JP2011114322A - Charge transporting compound, charge transporting film using the same, organic electroluminescent element, electrophotographic photosensitive member, method for producing charge transporting film, and novel charge transporting compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a charge transporting film, exhibiting superior charge transporting characteristics and superior curability even at the presence of oxygen, and to provide a novel charge transporting compound useful for the same. <P>SOLUTION: The charge transporting film containing a cross linking substance is composed of a composition containing a charge transporting compound having a partial structure represented by a formula (1) and a partial structure represented by a formula (2). In formula (1), Ar<SP>11</SP>and Ar<SP>12</SP>each represents an aryl group; n is either 1 or 2; R<SP>11</SP>represents an aryl group, an alkenyl group or the like when n is 1, an arylene group, an alkenylene group or the like when n is 2. In formula (2), R<SP>21</SP>and R<SP>22</SP>each represents an alkyl group, an aryl group or an acyl group. The crosslinking group represented by the formula (2) is bonded through either one of the partial structure represented by the formula (1), R<SP>21</SP>and R<SP>22</SP>, and the bonding number is 1-6. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel charge transporting compound, a charge transport film using the same, a method for producing the same, and an organic electroluminescent device and an electrophotographic photosensitive member which are preferred modes of use of the charge transport film, and particularly excellent in electrical characteristics and durability. The present invention relates to a charge transport film, a charge transport compound used for the production thereof, and a method for producing the charge transport film.

In recent years, various organic devices such as flexible, lightweight and inexpensive are expected and various organic devices have been developed. As typical organic devices, organic electroluminescence elements, organic photoelectric conversion elements (solar cells, imaging elements, etc.), organic transistors, touch panels, etc. are being developed. The charge transport films used in these devices have charge transport properties. In addition, various properties such as light stability, oxidation-reduction stability, durability such as mechanical strength, and suitability for manufacturing a thin film are required.
A typical method for forming an organic charge transport film includes a vacuum deposition method and a wet film formation method. The vacuum deposition method can be stacked, but a vacuum process is required and the apparatus becomes large. On the other hand, the wet film-forming method by coating does not require a vacuum process, and it is easy to increase the area, and it is easy to mix a plurality of materials having various functions in one layer (coating liquid). However, since it is difficult to form a laminate in the formation of a thin film of 1 μm or less such as an organic electroluminescent element, the driving stability is inferior to that of an element formed by a vacuum evaporation method, and it has reached a practical level except for a part. There is no current situation. In particular, the layering by the wet film forming method can be performed by stacking two layers by using an organic solvent and an aqueous solvent, but it is difficult to stack three or more layers.

Thus, as a technique suitable for forming a multilayer film, it has been shown that a cross-linking group is introduced into a charge transport material and cross-linked to insolubilize to realize multi-layer coating (see, for example, Patent Document 1). . In addition, by introducing a crosslinking group into the charge transport material and curing it in the electrophotographic photoreceptor, the mechanical strength is improved, and the electrophotographic characteristics such as sensitivity and residual potential are excellent, and stable even during repeated use. Has been disclosed (see, for example, Patent Document 2).
However, in the case of radical crosslinkable double bonds, when the curing reaction is performed in the air, there is a problem that polymerization inhibition due to oxygen occurs and sufficient curability cannot be obtained.

Also, an electrophotographic image forming apparatus generally charges a surface of an electrophotographic photosensitive member uniformly to a predetermined polarity and potential by a charging means, and the surface of the electrophotographic photosensitive member after charging is subjected to image exposure. After the electrostatic latent image is formed by selectively removing electricity, the latent image is developed as a toner image by attaching toner to the electrostatic latent image by the developing means, and the toner image is transferred by the transfer means. By transferring it to a medium, it is discharged as an image formed product.
In recent years, an electrophotographic photosensitive member has an advantage that high speed and high printing quality can be obtained, and thus has been remarkably used in the fields of copying machines, laser beam printers, and the like. Compared to electrophotographic photoreceptors using inorganic photoconductive materials such as alloys and cadmium sulfide, organic photoreceptors using organic photoconductive materials, which have the advantages of low cost and excellent manufacturability and disposal, are dominant It has become to.
In the organic photoreceptor, when a low-cost contact charging system is used as a charging system, there is a drawback that the photoreceptor is easily deteriorated and worn by being directly discharged on the surface of the photoreceptor.
In addition, when an intermediate transfer member is used as a transfer method, there is a concern that foreign matters mixed in the image quality forming apparatus may be caught between the intermediate transfer member and the photosensitive member and damage the photosensitive member. There is also a problem that a local excessive current flows easily.
For this reason, improvement in the strength of the electrophotographic photosensitive member is required. For example, it has been proposed to improve the strength by providing a protective layer on the surface, and a material system for forming various protective layers has been devised. For example, in recent years, a protective layer made of an acrylic material has attracted attention, and a film (for example, see Patent Document 3) obtained by applying and curing a liquid containing a photocurable acrylic monomer, or a monomer having a carbon-carbon double bond. A film formed by reacting a mixture of a charge transfer material having a carbon-carbon double bond and a binder resin with heat or light energy (see, for example, Patent Document 4) has been proposed.
Since the polymerization of these acrylic materials still has a problem of inhibition by oxygen, for example, a method of heating and curing after irradiation with radiation in a vacuum or an inert gas (see, for example, Patent Documents 5 and 6). ) Is disclosed.

JP 2008-198989 A JP 2000-147814 A Japanese Patent Laid-Open No. 7-146564 JP 2006-84711 A JP-A-5-40360 Japanese Patent Laid-Open No. 7-72640

As described above, among the cross-linking groups for improving the film strength, in the radical polymerization type double bond having an acrylic group, a methacryl group or the like that ensures a high cross-linking rate, the cross-linking rate is lowered due to polymerization inhibition by oxygen. When polymerization is performed under deoxygenation, equipment is required, and the coating merit that a coating film can be produced with simple equipment is reduced.
In view of this, the first problem to be solved by the present invention is that a charge transport film which can be easily manufactured, can be easily manufactured, has excellent mechanical strength, and can be laminated and applied even in the presence of oxygen. Is to provide. The second object of the present invention is to provide a charge transport film that retains good electrical characteristics and durability, and an organic electroluminescence device, an organic photoelectric conversion device, and an electrophotographic photosensitive member, which are suitable applications thereof. It is.
Furthermore, the third object of the present invention is to provide a method for forming a charge transport film that can be easily produced as the charge transport film of the present invention.
The fourth object of the present invention is to provide a novel crosslinkable charge transporting compound useful for the charge transport film of the present invention.

As a result of studies, the present inventors have found that the above problem can be solved by introducing a polymerizable group having a specific structure into a charge transporting compound, and the present invention has been completed. That is, the configuration of the present invention is as follows.
<1> A charge transport film comprising a crosslinked product comprising a composition containing a charge transporting compound having a partial structure represented by the general formula (1) and a partial structure represented by the general formula (2) is there.

[In the general formula (1), Ar ¹¹ and Ar ¹² each independently represent a substituted or unsubstituted aryl group, and R ¹¹ represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, and Represents a substituent selected from the group consisting of a substituted or unsubstituted alkynyl group. Q represents a single bond or an n-valent linking group, and does not exist when n is 1. n represents 1 or 2. In the general formula (2), R ²¹ and R ²² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted acyl group. The crosslinking group represented by the general formula (2) is bonded to the partial structure represented by the general formula (1) via any one of R ²¹ and R ²² , and the number of bonds is 1 to 6. ]
<2> The charge transporting compound having the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is a compound represented by the following general formula (A) < The charge transport film according to 1>.

[In the general formula (A), R ³¹ , R ³² and R ³³ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, and a substituted group. Or an unsubstituted aryl group having 6 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, n31, n32 and n33 each represents an integer of 0 to 6. L ³¹ and L ³² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, and a combination thereof, and n37 , N38 represents 0 to 1. R ³⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ³⁶ represents 1 carbon atom. Represents an alkyl group of -12 and an aryl group of 6-20 carbon atoms. n35 and n36 represent an integer of 0 to 6, and n35 and n36 are not 0 at the same time. ]
Since the compound has a high oxidation potential, it has an advantage of excellent oxidation stability.
<3> The charge transporting compound having the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is a compound represented by the following general formula (B) < The charge transport film according to 1>.

[In the general formula (B), R ⁴¹ , R ⁴² and R ⁴³ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, or Represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n41, n42 and n43 each represents an integer of 0 to 6, and n40 represents an integer of 0 to 2. R ⁴⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. L ⁴¹ and L ⁴² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, and a combination thereof, and n47 , N48 represents 0 to 1. R ⁴⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁴⁶ represents 1 carbon atom. Represents an alkyl group of -12 and an aryl group of 6-20 carbon atoms. n45 and n46 represent an integer of 0 to 6, and n45 and n46 are not 0 at the same time. ]
Since the compound has a conjugated chain in the molecule, the compound has an advantage that it has good hole mobility and is suitable for a hole transport material.
<4> The charge transporting compound having the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is a compound represented by the following general formula (C) < The charge transport film according to 1>.

[In the general formula (C), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon. Represents an alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n51, n52, n53, and n54 each represents an integer of 0 to 5, and n55 and n56 each represents 0 to 4 Represents an integer. L ⁵⁶ represents a single bond or a divalent linking group. L ⁵¹ and L ⁵² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, and a combination thereof, and n57 , N58 represents 0 to 1. R ⁵⁷ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁵⁸ represents 1 carbon atom. Represents an alkyl group of -12 and an aryl group of 6-20 carbon atoms. n59 and n60 represent an integer of 0 to 6, and n59 and n60 are not 0 at the same time. ]
The compound has an advantage of excellent charge mobility in an embodiment in which L ⁵⁶ is a single bond, and in an embodiment in which L ⁵⁶ is a divalent linking group, the compound has excellent oxidation stability due to a high oxidation potential. Have advantages.
<5> The charge transporting compound having the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is a compound represented by the following general formula (D) < The charge transport film according to 1>.

[In the general formula (D), R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number 1 to 20 represents an alkenyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n61, n62, n63, and n64 each represents an integer of 0 to 5, and n65 and n66 each represents an integer of 0 to 4. . L ⁶¹ and L ⁶² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, and a combination thereof, and n67 , N68 represents 0 to 1. R ⁶⁷ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁶⁸ represents 1 carbon atom. Represents an alkyl group of -12 and an aryl group of 6-20 carbon atoms. n69 and n70 represent an integer of 0 to 6, and n69 and n70 are not 0 at the same time. ]
The compound has an advantage of good charge mobility and excellent thermal stability of the formed cured film.
<6> An organic EL device comprising the charge transport film according to any one of <1> to <5>.
<7> An organic photoelectric conversion element comprising the charge transport film according to any one of <1> to <5>.
<8> An electrophotographic photosensitive member comprising the charge transport film according to any one of <1> to <5>.
<9> The electrophotographic photosensitive member according to claim 9, wherein the charge transport film according to any one of <1> to <5> is located in an outermost surface layer.
<10> A coating film preparation step of preparing a coating film in which a charge transporting compound having a partial structure represented by the general formula (1) and a partial structure represented by the general formula (2) and a polymerization initiator are mixed. The method for producing a charge transport film according to any one of <1> to <5>, further comprising: a crosslinked product forming step of heating the coating film to obtain a crosslinked product.
<11> The method for producing a charge transport film according to <10>, wherein the cross-linked product forming step is performed under a condition where an oxygen concentration on the surface of the coating film is 200 ppm or more.
<12> A charge transporting compound represented by the following general formula (A) or the following general formula (B).

[In the general formula (A), R ³¹ , R ³² and R ³³ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, and a substituted group. Or an unsubstituted aryl group having 6 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, n31, n32 and n33 each represents an integer of 0 to 6. L ³¹ and L ³² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, and a combination thereof, and n37 , N38 represents 0 to 1. R ³⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ³⁶ represents 1 carbon atom. Represents an alkyl group of -12 and an aryl group of 6-20 carbon atoms. n35 and n36 represent an integer of 0 to 6, and n35 and n36 are not 0 at the same time.]

[In the general formula (B), R ⁴¹ , R ⁴² and R ⁴³ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, and a substituted group. Alternatively, it represents an unsubstituted aryl group having 6 to 20 carbon atoms, n41, n42 and n43 each represents an integer of 0 to 6, and n40 represents an integer of 0 to 2. R ⁴⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. L ⁴¹ and L ⁴² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, and a combination thereof, and n47 , N48 represents 0 to 1. R ⁴⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁴⁶ represents 1 carbon atom. Represents an alkyl group of -12 and an aryl group of 6-20 carbon atoms. n45 and n46 represent an integer of 0 to 6, and n45 and n46 are not 0 at the same time. ]
<13> A charge transporting compound represented by the following general formula (C) or general formula (D).

[In the general formula (C), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon. Represents an alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n51, n52, n53, and n54 each represents an integer of 0 to 5, and n55 and n56 each represents 0 to 4 Represents an integer. L ⁵⁶ represents a single bond or a divalent linking group. L ⁵¹ and L ⁵² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, and a combination thereof, and n57 , N58 represents 0 to 1. R ⁵⁷ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁵⁸ represents 1 carbon atom. Represents an alkyl group of -12 and an aryl group of 6-20 carbon atoms. n59 and n60 represent an integer of 0 to 6, and n59 and n60 are not 0 at the same time. ]

[In the general formula (D), R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number 1 to 20 represents an alkenyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n61, n62, n63 and n64 each represents an integer of 0 to 5, and n65 represents an integer of 0 to 4. L ⁶¹ and L ⁶² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, or a combination thereof, and n67 , N68 represents 0 to 1. R ⁶⁷ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁶⁸ represents carbon. An alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms is represented. n69 and n70 represent an integer of 0 to 6, and n69 and n70 are not 0 at the same time. ]

The charge transporting compounds represented by the general formula (A) to the general formula (D) are novel compounds, and these compounds exhibit excellent electrotransport properties and have crosslinkable groups included in these compounds, that is, the above-described compounds. The crosslinkable group which is the partial structure represented by the general formula (2) exhibits excellent crosslinkability in the presence of oxygen.
If the novel crosslinkable charge transporting compound and its production method of the present invention are used, it can be polymerized even in the presence of oxygen, has excellent mechanical strength (scratch resistance, abrasion resistance), and has good electrical properties and durability. It is possible to provide a charge transport film that can be held and laminated.

According to the present invention, the polymerization proceeds sufficiently even in the presence of oxygen, can be easily produced, has excellent mechanical strength, can be laminated and applied, and has excellent electrical properties and durability for a long time. A film can be provided, and by applying this charge transport film, an organic EL element, an organic photoelectric conversion element, and an electrophotographic photoreceptor excellent in electrical characteristics and durability can be provided.
Furthermore, according to the present invention, it is possible to provide a method for forming a charge transport film that can easily produce a charge transport film having the above-described advantages.
Furthermore, according to this invention, the novel crosslinkable charge transport material useful for the said charge transport film | membrane of this invention can be provided.

1 is a schematic partial cross-sectional view showing a preferred embodiment of an electrophotographic photosensitive member of the present invention. FIG. 5 is a schematic partial cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention. FIG. 5 is a schematic partial cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention.

Hereinafter, the charge transport film of the present invention, its production method, the novel charge transport material and its application will be described in order.
<Charge transporting compound having a partial structure represented by the general formula (1) and a partial structure represented by the general formula (2)>
The crosslinkable charge transport material used in the present invention is a charge transport compound having a partial structure represented by the general formula (1) and a partial structure represented by the general formula (2) (hereinafter referred to as specific charge transport as appropriate). The charge transport film of the present invention can be obtained by using a composition containing this as a crosslinked product obtained by forming a crosslinked structure by applying energy such as heating.

In the general formula (1), Ar ¹¹ and Ar ¹² each independently represent a substituted or unsubstituted aryl group, and n represents 1 or 2. When n is 1, R ¹¹ represents a substituent selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group. Q represents a single bond or an n-valent linking group, and does not exist when n is 1. When n is 2, R ¹¹ is a substituted or unsubstituted arylene group obtained by removing one hydrogen atom from the above-described substituent, a substituted or unsubstituted alkelene group, and a substituted or unsubstituted alkynylene. This is a divalent linking group selected from the group consisting of groups, and the partial structure represented by the general formula (1) is linked to Q via R ¹¹ which is a linking group.

In the general formula (2), R ²¹ and R ²² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted acyl group. The bridging group represented by the general formula (2) is bonded to the partial structure represented by the general formula (1) via one of R ²¹ and R ²² , and in that case, the substituent R corresponding to the bonding site A linking group in which one hydrogen atom is removed from ²¹ or R ²² is linked to the partial structure represented by the general formula (1). One molecule of the charge transport material of the present invention may have 1 to 6 polymerizable partial structures represented by the general formula (2).
The partial structure (crosslinkable group) represented by the general formula (2) is excellent in polymerizability in the presence of oxygen, and by introducing it, the novel charge transport material of the present invention described later allows the oxygen atom to be used in an oxygen atmosphere. However, a high-strength cured film is formed.

The aryl group represented by Ar ¹¹ , Ar ¹² and R ¹¹ in the general formula (1) is preferably an aryl having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. A group such as phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl and the like. The aryl group represented by Ar ¹¹ and Ar ¹² may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 30 carbons, more preferably 1 to 20 carbons, and particularly preferably C1-C10, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably). Has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms. For example, vinyl, allyl, 2-butenyl, 3-pentenyl, styryl, 1,1-diphenylethene, phenyl Butadiene, 1,1-diphenylbutadiene, etc.), an alkynyl group (preferably having 2 to 30 carbon atoms) Preferably they are C2-C20, Most preferably, it is C2-C10, for example, a propargyl, 3-pentynyl etc. are mentioned, for example, An aryl group (Preferably C6-C30, More preferably C6-C 20, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl, and the like, amino groups (preferably having 0 to 30 carbon atoms, more preferably carbon atoms). A number of 0 to 20, particularly preferably a carbon number of 0 to 10, including an alkylamino group, an arylamino group, and a heterocyclic amino group, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino Etc.), an alkoxy group (preferably having 1 to 30 carbon atoms, More preferably, it is C1-C20, Most preferably, it is C1-C10, for example, a methoxy, an ethoxy, butoxy, 2-ethylhexyloxy etc.), an aryloxy group (preferably C6-C30). More preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), an aromatic heterocyclic oxy group (preferably C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy etc. are mentioned.

  An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably having a carbon number). 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl, and acyloxy groups (preferably 2 to 30 carbon atoms, more preferably carbon atoms). 2 to 20, particularly preferably 2 to 10 carbon atoms, for example, acetoxy, benzoyloxy An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonylamino), aryloxycarbonylamino group (Preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), sulfonylamino group (preferably 1 carbon atom) To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl groups (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methyl And carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Methylthio, ethylthio, etc.), ants Ruthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio and the like. ).

Aromatic heterocyclic thio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolyl And sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). ), Sulfinyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.) A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example diethyl phosphorus Acid amide, phenylphosphoric acid amide, etc.), hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxam An acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 1 to 12, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, Specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, ben Oxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, Examples thereof include trimethylsilyl and triphenylsilyl). These substituents may be further substituted.
Preferred examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, and a heterocyclic group, and particularly preferred are an alkyl group, an alkenyl group, an aryl group, and a diarylamino group. Is mentioned.

The alkenyl group represented by R ¹¹ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as vinyl, allyl, 2-butenyl, and 3-pentenyl. , Styryl, 1,1-diphenylethene, phenylbutadiene, 1,1-diphenylbutadiene and the like, and may be further substituted with the above-described substituents. The alkynyl group represented by R ¹¹ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. For example, propargyl, 3-pentynyl, phenylacetylinyl, etc. Can be mentioned.

  The partial structure represented by the general formula (2) may be directly bonded to the partial structure represented by the general formula (1) or may be bonded via a linking group. Preferred examples of the linking group in the case of intervening include an alkylene group, an arylene group, -O-, -COO-, -CO- group, and a linking group composed of a combination thereof, and preferably has 1 to 12 carbon atoms. Represents a linking group composed of an alkylene group, an arylene group having 6 to 12 carbon atoms, -O-, -COO-, -CO- group, and a combination thereof, and more preferably a linking group represented by the following specific examples. Represents. n12 represents 0 to 1;

In the bridging group represented by the general formula (2), R ²¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, preferably an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms. ~ 20 aryl group, more preferably an alkyl group having 1 to 12 carbon atoms (specifically, methyl, ethyl, iso-propyl, tert-butyl, 2-ethylhexyl, n-octyl, n-decyl, cyclopropyl, etc.) ), An aryl group having 6 to 14 carbon atoms (specifically, phenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl, etc.), particularly preferably an alkyl group having 1 to 6 carbon atoms.

R ²² has the same meaning as R ²¹ , but preferably —OR ²² is an alkoxy group, an aryloxy group, or an acyloxy group, more preferably an alkoxy group having 1 to 20 carbon atoms, or a carbon number. An aryloxy group having 6 to 20 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms (specifically, methoxy, ethoxy, iso-propyloxy, tert-butyloxy, n-octyl) Oxy, n-decyloxy, cyclopropyloxy, etc.), C1-14 aryl groups (specifically phenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl, etc.), C1-12 acyloxy groups (Specifically acetyloxy, benzoyloxy, pivaloyloxy, etc.), especially preferred Is an alkoxy group, an acyloxy group having 2 to 6 carbon atoms having 1 to 6 carbon atoms.
Here, when the general formula (2) is connected to the partial structure represented by the general formula (1) via —OR ²² , R ²² is removed, and a mode of connecting via an oxygen atom can be taken. . Further, when the general formula (2) is connected to the partial structure represented by the general formula (1) via ^{-OR 21, R 21} represents a linking group described above.
The number of the crosslinkable partial structures represented by the general formula (2) introduced into the general formula (1) is 1 to 6, preferably 1 to 4, and particularly preferably 2 to 4.

  The charge transporting compound having the partial structure represented by the general formula (1) and the partial structure represented by the general formula (2) is preferably a compound represented by the general formula (A) or the general formula (B). Particularly preferred is a compound represented by formula (C) or formula (D). The compound represented by the general formula (A) is obtained by introducing a crosslinkable group represented by the general formula (2) that can be polymerized in the presence of oxygen into triphenylamine having excellent hole transport properties. The group is linked to the phenyl ring of triphenylamine or to a substituent on triphenylamine, either directly or through a linking group as described above.

The alkyl group represented by R ³¹ , R ³² , and R ³³ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably And methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl and cyclohexyl groups. The alkenyl group represented by R ³¹ , R ³² and R ³³ is a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group as a substituent. Represents styryl, 1,1-diphenylethene, phenylbutadiene, or 1,1-diphenylbutadiene which may have The aryl group represented by R ³¹ , R ³² , and R ³³ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably a phenyl group that may be substituted by an alkyl group having 1 to 6 carbon atoms. , Phenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl, which may be substituted by a diarylamino group. The diarylamino group represented by R ³¹ , R ³² , and R ³³ has 12 to 20 carbon atoms, and the aryl group that the diarylamino group has is preferably a phenyl group, a naphthyl group, an anthranyl group, or a phenanthranyl group. n31, n32 and n33 each represent an integer of 0 to 6, preferably an integer of 0 to 3, and particularly preferably an integer of 0 to 2. L ³¹ and L ³² each represent a linking group composed of an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, or a combination thereof. The range is the same as L described in the general formula (1). n37 and n38 are 0 to 1. R ³⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, preferably 1 to 1 carbon atom. 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, more preferably alkyl groups having 1 to 12 carbon atoms (specifically, methyl, ethyl, iso-propyl, tert-butyl, 2-ethylhexyl, n-octyl) , N-decyl, cyclopropyl, etc.), aryl groups having 1 to 14 carbon atoms (specifically, phenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl, etc.), particularly preferably alkyl having 1 to 6 carbon atoms It is a group. R ³⁶ represents an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 20 carbon atoms, n35 and n36 represent an integer of 0 to 6, and n35 and n36 are not 0 at the same time.

  The compound represented by the general formula (A) particularly preferably takes an embodiment represented by the general formula (C).

The alkyl groups represented by R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, more preferably 1 carbon atom. To 6 alkyl groups, particularly preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n- Hexyl and cyclohexyl groups. The alkenyl group represented by R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ is a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, and more preferably a substituent having a carbon number. It represents 1 to 4 alkyl groups, styryl optionally having an alkoxy group, 1,1-diphenylethene, phenylbutadiene, and 1,1-diphenylbutadiene. The aryl group represented by R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples thereof include phenyl which may be substituted by an alkyl group, phenyl which may be substituted by a diarylamino group, p-methylphenyl, biphenyl, naphthyl, anthranyl and phenanthryl. n51, n52, n53, and n54 each represent an integer of 0 to 5, and n55 and n56 each represents an integer of 0 to 4. L ⁵¹ and L ⁵² represent an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —O—, —COO—, —CO— group, and a linking group composed of a combination thereof, and is preferable The range is the same as L described in the general formula (1). n57 and n58 are 0 to 1. R ⁵⁷ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁵⁸ represents 1 carbon atom. Represents an alkyl group of -12 and an aryl group of 6-20 carbon atoms. n59 and n60 represent an integer of 0 to 6, and n59 and n60 are not 0 at the same time.
L ⁵⁶ represents a single bond or a divalent linking group, and preferably a divalent substituent selected from a methylene group, an ethylene group, a phenylene group, and a vinylene group, which may have a single bond or a substituent. In addition, it is a divalent linking group formed by combining two or more of the divalent substituents.
Preferred examples of the substituent that can be introduced when the divalent linking group has a substituent include an alkyl group, an alkoxy group, and an aryl group. L ⁵⁶ is more preferably a single bond or a methylene group, ethylene group or phenylene group which may have a substituent, and the substituent is an alkyl group.
Another preferred embodiment of the charge transport compound according to the present invention is a compound represented by the general formula (B).

The alkyl groups represented by R ⁴¹ , R ⁴² and R ⁴³ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, Preferred are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl and cyclohexyl groups. The alkenyl groups represented by R ⁴¹ , R ⁴² and R ⁴³ are each independently a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms as a substituent. And styryl, 1,1-diphenylethene, phenylbutadiene, and 1,1-diphenylbutadiene which may have an alkoxy group. The aryl groups represented by R ⁴¹ , R ⁴² and R ⁴³ each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n41, n42 and n43 each represents an integer of 0 to 6, n40 represents an integer of 0 to 2.
R ⁴⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Examples of the substituent that can be introduced when the alkyl group or aryl group has a substituent include the same substituents as those in R ^{41 to} R ⁴¹ .
L ⁴¹ and L ⁴² each represent a linking group composed of an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, or a combination thereof. The range is the same as L described in the general formula (1). n47 and n48 each represents 0 to 1; R ⁴⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁴⁶ represents 1 carbon atom. Represents an alkyl group of -12 and an aryl group of 6-20 carbon atoms. n45 and n46 represent an integer of 0 to 6, and n45 and n46 are not 0 at the same time.
Another preferred embodiment of the charge transport compound according to the present invention is a compound represented by the general formula (D).

In the general formula (D), R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number. Represents an alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n61, n62, n63 and n64 each represents an integer of 0 to 5, and n65 and n66 each represents an integer of 0 to 4 Represents. L ⁶¹ and L ⁶² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, and a combination thereof, and n67 , N68 represents 0 to 1. R ⁶⁷ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁶⁸ represents 1 carbon atom. Represents an alkyl group of -12 and an aryl group of 6-20 carbon atoms. n69 and n70 represent an integer of 0 to 6, and n69 and n70 are not 0 at the same time.
Specific examples of the charge transporting compound represented by any one of the general formula (A), general formula (B), general formula (C), and general formula (D) [Exemplary Compound (H-A1)] To (H-D4)], the present invention is not limited to the following specific examples.

Next, a method for synthesizing the specific charge transporting compound according to the present invention will be described.
The specific charge transporting compound (hole transporting material) according to the present invention can be synthesized using a known method. For example, first, a triarylamine compound having an OH group or COORa (Ra: hydrogen, alkyl group, aryl group) via a linking group is synthesized by a known synthesis method. Examples of this synthesis method include the methods described in JP-A-2008-198989 and JP-A-2000-147814. Next, an OH group or COORa (Ra: hydrogen, alkyl group, aryl group) existing via a linking group of the obtained triarylamine compound is reacted according to the following formula to introduce a crosslinkable group, A specific charge transporting compound having a crosslinkable group can be synthesized. In the following formulae, R ²¹ and R ²² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted acyl group. X represents a halogen atom.

  The specific charge transporting compound is useful for forming a charge transporting film because it can sufficiently polymerize in the presence of oxygen and form a cured film having a charge transporting property having excellent mechanical strength by applying energy. Applications to various devices that require charge transportability are possible. Moreover, among the compounds, compounds having structures represented by the general formulas (A) to (D) are novel compounds.

<Charge transport film and production method thereof>
Next, the charge transport film of the present invention and the manufacturing method thereof will be described.
The method for producing a charge transport film according to the present invention comprises a coating film preparation step for preparing a coating film containing the specific charge transporting compound and a polymerization initiator, and a crosslinked product formation in which the coating film is heated to obtain a crosslinked product. And a process for producing a charge transport film.
In the production method of the present invention, the crosslinked product forming step is carried out with the oxygen concentration on the coating film surface because it is cured with high sensitivity due to the specific charge transporting compound of the present invention and is not easily affected by oxygen inhibition. It can be performed under the condition of 200 ppm or more.
(Coating film production process)
Examples of the method for forming a charge transport film using the specific charge transport compound used in the present invention include a method in which the specific charge transport compound is applied by a wet film forming method. By applying a wet film-forming method to film formation of the charge transport film, it is possible to easily apply a large area, so that an element can be efficiently produced, which is preferable from the viewpoint of cost reduction.

Examples of the wet film forming method applicable to the present invention include dipping method, spin coating method, dip coating method, casting method, die coating method, roll coating method, bar coating method, gravure coating method, spray coating method, and ink jet method. It can be used. Which of these film forming methods is applied may be appropriately selected according to materials such as an organic compound contained in the charge transport film to be formed.
When the film is formed by the wet film forming method, the drying step may be performed after the coating film is formed. In the drying step, conditions such as temperature and pressure are selected so that the coating layer formed by the wet film forming method is not damaged.

The coating solution for forming a charge transport film used in the wet film forming method (hereinafter, simply referred to as a coating solution as appropriate) contains at least the specific charge transporting compound according to the present invention and a polymerization initiator, and usually further if desired. It contains a coating film forming material such as an organic compound and other additives used in combination, and a solvent for dissolving or dispersing it.
The solvent used for preparing the coating solution for forming the charge transport film is not particularly limited, and may be selected according to various compounds contained in the coating solution.
Specific examples of the solvent include halogen solvents (chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone, methyl isobutyl ketone, Diisobutyl ketone, cyclohexanone, isophorone, menthone, etc.), aromatic solvents (benzene, toluene, xylene, decalin, naphthalene, biphenyl, alkyl-substituted biphenyl, etc.), ester solvents (ethyl acetate, n-propyl acetate, n-butyl acetate) , Methyl propionate, ethyl propionate, γ-butyrolactone, diethyl carbonate, etc.), ether solvents (tetrahydrofuran, dioxane, etc.), alcohols (for example, monohydric alcohols or dihydric alcohols, Tanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, etc. ), Amide solvents (dimethylformamide, dimethylacetamide, etc.), dimethyl sulfoxide, water and the like.
The solid content with respect to the solvent in the coating solution is not particularly limited, and the viscosity of the coating solution can be arbitrarily selected according to the film forming method.
Two or more organic solvents may be mixed and used. When mixing 2 or more types, it is preferable that a boiling point of at least one solvent is 80 degreeC or more and 300 degrees C or less, More preferably, a boiling point is 100 degreeC or more and 250 degrees C or less. A boiling point within this range is preferable for forming a uniform film.
The solvent is preferably purified. As the solvent purification method, specifically, (1) column purification treatment of silica gel, alumina, cationic ion exchange resin, anionic ion exchange resin, etc., (2) anhydrous sodium sulfate, anhydrous calcium sulfate, magnesium sulfate , Strontium sulfate, barium sulfate, barium oxide, calcium oxide, magnesium oxide, molecular sieves, dehydration treatment of zeolite, (3) distillation treatment, (4) bubbling treatment with inert gas (nitrogen, argon), (4) Examples of the method include removal of impurities by filtration, centrifugal sedimentation, and the like, and any method can be used. More preferred are (1) column purification treatment and (2) purification treatment by dehydration treatment.

Next, each component contained in the charge transport film forming coating solution will be described.
(Specific charge transport compound)
The coating liquid according to the present invention contains the specific charge transporting compound of the present invention. These can be used by arbitrarily selecting the aforementioned compounds.
These specific charge transporting compounds may contain only one kind in the coating solution, or two or more kinds may be used in combination.
The content of the specific charge transporting compound in the coating solution (or charge transport film) is preferably 30% by mass or more, more preferably 40 to 100% by mass, and still more preferably, based on the total solid content. It is used at 50 to 100% by mass.

The charge transport film containing the specific charge transporting compound of the present invention is formed by forming a cross-linked structure by the cross-linked product forming step described below, and in the coating solution for the purpose of efficiently forming a cross-linked product. A polymerization initiator is contained together with the specific charge transporting compound.
Here, the polymerization initiator used is not particularly limited as long as radicals generated by heat and other active species react with the polymerizable functional group in the specific charge transporting compound.
Examples of the thermal polymerization initiator that can be used include azobis compounds, peroxides, hydroperoxides, redox catalysts, and the like.
More specifically, inorganic peroxides such as potassium persulfate and ammonium persulfate; t-butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroper Organic peroxides such as oxide and dicumyl peroxide; 2,2′-azobisisobutyrate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) ), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobiscyanovaleric acid, 1,1′-azobis ( 1-acetoxy-1-phenylethane), dimethyl 2,2′-azobis (2-methylpropionate) ), 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis {2-methyl-N- [1,1′-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like. These initiators are preferably oil-soluble and particularly preferably azobis compounds. Accordingly, examples of particularly preferred thermal polymerization initiators include 2,2′-azobisisobutyrate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile). ), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4,4-trimethylpentane, 1,1′-azobis (1-acetoxy-1-phenylethane), Examples thereof include dimethyl 2,2′-azobis (2-methylpropionate).

  The content of the thermal polymerization initiator in the solid content in the coating solution for forming a charge transport film is preferably 0.1 to 10% by mass, and more preferably 0.2 to 8% by mass.

(Binder polymer)
The coating liquid for forming a charge transport film of the present invention may contain a polymer binder. Examples of the polymer binder include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, Polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, silicone resin, polyvinyl butyral, polyvinyl acetal, etc. can be used is there. When a polymer binder is contained, it can be easily applied and formed in a large area by a wet film forming method.

(Other additives)
The coating liquid for forming a charge transport film according to the present invention includes various additives (for example, antioxidants) depending on the purpose in addition to a specific charge transport compound, a polymerization initiator, a solvent and a binder polymer used in combination as required. , Charge transporting agent, film quality adjusting agent, etc.).
A coating solution containing these is formed into a film by the above-described method such as coating. The coating film is formed on any substrate on which a charge transport film is used. Depending on the purpose of the charge transport film, it may be formed directly on the support or may be formed on the surface of another formed layer.
The thickness of the coating film is also appropriately selected according to the purpose. For example, in the case of an organic electroluminescent element or a photoelectric conversion element, it is preferably about several nm to 1 μm, and preferably 1 μm to 100 μm for electrophotographic applications.

(Crosslinked product forming step)
Next, the formed coating film is heated to perform a crosslinked product forming step for obtaining a crosslinked product. A known method can be arbitrarily applied as the heating method. From the viewpoint of uniform formation of the crosslinked product, it is preferable to apply a temperature of 70 ° C. to 200 ° C. and heat for 1 minute to 2 hours.
In the present invention, the coating film containing the specific charge transporting compound and the polymerization initiator can be cured by heating in either deoxygenation or in the presence of oxygen, but the equipment load for deoxygenation is reduced. From this point of view, it is preferable that the resin can be sufficiently cured even in the presence of oxygen. Since the specific charge transporting compound of the present invention can be cured with high sensitivity, the production method of the present invention has an advantage that the coating film can be crosslinked and cured even under a condition where the oxygen concentration of the coating film surface is 200 ppm or more. Have.
The charge transport film thus formed is excellent in charge transport property, has good curability and is a high-strength crosslinked film, and therefore can be suitably used for various applications.

(Organic electroluminescence device)
Next, a light-emitting element using a charge transport film which is one of application modes of the charge transport film of the present invention will be described. First, the organic electroluminescent element will be described.
The organic electroluminescent element of the present invention has an anode and a cathode on a substrate, and an organic layer including a light emitting layer between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.
The light emitting device of the present invention usually emits light when a DC voltage (which may include an AC component) or a DC current of about 2 to 40 volts is applied between the transparent electrode and the back electrode. In driving the light emitting device of the present invention, JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234585, and JP-A-8-2441047. , US Pat. Nos. 5,828,429, 6,022,308, and Japanese Patent No. 2,784,615 can be used. Hereinafter, although each layer which comprises the light emitting laminated body used by this invention is explained in full detail, this invention is not limited by them.

The organic electroluminescence device of the present invention is a device comprising at least one layer of the charge transport film of the present invention which is a cross-linked product of the specific charge transporting compound, preferably at least one layer between the anode and the light emitting layer or the light emitting layer is generally used. The charge transport compound represented by formula (1) is crosslinked, and more preferably, at least one layer between the anode and the light emitting layer is crosslinked by the charge transport compound represented by formula (1). .
In the present invention, the organic layer is preferably laminated in the order of the hole transport layer, the light emitting layer, and the electron transport layer from the anode side. Further, a hole injection layer is provided between the hole transport layer and the anode, and / or an electron transporting intermediate layer is provided between the light emitting layer and the electron transport layer. Further, a hole transporting intermediate layer may be provided between the light emitting layer and the hole transport layer, and similarly, an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of layers.
(A) Substrate The substrate used in the present invention is preferably made of a material that does not allow moisture to permeate or a material that has a very low moisture permeability. The material preferably does not scatter or attenuate light emitted from the organic compound layer. Specific examples thereof include zirconia stabilized yttrium (YSZ), inorganic materials such as glass, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and other polyesters, polystyrene, polycarbonate, polyethersulfone, polyarylate, allyl diglycol carbonate, Examples thereof include organic materials such as polyimide, polycycloolefin, norbornene resin, and poly (chlorotrifluoroethylene). Among them, an organic material that is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation and workability, and has low air permeability and low moisture absorption can be particularly preferably used. The substrate may be formed of a single material or two or more materials. The material for the substrate may be appropriately selected according to the transparent electrode material. For example, when the transparent electrode is indium tin oxide (ITO), it is preferable to use a material having a small difference in lattice constant from ITO.

  The shape, structure, size, and the like of the substrate can be appropriately selected according to the use and purpose of the light emitting element. The shape is generally plate-like. The structure may be a single layer structure or a laminated structure. The substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the light emitting layer.

  A moisture permeation preventing layer (gas barrier layer) may be provided on the electrode-side surface of the substrate, the surface opposite to the electrode, or both. As a material constituting the moisture permeation preventing layer, it is preferable to use an inorganic material such as silicon nitride or silicon oxide. The moisture permeation preventing layer can be formed by a high frequency sputtering method or the like. Moreover, you may provide a hard-coat layer and an undercoat layer in a base material as needed.

(B) Transparent electrode Normally, the transparent electrode functions as an anode for supplying holes to the organic compound layer, but it can also function as a cathode. In this case, the back electrode functions as an anode. Hereinafter, the case where a transparent electrode is used as an anode will be described.

  The shape, structure, size, and the like of the transparent electrode are not particularly limited, and can be appropriately selected according to the use and purpose of the light emitting element. As a material for forming the transparent electrode, a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used, and a material having a work function of 4 eV or more is preferably used. Specific examples include tin oxide doped with antimony (ATO), tin oxide doped with fluorine (FTO), semiconductive metal oxides (tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), zinc oxide). Indium (IZO, etc.), metals (gold, silver, chromium, nickel, etc.), mixtures or laminates of these metals and conductive metal oxides, inorganic conductive substances (copper iodide, copper sulfide, etc.), organic conductivity Materials (polyaniline, polythiophene, polypyrrole, etc.) and laminates of this and ITO.

  The transparent electrode may be formed on the substrate by a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as CVD or plasma CVD method. it can. The formation method may be appropriately selected in consideration of suitability with the transparent electrode material. For example, when ITO is used as the material for the transparent electrode, a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like may be used. Further, when an organic conductive material is used as the material for the transparent electrode, a wet film forming method may be used.

  The patterning of the transparent electrode can be performed by chemical etching using photolithography, physical etching using a laser, or the like. Alternatively, patterning may be performed by vacuum deposition using a mask, sputtering, a lift-off method, a printing method, or the like.

  The formation position of the transparent electrode may be appropriately selected according to the use and purpose of the light-emitting element, but is preferably formed on the substrate. At this time, the transparent electrode may be formed on the entire surface of the substrate or only on a part thereof.

The thickness of the transparent electrode may be appropriately selected according to the material, but is usually 10 nm to 50 μm, preferably 50 nm to 20 μm. The resistance value of the transparent electrode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. The transparent electrode may be colorless and transparent or colored and transparent. In order to extract light emission from the transparent electrode side, the transmittance is preferably 60% or more, and more preferably 70% or more. The transmittance can be measured according to a known method using a spectrophotometer.

  Further, electrodes described in detail in “New development of transparent conductive film” (supervised by Yutaka Sawada, published by CMC, 1999) and the like can also be applied to the present invention. In particular, when using a plastic substrate having low heat resistance, it is preferable to use ITO or IZO as the transparent electrode material and to form a film at a low temperature of 150 ° C. or lower.

(C) Back electrode Normally, the back electrode has a function as a cathode for injecting electrons into the organic compound layer, but can also function as an anode. In this case, the transparent electrode functions as a cathode. Hereinafter, a case where the back electrode is a cathode will be described.

  The shape, structure, size, and the like of the back electrode are not particularly limited, and can be appropriately selected according to the use and purpose of the light emitting element. As a material for forming the back electrode, a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used, and a material having a work function of 4.5 eV or less is preferably used. Specific examples include alkali metals (Li, Na, K, Cs, etc.), alkaline earth metals (Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloy, lithium-aluminum alloy, magnesium-silver. Examples include alloys, indium, rare earth metals (ytterbium, etc.). These may be used alone, but in order to achieve both stability and electron injection properties, it is preferable to use two or more in combination. Among these materials, alkali metals and alkaline earth metals are preferable from the viewpoint of electron injecting property, and materials mainly composed of aluminum are preferable from the viewpoint of storage stability. Here, the material mainly composed of aluminum refers to aluminum alone, an alloy or a mixture of aluminum and 0.01 to 10% by mass of an alkali metal or alkaline earth metal (lithium-aluminum alloy, magnesium-aluminum alloy, etc.). . As materials for the back electrode, those described in detail in JP-A-2-15595, JP-A-5-121172 and the like can be used.

  The back electrode can be formed by a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as CVD or plasma CVD method. The formation method may be appropriately selected in consideration of suitability with the back electrode material. For example, when two or more metals are used as the back electrode material, the materials can be formed by sputtering simultaneously or sequentially.

  The back electrode can be patterned by chemical etching using photolithography or the like, physical etching using a laser, or the like. Alternatively, patterning may be performed by vacuum deposition using a mask, sputtering, a lift-off method, a printing method, or the like.

  The formation position of the back electrode may be appropriately selected according to the use and purpose of the light emitting element, but is preferably formed on the organic compound layer. At this time, the back electrode may be formed on the entire surface of the organic compound layer or only on a part thereof. Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or the like may be provided between the back electrode and the organic compound layer with a thickness of 0.1 to 5 nm. The dielectric layer can be formed by a vacuum deposition method, a sputtering method, an ion plating method, or the like.

  The thickness of the back electrode may be appropriately selected depending on the material, but is usually 10 nm to 5 μm, preferably 50 nm to 1 μm. The back electrode may be transparent or opaque. The transparent back electrode may be formed by thinly forming the above-described material layer to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

(D) Light emitting layer In the light emitting device of the present invention, the light emitting layer contains a phosphorescent compound. The phosphorescent compound used in the present invention is not particularly limited as long as it is a compound that can emit light from triplet excitons. As the phosphorescent compound, an orthometalated complex or a porphyrin complex is preferably used, and an orthometalated complex is more preferably used. Of the porphyrin complexes, a porphyrin platinum complex is preferred. The phosphorescent compounds may be used alone or in combination of two or more.

  The orthometalated complex referred to in the present invention is a material described in Akio Yamamoto, “Organic Metal Chemistry Fundamentals and Applications,” pages 150 and 232, Houhuabosha (1982), H.C. Yersin's “Photochemistry and Photophysics of Coordination Compounds”, pages 71-77 and pages 135-146, Springer-Verlag (1987), etc. The ligand forming the ortho-metalated complex is not particularly limited, but a 2-phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2- (2-thienyl) pyridine derivative, a 2- (1-naphthyl) pyridine derivative or A 2-phenylquinoline derivative is preferred. These derivatives may have a substituent. Moreover, you may have another ligand other than these essential ligands for ortho metalation complex formation. As the central metal forming the orthometalated complex, any transition metal can be used. In the present invention, rhodium, platinum, gold, iridium, ruthenium, palladium and the like can be preferably used. Of these, iridium is particularly preferable. An organic compound layer containing such an orthometalated complex is excellent in light emission luminance and light emission efficiency. Specific examples of the orthometalated complex are also described in paragraphs 0152 to 0180 of Japanese Patent Application No. 2000-254171.

  Although content in particular of the phosphorescence-emitting compound in a light emitting layer is not restrict | limited, For example, it is 0.1-70 mass%, and it is preferable that it is 1-20 mass%. If the content of the phosphorescent compound is less than 0.1% by mass or exceeds 70% by mass, the effect may not be sufficiently exhibited.

  In the present invention, the light emitting layer may contain a host compound, a hole transport material, an electron transport material, an electrically inactive polymer binder, and the like, if necessary.

  Host compounds include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives , Heterocyclic diesters such as carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives and naphthaleneperylene Carboxylic anhydride, phthalocyanine derivative, metal complex of 8-quinolinol derivative, metal phthalocyanine, metal complex having benzoxazole or benzothiazole as a ligand, polysilane compound, poly (N-vinylcarbazole) derivative, aniline copolymer , Conductive polymers such as thiophene oligomers and polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, and the like. A host compound may be used individually by 1 type, or may use 2 or more types together.

  The hole transport material is not particularly limited as long as it has any of the function of injecting holes from the anode, the function of transporting holes, and the function of blocking electrons injected from the cathode. It may be a molecular material or a polymer material. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, Conductive polymer such as thiophene oligomer, polythiophene, polythiophene derivative, polyphenylene derivative, polyphenylene vinylene derivative, polyfluor Ren derivatives and the like. These may be used alone or in combination of two or more. As the hole transporting material contained in the light emitting layer, the specific charge transporting compound of the present invention may be used.

  The electron transport material is not particularly limited as long as it has any of the function of injecting electrons from the cathode, the function of transporting electrons, and the function of blocking holes injected from the anode. For example, a triazole derivative , Oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthaleneperylene, etc. Ring tetracarboxylic anhydride, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal complexes with metallophthalocyanine, benzoxazole, benzothiazole, etc., aniline copolymers, thiophene oligomers, polythiophenes, etc. Conductive polymer, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives and the like can be used.

  As polymer binder, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, Polyurethane, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, silicone resin, polyvinyl butyral, polyvinyl acetal, etc. can be used. The light emitting layer containing the polymer binder can be easily applied and formed in a large area by a wet film forming method.

  The thickness of the light emitting layer is preferably 10 to 200 nm, and more preferably 20 to 80 nm. When the thickness exceeds 200 nm, the driving voltage may increase. When the thickness is less than 10 nm, the light emitting element may be short-circuited.

(E) Electron transport layer In the light-emitting device of the present invention, the above-described electron transport layer may contain the above-described polymer binder as necessary. The thickness of the electron transport layer is preferably 10 to 200 nm, and more preferably 20 to 80 nm. When the thickness exceeds 200 nm, the driving voltage may increase. When the thickness is less than 10 nm, the light emitting element may be short-circuited.

(F) Hole transport layer The light emitting element of this invention has a hole transport layer which consists of a hole transport material mentioned above, and a hole transport layer may contain the above-mentioned polymer binder. The light emitting device of the present invention may have a hole transport layer made of the specific charge transport compound described above, if necessary. Of the layers comprising the hole transport material of the present invention, at least one of the layers may be a coating film in which the hole transport material represented by the general formula (1) and a polymerization initiator are mixed. Manufactured by curing the film. The thickness of the hole transport layer is preferably 10 to 200 nm, more preferably 20 to 80 nm. When the thickness exceeds 200 nm, the driving voltage may increase. When the thickness is less than 10 nm, the light emitting element may be short-circuited.

(G) Others The light-emitting device of the present invention has a protective layer described in JP-A-7-85974, 7-192866, 8-22891, 10-275682, 10-106746, and the like. It may be. The protective layer is formed on the uppermost surface of the light emitting element. Here, the top surface refers to the outer surface of the back electrode when the base material, the transparent electrode, the organic compound layer, and the back electrode are laminated in this order, and the base material, the back electrode, the organic compound layer, and the transparent electrode in this order. When laminating, it refers to the outer surface of the transparent electrode. The shape, size, thickness and the like of the protective layer are not particularly limited. The material for forming the protective layer is not particularly limited as long as it has a function of suppressing intrusion or permeation of a light-emitting element such as moisture or oxygen into the element. Silicon, germanium oxide, germanium dioxide or the like can be used.

  The method for forming the protective layer is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular sensing epitaxy, cluster ion beam, ion plating, plasma polymerization, plasma CVD, laser CVD Thermal CVD method, coating method, etc. can be applied.

In addition, the light-emitting element is preferably provided with a sealing layer for preventing moisture and oxygen from entering. As a material for forming the sealing layer, a copolymer of tetrafluoroethylene and at least one comonomer, a fluorinated copolymer having a cyclic structure in the copolymer main chain, polyethylene, polypropylene, polymethyl methacrylate, polyimide, Polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, chlorotrifluoroethylene or a copolymer of dichlorodifluoroethylene and another comonomer, a water-absorbing substance having a water absorption of 1% or more, a water absorption of 0. 1% or less moisture-proof material, metal (In, Sn, Pb, Au, Cu, Ag, Al, Tl, Ni, etc.), metal oxide (MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, _{CaO, BaO, Fe 2 O 3} , Y 2 O 3, TiO 2 , etc.), metal fluorides (M _{F 2, LiF, AlF 3,} CaF 2 , etc.), liquid fluorinated carbon (perfluoroalkane, perfluoro amines, perfluoroether, etc.), the liquid fluorinated carbon as dispersed adsorbent moisture or oxygen, etc. Can be used.

(Photoelectric conversion element)
Next, details of the case where the charge transport film of the present invention is woken up by a photoelectric conversion element will be described.
The photoelectric conversion element of the present invention is a film in which an organic photoelectric conversion film sandwiched between at least two electrodes is made of a hole transporting photoelectric conversion material or an electron transporting photoelectric conversion material, and transports holes generated in the photoelectric conversion film Or at least one charge transport layer that transports electrons, and the charge transport film of the present invention is applied as a hole transport layer or an electron block layer.

First, the photoelectric conversion layer will be described.
[Organic pn compound]
Any organic p-type semiconductor (compound) constituting the hole-transporting photoelectric conversion film and any organic n-type semiconductor (compound) constituting the electron-transporting photoelectric conversion film may be used. Further, it may or may not have absorption in the ultraviolet region, visible region and infrared region, but is preferably a compound (organic dye) having absorption in the visible region. Further, a combination with a colorless p-type compound or an n-type compound, or an organic dye may be added thereto.

  The organic p-type semiconductor (compound) is a donor-type organic semiconductor (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound. For example, triarylamine compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, triphenylmethane compounds, carbazole compounds, polysilane compounds, thiophene compounds, phthalocyanine compounds, naphthalocyanine compounds, quinacridone compounds, cyanine compounds, merocyanine compounds, Oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), nitrogen-containing A metal complex having a heterocyclic compound as a ligand can be used. However, the present invention is not limited thereto, and as described above, any organic compound having an ionization potential smaller than that of the organic compound used as the n-type (acceptor) compound may be used as the donor organic semiconductor.

  Organic n-type semiconductors (compounds) are acceptor organic semiconductors (compounds), which are mainly represented by electron-transporting organic compounds and refer to organic compounds that easily accept electrons. More specifically, the organic compound having the higher electron affinity when two organic compounds are used in contact with each other. Therefore, as the acceptor organic compound, any organic compound can be used as long as it is an electron-accepting organic compound. For example, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), fullerenes, nitrogen atoms, oxygen atoms, sulfur atoms containing 5 to 7 members Heterocyclic compounds (e.g. pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, Benzotriazole, benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetra Indene, oxadiazole, imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, nitrogen-containing heterocyclic compounds And the like, and the like. Any organic compound having an electron affinity higher than that of the organic compound used as the donor organic compound may be used as the acceptor organic semiconductor.

Any p-type organic dye or n-type organic dye may be used, but preferably a cyanine dye, styryl dye, hemicyanine dye, merocyanine dye (including zero methine merocyanine (simple merocyanine)), three nucleus Merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenyl Methane dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo Dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone dye, phenoxazine dye, phthaloperylene dye, porphyrin dye, chlorophyll dye, phthalocyanine dye, naphthalocyanine dye, metal complex dye, condensed aromatic Examples thereof include carbocyclic dyes (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), and fullerene derivatives.
Among them, the quinacridone skeleton is selected from the viewpoints of having high photoelectric conversion performance, excellent color separation at the time of spectroscopy, high durability against long-time light irradiation, and easy vacuum deposition. Particularly preferred are organic materials and fullerenes (C60, C70 and derivatives thereof) containing a material, a phthalocyanine skeleton, and a naphthalocyanine skeleton.

The layer containing these organic compounds is formed by a dry film formation method or a wet film formation method. Specific examples of the dry film forming method include a physical vapor deposition method such as a vacuum deposition method, an ion plating method, and an MBE method, or a CVD method such as plasma polymerization. As the wet film forming method, a casting method, a spin coating method, a dipping method, an LB method, or the like is used.
In the case where a polymer compound is used as at least one of a p-type semiconductor (compound) or an n-type semiconductor (compound), it is preferable to form a film by a wet film forming method that is easy to manufacture. When a dry film formation method such as vapor deposition is used, it is difficult to use a polymer because it may be decomposed, and an oligomer thereof can be preferably used instead. On the other hand, when a low molecule is used, it is preferable to form a film by a dry film forming method such as co-evaporation.

[Specification of wavelength dependency of absorption of photoelectric conversion film]
Furthermore, the film absorption spectrum of the organic photoelectric conversion film at 400 nm or more has a film absorption spectrum that selectively corresponds to a region corresponding to at least one of blue light, green light, and red light, and the maximum value of the film absorption intensity in the region Is preferably 3 times or more of the maximum value of the film absorption intensity outside the region, more preferably 5 times or more, and particularly preferably 10 times or more. Further, the wavelength showing the maximum value of the absorption spectrum is 400 nm or more and 500 nm or less, 500 nm or more and 600 nm or less, or 600 nm or more and 700 nm, more preferably 420 nm or more and 480 nm or less, 520 nm or more and 580 nm or less, or 620 nm or more and 680 nm or less, Especially preferably, they are 430 nm or more and 470 nm or less, 530 nm or more and 570 nm or less, or 620 nm or more and 670 nm or less.

[Ip, Ea regulations]
Further, it has been found that the efficiency is improved when the ionization potential (Ip) and the electron affinity (Ea) of the photoelectric conversion film of the photoelectric conversion element capable of BGR spectroscopy satisfy the following requirements.
In the ionization potential (Ip ₁ ), electron affinity (Ea ₁ ), ionization potential (Ip ₂ ), and electron affinity (Ea ₂ ) of the hole transport photoelectric conversion film, Ip ₁ <Ip ₂ and Ea ₁ <is Ea _2.

Next, the charge transport layer that transports holes or electrons generated in the photoelectric conversion layer will be described.
The device of the present invention has a charge transporting layer separately from the photoelectric conversion layer, and is obtained by thermally crosslinking a specific charge transporting compound, at least one hole transporting layer (electron blocking layer: charge transporting according to the present invention). Film).
(Charge transport layer)
The device of the present invention may further have a charge transport layer, and the charge transport material used for the charge transport layer may have either a hole transport property or an electron transport property. Examples of the hole transport material include those described in the above-mentioned organic p-type semiconductor (compound), preferably triarylamine compounds, thiophene compounds, condensed aromatic carbocyclic compounds, phthalocyanine compounds, and nitrogen-containing heterocyclic compounds. A metal complex having a ligand, particularly preferably a triarylamine compound or a phthalocyanine compound.
As an electron transport material. Examples described in the above-mentioned organic N-type semiconductors (compounds) can be given, preferably 5- to 7-membered heterocyclic compounds containing nitrogen, oxygen, and sulfur atoms (which may be further condensed), condensed aromatics Metal complex having a group carbocyclic compound or nitrogen-containing heterocyclic compound as a ligand, more preferably a metal complex having a nitrogen-containing heterocyclic compound as a ligand, a nitrogen atom, an oxygen atom, or a sulfur atom. Or a 7-membered heterocyclic compound (which may be further condensed), more preferably a compound represented by formula (IV), a compound represented by formula (V), or a compound represented by formula (VI) The compound represented by the general formula (VII) is particularly preferable. Details and preferred ranges of the electron transporting material described in the general formula (IV) are described in detail in Japanese Patent Application No. 2004-082002.

(In general formula (IV), A represents a heterocycle in which two or more aromatic heterocycles are condensed, and the heterocycle groups represented by A may be the same or different. M represents an integer of 2 or more. L represents a linking group.
The compounds represented by the general formulas (V) to (VI) are synonymous with the compounds represented by the general formulas (9) to (10) described in JP-A-2002-338957 and tautomers thereof, Specific examples and synthesis methods are also the same.
The material constituting the charge transport layer may be a compound represented by the general formula (VII).

(In the general formula (VII), X represents O, S, Se, Te or N—R. R represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. Q ³ represents a nitrogen-containing aromatic. Represents an atomic group necessary for forming a group heterocycle, m represents an integer of 2 or more, and L represents a linking group.)

Next, the metal complex compound will be described.
The metal complex compound is a metal complex having a ligand having at least one nitrogen atom or oxygen atom or sulfur atom coordinated to the metal, and the metal ion in the metal complex is not particularly limited, but preferably beryllium ion, magnesium Ion, aluminum ion, gallium ion, zinc ion, indium ion, and tin ion, more preferably beryllium ion, aluminum ion, gallium ion, and zinc ion, and still more preferably aluminum ion and zinc ion.

  There are various known ligands contained in the metal complex. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag H. Examples include the ligands described in Yersin's 1987 issue, “Organometallic Chemistry-Fundamentals and Applications”, Akebono Yamamoto, Akio Yamamoto, 1982 issue, etc.

  The ligand is preferably a nitrogen-containing heterocyclic ligand (preferably having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and a monodentate ligand. Or a bidentate or higher ligand, preferably a bidentate ligand such as a pyridine ligand, a bipyridyl ligand, a quinolinol ligand, a hydroxyphenylazole ligand (hydroxyphenyl) Benzimidazole, hydroxyphenylbenzoxazole ligand, hydroxyphenylimidazole ligand)), alkoxy ligand (preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, particularly preferably carbon 1-10, for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), aryloxy ligands Preferably it has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, 2,4,6-trimethylphenyl And oxy, 4-biphenyloxy, etc.).

  Heteroaryloxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.) An alkylthio ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), arylthio ligand ( Preferably, it has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio, etc., a heteroarylthio ligand (preferably 1 to 1 carbon atoms). 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2 Benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc.), siloxy ligands (preferably having 1 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, particularly preferably 6 to 20 carbon atoms, for example, a triphenylsiloxy group, a triethoxysiloxy group, a triisopropylsiloxy group, and the like. More preferably, a nitrogen-containing heterocyclic ligand, an aryloxy ligand, a hetero An aryloxy group and a siloxy ligand, more preferably a nitrogen-containing heterocyclic ligand, an aryloxy ligand, and a siloxy ligand.

It has been found that when these electron transporting organic materials are used, the photoelectric conversion efficiency of the obtained photoelectric conversion film is remarkably increased and the durability is also improved.
Also, from the viewpoint of durability, a device structure in which a filter effect layer that absorbs light of 400 nm or less is provided in the device, and the charge transport layer does not absorb light is preferable, and the long wavelength end of the absorption spectrum of the charge transport layer Is more preferably shorter than the short wavelength end of the spectrum irradiated to the device.

[Charge transport layer deposition method]
The photoelectric transport layer is formed by a dry film formation method or a wet film formation method. Specific examples of the dry film forming method include a physical vapor deposition method such as a vacuum deposition method, an ion plating method, and an MBE method, or a CVD method such as plasma polymerization. As the wet film forming method, a casting method, a spin coating method, a dipping method, an LB method, or the like is used. The film forming method of the charge transport layer is preferably a dry method, and particularly preferably a vacuum deposition method.
A charge transport layer (charge transport film) formed from a composition in which a hole transport material, which is a specific charge transport compound of the present invention, and a polymerization initiator are mixed is crosslinked by applying a wet film formation method and then heating. It is preferable that the film is produced by curing the film.

〔electrode〕
The anode is defined as a hole transporting photoelectric conversion film or an electrode for extracting holes from the hole transport layer, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. A material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), metals such as gold, silver, chromium and nickel, and these metals and conductive metal oxides. Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, silicon compounds, and laminates of these with ITO, preferably conductive materials. In particular, ITO is preferable in terms of productivity, high conductivity, transparency, and the like. Although the film thickness of the anode can be appropriately selected depending on the material, it is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 500 nm.

  As the anode, a layer formed on a soda-lime glass, non-alkali glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength, but when glass is used, a thickness of 0.2 mm or more, preferably 0.7 mm or more is usually used. Various methods are used for producing the anode, depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), a coating of an indium tin oxide dispersion A film is formed by this method. The anode can be subjected to cleaning or other treatments to lower the drive voltage of the element and increase the light emission efficiency. For example, in the case of ITO, UV-ozone treatment, plasma treatment, etc. are effective.

  The cathode takes out electrons from the electron transporting photoelectric conversion layer or the electron transporting layer, and provides adhesion, electron affinity, ionization potential, stability, etc. with adjacent layers such as the electron transporting photoelectric conversion layer and the electron transporting layer. Chosen in consideration. As a material for the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, ITO, IZO, or a mixture thereof can be used. Specific examples include alkali metals (for example, Li, Na, K, etc.) And fluorides or oxides thereof, alkaline earth metals (for example, Mg, Ca, etc.) and fluorides or oxides thereof, gold, silver, lead, aluminum, sodium-potassium alloys or mixed metals thereof, lithium-aluminum alloys or Examples thereof include mixed metals, magnesium-silver alloys or mixed metals thereof, rare earth metals such as indium and ytterbium, preferably a material having a work function of 4 eV or less, more preferably aluminum, silver, gold or their Mixed metal and the like. The cathode can take not only a single layer structure of the compound and the mixture but also a laminated structure including the compound and the mixture. For example, a laminated structure of aluminum / lithium fluoride and aluminum / lithium oxide can be given. The film thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 1 μm.

For production of the cathode, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, and a coating method are used, and a metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Furthermore, a plurality of metals can be vapor-deposited simultaneously to form an alloy electrode, or a previously prepared alloy may be vapor-deposited. The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.
[General requirements]
In the present invention, it is preferable to use a photoelectric conversion element having at least two or more photoelectric conversion films, more preferably three or four layers, and particularly preferably three layers. The example described in No. 99866 is given.

These photoelectric conversion elements of the present invention can be particularly preferably used as an imaging element.
Moreover, in this invention, the case where a voltage is applied to these photoelectric conversion films, photoelectric conversion elements, and image sensors is preferable.
[Voltage application]
When a voltage is applied to the photoelectric conversion film according to the present invention, it is preferable in that the photoelectric conversion efficiency is improved. The applied voltage may be any voltage, but the required voltage varies depending on the film thickness of the photoelectric conversion film. That is, the photoelectric conversion efficiency improves as the electric field applied to the photoelectric conversion film increases, but the applied electric field increases as the film thickness of the photoelectric conversion film decreases even at the same applied voltage. Therefore, when the photoelectric conversion film is thin, the applied voltage may be relatively small. The electric field applied to the photoelectric conversion film is preferably 10 V / m or more, more preferably 1 × 10 ³ V / m or more, further preferably 1 × 10 ⁵ V / m or more, and particularly preferably 1 × 10 ⁶ V / m. m or more, most preferably 1 × 10 ⁷ V / m or more. There is no particular upper limit, but if an electric field is applied too much, an electric current flows even in a dark place, which is not preferable. Therefore, it is preferably 1 × 10 ¹² V / m or less, and more preferably 1 × 10 ⁹ V / m or less.

[Bulk heterojunction structure]
In the present invention, a p-type semiconductor layer and an n-type semiconductor layer are provided between a pair of electrodes, and at least one of the p-type semiconductor and the n-type semiconductor is an organic semiconductor, and these semiconductor layers It is preferable to contain a photoelectric conversion film (photosensitive layer) having a bulk heterojunction structure layer containing the p-type semiconductor and the n-type semiconductor as an intermediate layer. In such a case, in the photoelectric conversion film, by incorporating a bulk heterojunction structure in the organic layer, the disadvantage that the carrier diffusion length of the organic layer is short can be compensated, and the photoelectric conversion efficiency can be improved.
The bulk heterojunction structure is described in detail in Japanese Patent Application No. 2004-080639.
[Tandem structure]
In the present invention, a photoelectric conversion film (photosensitive layer) having a structure having two or more repeating structures (tandem structures) of a pn junction layer formed of a p-type semiconductor layer and an n-type semiconductor layer between a pair of electrodes ) Is preferable, and more preferably, a thin layer of a conductive material is inserted between the repetitive structures. The number of repeating structures (tandem structures) of the pn junction layer may be any number, but is preferably 2 to 50, more preferably 2 to 30, particularly preferably 2 or 10 in order to increase the photoelectric conversion efficiency. It is. The conductive material is preferably silver or gold, and most preferably silver.
In the present invention, the semiconductor having a tandem structure may be an inorganic material, but is preferably an organic semiconductor, and more preferably an organic dye.
The tandem structure is described in detail in Japanese Patent Application No. 2004-079930.
(Orientation regulation)
The present invention relates to an imaging device having a photoelectric conversion film having a p-type semiconductor layer, an n-type semiconductor layer (preferably a mixed / dispersed (bulk heterojunction structure) layer) between a pair of electrodes, and the p-type semiconductor and n Preferred is a photoelectric conversion film characterized by containing an organic compound whose orientation is controlled in at least one of the type semiconductors, and more preferably, the orientation is controlled by both the p-type semiconductor and the n-type semiconductor (possible N) when an organic compound is included.
As the organic compound used in the organic layer of the photoelectric conversion film, one having π-conjugated electrons is preferably used, but this π-electron plane is not perpendicular to the substrate (electrode substrate) but oriented at an angle close to parallel. The better it is. The angle with respect to the substrate is preferably 0 ° to 80 °, more preferably 0 ° to 60 °, still more preferably 0 ° to 40 °, still more preferably 0 ° to 20 °, and particularly preferably. It is 0 ° to 10 °, and most preferably 0 ° (that is, parallel to the substrate).
As described above, the organic compound layer whose orientation is controlled may be partially included in the entire organic layer, but preferably the proportion of the portion whose orientation is controlled with respect to the entire organic layer is 10% or more. More preferably, it is 30% or more, more preferably 50% or more, further preferably 70% or more, particularly preferably 90% or more, and most preferably 100%.
Such a state compensates for the shortcoming of the short carrier diffusion length of the organic layer by controlling the orientation of the organic compound in the organic layer in the photoelectric conversion film, and improves the photoelectric conversion efficiency.

In the case where the orientation of the organic compound of the present invention is controlled, it is more preferable that the heterojunction plane (for example, the pn junction plane) is not parallel to the substrate. It is more preferable that the heterojunction plane is oriented not at a parallel to the substrate (electrode substrate) but at an angle close to perpendicular. The angle with respect to the substrate is preferably 10 ° to 90 °, more preferably 30 ° to 90 °, further preferably 50 ° to 90 °, further preferably 70 ° to 90 °, and particularly preferably. 80 ° to 90 °, and most preferably 90 ° (ie perpendicular to the substrate).
The organic compound layer whose heterojunction surface is controlled as described above may be partially included in the entire organic layer. Preferably, the proportion of the portion where the orientation is controlled with respect to the entire organic layer is 10% or more, more preferably 30% or more, more preferably 50% or more, further preferably 70% or more, and particularly preferably 90%. Above, most preferably 100%. In such a case, the area of the heterojunction surface in the organic layer increases, the amount of carriers of electrons, holes, electron-hole pairs, etc. generated at the interface increases, and the photoelectric conversion efficiency can be improved.
In the above-described photoelectric conversion film (photoelectric conversion film) in which the orientation of both the heterojunction plane and the π-electron plane of the organic compound is controlled, the photoelectric conversion efficiency can be particularly improved.
These states are described in detail in Japanese Patent Application No. 2004-079931.

(Electrophotographic photoreceptor)
Hereinafter, the details when the charge transport film of the present invention is applied to electrophotography will be described.
The electrophotographic photosensitive member of the present invention includes the charge transport film of the present invention. The electrophotographic photosensitive member will be described.
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the electrophotographic photoreceptor of the present invention.
In FIG. 1, an undercoat layer 1 is provided on a conductive substrate 4, a photosensitive layer comprising a charge generation layer 2 and a charge transport layer 3 is provided thereon, and a protective layer 5 is provided on the surface.
2 to 3 are schematic sectional views showing other preferred embodiments of the electrophotographic photosensitive member of the present invention.
The electrophotographic photosensitive member shown in FIG. 2 includes a photosensitive layer having functions separated into a charge generating layer 2 and a charge transporting layer 3 in the same manner as the electrophotographic photosensitive member shown in FIG. In FIG. 3, the charge generation material and the charge transport material are contained in the same layer (charge generation / charge transport layer 6).
In FIG. 2, an undercoat layer 1 is provided on a conductive substrate 4, a photosensitive layer comprising a charge transport layer 3 and a charge generation layer 2 is provided thereon, and a protective layer 5 is provided on the surface. Yes. In FIG. 3, an undercoat layer 1 is provided on a conductive substrate 4, a charge generation / charge transport layer 6 is provided thereon, and a protective layer 5 is provided on the surface.
2 to 3, the protective layer 5 is a protective layer containing the above-described charge transporting compound of the present invention.
1 to 3, the undercoat layer may or may not be provided.
Hereinafter, each element will be described based on the electrophotographic photosensitive member shown in FIG. 1 as a representative example.

<Conductive substrate>
Examples of the conductive substrate 4 include a metal plate, a metal drum, and a metal belt formed using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, or platinum. Alternatively, a paper, a plastic film, a belt, or the like on which a conductive compound such as a conductive polymer or indium oxide, or a metal or alloy such as aluminum, palladium, or gold is applied, vapor-deposited, or laminated can be used.
When the electrophotographic photoreceptor 7 is used in a laser printer, the surface of the conductive substrate 4 has a center line average roughness Ra of 0.04 μm to 0 in order to prevent interference fringes generated when laser light is irradiated. The surface is preferably roughened to 5 μm. If Ra is less than 0.04 μm, it becomes close to a mirror surface, so that the effect of preventing interference tends to be insufficient. If Ra exceeds 0.5 μm, the image quality tends to be rough even if a film is formed. When non-interfering light is used for the light source, it is not particularly necessary to roughen the interference fringes, and it is possible to prevent the occurrence of defects due to the irregularities on the surface of the conductive substrate 4, and thus it is suitable for longer life.

Surface roughening methods include wet honing by suspending the abrasive in water and spraying it on the support, or centerless grinding and anodic oxidation in which the support is pressed against a rotating grindstone and continuously ground. Treatment etc. are preferred.
As another roughening method, a conductive or semiconductive powder is dispersed in a resin without roughening the surface of the conductive substrate 4 to form a layer on the surface of the support. A method of roughening with particles dispersed in the layer is also preferably used.
Here, the roughening treatment by anodic oxidation is to form an oxide film on the aluminum surface by anodizing in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the porous anodic oxide film formed by anodic oxidation is chemically active as it is, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the pores of the anodic oxide film are sealed with pressurized water vapor or boiling water (a metal salt such as nickel may be added) by volume expansion due to a hydration reaction, and a sealing process is performed to change to a more stable hydrated oxide. It is preferable.
The thickness of the anodized film is preferably 0.3 to 15 μm. When this film thickness is less than 0.3 μm, the barrier property against implantation tends to be poor and the effect tends to be insufficient. On the other hand, if it exceeds 15 μm, the residual potential tends to increase due to repeated use.

Further, the conductive substrate 4 may be subjected to treatment with an acidic aqueous solution or boehmite treatment. The treatment with an acidic treatment liquid comprising phosphoric acid, chromic acid and hydrofluoric acid is carried out as follows. First, an acidic treatment liquid is prepared. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is such that phosphoric acid is in the range of 10 to 11% by mass, chromic acid is in the range of 3 to 5% by mass, and hydrofluoric acid is in the range of 0.5 to 2% by mass. The concentration of these acids is preferably in the range of 13.5 to 18% by mass. The treatment temperature is preferably 42 to 48 ° C., but by keeping the treatment temperature high, a thicker film can be formed faster. The film thickness is preferably 0.3 to 15 μm. If it is less than 0.3 μm, the barrier property against injection tends to be poor and the effect tends to be insufficient. On the other hand, when it exceeds 15 μm, there is a tendency that the residual potential increases due to repeated use.
The boehmite treatment can be performed by immersing in pure water at 90 to 100 ° C. for 5 to 60 minutes, or by contacting with heated steam at 90 to 120 ° C. for 5 to 60 minutes. The film thickness is preferably 0.1 to 5 μm. This may be further anodized using an electrolyte solution with low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate, etc. Good.

<Underlayer>
The undercoat layer 1 may be formed only with the binder resin, or may be formed by containing inorganic particles in the binder resin.
As the inorganic particles, those having a powder resistance (volume resistivity) of about 10 ² to 10 ¹¹ Ω · cm are preferably used. This is because the undercoat layer 1 needs to obtain an appropriate resistance for leak resistance and carrier block property acquisition. In addition, if the resistance value of the inorganic particles is lower than the lower limit of the above range, sufficient leakage resistance cannot be obtained, and if it is higher than the upper limit of this range, there is a concern that the residual potential is increased.
Among these, inorganic particles such as tin oxide, titanium oxide, zinc oxide, and zirconium oxide are preferably used as the inorganic particles having the above resistance value, and zinc oxide is particularly preferably used.
In addition, the inorganic particles may be subjected to a surface treatment, and may be used in a mixture of two or more types such as those having different surface treatments or particles having different particle diameters.
As the inorganic particles, those having a specific surface area of 10 m ² / g or more by the BET method are preferably used. Those having a specific surface area value of 10 m ² / g or less tend to cause a decrease in chargeability and tend to make it difficult to obtain good electrophotographic characteristics.

Further, by incorporating inorganic particles and an acceptor compound, a product having excellent electrical properties for a long period of time and carrier blockability can be obtained. As the acceptor compound, any compound can be used as long as the desired characteristics can be obtained. Fluorenone compounds such as 2,4,5,7-tetranitro-9-fluorenone, 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, and 2,5 -Oxadiazole compounds such as bis (4-naphthyl) -1,3,4-oxadiazole, 2,5-bis (4-diethylaminophenyl) 1,3,4 oxadiazole, xanthone compounds, thiophene Compounds, electron transporting materials such as diphenoquinone compounds such as 3,3 ′, 5,5′tetra-t-butyldiphenoquinone, etc. Compounds having an anthraquinone structure are preferable.
The content of these acceptor compounds can be arbitrarily set as long as desired characteristics are obtained, but is preferably 0.01 to 20% by mass with respect to the inorganic particles. Furthermore, 0.05 to 10% by mass is preferable from the viewpoint of preventing charge accumulation and preventing aggregation of inorganic particles. Aggregation of inorganic particles makes the formation of a conductive path non-uniform and tends to cause deterioration in maintainability such as an increase in residual potential during repeated use, and also tends to cause image quality defects such as black spots.
The acceptor compound may be added only when the undercoat layer is applied, or may be previously attached to the surface of the inorganic particles. Examples of the method for imparting the acceptor compound to the surface of the inorganic particles include a dry method and a wet method.

When surface treatment is performed by a dry method, while stirring inorganic particles with a shearing mixer or the like, the acceptor compound dissolved directly or in an organic solvent is dropped and sprayed together with dry air or nitrogen gas to achieve uniformity. To be processed. The addition or spraying is preferably performed at a temperature below the boiling point of the solvent. Spraying at a temperature equal to or higher than the boiling point of the solvent is not preferred because it causes the solvent to evaporate before being uniformly stirred, causing the acceptor compound to locally accumulate, making it difficult to perform uniform processing. After addition or spraying, baking can be performed at 100 ° C. or higher. Baking can be carried out in an arbitrary range as long as the temperature and time allow the desired electrophotographic characteristics to be obtained.
As a wet method, inorganic particles are stirred in a solvent, dispersed using an ultrasonic wave, a sand mill, an attritor, a ball mill, etc., added with an acceptor compound, stirred or dispersed, and then uniformly treated by removing the solvent. . The solvent removal method is distilled off by filtration or distillation. After removing the solvent, baking can be performed at 100 ° C. or higher. Baking can be carried out in an arbitrary range as long as the temperature and time allow the desired electrophotographic characteristics to be obtained. In the wet method, water containing inorganic particles can also be removed before adding the surface treatment agent. For example, a method of removing with stirring and heating in a solvent used for the surface treatment, a method of removing by azeotropic distillation with the solvent Can also be used.
The inorganic particles can be subjected to a surface treatment before the acceptor compound is applied. Any surface treatment agent may be used as long as it has desired characteristics, and can be selected from known materials. For example, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a surfactant, and the like can be given. In particular, silane coupling agents are preferably used because they give good electrophotographic characteristics. Further, a silane coupling agent having an amino group is preferably used because it gives a good blocking property to the undercoat layer 1.
Any silane coupling agent having an amino group can be used as long as it can obtain desired electrophotographic photoreceptor characteristics. Specific examples include γ-aminopropyltriethoxysilane, N-β-. (Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, etc. However, it is not limited to these.
Moreover, 2 or more types of silane coupling agents can also be mixed and used. Examples of silane coupling agents that can be used in combination with the silane coupling agent having an amino group include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl)- γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyltri Examples include methoxysilane, etc. The present invention is not limited to.
As the surface treatment method, any known method can be used, but a dry method or a wet method can be used. Moreover, you may perform surface treatment by acceptor provision and a coupling agent etc. simultaneously.
The amount of the silane coupling agent with respect to the inorganic particles in the undercoat layer 1 can be arbitrarily set as long as the desired electrophotographic characteristics can be obtained. -10 mass% is preferable.

As the binder resin contained in the undercoat layer 1, any known resin can be used as long as it can form a good film and can obtain desired characteristics. For example, polyvinyl butyral or the like can be used. Acetal resin, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone Known polymer resin compounds such as resin, silicone-alkyd resin, phenol resin, phenol-formaldehyde resin, melamine resin, urethane resin, zirconium chelate compound, titanium chelate compound, aluminum chelate compound, titanium al Kishido compounds, organic titanium compounds, there can be used a known material such as a silane coupling agent. Further, a charge transporting resin having a charge transporting group, a conductive resin such as polyaniline, or the like can be used. Of these, resins 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. When these are used in combination of two or more, the mixing ratio can be appropriately set as necessary.
The ratio of the metal oxide to which the acceptor property is imparted in the coating solution for forming the undercoat layer and the binder resin, or the inorganic particles and the binder resin can be arbitrarily set within a range in which desired electrophotographic photoreceptor characteristics can be obtained.

Various additives can be used in the undercoat layer 1 in order to improve electrical characteristics, environmental stability, and image quality. As additives, known materials such as electron transport pigments such as polycyclic condensation systems and azo systems, zirconium chelate compounds, titanium chelate compounds, aluminum chelate compounds, titanium alkoxide compounds, organic titanium compounds, and silane coupling agents are used. be able to. Although the silane coupling agent is used for the surface treatment of the metal oxide, it can also be used as an additive added to the coating solution. Specific examples of the silane coupling agent used here include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (Aminoethyl) -γ-aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane and the like. Examples of zirconium chelate compounds include zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl zirconium acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, naphthene. Zirconate, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like.
Examples of titanium chelate compounds include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, Examples thereof include titanium lactate, titanium lactate ethyl ester, titanium triethanolamate, and polyhydroxytitanium stearate.
Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxy aluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) and the like.
These compounds can be used alone or as a mixture or polycondensate of a plurality of compounds.
As a solvent for adjusting the coating solution for forming the undercoat layer, any known organic solvent such as alcohol, aromatic, halogenated hydrocarbon, ketone, ketone alcohol, ether, ester, etc. You can choose. For example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, Usual organic solvents such as methylene chloride, chloroform, chlorobenzene, and toluene can be used.
Moreover, the solvent used for these dispersion | distribution can be used individually or in mixture of 2 or more types. When mixing, any solvent can be used as long as it can dissolve the binder resin as the mixed solvent.
As a dispersion method, known methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker can be used. Further, as the coating method used when the undercoat layer 1 is provided, conventional methods such as blade coating method, wire bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating method, etc. Can be used.
The undercoat layer 1 is formed on the conductive substrate using the undercoat layer-forming coating solution thus obtained.
The undercoat layer 1 preferably has a Vickers strength of 35 or more.
Furthermore, the undercoat layer 1 can be set to any thickness as long as desired characteristics can be obtained, but the thickness is preferably 15 μm or more, and more preferably 15 μm or more and 50 μm or less. preferable.
When the thickness of the undercoat layer 1 is less than 15 μm, sufficient leakage resistance cannot be obtained, and when it is 50 μm or more, a residual potential tends to remain during long-term use, so that it tends to cause abnormal image density. is there.
Further, the surface roughness (ten-point average roughness) of the undercoat layer 1 is ¼ n (n is the refractive index of the upper layer) to ½λ of the exposure laser wavelength λ used to prevent moire images. Adjusted. In order to adjust the surface roughness, particles such as a resin can be added to the undercoat layer. As the resin particles, silicone resin particles, cross-linked PMMA resin particles, and the like can be used.
In addition, the undercoat layer can be polished to adjust the surface roughness. As a polishing method, buffing, sand blasting, wet honing, grinding, or the like can be used.
The applied layer is dried to obtain an undercoat layer. Usually, the drying is performed at a temperature at which the solvent can be evaporated to form a film.

<Charge generation layer>
The charge generation layer 2 is a layer containing a charge generation material and a binder resin.
Examples of the charge generation material include azo pigments such as bisazo and trisazo, condensed aromatic pigments such as dibromoanthanthrone, perylene pigments, pyrrolopyrrole pigments, phthalocyanine pigments, zinc oxide, and trigonal selenium. Among these, for near-infrared exposure, metal and metal-free phthalocyanine pigments are preferable. In particular, hydroxygallium phthalocyanine disclosed in JP-A-5-263007, JP-A-5-279591, etc., Chlorogallium phthalocyanine disclosed in JP-A-5-98181, dichlorotin phthalocyanine disclosed in JP-A-5-11172, JP-A-5-11173, etc., JP-A-4-189873, More preferred is titanyl phthalocyanine disclosed in JP-A-5-43823. For near-ultraviolet laser exposure, condensed aromatic pigments such as dibromoanthanthrone, thioindigo pigments, porphyrazine compounds, zinc oxide, trigonal selenium, JP-A-2004-78147, and JP-A-2005. Bisazo pigments disclosed in JP-181992 are more preferred.

The binder resin used for the charge generation layer 2 can be selected from a wide range of insulating resins, and from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. You can also choose. Preferred binder resins include polyvinyl butyral resins, polyarylate resins (polycondensates of bisphenols and aromatic divalent carboxylic acids, etc.), polycarbonate resins, polyester resins, phenoxy resins, vinyl chloride-vinyl acetate copolymers, polyamides. Resins, acrylic resins, polyacrylamide resins, polyvinyl pyridine resins, cellulose resins, urethane resins, epoxy resins, caseins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, and the like. These binder resins can be used alone or in combination of two or more. The mixing ratio of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10 by mass ratio.
The charge generation layer 2 can be formed using a coating liquid in which the charge generation material and the binder resin are dispersed in a predetermined solvent.

Solvents used for dispersion include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene chloride. , Chloroform, chlorobenzene, toluene and the like, and these can be used alone or in admixture of two or more.
Moreover, as a method for dispersing the charge generating material and the binder resin in the solvent, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. By these dispersion methods, it is possible to prevent changes in the crystal form of the charge generation material due to dispersion. Further, at the time of this dispersion, it is effective that the average particle size of the charge generating material is 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less.
Further, when forming the charge generation layer 2, use usual methods such as blade coating method, Meyer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating method and the like. Can do.
The film thickness of the charge generation layer 2 thus obtained is preferably 0.1 to 5.0 μm, more preferably 0.2 to 2.0 μm.

<Charge transport layer>
The charge transport layer 3 includes, as charge transport materials, quinone compounds such as p-benzoquinone, chloranil, bromanyl and anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, and xanthone. Compounds, benzophenone compounds, cyanovinyl compounds, electron transport compounds such as ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, And hole transporting compounds such as hydrazone compounds. These charge transport materials can be used singly or in combination of two or more, but are not limited thereto.
From the viewpoint of mobility, the following structure is preferable.

(In the formula, R ⁹ represents a hydrogen atom or a methyl group, and 1 represents 1 or 2. Ar ⁶ and Ar ⁷ represent a substituted or unsubstituted aryl group, or —C ₆ H ₄ —C ( R ¹⁰ ) = C (R ¹¹ ) (R ¹² ), —C ₆ H ₄ —CH═CH—CH═C (R ¹³ ) (R ¹⁴ ), wherein R ^{10 to} R ¹⁴ are hydrogen atoms, substituted or unrepresented A substituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon number A substituted amino group substituted with an alkyl group in the range of 1 to 3;

(Wherein R ¹⁵ and R ^{15 ′} may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ¹⁶ , R ^{16 ′} , R ¹⁷ and R ^{17 ′} may be the same or different and are substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. An amino group, a substituted or unsubstituted aryl group, or —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), —CH═CH—CH═C (R ²¹ ) (R ²² ), R ^{18 to} R ²² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and m and n are integers of 0 to 2.)
Of these, triarylamine derivatives having —C ₆ H ₄ —CH═CH—CH═C ((R ¹³ ) (R ¹⁴ ) or —CH═CH—CH═C (R ²¹ ) (R ²² ) The benzidine derivative is excellent and preferable from the viewpoints of mobility, adhesion to a protective layer, and ghost.

  The binder resin used for the charge transport layer 3 is polycarbonate resin, polyester resin, polyarylate resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer. , Vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly- N-vinyl carbazole, polysilane, etc. are mentioned. Further, as described above, polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. These binder resins can be used alone or in combination of two or more. The compounding ratio of the charge transport material and the binder resin is preferably 10: 1 to 1: 5 by mass ratio. Of these, polycarbonate resins and polyarylate resins are preferred because of their excellent charge transportability and compatibility with charge transport materials. Further, when a charge transporting skeleton and a layer containing an acrylic or methacrylic group-containing compound are formed on the charge transport layer as a surface layer, the binder resin used for the charge transport layer has a viscosity average molecular weight of 50,000 or more, More preferably, it is more preferably 55000 or more because of excellent adhesiveness and crack resistance when forming the upper layer.

A polymer charge transport material can also be used as the charge transport material. As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, polyester-based polymer charge transport materials disclosed in JP-A-8-176293, JP-A-8-208820 and the like have high charge transport properties and are particularly preferable. The polymer charge transport material can be formed by itself, but may be formed by mixing with a binder resin described later.
The charge transport layer 3 can be formed using a coating solution for forming a charge transport layer containing the above constituent materials. Solvents used in the coating solution for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenation such as methylene chloride, chloroform and ethylene chloride. Ordinary organic solvents such as aliphatic hydrocarbons, cyclic or linear ethers such as tetrahydrofuran and ethyl ether can be used alone or in admixture of two or more. Moreover, a well-known method can be used as a dispersion | distribution method of said each constituent material.

The coating method for applying the coating solution for forming the charge transport layer on the charge generation layer 2 includes a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, Ordinary methods such as curtain coating can be used.
The film thickness of the charge transport layer 3 is preferably 5 to 50 μm, more preferably 10 to 30 μm.
In the present invention, the charge transport film of the present invention is used as the charge transport layer 3 or the charge generation / charge transport layer 6.

<Protective layer>
The electrophotographic photoreceptor may be provided with a protective layer for surface protection. Since the charge transport film of the present invention can be efficiently cured to form a high-strength film, the partial structure represented by the following general formula (1) and the partial structure represented by the general formula (2) of the present invention By providing a charge transporting film made of a charge transporting compound having the above on the outermost surface, the charge transporting layer may also serve as a protective layer. Ar ¹¹ , Ar ¹² , n, R ¹¹ , R ²¹ and R ²² in the following general formula (1) are as described above.

  Further, in the single-layer type photosensitive layer (charge generation / charge transport layer) 6, the specific charge transport compound is 5% or more from the viewpoint of strength with respect to the total solid content in the coating liquid for charge transport layer formation. , Preferably 10% or more, more preferably 15% or more. The content of the charge generation material is about 10 to 85% by mass, preferably 20 to 50% by mass. Moreover, it is preferable that content of a charge transport material shall be 5-50 mass%. The method for forming the single-layer type photosensitive layer (charge generation / charge transport layer) 6 is the same as the method for forming the charge generation layer 3 and the charge transport layer 4. The film thickness of the single-layer type photosensitive layer (charge generation / charge transport layer) 6 is preferably about 5 to 50 μm, and more preferably 10 to 40 μm.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention should not be construed as being limited thereto.

Example 1
(Synthesis Example 1: Specific Charge Transport Compound: Synthesis of Compound 101)
Specific charge transporting compound according to the present invention: Compound 101 was synthesized according to the following scheme.
(1-1. Synthesis of Compound 202)
Under air, 97.7 g of compound 201 (the following structure) and 1.5 L of N-methylpyrrolidone (hereinafter referred to as NMP) were added to the flask and heated to 80 ° C. Here, 150 g of N-bromosuccinimide was added little by little. The reaction was stirred at 80 ° C. for 3 hours. After the reaction solution was cooled to room temperature, 2.5 L of methanol was added. The precipitated powder was collected by filtration to obtain 133 g of compound 202 (the following structure). The NMR spectrum of the obtained Compound 202 is shown below.
¹ H-NMR (CDCl ₃ ): δ 6.95 (d, 8H), 7.12 (d, 4H), 7.37 (d, 8H), 7.44 (d, 4H)

  In the synthesis of the above-mentioned compound 202, the same reaction as above was carried out except that the reaction solvent was changed from NMP to toluene, and the brominating agent N-bromosuccinimide to 1,3-dibromo-5,5-dimethylhydantoin. Compound 202 was obtained.

(1-2. Synthesis of Compound 203)
30.0 g of compound 202 (compound having a partial structure represented by general formula (1)) obtained as described above in a nitrogen atmosphere, butyl acrylate (compound represented by general formula (2)) 24 mL, triethylamine 60 mL and NMP 300 mL were added to the flask, and the external temperature was heated to 150 degrees. To this, 0.32 g of t-Bu ₃ P · HBF ₄ and 82 mg of palladium acetate were added, and the mixture was further stirred for 2 hours. The obtained reaction solution was cooled to room temperature, and 300 mL of hydrochloric acid was added to the reaction solution. Extraction with ethyl acetate was performed, and the obtained organic layer was concentrated, and hexane was added to obtain a yellow powder. This powder was collected by filtration to obtain 31 g of compound 203 (a specific charge transporting compound represented by formula (C)). The NMR spectrum of the obtained Compound 203 is shown below.
¹ H-NMR (CDCl ₃ ): δ 0.96 (t, 12H), 1.47 (tq, 8H), 1.68 (dt, 8H), 4.23 (t, 8H), 6.34 (d , 4H), 7.12 (d, 8H), 7.20 (d, 4H), 7.45 (d, 8H), 7.53 (d, 8H), 7.63 (d, 4H)

  In the synthesis of Compound 203 described above, the reaction was carried out in the same manner as described above except that the reaction solvent was changed from NMP to toluene, and Compound 203 could be obtained in the same manner.

(1-3. Synthesis of Compound 204)
In the atmosphere, 31 g of compound 203, 1.7 g of palladium carbon, 32 g of ammonium formate, and 500 mL of isopropyl alcohol were added to the flask, and the mixture was stirred for 1 hour under reflux conditions. The obtained reaction solution was filtered through Celite, 500 mL of brine was added to the filtrate, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate and concentrated to obtain 26.2 g of compound 204. The NMR spectrum of the obtained Compound 204 is shown below.
¹ H ¹ H-NMR (CDCl ₃ ): δ 0.94 (t, 12H), 1.38 (tq, 8H), 1.63 (dt, 8H), 2.63 (t, 8H), 2.92 (T, 8H), 4.10 (t, 8H), 7.00-7.15 (m, 20H), 7.42 (d, 4H)

(1-4. Synthesis of Compound 205)
In the atmosphere, 15 g of Compound 204, 30 g of potassium hydroxide, 125 mL of water, and 125 mL of isopropyl alcohol were added to a 500 mL flask and stirred for 10 hours under heating and refluxing conditions. After allowing to cool to room temperature, 100 mL of 6M aqueous hydrochloric acid was added while cooling in an ice-water bath and stirred for 30 minutes. Then, a viscous solid precipitated. After removing the supernatant, 200 mL of water was added and stirred for 30 minutes. The obtained solid was collected by filtration and dried to obtain 8.24 g of compound 205. The NMR spectrum of the obtained Compound 205 is shown below.
¹ H-NMR (CDCl ₃ ): δ 2.53 (t, 8H), 2.78 (t, 8H), 6.90-7.00 (m, 12H), 7.17 (d, 8H), 7 .50 (d, 4H), 12.07-12.20 (bs, 4H)

(1-5. Synthesis of Compound 101)
Under atmosphere, at room temperature, 2.0 g of compound 205 and 10 mL of tetrahydrofuran were added to a 50 mL flask, and stirring was started. To this, 1.77 mL of triethylamine and compound 207 (the following structure) were sequentially added, and the mixture was further stirred for 5 hours. The precipitated crystals were removed by filtration, and 50 mL of 1M aqueous hydrochloric acid solution was added to the resulting solution. This mixture was extracted with 50 mL of ethyl acetate, and the resulting organic layer was dried over sodium sulfate and concentrated. The obtained crude product was produced by silica gel column chromatography (developing solution hexane / ethyl acetate = 2/1) to obtain 2.78 g of Compound 101 as a yellow viscous liquid. The NMR spectrum of the obtained compound 101 is shown below.
¹ H-NMR (CDCl ₃ ): δ 1.30 (t, 12H), 2.69 (t, 8H), 2.92 (t, 8H), 4.24 (q, 8H), 4.83 (s) , 8H), 5.76 (s, 4H), 6.35 (s, 4H), 6.98-7.14 (m, 20H), 7.43 (d, 4H)

(Example 2)
(Synthesis Example 2: Specific Charge Transporting Compound: Synthesis of Compound 102)
Specific charge transporting compound according to the present invention: Compound 102 was synthesized according to the following scheme.
(2-1. Synthesis of Compound 211)
Under a nitrogen stream and ice cooling, 18.2 g of DMF and 38 g of phosphorus oxychloride were sequentially added to a flask containing a mixture of 19.6 g of zinc chloride and 100 mL of toluene, and stirred for 20 minutes. 10g of compound 210 (the following structure) was added here, and it stirred at 100 degree | times for 12 hours. This was cooled to 50 degrees and water was added. The aqueous layer was removed, and the resulting organic layer was washed with an aqueous potassium carbonate solution. The organic layer was dried with sodium sulfate. The obtained toluene solution was transferred to a flask, to which 12.9 g of malonic acid and 10.5 g of piperidine were added, and the mixture was stirred under reflux conditions for 3 hours while removing water with Dean Stark. After cooling to room temperature, methanol (200 mL) and concentrated sulfuric acid (10 mL) were added thereto, and the mixture was stirred under reflux conditions for 15 hours. The resulting solution was extracted by adding water, and the organic layer was collected. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 15.3 g of compound 211 (the following structure).

(2-2. Synthesis of Compound 212)
Using the obtained compound 211 as a raw material, a compound 212 (the following structure) was synthesized by the same method as the method for synthesizing the compound 204.

(2-3. Synthesis of Compound 213)
The compound 212 was used as a raw material and was synthesized by the same method as the method for synthesizing the compound 205.

(2-4. Synthesis of Compound 102)
Compound 102 (specific charge transporting compound included in the general formula (A)) is the same as the method of synthesizing Compound 101 except that Compound 213 is used as a raw material, the base is changed to pyridine, and the solvent is changed to acetone. Was synthesized.

(Example 3)
(Synthesis Example 3: Specific Charge Transport Compound: Synthesis of Compound 103)
Specific charge transporting compound according to the present invention: Compound 103 (specific charge transporting compound included in general formula (C)) was synthesized according to the following scheme. The compound 207 used is the same as described above.

Example 4
(Synthesis Example 4: Specific Charge Transporting Compound: Synthesis of Compound 104)
Specific charge transporting compound according to the present invention: Compound 104 (specific charge transporting compound included in general formula (C)) was synthesized according to the following scheme. The compound 207 used is the same as described above.

(Example 5)
(Synthesis Example 5: Specific charge transporting compound: Synthesis of Compound 105)
Specific charge transporting compound according to the present invention: Compound 105 (specific charge transporting compound included in the compound containing a divalent linking group in the general formula (C)) was synthesized according to the following scheme.

(Example 6)
(Synthesis Example 6: Specific charge transporting compound: Synthesis of Compound 106)
Specific compound according to the present invention: Compound 106 (specific charge transporting compound included in general formula (D)) was synthesized according to the following scheme. The compound 207 used is the same as described above.

(Example 7: Charge transport film)
(7-1. Film Formation Using Coating Solution for Charge Transport Film Formation)
A compound described in the following composition is mixed, each component is dissolved to prepare a coating solution 1 for forming a charge transport film, and a coating solution is applied to a film thickness of 70 μm on a slide glass using a coating bar. Formed.
(Coating liquid 1 composition for forming a charge transport film)
Charge transporting compound (specific charge transporting compound or comparative compound: compound described in Table 1 below) 1.60 g
Polyarylate resin (polyarylate U polymer U-100: manufactured by Unitika Ltd.) 0.40 g
0.04g of radical initiator (V-601: Wako Pure Chemicals or OT-azo: Otsuka Chemical)
Toluene 4.00 g
Tetrahydrofuran 4.00 g

(7-2. Confirmation of curability of coating film in oxygen-existing atmosphere)
The formed coating film was cured by heating at 150 ° C. for 30 minutes in a nitrogen atmosphere in which the oxygen concentration was controlled to form a charge transport film. After cooling, the pencil hardness was measured according to JIS-K5400.
In addition, a sample solution consisting only of a specific charge transport material and a radical initiator that does not contain a polyarylate resin as a binder in the coating solution is prepared, applied on a polyimide film, heated and cured under the same conditions as described above, and the like. Evaluated. The results are shown in Table 1 below.

  As is apparent from Table 1, it can be seen that the charge transport film using the specific charge transport compound of the present invention is excellent in curability even in the presence of oxygen and forms a hard film with high hardness. On the other hand, even if it is a charge transporting compound having a polymerizable group, a film using a comparative compound formed a highly excellent film at a low oxygen concentration, but the curability decreased as the oxygen concentration increased. .

(7-3. Evaluation of reaction rate in cured product formation)
A coating solution for forming a charge transport film similar to Comparative Example 7-1, Comparative Example 7-4, Example 7-1, and Example 7-2 was prepared, applied on a copper plate, and cured under the same conditions. . The reaction rate of the crosslinking group was measured by measuring the IR spectrum of the uncured film and the cured film of these samples. In addition, as a measurement procedure, the obtained film | membrane was measured in the reflection mode with the infrared spectrometer (Shimadzu IRAffinity-1). With respect to the reaction rate, the peak of carbonyl absorption of the polyarylate resin was used as an internal standard, the double bond absorption strength was calculated as a relative value, and the reaction rate of the crosslinking group was calculated.

  From the above results, the specific charge transporting compound of the present invention has excellent mechanical properties under curing conditions in the presence of oxygen, in contrast to normal acrylic crosslinking groups that are not sufficiently cured in the presence of 200 ppm or more of oxygen. It was confirmed from the reaction rate that a cured film having strength and scratch resistance was obtained.

(Example 8: Formation of charge transport film by light)
(8-1. Formation of coating film Confirmation of photocurability in the presence of oxygen)
A coating solution 2 for forming a charge transport film having the following composition was prepared, and a sample solution was applied on a slide glass to a film pressure of 70 μm using a coating rod, and dried and coated on a slide dryer at 120 ° C. for 1 hour. A film was formed.
(Coating liquid 2 composition for forming a charge transport film)
Charge transporting compound (specific charge transporting compound or comparative compound: compounds described in Table 3 below) 1.60 g
Polyarylate resin (polyarylate U polymer U-100: manufactured by Unitika Ltd.) 0.40 g
Radical initiator (IRGACURE369: Ciba) 0.04g
Toluene 4.00 g
Tetrahydrofuran 4.00 g

(8-2. Confirmation of photocurability in an oxygen-existing atmosphere)
Next, the formed coating film is cured by light irradiation under the conditions of halogen lamp: irradiation intensity: 67 mW / cm ² and irradiation time: 30 seconds while heating to 120 ° C. while controlling the oxygen concentration. A cured film having a thickness of 25 μm was obtained. Then, pencil hardness was measured according to JIS-K5400. The results are shown in Table 3 below.

  From the above results, it can be seen that the coating solution for forming a charge transport film containing the specific charge transport compound of the present invention provides a film having excellent mechanical strength and scratch resistance under curing conditions in the presence of oxygen. .

(Example 9: Organic electroluminescent device)
(9-1. Production of organic electroluminescence device)
A coating solution described below is applied by spin coating on a glass substrate of 25 mm × 25 mm × 0.7 mm having an anode made of ITO having a thickness of 150 nm, and then the film thickness is reduced by the method described below. A 40 nm cured film was produced.
(Coating liquid 3 for forming charge transport film for thermosetting and curing method)
(Coating solution 3 composition for charge transport film formation)
A mixed solution of 1.60 g of a charge transporting compound (compound described in Table 4), 0.04 g of a radical initiator (V-601: Wako Pure Chemical Industries), 10.00 g of toluene and 10.00 g of tetrahydrofuran.
The coating solution was applied to form a coating film, and then heated and cured at 150 ° C. for 30 minutes to form a charge transport film.

(Photocuring charge transport film forming coating solution 4 and curing method)
(Coating liquid 4 composition for forming a charge transport film)
A mixed solution of 1.60 g of a charge transporting compound (compound described in Table 4), 0.04 g of a radical initiator (IRGACURE369: Ciba), 10.00 g of toluene, and 10.00 g of tetrahydrofuran.
The solution was applied to form a coating film, and then dried at 120 ° C. for 1 hour with a blow dryer. Next, while heating to 120 ° C., light irradiation was performed under the conditions of a halogen lamp: irradiation intensity: 67 mW / cm ² and irradiation time: 30 seconds to form a charge transport film.

On top of this, a chloroform solution of the light emitting layer constituting material was applied by a spin coating method, and dried by a blow dryer at 120 ° C. for 1 hour to form a light emitting layer.
(Light emitting layer forming coating solution)
A mixed solution of 2.00 g of poly (N-vinylcarbazole) (Tokyo Kasei), 0.10 g of fac-tris (2-phenylpyridine) iridium, and 30.00 g of chloroform.
On the formed light-emitting layer, a tris (8-quinolinolato) aluminum (III) complex was deposited to 50 nm as an electron transport material by a vacuum deposition method, and further aluminum was deposited thereon to form an electrode having a thickness of 200 nm. After forming the layer, it was sealed, and an organic electroluminescence device was obtained in which a charge transport layer, a light emitting layer, an electron transport layer, and an electrode layer were laminated in this order on an ITO-coated glass substrate.
Using the ITO film of the organic electroluminescence device as an anode and the Al electrode layer as a cathode, a direct current electric field is applied between the electrodes at room temperature and in the atmosphere to emit light, and the luminance is measured with a luminance meter (BM -8; manufactured by Topcon Corporation).

  The coating solution for forming a charge transport film containing a comparative compound is not sufficiently cured by thermal curing in the presence of oxygen, and the hole transport layer and the light emitting layer are mixed when the light emitting layer is applied, resulting in large light emission unevenness and low light emission luminance. On the other hand, according to the coating liquid for forming a charge transport film containing the specific charge transport compound of the present invention, an excellent cured film is formed even under the same conditions. Show.

(Example 10: photoelectric conversion element)
A hole transport material coating solution described below was applied onto a 25 mm square glass substrate with an ITO electrode by spin coating to form a charge transport film.
(Coating liquid 5 for thermosetting charge transport film formation and curing method)
(Coating liquid 5 composition for forming a charge transport film)
A mixed solution of 1.60 g of a charge transporting compound (compound described in Table 5), 0.04 g of a radical initiator (V-601: Wako Pure Chemical Industries), 10.00 g of toluene, and 10.00 g of tetrahydrofuran.
The coating solution was applied to form a coating film, and then heated and cured at 150 ° C. for 30 minutes to form a charge transport film having a thickness of 40 nm.

(Photocuring charge transport film forming coating solution 6 and curing method)
(Coating liquid 6 composition for forming a charge transport film)
A mixed solution of 1.60 g of a charge transporting compound (compound described in Table 5), 0.04 g of a radical initiator (IRGACURE369: Ciba), 10.00 g of toluene, and 10.00 g of tetrahydrofuran.
The solution was applied to form a coating film, and then dried at 120 ° C. for 1 hour with a blow dryer. Next, while heating to 120 ° C., light irradiation was performed under the conditions of halogen lamp: irradiation intensity: 67 mW / cm ² , irradiation time: 30 seconds to form a charge transport film having a thickness of 40 nm.

  After forming the charge transport film, under vacuum, as a p-type organic semiconductor of the photoelectric conversion layer, Silicon 2,3-naphthalocyanine bis (trihexylsilyloxide) (purchased from Sigma Aldrich Japan Co., Ltd. and subjected to sublimation purification), Fullerene C60 (sublimation product of Sigma Aldrich Japan Co., Ltd.), which is an N-type organic semiconductor, was co-deposited so as to be a total of 10 nm while maintaining a volume ratio of 1: 1, and the p-type organic semiconductor and fullerene C60 were mixed. A photoelectric conversion layer was produced. Furthermore, as a photoelectric conversion layer, Silicon 2,3-naphthalocyanine bis (trihexylsilyloxide) (same as above) was deposited to a film thickness of 20 nm to form a photoelectric conversion layer made of only a p-type organic semiconductor. Subsequently, sublimated and purified Alq3 was deposited to a thickness of 30 nm. On top of this, aluminum was further deposited to a thickness of 100 nm and then sealed.

  Next, the substrate was transferred to a metal vapor deposition chamber while maintaining a vacuum. On the organic thin film, aluminum was deposited as a counter electrode to a thickness of 1000 mm. The area of the photoelectric conversion region formed by the lowermost ITO electrode and the aluminum counter electrode was 2 mm × 2 mm. Without exposing this board | substrate to air | atmosphere, it conveyed to the glove box which kept the water | moisture content and oxygen each 1 ppm or less, and sealed with the glass which put the moisture absorption agent using UV curable resin.

The device thus fabricated was subjected to an external electric field (electric field strength of 1) of 1.0 × 10 ⁶ V / cm ² with respect to the device, using an Optel constant energy quantum efficiency measuring apparatus (source meter using Keithley 6430). 0.0 × 10 ⁶ V / cm), the dark current value flowing when no light was irradiated and the photocurrent value flowing when the light was irradiated were measured to calculate the external quantum efficiency. The area of the photoelectric conversion region was irradiated with light to a 1.5 mmφ region out of 2 mm × 2 mm. The amount of light irradiated was 50 μW / cm ² .

  The photo-cured film is lower in photoelectric conversion efficiency than the comparison between Examples 10-1 and 10-2 and Examples 10-3 and 10-4, and the charge transport film formed by thermosetting has good performance. I understand. However, according to the coating liquid for forming a charge transport film containing the comparative compound, good photoelectric conversion efficiency is exhibited under deoxygenation, but the photoelectric conversion efficiency is low in thermosetting in the presence of oxygen. On the other hand, an element having a charge transport film formed from a coating liquid for forming a charge transport film containing the specific charge transport compound of the invention showed excellent photoelectric conversion efficiency even in the presence of oxygen. Further, when the specific charge transporting compound of the present invention is used, the dark current is unexpectedly small compared with the comparative example, and an excellent SN ratio is given.

Example 11 Electrophotographic Photoreceptor
(Example 11-1)
On an aluminum plate having a thickness of 1 mm, 20 parts of a zirconium compound (trade name: Organochix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 2.5 parts of a silane compound (trade name: A1100, manufactured by Nihon Unicar) and polyvinyl butyral resin (trade name) : ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 45 parts of butanol were applied with a wire bar and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 1.0 μm.
Subsequently, a mixture of 15 parts by mass of titanyl phthalocyanine as a charge generating substance, 10 parts by mass of vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nihon Unicar) as a binder resin, and 300 parts by mass of n-butyl alcohol is made of glass. After being dispersed with a bead shaker for 1 hour with beads, the resulting coating solution is applied on the undercoat layer with a wire bar and dried by heating at 100 ° C. for 10 minutes to generate a charge of about 0.15 μm in thickness. A layer was formed.

  Next, 80 parts by mass of compound 101 obtained in Synthesis Example 1 above, 20 parts by mass of polyarylate resin (polyarylate U polymer U-100), and V601 (manufactured by Wako Pure Chemical Industries) on this charge generation layer. 0.5 parts by mass was added to 300 parts by mass of chlorobenzene and dissolved to prepare a coating solution for forming a charge transport film, which was applied onto the charge generation layer with a wire bar. The obtained coating film was heated and cured at 150 ° C. for 30 minutes under a nitrogen atmosphere (oxygen concentration 2%) in which the oxygen concentration was controlled to prepare an 18 μm charge transport layer.

(Example 11-2)
A photoconductor was prepared in the same manner as in Example 9-1 except that the oxygen concentration during curing of the charge transport layer was 200 ppm.
(Example 11-3)
A coating liquid for forming a charge transport film was prepared by replacing 0.5 parts by mass of the polymerization initiator V601 (manufactured by Wako Pure Chemical Industries, Ltd.) used for forming the charge transport layer of Example 11-1 with 0.05 g of IRGACURE 369 (manufactured by Ciba). Others were carried out similarly to Example 9-1, and formed the coating film by the coating liquid for charge transport film formation on a charge generation layer. This was dried at 120 ° C. for 1 hour, and then heated to 120 ° C. in a nitrogen atmosphere (oxygen concentration 2%) with controlled oxygen concentration, halogen lamp: irradiation intensity: 67 mW / cm ² , irradiation time: 30 Curing was performed by irradiation with light for 2 seconds to obtain a charge transport film having a thickness of 18 μm.

(Example 11-4)
A photoconductor was prepared in the same manner as in Example 9-3 except that the oxygen concentration during curing of the charge transport layer was 200 ppm.
(Examples 11-5 to 11-12)
A charge transport film was formed in the same manner as in Example 11-1 or 11-2 except that the material used for preparing the coating liquid for forming the charge transport film was changed as shown in Table 6 below, and a photoconductor was produced. evaluated.
(Comparative Examples 11-1 to 11-8)
A charge transport film was formed in the same manner as in Example 11-1 or 11-2 except that the material used for preparing the coating liquid for forming the charge transport film was changed as shown in Table 6 below, and a photoconductor was produced. evaluated.

(Evaluation of photoconductor)
The produced photoreceptor was evaluated for electrophotographic characteristics as follows (measured by a static method) using an electrostatic copying paper testing apparatus (SP-428 type, manufactured by Kawaguchi Electric Manufacturing Co., Ltd.). First, the photosensitive member was charged by -6 kV corona discharge, and the surface potential V0 when left in a dark place for 30 seconds was measured. Next, the light from the tungsten lamp was exposed so that the illuminance on the surface of the photoreceptor was 3 lux, and the exposure amount E50 required for the surface potential to attenuate to half of the initial surface potential V0 was measured. The same measurement was repeated 3000 times.

In contrast to the examples, it can be seen that the photocuring has a relatively large residual potential (the surface potential is less likely to attenuate), so that thermal curing is more suitable from the viewpoint of the residual potential. However, when thermally cured, the coating solution for forming a charge transport film using the comparative compound is not sufficiently cured under a high oxygen concentration, and there is a problem in film strength.
On the other hand, the coating liquid for forming a charge transport film containing the specific charge transport compound of the present invention has good curability in thermosetting even in the presence of oxygen, and a photoreceptor provided with this charge transport film Was able to lower the surface potential with low exposure.
In addition, even with materials having the same charge transporting functional skeleton, the characteristics differ greatly depending on the structure of the polymerized functional group, and the polymerized functional group in the specific charge transporting compound of the present invention is extremely effective for improving electrical characteristics. . Although the reason for this is not clear, it is presumed that the side reaction causing deterioration of electrical characteristics is suppressed because the polymerization functional group of the present invention can be effectively polymerized even in the presence of oxygen. The

  As shown in the above examples, the compound of the present invention can be thermally polymerized in the presence of oxygen (atmosphere) and has excellent mechanical and electrical properties such as solvent resistance and scratch resistance without using a deoxygenated environment. An element can be manufactured.

DESCRIPTION OF SYMBOLS 1 ... Undercoat layer, 2 ... Charge generation layer, 3 ... Charge transport layer, 4 ... Conductive substrate, 5 ... Protective layer, 6 ... Charge generation / charge transport layer, 7 ... Electrophotographic photoreceptor

Claims (13)

A charge transport film comprising a cross-linked product comprising a composition containing a charge transporting compound having a partial structure represented by the following general formula (1) and a partial structure represented by the following general formula (2).

[In the general formula (1), Ar ¹¹ and Ar ¹² each independently represents a substituted or unsubstituted aryl group. n represents 1 or 2. R ¹¹ represents a substituent selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group when n represents 1, wherein n is 2 represents a divalent linking group selected from the group consisting of a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, and a substituted or unsubstituted alkynylene group. Q represents a single bond or a divalent linking group and does not exist when n is 1. In the general formula (2), R ²¹ and R ²² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted acyl group. The partial structure represented by the general formula (2) is bonded to the partial structure represented by the general formula (1) via one of R ²¹ and R ²² , and the number of bonds is 1 to 6. ] The charge transporting compound having a partial structure represented by the general formula (1) and a partial structure represented by the general formula (2) is a compound represented by the following general formula (A): The charge transport membrane as described.

[In the general formula (A), R ³¹ , R ³² and R ³³ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, and a substituted group. Alternatively, it represents an unsubstituted aryl group having 6 to 20 carbon atoms or a diarylamino group having 12 to 20 carbon atoms, and n31, n32 and n33 each represents an integer of 0 to 6. L ³¹ and L ³² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, or a combination thereof, and n37 , N38 represents 0 or 1. R ³⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ³⁶ represents carbon. An alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms is represented. n35 and n36 represent an integer of 0 to 6, and n35 and n36 are not 0 at the same time. ] The charge transporting compound having a partial structure represented by the general formula (1) and a partial structure represented by the general formula (2) is a compound represented by the following general formula (B): The charge transport membrane as described.

[In the general formula (B), R ⁴¹ , R ⁴² and R ⁴³ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, or Represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n41, n42 and n43 each represents an integer of 0 to 6, and n40 represents an integer of 0 to 2. R ⁴⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. L ⁴¹ and L ⁴² each represent a linking group composed of an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, or a combination thereof; , N48 represents 0 or 1. R ⁴⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁴⁶ represents carbon. An alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms is represented. n45 and n46 represent an integer of 0 to 6, and n45 and n46 are not 0 at the same time. ] The charge transporting compound having a partial structure represented by the general formula (1) and a partial structure represented by the general formula (2) is a compound represented by the following general formula (C): The charge transport membrane as described.
[In the general formula (C), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon. Represents an alkenyl group of 1 to 20 or a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, n51, n52, n53 and n54 each represents an integer of 0 to 5, and n55 and n56 each represents 0 to Represents an integer of 4. L ⁵⁶ represents a single bond or a divalent linking group. L ⁵¹ and L ⁵² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, or a combination thereof, and n57 , N58 represents 0 or 1. R ⁵⁷ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁵⁸ represents carbon. An alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms is represented. n59 and n60 represent an integer of 0 to 6, and n59 and n60 are not 0 at the same time. ] The charge transporting compound having a partial structure represented by the general formula (1) and a partial structure represented by the general formula (2) is a compound represented by the following general formula (D): The charge transport membrane as described.
[In the general formula (D), R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number 1 to 20 represents an alkenyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n61, n62, n63 and n64 each represents an integer of 0 to 5, and n65 represents an integer of 0 to 4. L ⁶¹ and L ⁶² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, or a combination thereof, and n67 , N68 represents 0 to 1. R ⁶⁷ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁶⁸ represents carbon. An alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms is represented. n69 and n70 represent an integer of 0 to 6, and n69 and n70 are not 0 at the same time. ]   The organic electroluminescent element provided with the electric charge transport film of any one of Claims 1-5.   An organic photoelectric conversion element comprising the charge transport film according to any one of claims 1 to 5.   An electrophotographic photosensitive member comprising the charge transport film according to claim 1.   The electrophotographic photosensitive member according to claim 9, wherein the charge transport film according to claim 1 is located on the outermost surface layer. A coating film preparation step of preparing a coating film in which a charge transporting compound having a partial structure represented by the following general formula (1) and a partial structure represented by the following general formula (2) and a polymerization initiator are mixed;
The method for producing a charge transport film according to any one of claims 1 to 5, further comprising a crosslinked product forming step of heating the coating film to obtain a crosslinked product.

[In the general formula (1), Ar ¹¹ and Ar ¹² each independently represents a substituted or unsubstituted aryl group. n represents 1 or 2. R ¹¹ represents a substituent selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl group when n represents 1, wherein n is 2 represents a divalent linking group selected from the group consisting of a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, and a substituted or unsubstituted alkynylene group. Q represents a single bond or a divalent linking group and does not exist when n is 1. In the general formula (2), R ²¹ and R ²² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted acyl group. The partial structure represented by the general formula (2) is bonded to the partial structure represented by the general formula (1) via one of R ²¹ and R ²² , and the number of bonds is 1 to 6. ]   The method for producing a charge transport film according to claim 10, wherein the cross-linked product forming step is performed under a condition where an oxygen concentration on the surface of the coating film is 200 ppm or more. A charge transporting compound represented by the following general formula (A) or the following general formula (B).

[In the general formula (A), R ³¹ , R ³² and R ³³ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, and a substituted group. Alternatively, it represents an unsubstituted aryl group having 6 to 20 carbon atoms or a diarylamino group having 12 to 20 carbon atoms, and n31, n32 and n33 each represents an integer of 0 to 6. L ³¹ and L ³² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, or a combination thereof, and n37 , N38 represents 0 to 1. R ³⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ³⁶ represents carbon. An alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms is represented. n35 and n36 represent an integer of 0 to 6, and n35 and n36 are not 0 at the same time.]

[In the general formula (B), R ⁴¹ , R ⁴² and R ⁴³ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, or Represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n41, n42 and n43 each represents an integer of 0 to 6, and n40 represents an integer of 0 to 2. R ⁴⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. L ⁴¹ and L ⁴² each represent a linking group composed of an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, or a combination thereof; , N48 represents 0 or 1. R ⁴⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁴⁶ represents carbon. An alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms is represented. n45 and n46 represent an integer of 0 to 6, and n45 and n46 are not 0 at the same time. ] A charge transporting compound represented by the following general formula (C) or the following general formula (D).
[In the general formula (C), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon. Represents an alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n51, n52, n53, and n54 each represents an integer of 0 to 5, and n55 and n56 each represents 0 to 4 Represents an integer. L ⁵⁶ represents a single bond or a divalent linking group. L ⁵¹ and L ⁵² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, and a combination thereof, and n57 , N58 represents 0 to 1. R ⁵⁷ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁵⁸ represents carbon. An alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms is represented. n59 and n60 represent an integer of 0 to 6, and n59 and n60 are not 0 at the same time. ]
[In the general formula (D), R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number 1 to 20 represents an alkenyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n61, n62, n63 and n64 each represents an integer of 0 to 5, and n65 represents an integer of 0 to 4. L ⁶¹ and L ⁶² represent a linking group comprising an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —COO—, —CO— group, or a combination thereof, and n67 , N68 represents 0 to 1. R ⁶⁷ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, and R ⁶⁸ represents carbon. An alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms is represented. n69 and n70 represent an integer of 0 to 6, and n69 and n70 are not 0 at the same time. ]