JP4376803B2 - Electrostatic latent image carrier, process cartridge, image forming method, and image forming apparatus - Google Patents

Description

  The present invention relates to an electrostatic latent image carrier using a novel azo compound, a process cartridge, an image forming method, and an image forming apparatus.

  Conventionally, as a photoconductor of an electrostatic latent image carrier (hereinafter, also referred to as “photosensitive member”, “electrophotographic photosensitive member”, or “photoconductive insulator”) used in an electrophotographic system, In general, inorganic photoconductors and organic photoconductors are known. Here, the “electrophotographic method” generally means that in a dark place, a photoconductive photoreceptor is charged to expose an image, and the charge of the exposed portion is selectively dissipated to obtain an electrostatic latent image. The latent image portion is developed with toner to form a visible image, which means an image forming process called a so-called Carlson process. The photoconductor using the organic photoconductor is more flexible than the photoconductor using the inorganic photoconductor, the degree of freedom of the photosensitive wavelength range, film formability, flexibility, film transparency, mass productivity, toxicity, Since it has advantages in terms of cost and the like, a photoreceptor using an organic material has been actively developed and put into practical use.

Examples of the organic photoconductor include azo compounds (see Patent Literature 1 and Patent Literature 2), phthalocyanine compounds (see Patent Literature 3 and Patent Literature 4), perylene compounds (see Patent Literature 5 and Patent Literature 6), many A ring quinone compound (see Patent Document 7), a squarylium compound (see Patent Document 8 and Patent Document 9), and the like are known.
Among these, azo compounds are easy to synthesize, have a high degree of freedom in molecular design, and have different electrophotographic characteristics and spectral sensitivity ranges due to differences in molecular structure such as azo component, coupler component, and bonding mode. As a photoconductor for analog recording, it has been actively studied as a photoconductor for digital recording.

  Examples of azo compounds having good sensitivity known so far include, for example, an azo compound having a carbazole skeleton (see Patent Document 10), an azo compound having a distyrylbenzene skeleton (see Patent Document 11), and triphenylamine. An azo compound having a skeleton (see Patent Document 12), an azo compound having a dibenzothiophene skeleton (see Patent Document 13), an azo compound having an oxadiazole skeleton (see Patent Document 14), an azo compound having a fluorenone skeleton (Patent Document) 15), an azo compound having a bistilbene skeleton (see Patent Document 16), an azo compound having a distyryloxadiazole skeleton (see Patent Document 17), an azo compound having a distyrylcarbazole skeleton (see Patent Document 18), Etc.

  Moreover, as a coupler compound used for the said azo compound, a naphthol type coupler (refer patent document 19), a benzcarbazole type coupler (refer patent document 20), a naphthalimide type coupler (refer patent document 21), a perinone type, for example. Couplers (see Patent Document 22), azulene couplers (see Patent Document 23), anthracene couplers (see Patent Document 24), and the like are already known.

  However, in this case, since the conventional azo compound generally has low sensitivity and durability, when it is used for a laminated type photoreceptor that is one form of an electrophotographic photoreceptor, it has a practically sufficient performance. However, in order to satisfy various requirements required for the electrophotographic process, further improvement in sensitivity and durability is desired.

  Further, most of the laminated type photoreceptors have a structure comprising a layer having a charge generation function (CGL) and a layer having a charge transport function (CTL), and are usually used in a negative charging process. . The reasons are as follows: (1) The stacked type has a high mechanical strength, and a charge transport layer (CTL) capable of designing the film thickness is disposed on the surface layer, so that sufficient mechanical properties can be obtained in a state where it is subjected to the process. This is because the durability can be maintained on the photoconductor. In addition, (2) organic materials that exhibit high charge mobility that does not hinder high-speed copying processes are limited to donor compounds that exhibit almost the property of hole transfer so far. This is because a photoconductor having a charge transport layer (CTL) formed of a compound arranged on the surface side becomes negatively charged.

  However, such a function separation structure creates a new problem. The first is derived from the negative charge of the photoreceptor. A highly reliable charging method in the electrophotographic process is based on corona charging or contact charging, and this method is adopted in most copying machines and printers. However, the negative charge is unstable compared to the positive charge. In addition, the negative corona charging is accompanied by more generation of ozone and NOx, which are substances that cause chemical damage, and therefore causes environmental problems or damage to the photoreceptor. On the other hand, although contact charging generates very small amounts of ozone and NOx, there is a problem in that the charging is close to the photoconductor, so that the photoconductor is greatly damaged.

  The second is derived from the laminated structure of the photoreceptor. In the production of a photoreceptor using an organic material, it is possible to use a solution coating method that is cheaper than a vacuum deposition method. However, at least two coating operations are usually used to produce a laminated photoreceptor, usually on a conductive support (between the conductive support and the photosensitive layer) in order to ensure the chargeability of the photoreceptor. Since the intermediate layer is provided, three coating operations are required. These multiple coating operations lead to an increase in the cost of the photoreceptor. In addition, in order to maintain a good balance between sensitivity and durability and obtain a good image, the thickness of the charge generation layer (CGL) must be controlled in the sub-micron range, which further increases the manufacturing cost. It has become.

  Considering these problems, it is desirable that the photoconductor using the organic material has a single layer type configuration that can be used in a positive charging process, and the single layer type photoconductor is used as it is or with some modifications. If it can be used in a negative charging process, it is possible to provide a photoreceptor having the advantage of being inexpensive and having a high degree of freedom in the use environment.

Examples of the single layer type photoreceptor include (1) a charge transfer complex photoreceptor composed of polyvinylcarbazole and trinitrofluorenone (see Patent Document 25), and (2) a eutectic complex composed of thiapyrylium dye and polycarbonate (Non-patent Document). 1), (3) a photoreceptor in which a perylene pigment and a hydrazone compound are dispersed in a resin (see Patent Document 26), and the like.
Among these, the above (1) and (2) have low sensitivity of the photosensitive member and low electrostatic and mechanical durability, and there is a problem in terms of repeated use. Further, the above (3) has a disadvantage that is not suitable for a high-speed copying process because the sensitivity of the photoreceptor is low. In addition, a system in which components of a layered photoreceptor that has been put into practical use simply has low charging potential and sensitivity, and in particular, low light resistance, electrostatic and mechanical durability. There is a drawback that the characteristics are greatly fluctuated.

  As described above, the development of a highly sensitive and durable organic material has been an issue for a single layer type photoreceptor. In particular, in the case of a charge generation material, the point of charge generation differs from the surface of a photosensitive layer, unlike a multilayer type photoreceptor. Therefore, light resistance and durability higher than those used for multilayer photoconductors are required, and there is still no sufficiently satisfactory performance, and its rapid development is strongly desired. Currently.

JP 54-22834 A JP 61-151659 A JP 48-34189 A Japanese Patent Laid-Open No. 57-14874 JP-A-53-98825 JP-A 63-266457 JP 61-48861 A JP-A-49-105536 JP 58-21416 A JP-A-53-95033 JP-A-53-133445 JP-A-53-132347 Japanese Patent Laid-Open No. 54-21728 JP 54-12742 A JP 54-22834 A JP 54-17733 A JP 54-2129 A Japanese Patent Laid-Open No. 54-14967 JP 47-37543 A JP 58-122967 A JP 54-79632 A Japanese Patent Laid-Open No. 57-176055 Japanese Patent Application Laid-Open No. 60-10256 Japanese Patent Laid-Open No. 61-257993 US Pat. No. 3,489,237 JP-A-2-37354 J. et al. Appl. Phys. , 49, 5555 (1978)

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides an electrostatic latent image carrier having practical sensitivity and excellent durability for a laser printer as well as a high-speed copying machine, and a process using the electrostatic latent image carrier. An object is to provide a cartridge, an image forming method, and an image forming apparatus.

Means for solving the problems are as follows. That is,
<1> An electrostatic latent image carrier having a support and at least a photosensitive layer on the support, the photosensitive layer containing an azo compound represented by the following structural formula (1) It is.
However, in the structural formula (1), Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may be bonded via a bonding group, and these may be further substituted with a substituent. Good. Cp ₁ represents a divalent to hexavalent coupler residue represented by the following structural formula (1-1). Cp ₂ represents a monovalent coupler residue. n ₁ represents an integer of 2 . n ₂ represents an integer of 1 .
However, in the structural formula (1-1), R ¹ , R ² , R ³ , and R ⁴ may be the same as or different from each other, a hydrogen atom, a halogen atom, an amino group, or a hydroxy group. Represents a group, a nitro group, a cyano group, an alkyl group, or an alkoxy group. In addition, R ¹ , R ² , R ³ , and R ⁴ may be bonded to each other directly or indirectly to form a ring. X ¹ represents a hydrocarbon group or a heterocyclic group, and these may be further substituted with a substituent. n ₃ represents an integer of 2 .
<2> The electrostatic latent image carrier according to <1>, wherein the photosensitive layer is a single layer.
<3> The electrostatic latent image carrier according to <1>, wherein the photosensitive layer is a laminate having at least a charge generation layer and a charge transport layer.
<4> The electrostatic latent image carrier according to any one of <1> to <3>, wherein the hydrocarbon group in X ¹ is any one of an alkylene group and an aromatic hydrocarbon group.
<5> The electrostatic latent image carrier according to any one of <1> to <4>, wherein the hydrocarbon group in X ¹ is a divalent aromatic hydrocarbon group.
<6> Cp ₂ at least one of the following structural formula (1-2), (1-3), (1-4), and the <1> is a coupler residue represented by (1-5) To <5>.
However, in the structural formula (1-2), Z ¹ represents a hydrocarbon ring group or a heterocyclic group, which may be further substituted with a substituent. R ⁵ represents a hydrogen atom or a hydrocarbon group, which may be further substituted with a substituent. Y ¹ represents a hydrocarbon ring group or a heterocyclic group, and these may be further substituted with a substituent.
However, in the structural formulas (1-3) and (1-4), W ¹ represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group containing a nitrogen atom in the ring. These may be further substituted with a substituent.
However, in the structural formula (1-5), A ¹ represents an aromatic hydrocarbon group or a heterocyclic group, and these may be further substituted with a substituent. m represents an integer of 1 to 6.
<7> The electrostatic latent image carrier according to any one of <1> to <6>, wherein Ar is represented by the following structural formula (1-6).
<8> The electrostatic latent image carrier according to any one of <1> to <7>, wherein the azo compound is used as a charge generation material.
<9> The electrostatic latent image carrier according to any one of <1> to <8>, wherein the photosensitive layer contains a charge transport material.
<10> The electrostatic latent image carrier according to <9>, wherein the charge transport material is a stilbene compound represented by the following structural formula (2).
However, in the structural formula (2), T ¹ and T ² represent an alkyl group or an aryl group which may be the same as or different from each other, and these are further substituted with a substituent. Also good. T ¹ and T ² may form a ring with each other. T ³ and T ⁴ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may be further substituted with a substituent. Ar ′ represents an aryl group or a heterocyclic group, and these may be further substituted with a substituent.
<11> The electrostatic latent image carrier according to <9>, wherein the charge transport material is a polymer charge transport material.
<12> The electrostatic latent image carrier according to <11>, wherein the polymer charge transport material is at least one polymer selected from polycarbonate, polyurethane, polyester, and polyether.
<13> The electrostatic latent image carrier according to any one of <11> to <12>, wherein the polymer charge transport material is a polymer compound having a triarylamine structure.
<14> The electrostatic latent image carrier according to <13>, wherein the polymer compound having a triarylamine structure is a polycarbonate having a triarylamine structure.
<15> The polycarbonate having a triarylamine structure is the electrostatic latent image carrier according to <14>, which is represented by the following structural formula (3).
However, in the structural formula (3), R ⁶ and R ⁷ represent a substituted or unsubstituted aryl group that may be the same or different from each other, and represent Ar ¹ , Ar ² , and Ar ^3. Represent the same or different arylene groups. k and j represent composition ratios, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the degree of polymerization. X ² represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following structural formula (3-1).
However, in the structural formula (3-1), R ⁸ and R ⁹ may be the same as or different from each other, and may represent different halogen atoms, alkyl groups, or aryl groups, and these may be substituted. Further, it may be substituted. l and m represent the integer of 0-4. Y represents a single bond, a linear, branched or cyclic alkylene group, —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO—O—Z—O—CO—. (However, Z represents an aliphatic divalent group) or the following structural formula (3-2).
However, in said structural formula (3-2), a represents the integer of 1-20. b represents an integer of 1 to 2000. R ¹⁰ and R ¹¹ represent an alkyl group or an aryl group which may be the same as or different from each other, and these may be further substituted with a substituent.
<16> The polycarbonate having a triarylamine structure is the electrostatic latent image carrier according to <14>, which is represented by the following structural formula (4).
However, in the structural formula (4), Ar ⁴ , Ar ⁵ , Ar ⁷ and Ar ⁸ represent a substituted or unsubstituted arylene group which may be the same or different from each other, and Ar ⁶ represents a substituted or unsubstituted group. Represents an aryl group. Z ² represents an arylene group or ^{-Ar 9} -Za-Ar 9 - (provided that, Ar ⁹ is .Za to represent a substituted or unsubstituted arylene group, O, represents S or an alkylene group.) Represents the. R ¹² and R ¹³ represent a linear or branched alkylene group or —O—. h represents 0 or 1; k and j represent composition ratios, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the degree of polymerization. X ³ represents a substituted or unsubstituted aliphatic divalent group, a substituted or unsubstituted cyclic aliphatic divalent group, a substituted or unsubstituted aromatic divalent group, or a divalent group formed by linking these, or The divalent group represented by the following structural formula (4-1), structural formula (4-2), and structural formula (4-3) is represented.
However, in the structural formulas (4-1), (4-2), and (4-3), R ²⁴ , R ²⁵ , R ⁵⁵ , and R ⁵⁶ are substituted or unsubstituted alkyl. Represents a group, a substituted or unsubstituted aryl group or a halogen atom. l and m each represents an integer of 0 to 4. s and t each represents an integer of 0 to 3. When a plurality of R ²⁴ , R ²⁵ , R ⁵⁵ , and R ⁵⁶ are present, they may be the same or different. Y is a divalent group composed of a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, an alkylene group having 1 to 10 carbon atoms, one or more oxygen atoms, and a sulfur atom. Group, —O—, —S—, —SO—, —SO ₂ —, —CO—, —COO—, —CO—O—Z ₁ —O—CO—, —CO—Z ₂ —CO— (provided that In the formula, Z ₁ and Z ₂ represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group), or the following structural formula (4-1-1), structural formula (4- The structural formula (4-1-8) is represented from 1-2).
However, in the structural formula (4-1-1), R ²⁶ and R ²⁷ each represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
R ⁵⁷ , R ⁵⁸ , and R ⁶⁴ represent a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group. R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , and R ⁶³ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group. R ⁵⁸ and R ⁵⁹ may combine to form a carbocyclic ring having 5 to 12 carbon atoms. R ₆₅ and R ₆₆ represent an end bond or an alkylene group having 1 to 4 carbon atoms. a is an integer of 1 to 20, b is an integer of 1 to 2000, u and w are integers of 0 to 4, and v is 1 or 2. When a plurality of R ²⁶ , R ²⁷ , R ⁵⁷ , and R ⁶⁴ are present, they may be the same or different.
<17> The electrostatic latent image carrier according to any one of <1> to <16>, wherein the photosensitive layer further contains an acceptor compound.
<18> The electrostatic latent image carrier according to <17>, wherein the acceptor compound is a 2,3-diphenylindene compound represented by the following structural formula (5).
In the structural formula (5), Q ¹ , Q ² , Q ³ , and Q ⁴ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group, a cyano group, or Represents a nitro group. Q ⁵ and Q ⁶ represent a hydrogen atom, an aryl group, a cyano group, an alkoxycarbonyl group, or an aryloxycarbonyl group, which may be the same as or different from each other, and these are further substituted with a substituent. May be.
<19> The electrostatic latent image carrier according to any one of <1> to <18>, wherein the photosensitive layer further contains a phenol compound.
<20> The electrostatic latent image carrier according to <19>, wherein the phenol compound is represented by the following structural formula (6).
However, in the structural formula (6), E ^{1 to} E ⁸ represent a hydrogen atom, an alkyl group, an alkoxycarbonyl group, an aryl group, or an alkoxy group, which may be the same as or different from each other. These may be further substituted with a substituent.
<21> The electrostatic latent image bearing member according to any one of <1> to <20> and the electrostatic latent image formed on the electrostatic latent image bearing member are developed with toner to be visible. And a developing unit that forms an image, and is detachable from the main body of the image forming apparatus.
<22> The electrostatic latent image carrier according to any one of <1> to <20>, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and toner At least developing means for forming a visible image by developing the toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. An image forming apparatus.
<23> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier according to any one of <1> to <20>, and using the toner for the electrostatic latent image An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.

The electrostatic latent image carrier of the present invention has a support and at least a photosensitive layer on the support, and the photosensitive layer contains an azo compound represented by the structural formula (1). The azo compound of the present invention is a novel compound having a specific imide structure in the coupler residue, and is intended to increase the sensitivity of the photoreceptor, improve electrostatic properties, and further improve light resistance and durability. . The reason for this improvement in characteristics is not clear at this time, but the novel coupler residue having a plurality of specific imide structures used in the present invention in the same molecule protects the azo group of the azo compound with the coupler residue. It is presumed that the steric contribution that can be made and the electronic contribution that raises the oxidation potential of the azo compound are made. Furthermore, the molecular structure of the azo compound resulting from them and the intermolecular interaction caused by the molecular structure have a great influence on efficient charge generation in the photosensitive layer, and the light and oxidation of the azo compound itself. It is thought that the stability against property gas etc. is improved.
In this case, an embodiment having a single photosensitive layer, an embodiment in which the photosensitive layer is a laminate having at least a charge generation layer and a charge transport layer, an embodiment containing the azo compound of the present invention as a charge generation material, and the photosensitive layer An embodiment containing a charge transport material, an embodiment containing an acceptor compound, an embodiment containing a phenol compound, and the like are preferable.
When the photosensitive layer contains a charge transport material, charges can be transported quickly, and high durability of chargeability, sensitivity, and electrostatic characteristics can be realized. In addition, when the charge transport material is a polymer charge transport material, a very homogeneous charge transfer matrix is formed in the photosensitive layer, the charge injection from the charge generation material, the charge transfer is smoother, and the mechanical A photoconductor with improved mechanical strength is obtained. These are due to the fact that the polymer charge transport material of the present invention is a polymer of at least one of polycarbonate, polyurethane, polyester, and polyether, resulting in good film formability, high mechanical strength, and excellent wear resistance. It is thought to express sex. Moreover, high mobility is also achieved by the polymer charge transport material of the present invention having a triarylamine structure. Among the polymer charge transport materials of the present invention, particularly when the polymer charge transport material is a polycarbonate having a triarylamine structure, it is effective in improving various properties. Further, the combined use of the polymer charge transporting material makes it possible to cope with a wet process that has been difficult with a conventional single-layer type photoreceptor. In addition, by using an acceptor compound in combination, the majority of the electrons generated by light irradiation can be moved to the acceptor compound side, and charging properties, sensitivity, High durability of characteristics can be realized. Furthermore, by using the phenol compound in combination, the phenol compound works as an antioxidant, so that high durability of electrostatic characteristics can be realized.

  The process cartridge of the present invention has at least an electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using toner to form a visible image. Thus, the electrostatic latent image carrier of the present invention is used as the electrostatic latent image carrier. In the process cartridge, the developing means develops the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a visible image. At this time, since the electrostatic latent image bearing member of the present invention is used as the electrostatic latent image bearing member, it has excellent durability and high stability and high electrostatic characteristics even when the copying process is repeated. A quality image is obtained.

  The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image. At least a developing step, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. An electrostatic latent image carrier is used. In the image forming method, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. At this time, since the electrostatic latent image bearing member of the present invention is used as the electrostatic latent image bearing member, it has excellent durability and high stability and high electrostatic characteristics even when the copying process is repeated. A quality image is obtained.

  An image forming apparatus according to the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and a visible image developed with toner. Development means for forming the image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. The electrostatic latent image carrier of the present invention is used. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. At this time, since the electrostatic latent image bearing member of the present invention is used as the electrostatic latent image bearing member, it has excellent durability and high stability and high electrostatic characteristics even when the copying process is repeated. A quality image is obtained.

According to the present invention, various problems in the past can be solved, and the electrostatic latent image carrier (electrophotographic photosensitive member) using a novel azo compound having a specific imide structure in the coupler residue has good chargeability and sensitivity. In addition, it is excellent in light resistance and durability, and is suitable for low-speed to high-speed copying processes. Furthermore, photosensitivity for page printers using LD or LED light for light writing from monochrome or full-color analog copying machines. It is possible to apply up to the body.
In addition, the process cartridge, the image forming method, and the image forming apparatus using the electrophotographic photosensitive member of the present invention are excellent in charging property, sensitivity, durability, and stable electrostatic characteristics even when the copying process is repeated. It is rich and high quality.

(Electrostatic latent image carrier)
The electrostatic latent image carrier of the present invention has a support and at least a photosensitive layer on the support, and the photosensitive layer contains an azo compound represented by the following structural formula (1).
In the first embodiment, the electrostatic latent image carrier of the present invention is provided with a single photosensitive layer on a support, and further includes an intermediate layer, a protective layer, and other layers as necessary. (Hereinafter, it may be referred to as “single layer type photoreceptor”). In the second embodiment, a support, and a photosensitive layer including at least a charge generation layer and a charge transport layer in this order are provided on the support. Further, if necessary, an intermediate layer, a protective layer, and the like (Hereinafter sometimes referred to as a “stacked photoreceptor”). In the second embodiment, the charge generation layer and the charge transport layer may be laminated in reverse.

  Hereinafter, the azo compound represented by the following structural formula (1) will be described in detail. The azo compound is a novel compound having a specific imide structure in the coupler residue and is preferably used as a charge generation material, but can also play a role other than the charge generation material.

However, in the structural formula (1), Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may be bonded via a bonding group, and these may be further substituted with a substituent. Good. Cp ₁ represents a divalent to hexavalent coupler residue represented by the following structural formula (1-1). Cp ₂ represents a monovalent coupler residue. n ₁ represents an integer of 2 . n ₂ represents an integer of 1 .
However, in the structural formula (1-1), R ¹ , R ² , R ³ , and R ⁴ may be the same as or different from each other, a hydrogen atom, a halogen atom, an amino group, or a hydroxy group. Represents a group, a nitro group, a cyano group, an alkyl group or an alkoxy group. In addition, R ¹ , R ² , R ³ , and R ⁴ may be bonded to each other directly or indirectly to form a ring. X ¹ represents a hydrocarbon group or a heterocyclic group, and these may be further substituted with a substituent. n ₃ represents an integer of 2 .

It is preferable that at least one of the Cp ₂ is a coupler residue represented by the following structural formulas (1-2), (1-3), (1-4), and (1-5).
However, in the structural formula (1-2), Z ¹ represents a hydrocarbon ring group or a heterocyclic group, which may be further substituted with a substituent. R ⁵ represents a hydrogen atom or a hydrocarbon group, which may be further substituted with a substituent. Y ¹ represents a hydrocarbon ring group or a heterocyclic group, and these may be further substituted with a substituent.

However, in the structural formulas (1-3) and (1-4), W ¹ represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group containing a nitrogen atom in the ring. These may be further substituted with a substituent.

However, in the structural formula (1-5), A ¹ represents an aromatic hydrocarbon group or a heterocyclic group, and these may be further substituted with a substituent. m represents an integer of 1 to 6.

The Ar is preferably represented by the following structural formula (1-6).

First, the central skeleton (Ar portion) in the azo compound represented by the structural formula (1) will be described in detail.
Examples of the aromatic hydrocarbon group and aromatic heterocyclic group that may be bonded via the bonding group represented by Ar in the structural formula (1) include an aromatic hydrocarbon, a heterocyclic ring, and the aromatic ring directly. Or the thing couple | bonded with the aromatic group or the non-aromatic group etc. are mentioned.
Examples of the aromatic hydrocarbon include benzene, naphthalene, fluorene, phenanthrene, anthracene, and pyrene.
Examples of the heterocyclic ring include furan, thiophene, pyridine, indole, benzothiazole, carbazole, acridone, dibenzothiophene, benzoxazole, benzotriazole, oxadiazole, thiadiazole, dibenzophenazine, and the like.
Examples of the aromatic ring bonded directly or with an aromatic group or non-aromatic group include, for example, triphenylamine, diphenylamine, N-methyldiphenylamine, biphenyl, terphenyl, binaphthyl, fluorenone, phenanthrenequinone, anthraquinone Benzanthrone, diphenyloxadiazole, phenylbenzoxazole, diphenylmethane, diphenylsulfone, diphenyl ether, benzophenone, stilbene, distyrylbenzene, tetraphenyl-p-phenylenediamine, tetraphenylbenzidine monopyridyldiphenylamine, and the like.
Examples of the substituent that the above ring has include an alkyl group, an alkoxy group, a halogen atom, an amino group hydroxy group, a nitro group, a cyano group, and a halomethyl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the amino group include a dimethylamino group, a diethylamino group, and a diphenylamino group.
Among these, the fluorenone-based central skeleton represented by the following structural formula (1-6) is particularly preferable in that the azo compound obtained in the present invention exhibits high sensitivity and excellent durability.

Tables 1 to 3 below show examples of the central skeleton (Ar portion).

Next, the coupler residue Cp ₁ of the azo compound of the present invention will be described in detail.
Cp ₁ represents a divalent to hexavalent coupler residue represented by the following structural formula (1-1).

In the structural formula (1-1), R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a methoxy group, an ethoxy group or the like Alkoxy group; halogen atom such as fluorine atom, chlorine atom and bromine atom; amino group such as dimethylamino group, diethylamino group and diphenylamino group; hydroxy group, nitro group, cyano group, acetyl group and substituent A good benzoyl group, an alkoxycarbonyl group, a phenoxycarbonyl group which may have a substituent, a carbamoyl group which may have a substituent, and the like are represented. However, R ₁ and R ₂ may form a ring with a substituted or unsubstituted alkylene such as a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentylene group, or An aromatic ring such as a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring may be formed.
Examples of the substituent include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, alkoxy groups such as methoxy group and ethoxy group, halogen atoms such as fluorine atom, chlorine atom, and bromine atom, dimethylamino group, and diethylamino group. Group, amino group such as diphenylamino group, hydroxy group, nitro group, cyano group, acetyl group, benzoyl group which may have a substituent, alkoxycarbonyl group, phenoxycarbonyl group which may have a substituent, substituted And a carbamoyl group which may have a group.

In the structural formula (1-1), X ¹ represents a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted heterocyclic group. Examples of the hydrocarbon group, for example, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, a propylene group, a butylene group, a cyclopentylene group, an alkylene group such as cyclohexylene group, phenylene group, naphthylene Group, aromatic hydrocarbon group such as phenanthrylene group, xylylene group, and the like , and further, a trivalent to hexavalent hydrocarbon group in which 1 to 4 hydrogen atoms are liberated from the divalent aromatic hydrocarbon group. Is mentioned. Examples of the heterocyclic group include a pyrazole diyl group, an imidazole diyl group, a pyridine diyl group, a pyrimidine diyl group, an indole diyl group, a benzimidazole diyl group, and a quinoline diyl group. And a trivalent to hexavalent heterocyclic group in which 1 to 4 hydrogen atoms are released from the cyclic group.
Among these, in particular, an alkylene group and a divalent aromatic hydrocarbon group are suitable for the purpose of the present invention because the resulting azo compound has high sensitivity and excellent durability.

  The hydrocarbon group and heterocyclic group may be bonded directly or with an aromatic group or a non-aromatic group, for example, a biphenyldiyl group, diphenylmethanediyl group, diphenyletherdiyl group, benzophenonediyl group, benzanilidediyl group, etc. Is mentioned. Examples of the substituent of the hydrocarbon ring or the heterocyclic ring include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, substituted alkyl groups such as a benzyl group, a phenethyl group, and a methoxymethyl group; a methoxy group, Alkoxy groups such as ethoxy groups and phenoxy groups; phenyl groups which may have substituents; aromatic groups such as naphthyl groups, anthracenyl groups, phenanthrenyl groups and pyrenyl groups which may have substituents; fluorine atoms, chlorine Halogen atoms such as atoms and bromine atoms; hydroxy groups, carboamino groups such as amino groups which may have substituents, acetylamino groups and benzoylamino groups which may have substituents, nitro groups, cyano groups, acetyl groups Group, benzoyl group which may have a substituent, alkoxycarbonyl group, phenoxycarbonyl group which may have a substituent, It is a carbamoyl group, and the like.

The coupler compound corresponding to the structural formula (1-1) can be produced by the following method.
For example, a system containing an ester compound represented by the following structural formula (i) and an amine compound represented by the following structural formula (ii) containing at least one solvent selected from a glycol solvent or a glycerol solvent A coupler compound represented by the following structural formula (iii) is obtained by performing an ester / amide exchange reaction therein.

In the Structural Formula (i), (ii) and ^{(iii), R 1, R} 2, R 3, and ^{R 4} is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an amino group, hydroxy group, Represents a nitro group or a cyano group. R ⁵ represents a substituted or unsubstituted alkyl group. However, R ¹ and R ² may form a ring or an aromatic ring by a substituted or unsubstituted alkylene group. X ¹ represents a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted heterocyclic group. n ₃ represents an integer of 2 .

  Moreover, even when an acid anhydride compound represented by the following structural formula (iv) and an amine compound represented by the following structural formula (ii) are reacted in the presence of an acid catalyst, it is represented by the following structural formula (iii). A coupler compound can be produced.

However, in said structural formula (ii), structural formula (iii), and structural formula (iv), R < ¹ >, R < ² >, R < ³ >, and R < ⁴ > are a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, amino Represents a group, a hydroxy group, a nitro group, or a cyano group. However, R ¹ and R ² may form a ring or an aromatic ring by a substituted or unsubstituted alkylene group. X ¹ represents a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted heterocyclic group. n ₃ represents an integer of 2 .

Hereinafter, Tables 4 to 6 show examples of coupler compounds corresponding to the coupler residue Cp ₁ represented by the structural formula (1-1).

<Examples of coupler compounds>

The azo compound of the present invention has a monovalent coupler residue Cp ₂ when n ₂ = 1 . Examples of the monovalent coupler residue Cp ₂ include those represented by the following structural formula (v), structural formula (vi), and structural formula (vii).

In the structural formula (v), the structural formula (vi), and the structural formula (vii), R ¹ , R ² , R ³ , and R ⁴ are a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an amino group, A hydroxy group, a nitro group, a cyano group, an acetyl group, an optionally substituted benzoyl group, an alkoxycarbonyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted carbamoyl group, And so on.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxyl group include a methoxy group and an ethoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the amino group include a dimethylamino group, a diethylamino group, and a diphenylamino group.
In addition, R ¹ , R ² , R ³ , and R ⁴ may be substituted or unsubstituted groups such as a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentylene group, or the like. A ring may be formed by an unsubstituted alkyl group, or an aromatic ring such as a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring may be formed.
Examples of the substituent of the ring include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an alkoxy group such as a methoxy group and an ethoxy group, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and a dimethylamino group Amino group such as diethylamino group and diphenylamino group, hydroxy group, nitro group, cyano group, acetyl group, benzoyl group which may have a substituent, alkoxycarbonyl group, phenoxycarbonyl group which may have a substituent And a carbamoyl group which may have a substituent.

In the structural formula (v), X represents a hydrogen atom, an alkyl group, a cyclic alkyl group, an aromatic hydrocarbon group, a heterocyclic group, an alkylamino group, an aromatic amino group, a carboamino group, or the like.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. Examples of the heterocyclic group include pyridyl group, pyrazino group, quinolino group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, imidazolyl group, benzoimidazolyl group, indolyl group and the like. Examples of the alkylamino group include a methylamino group and an ethylamino group. Examples of the aromatic amino group include a phenylamino group and a naphthylamino group. Examples of the carboamino group include an acetylamino group and a benzoylamino group.
Examples of these substituents include alkyl groups, substituted alkyl groups, alkoxy groups, aromatic groups, halogen atoms, hydroxy groups, amino groups that may have substituents, acetylamino groups, carboamino groups, nitro groups, and cyano groups. , An acetyl group, an optionally substituted benzoyl group, an alkoxycarbonyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted carbamoyl group, and the like.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the substituted alkyl group include a benzyl group, a phenethyl group, and a methoxymethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a phenoxy group. Examples of the aromatic group include a phenyl group that may have a substituent, a naphthyl group that may have a substituent, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

  Among the coupler residues represented by the structural formula (v), a coupler residue in which X is a substituted or unsubstituted alkyl group or a substituted or unsubstituted cyclic alkyl group is preferable. Among these, a coupler residue represented by the following structural formula (viii) is particularly preferable because the azo compound obtained in the present invention exhibits high sensitivity and excellent charging stability.

In the structural formula (viii), A ¹ represents an aromatic hydrocarbon group such as phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, pyridyl group, pyrazino group, quinolino group, oxazolyl group, benzooxazolyl Group, thiazolyl group, benzothiazolyl group, imidazolyl group, benzimidazolyl group, indolyl group and other heterocyclic groups such as methyl, ethyl, propyl, butyl and other alkyl groups, benzyl group, phenethyl Group, substituted alkyl group such as methoxymethyl group, alkoxy group such as methoxy group, ethoxy group, phenoxy group, phenyl group which may have a substituent, halogen atom such as fluorine atom, chlorine atom, bromine atom, trifluoro Methyl group, cyano group, alkoxycarbonyl group, may have a substituent Carbamoyl group and the like. Moreover, m represents the integer of 1-6.

  In the structural formula (vi) and structural formula (vii), Y represents a substituted or unsubstituted alkylene group, a divalent organic residue having a substituted or unsubstituted aromaticity, a substituted or unsubstituted heterocyclic ring. Divalent organic residue having aromaticity, carbonyl group-containing divalent organic residue represented by -CO-Z- (where Z is a substituted or unsubstituted alkylene group, substituted or unsubstituted aromatic Represents a divalent organic residue having a property, and a divalent organic residue having a substituted or unsubstituted heteroaromatic property.

Examples of the alkylene group include an ethylene group, a propylene group, a butylene group, a cyclopentyl group, and a cyclohexyl group. However, an aromatic ring may be formed by a carbon-carbon bond of an alkylene group.
Examples of the aromatic divalent organic residue include an o-phenylene group, 1,8-naphthylene group, 2,3-naphthylene group, 1,2-anthrylene group, 9,10-phenanthrylene group, and the like. Is mentioned.
Examples of the divalent organic residue having heterocyclic aromaticity include 3,4-pyrazolediyl group, 2,3-pyridinediyl group, 5,6-pyrimidinediyl group, and 6,7-benzimidazolediyl. Group, 6,7-quinolinediyl group, and the like.
Examples of the carbonyl group-containing divalent organic residue include a 2-benzoyl group and a 2-naphthylcarbonyl group.
Examples of these substituents include alkyl groups such as methyl, ethyl, propyl, and butyl groups, substituted alkyl groups such as benzyl, phenethyl, and methoxymethyl groups, and alkoxy groups such as methoxy, ethoxy, and phenoxy groups. , An optionally substituted phenyl group, an optionally substituted naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group and other aromatic groups, a fluorine atom, a chlorine atom, a bromine atom and other halogen atoms, Carboxyamino group such as hydroxy group, amino group optionally having substituent, acetylamino group, benzoylamino group optionally having substituent, nitro group, cyano group, acetyl group, substituent Good benzoyl group, alkoxycarbonyl group, phenoxycarbonyl group optionally having substituent, carbamoyl optionally having substituent Such as a group, and the like.

  Among the coupler residues represented by the structural formula (vi) and the structural formula (vii), the coupler residues represented by the following structural formula (ix) and the following structural formula (x) are preferable.

  Among these, a coupler residue in which Y is a substituted or unsubstituted alkylene group or a substituted or unsubstituted carbonyl group-containing divalent organic residue is preferable. Among these, Y is a coupler residue represented by the following structural formula (xi) or the following structural formula (xii), and the azo compound obtained by the present invention exhibits high sensitivity and excellent charging stability. Therefore, it is preferable.

B ₁ in the structural formula (xi) and B ₂ in the structural formula (xii) are divalent groups of an aromatic hydrocarbon ring such as an o-phenylene group or a 2,3-naphthylene group, 2,3- A divalent group of an aromatic heterocyclic ring such as a pyrinyl group, a 3,4-pyrazolyl group, a 2,3-pyridylyl group, a 4,5-pyridylyl group, a 4,5-imidazolyl group, and the like. Is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; an alkoxy group such as a methoxy group, an ethoxy group or a phenoxy group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; .

  The coupler compounds corresponding to the structural formula (v), the structural formula (vi), and the structural formula (vii) are disclosed in known methods, for example, Japanese Patent Application Laid-Open Nos. 2003-08252 and 2003-206411. According to a known method, it can be produced by subjecting a corresponding ester compound and an amine compound to an ester / amide exchange reaction (including a cyclization reaction).

Hereinafter, Table 7 to Table 26 show examples of coupler compounds corresponding to the coupler residue Cp ₂ represented by the structural formula (v), the structural formula (vi), and the structural formula (vii).

<Examples of coupler compounds>

<Examples of coupler compounds>

<Examples of coupler compounds>

<Examples of coupler compounds>

In the azo compound of the present invention, a monovalent coupler residue other than the structural formula (v), the structural formula (vi), and the structural formula (vii) can be used.
Examples of the coupler residue Cp ₂ that may coexist other than the structural formula (v), the structural formula (vi), and the structural formula (vii) include compounds having a phenolic hydroxyl group such as phenols and naphthols; Aromatic amino compounds having amino groups; compounds having amino groups and phenolic hydroxyl groups such as aminonaphthols; compounds having aliphatic or aromatic enol ketone groups (compounds having active methylene groups), etc. . Further, preferred are those represented by the following structural formula (Cp1) to the following structural formula (Cp15).

In the structural formulas (Cp1) to (Cp4), X ¹ , Y ¹ , Z ¹ , l and m each represent the following.
X ¹ represents —OH, —N (R ¹¹ ) (R ¹² ), or —NHSO ₂ —R ¹³ . (However, R ¹¹ and R ¹² represent a hydrogen atom or a substituted or unsubstituted alkyl group. R ¹³ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.)
Y ¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxy group, a sulfo group, a substituted or unsubstituted sulfamoyl group, or —CON (R ¹⁴ ) (Y ² ). ((R ¹⁴ represents a hydrogen atom, an alkyl group or a substituted product thereof, a phenyl group or a substituted product thereof. Y ² represents a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or —N═ C (R ¹⁵ ) (R ¹⁶ ) (wherein R ¹⁵ is a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof or a styryl group or a substituted product thereof, R ¹⁶ is a hydrogen atom, an alkyl group, Represents a phenyl group or a substituted product thereof, or R ¹⁵ and R ¹⁶ may form a ring together with carbon atoms bonded to them.)
Z ¹ represents a hydrocarbon ring or a substituted product thereof or a heterocyclic ring or a substituted product thereof.
l represents an integer of 1 or 2. m represents an integer of 1 or 2.

However, in the structural formula (Cp5), R ¹⁷ represents a substituted or unsubstituted hydrocarbon group. X ¹ represents the same meaning as described above.

However, in the structural formula (Cp6), W ¹ represents a divalent group of an aromatic hydrocarbon or a divalent group of a heterocyclic ring containing a nitrogen atom in the ring. These rings may be substituted or unsubstituted. X ₁ represents the same meaning as described above.

However, in the structural formula (Cp7), R ¹⁸ represents an alkyl group, a carbamoyl group, a carboxy group, or an ester thereof. Ar ¹ represents a hydrocarbon ring group or a substituted product thereof. X ¹ represents the same meaning as described above.

However, in the structural formulas (Cp8) and (Cp9), R ¹⁹ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Ar ² represents a hydrocarbon ring group or a substituted product thereof.

Examples of the hydrocarbon ring for Z ^{1 in} the structural formulas (Cp1) to (Cp4) include a benzene ring and a naphthalene ring. Examples of the heterocyclic ring that may have a substituent include an indole ring, a carbazole ring, a benzolane ring, and a dibenzofuran ring. Examples of the substituent in the ring of Z ¹ include halogen atoms such as chlorine atom and bromine atom.
Examples of the hydrocarbon ring group for Y ² or R ¹⁵ include a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group. Examples of the heterocyclic group include a pyridyl group, a thienyl group, a furyl group, an indolyl group, a benzofuranyl group, a carbazolyl group, and a dibenzofuranyl group. Furthermore, examples of the ring formed by combining R ¹⁵ and R ¹⁶ include a fluorene ring.
Examples of the substituent in the hydrocarbon ring group or heterocyclic group of Y ² or R ¹⁵ or the ring formed by R ¹⁵ and R ¹⁶ include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, methoxy group, Alkoxy groups such as ethoxy group, propoxy group, butoxy group, halogen atoms such as chlorine atom and bromine atom, dialkylamino groups such as dimethylamino group and diethylamino group, halomethyl groups such as trifluoromethyl group, nitro group, cyano group position , Carboxyl groups or esters thereof, hydroxyl groups, sulfonate groups such as —SO ₃ Na, and the like.
Examples of the substituent of the phenyl group of R ¹⁴ include a halogen atom such as a chlorine atom or a bromine atom.
Representative examples of the hydrocarbon group for R ¹⁷ or R ¹⁹ include alkyl groups such as a methyl group, ethyl group, propyl group, and butyl group, aryl groups such as a phenyl group, and substituted products thereof.
Examples of the substituent in the hydrocarbon group of R ¹⁷ or R ¹⁹ include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a chlorine atom, A halogen atom such as a bromine atom, a hydroxyl group, a nitro group and the like can be mentioned.
Typical examples of the hydrocarbon ring group in Ar ¹ or Ar ² include a phenyl group and a naphthyl group, and examples of the substituent in these groups include a methyl group, an ethyl group, a propyl group, and a butyl group. Alkoxy groups such as alkyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, halogen atoms such as nitro groups, chlorine atoms, bromine atoms, dialkylamino groups such as cyano groups, dimethylamino groups, diethylamino groups, etc. .
Further, it is appropriate especially hydroxyl groups in the X ^1.
Among the coupler residues, it is represented by the structural formula (Cp2), the structural formula (Cp5), the structural formula (Cp6), the structural formula (Cp7), the structural formula (Cp8), and the structural formula (Cp9). Coupler residues are preferred, and among these, those in which X ¹ in the above structural formula is a hydroxyl group are preferred.

  Among the coupler residues represented by the structural formula (Cp2), a coupler residue represented by the following structural formula (Cp10) is particularly preferable, and a coupler residue represented by the following structural formula (Cp11) is more preferable.

However, in the structural formula (Cp10), Y ¹ and Z ¹ represent the same meaning as described above.
However, in said structural formula (Cp11), Z < ¹ >, Y < ² > and R < ¹⁴ > represent the same meaning as the above.

Furthermore, among the preferable coupler residues, a coupler residue represented by the following structural formula (Cp12) or the following structural formula (Cp13) is particularly preferable.
In the structural formula (Cp12) and the structural formula (Cp13), Z ¹ , R ¹⁴ , R ¹⁵ and R ¹⁶ represent the same meaning as described above. In addition, examples of R ²⁰ include the above-described substituent of Y ² .

  Of the coupler residues represented by the structural formula (Cp6), a coupler residue represented by the following structural formula (Cp14) or the following structural formula (Cp15) is particularly preferable.

In the structural formulas (Cp14) and (Cp15), W ¹ represents a divalent group of an aromatic hydrocarbon or a divalent group of a heterocyclic ring containing a nitrogen atom in the ring. These rings may be substituted or unsubstituted.

  Among the preferred coupler residues, in particular, the coupler residues represented by the structural formula (Cp11), the structural formula (Cp14), and the structural formula (Cp15) are highly sensitive and excellent in azo compounds obtained in combination. It is preferable because it exhibits high charging stability.

Hereinafter, Tables 27 to 51 show examples of coupler compounds corresponding to the coupler residue Cp ₂ that may coexist other than the coupler residue.

  As described above, specific examples of the azo compound of the present invention are shown in the following Tables 52 to 53. For simplicity, the central skeleton (Ar portion) and the coupler compound are shown, and each of them is shown. The azo compound is represented by a combination of numbers, but is not limited thereto.

-Method for producing azo compound-
The azo compound of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, but can be produced by the following method. For example, when n ₂ = 1, a diazonium compound represented by the following structural formula (xiii) is combined with a coupler compound represented by the following structural formula (xiv) and a coupler compound represented by the following structural formula (xv): The diazonium salt compound obtained by the first coupling reaction is isolated and then the corresponding coupler compound is further reacted to represent the following structural formula (1). The azo compound of the present invention is obtained.

In the structural formula (1), the structural formula (xiii), the structural formula (xiv), and the structural formula (xv), Ar is a substituted or unsubstituted aromatic group that may be bonded via a bonding group. Represents a hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group. Cp ₁ represents a bivalent to hexavalent coupler residue, and Cp ₂ represents a monovalent coupler residue. Z ⁻ represents Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , ClO ₄ ⁻ , SO ₄ ²⁻ , a group represented by the following structural formula (xvi) , AsF ₆ ⁻ , SbF ₆ ^— and other anionic functional groups. n ₁ represents an integer of 2 . n ₂ represents an integer of 1 .

  In the above reaction, as a by-product, an oligomer azo compound or a polymer azo compound formed by coupling the diazonium compound represented by the structural formula (xiii) and the coupler compound represented by the structural formula (xiv), In some cases, a monoazo compound or a disazo compound produced by coupling the diazonium compound represented by the structural formula (xiii) and the coupler compound represented by the structural formula (xv) may be produced. In these, these by-products may be used without separation.

The photosensitive layer in the single-layer type photoreceptor includes a charge generation material, a charge transport material, a binder resin, and other components as necessary. As the charge generating substance, an azo compound represented by the structural formula (1) is preferably used.
The film thickness of the photosensitive layer is preferably 5 to 50 μm, and more preferably 5 to 30 μm. When the film thickness is less than 5 μm, the chargeability may decrease, and when it exceeds 50 μm, the sensitivity may decrease.
The charge generation layer in the multilayer photoconductor is a layer having a charge generation function, containing a charge generation material having a charge generation function as a main component, a binder resin, and further containing other components as required. As the charge generating substance, an azo compound represented by the structural formula (1) is preferably used.
The thickness of the charge generation layer is preferably 0.01 to 5 μm, more preferably 0.05 to 2 μm. If the film thickness is less than 0.01 μm, the generation of electric charges may be insufficient. If the film thickness exceeds 5 μm, the residual potential increases and is not practical.
The charge transport layer in the multilayer photoconductor is a layer having a charge transport function, and includes a charge transport material having a charge transport function as a main component, a binder resin, and, if necessary, other components. The thickness of the charge transport layer is preferably 5 to 50 μm, and more preferably 5 to 30 μm. If the film thickness is less than 5 μm, the amount of charge may be insufficient, and if it exceeds 50 μm, the residual potential increases and is not practical.

  When the photosensitive layer is formed by dispersing or dissolving the azo compound represented by the structural formula (1), the average particle size of the azo compound is preferably 2 μm or less in order to improve the dispersibility in the layer. Is more preferable. In addition, if the average particle size is too small, the particles tend to aggregate, and the resistance of the layer may increase, or crystal defects may increase and the sensitivity and repeatability may decrease. In consideration of the limit in miniaturization, the lower limit of the average particle diameter is preferably 0.01 μm.

The content of the azo compound represented by the structural formula (1) in the photosensitive layer is preferably 0.1 to 50% by mass and more preferably 0.3 to 30% by mass in the case of a single layer type. When the content is less than 0.1% by mass, the generation of electric charges may be insufficient. When the content exceeds 50% by mass, the mechanical durability may be lowered and the residual potential may be increased.
Moreover, in the case of a laminated type, 20 mass% or more is preferable and 50 mass% or more is more preferable. If the content is less than 20% by mass, charge generation may be insufficient.

In addition to the azo compound represented by the structural formula (1), the photosensitive layer or charge generation layer of the present invention may contain a charge generation material composed of an inorganic material or an organic material. Examples of the inorganic substance include selenium, selenium-tellurium, cadmium sulfide, cadmium sulfide-selenium, and α-silicon.
Examples of the organic substance include C-I Pigment Blue 25 (Color Index CI 21180), C-I Pigment Red 41 (CI 21200), C-I Acid Red 52 (CI 45100), C-I Basic Red 3 (CI 45210), and a carbazole skeleton. Azo pigments (Japanese Patent Laid-Open No. 53-95033), azo pigments having a distyrylbenzene skeleton (Japanese Patent Laid-Open No. 53-133445), azo pigments having a triphenylamine skeleton (Japanese Patent Laid-Open No. 53-132347) , An azo pigment having a dibenzothiophene skeleton (Japanese Patent Laid-Open No. 54-21728), an azo pigment having an oxadiazole skeleton (Japanese Patent Laid-Open No. 54-12742), and an azo pigment having a fluorenone skeleton (Japanese Patent Laid-Open No. Sho 54- No. 22834), screw An azo pigment having a tilbene skeleton (Japanese Patent Laid-Open No. 54-17733), an azo pigment having a distyryl oxadiazole skeleton (Japanese Patent Laid-Open No. 54-2129), an azo pigment having a distyryl carbazole skeleton (Japanese Patent Laid-Open No. Azo pigments such as C.I. Pigment Blue 16 (CI 74100), phthalocyanine-based pigments such as titanyl phthalocyanine, such as C. I.But Brown 5 (CI 73410), C. I. Batdie (CI 73030) and the like. Indico pigments, perylene pigments such as Argo Scarlet B (manufactured by Bayer), Insence Scarlet R (manufactured by Bayer), and the like.

The charge generating material used in the photosensitive layer may be used after a specific crystal conversion treatment. Examples of the crystal conversion treatment method include solvent treatment, mechanical treatment, and heat treatment. The solvent treatment means a suspension stirring treatment of a pigment in a solvent at room temperature or under heating. Wherein the milling process, for example, represents the glass beads, steel over Rubys, sand mill using alumina balls or the like, using a milling apparatus such as a ball mill, a process for performing normal temperature or under heating. The milling process may be performed in a system in which a solvent is added together with the milling media. Solvents used for these treatments include, for example, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidine, dimethyl sulfoxide, toluene, xylene, monochlorobenzene, 1,2-dichloroethane. 1,1,1-trichloroethane, dichloromethane, 1,1,2-trichloroethane, trichloroethylene, tetrahydrofuran, dioxane, dioxolane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, Examples include butanol and 2-methoxyethanol.
These charge generation materials may be used alone or in combination of two or more.

-Charge transport material-
The photosensitive layer or charge transport layer of the present invention preferably contains a charge transport material. Examples of the charge transport material include poly-N-carbazole or derivatives thereof, poly-γ-carbazolylethyl glutamate or derivatives thereof, pyrene-formaldehyde condensates or derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, oxazole derivatives, imidazole. Derivatives, triphenylamine derivatives, low molecular charge transport materials represented by the following structural formulas (T1) to (T18), and polymer charge transport materials represented by the following structural formulas (1D) to (11D) are preferably used. The

  Although it represents the exemplary compound of the low molecular charge transport material represented by the structural formulas (T1) to (T18), it is not limited thereto.

However, in the structural formula (T1), R ¹ represents a methyl group, an ethyl group, a 2-hydroxyethyl group, or a 2-chloroethyl group. R ² represents a methyl group, an ethyl group, a benzyl group or a phenyl group. R ³ represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group, or a nitro group.

  Examples of the compound represented by the structural formula (T1) include 9-ethylcarbazole-3-aldehyde-1-methyl-1-phenylhydrazone, 9-ethylcarbazole-3-aldehyde-1-benzyl-1-phenyl. And hydrazone, 9-ethylcarbazole-3-aldehyde-1,1-diphenylhydrazone, and the like.

However, in the structural formula (T2), Ar ¹ represents a naphthalene ring, an anthracene ring, a styryl ring, a substituted product thereof, a pyridine ring, a furan ring, or a thiophene ring. R ⁴ represents an alkyl group or a benzyl group.

  Examples of the compound represented by the structural formula (T2) include 4-diethylaminostyryl-β-aldehyde-1-methyl-1-phenylhydrazone, 4-methoxynaphthalene-1-aldehyde-1-benzyl-1-phenyl. And hydrazone.

However, in the structural formula (T3), R ⁵ represents an alkyl group, a benzyl group, a phenyl group, or a naphthyl group. R ⁶ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, a diaralkylamino group, or a diarylamino group. n represents an integer of 1 to 4. When n is 2 or more, R ⁶ may be the same or different. R ₇ represents a hydrogen atom or a methoxy group.

  Examples of the compound represented by the structural formula (T3) include 4-methoxybenzaldehyde-1-methyl-1-phenylhydrazone, 2,4-dimethoxybenzaldehyde-1-benzyl-1-phenylhydrazone, and 4-diethylaminobenzaldehyde. -1,1-diphenylhydrazone, 4-methoxybenzaldehyde-1- (4-methoxy) phenylhydrazone, 4-diphenylaminobenzaldehyde-1-benzyl-1-phenylhydrazone, 4-dibenzylaminobenzaldehyde-1,1-diphenyl And hydrazone.

However, in the structural formula (T4), R ⁸ represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group, or a heterocyclic group. R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a chloroalkyl group, or a substituted or unsubstituted aralkyl group. R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing heterocyclic ring. R ¹¹ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen atom.

  Examples of the compound represented by the structural formula (T4) include 1,1-bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl) methane, and 1,1-bis (4-dibenzyl). Aminophenyl) propane, 2,2′-dimethyl-4,4′-bis (diethylamino) -triphenylmethane, and the like.

However, in the structural formula (T5), R ¹² represents a hydrogen atom or a halogen atom. Ar ² represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group or carbazolyl group.

  Examples of the compound represented by the structural formula (T5) include 9- (4-diethylaminostyryl) anthracene, 9-bromo-10- (4-diethylaminostyryl) anthracene, and the like.

However, in the structural formula (T6), R ¹³ represents a hydrogen atom, a halogen atom, a cyano group, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Ar ³ represents a group represented by the following structural formula.

In Structural ^{Formula, R 14} represents an alkyl group having 1 to 4 carbon atoms. R ¹⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a dialkylamino group. n is 1 or 2, and when n is 2, R ¹⁵ may be the same or different, and R ¹⁶ and R ¹⁷ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, Or represents a substituted or unsubstituted benzyl group.

  Examples of the compound represented by the structural formula (T6) include 9- (4-dimethylaminobenzylidene) fluorene, 3- (9-fluorenylidene) -9-ethylcarbazole, and the like.

However, in the structural formula (T7), R ¹⁸ represents a carbazolyl group, a pyridyl group, a thienyl group, an indolyl group, a furyl group, or a substituted or unsubstituted phenyl group, a styryl group, a naphthyl group, or an anthryl group, respectively. These are further selected from dialkylamino groups, alkyl groups, alkoxy groups, carboxy groups or esters thereof, halogen atoms, cyano groups, aralkylamino groups, N-alkyl-N-aralkylamino groups, amino groups, nitro groups, and acetylamino groups. May be substituted with a substituent selected from the group consisting of:

  Examples of the compound represented by the structural formula (T7) include 1,2-bis (4-diethylaminostyryl) benzene, 1,2-bis (2,4-dimethoxystyryl) benzene, and the like.

However, in the structural formula (T8), R ¹⁹ represents a lower alkyl group, a substituted or unsubstituted phenyl group, or a benzyl group. R ²⁰ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, an amino group, an amino group substituted with a lower alkyl group or a benzyl group, and n represents an integer of 1 or 2.

  Examples of the compound represented by the structural formula (T8) include 3-styryl-9-ethylcarbazole, 3- (4-methoxystyryl) -9-ethylcarbazole, and the like.

However, in the structural formula (T9), R ²¹ represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. R ²² and R ²³ represent an alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group. R ²⁴ represents a hydrogen atom, a lower alkyl group, or a substituted or unsubstituted phenyl group. Ar ⁴ represents a substituted or unsubstituted phenyl group or naphthyl group.

  Examples of the compound represented by the structural formula (T9) include 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4-diphenylaminostyryl) naphthalene, 1- ( 4-diethylaminostyryl) naphthalene, and the like.

However, in the structural formula (T10), n represents an integer of 0 or 1. R ²⁵ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted phenyl group. Ar ₅ represents a substituted or unsubstituted aryl group. R ²⁶ represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group. A ¹ represents a group represented by the following structural formula, a 9-anthryl group, or a substituted or unsubstituted carbazolyl group.
In the structural formula, R ²⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a group represented by the following structural formula. m represents an integer of 0 to 3. When m is 2 or more, R ²⁷ may be the same or different. When n is 0, A ¹ and R ²⁵ may form a ring together.
In the structural formulas, R ²⁸ and R ²⁹ represent an alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group. R ²⁸ and ^{R 29} may be the same or ^{different, R 29} may form a ring.

  Examples of the compound represented by the structural formula (T10) include 4′-diphenylamino-α-phenylstilbene, 4′-bis (4-methylphenyl) amino-α-phenylstilbene, and the like.

However, in the structural formula (T11), R ³⁰ , R ^31, and R ³² represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, or a dialkylamino group. n represents 0 or 1.

  Examples of the compound represented by the structural formula (T11) include 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazoline.

However, in the structural formula (T12), R ³³ and R ³⁴ represent an alkyl group including a substituted alkyl group, or a substituted or unsubstituted aryl group. A ² represents a substituted amino group, a substituted or unsubstituted aryl group or an allyl group.

  Examples of the compound represented by the structural formula (T12) include 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, 2-N, N-diphenylamino-5- ( 4-diethylaminophenyl) -1,3,4-oxadiazole, 2- (4-dimethylaminophenyl) -5- (4-diethylaminophenyl) -1,3,4-oxadiazole, and the like.

However, in the structural formula (T13), X ₁ represents a hydrogen atom, a lower alkyl group, or a halogen atom. R ₃₅ represents an alkyl group containing a substituted alkyl group or a substituted or unsubstituted aryl group. A ₃ represents a substituted amino group or a substituted or unsubstituted aryl group.

  Examples of the compound represented by the structural formula (T13) include 2-N, N-diphenylamino-5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole, 2- (4-diethylaminophenyl) -5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole, and the like.

In the Structural Formula _{(T14), R 36} is a lower alkyl group, a lower alkoxy group or a halogen atom, n represents an integer of 0-4. R ₃₇ and R ₃₈ may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom.

  Examples of the benzidine compound represented by the structural formula (T14) include N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4 ′. -Diamine, 3,3'-dimethyl-N, N, N ', N'-tetrakis (4-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine, and the like.

In the Structural formula _{(T15), R 39, R} 41 and _{R 42,} a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, Represents a halogen atom or a substituted or unsubstituted aryl group. R ₄₀ represents a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group, or a halogen atom. However, R ₃₉ , R ₄₀ , R ₄₁ and R ₄₂ are excluded when they are all hydrogen atoms. K, l, m, and n are integers of 1, 2, 3, or 4, and when each is an integer of 2, 3, or 4, R ₃₉ , R ₄₀ , R _41, and R ₄₂ are the same or different. It may be.

  Examples of the biphenylamine compound represented by the structural formula (T15) include 4′-methoxy-N, N-diphenyl- [1,1′-biphenyl] -4-amine, 4′-methyl-N, N. -Bis (4-methylphenyl)-[1,1'-biphenyl] -4-amine, 4'-methoxy-N, N-bis (4-methylphenyl)-[1,1'-biphenyl] -4- Amines, and the like.

However, in the structural formula (T16), Ar ₆ represents a condensed polycyclic hydrocarbon group having 18 or less carbon atoms. R ₄₃ and R ₄₄ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, or a substituted or unsubstituted phenyl group, and may be the same or different.

  Examples of the triarylamine compound represented by the structural formula (T16) include 1-diphenylaminopyrene, 1-di (p-tolylamino) pyrene, and the like.

However, Ar ₇ in the structural formula (T17) represents a substituted or unsubstituted aromatic hydrocarbon group. A ₄ represents a group represented by the following structural formula.
In the structural formula, Ar ₈ represents a substituted or unsubstituted aromatic hydrocarbon group. R ₄₅ and R ₄₆ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

  Examples of the diolefin aromatic compound represented by the structural formula (T17) include 1,4-bis (4-diphenylaminostyryl) benzene and 1,4-bis [4-di (p-tolyl) aminostyryl. ] Benzene, etc.

However, in the structural formula (T18), Ar ₉ represents a substituted or unsubstituted aromatic hydrocarbon group. R ₄₇ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. n is 0 or 1, m is 1 or 2, and when n = 0 and m = 1, Ar ₉ and R ₄₇ may jointly form a ring.

  Examples of the styrylpyrene compound represented by the structural formula (T18) include 1- (4-diphenylaminostyryl) pyrene, 1- [4-di (p-tolyl) aminostyryl] pyrene, and the like.

  Among the low molecular charge transport materials, stilbene compounds are particularly preferably used because of their good compatibility with the polymer matrix and high charge transport ability. Among these, the stilbene compound represented by the structural formula (T9) and the structural formula (T10), and the stilbene compound represented by the following structural formula (2) are used in combination with the azo compound of the present invention. This is particularly preferable because it exhibits excellent electrostatic characteristics.

However, in the structural formula (2), T ¹ and T ² represent an alkyl group or an aryl group which may be the same as or different from each other, and these are further substituted with a substituent. Also good. T ¹ and T ² may form a ring with each other. T ³ and T ⁴ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may be further substituted with a substituent. Ar ′ represents an aryl group or a heterocyclic group, and these may be further substituted with a substituent.

  The content of the low molecular charge transport material in the photosensitive layer (photosensitive layer in the case of a single layer type photoreceptor, charge transport layer in the case of a laminated type photoreceptor) is preferably 15 to 95% by mass. 90 mass% is more preferable. When the content is less than 15% by mass, charge transport may be insufficient, and when the content exceeds 95% by mass, mechanical durability may be deteriorated.

-Polymer charge transport material-
As the polymer charge transporting material of the present invention, a polymer comprising at least one of polycarbonate, polyurethane, polyester, and polyether is used. Among these, a polymer charge transport material having a triarylamine structure is preferable. Among these, a polycarbonate having a triarylamine structure is particularly preferable, and among these, a polycarbonate having a triarylamine structure represented by the following structural formulas (1D) to (11D) is particularly preferable.

Next, the polymer charge transport material represented by the following structural formula (1D) will be described in detail.
In the structural formula (1D), R ′ ₁ , R ′ ₂ and R ′ ₃ each independently represent a substituted or unsubstituted alkyl group or a halogen atom, and R ′ ₄ represents a hydrogen atom or a substituted or unsubstituted group. Represents a substituted alkyl group. R ₁ and R ₂ represent a substituted or unsubstituted aryl group. o, p, and q each independently represents an integer of 0 to 4. k and j represent composition ratios, 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, n represents the number of repeating units, and is an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following structural formula (A).
However, in said structural formula (A), R <_24> , R < ₂₅ > represents a substituted or unsubstituted alkyl group, an aryl group, or a halogen atom each independently, and l and m represent the integer of 0-4. Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO—O—. Z-O-CO- (wherein Z represents an aliphatic divalent group) or the following structural formula (B). R ₂₄ and R ₂₅ may be the same or different.
However, in said structural formula (B), a represents the integer of 1-20. b represents an integer of 1 to 2000. R ₂₆ and R ₂₇ represent a substituted or unsubstituted alkyl group or aryl group. R ₂₆ and R ₂₇ may be the same or different.

In the structural formula (1D), the alkyl group of R ′ ₁ , R ′ ₂ , R ′ ₃ is preferably a linear or branched chain having 1 to 12 carbon atoms, particularly 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. These alkyl groups are further a fluorine atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 1 carbon atom. It may contain a phenyl group substituted with 4 alkoxy groups. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the substituted or unsubstituted alkyl group for R ′ ₄ include the same groups as those described above for R ′ ₁ , R ′ ₂ , and R ′ ₃ . Examples of the aryl group of R ₁ and R ₂ include aromatic hydrocarbon groups such as phenyl groups, naphthyl groups, pyrenyl groups, 2-fluorenyl groups, 9,9-dimethyl-2-fluorenyl groups, azulenyl groups, anthryl groups, and triphenylenyls. Group, chrycenyl group, fluorenylidenephenyl group, condensed polycyclic group such as 5H-dibenzo [a, d] cycloheptenylidenephenyl group, non-condensed polycyclic group such as biphenylyl group and terphenylyl group, thienyl group, benzothienyl And heterocyclic groups such as a group, a furyl group, a benzofuranyl group, and a carbazolyl group.

The above-mentioned aryl group may have a group shown below as a substituent.
(1) A halogen atom, a trifluoromethyl group, a cyano group, a nitro group, etc. are mentioned.
(2) Alkyl group: the same as those shown as the alkyl groups for R ′ ₁ , R ′ ₂ and R ′ ₃ above.
(3) Alkoxy group (—OR ₄₁ ): R ₄₁ represents the alkyl group shown in the above (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) Aryloxy group: Examples of the aryl group include a phenyl group and a naphthyl group. These may contain a C1-C4 alkoxy group, a C1-C4 alkyl group or a halogen atom as a substituent. Specifically, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group, etc. Can be mentioned.
(5) Substituted mercapto group or aryl mercapto group: Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) Alkyl-substituted amino group: The alkyl group represents the alkyl group shown in the above (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
(7) Acyl group: Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

  X is a main chain obtained by using a diol compound of the following structural formula (C) together when a diol compound having a triarylamino group of the following structural formula (1D ′) is polymerized using a phosgene method, a transesterification method, or the like. Introduced in. In this case, the polycarbonate to be produced is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group represented by the following structural formula (1D ') and a bischloroformate derived from the following structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.

  Examples of the diol compound of the structural formula (C) include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol And aliphatic diols such as polytetramethylene ether glycol; cyclic aliphatic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, and cyclohexane-1,4-dimethanol.

  Examples of the diol having an aromatic ring include 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4- Hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxypheny ) Propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide, 3 , 3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl oxide, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) Fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol-bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate), 1, 3-bis 4-hydroxyphenyl) - tetramethyldisiloxane, phenol-modified silicone oil, and the like.

Next, the polymer charge transport material represented by the following structural formula (2D) will be described in detail.
However, in said structural formula (2D), R < ₃ >, R < ₄ > represents a substituted or unsubstituted aryl group, Ar < ₁ >, Ar < ₂ >, Ar < ₃ > represents the same or different arylene group. k and j represent compositions, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the number of repeating units and is an integer of 5 to 5000. X represents a group similar to that described in the structural formula (1D).

Examples of the aryl group of R ₃ and R ₄ include an aromatic hydrocarbon group such as a phenyl group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, and triphenylenyl. Group, chrysenyl group, fluorenylidenephenyl group, condensed polycyclic group such as 5H-dibenzo [a, d] cycloheptenylidenephenyl group, thienyl group, benzothienyl group, furyl group, benzofuranyl group, carbazolyl group and the like Examples thereof include a cyclic group, a biphenylyl group, a terphenylyl group, and a non-condensed polycyclic group represented by the following structural formula (a).
However, in the structural formula (a), W represents —O—, —S—, —SO—, —SO ₂ —, —CO— and the following structural formulas (b), (c), (d), or The divalent group represented by (e) is represented.
However, in the structural formulas (b) to (e), c represents an integer of 1 to 12. d, e, and f represent an integer of 1 to 3.

_As the arylene group Ar _1, Ar 2, Ar _3, include a divalent group of the aryl group represented by R 3, _{R 4.} The aryl group of R ₃ and R _{4 and} the arylene group of Ar ₁ , Ar ₂ , and Ar ₃ may have the following groups as substituents. These substituents are also specific examples of R ₃₁ , R ₃₂ and R _{33 in} the structural formulas (a), (d) and (e).

(1) A halogen atom, a trifluoromethyl group, a cyano group, a nitro group, etc. are mentioned.
(2) Alkyl group: Preferably, it is a linear or branched alkyl group having 1 to 12 carbon atoms, especially 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and these alkyl groups are further fluorine atoms. A phenyl group substituted with a hydroxyl group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Good. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (—OR ₄₁ ): R ₄₁ represents the alkyl group shown in the above (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) Aryloxy group: Examples of the aryl group include a phenyl group and a naphthyl group. These may contain a C1-C4 alkoxy group, a C1-C4 alkyl group, or a halogen atom as a substituent. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. It is done.
(5) Substituted mercapto group or aryl mercapto group: Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) Structural formula: The substituted amino group represented by -N (R < ₄₂ >) (R _<43> ), etc. are mentioned.
However, in the structural formula, R ₄₂ and R ₄₃ each independently represent an alkyl group represented by the above (2) or an aryl group represented by the above R ₃ or R _4. Preferred aryl groups include, for example, a phenyl group , Biphenyl group or naphthyl group, and these may contain a C1-C4 alkoxy group, a C1-C4 alkyl group or a halogen atom as a substituent. Moreover, you may form a ring in cooperation with the carbon atom on an aryl group. Specifically, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino group, Examples include a yurolidyl group.
(7) An alkylenedioxy group such as a methylenedioxy group or a methylenedithio group, or an alkylenedithio group.

  X is obtained by polymerizing a diol compound having a triarylamino group represented by the following structural formula (2D ′) using a phosgene method, a transesterification method, or the like, by using the diol compound represented by the following structural formula (C) together. Introduced in. In this case, the polycarbonate to be produced is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group represented by the following structural formula (2D ') and a bischloroformate derived from the following structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.

Examples of the diol compound of the structural formula (C) include those exemplified in the description of the structural formula (1D).

Next, the polymer charge transport material represented by the structural formula (3D) will be described in detail.
In the Structural Formula _{(3D), R 5, R} 6 represents a substituted or unsubstituted aryl _{group, Ar 4, Ar 5, Ar} 6 independently represent an arylene group. k and j represent compositions, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the number of repeating units and is an integer of 5 to 5000. X represents a group similar to that described in the structural formula (1D).

Examples of the aryl group of R ₅ and R ₆ include an aromatic hydrocarbon group such as a phenyl group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, and triphenylenyl. Group, chrycenyl group, fluorenylidenephenyl group, condensed polycyclic group such as 5H-dibenzo [a, d] cycloheptenylidenephenyl group, non-condensed polycyclic group such as biphenylyl group and terphenylyl group, thienyl group, benzothienyl And heterocyclic groups such as a group, a furyl group, a benzofuranyl group, and a carbazolyl group.

_As the arylene group _{Ar 4, Ar 5, Ar 6} , include a divalent group of the aryl group represented by R 5, _{R 6.} The aryl group of R ₅ and R _{6 and} the arylene group of Ar ₄ , Ar ₅ and Ar ₆ may have the following groups as substituents.
(1) A halogen atom, a trifluoromethyl group, a cyano group, a nitro group, etc. are mentioned.
(2) Alkyl group: Preferably it is a C1-C12, especially 1-8, More preferably, it is a linear or branched alkyl group of 1-4, These alkyl groups are a fluorine atom, a hydroxyl group, and a cyano group. , A phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms may be contained. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.
(3) Alkoxy group (—OR ₄₁ ): R ₄₁ represents the alkyl group shown in the above (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano Examples include ethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
(4) Aryloxy group: Examples of the aryl group include a phenyl group and a naphthyl group. These may contain a C1-C4 alkoxy group, a C1-C4 alkyl group, or a halogen atom as a substituent. Specifically, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6-methyl-2-naphthyloxy group, etc. Can be mentioned.
(5) Substituted mercapto group or aryl mercapto group: Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) Alkyl-substituted amino group: The alkyl group represents the alkyl group shown in the above (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group.
(7) Acyl group: Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

  X is obtained by polymerizing a diol compound having a triarylamino group represented by the following structural formula (3D ′) by using a diol compound represented by the following structural formula (C) in combination with a phosgene method or a transesterification method. Introduced in. In this case, the polycarbonate to be produced is a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group represented by the following structural formula (3D ') and a bischloroformate derived from the following structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.

  Specific examples of the diol compound of the structural formula (C) include those exemplified in the description of the structural formula (1D).

Next, the polymer charge transport material represented by the following structural formula (4D) will be described in detail.
However, the structural formula _{(4D), R 7, R} 8 represents a substituted or unsubstituted aryl _{group, Ar 7, Ar 8, Ar} 9 independently represent an arylene group. k and j represent compositions, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the number of repeating units and is an integer of 5 to 5000. r represents an integer of 1 to 5. X represents a group similar to that described in the structural formula (1D).

Examples of the aryl group of R ₇ and R ₈ include those exemplified as specific examples of the aryl group of R ₅ and R ₆ in the description of the structural formula (3D). Ar ₇ , Ar ₈ , Ar ₉ Specific examples of the arylene group include divalent groups of those aryl groups. Specific examples of the substituent in the aryl group or arylene group include those exemplified as the substituent in the aryl group or arylene group in the description of the structural formula (3D).

X is obtained by polymerizing a diol compound having a triarylamino group represented by the following structural formula (4D ′) using a phosgene method, a transesterification method, or the like, by using the diol compound represented by the following structural formula (C) together. Introduced in. In this case, the produced polycarbonate becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group represented by the following structural formula (4D ′) and a bischloroformate derived from the following structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.
Specific examples of the diol compound represented by the structural formula (C) include those exemplified in the description of the structural formula (1D).

Next, the polymer charge transport material represented by the following structural formula (5D) will be described in detail.
In the Structural Formula _{(5D), R 9, R} 10 represents a substituted or unsubstituted aryl _{group, Ar 10, Ar 11, Ar} 12 represents an identical or different arylene groups. X ₁ and X ₂ represent a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group. k and j represent composition ratios, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the number of repeating units and is an integer of 5 to 5000. X represents a group similar to that described in the structural formula (1D).

Specific examples of the aryl group of R ₉ and R ₁₀ include those exemplified as specific examples of the aryl group of R ₅ and R ₆ in the description of the structural formula (3D). Ar ₁₀ , Ar ₁₁ , Specific examples of the arylene group for Ar ₁₂ include divalent groups of these aryl groups. Specific examples of the substituent in the aryl group or arylene group include those exemplified as the substituent in the aryl group or arylene group in the description of the structural formula (3D). Examples of the substituent in the ethylene group or vinylene group of X ₁ and X ₂ include a cyano group, a halogen atom, a nitro group, and aryl exemplified as specific examples of the aryl group of R ₅ and R ₆ in the description of the structural formula (3D). Group, or the alkyl group exemplified as the substituent in the aryl group or arylene group in the description of the structural formula (3D).

X is a main chain obtained by using a diol compound of the following structural formula (C) together when a diol compound having a triarylamino group of the following structural formula (5D ′) is polymerized using a phosgene method, a transesterification method, or the like. Introduced in. In this case, the produced polycarbonate becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group represented by the following structural formula (5D ′) and a bischloroformate derived from the following structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.
Specific examples of the diol compound represented by the structural formula (C) include those exemplified in the description of the structural formula (1D).

Next, the polymer charge transport material represented by the following structural formula (6D) will be described in detail.
In the Structural Formula _{(6D), R 11, R} 12, R 13, R 14 represents a substituted or unsubstituted aryl _{group, Ar 13, Ar 14, Ar} 15, Ar 16 are identical or different arylene group Represents. Y ₁ , Y ₂ and Y ₃ represent a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom or a vinylene group, and are the same Or different. k and j represent composition ratios, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the number of repeating units and is an integer of 5 to 5000. X represents a group similar to that described in the structural formula (1D).

Specific examples of the aryl group represented by R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ include those exemplified as specific examples of the aryl group represented by R ₅ and R ₆ in the description of the structural formula (3D). Specific examples of the arylene groups of Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ include divalent groups of these aryl groups. Specific examples of the substituent in the aryl group or arylene group include those exemplified as the substituent in the aryl group or arylene group in the description of the structural formula (3D).

Examples of the alkylene group for Y ₁ , Y ₂ , and Y ₃ include a divalent group derived from an alkyl group exemplified as a substituent for an aryl group or an arylene group in the description of the structural formula (3D). Specifically, methylene group, ethylene group, 1,3-propylene group, 1,4-butylene group, 2-methyl-1,3-propylene group, difluoromethylene group, hydroxyethylene group, cyanoethylene group, methoxyethylene Group, phenylmethylene group, 4-methylphenylmethylene group, 2,2-propylene group, 2,2-butylene group, diphenylmethylene group and the like. Examples of the cycloalkylene group include a 1,1-cyclopentylene group, a 1,1-cyclohexylene group, and a 1,1-cyclooctylene group. Examples of the alkylene ether group include a dimethylene ether group, a diethylene ether group, an ethylene methylene ether group, a bis (triethylene) ether group, and a polytetramethylene ether group.

X is obtained by polymerizing a diol compound having a triarylamino group represented by the following structural formula (6D ′) by using a phosgene method, a transesterification method, or the like, in combination with a diol compound represented by the following structural formula (C). Introduced in. In this case, the produced polycarbonate becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group represented by the following structural formula (6D ′) and a bischloroformate derived from the following structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.
Specific examples of the diol compound represented by the structural formula (C) include those exemplified in the description of the structural formula (1D).

Next, the polymer charge transport material represented by the following structural formula (7D) will be described in detail.
However, in the structural formula (7D), R ₁₅ and R ₁₆ represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₅ and R ₁₆ may form a ring. Ar ₁₇ , Ar ₁₈ and Ar ₁₉ represent the same or different arylene groups. k and j represent composition ratios, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the number of repeating units and is an integer of 5 to 5000. X represents a group similar to that described in the structural formula (1D).

Specific examples of the aryl group of R ₁₅ and R ₁₆ include those exemplified as specific examples of the aryl group of R ₅ and R ₆ in the description of the structural formula (3D). Also, R ₁₅ and R ₁₆ can be exemplified. Examples of the case where 9 forms a ring include 9-fluorinidene, 5H-dibenzo [a, d] cycloheptenylidene, and the like. Specific examples of the arylene group for Ar ₁₇ , Ar ₁₈ , and Ar ₁₉ include divalent groups of these aryl groups. Specific examples of the substituent in the aryl group or arylene group include those exemplified as the substituent in the aryl group or arylene group in the description of the structural formula (3D).

X is obtained by polymerizing a diol compound having a triarylamino group represented by the following structural formula (7D ′) using a phosgene method, a transesterification method, or the like, by using the diol compound represented by the following structural formula (C) together. Introduced in. In this case, the produced polycarbonate becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group represented by the following structural formula (7D ′) and a bischloroformate derived from the following structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.
Specific examples of the diol compound represented by the structural formula (C) include those exemplified in the description of the structural formula (1D).

Next, the polymer charge transport material represented by the following structural formula (8D) will be described in detail.
However, in the structural formula (8D), R ₁₇ represents a substituted or unsubstituted aryl group, and Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , and Ar ₂₃ represent the same or different arylene groups. k and j represent compositions, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the number of repeating units and is an integer of 5 to 5000. X represents a group similar to that described in the structural formula (1D).

Specific examples of the aryl group of R ₁₇ include those exemplified as specific examples of the aryl group of R ₅ and R ₆ in the description of the structural formula (3D). Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , Specific examples of the arylene group for Ar ₂₃ include divalent groups of these aryl groups. Specific examples of the substituent in the aryl group or arylene group include those exemplified as the substituent in the aryl group or arylene group in the description of the structural formula (3D).

X is obtained by polymerizing a diol compound having a triarylamino group represented by the following structural formula (8D ′) using a phosgene method, a transesterification method, or the like, by using a diol compound represented by the following structural formula (C) together. Introduced in. In this case, the produced polycarbonate becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following structural formula (8D ′) and a bischloroformate derived from the following structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.
Specific examples of the diol compound represented by the structural formula (C) include those exemplified in the description of the structural formula (1D).

Next, the polymer charge transport material represented by the following structural formula (9D) will be described in detail.
However, in said structural formula (9D), R < ₁₈ >, R < ₁₉ >, R < ₂₀ > and R < ₂₁ > represent a substituted or unsubstituted aryl group, and Ar < ₂₄ >, Ar < ₂₅ >, Ar < ₂₆ >, Ar < ₂₇ >, Ar < ₂₈ > are the same. Or represents a different arylene group. k and j represent compositions, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the number of repeating units and is an integer of 5 to 5000. X represents a group similar to that described in the structural formula (1D).

Specific examples of the aryl group of R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ include those exemplified as specific examples of the aryl group of R ₅ and R ₆ in the description of the structural formula (3D). Ar Specific examples of the arylene group of ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ , Ar ₂₈ include divalent groups of these aryl groups. Specific examples of the substituent in the aryl group or arylene group include those exemplified as the substituent in the aryl group or arylene group in the description of the structural formula (3D).

X is a main chain obtained by using a diol compound of the following structural formula (C) together when a diol compound having a triarylamino group of the following structural formula (9D ′) is polymerized using a phosgene method, a transesterification method, or the like. Introduced in. In this case, the produced polycarbonate becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction of a diol compound having a triarylamino group of the following structural formula (9D ′) and a bischloroformate derived from the following structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.
Specific examples of the diol compound represented by the structural formula (C) include those exemplified in the description of the structural formula (1D).

Next, the polymer charge transport material represented by the following structural formula (10D) will be described in detail.
However, in said structural formula (10D), R < ₂₂ >, R < ₂₃ > represents a substituted or unsubstituted aryl group, Ar < ₂₉ >, Ar < ₃₀ >, Ar < ₃₁ > represents the same or different arylene group. k and j represent compositions, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the number of repeating units and is an integer of 5 to 5000. X represents a group similar to that described in the structural formula (1D).

Specific examples of the aryl group of R ₂₂ and R ₂₃ include those exemplified as specific examples of the aryl group of R ₅ and R ₆ in the description of the structural formula (3D). Ar ₂₉ , Ar ₃₀ , Specific examples of the arylene group for Ar ₃₁ include divalent groups of these aryl groups. Specific examples of the substituent in the aryl group or arylene group include those exemplified as the substituent in the aryl group or arylene group in the description of the structural formula (3D).

X is a main chain obtained by using a diol compound of the following structural formula (C) together when a diol compound having a triarylamino group of the following structural formula (10D ′) is polymerized using a phosgene method, a transesterification method, or the like. Introduced in. In this case, the produced polycarbonate becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group represented by the following structural formula (10D ′) and a bischloroformate derived from the following structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.
Specific examples of the diol compound represented by the structural formula (C) include those exemplified in the description of the structural formula (1D).

Next, the polymer charge transport material represented by the following structural formula (11D) will be described in detail.
However, in the structural formula (11D), Ar ₃₂ , Ar ₃₃ , Ar _35, and Ar ₃₆ represent a substituted or unsubstituted arylene group. Ar34 represents a substituted or unsubstituted aryl group. Z represents an arylene group or —Ar ₃₇ —Za—Ar ₃₇ —. Ar ₃₇ represents a substituted or unsubstituted arylene group. Za represents O, S or an alkylene group. R and R ′ represent a linear or branched alkylene group or —O—. h represents 0 or 1. k and j represent composition ratios, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the number of repeating units and is an integer of 5 to 5000.

X is a substituted or unsubstituted aliphatic divalent group, a substituted or unsubstituted cyclic aliphatic divalent group, a substituted or unsubstituted aromatic divalent group, or a divalent group formed by linking these, or The divalent group represented by Structural Formula (A ′), Structural Formula (F), and Structural Formula (G) is represented.
However, in the structural formula (A ′), the structural formula (F), and the structural formula (G), R ²⁴ , R ²⁵ , R ⁵⁵ , and R ⁵⁶ are each independently a substituted or unsubstituted alkyl group, substituted Alternatively, it represents an unsubstituted aryl group or a halogen atom. l and m each independently represent an integer of 0 to 4. s and t each independently represent an integer of 0 to 3. When a plurality of R ²⁴ , R ²⁵ , R ⁵⁵ , and R ⁵⁶ are present, they may be the same or different. Y is a divalent group composed of a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, an alkylene group having 1 to 10 carbon atoms, one or more oxygen atoms, and a sulfur atom. Group, —O—, —S—, —SO—, —SO ₂ —, —CO—, —COO—, —CO—O—Z ₁ —O—CO—, —CO—Z ₂ —CO— (provided that In the formula, Z ₁ and Z ₂ represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group), or a structural formula from the following structural formula (B) or the following structural formula (H). (N).

However, in the structural formula (B), R ²⁶ and R ²⁷ each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
In Structural Formula (H) to Structural Formula (N), R ⁵⁷ , R ⁵⁸ , and R ⁶⁴ are each a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group Represents an aryl group. R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , and R ⁶³ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group Represents. R ⁵⁸ and R ⁵⁹ may combine to form a carbocyclic ring having 5 to 12 carbon atoms. R ₆₅ and R ₆₆ represent an end bond or an alkylene group having 1 to 4 carbon atoms. a is an integer of 1 to 20, b is an integer of 1 to 2000, u and w are integers of 0 to 4, and v is 1 or 2. When there are a plurality of R ²⁶ , R ²⁷ , R ⁵⁷ and R ⁶⁴ , they may be the same or different.

Specific examples of the aryl group of Ar ₃₄ include those exemplified as specific examples of the aryl group of Ar ₅ and Ar ₆ in the description of the structural formula (3D). Specific examples of the arylene group of Ar ₃₂ , Ar ₃₃ , Ar ₃₅ , Ar ₃₆ include divalent groups of these aryl groups. In addition, specific examples of the substituent in the aryl group and the arylene group include those exemplified as the substituent in the aryl group or the arylene group in the description of the structural formula (3D).

X is introduced by using a diol compound of the following structural formula (C) together when polymerizing a diol compound of the following structural formula (11D ′) using a phosgene method, a transesterification method, or the like. In this case, the produced polycarbonate becomes a random polymer or a block polymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound of the structural formula (11D ′) and a bischloroformate derived from the structural formula (C). In this case, the produced polycarbonate becomes an alternating copolymer.
Specific examples of the diol compound represented by the structural formula (C) include those exemplified in the description of the structural formula (1D).

  Among the polymer charge transport materials, the polymer charge transport materials represented by the structural formula (2D) and the structural formula (11D) have high charge transport ability and good film forming properties. It is particularly preferred because it exhibits excellent electrostatic properties and wear resistance when used in combination with a compound.

  Specific examples of the polymer charge transport material represented by the structural formula (1D) to the structural formula (11D) are shown below, but are not limited thereto.

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

  The content of the polymer charge transport material in the photosensitive layer (photosensitive layer in the case of a single layer type photoreceptor, charge transport layer in the case of a multilayer type photoreceptor) is preferably 20% by mass or more, and 30% by mass. The above is more preferable. When the content is less than 20% by mass, the charge transport amount may be insufficient.

  The photosensitive layer of the present invention preferably further contains an acceptor compound. Examples of the acceptor compound include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2 , 4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-indeno4H-indeno [1,2-b] thiophen-4-one, 1,3, Preferred examples include 7-trinitrodibenzothiophene-5,5-dioxide, the following structural formula (Q-1), and an acceptor compound represented by the following structural formula (Q-2). These may be used individually by 1 type and may use 2 or more types together.

  Furthermore, the 2,3-diphenylindene compound represented by the following structural formula (5) is preferably used because of its good compatibility with the polymer matrix and high electron transport ability.

In the Structural Formula ^(5), Q 1 ~Q ⁴ is a hydrogen atom, a fluorine atom, a halogen atom such as a chlorine atom, a methyl group, an ethyl group, n- propyl group, iso- propyl, n- butyl group , An alkyl group such as t-butyl group; a substituted alkyl group such as benzyl group, methoxymethyl group, methoxyethyl group, cyano group, or nitro group. Q ⁵ and Q ⁶ are each a halogen atom such as a hydrogen atom, a fluorine atom or a chlorine atom, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group or a t-butyl group; Substituted alkyl groups such as benzyl group, methoxymethyl group and methoxyethyl group, alkoxycarbonyl groups such as cyano group, methoxycarbonyl group and ethoxycarbonyl group, substituted alkylcarbonyl groups such as benzyloxycarbonyl group and methoxyethylcarbonyl group, phenyl group Represents an aryl group such as a naphthyl group, and examples of the substituent include alkyl groups such as a methyl group and an ethyl group, and halogen atoms such as a phenyl group, a methoxy group, an ethoxy group, a phenoxy group, a fluorine atom, and a chlorine atom.

  In the structural formula (5), (2,3-diphenyl-1-indene) malononitrile represented by the following structural formula (Q-3) is particularly preferably used.

The acceptor compound may be used alone or in combination of two or more.
The content of the acceptor compound in the photosensitive layer is preferably 1 to 40% by mass, and more preferably 5 to 40% by mass. When the content is less than 1% by mass, the charge transport may be insufficient, and when it exceeds 40% by mass, the mechanical durability may decrease and the residual potential may increase.

In the photosensitive layer of the present invention, a binder can be further added as necessary.
The binder is not particularly limited, and any substance can be used as long as it is a conventionally known binder for an electrophotographic photosensitive member having good insulating properties, such as polyethylene resin and polyvinyl butyral resin. , Polyvinyl formal resin, polystyrene resin, phenoxy resin, polypropylene resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, polyamide resin, silicone Resins, addition polymerization resins such as melamine resins, polyaddition resins, polycondensation resins, and copolymer resins containing two or more repeating units of these resins, such as vinyl chloride-vinyl acetate copolymers , Styrene-acrylic copolymer, vinyl chloride - vinyl acetate - other insulating resins such as maleic anhydride copolymer resin, polymer organic semiconductor poly -N- vinylcarbazole, and the like.
These may be used individually by 1 type and may use 2 or more types together.
The content of the binder in the photosensitive layer is preferably 30 to 95% by mass, and more preferably 40 to 70% by mass.

  In the photosensitive layer, additives such as a plasticizer, an antioxidant, a light stabilizer, a heat stabilizer and a lubricant can be added as necessary. Examples of the plasticizer include halogenated paraffin, dimethylnaphthalene, dibutyl phthalate, and the like. Examples of the antioxidant or light stabilizer include phenol compounds, hydroquinone compounds, hindered phenol compounds, hindered amine compounds, and compounds in which hindered amine and hindered phenol are present in the same molecule.

Among the phenol compounds, those represented by the following structural formula (6) are particularly preferable because they are effective in improving the chargeability in repeated use.
However, in the structural formula (6), E ^{1 to} E ⁸ are a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, or an alkyl group, Substituted alkyl groups such as benzyl group, methoxymethyl group and methoxyethyl group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, substituted alkylcarbonyl groups such as benzyloxycarbonyl group and methoxyethylcarbonyl group, phenyl group and naphthyl group Examples of the substituent include alkyl groups such as a methyl group and an ethyl group, and halogen atoms such as a phenyl group, a methoxy group, an ethoxy group, a phenoxy group, a fluorine atom, and a chlorine atom.

  Specific examples of the phenol compound represented by the structural formula (6) are shown below, but the phenol compound according to the present invention is not limited thereto.

  The content of the phenol compound in the photosensitive layer is preferably 0.1 to 50% by mass, and more preferably 0.1 to 30% by mass. When the content of the phenolic compound is less than 0.1% by mass, the effect of improving the durability during repeated use may not be sufficient, and when it exceeds 50% by mass, the mechanical durability is deteriorated, and Sensitivity may decrease.

-Support-
The support is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose. For example, a metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, or platinum ; Metal oxides such as tin oxide and indium oxide are deposited or sputtered to form film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. It is possible to use a pipe that has been subjected to surface treatment such as cutting, super-finishing, and polishing after the pipe is made by this method. Further, an endless nickel belt and an endless stainless steel belt disclosed in JP-A-52-36016 can also be used as a support.

In addition, those in which conductive powder is dispersed in an appropriate binder resin and coated on the support can also be used as the support of the present invention.
Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, or metal oxide powder such as conductive tin oxide and ITO. Etc. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, Thermoplastic, thermosetting resin or photo-curing resin such as melamine resin, urethane resin, phenol resin, alkyd resin and the like can be mentioned. The conductive layer can be provided by dispersing and applying these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  Furthermore, it is electrically conductive by a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support of the present invention.

In the latent electrostatic image bearing member (photosensitive member), an intermediate layer may be provided on the support, if necessary, in order to improve adhesion and static charge blocking. The intermediate layer is generally composed of a resin as a main component. However, considering that the photosensitive layer is coated with a solvent on these resins, it is desirable that the intermediate layer be a resin having a high solvent resistance with respect to a general organic solvent. .
Examples of the resin include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane resins, melamine resins, phenol resins, alkyd-melamine resins, Examples thereof include curable resins that form a three-dimensional network structure such as epoxy resins.

To the intermediate layer, fine powder pigments of metal oxides exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added in order to prevent moire and reduce residual potential. These intermediate layers can be formed by using an appropriate solvent and coating method like the above-mentioned photosensitive layer. Furthermore, as the intermediate layer, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used. In addition, those prepared by anodizing Al ₂ O ₃ , organic substances such as polyparaxylylene (parylene), inorganic substances such as SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ by vacuum thin film fabrication method The provided one can also be used satisfactorily.
The thickness of the intermediate layer is preferably 0 to 5 μm.

In the photoreceptor, a protective layer may be provided on the photosensitive layer as necessary in order to improve mechanical durability such as friction resistance. Examples of the material used for the protective layer include ABS resin, olefin-vinyl monomer copolymer resin, chlorinated polyether resin, allyl resin, phenol resin, polyacetal resin, polyamide resin, polyamideimide resin, and polyacrylate resin. , Polyallylsulfone resin, polybutylene resin, polybutylene terephthalate resin, polycarbonate resin, polyethersulfone resin, polyethylene resin, polyethylene terephthalate resin, polyimide resin, acrylic resin, polypropylene resin, polyphenylene oxide resin, polysulfone resin, polystyrene resin, AS resin Butadiene-styrene copolymer resin, polyurethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, epoxy resin, and the like. For the purpose of improving wear resistance, the protective layer is made of a fluororesin such as polytetrafluoroethylene, a silicone resin, and an inorganic material such as titanium oxide, tin oxide, or potassium titanate dispersed in these resins. Can be added. As a method for forming the protective layer, a normal coating method can be employed.
The thickness of the protective layer is preferably 0.1 to 10 μm. In addition to the above, a known material such as a-C or a-SiC formed by a vacuum thin film manufacturing method can also be used as the protective layer.

-Method for producing electrostatic latent image carrier (electrophotographic photosensitive member)-
The photoreceptor of the present invention is prepared by dissolving or dispersing the above materials in an organic solvent to prepare a photosensitive layer forming solution, and applying this to the conductive support or via an intermediate layer by dipping or blade coating. It is formed by applying and drying by the method of spraying. If necessary, the charge generation material can be dispersed in advance and dissolved or dispersed together with other materials to prepare the photosensitive layer forming solution. Examples of the dispersion method include ball mill dispersion, ultrasonic dispersion, and homomixer dispersion.
Examples of the solvent used for preparing the dispersion or solution of the photosensitive layer include N, N-dimethylformamide, toluene, xylene, monochlorobenzene, 1,2-dichloroethane, 1,1,1-trichloroethane, Examples include dichloromethane, 1,1,2-trichloroethane, trichloroethylene, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, dioxane, dioxolane, and the like.

  The electrostatic latent image bearing member (electrophotographic photosensitive member) of the present invention can be applied to general electrophotographic apparatuses such as copying machines, laser printers, LED printers, and liquid crystal shutter printers. The present invention can be widely applied to apparatuses such as applied displays, recording, light printing, plate making and facsimile.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. A developing means for forming the image forming apparatus, and further having other means such as a charging means, an exposure means, a developing means, a transfer means, a cleaning means, and a static elimination means, which are appropriately selected as necessary. .
The latent electrostatic image bearing member includes the above-described single-layer photosensitive layer on the support, or a photosensitive layer including a charge generation layer and a charge transport layer in this order, and the photosensitive layer has the structural formula (1). The azo compound represented by this is included.
The developing means includes a developer container that contains the toner or the developer, and an electrostatic latent image carrier that carries and transports the toner or developer contained in the developer container. It may have at least a layer thickness regulating member or the like for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably mounted on various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

Here, as the process cartridge, for example, as shown in FIG. 1, a photosensitive member 101 is incorporated, and in addition, a charging unit 102, an exposure unit 103, a developing unit 104, a transfer unit 105, a cleaning unit 107, and a charge eliminating unit 108. In addition, other members are included as necessary.
The photoconductor 101 includes a support and a photoconductive layer including at least a charge generation layer and a charge transport layer in this order on the support. As the charging member 102, a known charging member is used as described above, and an electric field is applied to the photoreceptor.
A light source capable of writing with high resolution is used for the exposure means 103. An arbitrary charging member (preferably scorotron charging) is used for the charging means 102.

  The image forming apparatus of the present invention is configured by integrally combining the above-described photosensitive member and components such as a developing device and a cleaning device as a process cartridge, and this unit is configured to be detachable from the apparatus main body. Also good. Alternatively, at least one of a charging device, an image exposure device, a developing device, a transfer device, a separator, and a cleaning device is integrally supported together with a photosensitive member to form a process cartridge, which is a single unit that is detachable from the apparatus main body. Further, it may be configured to be detachable using guide means such as a rail of the apparatus main body.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon and the like are preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back surface side of the electrostatic latent image carrier may be adopted.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer, and can be appropriately selected from known ones. For example, the toner or developer is accommodated. Preferred examples include those having at least a developing unit capable of bringing the toner or developer into contact or non-contact with the electrostatic latent image.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multicolor developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means, the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

Here, an aspect of the image forming apparatus of the present invention will be described with reference to FIG.
FIG. 2 is a schematic diagram for explaining the image forming apparatus of the present invention, and a modified example as described later also belongs to the category of the present invention.
A photosensitive member 201 as an electrostatic latent image carrier has a single photosensitive layer or a photosensitive layer including at least a charge generation layer and a charge transport layer in this order on a support, and the photosensitive layer has the structural formula. The azo compound represented by (1) is included. Although the photoconductor 201 has a drum shape, it may have a sheet shape or an endless belt shape.
As the charging member 203, a wire-type charging member or a roller-shaped charging member is used. A scorotron charging member is preferably used for high-speed charging. Although the photosensitive member is charged by this charging member, the higher the electric field strength applied to the photosensitive member, the better the dot reproducibility.
The image exposure unit 205 uses a light source that can ensure high luminance and can write at high resolution (600 dpi or higher resolution) such as a light emitting diode (LED), a semiconductor laser (LD), and electroluminescence (EL). .

  A known charger can be used as the transfer means, but a combination of the transfer charger 210 and the separation charger 211 as shown in FIG. 2 is effective. In addition, a transfer belt and a transfer roller can be used, and it is desirable to use a contact type such as a transfer belt or a transfer roller that generates less ozone. As a voltage / current application method during transfer, either a constant voltage method or a constant current method can be used. The current method is more desirable.

The developing member 206 has one developing sleeve, and the toner developed on the photoreceptor 1 is transferred to the transfer paper 209.
Further, the toner image formed on the photosensitive member is transferred to the transfer paper and becomes an image on the transfer paper. At this time, there are two methods. One is a method of directly transferring the toner image developed on the surface of the photoreceptor as shown in FIG. 2 to the transfer paper, and the other is once the toner image is transferred from the photoreceptor to the intermediate transfer body, and this is transferred to the transfer paper. It is the method of transferring to. Either case can be used in the present invention.
As such a transfer member, a known member can be used as long as the structure of the present invention can be satisfied.
When positive (negative) charging is performed on the photosensitive member and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.

  As a light source such as the static elimination lamp 202, all luminescent materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. . Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

Such a light source or the like irradiates the photosensitive member with light by providing a process such as a transfer process, a static elimination process, a cleaning process, or a pre-exposure using light irradiation in addition to the process shown in FIG.
This neutralization mechanism can be omitted when the AC component is used in a superposed manner in the previous charging method, or when the residual potential of the photoreceptor is small. Further, instead of optical static elimination, an electrostatic static elimination mechanism (for example, a static elimination brush applied with a reverse bias or grounded) can be used. In FIG. 2, 208 is a registration roller, and 212 is a separation claw.

  In addition, the toner developed on the photoconductor 201 by the developing unit 206 is transferred to the transfer paper 209. When toner remaining on the photoconductor 201 is generated, the fur brush 214 and the blade 215 remove the toner from the photoconductor. Removed. Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 3 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter also referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and the exposure. An exposure device 30 as a means, a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger (not shown) for applying a charge to the toner image on the intermediate transfer member 50 is connected to the photosensitive member 10 and the intermediate transfer member in the rotational direction of the intermediate transfer member 50. It is disposed between the contact portion with the body 50 and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 illustrated in FIG. 3, for example, the charging roller 20 uniformly charges the photosensitive drum 10. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 illustrated in FIG. 4 does not include the developing belt 41 in the image forming apparatus 100 illustrated in FIG. 3, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and the like around the photoconductor 10. Except that the cyan developing unit 45C is directly opposed, it has the same configuration as the image forming apparatus 100 shown in FIG. 3 and exhibits the same function and effect. In FIG. 4, the same components as those in FIG. 3 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 5 is a tandem color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 5. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full color image (color copy) using the tandem image forming apparatus will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem image forming apparatus. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each of the image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem image forming apparatus is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 6), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, and the toner image is an intermediate transfer member. The image forming apparatus includes a transfer charger 62 for transferring the image onto 0, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out the sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming apparatus and the image forming method of the present invention, by adopting an electrostatic latent image carrier (electrophotographic photoreceptor) using a novel azo compound having a specific imide structure in the coupler residue, It has good sensitivity and excellent durability, and is stable in electrostatic characteristics even when the copying process is repeated, so that high image quality can be obtained efficiently.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example at all.

(Synthesis Example 1)
-2-Synthesis of (t-butoxy) -7,8-naphthalic acid dimethyl ester-
35.25 g (0.2 mol) of pt-butoxystyrene and 56.84 g (0.4 mol) of acetylenedicarboxylic acid dimethyl ester were dissolved in 200 ml of nitrobenzene and reacted at 140 ° C. for 5 hours. After allowing to cool, nitrobenzene was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: n-hexane: ethyl acetate = 9: 1) to obtain 40.78 g of a crude product. Subsequently, recrystallization was performed with diisopropyl ether to synthesize 36.63 g (yield 57.9% by mass) of 2- (t-butoxy) -7,8-naphthalic acid dimethyl ester as a target naphthalene compound.
The melting point of the obtained naphthalene compound was 82.0 to 83.0 ° C. FIG. 7 shows an infrared absorption spectrum of this naphthalene compound measured by a Fourier transform infrared spectrophotometer FT-720 (manufactured by Horiba, Ltd.). Table 54 shows the results of elemental analysis measured with an organic element analyzer CHN coder MT-5 (manufactured by Nayako Analytical Industrial Co., Ltd.).

(Synthesis Example 2)
2-Synthesis of hydroxy-7,8-naphthalic acid dimethyl ester
31.63 g (0.1 mol) of 2- (t-butoxy) -7,8-naphthalic acid dimethyl ester obtained in Synthesis Example 1 was dissolved in 120 ml of methylene chloride, and 57.01 g of trifluoroacetic acid ( 0.5 mol) was added dropwise over 10 minutes, and the reaction was carried out for 3 hours under the same conditions. Then, the reaction product was poured into ice, and water was added for phase separation. The methylene chloride phase was washed twice with water and dehydrated with anhydrous magnesium sulfate. The magnesium sulfate was removed by filtration, and the residue obtained by distilling off methylene chloride was recrystallized from toluene to give 24.31 g (yield 93.4% by mass) of 2-hydroxy-7,8 as the desired naphthalene compound. -Naphthalic acid dimethyl ester was synthesized.
The melting point of the obtained naphthalene compound was 139.0-139.8 ° C. FIG. 8 shows an infrared absorption spectrum of this naphthalene compound measured by a Fourier transform infrared spectrophotometer FT-720 (manufactured by Horiba, Ltd.). Table 55 shows the results of elemental analysis measured with an organic element analyzer CHN coder MT-5 (manufactured by Nayako Analytical Industrial Co., Ltd.).

(Synthesis Example 3)
-Coupler compound no. Synthesis of H5
Nitrogen 2-hydroxy-7,8-naphthalic acid dimethyl ester 15.61 g (0.06 mol) obtained in Synthesis Example 2 and 1,6-diaminohexane 3.49 g (0.03 mol) were added to 100 ml of ethylene glycol in nitrogen. The reaction was stirred at 140 ° C. for 6 hours under a gas stream. After allowing to cool, the reaction product is poured onto ice and acidified with hydrochloric acid, and then the precipitated crystals are collected by filtration, washed with 500 ml of ion-exchanged water, and dried under reduced pressure at 60 ° C. to obtain 8.37 g of a crude product. It was. The obtained crude product was dissolved by heating in 80 ml of DMF (N, N-dimethylformamide), filtered while hot, then reprecipitated in 200 ml of n-butanol, and 7.70 g (yield 50.5% by mass). N, N′-hexamethylenebis (2-hydroxy-7,8-naphthalimide) (Exemplary Compound No. H5) was obtained as an orange coupler compound.
About the obtained coupler compound, the infrared absorption spectrum measured with the Fourier transform infrared spectrophotometer FT-720 (made by Horiba, Ltd.) is shown in FIG. Table 56 shows the results of elemental analysis measured with an organic element analyzer CHN coder MT-5 (manufactured by Nayako Analytical Industrial Co., Ltd.).

(Synthesis Example 4)
-Azo compound no. Synthesis of P21
0.508 g (1 mmol) of N, N′-hexamethylenebis (2-hydroxy-7,8-naphthalimide) (coupler compound, exemplified compound No. H5) obtained in Synthesis Example 3 was added to DMF (N, N -Dimethylformamide) was dissolved in 100 ml. Next, 0.816 g (2 mmol) of 9-fluorenone-2,7-bisdiazonium tetrafluoroborate previously synthesized from 2,7-diamino-9-fluorenone was added to this solution at room temperature and stirred at room temperature for 10 minutes. did.
Next, a solution consisting of 0.595 g (2 mmol) of 2-hydroxy-3- (2-chlorophenylcarbamoyl) naphthalene (an exemplary compound of coupler No. 17) and 40 ml of DMF (N, N-dimethylformamide) was added. Subsequently, 8.23 g of 10 mass% sodium acetate aqueous solution was dripped over 10 minutes, and it was made to react by stirring at room temperature for 6 hours. Next, the produced precipitate was separated by filtration, washed 5 times with 120 ml of DMF (N, N-dimethylformamide) at room temperature, and washed 3 times with 120 ml of water. It dried at 70 degreeC under pressure reduction, and obtained 0.537 g (yield 34.2 mass%) of the azo compound of the synthesis example 4 (exemplary compound No. P21).
About the obtained azo compound, the infrared absorption spectrum measured with the Fourier-transform infrared spectrophotometer FT-720 (made by Horiba, Ltd.) is represented in FIG. Table 57 shows the results of elemental analysis measured with an organic element analyzer CHN coder MT-5 (manufactured by Nayako Analytical Industrial Co., Ltd.).

Example 1
-Production of single-layer type electrostatic latent image carrier (electrophotographic photosensitive member)-
A polyamide resin (CM-8000: manufactured by Toray Industries, Inc.) solution dissolved in a methanol / butanol mixed solvent is applied onto an aluminum vapor-deposited polyester film with a doctor blade, dried at 100 ° C. for 5 minutes, and an intermediate thickness of 0.5 μm. A layer was formed. Next, 0.5 g of the azo compound (Exemplary Compound No. P21) obtained in Synthesis Example 4 was ball milled together with a solution consisting of 0.5 g of a polycarbonate resin (PCX-5: manufactured by Teijin Chemicals Ltd.) and 19 g of tetrahydrofuran. Then, the composition ratio is 2% by mass of the azo compound, 50% by mass of the polycarbonate resin, 30% by mass of the charge transport material (CTM-1) represented by the following structural formula, and the acceptor compound represented by the following structural formula (Q-3). (2,3-diphenyl-1-indene) malononitrile 18% by weight, silicone oil (KF-50: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.001% by weight as a charge transport material, acceptor compound, tetrahydrofuran And a silicone oil were added to prepare a photoreceptor coating solution having a solid content of 20% by mass.
The obtained photoreceptor coating solution was applied onto the intermediate layer with a doctor blade, dried at 120 ° C. for 20 minutes, and a single layer type electrostatic latent image carrier of Example 1 having a 20 μm thick photosensitive layer ( An electrophotographic photoreceptor was prepared.

(Example 2)
-Production of single-layer type electrostatic latent image carrier (electrophotographic photosensitive member)-
In Example 1, except that an azo compound (Exemplary Compound No. P15) was used as the azo compound, and an acceptor compound (Exemplary Compound No. Q-1) represented by the following structural formula was used as the acceptor compound. In the same manner as in Example 1, a single layer type electrostatic latent image carrier (electrophotographic photosensitive member) of Example 2 was produced.

(Example 3)
-Production of single-layer type electrostatic latent image carrier (electrophotographic photosensitive member)-
A polyamide resin (CM-8000: manufactured by Toray Industries, Inc.) solution dissolved in a methanol / butanol mixed solvent is applied onto an aluminum vapor-deposited polyester film with a doctor blade, dried at 100 ° C. for 5 minutes, and an intermediate layer having a thickness of 0.5 μm. Was provided. Next, 0.5 g of an azo compound (Exemplary Compound No. P13) was dispersed by ball milling together with a solution consisting of 0.5 g of a polycarbonate resin (PCX-5: manufactured by Teijin Chemicals Ltd.) and 19 g of tetrahydrofuran, and then the composition ratio was azo. 2% by mass of the compound, 47.5% by mass of the polycarbonate resin, 30% by mass of the charge transport material represented by the structural formula (CTM-1), 18% by mass of the acceptor compound represented by the structural formula (Q-3), A charge transport material, an acceptor compound so that the phenol compound represented by the structural formula (E-2) is 2.5% by mass and silicone oil (KF-50: manufactured by Shin-Etsu Chemical Co., Ltd.) is 0.001% by mass; A phenol compound, tetrahydrofuran, and silicone oil were added to prepare a photoreceptor coating solution having a solid content of 20% by mass.
The obtained photoreceptor coating solution was applied onto the intermediate layer with a doctor blade, dried at 120 ° C. for 20 minutes, and a single layer type electrostatic latent image carrier of Example 3 having a photosensitive layer with a thickness of 20 μm. (Electrophotographic photosensitive member) was produced.

(Example 4)
-Production of single-layer type electrostatic latent image carrier (electrophotographic photosensitive member)-
A polyamide resin (CM-8000: manufactured by Toray Industries, Inc.) solution dissolved in a methanol / butanol mixed solvent is applied onto an aluminum vapor-deposited polyester film with a doctor blade and dried at 100 ° C. for 5 minutes to form an intermediate layer having a thickness of 0.5 μm. Provided. Next, 0.5 g of an azo compound (Exemplary Compound No. P34) was ball-milled and dispersed together with a solution comprising 0.5 g of a polymeric charge transport material (Exemplary Compound No. 2D-15) and 19 g of tetrahydrofuran, and then the composition ratio was 2% by mass of azo compound, 80% by mass of polymer charge transporting material, 18% by mass of acceptor compound represented by the structural formula (Q-3), silicone oil (KF-50: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.001 A polymer charge transporting substance, an acceptor compound, tetrahydrofuran, and silicone oil were added so as to be mass% to prepare a photoreceptor coating solution having a solid content of 20 mass%.
The obtained photoreceptor coating solution was applied onto the intermediate layer with a doctor blade, dried at 120 ° C. for 20 minutes, and a single layer type electrostatic latent image carrier of Example 4 having a photosensitive layer with a thickness of 20 μm. (Electrophotographic photoreceptor) was produced.

(Example 5)
-Production of single-layer type electrostatic latent image carrier (electrophotographic photosensitive member)-
In Example 4, instead of the azo compound, the polymer charge transporting material, and the acceptor compound, an azo compound (Exemplary Compound No. P24), a polymer charge transporting material (Exemplary Compound No. 2D-08), an acceptor compound A single-layer electrostatic latent image carrier (electrophotographic photosensitive member) of Example 5 was produced in the same manner as Example 4 except that (Structural Formula (Q-1)) was used.

(Example 6)
-Production of single-layer type electrostatic latent image carrier (electrophotographic photosensitive member)-
In Example 4, instead of the azo compound, the polymer charge transport material, and the acceptor compound, an azo compound (Exemplary Compound No. P18), a polymer charge transport material (Exemplary Compound No. 4D-01), and an acceptor A single layer type electrostatic latent image carrier (electrophotographic photosensitive member) of Example 6 was produced in the same manner as in Example 4 except that the organic compound (Structural Formula (Q-3)) was used.

(Example 7)
-Production of single-layer type electrostatic latent image carrier (electrophotographic photosensitive member)-
A polyamide resin (CM-8000: manufactured by Toray Industries, Inc.) solution dissolved in a methanol / butanol mixed solvent is applied on an aluminum vapor-deposited polyester film with a doctor blade and dried at 100 ° C. for 5 minutes to provide a 0.5 μm intermediate layer. It was. Next, 0.5 g of an azo compound (Exemplary Compound No. P45) is ball-milled and dispersed together with a solution comprising 0.5 g of a polymeric charge transport material (Exemplary Compound No. 11D-02) and 19 g of tetrahydrofuran, and then the composition ratio is 1. 2% by mass of an azo compound, 77.5% by mass of a polymer charge transporting substance, 18% by mass of an acceptor compound represented by the structural formula (Q-3), and a phenol compound represented by the structural formula (E-2). Polymer charge transport material, acceptor compound, phenolic compound, tetrahydrofuran and silicone oil were added to a solid content of 5% by mass, silicone oil (KF-50: Shin-Etsu Chemical Co., Ltd.) 0.001% by mass. A 20 mass% photoreceptor coating solution was prepared.
The obtained photoreceptor coating solution was applied onto the intermediate layer with a doctor blade, dried at 120 ° C. for 20 minutes, and a single layer type electrostatic latent image carrier of Example 7 having a photosensitive layer with a thickness of 20 μm. (Electrophotographic photoreceptor) was produced.

(Example 8)
-Production of single-layer type electrostatic latent image carrier (electrophotographic photosensitive member)-
In Example 7, instead of the azo compound, the polymer charge transport material, the acceptor compound, and the phenol compound, an azo compound (Exemplary Compound No. P28), a polymer charge transport material (Exemplary Compound No. 2D-17) In the same manner as in Example 7 except that an acceptor compound (the structural formula (Q-2)) and a phenol compound (the structural formula (E-1)) were used, the single-layer electrostatic of Example 8 was used. A latent image carrier (electrophotographic photosensitive member) was produced.

(Comparative Example 1)
-Production of single-layer type electrostatic latent image carrier (electrophotographic photosensitive member)-
In Example 1, the sensitization of Comparative Example 1 was performed in the same manner as in Example 1 except that the azo compound (CGM-1) represented by the following structural formula was used instead of the azo compound (Exemplary Compound No. P21). The body was made.

  For each of the electrophotographic photoreceptors of Examples 1 to 8 and Comparative Example 1 obtained, electrostatic property evaluation, wear amount evaluation, and repeated property evaluation were performed as follows.

<Evaluation of electrostatic characteristics>
For each of the single-layer electrophotographic photosensitive members of Examples 1 to 8 and Comparative Example 1, using an electrostatic copying paper test apparatus EPA-8200 (manufactured by Kawaguchi Denki Seisakusho) in an environment of 25 ° C./55% RH, Then, a +6 kV corona discharge was carried out for 20 seconds to charge. Subsequently, after leaving it to stand in a dark place for 20 seconds, the surface potential V ₀ (V) was measured. Next, the tungsten lamp is irradiated so that the illuminance on the surface of the photosensitive member becomes 5.3 (lux), and the time (sec) until the surface potential becomes 1/2 of V ₀ is obtained. The half exposure amount E _1/2 (lux · sec) was calculated as sensitivity. The results are shown in Table 58.

<Abrasion amount evaluation>
About each single layer type electrophotographic photosensitive member of Examples 4 to 8 and Comparative Example 1, the surface of the photosensitive member is CS-5 with a Taber abrasion tester (manufactured by Toyo Seiki Co., Ltd.) according to the industrial standard JIS K7204 (1995). Using a wear wheel, a wear test was performed at 3000 rpm with a load of 1 kg, and the amount of wear was measured. The results are shown in Table 59.

From the results in Table 59, it can be seen that the electrostatic latent image bearing members (photoconductors) of Examples 4 to 8 of the present invention have superior wear resistance as compared with Comparative Example 1.

<Repetitive characteristic evaluation>
Each single-layer type electrophotographic photosensitive member of Example 1, Example 8, and Comparative Example 1 is mounted on a drum having a linear velocity of 260 mm / s, and positive charging, exposure, and light quench are repeated 5000 times, initial, and 5000 The charging potential Vd (V) after rotation and the post-exposure potential Vl (V) were measured. The results are shown in Table 60.

From the results of Table 60, the electrostatic latent image carrier (photoreceptor) of Examples 1 and 8 of the present invention has a very small potential fluctuation even after 5000 times as compared with Comparative Example 1, and has a stable repetitive characteristic. It is recognized that

Example 9
-Production of electrostatic latent image carrier (electrophotographic photosensitive member)-
7.5 parts by mass of the azo compound (Exemplary Compound No. P21) obtained in Synthesis Example 4 and 500 parts by mass of a 0.5% by mass tetrahydrofuran solution of a polyester resin (Byron 200; manufactured by Toyobo Co., Ltd.) were pulverized in a ball mill. The mixture was mixed to prepare a charge generation layer coating solution. The obtained charge generation layer coating solution was applied onto an aluminum vapor-deposited polyester film with a doctor blade and naturally dried to form a charge generation layer having a thickness of about 1 μm.
Next, 1 part by mass of α-phenyl-4′-bis (4-methylphenyl) aminostilbene (exemplary compound No. D3) as a charge transport material, 1 part by mass of a polycarbonate resin (Panlite K1300; manufactured by Teijin Chemicals Ltd.), And 8 parts by mass of tetrahydrofuran were mixed to prepare a charge transport layer coating solution. The obtained charge transport layer coating solution was applied onto the charge generation layer with a doctor blade and dried at 80 ° C. for 2 minutes and then at 120 ° C. for 5 minutes to form a charge transport layer having a thickness of about 20 μm. . Thus, an electrostatic latent image carrier (electrophotographic photosensitive member) of Example 9 was produced.

(Examples 10 to 23)
-Production of electrostatic latent image carrier (electrophotographic photosensitive member)-
In place of the azo compounds and charge transport materials used in Example 9, the azo compounds and charge transport materials shown in Table 61 were used, respectively. An electrostatic latent image carrier (electrophotographic photosensitive member) was produced.

(Comparative Example 2)
-Production of electrostatic latent image carrier (electrophotographic photosensitive member)-
In Example 9, in place of the azo compound, an azo compound (CGM-1) represented by the following structural formula (CGM-1) was used, and the electrostatic latent of Comparative Example 2 was obtained in the same manner as in Example 9. An image carrier (electrophotographic photoreceptor) was produced.

  The obtained electrophotographic photosensitive members of Examples 9 to 23 and Comparative Example 2 were subjected to electrostatic property evaluation and chemical durability test as follows.

<Evaluation of electrostatic characteristics>
Each electrophotographic photoreceptor obtained was subjected to a corona discharge of −6 kV for 20 seconds in the dark using an electrostatic copying paper test apparatus EPA-8200 (manufactured by Kawaguchi Electric) in an environment of 25 ° C./55% RH. Charged. Subsequently, after leaving it to stand in a dark place for 20 seconds, the surface potential V ₀ (V) was measured. Next, the tungsten lamp is irradiated so that the illuminance on the surface of the photosensitive member becomes 5.3 (lux), and the time (sec) until the surface potential becomes 1/2 of V ₀ is obtained. The half exposure amount E _1/2 (lux · sec) was calculated as the sensitivity. The results are shown in Table 61.

Charge transport material no. D1: 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazoline Charge transport material No. D2: 9-ethylcarbazole-3-aldehyde-1-methyl-1-phenylhydrazone Charge transport material No. D3: α-phenyl-4′-bis (4-methylphenyl) aminostilbene Charge transport material No. D4: α-Phenyl-4′-diphenylaminostilbene

<Chemical durability test>
Each electrophotographic photosensitive member produced in Example 9, Example 11, Examples 13-17 and Comparative Example 2 was left in a NOx gas (NO = 40 ppm / NO ₂ = 10 ppm) exposure tester for 40 hours at room temperature. Subsequently, the extracted electrophotographic photosensitive member was evaluated for electrostatic characteristics in the same manner as before exposure to NOx gas, and the rate of change in surface potential V ₀ before and after exposure to NOx gas (surface potential after exposure to NOx gas / NOx gas exposure). Previous surface potential was calculated. The results are shown in Table 62.

From the results in Table 62, the electrostatic latent image carriers (photoconductors) of Examples 9, 11 and 13 to 17 of the present invention have a surface potential after exposure to NOx gas as compared with Comparative Example 2. No change was observed, and it was confirmed that the battery had stable charging characteristics.

(Example 24)
-Production of electrostatic latent image carrier (electrophotographic photosensitive member)-
A polyamide resin (CM-8000; manufactured by Toray Industries, Inc.) solution dissolved in a mixed solvent of methanol / n-butanol = 4/1 (vol ratio) was applied on an aluminum vapor-deposited polyester film with a doctor blade, and 5 minutes at 100 ° C. This was dried to form an intermediate layer having a thickness of 0.5 μm.
Next, 7.5 parts by mass of the azo compound (Exemplary Compound No. P21) obtained in Synthesis Example 4 and 500 parts by mass of a 0.5% tetrahydrofuran solution of polyvinyl butyral resin (XYHL; manufactured by Union Carbide Corporation) were ball milled. The mixture was pulverized and mixed to prepare a charge generation layer coating solution. The obtained charge generation layer coating solution was applied onto the intermediate layer with a doctor blade and naturally dried to form a charge generation layer having a thickness of about 1 μm.
Next, 1 part by mass of α-phenyl-4′-bis (4-methylphenyl) aminostilbene (Exemplary Compound No. D3) as a charge transport material, 1 part by mass of a polycarbonate resin (PCX-5; manufactured by Teijin Chemicals Ltd.) Then, 0.001 part by mass of silicone oil (KF-50; manufactured by Shin-Etsu Chemical Co., Ltd.) and 8 parts by mass of tetrahydrofuran were mixed to prepare a charge transport layer coating solution. The obtained charge transport layer coating solution was applied onto the charge generation layer with a doctor blade and dried at 80 ° C. for 2 minutes and then at 120 ° C. for 5 minutes to form a charge transport layer having a thickness of about 20 μm. Thus, an electrostatic latent image carrier (electrophotographic photosensitive member) of Example 24 was produced.

(Example 25)
-Production of electrostatic latent image carrier (electrophotographic photosensitive member)-
In Example 24, the electrostatic latent image carrying of Example 25 was performed in the same manner as in Example 24 except that the azo compound (Exemplary Compound No. P34) was used instead of the azo compound (Exemplary Compound No. P21). A body (electrophotographic photoreceptor) was produced.

(Example 26)
-Production of electrostatic latent image carrier (electrophotographic photosensitive member)-
In Example 24, the electrostatic latent image carrying of Example 26 was performed in the same manner as in Example 24 except that the azo compound (Exemplary Compound No. P15) was used instead of the azo compound (Exemplary Compound No. P21). A body (electrophotographic photoreceptor) was produced.

(Comparative Example 3)
-Production of electrostatic latent image carrier (electrophotographic photosensitive member)-
In Example 24, the static of Comparative Example 3 was obtained in the same manner as in Example 24 except that the azo compound represented by the following structural formula (CGM-1) was used instead of the azo compound (Exemplary Compound No. P21). An electrostatic latent image carrier (electrophotographic photosensitive member) was produced.

<Repetitive characteristic evaluation>
Each of the electrophotographic photosensitive members of Examples 24-26 and Comparative Example 3 is mounted on a drum having a linear speed of 260 mm / s, and negative charging, white exposure, and light quench are repeated 5000 times, and charging at the initial stage and after 5000 times. The potential Vd (V) and the post-exposure potential Vl (V) were measured. The results are shown in Table 63.

From the results shown in Table 63, the electrostatic latent image carriers (photoconductors) of Examples 24-26 of the present invention have very small potential fluctuations even after 5000 times as compared with Comparative Example 3, and have stable repetitive characteristics. It is accepted to have.

  The electrostatic latent image carrier of the present invention has good chargeability and sensitivity, is excellent in light resistance and durability, and is suitable for a low-speed to high-speed copying process, and further, an analog copying machine for monochrome or full color Therefore, it can be widely applied to photoconductors for page printers using LD or LED light for optical writing.

FIG. 1 is a schematic explanatory diagram showing an example of the process cartridge of the present invention. FIG. 2 is a schematic explanatory diagram illustrating an example of the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory diagram showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory diagram showing another example in which the image forming method of the present invention is implemented by the image forming apparatus of the present invention. FIG. 5 is a schematic explanatory diagram showing an example in which the image forming method of the present invention is carried out by the image forming apparatus (tandem color image forming apparatus) of the present invention. 6 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. 7 is an infrared absorption spectrum diagram of the naphthalene compound used in the present invention obtained in Synthesis Example 1. FIG. FIG. 8 is an infrared absorption spectrum diagram of the naphthalene compound used in the present invention obtained in Synthesis Example 2. FIG. 9 is an infrared absorption spectrum diagram of the coupler compound used in the present invention obtained in Synthesis Example 3. 10 is an infrared absorption spectrum diagram of the azo compound of the present invention (Exemplary Compound No. 21) obtained in Synthesis Example 4. FIG.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Constant current source 55 Switching claw 56 Discharging roller 57 Discharging tray 60 Cleaning device 61 Developing device 62 Transfer charging device 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 71 Cleaning blade 72 Support member 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 101 Photoconductor 102 Charging means 103 Exposure 104 Developing means Reference Signs List 105 Transfer body 106 Transfer means 107 Cleaning means 120 Tandem developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper path 147 Conveying roller 148 Paper feeding path 150 Copying apparatus main body 200 Paper feeding table 201 Photoconductor 202 Static elimination lamp 203 Charger charger 204 Eraser 205 Image exposure unit 206 Development unit 207 Pre-transfer charger 208 Registration roller 209 Transfer paper 210 Transfer charger 211 Separation Charger 212 Separation claw 213 Charger before cleaning 214 Fur brush 215 Cleaning brush 300 Scanner 400 Automatic document feeder (ADF)

Claims (23)

An electrostatic latent image carrier comprising: a support; and at least a photosensitive layer on the support, wherein the photosensitive layer contains an azo compound represented by the following structural formula (1).
However, in the structural formula (1), Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may be bonded via a bonding group, and these may be further substituted with a substituent. Good. Cp ₁ represents a divalent to hexavalent coupler residue represented by the following structural formula (1-1). Cp ₂ represents a monovalent coupler residue. n ₁ represents an integer of 2 . n ₂ represents an integer of 1 .
However, in the structural formula (1-1), R ¹ , R ² , R ³ , and R ⁴ may be the same as or different from each other, a hydrogen atom, a halogen atom, an amino group, or a hydroxy group. Represents a group, a nitro group, a cyano group, an alkyl group, or an alkoxy group. In addition, R ¹ , R ² , R ³ , and R ⁴ may be bonded to each other directly or indirectly to form a ring. X ¹ represents a hydrocarbon group or a heterocyclic group, and these may be further substituted with a substituent. n ₃ represents an integer of 2 .   The electrostatic latent image carrier according to claim 1, wherein the photosensitive layer is a single layer.   The electrostatic latent image carrier according to claim 1, wherein the photosensitive layer is a laminate having at least a charge generation layer and a charge transport layer. The electrostatic latent image carrier according to any one of claims 1 to 3, wherein the hydrocarbon group in X ¹ is an alkylene group or an aromatic hydrocarbon group. The electrostatic latent image carrier according to any one of claims 1 to 4, wherein the hydrocarbon group in X ¹ is a divalent aromatic hydrocarbon group. At least one of cp _2, the following structural formula (1-2), (1-3), (1-4), and any of claims 1 to 5, which is a coupler residue represented by (1-5) An electrostatic latent image carrier according to any one of the above.
However, in the structural formula (1-2), Z ¹ represents a hydrocarbon ring group or a heterocyclic group, which may be further substituted with a substituent. R ⁵ represents a hydrogen atom or a hydrocarbon group, which may be further substituted with a substituent. Y ¹ represents a hydrocarbon ring group or a heterocyclic group, and these may be further substituted with a substituent.
However, in the structural formulas (1-3) and (1-4), W ¹ represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group containing a nitrogen atom in the ring. These may be further substituted with a substituent.
However, in the structural formula (1-5), A ¹ represents an aromatic hydrocarbon group or a heterocyclic group, and these may be further substituted with a substituent. m represents an integer of 1 to 6. The electrostatic latent image carrier according to claim 1, wherein Ar is represented by the following structural formula (1-6).
  The electrostatic latent image carrier according to claim 1, wherein an azo compound is used as a charge generating substance.   9. The electrostatic latent image carrier according to claim 1, wherein the photosensitive layer contains a charge transport material. The electrostatic latent image carrier according to claim 9, wherein the charge transport material is a stilbene compound represented by the following structural formula (2).
However, in the structural formula (2), T ¹ and T ² represent an alkyl group or an aryl group which may be the same as or different from each other, and these are further substituted with a substituent. Also good. T ¹ and T ² may form a ring with each other. T ³ and T ⁴ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these may be further substituted with a substituent. Ar ′ represents an aryl group or a heterocyclic group, and these may be further substituted with a substituent.   The electrostatic latent image carrier according to claim 9, wherein the charge transport material is a polymer charge transport material.   The electrostatic latent image carrier according to claim 11, wherein the polymer charge transport material is at least one polymer selected from polycarbonate, polyurethane, polyester, and polyether.   The electrostatic latent image carrier according to claim 11, wherein the polymer charge transport material is a polymer compound having a triarylamine structure.   The electrostatic latent image carrier according to claim 13, wherein the polymer compound having a triarylamine structure is a polycarbonate having a triarylamine structure. The electrostatic latent image carrier according to claim 14, wherein the polycarbonate having a triarylamine structure is represented by the following structural formula (3).
However, in the structural formula (3), R ⁶ and R ⁷ represent a substituted or unsubstituted aryl group that may be the same or different from each other, and represent Ar ¹ , Ar ² , and Ar ^3. Represent the same or different arylene groups. k and j represent composition ratios, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the degree of polymerization. X ² represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following structural formula (3-1).
However, in the structural formula (3-1), R ⁸ and R ⁹ may be the same as or different from each other, and may represent different halogen atoms, alkyl groups, or aryl groups, and these may be substituted. Further, it may be substituted. l and m represent the integer of 0-4. Y represents a single bond, a linear, branched or cyclic alkylene group, —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO—O—Z—O—CO—. (However, Z represents an aliphatic divalent group) or the following structural formula (3-2).
However, in said structural formula (3-2), a represents the integer of 1-20. b represents an integer of 1 to 2000. R ¹⁰ and R ¹¹ represent an alkyl group or an aryl group which may be the same as or different from each other, and these may be further substituted with a substituent. The electrostatic latent image carrier according to claim 14, wherein the polycarbonate having a triarylamine structure is represented by the following structural formula (4).
However, in the structural formula (4), Ar ⁴ , Ar ⁵ , Ar ⁷ and Ar ⁸ represent a substituted or unsubstituted arylene group which may be the same or different from each other, and Ar ⁶ represents a substituted or unsubstituted group. Represents an aryl group. Z ² represents an arylene group or ^{-Ar 9} -Za-Ar 9 - (provided that, Ar ⁹ is .Za to represent a substituted or unsubstituted arylene group, O, represents S or an alkylene group.) Represents the. R ¹² and R ¹³ represent a linear or branched alkylene group or —O—. h represents 0 or 1; k and j represent composition ratios, and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9. n represents the degree of polymerization. X ³ represents a substituted or unsubstituted aliphatic divalent group, a substituted or unsubstituted cyclic aliphatic divalent group, a substituted or unsubstituted aromatic divalent group, or a divalent group formed by linking these, or The divalent group represented by the following structural formula (4-1), structural formula (4-2), and structural formula (4-3) is represented.
However, in the structural formula (4-1), the structural formula (4-2), and the structural formula (4-3), R ²⁴ , R ²⁵ , R ⁵⁵ , and R ⁵⁶ may be the same or different from each other. And represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom. l and m represent the integer of 0-4. s and t represent the integer of 0-3. When a plurality of R ²⁴ , R ²⁵ , R ⁵⁵ , and R ⁵⁶ are present, they may be the same or different. Y is a divalent group composed of a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, an alkylene group having 1 to 10 carbon atoms, one or more oxygen atoms, and a sulfur atom. Group, —O—, —S—, —SO—, —SO ₂ —, —CO—, —COO—, —CO—O—Z ₁ —O—CO—, —CO—Z ₂ —CO— (provided that In the formula, Z ₁ and Z ₂ represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group), or the following structural formula (4-1-1), structural formula (4- The structural formula (4-1-8) is represented from 1-2).
However, in the structural formula (4-1-1), R ²⁶ and R ²⁷ represent a substituted or unsubstituted alkyl group or an aryl group which may be the same or different from each other, and these may be further substituted. May be substituted.
R ⁵⁷ , R ⁵⁸ , and R ⁶⁴ represent a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group. R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , and R ⁶³ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, substituted or An unsubstituted aryl group is represented. R ⁵⁸ and R ⁵⁹ may combine to form a carbocyclic ring having 5 to 12 carbon atoms. R ₆₅ and R ₆₆ represent an end bond or an alkylene group having 1 to 4 carbon atoms. a is an integer of 1 to 20, b is an integer of 1 to 2000, u and w are integers of 0 to 4, and v is 1 or 2. When a plurality of R ²⁶ , R ²⁷ , R ⁵⁷ , and R ⁶⁴ are present, they may be the same or different.   The electrostatic latent image carrier according to claim 1, wherein the photosensitive layer further contains an acceptor compound. The electrostatic latent image carrier according to claim 17, wherein the acceptor compound is a 2,3-diphenylindene compound represented by the following structural formula (5).
In the structural formula (5), Q ¹ , Q ² , Q ³ , and Q ⁴ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group, a cyano group, or Represents a nitro group. Q ⁵ and Q ⁶ represent a hydrogen atom, an aryl group, a cyano group, an alkoxycarbonyl group, or an aryloxycarbonyl group, which may be the same as or different from each other, and these are further substituted with a substituent. May be.   The electrostatic latent image carrier according to claim 1, wherein the photosensitive layer further contains a phenol compound. The electrostatic latent image carrier according to claim 19, wherein the phenol compound is represented by the following structural formula (6).
However, in the structural formula (6), E ^{1 to} E ⁸ represent a hydrogen atom, an alkyl group, an alkoxycarbonyl group, an aryl group, or an alkoxy group, which may be the same as or different from each other. These may be further substituted with a substituent.   The electrostatic latent image carrier according to any one of claims 1 to 20, and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using a toner to form a visible image. And a process cartridge that is detachable from the main body of the image forming apparatus.   The electrostatic latent image carrier according to any one of claims 1 to 20, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and development using toner An image forming apparatus comprising: a developing unit that forms a visible image; a transfer unit that transfers the visible image to a recording medium; and a fixing unit that fixes the transferred image transferred to the recording medium.   An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier according to any one of claims 1 to 20, and developing the electrostatic latent image with toner to form a visible image An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium.