JP2958101B2 - Carbazole-based polycarbonate, method for producing the same, and electrophotographic photoreceptor using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a carbazole-based polycarbonate suitably used as a charge transfer material for an electrophotographic photoreceptor and a method for producing the same.

The present invention also relates to an electrophotographic photosensitive member using the carbazole-based polycarbonate.

[Related Art] In a recent electrophotographic photoreceptor, a layered organic electrophotographic photoreceptor, that is, a photosensitive layer has at least two layers: a charge generation layer that generates charges by exposure and a charge transport layer that transports charges. Those having layers are becoming mainstream. In this type of organic electrophotographic photoreceptor, as a charge transport layer,
A material obtained by dispersing and casting a charge transfer material in a binder resin, particularly polycarbonate, is used.

Conventionally, in this type of organic electrophotographic photoreceptor, in order to improve the photoconductivity of the charge transfer material, a large amount of the charge transfer material is dispersed and dissolved in polycarbonate which is a binder resin. Is 4 by weight
It accounts for ~ 50%. Therefore, there is a problem that the original function of polycarbonate as a binder resin for the purpose of improving printing durability is not sufficiently exhibited.

As one method for solving this problem, Japanese Patent Laid-Open Publication No.
In Japanese Patent Application Laid-Open Publication No. H11-209, a polyarylamine obtained by copolymerizing an arylamine-based low-molecular compound, which is a low-molecular charge transfer material, with an alkyl chloroformate compound or bisphenol A at a weight ratio of 1: 1 is disclosed. The polyarylamine is a polycarbonate having a photoconductive action by itself, and is intended to solve the above-mentioned problems by using the polyarylamine for the charge transport layer instead of the conventional charge transfer substance dissolving type. It has been proposed.

The idea of utilizing polycarbonate having photoconductivity by itself in the charge transport layer as a charge transfer material and a binder resin seems to be an effective method for solving the above-mentioned problems.

However, when the above-mentioned conventional photoconductive polyarylamine is used for the charge transport layer, there is a problem that sufficient printing durability cannot be obtained.

Further, although the electrical properties of the conventional photoconductive polyarylamine as a charge transporting layer are somewhat improved as compared with those of the conventional dispersion dissolution type, they have not been significantly improved.

As a carbazole-based polymer, polyvinyl carbazole has been studied as a typical photoconductive polymer, and is currently used as an electrophotographic photoreceptor, but sufficient electrical properties have not been obtained using this polymer alone.

[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned problems and to suitably use the photosensitive layer of an electrophotographic photosensitive member, particularly a charge transport layer, as a charge transfer material or a charge transfer material and a binder resin. An object of the present invention is to provide an excellent photoconductive carbazole-based polycarbonate which can easily realize an electrophotographic photosensitive member excellent in printing durability and electric characteristics.

Another object of the present invention is to provide a practically advantageous production method that can be suitably used as a method for producing the carbazole-based polycarbonate.

It is a further object of the present invention to provide an electrophotographic photoreceptor which solves the above problems and has improved electric characteristics and printing durability of a charge transport layer.

[Means for Solving the Problems] The present inventors can suitably use the charge transport layer of the organic electrophotographic photoreceptor as a charge transfer material and also as a binder resin. We worked diligently to develop a new photoconductive polycarbonate that can improve printability. As a result, they have found that a specific carbazole-based repeating unit or a carbazole-based polycarbonate having a novel structure comprising the same and a bisphenol-based repeating unit is a photoconductive polycarbonate satisfying the above-mentioned object. Further, in an organic electrophotographic photoreceptor having at least two layers having a photosensitive layer and a charge transporting layer, by using the photoconductive carbazole-based polycarbonate as a charge transporting substance or a charge transporting substance and a binder resin, excellent electrical properties are obtained. It has been found that an electrophotographic photoreceptor having excellent performance such as having a charge transport layer exhibiting printing durability can be obtained.

In addition, as a result of various studies on the method for producing the carbazole-based polycarbonate of the present invention, a specific dihydroxy compound having a carbazole structure or a bisphenol compound and a bisphenol compound were reacted with a carbonate-forming compound to obtain a carbazole-based polycarbonate of the present invention. It has been found that polycarbonate can be advantageously produced.

The present inventors have completed the present invention based on these findings.

That is, the present invention provides the following general formula (I) (Where p and q are each independently 0 or 1, i and j are each independently an integer of 1 to 3, and Ar ¹ is Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl or alkoxyl group having 1 to 5 carbon atoms, —CN or —NO ₂ , and Ar ² has 6 carbon atoms. R ¹ is an aryl group or a substituted aryl group having 6 to 12 carbon atoms, R ² and R ³ are each independently a hydrogen atom, a halogen atom, a carbon atom number; It is an alkyl group having 1 to 6 or an aryl group having 6 to 12 carbon atoms or a substituted aryl group. ) And the following general formula (II) (Wherein, R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group or a substituted aryl group having 6 to 12 carbon atoms, and k and 1 are Each independently is an integer from 1 to 4, X is CH _{2 g} , single bond, -O-, -S-, -SO- or -SO ₂
Wherein R ⁶ and R ⁷ are each independently a hydrogen atom, —CF ₃ ,
An alkyl group having 1 to 6 carbon atoms or an aryl group or a substituted aryl group having 6 to 12 carbon atoms, h is an integer of 4 to 10, and g is an integer of 2 to 10. ) Wherein the content of the repeating unit represented by the general formula (I) is the same as that of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II). In the range represented by the following formula: O <[(I) / {(I) + (II)}] ≦ 1, and 0.5 g using methylene chloride as a solvent.
/ dl concentration solution at 20 ° C has reduced viscosity [η _sp / C] of 0.2
A carbazole-based polycarbonate having a dl / g or more is provided.

Further, the present invention provides a practically advantageous method for producing the carbazole-based polycarbonate of the present invention as described above, using the following general formula: (Where p, q, i, j, Ar ¹ , Ar ² , R ¹ , R ² and R ³ are
Each has the same meaning as in formula (I). Or a compound represented by the general formula (III) and a compound represented by the following general formula (IV) (Where k, l, R ⁴ , R ⁵ and X each have the same meaning as in the above formula (II)). And a method for producing a carbazole-based polycarbonate characterized by the following.

Further, the present invention provides an electrophotographic photoreceptor characterized in that the carbazole-based polycarbonate is used as a charge transfer material, as a particularly preferred application example of the carbazole-based polycarbonate of the present invention.

In the repeating unit represented by the general formula (I),
R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group or a substituted aryl group having 6 to 12 carbon atoms, and as the halogen atom, a fluorine atom , A chlorine atom, a bromine atom and an iodine atom. Among these, a chlorine atom is particularly preferred.

Regarding R ² and R ³ , examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec-
Examples thereof include a butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an isohexyl group, and a cyclohexyl group. Of these alkyl groups, a methyl group, an ethyl group and the like are usually preferred, and a methyl group is particularly preferred.

Further, regarding R ² and R ³ , as the aryl group or substituted aryl group having 6 to 12 carbon atoms, for example, phenyl group, tolyl group, various methylfetyl groups such as xylyl group,
Examples include alkylphenyl groups such as various ethylphenyl groups and various propylphenyl groups, biphenylyl groups, various alkylbiphenylyl groups, 1- or 2-naphthyl groups, various alkylnaphthyl groups, and the like. Among these aryl groups or substituted aryl groups, a phenyl group is particularly preferred.

In each of R ² and R ³ , among the various groups exemplified above, a hydrogen atom, a methyl group, and the like are particularly preferable.

Further, i and j indicating the numbers of the substituents R ² and R ³ are as described above, respectively. When R ² and R ³ are not a hydrogen atom, each of them is preferably 1 or 2.

In the repeating unit represented by the general formula (I),
R ⁹ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, is a -CN or -NO _2, as the halogen atom, Examples of the halogen atom include those exemplified above. Among them, a chlorine atom is preferable.

Regarding R ⁸ and R ⁹ , examples of the alkyl group having 1 to 5 carbon atoms include those having 1 to 5 carbon atoms in the above-described alkyl groups. Among them, a methyl group is preferable.

Regarding R ⁸ and R ⁹ , examples of the alkoxyl group having 1 to 5 carbon atoms include a methoxyl group, an ethoxyl group, and an n-
Examples include a propoxyl group, an isopropoxyl group, an n-butoxyl group, an isobutoxyl group, a sec-butoxyl group, a tert-butoxyl group, an n-pentyloxy group, and an isopentyloxy group. Among these, a methoxyl group and an ethoxyl group are preferred.

Among the various groups exemplified above, R ⁸ and R ⁹ are particularly preferably a hydrogen atom and a methyl group.

In the repeating unit represented by the general formula (I),
Preferable groups for Ar ¹ include a phenylene group, particularly preferably a 1,4-phenylene group.

In the repeating unit represented by the general formula (I),
Ar ² is an aryl group or a substituted aryl group having 6 to 12 carbon atoms, and specific examples of the aryl group and the substituted aryl group include those exemplified above. Of these, a phenyl group is preferred.

In the repeating unit represented by the general formula (I), R ¹
Is an aryl group or a substituted aryl group having 6 to 12 carbon atoms, and specific examples of the aryl group and the substituted aryl group include those exemplified above. Among them, a phenyl group, a naphthyl group, particularly a 2-naphthyl group, a tolyl group, particularly a p-tolyl group, are preferred.

Representative examples of the repeating unit represented by the general formula (I) I include, for example, Is mentioned.

In the repeating unit represented by the general formula (II),
R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group or a substituted aryl group having 6 to 12 carbon atoms. Examples are given. Among them, a chlorine atom is preferred.

Regarding R ⁴ and R ⁵ , examples of the alkyl group having 1 to 6 carbon atoms include those described above, and among them, a methyl group, an ethyl group, and the like are preferable.

Regarding R ⁴ and R ⁵ , examples of the aryl group or substituted aryl group having 6 to 12 carbon atoms include those exemplified above, and among them, a phenyl group is preferable.

Among the various groups exemplified above, R ⁴ and R ⁵ are preferably a hydrogen atom, a methyl group, a phenyl group, or the like.

X in the repeating unit represented by the general formula (II)
Is selected from the above-mentioned various divalent groups or single bonds.

Y is In the case of R ⁶ and R ⁷ are each independently a hydrogen atom, -CF ₃ ,
It is an alkyl group having 1 to 6 carbon atoms or an aryl group or a substituted aryl group having 6 to 12 carbon atoms. Examples of the alkyl group and the aryl group include those described above. Particularly preferred groups for R ⁶ and R ⁷ include, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, a phenyl group and the like.

Y is In the case of this, as the 1,1-cycloalkylidene group,
-Cyclopentylidene group, 1,1-cyclohexylidene group, 1,1-cyclooctylidene group and the like, and in particular, 1,1-cyclohexylidene group in which h = 5 is preferred. preferable.

When Y is CH _{2 g} , examples of the polymethylene group include dimethylene group, trimethylene group, tetramethylene group, hexamethylene group, octamethylene group, and decamethylene group.

Preferred examples of X include, for example, CH ₂ CH ₂ , —O—, —S—, —SO—, —SO ₂ —, a single bond, and the like can be given. Among these, Are preferred.

Note that the values of k and 1 in the general formula (II) are each independently an integer of 1 to 4, and when R ⁴ and R ⁵ are not hydrogen atoms, 1 or 2 is preferable.

The carbazole-based polycarbonate of the present invention comprises at least one kind of the repeating unit (I), or at least one kind of the repeating unit (I) and at least one kind of the repeating unit (II). Consists of

That is, the content ratio of the repeating unit (I) in the carbazole-based polycarbonate of the present invention is represented by the following formula 0 <[(I) / ｛in molar ratio with respect to the total of the repeating unit (I) and the repeating unit (II). (I) + (II)}] ≦ 1 can be arbitrarily selected.

Here, this ratio is 0, that is, the repeating unit (I)
In the case of a polycarbonate containing no, there is no photoconductivity as it is, and even if a low-molecular charge transfer material is decomposed and dissolved therein and used as a charge transport layer of an electrophotographic photoreceptor, the electrical properties are not affected. And the printing durability cannot be sufficiently satisfied, and the object of the present invention cannot be achieved.

That is, one of the important points in the present invention is to have the repeating unit (I) having a specific carbazole-type structure.

The preferred range of the content of the repeating unit (I) is usually 0.01 <[(I) / {(I) + (II)}] ≦ 1.

Incidentally, the carbazole-based polycarbonate of the present invention,
As long as the object of the present invention is not hindered, other repeating units other than those described above may be contained, and other polymer components and additives can be appropriately added and used.

In the carbazole-based polycarbonate of the present invention,
Another important point is the concentration using methylene chloride as a solvent.
Reduced viscosity of 0.5g / dl solution at a temperature of 20 ° C [η _sp / C]
Is 0.2 dl / g or more.

When the reduced viscosity [η _sp / C] is less than 0.2 dl / g, properties such as the original mechanical strength as a polycarbonate, particularly when used in a charge transport layer of an electrophotographic photoreceptor, have sufficient printing durability. I can't get it.

The preferred range of the reduced viscosity [η _sp / C] is 0.2 to 5.0 dl /
g, particularly preferably 0.3 to 4.0 dl / g.

As described above, a specific structure and a specific reduced viscosity [η _sp /
The carbazole-based polycarbonate of the present invention having C] is a polycarbonate having photoconductivity and can be used for various applications, but is particularly advantageous as a charge transfer material and binder resin for an electrophotographic photosensitive member as described later. Can be used for

The carbazole-based polycarbonate polymer of the present invention,
The production method is not particularly limited, and it can be produced by various methods according to a known method using an appropriate monomer. Particularly, it can be advantageously produced by the method of the present invention described below.

That is, the method for producing the carbazole-based polycarbonate of the present invention in a practically advantageous manner is represented by the following general formula (II)
I) (Where p, q, i, j, Ar ¹ , Ar ² , R ¹ , R ² and R ³ are
Each has the same meaning as in formula (I). Or a compound represented by the general formula (III) and a compound represented by the following general formula (IV) (Where k, l, R ⁴ , R ⁵ and X each have the same meaning as in the above formula (II)). It is performed by

P, q, i, j, Ar ¹ , Ar in the general formula (III)
Specific examples of the ^2, R ^1, R ² and R ^3, preferred examples like are the same as defined above.

Further, k, l, R ⁴ , R ⁵ and X in the general formula (IV)
Specific examples, preferred examples, and the like are the same as described above.

Representative examples of the compound represented by the general formula (III), that is, the dihydroxycarbazole compound, include the following.

Representative examples of the compound represented by the general formula (IV), that is, bisphenol compound (IV) include, for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-
(Hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 4,4-bis (4-hydroxyphenyl)
Heptane, 1,1-bis (4-hydroxyphenyl) -1,1
-Diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenyltan, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, bis (4-hydroxyphenyl) ether, bis (4- (Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl -4-hydroxyphenyl) propane, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) methane, 1,1 -Bis (3-methyl-4
-Hydroxyphenyl) cyclohexane, 4,4'-dihydroxybiphenyl, 2,2-bis (2-methyl-4-hydroxyphenyl) propane, 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) Butane, 1,1
-Bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1,1-bis (2-tert-butyl-
4-hydroxy-5-methylphenyl) propane, 1,1
-Bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-
4-hydroxy-5-methylphenyl) isobutane, 1,
1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -1-phenylmethane, 1, 1-bis (2-tert-amyl-4-hydroxy-5-methylphenyl) butane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, 2 , 2-Bis (3-chloro-4-hydroxyphenyl) propane, 2,
2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane , 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4) -Hydroxy-5-chlorophenyl) propane, 2,2-bis (3,5-dichloro-
4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, bis (3 -Fluoro-4-hydroxyphenyl) ether, 3,3'-difluoro-4,4'-dihydroxybiphenyl, and 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane. Among these, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane and the like are preferable. Used for

As the carbonate-forming compound, various compounds used in a general polycarbonate production field can be used. Typical examples thereof include various carbonyl halides such as phosgene, haloformates such as a chloroformate compound, and a carbonate compound.

 Of these, phosgene is particularly preferably used.

In the method of the present invention, one or more of the above-mentioned dihydroxycarbazole compounds (III) is reacted with at least one of the above-mentioned carbonate-forming compounds, or alternatively, the above-mentioned dihydroxycarbazole compound (III)
And at least one of the above and the bisphenol compound (IV)
The carbazole-based polycarbonate of the present invention is produced by reacting one or more of the above with at least one of the above-mentioned carbonate-forming compounds to carry out a polycondensation reaction.

By appropriately selecting the ratio of the dihydroxycarbazole compound (III) and the bisphenol compound (IV) to be used, the repeating unit (I) and the repeating unit (II)
Can be adjusted at will.

The method of this reaction (reaction atmosphere, conditions, reaction method, operation method, and the like) is not particularly limited, and usually, a known method used in the production of polycarbonate may be appropriately applied.

For example, when a carbonyl dihalide such as phosgene or a haloformate such as chloroformate is used as the carbonate-forming compound, this reaction is carried out in an appropriate solvent in an acid acceptor (eg, an alkali metal hydroxide or an alkali metal hydroxide). The reaction can be carried out in the presence of a basic alkali metal compound such as a metal carbonate or an organic base such as pyridine.

As the alkali metal hydroxide and the alkali metal carbonate, various types can be used, but from an economical viewpoint,
Usually, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like are suitably used. They are,
Usually, it is suitably used as an aqueous solution.

The proportion of the carbonate-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing the compound into the reaction system can be suitably employed.

The use ratio of the acid acceptor may be appropriately determined in the same manner in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, the acid acceptor is used in an amount of 2 equivalents or a slight excess thereof relative to the total number of moles of the dihydroxycarbazole compound (III) and the bisphenol compound (IV) to be used (1 mole is usually equivalent). Is preferred.

As the solvent, various solvents such as those used in the production of known polycarbonates may be used alone or as a mixed solvent. As typical examples, for example, hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene can be suitably used.

Further, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used to promote the polycondensation reaction, and p-tert- is used to adjust the degree of polymerization.
It is desirable to carry out the reaction by adding a molecular weight regulator such as butylphenol or phenylphenol.

If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

The reaction is usually performed at a temperature in the range of 0 to 150C, preferably 5 to 40C.

The reaction pressure can be any of reduced pressure, normal pressure, and pressurized pressure. Usually, the reaction can be suitably performed at normal pressure or about the self-pressure of the reaction system.

The reaction time is generally about 0.5 minute to 10 hours, preferably about 1 minute to 2 hours.

As a reaction method, any of a continuous method, a semi-continuous method, a batch method, and the like can be adopted.

The reduced viscosity [η _sp / C] of the obtained polymer can be adjusted to the above range by various methods such as selection of the reaction conditions and the amount of the molecular weight modifier used. In some cases, the obtained polymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to obtain a predetermined reduced viscosity [η _sp / C] can also be obtained.

The obtained reaction product (crude product) can be subjected to various post-treatments such as a known separation / purification method and recovered as a polycarbonate having a desired purity (purity).

The electrophotographic photoreceptor of the present invention is characterized in that the carbazole-based polycarbonate of the present invention is used as a charge transfer material in a photosensitive layer.

That is, as long as the electrophotographic photoreceptor of the present invention utilizes the carbazole-based polycarbonate of the present invention as a charge transfer material, any of various known electrophotographic photoreceptors may be used, and any type of photosensitive layer may be used. However, it is preferable to provide an organic electrophotographic photoreceptor having at least one charge generation layer and at least one charge transport layer.

The carbazole-based polycarbonate of the present invention may be used in any part of an electrophotographic photoreceptor, but is usually used as a charge transfer material used for a charge transport layer, preferably as a charge transfer material and binder resin. In the case of a multi-layer type electrophotographic photoreceptor having two charge transport layers, it is preferable to use it for all the charge transport layers.

In the electrophotographic photoreceptor of the present invention, the carbazole-based polycarbonate of the present invention may be used alone or in combination of two or more. If desired, other binder resin components such as polycarbonate may be contained as long as the object of the present invention is not impaired. Further, an additive such as an antioxidant may be contained, and if necessary, another low-molecular or high-molecular charge transfer substance may be added.

The electrophotographic photoreceptor of the present invention has a photosensitive layer on a conductive substrate. When the photosensitive layer has a charge generation layer and a charge transport layer, the charge transport layer may be laminated on the charge generation layer, or the charge generation layer may be laminated on the charge transport layer. Further, a conductive or insulating protective film may be formed on the surface layer as needed. Further, an intermediate layer such as an adhesive layer for improving the adhesion between the layers or a blocking layer serving as a charge blocking layer may be formed.

As the conductive substrate material used in the electrophotographic photoreceptor of the present invention, various materials such as known materials can be used, and specifically, for example, aluminum, brass,
Conduction treatment by coating conductive materials such as aluminum, nickel, chromium, palladium, graphite, etc. on metal plates or metal sheets, metal drums, and plastic sheets of copper, nickel, steel, etc. by vapor deposition, sputtering, coating, etc. Or a substrate obtained by subjecting a substrate such as glass, plastic plate, cloth, paper or the like to a conductive treatment, or a metal subjected to a metal oxide treatment by electrolytic oxidation or the like.

The charge generation layer has at least a charge generation material, and the charge generation layer is formed by forming a layer of the charge generation material on a substrate serving as a base by vacuum evaporation, sputtering, or the like, or forming a substrate serving as the base. It can be obtained by forming a layer formed by binding a charge generation material using a binder resin thereon. As a method for forming the charge generation layer using a binder resin, various methods such as a known method can be used.Typically, for example, a coating liquid in which a charge generation material is dispersed or dissolved in a suitable solvent together with a binder resin is used. For example, a method in which the composition is applied onto a substrate serving as a predetermined base and dried is preferably used.

As the charge generation material in the charge generation layer, various materials such as known materials can be used.Specifically, for example, amorphous selenium, selenium alone such as trigonal selenium, selenium-tellurium and the like selenium alloys, selenium compounds such as As ₂ Se ₃ or selenium-containing compositions, zinc oxide, CdS-S
Inorganic materials composed of Group II and IV elements such as e, oxide-based semiconductors such as titanium oxide, various inorganic materials such as silicon-based materials such as amorphous silicon, metals or non-metallic phthalocyanines, cyanines, bisazo compounds, Examples include various organic materials such as anthoacene, pyrene, perylene, pyrylium salt, thiapyrylium salt, polyvinyl carbazole, and squarium pigment.

These may be used alone or in a combination of two or more.

The binder resin in the charge generation layer is not particularly limited, and various kinds of known resins can be used,
Specifically, for example, polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl chloride-vinyl acetate copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate, polyamide, polyketone, polyacrylamide, butyral resin, polyester and the like Thermosetting resins such as thermoplastic resins, polyurethanes, epoxy resins, and phenolic resins can be used.

The carbazole-based polycarbonate may be used as a binder resin in the charge generation layer.

The charge transport layer can be obtained by forming a carbazole-based polycarbonate layer of the present invention on a substrate serving as a base.

As a method for forming the charge transport layer, various methods such as a known method can be used, and usually, the carbazole-based polycarbonate of the present invention is dispersed alone or in an appropriate solvent together with another binder resin. A method in which the dissolved coating liquid is applied onto a substrate serving as a predetermined base and dried is preferably used.

In the charge transport layer, the carbazole-based polycarbonate of the present invention can be used alone or in a combination of two or more.

In addition, other charge transfer materials can be used in combination with the carbazole-based polycarbonate of the present invention as long as the object of the present invention is not impaired.

Examples of the charge transfer material other than the carbazole-based polycarbonate of the present invention that can be used in the present invention include, for example, conventionally used electron transfer materials and hole transfer materials.

Specific examples of the electron transfer material include, for example, chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-tetra Fluorenone, 2,4,7-trinitro-9-dicyanomethylenefluorenone, 2,4,5,7-tetranitroxanthone, 2,4,9-trinitrothioxanthone or 3,5-dimethyl-3 ',
There are electron-withdrawing substances such as diphenoquinone derivatives such as 5'-di-tert-butyl-4,4'-diphenoquinone, and those obtained by polymerizing these electron-withdrawing substances. These may be used alone or in a combination of two or more.

As the hole-transporting substance, pyrene, N-ethylcarbazole, N-isopropylcarbazole, N-methyl-
N-phenylhydrazino-3-methylidene, 9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-10-ethylphenothiazine, N , N-Diphenylhydrazino-3-methylidene-10
-Ethylphenoxazine, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, p-diethylaminobenzaldehyde-N-α-naphthyl-N-phenylhydrazone, p-pyrrolidinobenzaldehyde-N,
N-diphenylhydrazone, 1,3,3-trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone,
p-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 1-phenyl-1,2,3,4-
Tetrahydroquinoline-6-carboxaldehyde-
Hydrazones such as 1 ', 1'-diphenylhydrazone;
5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [quinolyl (2) ] -3- (p-Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [Lepidyl (2)]-3- (p-
Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [6-methoxy-pyridyl (2)]-3- (p-diethylaminostyryl) -5-
(P-diethylaminophenyl) pyrazolin, 1- [pyridyl (5) -3- (p-diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylamino Phenyl) pyrazolin, 1- [pyridyl (2)]-3- (p-
Diethylaminostyryl) -4-methyl-5- (p-diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3- (α-methyl-p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (p-diethylaminostyryl) -4-methyl-5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (α-benzyl-
pyrazolines such as p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and spiropyrazoline, 2- (p-diethylaminostyryl) -δ-
Oxazole compounds such as diethylaminobenzoxazole, 2- (p-diethylaminophenyl) -4- (p-dimethylaminophenyl) -5- (2-chlorophenyl) oxazole, 2- (p-diethylaminostyryl) -6-diethylaminobenzo A thiazole compound such as thiazole, a triarylmethane compound such as bis (4-diethylamino-2-methylphenyl) -phenylmethane, 1,1-bis (4-N, N-diethylamino-2-methylphenyl) heptane, 1,1,2,2-tetrakis (4-
Polyarylamines such as (N, N-dimethylamino-2-methylphenyl) ethane, N, N'-diphenyl-N, N, N '
-Bis (methylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (ethylphenyl) benzidine, N,
N'-diphenyl-N, N'-bis (propylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (butylphenyl) benzidine, N, N'-diphenyl-N, N'-bis ( Isopropylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (secondary butylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (tertiarybutylphenyl) benzidine, N , N'-diphenyl-N, N'-bis (chlorophenyl) benzidine and other benzidine compounds, butadiene compounds, triphenylamine, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine,
Examples thereof include poly-9-vinylphenylanthracene, organic polysilane, pyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin.

These may be used alone or in a combination of two or more.

Specific examples of the solvent used in forming the charge generation layer and the charge transport layer include, for example, benzene, toluene, xylene, aromatic solvents such as chlorobenzene, acetone, methyl ethyl ketone, ketones such as cyclohexanone, methanol, Ethanol, alcohols such as isopropanol, ethyl acetate, esters such as ethyl cellosolve, carbon tetrachloride, carbon tetrabromide, chloroform, dichloromethane, halogenated hydrocarbons such as tetrachloroethane,
Examples thereof include ethers such as tetrahydrofuran and dioxane, dimethylformamide, dimethylsulfoxide, and diethylformamide.

These solvents may be used alone or in combination of two or more.

The coating of each layer can be performed using various coating devices such as known ones.Specifically, for example, using an applicator, a spray coater, a bar coater, a chip coater, a roll coater, a dip coater, a doctor blade or the like Can do it.

The electrophotographic photoreceptor of the present invention uses a conventional polycarbonate resin or the like as a binder resin, and disperses and dissolves a conventional charge transfer material in the conventional electrophotographic photoreceptor. Compared with the electrophotographic photoreceptor using a polyarylamine (photoconductive polycarbonate) as a charge transfer material or a charge transfer material and a binder resin, it has particularly excellent printing durability and electric characteristics. It is an electrophotographic photoreceptor having high performance and can be usefully used in various electrophotographic photoreceptor applications.

[Examples] Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these Examples, and various modifications may be made without departing from the spirit of the present invention. And applications are possible.

In the following, the electrophotographic characteristics were measured using an electrostatic charging tester (EPA-8100, manufactured by Kawaguchi Manufacturing Co., Ltd.)
Evaluation was performed by performing a corona discharge of 6 kV and measuring an initial surface potential (V ₀ ), a residual potential (V _R ) after light irradiation (10 Lux), and a half-life exposure amount (E _1/2 ).

Synthesis Example 1-Synthesis of dihydroxycarbazole compound-Report of Litt et al. (Macromolecules, 19 , 516 (1
986)) According to the synthesis method described above, after brominating 9-phenylcarbazole as shown in the following reaction formula, the obtained 3,6-dibromo-9-phenylcarbazole is methoxylated with sodium methoxide, and then tribrominated. Demethylation was performed using boron chloride to synthesize the desired 3,6-dihydroxy-9-phenylcarbazole.

Synthesis Example 2-Synthesis of dihydroxycarbazole compound-A report by Tucher et al. (J. Chem. Soc., 547 (192)
6) According to the synthesized method, as shown in the following reaction formula,
After iodination of 9-phenylcarbazole, an Ullmann condensation reaction with diarylamine was performed, and finally, demethylation was performed using boron tribromide to obtain a desired dihydroxycarbazole compound.

Example 1 34.4 g (0.125 mol) of 3,6-dihydroxy-9-phenylcarbazole obtained in Synthesis Example 1 and 2,2-bis (4-hydroxyphenyl) were added to 550 ml of a 2 N aqueous sodium hydroxide solution. A solution of 28.5 g (0.125 mol) of propane, 400 ml of methylene chloride, 0.8 g of p-tert-butylphenol as a molecular weight regulator and 10% as a catalyst
3 ml of a triethylamine aqueous solution was introduced into a 1-liter flask. The reaction solution was vigorously stirred while the temperature of the solution was kept at around 10 ° C. by external cooling, and phosgene was blown in at a rate of 340 ml / min for 30 minutes.

Thereafter, stirring was continued for 1 hour to complete the polymerization. After completion of the reaction, the organic layer was diluted by adding 50 ml of methylene chloride,
After washing with water, diluted hydrochloric acid and water in that order, the resultant was poured into methanol to obtain a polycarbonate.

This polymer has a concentration of 0.5 g using methylene chloride as a solvent.
reduced viscosity at 20 ° C [η _sp / C] of 0.52dl /
g.

Incidentally, the structure and composition of the obtained polymer was ¹ H-NM
Analysis by R spectrum confirmed that the composition consisted of the following repeating units and composition.

FIG. 1 shows a chart of the ¹ H-NMR spectrum of the polymer.

A 10% by weight solution of the above polycarbonate as a charge transport material in 10% by weight of methylene chloride was prepared and used as a coating solution for forming a charge transfer layer.

On an approximately 0.5 μm charge generation layer of oxotitanium phthalocyanine formed on an aluminum conductive substrate,
This coating solution was applied by a dip coating method, and after drying, a 20 μm charge transport layer was provided to produce a laminated electrophotographic photosensitive member.

The electrophotographic characteristics of the electrophotographic photoreceptor, such as the initial potential after corona charging, the residual potential after light irradiation, and the half-life exposure amount, are obtained by copolymerizing a hydroxyarylamine with a diethylene glycol bischloroformate compound. Compared to the electrophotographic photoreceptor used (Comparative Example 1),
It showed good values. Further, the electrophotographic photoreceptor using polycarbonate made of bisphenol A as a binder resin (Comparative Example 2) showed a value better than the electrophotographic characteristics.
The results are shown in Table 1.

The wear characteristics of the charge transport layer were measured using a gas abrasion tester (manufactured by Suga Test Instruments Co., Ltd.) with a load of 100 g and a reciprocation of 30 times.
The test was performed under the condition of 0 times, and the results are shown in Table 2.

Example 2 55 g (0.20 mol) of 3,6-dihydroxy-9-phenylcarbazole obtained in Synthesis Example 1 as a monomer and 1,1-
Bis (4-hydroxyphenyl) cyclohexane 13.4g
(0.05 mol), except that polycarbonate ([η _sp /C]=0.51) consisting of the following structural units was used in the same manner as in Example 1.
dl / g).

Using this polycarbonate, a laminated electrophotographic photosensitive member was produced in the same manner as in Example 1. Table 1 shows the electrophotographic characteristics of this electrophotographic photosensitive member, and Table 2 shows the wear characteristics of the charge transport layer.

Example 3 As a monomer, 13.8 g (0.05 mol) of 3,6-dihydroxy-9-phenylcarbazole obtained in Synthesis Example 1 and 1,1
A polycarbonate having the following structural unit ([η _sp /C]=0.57 dl) was prepared in the same manner as in Example 1 except that 70.4 g (0.20 mol) of -bis (4-hydroxyphenyl) -1,1-diphenylmethane was used. / g).

Using this polycarbonate, a laminated electrophotographic photosensitive member was produced in the same manner as in Example 1. Table 1 shows the electrophotographic characteristics of this electrophotographic photosensitive member, and Table 2 shows the wear characteristics of the charge transport layer.

Example 4 In a flask having an inner volume of 200 ml, the 3,6-
6 g (0.022 mol) of dihydroxy-9-phenylcarbazole, 50 ml of pyridine and 50 ml of methylene chloride were added, and phosgene was blown into the mixture while stirring and cooling with ice.

Next, the reaction system was heated to 65 ° C. and refluxed for 2 hours, and the obtained reaction product was filtered and poured into a large amount of methanol. As a result, a carbazole compound homopolymer ([η _{sp /} C] 0.49 dl / g) having the following structural units was obtained.

Using this polycarbonate, a laminated electrophotographic photosensitive member was produced in the same manner as in Example 1. Table 1 shows the electrophotographic characteristics of this electrophotographic photosensitive member, and Table 2 shows the wear characteristics of the charge transport layer.

Example 5 Example 5 was repeated except that 30.5 g (0.05 mol) of the dihydroxycarbazole compound obtained in Synthesis Example 2 and 45.6 g (0.20 mol) of 2,2-bis (4-hydroxyphenyl) propane were used as monomers. Similarly, a polycarbonate having the following structural unit ([η _sp /C]=0.55 dl / g) was obtained.

Using this polycarbonate, a laminated electrophotographic photosensitive member was produced in the same manner as in Example 1. Table 1 shows the electrophotographic characteristics of this electrophotographic photosensitive member, and Table 2 shows the wear characteristics of the charge transport layer.

Comparative Example 1 Referring to Example 3 of JP-A-1-9964, N,
N'-diphenyl-N, N'-bis (4-hydroxyphenyl)-[1,1'-biphenyl] -4,4'-diamine 65 g
(0.125 mol) and 23.38 g (0.125 mol) of diethylene glycol bischloroformate were obtained as a polycarbonate ([η _sp /C]=0.42 dl / g) having the following structural units.

Using this polycarbonate, a laminated electrophotographic photosensitive member was produced in the same manner as in Example 1. Table 1 shows the electrophotographic characteristics of this electrophotographic photosensitive member, and Table 2 shows the wear characteristics of the charge transport layer.

Comparative Example 2 9-phenylcarbazole having the following structural formula as a charge transfer material A 10% by weight methylene chloride solution of polycarbonate composed of bisphenol A containing 50% by weight was used as a coating solution for forming a charge transport layer, and a laminated electrophotographic photosensitive member similar to that of Example 1 was produced. . Table 1 shows the electrophotographic characteristics of the electrophotographic photosensitive member, and Table 2 shows the abrasion characteristics of the charge transport layer.
It is shown in the table.

[Effects of the Invention] According to the present invention, an electrophotographic material which can be suitably used as a charge transfer material or a charge transfer material and a binder resin in a photosensitive layer of an electrophotographic photosensitive member, and is particularly excellent in printing durability and electrical characteristics. An excellent photoconductive carbazole-based polycarbonate which can easily realize a photoreceptor can be provided.

Further, according to the production method of the present invention, the carbazole-based polycarbonate of the present invention can be efficiently produced.

Furthermore, according to the present invention, it is possible to provide a high-performance electrophotographic photoreceptor having excellent electric characteristics as a charge transport layer and an electrophotographic photoreceptor and excellent printing durability.

[Brief description of the drawings]

FIG. 1 is a ^1- NMR spectrum of the carbazole-based polycarbonate obtained in Example 1.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-61-66718 (JP, A) JP-A-61-66717 (JP, A) JP-A-1-9964 (JP, A) JP-A-1- 19049 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 64/00-64/42 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound represented by the following general formula (I) (Where p and q are each independently 0 or 1, i and j are each independently an integer of 1 to 3, and Ar ¹ is Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl or alkoxyl group having 1 to 5 carbon atoms, —CN or —NO ₂ , and Ar ² has 6 carbon atoms. R ¹ is an aryl group or a substituted aryl group having 6 to 12 carbon atoms, R ² and R ³ are each independently a hydrogen atom, a halogen atom, a carbon atom number; It is an alkyl group having 1 to 6 or an aryl group having 6 to 12 carbon atoms or a substituted aryl group. ) And the following general formula (II) (Wherein, R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group or a substituted aryl group having 6 to 12 carbon atoms, and k and 1 are Each independently is an integer from 1 to 4, X is CH _{2 g} , single bond, -O-, -S-, -SO- or -SO ₂
Wherein R ⁶ and R ⁷ are each independently a hydrogen atom, —CF ₃ ,
An alkyl group having 1 to 6 carbon atoms or an aryl group or a substituted aryl group having 6 to 12 carbon atoms, h is an integer of 4 to 10, and g is an integer of 2 to 10. ) Wherein the content of the repeating unit represented by the general formula (I) is the same as that of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II). In the range represented by the following formula: O <[(I) / {(I) + (II)}] ≦ 1, and 0.5 g using methylene chloride as a solvent.
/ dl concentration solution at 20 ° C has reduced viscosity [η _sp / C] of 0.2
A carbazole-based polycarbonate having a dl / g or more. 2. The following general formula (III) (Wherein p and q are each independently 0 or 1, i and j are each independently an integer of 1 to 3, and Ar ¹ is Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl or alkoxyl group having 1 to 5 carbon atoms, —CN or —NO ₂ , and Ar ² has 6 carbon atoms. R ¹ is an aryl group or a substituted aryl group having 6 to 12 carbon atoms, R ² and R ³ are each independently a hydrogen atom, a halogen atom, a carbon atom number; It is an alkyl group having 1 to 6 or an aryl group having 6 to 12 carbon atoms or a substituted aryl group. Or a compound represented by the general formula (III) and a compound represented by the following general formula (IV) (Wherein, R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group or a substituted aryl group having 6 to 12 carbon atoms, and k and 1 are Each independently is an integer from 1 to 4, X is CH _{2 g} , single bond, -O-, -S-, -SO- or -SO ₂
Wherein R ⁶ and R ⁷ are each independently a hydrogen atom, —CF ₃ ,
An alkyl group having 1 to 6 carbon atoms or an aryl group or a substituted aryl group having 6 to 12 carbon atoms, h is an integer of 4 to 10, and g is an integer of 2 to 10. The method for producing a carbazole-based polycarbonate according to claim 1, wherein the compound represented by the formula (1) is reacted with a carbonate-forming compound. 3. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate, wherein the carbazole-based polycarbonate according to claim 1 is used as a charge transfer material in said photosensitive layer. body.