, 1.1 g of copper sulfate pentahydrate, and 40 ml of n-tridecane. The mixture was stirred for 20 hours while heating at 220 ° C. while flowing nitrogen. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 20 g of sodium sulfate was added and stirred for 10 minutes, and then sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 47.0 g of I-7b (yield 72%).

  To a 3 L three-necked flask, 43.6 g of I-7b and 450 ml of tetrahydrofuran were added, an aqueous solution in which 4.4 g of sodium hydroxide was dissolved in 450 ml of water was added, and the mixture was stirred at 60 ° C. for 3 hours. Thereafter, the reaction solution was added dropwise to 1 L of water / 20 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. The solid was further added with 50 ml of an acetone / water mixed solvent (volume ratio 40/60), stirred in a suspended state, collected by suction filtration, and vacuum-dried for 10 hours to obtain 31.2 g of I-7c. (Yield 74%).

To a 500 ml three-necked flask, 29.5 g of I-7c, 11.8 g of 4-chloromethylstyrene, 10.6 g of potassium carbonate, 0.17 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide) were added. The mixture was flowed and stirred at 75 ° C. for 3 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 29.7 g of the charge transfer agent I-7 of the present invention (yield 79%). .
FIG. 4 shows the IR spectrum of the obtained compound (I) -7.

<Synthesis Example 2>
—Synthesis of Charge Transfer Agent I-15 of the Present Invention—
In a 500 ml three-necked flask, 68.3 g of 4,4′-bis (2-methoxycarbonylethyl) diphenylamine, 46.4 g of 4-iodoxylene, 30.4 g of potassium carbonate, 1.5 g of copper sulfate pentahydrate, 50 ml of n-tridecane Was added, and the system was stirred for 20 hours while heating at 220 ° C. while flowing nitrogen. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 20 g of sodium sulfate was added and stirred for 10 minutes, and then sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 65.1 g of I-15a (yield 73%).

  To a 3 L three-necked flask, 59.4 g of I-15a and 450 ml of tetrahydrofuran were added, and an aqueous solution in which 11.7 g of sodium hydroxide was dissolved in 450 ml of water was added thereto, followed by stirring at 60 ° C. for 3 hours. Thereafter, the reaction solution was added dropwise to 1 L of water / 60 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. Further, 50 ml of an acetone / water mixed solvent (volume ratio 40/60) was added to this solid and stirred in a suspended state, and then collected by suction filtration and vacuum-dried for 10 hours to obtain 46.2 g of I-15b. (Yield 83%).

To a 500 ml three-necked flask were added 29.2 g of I-15b, 23.5 g of 4-chloromethylstyrene, 21.3 g of potassium carbonate, 0.17 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide). The mixture was flowed and stirred at 75 ° C. for 3 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 36.4 g of the charge transfer agent I-15 of the present invention (yield 80%). .
FIG. 5 shows the IR spectrum of the obtained compound (I) -15.

<Synthesis Example 3>
—Synthesis of Charge Transfer Agent I-17 of the Present Invention—
In a 500 ml three-necked flask, 68.3 g of 4,4′-bis (2-methoxycarbonylethyl) diphenylamine, 56.0 g of 4-iodobiphenyl, 30.4 g of potassium carbonate, 1.5 g of copper sulfate pentahydrate, 50 ml of n-tridecane Was added, and the system was stirred for 20 hours while heating at 220 ° C. while flowing nitrogen. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 20 g of sodium sulfate was added and stirred for 10 minutes, and then sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 74.0 g of I-17a (yield 75%).

  To a 3 L three-necked flask, 65.8 g of I-17a and 450 ml of tetrahydrofuran were added, and an aqueous solution obtained by dissolving 11.7 g of sodium hydroxide in 450 ml of water was added thereto, followed by stirring at 60 ° C. for 3 hours. Thereafter, the reaction solution was added dropwise to 1 L of water / 60 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. Further, 50 ml of an acetone / water mixed solvent (volume ratio 40/60) was added to this solid and stirred in a suspended state, and then collected by suction filtration and vacuum-dried for 10 hours to obtain 53.4 g of I-17b. (Yield 86%).

To a 500 ml three-necked flask were added 32.6 g of I-17b, 23.5 g of 4-chloromethylstyrene, 21.3 g of potassium carbonate, 0.17 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide). The mixture was flowed and stirred at 75 ° C. for 3 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 36.8 g of the charge transfer agent I-17 of the present invention (yield 81%). .
FIG. 6 shows the IR spectrum of the obtained compound (I) -17.

<Synthesis Example 4>
—Synthesis of Charge Transfer Agent I-23 of the Present Invention—
In a 500 ml three-necked flask, 56.7 g of methyl 3- [4- (3,4-dimethylphenylamino) phenyl)] propionate, 43.4 g of 4,4′-diiodo 3,3′-dimethyl-1,1′-biphenyl, 30.4 g of potassium carbonate, 1.5 g of copper sulfate pentahydrate and 50 ml of n-tridecane were added, and the system was stirred for 20 hours while heating at 220 ° C. while flowing nitrogen. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 48.4 g of I-23a (yield 65%).

  37.3 g of I-23a and 350 ml of tetrahydrofuran were added to a 3 L three-necked flask, and an aqueous solution in which 4.4 g of sodium hydroxide was dissolved in 350 ml of water was added thereto, followed by stirring for 5 hours while heating to 60 ° C. Thereafter, the reaction solution was dropped into 1 L of water / 20 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. The solid was further added with 50 ml of an acetone / water mixed solvent (volume ratio 40/60), stirred in a suspended state, collected by suction filtration, and vacuum-dried for 10 hours to obtain 32.6 g of I-23b. (Yield 91%).

To a 500 ml three-necked flask was added 25.1 g of I-23b, 11.8 g of 4-chloromethylstyrene, 10.6 g of potassium carbonate, 0.09 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide), and the system was filled with nitrogen. The mixture was flowed and stirred at 75 ° C. for 5 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 28.2 g of the charge transfer agent I-23 of the present invention (yield 85%). .
The IR spectrum of the obtained compound (I) -23 is shown in FIG.

<Synthesis Example 5>
—Synthesis of Charge Transfer Agent I-25 of the Present Invention—
In a 500 ml three-necked flask, 51.1 g of methyl 3- [4- (phenylamino) phenyl] propionate, 43.4 g of 1,2-bis (4-iodophenyl) ethane, 30.4 g of potassium carbonate, copper sulfate pentahydrate 1.5 g and 50 ml of n-tridecane were added, and the system was stirred for 20 hours while being heated at 220 ° C. with nitrogen flow. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 51.7 g of I-25a (yield 75%).

  34.4 g of I-25a and 350 ml of tetrahydrofuran were added to a 3 L three-necked flask, and an aqueous solution in which 4.4 g of sodium hydroxide was dissolved in 350 ml of water was added thereto, followed by stirring for 5 hours while heating to 60 ° C. Thereafter, the reaction solution was dropped into 1 L of water / 20 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. The solid was further added with 50 ml of an acetone / water mixed solvent (volume ratio 40/60), stirred in a suspended state, collected by suction filtration, and vacuum-dried for 10 hours to obtain 28.4 g of I-25b. (Yield 86%).

To a 500 ml three-necked flask were added 23.1 g of I-25b, 11.8 g of 4-chloromethylstyrene, 10.6 g of potassium carbonate, 0.09 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide), and nitrogen was added to the system. The mixture was flowed and stirred at 75 ° C. for 5 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 25.6 g of the charge transfer agent I-25 of the present invention (yield 82%). .
An IR spectrum of the obtained compound (I) -25 is shown in FIG.

<Synthesis Example 6>
—Synthesis of Charge Transfer Agent I-27 of the Present Invention—
In a 500 ml three-necked flask, 56.7 g of methyl 3- [4- (3,4-dimethylphenylamino) phenyl] propionate, 43.4 g of 1,2-bis (4-iodophenyl) ethane, 30.4 g of potassium carbonate, sulfuric acid Copper pentahydrate 1.5g and n-tridecane 50ml were added, and it stirred for 20 hours, heating at 220 degreeC under nitrogen flow in the system. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 54.4 g of I-27a (yield 73%).

  37.3 g of I-27a and 350 ml of tetrahydrofuran were added to a 3 L three-necked flask, and an aqueous solution in which 4.4 g of sodium hydroxide was dissolved in 350 ml of water was added thereto, followed by stirring for 5 hours while heating to 60 ° C. Thereafter, the reaction solution was dropped into 1 L of water / 20 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. The solid was further added with 50 ml of an acetone / water mixed solvent (volume ratio 40/60), stirred in a suspended state, collected by suction filtration, and vacuum-dried for 10 hours to obtain 29.4 g of I-27b. (Yield 82%).

To a 500 ml three-necked flask was added 25.1 g of I-27b, 11.8 g of 4-chloromethylstyrene, 10.6 g of potassium carbonate, 0.09 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide), and the system was filled with nitrogen. The mixture was flowed and stirred at 75 ° C. for 5 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 26.2 g of the charge transfer agent I-27 of the present invention (yield 79%). .
FIG. 9 shows the IR spectrum of the obtained compound (I) -27.

<Synthesis Example 7>
—Synthesis of Charge Transfer Agent I-30 of the Present Invention—
In a 500 ml three-necked flask, 66.3 g of methyl 3- [4- (4-phenyl) phenylamino) phenyl] propionate, 43.4 g of 1,2-bis (4-iodophenyl) ethane, 30.4 g of potassium carbonate, copper sulfate 1.5 g of pentahydrate and 50 ml of n-tridecane were added, and the system was stirred for 20 hours while heating at 220 ° C. with nitrogen flow. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 62.2 g of I-30a (yield 74%).

  42.1 g of I-30a and 350 ml of tetrahydrofuran were added to a 3 L three-necked flask, and an aqueous solution in which 4.4 g of sodium hydroxide was dissolved in 350 ml of water was added thereto, followed by stirring for 5 hours while heating to 60 ° C. Thereafter, the reaction solution was dropped into 1 L of water / 20 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. The solid was further added with 50 ml of an acetone / water mixed solvent (volume ratio 40/60), stirred in a suspended state, collected by suction filtration, and vacuum-dried for 10 hours to obtain 34.1 g of I-30b. (Yield 84%).

To a 500 ml three-necked flask were added 28.5 g of I-30b, 11.8 g of 4-chloromethylstyrene, 10.6 g of potassium carbonate, 0.09 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide). The mixture was flowed and stirred at 75 ° C. for 5 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 26.7 g of the charge transfer agent I-30 of the present invention (yield 73%). .
FIG. 10 shows the IR spectrum of the obtained compound (I) -30.

<Synthesis Example 8>
—Synthesis of Charge Transfer Agent I-43 of the Present Invention—
In a 500 ml three-necked flask, 68.3 g of 4,4′-bis (2-methoxycarbonylethyl) diphenylamine, 43.4 g of 4,4′-diiodo 3,3′-dimethyl-1,1′-biphenyl, 30.4 g of potassium carbonate, Copper sulfate pentahydrate (1.5 g) and n-tridecane (50 ml) were added, and the system was stirred for 20 hours while heating at 220 ° C. with nitrogen flow. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 56.0 g of I-43a (yield 65%).
43.1 g of I-43a and 350 ml of tetrahydrofuran were added to a 3 L three-necked flask, and an aqueous solution in which 8.8 g of sodium hydroxide was dissolved in 350 ml of water was added thereto, followed by stirring for 5 hours while heating to 60 ° C. Thereafter, the reaction solution was added dropwise to 1 L of water / 40 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. The solid was further added with 50 ml of an acetone / water mixed solvent (volume ratio 40/60), stirred in a suspended state, collected by suction filtration, and vacuum-dried for 10 hours to obtain 36.6 g of I-43b. (Yield 91%).
To a 500 ml three-necked flask, 28.2 g of I-43b, 23.5 g of 4-chloromethylstyrene, 21.3 g of potassium carbonate, 0.09 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide) were added. The mixture was flowed and stirred at 75 ° C. for 5 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 37.8 g of the charge transfer agent I-43 of the present invention (yield 85%). .
An IR spectrum of the obtained compound (I) -43 is shown in FIG.

<Synthesis Example 9>
—Synthesis of Charge Transfer Agent I-46 of the Present Invention—
To a 3 L three-necked flask, 43.1 g of I-43a and 300 ml of tetrahydrofuran were added, and the system was stirred and purged with nitrogen. Then, 16.3 g of sodium borohydride was added. Thereafter, 50 ml of methanol was added dropwise over 2 hours while heating under reflux. The mixture was further refluxed for 2 hours, then cooled to 0 ° C., and 300 ml of 2N hydrochloric acid was added dropwise over 1 hour, and the temperature was gradually returned to room temperature. Thereafter, 400 ml of ethyl acetate was added to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 28.5 g of I-46a (yield 76%).

  To a 500 ml three-necked flask, 26.2 g of I-46a, 14.9 g of succinic anhydride, and 70 ml of tetrahydrofuran were added, and 14.9 g of triethylamine and 0.2 g of N, N-dimethylaminopyridine were stirred while flowing through the system. Was added and stirred for another 2 hours. Thereafter, 200 ml of 1N hydrochloric acid was added, and 300 ml of ethyl acetate was further added to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 35.0 g of I-46b (yield 87%).

To a 500 ml three-necked flask was added 23.0 g of I-46b, 13.4 g of 4-chloromethylstyrene, 12.2 g of potassium carbonate, 0.05 g of nitrobenzene, and 100 ml of DMF (N, N-dimethylformamide), and the system was filled with nitrogen. The mixture was flowed and stirred at 75 ° C. for 5 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 26.1 g of the charge transfer agent I-46 of the present invention (yield 81%). .
FIG. 12 shows the IR spectrum of the obtained compound (I) -46.

<Synthesis Example 10>
—Synthesis of Charge Transfer Agent I-53 of the Present Invention—
In a 500 ml three-necked flask, 68.3 g of 4,4′-bis (2-methoxycarbonylethyl) diphenylamine, 43.4 g of 1,2-bis (4-iodophenyl) ethane, 30.4 g of potassium carbonate, copper sulfate pentahydrate 1.5 g and 50 ml of n-tridecane were added, and the system was stirred for 20 hours while being heated at 220 ° C. with nitrogen flow. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 59.4 g of I-53a (yield 69%).

  To a 3 L three-necked flask, 43.1 g of I-53a and 350 ml of tetrahydrofuran were added, an aqueous solution in which 8.8 g of sodium hydroxide was dissolved in 350 ml of water was added, and the mixture was stirred for 5 hours while heating to 60 ° C. Thereafter, the reaction solution was added dropwise to 1 L of water / 40 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. The solid was further added with 50 ml of an acetone / water mixed solvent (volume ratio 40/60), stirred in a suspended state, collected by suction filtration, and vacuum-dried for 10 hours to obtain 34.2 g of I-53b. (Yield 85%).

To a 500 ml three-necked flask was added 28.2 g of I-53b, 23.5 g of 4-chloromethylstyrene, 21.3 g of potassium carbonate, 0.09 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide). The mixture was flowed and stirred at 75 ° C. for 5 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 35.1 g of the charge transfer agent I-53 of the present invention (yield 79%). .
The IR spectrum of the obtained compound (I) -53 is shown in FIG.

<Example 1>
-Fabrication of charge transport film-
A coating liquid for forming a charge transport film having the following composition was prepared.
(Charge transport agent)
Charge transport material synthesized in Synthesis Example 1 ((I) -15): 100 parts by mass (initiator)
V-601 (Wako Pure Chemical Industries, Ltd.): 2 parts by mass (solvent)
Tetrahydrofuran (THF) / toluene mixed solvent (mass ratio 40/60): 150 parts by mass

An ITO glass substrate provided with an ITO film on a glass substrate was prepared, and the ITO film was etched into a strip shape having a width of 2 mm to form an ITO electrode (anode). The ITO glass substrate was ultrasonically cleaned with isopropanol (for electronics industry, manufactured by Kanto Chemical Co., Ltd.) and then dried with a spin coater.
On the surface of the ITO glass substrate on which the ITO electrode is formed, the coating solution for forming a charge transporting film is applied and heated at 150 ° C. for 40 minutes in an atmosphere having an oxygen concentration of about 100 ppm. Film 1 was formed.

(Measurement of mobility stability)
The mobility was repeatedly measured 100 times by applying an electric field of 30 V / μm to the charge transporting film using TOF-401 (manufactured by Sumitomo Heavy Industries), and the stability of the mobility was evaluated from the following formula.
“||” indicates an absolute value. A ++ indicates the best characteristics.

Mobility stability =
| (Mobility of first measurement) − (mobility of 100th measurement) | / (mobility of first measurement)
A ++: Less than 0.05 A +: 0.05 or more and less than 0.08 A: 0.08 or more and less than 0.1 B: 0.1 or more and less than 0.2 C: 0.2 or more

-Fabrication of organic electroluminescent devices-
An ITO glass substrate provided with an ITO film on a glass substrate was prepared, and the ITO film was etched into a strip shape having a width of 2 mm to form an ITO electrode (anode). The ITO glass substrate was ultrasonically cleaned with isopropanol (for electronics industry, manufactured by Kanto Chemical Co., Ltd.) and then dried with a spin coater.
Next, a thin film having a thickness of 0.015 μm was formed by vacuum deposition of copper phthalocyanine purified by sublimation on the surface of the ITO glass substrate on which the ITO electrode was formed.
The charge transporting film-forming coating solution was applied onto the copper phthalocyanine film and heated at 145 ° C. for 40 minutes in an atmosphere having an oxygen concentration of about 100 ppm to form a 0.05 μm thin film. Thereby, a hole transport layer having a two-layer structure was formed on the ITO electrode.
Next, tris (8-hydroxyquinoline) aluminum (Alq) was vapor-deposited as a light emitting material on the hole transport layer to form a light emitting layer having a thickness of 0.060 μm.
Further, a Mg—Ag alloy was vapor-deposited on the light emitting layer by co-evaporation to form a strip-shaped Mg—Ag electrode (cathode) having a width of 2 mm and a thickness of 0.13 μm, whereby an organic electroluminescent device 1 was obtained. . The ITO electrode and the Mg—Ag electrode were formed so that their extending directions were orthogonal to each other. The effective area of the obtained organic electroluminescent element 1 was 0.04 cm ² .

<Comparative Example 1>
A comparative charge transporting film 1 and a comparative organic electroluminescent element 1 were obtained in the same manner as in Example 1 except that the charge transporting material (I-15) was changed to the comparative compound (AC-1) having the following structure. It was. This is referred to as a comparative organic electroluminescent element 1.

<Comparative Example 2>
A comparative charge transporting film 2 and a comparative organic electroluminescent element 2 were obtained in the same manner as in Example 1 except that the charge transporting material (I-15) was changed to the comparative compound (AC-2) having the following structure. It was. This is referred to as a comparative organic electroluminescent element 2.

<Examples 2 to 16>
In Example 1, charge transport films 2 to 16 and organic electroluminescent elements 2 to 16 were obtained in the same manner as in Example 1 except that the charge transport material, initiator, and solvent were changed to those described in Table 3. It was.

(Evaluation of device characteristics)
About the organic electroluminescent element obtained by the Example and the comparative example, the element characteristic was evaluated as follows.

<Maximum brightness>
In a vacuum (0.125 Pa), the ITO electrode was positive (anode) and the Mg-Ag electrode was negative (cathode). A direct current voltage was applied between them to emit light, and the maximum luminance at that time was evaluated. The results are shown in Table 3.
The evaluation standard for the maximum luminance is as follows. (The unit of the numerical value is cd / m ² )
A ++ indicates the best characteristics.
A ++: 800 or more
A: 750 or more and less than 800 A: 700 or more and less than 750 B: 650 or more and less than 700 C: Less than 650

<Element life>
In addition, the emission lifetime of the organic electroluminescent element was measured in dry nitrogen as follows. At room temperature, the initial luminance is 500 cd / m ² by DC driving method (DC driving), and the luminance (initial luminance L0: 500 cd / m ² ) of the element of Comparative Example 1 is (luminance L / initial luminance L0) = 0.5. The relative time when the driving time at the time of becoming 1.0 is the relative time and the voltage increase at the time when the luminance of the element becomes (luminance L / initial luminance L0) = 0.5 (= voltage / initial driving) Voltage).
The evaluation criteria for the relative time (L / L0 = 0.5) and voltage increase (when L / L0 = 0.5) are as follows.

-Relative time (L / L0 = 0.5)
A ++ indicates the best characteristics.
A ++: 1.6 or more A +: 1.4 or more and less than 1.6 A: 1.2 or more and less than 1.4 B: 1.0 or more and less than 1.2 C: Less than 1.0

-Voltage rise (when L / L0 = 0.5)
A ++ indicates the best characteristics.
A ++: 1.0 or more and less than 1.1 A +: 1.1 or more and less than 1.2 A: 1.2 or more and less than 1.3 B: 1.3 or more and less than 1.4 C: 1.4 or more

VE-073: Polymerization initiator (Wako Pure Chemical Industries, Ltd.)
OTazo-15: polymerization initiator (manufactured by Otsuka Chemical)

DESCRIPTION OF SYMBOLS 1 ... Base | substrate, 2 ... Photosensitive layer, 2A ... Charge generation layer, 2B, 2B-1, 2B-2 ... Charge transport layer, 4 ... Undercoat layer, 6 ... Function-integrated type photosensitive layer

Claims (11)

A reactive compound represented by the following general formula ( II ).

(In the general formula ( II ), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, and Ar ⁵ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group. . D is below in formula (III) a group represented .c1 to c5 represents a 2 an integer 0 or more, respectively, the sum of c1 to c5 is 2 to 8 integer .k is 0 or 1 in is.)

(In General Formula (III), L is a divalent linking group formed by combining —C (═O) —O— and — (CH ₂ ) n— (where n is an integer of 1 or more and 10 or less). ) The reactive compound according to claim 1, wherein the group represented by the general formula (III) is a group represented by the following general formula (IV).

(In general formula (IV), p represents an integer of 0 or more and 4 or less.) The reactive compound according to claim 2 , wherein the group represented by the general formula (IV) is a group represented by the following general formula (V).

(In general formula (V), p represents an integer of 0 or more and 4 or less.) The reactive compound according to any one of claims 1 to 3 , wherein the total of c1 to c5 in the general formula (II) is an integer of 2 to 6. The reactive compound according to claim 4 , wherein the total of c1 to c5 in the general formula (II) is an integer of 3 or more and 6 or less. The reactive compound according to claim 5 , wherein the total of c1 to c5 in the general formula (II) is an integer of 4 or more and 6 or less.   A reactive compound represented by the following general formula (II).

(In the general formula (II), Ar ¹ To Ar ⁴ Each independently represents a substituted or unsubstituted aryl group. Ar ⁵ Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylene group. D is a group represented by the following general formula (IV). c1 to c5 each represent 0 or 1, and the sum of c1 to c5 is 1. k is 0 or 1. )

(In general formula (IV), p represents an integer of 0 or more and 4 or less.)   The reactive compound according to claim 7, wherein the group represented by the general formula (IV) is a group represented by the following general formula (V).

(In general formula (V), p represents an integer of 0 or more and 4 or less.)   The charge transport film | membrane containing the structure derived from the reactive compound as described in any one of Claims 1-8, or this reactive compound.   A charge transport film comprising a polymerized or cured film of a composition containing the reactive compound according to any one of claims 1 to 8.   A photoelectric conversion device comprising the charge transporting film according to claim 9.