JP2001066810A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the image quality reproducibility, wear resistance, durability and photosensitivity by forming a photosensitive layer containing at least a high molecular electric charge transferring material having a specified electric charge transferring structure. SOLUTION: The electrophotographic photoreceptor has at least a photosensitive layer containing at least a high molecular electric charge transferring material on an electrically conductive substrate and the high molecular electric charge transferring material has 30-70wt.% electric charge transferring structure based on the total molecular weight of the material. A polycarbonate, polyurethane, polyester or polyether is useful as the polymer structure of the high molecular electric charge transferring material and a polycarbonate having a triarylamine structure as the electric charge transferring structure is particularly preferable. The triarylamine structure is, e.g. triphenylamine, diphenylaminobiphenyl, tetraphenylbenzidine, tetraphenylphenylenediamine or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electrophotographic photosensitive member, and more particularly, to an electrophotographic photosensitive member used for an electrophotographic copying machine, a printer, and the like.

[0002]

2. Description of the Related Art An electrophotographic method using an electrophotographic photosensitive member applied to a copying machine, a facsimile, a laser printer, a direct digital plate making machine, etc. is at least a process of charging, image exposing, and developing the electrophotographic photosensitive member. After that, the toner image is transferred to an image carrier (transfer paper), fixed, and the surface of the electrophotographic photosensitive member is cleaned.

The basic characteristics required of an electrophotographic photoreceptor in this electrophotographic method include that it can be charged to an appropriate potential in a dark place and that there is little dissipation of electric charge in a dark place. It can be dissipated.

Further, in addition to these characteristics, long-term reliability such as image quality characteristics, low pollution, and low cost are required. Conventionally, as a photoreceptor used in the electrophotographic method, a photoconductive layer mainly composed of selenium or a selenium alloy is provided on a conductive support, and an inorganic photoconductive material such as zinc oxide and cadmium sulfide is used. Those dispersed in a binder and those using an amorphous silicon-based material are generally known, but in recent years, the cost is low, the degree of freedom in photoconductor design is high, and there is no pollution. For this reason, organic photoconductors have been widely used.

[0005] Organic electrophotographic photoreceptors include a photoconductive resin represented by polyvinyl carbazole (PVK), P
VK-TNF (2,4,7-trinitrofluorenone)
A charge-transfer complex type represented by, a pigment dispersion type represented by a phthalocyanine-binder, a function-separated type photoconductor using a combination of a charge-generating substance and a charge-transporting substance, and the like are known. Photoreceptors are receiving attention.

The mechanism of the formation of an electrostatic latent image in a function-separated type photoreceptor is that, when the photoreceptor is charged and irradiated with light, the light passes through a transparent charge transport layer and is charged by the charge generating substance in the charge generation layer. The absorbed charge-generating substance, which has absorbed light, generates charge carriers, which are injected into the charge-transporting layer, move in the charge-transporting layer in accordance with the electric field generated by the charging, and charge the photoreceptor surface. The latent image is formed by neutralization. In a function-separated type photoreceptor, it is known and useful to use a charge transport material having absorption mainly in the ultraviolet region and a charge generation material having absorption mainly in the visible region.

However, most of the charge transporting materials of the organic electrophotographic photoreceptor used in the electrophotographic method have been developed as low molecular weight compounds, and since the low molecular weight compounds alone do not have a film forming property, they are usually inactive. It is used by being dispersed and mixed in a polymer. However, the charge transport layer composed of a low-molecular charge transport material and an inert polymer is generally soft, and when repeatedly used in an electrophotographic process, the film is abraded by a mechanical load on the photoreceptor surface by a developing system or a cleaning system. A disadvantage is the low abrasion resistance, which tends to occur.

Further, the charge transport layer of this structure has a limit in charge mobility, which has been an obstacle to speeding up or miniaturizing the electrophotographic process. This is due to the fact that the content of the low-molecular charge transporting substance is usually used at 50% by weight or less. That is, the charge mobility can be certainly increased by increasing the content of the low-molecular charge transport material, but at the same time, the film-forming property and the abrasion resistance deteriorate.

As a technique for improving the characteristics of the organic photoreceptor, a technique in which a binder resin of the organic photoreceptor is improved (JP-A-5-216250) and a polymer type charge transport material (JP-A-51-73888). Gazette, JP-A-54-852
7, JP-A-54-11737, JP-A-56
JP-A-150749, JP-A-57-78402, JP-A-63-285552, JP-A-64-1
728, JP-A-64-13061, JP-A-64-19049, JP-A-3-50555, JP-A-4-175337, JP-A-4-225
No. 014, JP-A-4-230767, JP-A-5-232727, JP-A-5-310904 and the like have been noticed and disclosed.

In the above publication, the improved binder resin of the charge transporting layer does not exhibit remarkable improvement in abrasion resistance due to the composition ratio of the low molecular charge transporting substance. On the other hand, in the case of using the polymer type charge transporting material, the film abrasion is improved because the charge transporting layer component is almost polymerized, but the effect is expected to be significantly reduced depending on the structure of the polymer charge transporting material used. Endurance may not be obtained.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electrophotographic photoreceptor which achieves high performance, long life, and high reliability at a high level. It is an object of the present invention to provide an organic electrophotographic photoreceptor which is excellent in durability and photosensitivity.

[0012]

Means for Solving the Problems As a result of intensive studies on the above objects by the present inventors, in an electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, this photosensitive layer has at least a polymer charge. The polymer charge transport material has a total molecular weight of 30.
It has been discovered that the above object can be achieved by having a charge transport structure of not less than 70% by weight and not more than 70% by weight, and the present invention has been accomplished.

Further, it is clear that polycarbonate, polyurethane, polyester and polyether are useful as the polymerized structure of the high molecular charge transporting material, and particularly preferable is a polycarbonate having a triarylamine structure as the charge transporting structure. Was.

A conventional electrophotographic photoreceptor uses a charge transport layer in which a low-molecular charge transport material is dispersed in a polymer resin binder by about 50% by weight due to the restriction of the sensitivity of light attenuation. It has a drawback that film shaving is likely to occur during use. Due to the abrasion of the charge transport layer, there is a problem that the charge potential of the photoreceptor decreases and an abnormal image is generated. On the other hand, in recent years, studies have been made to use a polymer charge transport material as a main component of the photosensitive layer. As a result, a large amount of low molecular components (conventional low molecular charge transport material)
Need not be contained, and film abrasion accompanying the improvement in the strength of the photosensitive layer has been reduced. However, there has been a situation in which the effect is significantly reduced due to the structure of the polymer charge transporting material used, and the expected durability cannot be obtained.

In the present invention, as a result of intensive studies on the above problem, the proportion of the charge transport structure in the structure of the polymer charge transport material used in the photosensitive layer is an important factor for abrasion resistance. By setting the charge transport structure in the polymer charge transporting material to 30% by weight or more and 70% by weight or less of the total molecular weight of the polymer charge transporting material, a high-performance, long-life photoreceptor having excellent wear resistance can be obtained. Was found.

The photosensitive layer needs to have a certain level of mobility due to the restrictions on charge transport. If the mobility is low, the sensitivity is reduced, the potential of the exposed portion is repeatedly accumulated during repeated use, and the copy quality such as the image density is lowered. Deterioration occurs. In the photosensitive layer, the charge moves between the charge transport structures by hopping, so that the mobility depends on the concentration of the charge transport structures. Therefore, in order to maintain a stable light attenuation characteristic for a long period of time, a certain amount of the charge transport structure in the photosensitive layer is required, and the amount is about 40% by weight of the whole photosensitive layer. The photosensitive layer comprising the polymer charge transporting material of the present invention can be added with a low molecular weight charge transporting material. However, when the amount of addition is 10% or more of the total amount of the photosensitive layer, wear is significantly increased. Therefore, in order to maintain abrasion resistance and stable light attenuation characteristics, the charge transport structure in the polymer charge transport material needs to be at least 30% by weight or more of the total molecular weight of the polymer charge transport material.

On the other hand, when the charge transport structure in the polymer charge transport material is very large, the charge transfer is good, but a problem arises in abrasion resistance. If there are too many repeating units having a bulky charge transport structure in the polymer charge transport structure, the photosensitive layer will be distorted and the internal stress will increase, and as a result, film scraping will be accelerated. Further, due to the limitation of the liquid viscosity in the coating of the photosensitive layer, when the molecular weight of the repeating unit increases, the length of the main chain becomes shorter, the rigidity of the photosensitive layer decreases, and the abrasion increases. In addition, if there are many bulky charge-transporting structures, ozone and nitrogen oxides generated by corona discharge etc. will easily penetrate into the photosensitive layer, and abnormal images such as background stains due to deterioration of chargeability due to repeated use over a long period of time. More likely to occur. From these points, it is necessary to suppress the charge transport structure in the polymer charge transport material to 70% by weight or less of the total molecular weight of the polymer charge transport material.

In the present invention, since the polymer charge transporting material is one of the main components of the charge transporting layer, it needs to have high strength and toughness by itself. In this regard, polycarbonate, polyurethane, polyester, and polyether are preferable as the polymerized structure of the polymer charge transport material,
Among them, polycarbonate is particularly optimal.

The function of the polymer charge transport material is
It is necessary to move the charge injected from the charge generating material at high speed. If the movement of the charges is slow, the potential of the exposed portion rises and the image density decreases. In the present invention, good images can be continuously obtained by having a triarylamine structure, which is a high-mobility structural unit, as the charge transport structure of the polymer charge transport material.

The above findings have been found, and the present invention has been accomplished. Next, the polymer charge transport material used in the present invention will be described. As the polymer charge transport material, the following general polymer materials can be used.

(A) Polymer having a carbazole ring For example, poly-N-vinyl carbazole,
No. 82056, JP-A-54-9632, JP-A-54-11737, JP-A-4-175337, JP-A-4-183719, JP-A-6-23
Compounds described in JP-A-4841 are exemplified.

(B) Polymer having a hydrazone structure For example, JP-A-57-78402 and JP-A-61-78402
JP-A-20953, JP-A-61-296358,
JP-A-1-134456, JP-A-1-17916
No. 4, JP-A-3-180851, JP-A-3-180851
180852, JP-A-3-50555, JP-A-5-310904, JP-A-6-234840
And the like.

(C) Polymer having triarylamine structure For example, N, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-134457, JP-A-2-282264, Kaihei 2-304456
JP, JP-A-4-133065, JP-A-4-13-1
Compounds described in JP-A-33066, JP-A-5-40350, and JP-A-5-202135 are exemplified.

(D) Other Polymers For example, a formaldehyde condensation polymer of nitropyrene, JP-A-51-73888, JP-A-56-15074
9, JP-A-6-234836 and JP-A-6-34836.
Compounds described in JP-A-234837 are exemplified.

The polymer having an electron donating group used in the present invention includes not only the above-mentioned polymer but also a copolymer of a known monomer, a block polymer, a graft polymer, a star polymer, For example, it is also possible to use a crosslinked polymer having an electron donating group as disclosed in JP-A-3-109406.

The following compounds are exemplified as polycarbonates, polyurethanes, polyesters, and polyethers having a triarylamine structure, which are more useful as the polymer charge transporting material used in the present invention. For example, JP-A-64-1728 and JP-A-64-13
No. 061, JP-A-64-19049, JP-A-4-11627, JP-A-4-225014, JP-A-4-230767, JP-A-4-320
No. 420, JP-A-5-232727, JP-A-6-234838, JP-A-6-234839, JP-A-6-295077, JP-A-7-563
74, JP-A-7-325409, JP-A-9
-80772, JP-A-9-80783, JP-A-9-80784, JP-A-9-127713, JP-A-9-212877, JP-A-9-22
No. 2,740, JP-A-9-265197, JP-A-9-265201, JP-A-9-297419, JP-A-9-309495, and the like.

Further, as a polycarbonate having a triarylamine structure, which is more useful as a polymer charge transporting material used in the present invention, a polycarbonate having a triarylamine structure represented by the following general formulas 1 to 10 can be mentioned. The polymer charge transport materials represented by the general formulas 1 to 10 are exemplified below, and specific examples are shown.

[0028]

Embedded image

In the formula, R ₁ , R ₂ and R ₃ each independently represent a substituted or unsubstituted alkyl group or halogen atom,
₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, R ₅
, R ₆ are a substituted or unsubstituted aryl group, o, p, q
Are each independently an integer from 0 to 4, and k and j each represent a composition and are adjusted so that the charge transport structure is 30% by weight or more and 70% by weight or less. n represents the number of repeating units;
Is an integer. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula.

[0030]

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In the formula, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or halogen atom. l, m is an integer of 0 to 4, Y is a single bond, a linear C1-12, branched or cyclic alkylene group, -O -, - S -, - SO -, - SO 2 - , −
CO—, —CO—O—Z—O—CO— (wherein Z represents an aliphatic divalent group) or

[0032]

Embedded image

(Where a is an integer of 1 to 20, b is 1 to 2
An integer of 000, R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group. ). Where R
₁₀₁ and R ₁₀₂ and R ₁₀₃ and R ₁₀₄ may be the same or different.

Specific examples of the general formula 1 R ₁ , R ₂ and R ₃ each independently represent a substituted or unsubstituted alkyl group or a halogen atom. Specific examples thereof include the following. They may be the same or different.

The alkyl group is preferably C ₁ -C
_{12 is a} C ₁ -C ₈ , more preferably a C ₁ -C ₄ , linear or branched alkyl group, and these alkyl groups are furthermore a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄
A C ₄ alkoxy group, a phenyl group, or a halogen atom,
It may contain a phenyl group substituted with a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-
Butyl, trifluoromethyl, 2-hydroxyethyl, 2-cyanoethyl, 2-ethoxyethyl, 2-methoxyethyl, benzyl, 4-chlorobenzyl, 4-methylbenzyl, 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.

R ₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and specific examples of the alkyl group are the same as those described above for R ₁ , R ₂ and R ₃ .

R ₅ and R _{6 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo
[A, d] Cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group and the like as non-fused polycyclic group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The above-mentioned aryl group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) Examples of the alkyl group include the same as those described above for R ₁ , R ₂ and R ₃ . (3) As the alkoxy group (-OR ₁₀₅ ), R ₁₀₅ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. These are C ₁ -C
It may contain a ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. In particular,
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. (5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group. (7) Specific examples of the acyl group 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 the diol compound of the following general formula (B) together with a diol compound having a triarylamino group of the following general formula (A) when the diol compound is polymerized by a phosgene method, a transesterification method or the like. Introduced inside. In this case, the produced polycarbonate resin 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 of the following general formula (A) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0043]

Embedded image

The following are specific examples of the diol compound of the general formula (B). 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-propane Aliphatic diols such as diol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene ether glycol, and cyclic aliphatic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, cyclohexane-1,4-dimethanol Is mentioned.

The diol having an aromatic ring includes
4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 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-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4'-dihydroxydiphenyl sulfide, 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.

[0046]

Embedded image

In the formula, R ₇ and R ₈ are substituted or unsubstituted aryl groups, and Ar ₁ , Ar ₂ and Ar ₃ are the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1.

Specific Examples of General Formula 2 R ₇ and R _{8 each} represent a substituted or unsubstituted aryl group.
Specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo
[A, d] cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group or non-fused polycyclic group, or

[0050]

Embedded image

Where W is -O-, -S-, -SO-,
—SO ₂ —, —CO— and the following divalent groups are represented.

[0052]

Embedded image It is represented by

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₁ , Ar ₂ and Ar ₃ include the divalent groups of the aryl groups represented by R ₇ and R ₈ , which may be the same or different.

The above aryl group and arylene group may have the following groups as substituents. Further, these substituents are represented as specific examples of R ₁₀₆ , R ₁₀₇ and R _{108 in} the above general formula. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C ₁ -C ₁₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are furthermore a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ group.
An alkoxy group, a phenyl group, or a halogen atom, C ₁
It may contain a phenyl group substituted with a C ₄ to C ₄ alkyl group or a C ₁ to C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, trifluoromethyl, 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) an alkoxy group - The (OR _109), R ₁₀₉ represents an alkyl group specified in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. These are C ₁ -C
It may contain a ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. In particular,
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. (5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.

(6)

Embedded image

In the formula, R ₁₁₀ and R ₁₁₁ are each independently (2)
Represents, for example, a phenyl group, a biphenyl group, or a naphthyl group, which is a C ₁ to C ₄ alkoxy group, a C ₁ to C ₄ alkyl group or a halogen. An atom may be contained as a substituent. Further, a ring may be formed together with a carbon atom on the aryl group. Specifically, a diethylamino group, an N-methyl-N-phenylamino group, N,
Examples include an N-diphenylamino group, an N, N-di (p-tolyl) amino group, a dibenzylamino group, a piperidino group, a morpholino group, and a uroridyl group. (7) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.

X is a main chain obtained by using a diol compound of the following general formula (B) in combination with a diol compound having a triarylamino group of the following general formula (C) by using a phosgene method, a transesterification method or the like. Introduced inside. In this case, the produced polycarbonate resin 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 general formula (C) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0059]

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0060]

Embedded image

In the formula, R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group, and Ar ₄ , Ar ₅ and Ar ₆ represent the same or different arylene groups. X, k, j and n are represented by the general formula 1
Is the same as

Specific Examples of General Formula 3 R ₉ and R _{10 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo
[A, d] Cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group and the like as non-fused polycyclic group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₄ , Ar ₅ and Ar ₆ include the divalent groups of the aryl groups represented by R ₉ and R ₁₀ , which may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ group.
An alkoxy group, a phenyl group, or a halogen atom, C ₁
It may contain a phenyl group substituted with a C ₄ to C ₄ alkyl group or a C ₁ to C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, trifluoromethyl, 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) As the alkoxy group (—OR ₁₁₂ ), R ₁₁₂ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. This is C _1-
A C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom may be contained 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 and the like can be mentioned. Can be (5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (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 general formula (B) together with a diol compound having a triarylamino group of the following general formula (D) when the diol compound is polymerized by a phosgene method, a transesterification method or the like. Introduced inside. In this case, the produced polycarbonate resin 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 general formula (D) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0068]

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0069]

Embedded image

In the formula, R ₁₁ and R ₁₂ represent a substituted or unsubstituted aryl group, Ar ₇ , Ar ₈ and Ar ₉ represent the same or different arylene groups, and s represents an integer of 1 to 5. X, k, j and n are the same as in the case of the general formula 1.

Specific examples of general formula 4 R ₁₁ and R ₁₂ represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo
[A, d] Cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group and the like as non-fused polycyclic group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₇ , Ar ₈ , and Ar ₉ include the divalent groups of the aryl groups represented by R ₁₁ and R ₁₂ , which may be the same or different.

The above aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ group.
An alkoxy group, a phenyl group, or a halogen atom, C ₁
It may contain a phenyl group substituted with a C ₄ to C ₄ alkyl group or a C ₁ to C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, trifluoromethyl, 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) As the alkoxy group (—OR ₁₁₃ ), R ₁₁₃ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. These are C ₁ -C
It may contain a ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. In particular,
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. (5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is the main chain of a diol compound having a triarylamino group represented by the following general formula (E) when the diol compound having the triarylamino group is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin 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 general formula (E) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0077]

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0078]

Embedded image

In the formula, R ₁₃ and R ₁₄ are substituted or unsubstituted aryl groups, Ar ₁₀ , Ar ₁₁ , and Ar ₁₂ are the same or different arylene groups; X ₁ and X ₂ are substituted or unsubstituted ethylene groups; Represents a substituted or unsubstituted vinylene group. X, k, j and n are the same as in the case of the general formula 1.

Specific examples of general formula 5 R ₁₃ and R ₁₄ represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo
[A, d] Cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group and the like as non-fused polycyclic group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₁₀ , Ar ₁₁ and Ar ₁₂ include the divalent groups of the aryl groups represented by R ₁₃ and R ₁₄ , which may be the same or different.

The above aryl group and arylene group are as follows:
It may have the group shown as a substituent. (1) halogen atom, trifluoromethyl group, cyano
Group, nitro group. (2) The alkyl group is preferably C 1₁~ C₁₂
Especially C₁~ C₈And more preferably C₁~ C_FourDirectly
A chain or branched chain alkyl group;
The group further includes a fluorine atom, a hydroxyl group, a cyano group,₁~ C
_FourAn alkoxy group, a phenyl group, or a halogen atom,
C₁~ C_FourAlkyl group or C₁~ C_Four Alcoqui
It may contain a phenyl group substituted with a thio group. concrete
Include methyl, ethyl, n-propyl, i-pro
Pill, t-butyl, s-butyl, n-butyl, i-
Butyl group, trifluoromethyl group, 2-hydroxyethyl
Group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxy
Siethyl group, benzyl group, 4-chlorobenzyl group, 4-methyl
Benzyl group, 4-methoxybenzyl group, 4-phenylben
And a ziryl group. (3) alkoxy group (-OR₁₁₄) Is R₁₁₄
Represents an alkyl group defined in (2). In particular,
Methoxy, ethoxy, n-propoxy, i-pro
Oxy, t-butoxy, n-butoxy, s-butoxy
Xy, i-butoxy, 2-hydroxyethoxy, 2-
Cyanoethoxy group, benzyloxy group, 4-methylbenzyl
And a oxy group and a trifluoromethoxy group. (4) As the aryloxy group, as an aryl group,
And a phenyl group and a naphthyl group. This is C₁~ C
_FourAn alkoxy group of C₁~ C_FourAlkyl group or halo
A gen atom may be contained as a substituent. In particular,
Phenoxy group, 1-naphthyloxy group, 2-naphthyloxy
Group, 4-methylphenoxy group, 4-methoxyphenoxy group,
4-chlorophenoxy group, 6-methyl-2-naphthyloxy
And the like. (5) a substituted mercapto group or an arylmercapto group;
Specifically, methylthio, ethylthio,
Nilthio group, p-methylphenylthio group and the like.
You. (6) As the alkyl-substituted amino group, the alkyl group is
Represents an alkyl group defined in (2). Specifically,
Tylamino group, diethylamino group, N-methyl-N-propyl
Propylamino group, N, N-dibenzylamino group and the like
Can be (7) As the acyl group, specifically, an acetyl group,
Pionyl group, butyryl group, malonyl group, benzoyl group, etc.
Is mentioned.

X₁, X_TwoIs substituted or unsubstituted ethyl
Represents a substituted or unsubstituted vinylene group.
As the substituent, a cyano group, a halogen atom, a nitro group,
Note R ₁₃, R₁₄And the alkyl group of the above (2) is
No.

X is the main chain of a diol compound having a triarylamino group represented by the following general formula (F) when the diol compound is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin 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 general formula (F) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0087]

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0088]

Embedded image

In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are a substituted or unsubstituted aryl group, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and A
r ₁₆ is the same or different arylene group, Y ₁ , Y ₂ and Y ₃ are 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, It represents a sulfur atom or a vinylene group and may be the same or different. X, k, j
And n are the same as in the case of the general formula 1.

Specific Examples of General Formula 6 R ₁₅ , R ₁₆ , R ₁₇ , and R ₁₈ represent a substituted or unsubstituted aryl group. Specific examples thereof include the following. May also be different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo
[A, d] Cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group and the like as non-fused polycyclic group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and A
The arylene group represented by r ₁₆ includes R ₁₅ , R ₁₆ , R
Examples of the above-mentioned divalent group of the aryl group represented by ₁₇ and R ₁₈ are the same or different.

The above aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) The alkyl group is preferably C ₁ -C ₁₂
Particularly, it is a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are furthermore a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C 4 group.
_4, an alkoxy group, a phenyl group, or a halogen atom, C
It may contain a phenyl group substituted with ₁ ~ C ₄ alkyl or alkoxy group of C ₁ ~ C _4. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, trifluoromethyl, 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) As the alkoxy group (—OR ₁₁₅ ), R ₁₁₅ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. These are C ₁ -C
It may contain a ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. In particular,
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.

Y ₁ , Y ₂ and Y ₃ are 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, a vinylene group, And may be the same or different.

The alkylene group represents a divalent group derived from the alkyl group shown in the above (2). 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, Examples thereof include a 2-butylene group and a diphenylmethylene group.

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 a main chain of a diol compound having a triarylamino group represented by the following general formula (G) when the diol compound is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin 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 general formula (G) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0100]

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0101]

Embedded image

In the formula, R ₁₉ and R ₂₀ represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ and Ar ₁₉ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1.

Specific Examples of General Formula 7 R ₁₉ and R _{20 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a ,
d] A cycloheptenylidenephenyl group and a non-fused polycyclic group include a biphenylyl group and a terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

When R ₁₉ and R ₂₀ form a ring, 9
-Fluorinylidene, 5H-dibenzo [a, d] cyclohebutenylidene and the like.

The arylene groups represented by Ar ₁₇ , Ar ₁₈ and Ar ₁₉ include the divalent groups of the aryl groups represented by R ₁₉ and R ₂₀ , which may be the same or different.

The above aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ group.
An alkoxy group, a phenyl group, or a halogen atom, C ₁
It may contain a phenyl group substituted with a C ₄ to C ₄ alkyl group or a C ₁ to C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, trifluoromethyl, 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) As the alkoxy group (-OR ₁₁₆ ), R ₁₁₆ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. These are C ₁ -C
It may contain a ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. In particular,
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. (5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is the main chain of the diol compound having a triarylamino group represented by the following general formula (H) when the diol compound is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin 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 general formula (H) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0110]

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0111]

Embedded image

Where R_{twenty one}Is substituted or unsubstituted ally
Group, Ar₂₀, Ar_{twenty one}, Ar_{twenty two}, Ar _{twenty three}Are the same or different
Represents an arylene group. X, k, j and n are general
This is the same as in the case of Expression 1.

Specific Examples of General Formula 8 R ₂₁ represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo
[A, d] Cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group and the like as non-fused polycyclic group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

Ar ₂₀ , Ar ₂₁ , Ar ₂₂ and A
The arylene group represented by r ₂₃ includes the divalent group of the aryl group represented by R ₂₁ , and may be the same or different.

The above aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ group.
An alkoxy group, a phenyl group, or a halogen atom, C ₁
It may contain a phenyl group substituted with a C ₄ to C ₄ alkyl group or a C ₁ to C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, trifluoromethyl, 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) As the alkoxy group (—OR ₁₁₇ ), R ₁₁₇ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. These are C ₁ -C
It may contain a ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. In particular,
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. (5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is a main chain of a diol compound having a triarylamino group represented by the following general formula (J) when the diol compound is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin 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 general formula (J) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0119]

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0120]

Embedded image

In the formula, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are substituted or unsubstituted aryl groups, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ and A
r ₂₇ and Ar ₂₈ represent the same or different arylene groups.
X, k, j and n are the same as in the case of the general formula 1.

Specific Examples of General Formula 9 R ₂₂ , R ₂₃ , R ₂₄ , and R _{25 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following. May also be different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo
[A, d] Cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group and the like as non-fused polycyclic group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

Further, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇
And arylene groups represented by Ar ₂₈ include R ₂₂ , R
_The divalent groups of the above aryl groups represented by ₂₃ , R ₂₄ and R ₂₅ may be mentioned, and may be the same or different.

The above aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ group.
An alkoxy group, a phenyl group, or a halogen atom, C ₁
It may contain a phenyl group substituted with a C ₄ to C ₄ alkyl group or a C ₁ to C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, trifluoromethyl, 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) As the alkoxy group (—OR ₁₁₈ ), R ₁₁₈ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. These are C ₁ -C
It may contain a ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. In particular,
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. (5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is the main chain of the diol compound having a triarylamino group represented by the following general formula (L) when the diol compound is polymerized by a phosgene method, a transesterification method or the like. Introduced inside. In this case, the produced polycarbonate resin 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 general formula (L) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0128]

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0129]

Embedded image

In the formula, R₂₆, R₂₇Is substituted or unsubstituted
Aryl group of Ar₂₉, Ar₃₀, Ar ₃₁Are the same or different
Represents an arylene group. X, k, j and n are general
This is the same as in the case of Expression 1.

Specific examples of general formula 10 R ₂₆ and R _{27 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.

Phenyl group as aromatic hydrocarbon group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl as condensed polycyclic group Group, fluorenylidenephenyl group, 5H-dibenzo
[A, d] Cycloheptenylidenephenyl group, biphenylyl group, terphenylyl group and the like as non-fused polycyclic group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₂₉ , Ar ₃₀ and Ar ₃₁ include the divalent groups of the aryl groups represented by R ₂₆ and R ₂₇ , which may be the same or different.

The above aryl group and arylene group may have the following groups as substituents. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ group.
An alkoxy group, a phenyl group, or a halogen atom, C ₁
It may contain a phenyl group substituted with a C ₄ to C ₄ alkyl group or a C 1 to C ₄ alkoxy group. In particular,
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,
Examples include a 2-cyanoethyl group, a 2-ethoxyethyl group, a 2-methoxyethyl group, a benzyl group, a 4-chlorobenzyl group, a 4-methylbenzyl group, a 4-methoxybenzyl group, and a 4-phenylbenzyl group. (3) As the alkoxy group (—OR ₁₁₉ ), R ₁₁₉ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group. (4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. These are C ₁ -C
It may contain a ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. In particular,
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. (5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, and an N, N-dibenzylamino group. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is the main chain when a diol compound having a triarylamino group represented by the following general formula (M) is polymerized by a phosgene method, a transesterification method or the like, by using a diol compound represented by the following general formula (B) in combination. Introduced inside. In this case, the produced polycarbonate resin 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 general formula (M) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0137]

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

Next, the charge transport structure of the polymer charge transport material used in the present invention will be described. The charge transport structure refers to the following structural unit. Carbazole structure, hydrazone structure, pyrazoline structure, triarylamine structure, amidine structure,
An electron-donating group such as a dialkylamino group or a nitro group, anthracene having an electron-withdrawing group such as a cyano group, pyrene, a fused polycyclic structure such as phenanthrene, a heterocyclic structure having an electron-withdrawing group or an electron-donating group, In addition, when a π-electron conjugate system such as an allyl group or an aryl group is directly extended in a structure of the above-described structure, or a substituent whose conjugate system is expanded by intervening an unpaired electron such as a nitrogen atom or an oxygen atom, these Is included in the above structural unit as a charge transport structure.
When an alkyl group is present in the conjugated system, the first hydrocarbon portion is also included in the charge transporting structural unit.

Among these charge transport structures, a triarylamine structure, which is a high-mobility structural unit, is particularly useful. Specific examples include triphenylamine, diphenylaminobiphenyl, tetraphenylbenzidine, tetraphenylphenylenediamine, and styryl groups,
A structure in which a conjugated system is expanded by an aryl ether group or the like can be given.

In the present invention, the charge transport structure of the polymer charge transport material is 30% by weight of the total molecular weight of the polymer charge transport material.
As described above, the content of the charge transporting structure is not more than 70% by weight, and the ratio of the charge transporting structure is such that the molecular weight of the charge transporting structural unit is in this range with respect to the total molecular weight of the polymer charge transporting substance. pointing.

The electrophotographic photosensitive member used in the present invention will be described below in detail with reference to the drawings. In the present invention, the photosensitive layer is a single-layer type electrophotographic photoreceptor in which a charge generating substance is dispersed in a charge transporting layer, and a laminated type electrophotographic photoreceptor in which a charge generating layer and a charge transporting layer are sequentially laminated from the conductive support side. Used in any one of the above configurations. Of these configurations, the laminated photoconductor will be described first.

FIG. 1 is a cross-sectional view schematically showing one example of the electrophotographic photosensitive member of the present invention, in which a photosensitive layer 2 comprising a charge generating layer 22 and a charge transporting layer 23 on a conductive support 21 is shown.
4 are provided.

FIG. 2 is a cross-sectional view schematically showing an electrophotographic photosensitive member having another structure, in which a conductive support 21 and a photosensitive layer 24 are provided.
An undercoating layer 25 is provided between them.

FIG. 3 is a cross-sectional view schematically showing an electrophotographic photosensitive member having another structure, in which a protective layer 26 is provided on the photosensitive layer 24.

FIG. 4 is a cross-sectional view schematically showing an electrophotographic photosensitive member having still another configuration. An undercoat layer 25 is provided between a conductive support 21 and a photosensitive layer 24. A protective layer 26 is provided thereon.

As the conductive support 21, a volume resistance of 10
Those exhibiting conductivity of ¹⁰ Ωcm or less, such as aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum,
Metals such as iron, oxides such as tin oxide and indium oxide coated on film or cylindrical plastic or paper by evaporation or sputtering, or plates made of aluminum, aluminum alloy, nickel, stainless steel, etc. D. I. , I .; I. , Extrusion, drawing, etc., after forming into a tube, cutting, super finishing,
A tube or the like that has been surface-treated by polishing or the like can be used.

Next, the charge generation layer 22 will be described.
The charge generation layer 2 is a layer containing a charge generation substance as a main component, and may use a binder resin as needed. As the charge generation substance, an inorganic material and an organic material can be used.

Examples of the inorganic material include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. In the case of amorphous silicon, a material obtained by terminating a dangling bond with a hydrogen atom or a halogen atom, or a material obtained by doping a boron atom, a phosphorus atom or the like is preferably used.

On the other hand, known materials can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulhenium salt pigments, methine squaric acid pigments, azo pigments having a carbazole skeleton, azo pigments having a triphenylamine skeleton, azo pigments having a diphenylamine skeleton, dibenzo Azo pigment having a thiophene skeleton, azo pigment having a fluorenone skeleton, azo pigment having an oxadiazol skeleton, azo pigment having a bisstilbene skeleton, azo pigment having a distyryl oxadiazol skeleton, distyryl carbazole skeleton Azo pigments, perylene pigments, anthraquinone pigments or polycyclic quinone pigments, quinone imine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, Jigoido pigments, bisbenzimidazo - such as Le based pigments. These charge generating substances can be used alone or as a mixture of two or more.

The binder resin optionally used for the charge generation layer 22 includes polyamide, polyurethane,
Epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene,
Poly-N-vinyl carbazole, polyacrylamide and the like are used. These binder resins can be used alone or as a mixture of two or more. Also,
As the binder resin for the charge generation layer, the above-described polymer charge transport material can be used in addition to the binder resin described above. Further, a low molecular charge transport material may be added as needed.

The low-molecular-weight charge transporting material that can be used in combination with the charge generating layer 22 includes a hole transporting material and an electron transporting material.

Examples of the electron transporting material include chloranil, bromanil, 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-
Electron accepting substances such as trinitro-4H-indeno [1,2-b] thiophen-4-one and 1,3,7-trinitrodibenzothiophene-5,5-dioxide are exemplified. These electron transport materials can be used alone or as a mixture of two or more.

As the hole transporting material, the following electron donating materials can be used, and are preferably used. For example, oxazole derivatives, oxadiazol derivatives, imidazole derivatives, triphenylamine derivatives, 9-
(P-diethylaminostyrylanthracene), 1,1
-Bis- (4-dibenzylaminophenyl) propane,
Styryl anthracene, styryl pyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives,
Examples include acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. These hole transport materials can be used alone or as a mixture of two or more.

The method for forming the charge generation layer 22 includes a vacuum thin film preparation method and a casting method from a solution dispersion system.

The former method includes a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method,
Reactive sputtering, CVD, or the like is used, and the above-described inorganic and organic materials can be formed favorably.

In order to form a charge generation layer by the casting method described later, the above-mentioned inorganic or organic charge generation material is used together with a binder resin if necessary using a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane or butanone. It can be formed by dispersing with a ball mill, an attritor, a sand mill, or the like, diluting the dispersion liquid appropriately, and applying. The coating can be performed by a dip coating method, a spray coating method, a bead coating method, or the like.

The thickness of the charge generation layer provided as described above is suitably about 0.01 to 5 μm, and preferably 0.05 to 2 μm.

Next, the charge transport layer 23 will be described.
The charge transporting layer 23 is a layer containing a polymer charge transporting material as a main component, and can be formed by dissolving or dispersing the polymer charge transporting material in a suitable solvent, coating and drying. The above-mentioned compound is used as the polymer charge transporting material. As described above, the ratio of the charge transporting structure in the polymer charge transporting material to the total molecular weight of the polymer charge transporting material depends on the abrasion resistance of the charge transporting layer and the time of use. Is important for the charge stability of the toner.
The ratio of the polymer charge transport material to all components of the charge transport layer is 60 parts by weight or more. If necessary, a suitable low-molecular charge transport material, a binder resin, a plasticizer, and a leveling agent can be added to the charge transport layer 23.

As the low-molecular charge transporting substance that can be used in combination with the charge transporting layer 23, the same substance as described in the description of the charge generating layer 22 can be used. The amount of the low molecular weight charge transporting substance to be used is suitably about 0 to 10 parts by weight based on all components of the charge transporting layer, and if it is more than this, the wear resistance of the charge transporting layer is impaired.

Examples of the binder resin that can be used in combination with the charge transport layer 23 include polycarbonate (bisphenol A type, bisphenol Z type), polyester, methacrylic resin, acrylic resin, vinyl chloride, vinyl acetate, and polystyrene. , Phenol resin, epoxy resin, polyurethane, polyvinylidene chloride, alkyd resin, silicone resin, polyvinyl carbazole, polyvinyl butyral
, Polyvinyl formal, polyacrylate, polyacrylamide, phenoxy resin and the like. These binders can be used alone or as a mixture of two or more. An appropriate amount of the binder resin is about 0 to 70 parts by weight based on 100 parts by weight of the polymer charge transporting substance.

As the plasticizer that can be used in combination with the charge transport layer 23, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, About 0 to 30 parts by weight per 100 parts by weight of the charge transporting material is appropriate.

Examples of the leveling agent which can be used in combination with the charge transport layer 23 include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. The amount of the binder resin 100
About 0 to 1 part by weight based on parts by weight is appropriate. The thickness of the charge transport layer 23 is suitably about 5 to 100 μm,
Preferably, about 10 to 40 μm is appropriate.

The electrophotographic photosensitive member used in the present invention includes:
An undercoat layer 25 can be provided between the conductive support 21 and the photosensitive layer 24, and the undercoat layer 25 improves adhesion.
It is provided for the purpose of preventing, for example, moiré, improving the coatability of the upper layer, reducing the residual potential, and preventing charge injection from the conductive support. The undercoat layer 25 generally contains a resin as a main component. However, considering that a photosensitive layer is coated thereon with a solvent, these resins are preferably resins having high solubility resistance to general organic solvents. . Examples of such a resin include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymerized nylon and methoxymethylated nylon, polyurethane, melamine resin, alkyd-melamine resin, and epoxy resin. And a curable resin that forms a three-dimensional network structure. Also, titanium oxide, silica, alumina, zirconium oxide, tin oxide,
A fine powder such as a metal oxide exemplified by indium oxide or a metal sulfide or a metal nitride may be added. These undercoat layers 25 can be formed using an appropriate solvent and a coating method as in the case of the photosensitive layer in the previous operation.

Further, as the undercoat layer 5 of the present invention, a metal oxide layer formed by a sol-gel method using a silane coupling agent, a titanium coupling agent, a chromium coupling agent or the like is also useful. .

In addition, the undercoat layer 25 of the present invention has A
l ₂ O ₃ provided by anodic oxidation, organic substances such as polyparaxylylene (parylene), SiO, SnO ₂ , T
Those provided with an inorganic substance such as iO ₂ , ITO, CeO ₂ by a vacuum thin film manufacturing method can also be used favorably. The thickness of the undercoat layer is 0
５5 μm is appropriate.

In the electrophotographic photosensitive member of the present invention, a protective layer 26 may be provided on the photosensitive layer 24 for the purpose of protecting the photosensitive layer. Materials used for this include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide,
Polyacrylate, polyallyl sulfone, polybutylene, polybutylene terephthalate, polycarbonate,
Polyether sulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide,
Resins such as polysulfone, AS resin, AB resin, BS resin, polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin. For the purpose of improving abrasion resistance, the protective layer may be made of a fluororesin such as polytetrafluoroethylene, a silicone resin, or a material in which an inorganic material such as titanium oxide, tin oxide or potassium titanate is dispersed in these resins. Can be added.

As a method for forming the protective layer 26, an ordinary coating method is employed. The thickness of the protective layer is 0.5 to 10
About μm is appropriate. In addition to the above, known materials such as iC and a-SiC formed by a vacuum thin film manufacturing method can also be used as the protective layer.

In the present invention, an antioxidant can be added for the purpose of improving environmental resistance, especially for the purpose of preventing a decrease in sensitivity and an increase in residual potential. The antioxidant may be added to any layer containing an organic substance, but good results are obtained when it is added to the charge transport layer.

Examples of the antioxidants that can be used in the present invention include the following. Phenol compounds 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3 , 5-di-t-
Butyl-4-hydroxyphenyl) propionate,
2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
Ethyl-6-t-butylphenol), 4,4'-thiobis- (3-methyl-6-t-butylphenol),
4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-
t-butyl-4'-hydroxyphenyl) propione-
G] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] cricol ester, tocopherols and the like.

Paraphenylenediamines N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-
Phenylenediamine, N, N'-di-isopropyl-p
-Phenylenediamine, N, N'-dimethyl-N, N '
-Di-t-butyl-p-phenylenediamine and the like.

Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t
-Octyl-5-methylhydroquinone, 2- (2-octadecenyl) -5-methylhydroquinone and the like.

Organic sulfur compounds: dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate and the like.

Organic phosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

These compounds are known as antioxidants for rubbers, plastics, fats and oils, and commercially available products can be easily obtained.

In the present invention, the addition amount of the antioxidant is 0.1 to 30 parts by weight based on 100 parts by weight of the polymer charge transporting substance.

Next, an electrophotographic photosensitive member having a single-layered photosensitive layer according to the present invention will be described. The photoreceptor having a single layer structure is a single layer of the photosensitive layer having the laminated structure of the charge generation layer and the charge transport layer shown in FIGS. 1 to 4, wherein the charge generation material is mainly composed of a polymer charge transport material. And dispersed in the charge transport layer. In this configuration, the same charge generation substance as described above can be used, and the amount of the charge generation substance is 0.1 to 10 parts by weight with respect to the whole photosensitive layer. Further, the additive described in the charge transport layer 23 can be similarly used in the single-layered photosensitive layer, and is used in the same thickness as the charge transport layer.

Further, if necessary, the undercoat layer 25 and the protective layer 26 can be provided on a single-layer photosensitive layer.

[0178]

Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples. All parts used in the examples are parts by weight.

Example 1 A coating liquid for an undercoat layer, a coating liquid for a charge generation layer, and a coating liquid for a charge transport layer were sequentially coated and dried on an aluminum drum having a diameter of 30 mm. An electrophotographic photoreceptor of the present invention was obtained by forming a 5 μm undercoat layer, a 0.2 μm charge generation layer, and a 22 μm charge transport layer.

[Coating liquid for undercoat layer] Alkyd resin (Veccosol 1307-60-E)
L, manufactured by Dainippon Ink and Chemicals, Inc. 6 parts Melamine resin (Super Beckamine G-821-6)
0, Dainippon Ink and Chemicals) 4 parts Titanium oxide 40 parts Methyl ethyl ketone
50 copies

[Coating Liquid for Charge Generating Layer] Oxo titanium phthalocyanine pigment
3 parts polyvinyl butyral (XYHL, UCC)
2 parts tetrahydrofuran
120 copies

[Coating Solution for Charge Transport Layer] Polymer charge transport material:

Embedded image 10 parts methylene chloride
65 parts

Example 2 A photoconductor was prepared in the same manner as in Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 10 parts methylene chloride
65 parts

Example 3 A photoconductor was prepared in the same manner as that of Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 10 parts methylene chloride
65 parts

Example 4 A photoconductor was prepared in the same manner as that of Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 10 parts methylene chloride
65 parts

Example 5 A photoconductor was prepared in the same manner as in Example 1, except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 10 parts methylene chloride
65 parts

Example 6 A photoconductor was prepared in the same manner as that of Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 10 parts methylene chloride
65 parts

Example 7 A photoconductor was prepared in the same manner as that of Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 10 parts methylene chloride
65 parts

Example 8 A photoconductor was prepared in the same manner as in Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 9 copies

Low molecular charge transport material

Embedded image 1 part methylene chloride
60 parts

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 10 parts methylene chloride
65 parts

Comparative Example 2 A photoconductor was prepared in the same manner as in Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 10 parts methylene chloride
65 parts

Comparative Example 3 A photoconductor was prepared in the same manner as in Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 10 parts methylene chloride
65 parts

Comparative Example 4 A photoconductor was prepared in the same manner as in Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 9 copies

Low molecular charge transport material

Embedded image 1 part methylene chloride
60 parts

Comparative Example 5 A photoconductor was prepared in the same manner as in Example 1 except that the charge transport coating solution of Example 1 was changed as follows. Polymer charge transport material:

Embedded image 8 copies

Low molecular charge transport material

Embedded image 2 parts methylene chloride
60 parts

Comparative Example 6 A photoconductor was prepared in the same manner as in Example 1, except that the coating solution for the charge transport layer in Example 1 was changed to the following. [Coating liquid for charge transport layer] Bisphenol A polycarbonate (Panlite C14
00, Teijin Chemicals) 10 parts

Low molecular charge transport material:

Embedded image 10 parts methylene chloride
100 copies

After the electrophotographic photoreceptors of Examples 1 to 8 and Comparative Examples 1 to 6 produced as described above were used for mounting, they were evaluated as follows. [Evaluation method of actual machine running characteristics] 50,000 sheets of each photosensitive member were subjected to a paper passing test using a commercially available electrophotographic copying machine Imagio MF2200 (manufactured by Ricoh Co., Ltd.). During and after the paper passing test, the evaluation of the image quality characteristics and the wear amount of the photosensitive layer of the photoreceptor was performed at appropriate times. Image quality: Comprehensive evaluation of solid density, fine line reproducibility, abnormal image, etc. Abrasion: Amount of decrease in photosensitive layer thickness due to actual machine running The evaluation results are shown in Table 1.

[0201]

【table 1】

As is clear from Table 1, the electrophotographic photoreceptors of Examples 1 to 8 satisfying the claims of the present invention have low abrasion of the photosensitive layer and can stably produce high-quality images for a long period of time. I understand that it can be done. On the other hand, the photosensitive members of Comparative Examples 1, 2, 5, and 6 generate abnormal images due to abrasion, and the photosensitive members of Comparative Examples 3 and 4 have good abrasion resistance, but have high image potential failure due to a high potential of the exposed portion. Occurred.

Accordingly, in the electrophotographic photosensitive member having at least a photosensitive layer on the conductive support of the present invention, the photosensitive layer contains at least a polymer charge transport material, and the polymer charge transport material is a polymer charge transport material. 3 of total molecular weight of transport substance
By having a charge transport structure of 0% by weight or more and 70% by weight or less, it becomes possible to provide an electrophotographic photoreceptor that achieves a long life with excellent abrasion resistance and high reliability at a high level.

[0204]

As described above, according to the present invention, a long-life, high-reliability electrophotographic photosensitive member having excellent wear resistance can be obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a configuration of an electrophotographic photosensitive member of the present invention.

FIG. 2 is a cross-sectional view illustrating a configuration of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a cross-sectional view illustrating a configuration of the electrophotographic photosensitive member of the present invention.

FIG. 4 is a cross-sectional view illustrating a configuration of the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 21 ... Conductive support 22 ... Charge generation layer photosensitive layer 23 ... Charge transport layer Undercoat layer 24 ... Photosensitive layer 25 ... Undercoat layer 26 ... Protective layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Katsuichi Ota 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Hiroshi Tamura 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh F term (reference) 2H068 AA20 AA21 AA37 BB23 BB25 BB26 BB29 BB40 BB49 BB51 BB53 BB54

Claims (5)

[Claims] 1. An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the photosensitive layer contains at least a polymer charge transport material, and the polymer charge transport material is a polymer charge transport material. 30% by weight or more of the molecular weight,
An electrophotographic photosensitive member having a charge transport structure of 70% by weight or less. 2. The electrophotographic photoreceptor according to claim 1, wherein the polymer charge transporting material is at least one polymer of polycarbonate, polyurethane, polyester, and polyether. 3. The electrophotographic photoreceptor according to claim 1, wherein the charge transport structure of the polymer charge transport material is a polymer compound having a triarylamine structure. 4. The electrophotographic photoreceptor according to claim 1, wherein the polymer charge transporting material is a polycarbonate having a triarylamine structure. 5. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer is a laminated electrophotographic photosensitive member in which a charge generation layer and a charge transport layer are sequentially laminated.