JPH09204053A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase printing durability and sensitivity by incorporating polycarbonate consisting of specified structural units obtd. by copolymerizing bisphenol A with isophorone as a resin binder and a specified hydrazone compd. as an electric charge transferring material into an electric charge transferring layer. SOLUTION: This photoreceptor is a laminate type electrophotographic org. photoreceptor obtd. by laminating an electric charge generating layer and an electric charge transferring layer on an electrically conductive substrate. The electric charge transferring layer contains polycarbonate consisting of structural units represented by formulae I, II and obtd. by copolymerizing bisphenol A with isophorone as a resin binder and a hydrazone compd. represented by formula III as an electric charge transferring material. In the formulae I, II, each of R<a> -R<d> is H or optionally substd. alkyl and 0.01<=m/ (1+m)<=0.5. In the formula III, each of R<1> -R<5> is H, halogen, optionally substd. alkyl, allyl, aryl, alkenyl, aralkyl, alkoxy, acyl or a heterocyclic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoconductor for electrophotography, and more specifically, it is a laminated type for use in an electrophotographic printer, a copying machine or the like, which is formed by laminating a charge generation layer and a charge transport layer containing organic materials. The present invention relates to an organic photoconductor for electrophotography.

[0002]

2. Description of the Related Art A photoconductor for electrophotography has a structure in which a photoconductor layer having a photoconductive function is laminated on a conductive substrate. Organic photoconductors for electrophotography containing an organic compound as a functional component responsible for charge generation and transport, and in particular, a laminated-type true organic photoconductor for electrophotography formed by laminating functional layers such as a charge generation layer and a charge transport layer are materials. Has the advantages of high selectivity, easy functional design, high productivity, and excellent safety.
Applications to various printers such as copying machines have been actively pursued in recent years.

[0003]

However, such a laminated organic photoreceptor does not always satisfy all the required performances required for the photoreceptor.
In particular, there is a strong demand for higher printing durability as well as for higher speed and smaller size.

Among the above-mentioned problems, regarding the improvement of printing durability,
In particular, it is essential to improve the performance of the resin binder contained in the charge transport layer. Polycarbonate resins such as bisphenol A type, Z type, and bisphenol A / biphenyl copolymers and polystyrene resins have been used as the resin binder for the charge transport layer, and have been improved, but they are still satisfactory. Has not been obtained.

On the other hand, regarding the improvement of sensitivity, there have been several reports in recent years suggesting the possibility of being realized by a combination of a charge transport substance and a resin binder for a charge transport layer. However, the current situation is that the sensitivity is not high enough to meet the demand for particularly high speed and miniaturization today.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to realize a so-called laminated type organic photoconductor for electrophotography with higher printing durability and higher sensitivity than ever before.

[0007]

In order to solve the above problems, the present invention has the following configurations. (1) In a laminated type organic photoconductor for electrophotography, which comprises at least a charge generation layer and a charge transport layer laminated on a conductive substrate, the following structural formula [ia] and formula as a resin binder in the charge transport layer: [Ib], (In the formula, R ^a , R ^b , R ^c and R ^d represent a hydrogen atom or an optionally substituted alkyl group. 0.01 ≦ m /
(1 + m) ≦ 0.5) containing a bisphenol A / isophorone copolymerized polycarbonate having a structural unit represented by the following structural formula [I] as a charge transporting substance: (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, an allyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, Indicates an acyl group or heterocyclic group)
An electrophotographic photoreceptor containing at least one hydrazone compound represented by

(2) In the electrophotographic photoreceptor of (1), the following structural formula [I is used instead of the hydrazone compound.
I], (In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R
¹² and R ¹³ are a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, allyl group, aryl group,
An electrophotographic photoreceptor containing at least one butadiene compound represented by alkenyl group, aralkyl group, alkoxy group, acyl group or heterocyclic group, amino group and dialkylamino group).

(3) In the electrophotographic photoreceptor of (1), the following structural formula [II is used instead of the hydrazone compound.
I], (In the formula, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, an allyl group, an aryl group, an aralkyl group, an alkoxy group, An electrophotographic photoreceptor containing at least one diamine compound represented by an acyl group or a heterocyclic group).

(4) In the electrophotographic photoreceptor of (1), the following structural formula [I is used instead of the hydrazone compound.
V], (Wherein R ²⁰ , R ²¹ , R ²² and R ²³ represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, an alkoxy group or an aryl group) and at least one indoline compound is contained. It is a photoconductor for electrophotography.

(5) In the electrophotographic photoreceptor of (1) above, the following structural formula [V] is substituted for the hydrazone compound: (In the formula, R ²⁴ , R ²⁵ , R ^26, and R ²⁷ represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, an alkoxy group, or an aryl group). It is a photoconductor for electrophotography.

(6) In the electrophotographic photoconductor of (1), the following structural formula [V is used instead of the hydrazone compound.
I], (In the formula, R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are each a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, allyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, acyl group or A heterocyclic group, R ³²
Is a hydrogen atom, a halogen atom, or an alkyl group which may be substituted).
It is an electrophotographic photoreceptor containing a seed.

(7) In the electrophotographic photoreceptor of (1), the following structural formula [VI is used instead of the hydrazone compound.
I], (In the formula, R ³³ , R ³⁴ , R ^35, and R ³⁶ are a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, allyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, acyl group, or A heterocyclic group, and R ³⁷ , R ^38, and R ³⁹ each represent at least one distyrylbenzene compound represented by a hydrogen atom, a halogen atom, or an optionally substituted alkyl group). It is the body.

(8) In the electrophotographic photoreceptors (1) to (7), the following structural formula [ia-1] is used as a resin binder together with the bisphenol A / isophorone copolymerized polycarbonate. A bisphenol A-type polycarbonate having a structural unit represented by the following structural formula [ii-a], A bisphenol Z type polycarbonate having a structural unit represented by the following structural formula [ia-1] and formula [ii-b], Is a photoconductor for electrophotography, in which at least one resin binder selected from the group consisting of bisphenol A / biphenyl copolymerized polycarbonate having the structural unit represented by is mixed and used.

(9) In the electrophotographic photoreceptors of (1) to (8), the bisphenol A is contained in the charge generation layer.
An electrophotographic photoreceptor using isophorone copolycarbonate.

(10) In the electrophotographic photoreceptors (1) to (9), an electrophotography using a resin layer or a resin film in which fine metal oxide powder is dispersed as an undercoat layer on a conductive substrate. It is a photoconductor.

In the electrophotographic photoreceptor of the present invention, the bisphenol A / isophorone copolymerized polycarbonate resin binder and the above formulas [I], [II], [III],
By combining each of the charge-transporting substances represented by [IV], [V], [VI] or [VII], a conventionally known resin binder and each of the charge-transporting substances represented by [I] to [VII] Compared with the case where a substance is combined, the printing durability is greatly improved, and the sensitivity is simultaneously improved.

Further, by using the bisphenol A / isophorone copolymerized polycarbonate resin binder mixed with the bisphenol A type polycarbonate or Z type polycarbonate or the bisphenol A / biphenyl copolymerized polycarbonate, the printing durability is remarkably improved. Is obtained.

Furthermore, a marked improvement in sensitivity can be obtained by using the bisphenol A / isophorone copolymerized polycarbonate as the resin binder of the charge generation layer.

In addition, by using a resin film or a resin film in which fine powder of metal oxide is dispersed as an undercoat layer on a conductive substrate, the theoretical basis thereof is not yet clarified, but it is more remarkable. Improved sensitivity can be obtained.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The so-called negatively charged laminated type photoreceptor shown in FIG. 1 comprises a support 1, an undercoat layer 2, a charge generation layer 3 and a charge transport layer 4. In addition, the so-called positive charging laminated type photoreceptor shown in FIG. 2 has a support 11, an undercoat layer 12 and a charge transport layer 1.
4, a charge generation layer 13 and a coating layer 15. Hereinafter, the electrophotographic photoreceptor of the present invention will be specifically described by taking a negatively charged laminated photoreceptor as an example.

As the support, a conductive base such as an aluminum cylinder or an aluminum vapor-deposited film is used alone, or the surface of the conductive base is anodized, or the surface is modified with an undercoat layer such as a resin coating. What was done can be used.

Materials for the polymer dispersion coating used for the undercoat layer include casein, polyvinyl alcohol, nylon,
An insulating polymer such as melamine or cellulose, a conductive polymer such as polythiophene, polypyrrole, or polyaniline, or a polymer containing a metal oxide powder such as titanium dioxide or zinc oxide can be used.

The charge generation layer is composed of a charge generation material and a resin binder. Specific examples of the charge generating material include various phthalocyanine compounds represented by the following structural formulas VIII-1 to VIII-31, azo compounds, polycyclic quinone compounds, squarylium compounds, and derivatives thereof.

[0025]

[0026]

[0027]

[0028]

[0029]

As the resin binder for the charge generation layer,
Polycarbonate, polyester, polyamide, polyurethane, epoxy polyvinyl butyral, polyvinyl acetal, phenoxy resin, silicone resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, formal resin, cellulose resin, or a copolymer thereof, and These halides and cyanoethyl compounds can be used. However, as described above, by using the bisphenol A / isophorone copolymerized polycarbonate for the charge generation layer, a marked improvement in sensitivity can be obtained.

The charge transport layer comprises a charge transport material and a resin binder. Specific examples of the charge transport material include various hydrazone compounds represented by the following structural formulas I-1 to I-10, various butadiene compounds represented by the following structural formulas II-1 to II-8, and the following structural formulas III-1 to III. -5, various diamine compounds, various indoline compounds represented by the following structural formulas IV-1 to IV-2, indole compounds represented by the following structural formula V-1, and various stilbenes represented by the following structural formulas VI-1 to VI-10 The compound and various distyrylbenzene compounds represented by the following structural formulas VII-1 to VII-10 can be used alone or in combination.

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

As the resin binder for the charge transport layer, bisphenol A type, PCZ type and bisphenol A.
Biphenyl copolymer polycarbonate, polystyrene,
Although polyphenylene ether acrylic resin and the like are widely used as known materials, in the present invention, the bisphenol A / isophorone copolymerized polycarbonate alone system,
Alternatively, a mixed system of the polycarbonate and bisphenol A type, Z type or bisphenol A / biphenyl copolymerized polycarbonate can be used. Further, these polycarbonates can be used in combination of three or more kinds.

The optimum average molecular weight range of the bisphenol A / isophorone copolymerized polycarbonate used in the present invention is 10,000 to 100,000. As a specific example, the following structural formulas [ia-1 to 3], [ib], Examples of the structural unit include: Also,
When such a bisphenol A / isophorone copolymerized polycarbonate is used by mixing with a bisphenol A type, Z type or a bisphenol A / biphenyl copolymerized polycarbonate, the weight mixing ratio thereof should be within the range of 99: 1 to 1: 1. it can.

The various polycarbonates are effective not only in a combination of two types but also in a combination of three or more types. On the other hand, as the antioxidant added to the charge transport layer, as a specific example, the following structural formula IX-1
The antioxidants shown in to IX-42 can be used alone or in appropriate combination.

[0041]

[0042]

[0043]

[0044]

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. Example 1 An aluminum cylindrical substrate provided with an alumite layer having a thickness of about 7 μm was used as a support. As the charge generating substance, the above structural formula VI
1 part by weight of phthalocyanine shown in II-3 and modified vinyl chloride resin (trade name: MR11
0, 1 part by weight of Nippon Zeon Co., Ltd. and 50 parts by weight of dichloromethane were mixed and kneaded with a mixer for 3 hours to prepare a coating liquid, thereby preparing a coating liquid for the charge generation layer.

Next, as the charge transport material, the above structural formula I-
100 parts by weight of the compound represented by 4 and 100 parts by weight of the bisphenol A / isophorone copolymerized polycarbonate represented by the structural units [ia-1] and [ib] as a resin binder, and the structural formula as an antioxidant. 5 parts by weight of the compound represented by IX-2 was dissolved in 700 parts by weight of dichloromethane to prepare a coating solution for the charge transport layer. Using the above coating solution, a charge generation layer and a charge transport layer were sequentially formed on the support with a thickness of 0.5 μm and 25 μm, respectively, by a dip (Dip method) method to prepare a photoconductor for a printer. .

Example 2 All were the same as Example 1 except that the binder of the charge generation layer was a modified vinyl chloride resin made of the bisphenol A / isophorone copolymerized polycarbonate represented by the above structural units [ia-1] and [ib]. A photoconductor was prepared under the same materials and conditions.

Example 3 Instead of an alumite layer as a subbing layer, a number average molecular weight of 3 was used.
Ten thousand polyamides (trade name: T171, Daicel Corporation)
4 parts by weight of Hüls) and 1 part by weight of styrene-maleic acid resin (trade name: Slappers AP, manufactured by BASF Japan Ltd.), 200 parts by weight of methanol and 10 parts of 1-butanol.
Using a resin coating solution prepared by dissolving in a mixed solvent with 0 part by weight, a resin coating of 0.1 μm was formed on the cylindrical substrate by a dipping method, and a support was prepared in this manner. A photoconductor was prepared using the same materials and conditions as in Example 1.

Example 4 As the charge transporting resin binder, the above structural unit [ia-
1], 80% by weight of the bisphenol A / isophorone copolymerized polycarbonate represented by [ib] and 20 parts by weight of the bisphenol A type polycarbonate represented by the structural unit [ia-1] were used. A photoconductor was prepared using the same materials and conditions as in Example 1.

Example 5 As the charge transporting resin binder, the above structural unit [ia-
1], 80 parts by weight of bisphenol A / isophorone copolymerized polycarbonate represented by [ib] and 20 parts by weight of Z-type polycarbonate represented by the structural unit [ii-a] were used in all Examples. A photoconductor was prepared using the same material and conditions as in No. 1.

Example 6 As the charge transporting resin binder, the above structural unit [ia-
1] and 80 parts by weight of bisphenol A / isophorone copolymerized polycarbonate represented by [ib] and 20 parts by weight of bisphenol A / biphenyl copolymerized polycarbonate represented by the structural units [ia-1] and [ii-b]. A photoconductor was prepared using the same materials and conditions as in Example 1 except that the mixed system was used.

Example 7 As the charge transporting resin binder, the above structural unit [ia-
2] and [ib], except that the bisphenol / isophorone copolymerized polycarbonate was used, a photoconductor was prepared under the same materials and conditions as in Example 1.

Example 8 As the charge transporting resin binder, the above structural unit [ia-
3] and [ib], except that the bisphenol / isophorone copolymerized polycarbonate was used, a photoconductor was prepared under the same materials and conditions as in Example 1.

Example 9 All the same materials and conditions as in Example 1 except that the compound represented by the structural formula II-1 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Example 10 The same materials and conditions as in Example 1 were used except that the compound represented by the structural formula I-4 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Example 11 All the same materials and conditions as in Example 1 were used except that the compound represented by the structural formula IV-4 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Example 12 The same materials and conditions as in Example 1 were used except that the compound represented by the structural formula V-1 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Example 13 The same materials and conditions as in Example 1 were used except that the compound represented by the structural formula I-4 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Example 14 The same materials and conditions as in Example 1 were used except that the compound represented by the structural formula I-4 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Example 15 An aluminum cylindrical substrate provided with an alumite layer having a thickness of about 7 μm was used as a support. 1 part by weight of the bisazo compound represented by the structural formula VIII-17 as a charge generating substance, and 1 part by weight of polyvinyl butyral resin (trade name: BM-2: manufactured by Sekisui Chemical Co., Ltd.) as a resin binder are mixed with 60 parts by weight of methyl ethyl ketone. Then, the mixture was kneaded with a mixer for 3 hours to prepare a coating liquid, and a coating liquid for the charge generation layer was prepared.

100 parts by weight of the compound represented by the structural formula I-4 as a charge transport material, and a resin binder,
Dichloromethane 700 was prepared by adding 100 parts by weight of the bisphenol A / isophorone copolymerized polycarbonate represented by the structural units [ia-1] and [ib] and 5 parts by weight of the compound represented by the structural formula IX-4 as an antioxidant. It was dissolved in parts by weight to prepare a charge transport coating solution. A charge generation layer and a charge transport layer were sequentially formed on the support by the dip method using the above coating solution to prepare a photoconductor for a copying machine.

Example 16 Example 13 was repeated except that the resin binder of the charge generation layer was changed from polyvinyl butyral resin to bisphenol A / isophorone copolymerized polycarbonate represented by the above structural units [ia-1] and [ib]. A photoconductor was manufactured using the same material and under the same conditions.

Example 17 As the undercoat layer, a number average molecular weight of 3 was used instead of the alumite layer.
Ten thousand polyamides (trade name: T171, Daicel Corporation)
4 parts by weight of Hüls) and 1 part by weight of styrene-maleic acid resin (trade name: Spraverse AP, manufactured by BASF Japan Ltd.), 200 parts by weight of methanol and 10 parts of 1-butanol.
Using a resin coating solution prepared by dissolving in a mixed solvent with 0 part by weight, a resin coating of 0.1 μm was formed on the cylindrical substrate by a dipping method, and a support was prepared in this manner. A photoconductor was manufactured using the same material and under the same conditions as in Example 14.

Example 18 As a resin binder for charge transport, the above structural unit [ia-
1] and [ib], except that a mixed system of 80 parts by weight of the bisphenol A / isophorone copolymerized polycarbonate and 20 parts by weight of the bisphenol A type polycarbonate is used, all the same materials and the same conditions as in Example 13 Was produced.

Example 19 As a charge transporting resin binder, the above structural unit [ia-
1] and [ib] except that a mixed system of 80 parts by weight of the bisphenol A / isophorone copolymerized polycarbonate and 20 parts by weight of the Z-type polycarbonate was used, and the photoreceptor was prepared under the same materials and under the same conditions as in Example 13. Was produced.

Example 20 As a charge transporting resin binder, the above structural unit [ia-
1], the same materials and conditions as in Example 13 except that a mixed system of 80 parts by weight of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib] and 20 parts by weight of the bisphenol A / biphenyl copolymerized polycarbonate was used. Then, a photoconductor was prepared.

Example 21 All the same materials and conditions as in Example 13 except that the compound represented by the structural formula I-4 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Example 22 All materials were the same as in Example 13 except that the compound represented by the structural formula III-4 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Example 23 The same materials and conditions as in Example 13 were used except that the compound represented by the structural formula IV-4 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Example 24 All the same materials and conditions as in Example 13 except that the compound represented by the structural formula I-4 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Example 25 Instead of the compound represented by I-4 as the charge transport material,
Example 1 except that the compound represented by VI-4 was used
A photoconductor was prepared using the same material and conditions as in No. 3.

Example 26 The same materials and conditions as in Example 13 were used except that the compound represented by the structural formula I-4 was used as the charge transporting material instead of the compound represented by the structural formula I-4. A photoconductor was prepared.

Comparative Example 1 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions as in Example 1 except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 2 As the charge transporting resin binder, the above structural unit [ia-
1] and Example 1 except that 100 parts by weight of the Z-type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib].
A photoconductor was manufactured using the same material and under the same conditions.

Comparative Example 3 As the charge transporting resin binder, the above structural unit [ia-
1] and [ib], instead of the bisphenol A / isophorone copolycarbonate, 100 parts by weight of the bisphenol A / biphenyl copolycarbonate was used, and the same material and the same conditions as in Example 1 were used. The body was made.

Comparative Example 4 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 7, except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 5 As the charge transporting resin binder, the above structural unit [ia-
1] and [ib] were replaced with the bisphenol A / isophorone copolymerized polycarbonate, and a photoconductor was prepared under the same conditions and conditions as in Example 8 except that 100 parts by weight of the bisphenol A type polycarbonate was used. did.

Comparative Example 6 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 9 except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 7 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 10, except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 8 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 11, except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 9 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 12, except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 10 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 13 except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 11 As a charge transporting resin binder, the above structural unit [ia-
1] and Example 1 except that 100 parts by weight of the Z-type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib].
A photoconductor was prepared using the same material and conditions as in No. 3.

Comparative Example 12 As the charge transporting resin binder, the above structural unit [ia-
1] and [ib], instead of the bisphenol A / isophorone copolymerized polycarbonate, 100 parts by weight of the above bisphenol A / biphenyl copolymerized polycarbonate was used, and all were exposed under the same materials and conditions as in Example 13. The body was made.

Comparative Example 13 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 19 except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 14 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 20, except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 15 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 21, except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 16 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 22, except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 17 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 23 except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Comparative Example 18 As the charge transporting resin binder, the above structural unit [ia-
1], a photoconductor was prepared under the same conditions and conditions as in Example 24 except that 100 parts by weight of the bisphenol A type polycarbonate was used instead of the bisphenol A / isophorone copolymerized polycarbonate shown in [ib]. did.

Evaluation of Photoreceptor Electrophotographic properties of the photoreceptors produced in the above-mentioned Examples and Comparative Examples were evaluated. Regarding printing durability, various photoconductors were installed in a laser beam printer and a copying machine in which the outputs of the charging mechanism, the exposure mechanism, and the neutralization mechanism were fixed, and the temperature and humidity (20
In the atmosphere of (° C, 50 RH), actually pass the printer paper and the copy paper, and in the case of the printer, the A4 paper amount of the photoconductor film after printing 20,000 sheets, and in the case of the copying machine, the A4
Evaluation was performed by measuring the amount of film abrasion of the photoconductor film after copying 80,000 sheets of paper.

The sensitivity characteristics were evaluated by the EDA evaluation method using a photoconductor drum tester. Specifically, as the exposure light source, in the case of a printer, 1 μJ / cm ² of monochromatic light having a wavelength of 780 nm is used, and in the case of a copying machine, 1 lux of white light is used, and the initial charging potential is set to 600 V. The amount of half-exposure was determined by continuously exposing monochromatic light or white light and measuring the time until the charging potential was halved. These results are shown in Table 1 below for the photoconductors for printers and in Table 2 below for the photoconductors for copying machines.

[0093]

[Table 1]

[0094]

[Table 2]

As is clear from the above results, the bisphenol A / isophorone copolymerized polycarbonate of the present invention was used as the resin binder, and hydrazone, butadiene, diamine, indoline, indole, stilbene, and distyrylbenzene compounds were used as the charge transporting substances. By using both of them in combination, a conventionally known bisphenol A-type polycarbonate, Z-type polycarbonate or bisphenol A / biphenyl copolymer polycarbonate is used as a resin binder. In any charge transport material system, printing durability can be improved by improving sensitivity and reducing the amount of film abrasion.

In addition, bisphenol A in the present invention
In a mixed system in which isophorone copolymerized polycarbonate and bisphenol A-type polycarbonate or Z-type polycarbonate or bisphenol A / biphenyl copolymer polycarbonate, respectively, are mixed, the sensitivity is improved, and in particular, significant reduction in the amount of film scraping results in significant printing durability. Achieved improvement in sex.

Further, by using the bisphenol A / isophorone copolymerized polycarbonate as the resin binder of the charge generating layer, the sensitivity can be remarkably improved. In addition, by providing a resin film or a resin film in which metal oxide fine powder is dispersed as an undercoat layer on the conductive substrate, particularly remarkable sensitivity improvement is achieved.

[0098]

In the electrophotographic photoreceptor of the present invention,
Compared with the case where a conventionally known resin binder and each charge transporting material are used in combination in the charge transporting layer, the printing durability is significantly improved, and at the same time, the sensitivity is also improved. Further, by using such a resin binder in a specific mixed system, more remarkable improvement in printing durability can be obtained.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a laminated structure of a negatively charged laminated electrophotographic photoreceptor.

FIG. 2 is a cross-sectional view showing a laminated structure of a positively charged laminated electrophotographic photoreceptor.

[Explanation of symbols]

 1, 11 support 2, 12 undercoat layer 3, 13 charge generation layer 4, 14 charge transport layer 15 coating layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03G 5/06 318 G03G 5/06 318B 322 322 5/14 101 5/14 101E

Claims (10)

[Claims] 1. A laminated type organic photoconductor for electrophotography, which comprises a conductive substrate and at least a charge generation layer and a charge transport layer laminated on the conductive substrate. And the expression [ib], (In the formula, R ^a , R ^b , R ^c and R ^d represent a hydrogen atom or an optionally substituted alkyl group. 0.01 ≦ m /
(1 + m) ≦ 0.5) containing a bisphenol A / isophorone copolymerized polycarbonate having a structural unit represented by the following structural formula [I] as a charge transporting substance: (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, an allyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, Indicates an acyl group or heterocyclic group)
An electrophotographic photoreceptor comprising at least one hydrazone compound represented by 2. The following structural formula [II] in place of the hydrazone compound: (In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R
¹² and R ¹³ are a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, allyl group, aryl group,
The electrophotographic photosensitive member according to claim 1, further comprising at least one butadiene compound represented by an alkenyl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group, an amino group and a dialkylamino group. 3. The following structural formula [III] in place of the hydrazone compound: (In the formula, R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, an allyl group, an aryl group, an aralkyl group, an alkoxy group, The electrophotographic photosensitive member according to claim 1, which contains at least one diamine compound represented by an acyl group or a heterocyclic group). 4. The following structural formula [IV] in place of the hydrazone compound: (Wherein R ²⁰ , R ²¹ , R ²² and R ²³ represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, an alkoxy group or an aryl group) and at least one indoline compound is contained. Claim 1
The photoconductor for electrophotography according to the above. 5. The following structural formula [V], in place of the hydrazone compound, (In the formula, R ²⁴ , R ²⁵ , R ^26, and R ²⁷ represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, an alkoxy group, or an aryl group). Claim 1
The photoconductor for electrophotography according to the above. 6. The following structural formula [VI], in place of the hydrazone compound: (In the formula, R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are each a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, allyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, acyl group or A heterocyclic group, R ³²
Is a hydrogen atom, a halogen atom, or an alkyl group which may be substituted).
The electrophotographic photoreceptor according to claim 1, further comprising a seed. 7. The following structural formula [VII], in place of the hydrazone compound, (In the formula, R ³³ , R ³⁴ , R ^35, and R ³⁶ are a hydrogen atom, a halogen atom, or an optionally substituted alkyl group, allyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, acyl group, or A heterocyclic group, and R ³⁷ , R ³⁸ and R ³⁹ each represent at least one distyrylbenzene compound represented by a hydrogen atom, a halogen atom or an optionally substituted alkyl group. Electrophotographic photoconductor. 8. A resin binder, together with the bisphenol A / isophorone copolymerized polycarbonate, represented by the following structural formula [ia-1]: A bisphenol A-type polycarbonate having a structural unit represented by the following structural formula [ii-a], A bisphenol Z-type polycarbonate having a structural unit represented by the following structural formula [ia-1] and formula [ii-b], The electrophotographic use according to any one of claims 1 to 7, wherein at least one resin binder selected from the group consisting of bisphenol A / biphenyl copolymerized polycarbonate having the structural unit represented by Photoconductor. 9. The bisphenol A in the charge generation layer.
・ Claim 1 using isophorone copolycarbonate
9. The electrophotographic photosensitive member according to any one of items 8 to 8. 10. The electrophotographic photosensitive member according to claim 1, wherein a resin layer or a resin film in which fine metal oxide powder is dispersed is used as the undercoat layer on the conductive substrate.