JPH04320420A - Polycarbonate, its production thereof, and electrophotographic photoreceptor produced therefrom - Google Patents

Abstract

PURPOSE:To produce a photoconductive polycarbonate excellent in abrasion resistance, electrophotographic characteristics, etc., and useful as a charge transfer material by reacting a specific dihydroxyarylamine compd. with a carbonate-forming compd. CONSTITUTION:A dihydroxyarylamine compd. of formula I (wherein R<1> is H or 1-5C alkyl; X<1> is H, 1-5C alkyl, or a group of formula II or III; R<2> is H or 1-5C alkyl; Y is H or an arom. amino group; X<2> is a group of formula II or III; and Z is a direct bond, O, or S) alone or together with a dihydric phenol compd. of formula IV (wherein W<1> is H, halogen, or 1-6C alkyl; Q is a direct bond, O, or S; and (k) is 1-4) is allowed to react with a carbonate-forming compd. to give a polycarbonate comprising repeating units of formula V alone or together with repeating units of formula VI and having a reduced viscosity of 0.1dl/g or higher (0.5g/dl methylene chloride soln., at 20 deg.C).

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to electrophotographic photoreceptors, EL
The present invention relates to polycarbonate, which is a novel polymer that can be suitably used as a charge transport material in a charge transport layer of an electrophotographic photoreceptor in devices, solar cells, etc., and a suitable method for producing the same. The present invention also relates to an electrophotographic photoreceptor using the polycarbonate as a charge transfer material.

0002

2. Description of the Related Art Recent electrophotographic photoreceptors have a photosensitive layer that includes at least a charge generation layer (CG) that generates charges upon exposure to light.
A laminated organic electrophotographic photoreceptor (OPC) having two or more layers having a charge transport layer (CTL) and a charge transport layer (CTL) for transporting charges has become mainstream. The charge transport layer in this type of organic electrophotographic photoreceptor uses a charge transport material (CTM) dispersed and cast in a binder resin, especially polycarbonate (PC) as the binder resin. The charge transfer substance dissolved and dispersed in polycarbonate as a binder resin currently accounts for 40 to 50% of the charge transfer substance on a weight basis in order to improve the photoconductive effect, and for this reason, this type of electrophotographic photosensitive material is In the body, the inherent properties of polycarbonate as a binder resin for the purpose of improving printing durability, etc. (for example, sufficiently imparting or improving mechanical strength such as surface hardness, peeling resistance, adhesion, abrasion resistance, etc.) However, there is a problem in that the properties (characteristics that provide sufficient durability) are not fully exhibited. Therefore, although various attempts have been made in the past to solve this problem, it cannot be said that this problem has been sufficiently solved by any of the conventional techniques.

In any case, among these conventional techniques, a technique using a polymer-based electrophotographic photoreceptor that also functions as a binder resin or a component thereof deserves particular attention. For example, the polyarylamine compound disclosed in JP-A-1-7764 is a photoconductive compound obtained by copolymerizing an arylamine-based low-molecular compound, which itself is a charge transfer substance, with an alkyl chloroformate compound. The technique of using polycarbonate as a charge transport material and a binder resin or its components in the charge transport layer of an organic electrophotographic photoreceptor is one means for solving the above-mentioned problems. Particularly noteworthy. However, even with this conventional photoconductive polycarbonate, printing durability has not been sufficiently improved. In addition, the electrical properties of the charge transport layer are slightly improved when this conventional photoconductive polycarbonate is used in the charge transport layer compared to the case of a conventional dispersion system, but the improvement is not significant. Not yet reached. As described above, there may be various reasons why properties such as electrical properties and printing durability cannot be sufficiently improved by using the conventional photoconductive polycarbonate. It is a polymer in which an arylamine-based low-molecular charge transfer substance and an alkyl chloroformate compound are necessarily copolymerized at a molar ratio of 1:1, and the molar ratio cannot be adjusted. It is possible to point out the points in the chain.

0004

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. An object of the present invention is to solve the above-mentioned problems and to be able to suitably be used as a charge transfer substance or a charge transfer substance/binder resin in a photosensitive layer of an organic electrophotographic photoreceptor, particularly in a charge transport layer, and in particular to improve printing durability. and high performance with excellent electrical characteristics (high sensitivity, high image quality, durability, etc.)
An object of the present invention is to provide polycarbonate, which is a photoconductive polymer with a novel structure, which can easily realize an electrophotographic photoreceptor. Another object of the present invention is to provide a practically advantageous manufacturing method that can be suitably used as a method for manufacturing the polycarbonate of the present invention. Furthermore, another object of the present invention is to solve the above-mentioned problems by using the polycarbonate of the present invention as a charge transfer material in at least a charge transport layer, to have excellent printing durability and electrical properties, and to be able to withstand long periods of time. Electrophotographic photoreceptors with significantly improved practical performance, such as maintaining excellent surface hardness and other mechanical strength (printing durability, etc.) and excellent electrophotographic properties (high sensitivity, high image quality, etc.) throughout use. It is about providing.

[0005]

[Means for Solving the Problems] The present inventors have found that the resin can be suitably used as a charge transport substance and binder resin for the charge transport layer of an organic electrophotographic photoreceptor, and that the charge transport layer has improved printing durability and electrical resistance. We conducted intensive research to develop a new photoconductive polycarbonate that can sufficiently improve both physical and physical properties. As a result, polycarbonate with a new structure (homopolymerized and copolymers) are photoconductive polycarbonates that satisfy the above objectives. In addition, by using this photoconductive polycarbonate as a charge transport substance or a charge transport substance and binder resin in the charge transport layer of an organic electrophotographic photoreceptor, a charge transport layer exhibiting excellent electrical properties and printing durability can be obtained. It has been found that an electrophotographic photoreceptor with excellent performance can be obtained.

[0006] Furthermore, as a result of various studies on the method for producing the polycarbonate of the present invention, it has been found that a dihydroxyarylamine compound having a specific structure having an arylamine-type structural unit in the side chain, or a dihydroxyarylamine compound having a specific structure having an arylamine-type structural unit in the side chain, or this as a raw material for various bisphenol-based polycarbonates. It has been found that the polycarbonate of the present invention can be advantageously produced by reacting the dihydric phenol compound (bisphenol compound) used with a carbonate-forming compound.

The present inventors have completed the present invention mainly based on the above findings. That is, the present invention relates to a repeating unit [I] represented by the following general formula [I] or the repeating unit [I] and the following general formula [II]
Repeating unit [II]

embedded image {However, in formula [I], R1 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; an aromatic amino group represented by formula [III] or an aromatic amino group represented by formula [IV]

[Formula 17] [However, R2 is each independently a hydrogen atom or a carbon number 1
~5 alkyl group, Y is a hydrogen atom, an aromatic amino group represented by formula [V] or an aromatic amino group represented by formula [VI]

embedded image (R3 is each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ], and X2 is an aromatic amino group represented by the above formula [III] or the above formula [I
V] represents an aromatic amino group represented by X1 and X2
may be the same or different, and Z is a direct bond, -O-, -S-, -SO2-, -(CH2)p
- (however, p is an integer from 2 to 10), the following formula [V
II]

[Chemical formula 19] (However, q is an integer of 4 to 10.) Cyclohexylidene group or the following formula [VIII]

embedded image (wherein R4 is each independently a hydrogen atom, -CF3, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms). Further, in formula [II], W1 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Q represents a direct bond, -O- , -S-, -SO-
, -SO2 -, -(CH2)n - (where n is 2
It is an integer between ~10. ), the following formula [IX]

[Chemical formula 21] (However, m is an integer of 4 to 10.) Cycloalkylidene group or the following formula [X]

[Chemical formula 22] (However, W2 is each independently a hydrogen atom, a carbon number of 1 to
6 alkyl group or halogen-substituted alkyl group, or an aryl group having 6 to 12 carbon atoms. ), and k represents an integer of 1 to 4. }, and the content ratio of the repeating unit [I] is a molar ratio of 0<{[I]/
([I]+[II])}≦1, and the reduced viscosity [ηsp/C] at 20°C of a solution with a concentration of 0.5 g/dl using methylene chloride as a solvent is 0.1 dl.
/g or more.

The present invention also provides the following general formula [XI]

[
(However, in the formula, R1, X1, X2 and Z each have the same meanings as above.) Alternatively, the dihydroxyarylamine compound and the following general formula [XII]

A dihydric phenol compound represented by the following formula (wherein W1, Q and k each have the same meanings as above) is reacted with a carbonate ester-forming compound. The present invention provides a method for producing polycarbonate. Furthermore, the present invention also provides an electrophotographic photoreceptor characterized in that the polycarbonate of the present invention is used as a charge transfer material, as a particularly preferred example of the use of the polycarbonate of the present invention.

In the repeating unit [I] of the general formula [I], R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and examples of this alkyl group include a methyl group, an ethyl group, an n- Propyl group, isopropyl group, n-
butyl group, sec-butyl group, isobutyl group, tert
-butyl group, n-pentyl group, isopentyl group, sec
-pentyl group, etc. Among these, a hydrogen atom and a lower alkyl group such as a methyl group are preferred, and a hydrogen atom is particularly preferred.

In the general formula [I], X1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aromatic amino group represented by the formula [III], or an aromatic amino group represented by the formula [IV] On the other hand, X2 is an aromatic amino group represented by formula [III] or an aromatic amino group represented by formula [IV]. X1 and X2 may be the same or different. That is, in the hydroxyarylamine compound of the present invention, at least one phenylene group of its bisphenol type skeleton has an aromatic amino group represented by formula [III] or [IV] as a substituent. When X1 is an alkyl group, the alkyl group is
The various alkyl groups exemplified above for R1 can be mentioned, among which those with low steric hindrance are preferred;
Particularly preferred is a methyl group. A hydrogen atom can also be mentioned as one of the particularly preferable examples of X1.

In the aromatic amino group represented by formula [III] or formula [IV], R2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and examples of the alkyl group include those exemplified for R1. The various alkyl groups mentioned above can be mentioned. As R2, a hydrogen atom, a methyl group, etc. are preferable. On the other hand, Y represents a hydrogen atom, an aromatic amino group represented by the above formula [V], or an aromatic amino group represented by the above formula [VI]. Here, R3 in these aromatic amino groups represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and examples of the alkyl group include the various alkyl groups listed above for R1. As R3, a hydrogen atom, a methyl group, etc. are preferable.

In the aromatic amino group, that is, the diarylamino group represented by the above formula [V], the pair of phenyl groups to which R3 is bonded are each independently an unsubstituted phenyl group or a substituted with the above alkyl group. It can be an alkylphenyl group. Among these, phenyl group,
Methylphenyl group etc. are preferable, especially phenyl group, p
-Methylphenyl group etc. are preferred. Specific examples of the aromatic amino group [V] include diphenylamino group, bis(4-methylphenyl)amino group, N-phenyl-N-(4-methylphenyl)amino group, bis(3-methyl phenyl)amino group, bis(4-ethylphenyl)
Examples include an amino group, a bis(4-propylphenyl)amino group, a bis(4-butylphenyl)amino group, and a bis(4-pentylphenyl)amino group. Among these, diphenylamino group, bis(4-methylphenyl)amino group, etc. are particularly preferred.

[0013] The aromatic amino group represented by the above formula [VI], that is, the carbazole type amino group, has a pair of 1,2-phenylene groups to which R3 is bonded. It can be an unsubstituted 1,2-phenylene group or a 1,2-phenylene group substituted with the alkyl group, that is, an alkyl-1,2-phenylene group. Among these, alkyl-1, such as 1,2-phenylene group and methyl-1,2-phenylene group,
A 2-phenylene group is preferred, and a 1,2-phenylene group, a 4-methyl-1,2-phenylene group, and the like are particularly preferred. The aromatic amino group [VI] includes a residue formed by abstracting a hydrogen atom from an amino group (>NH) in carbazole (hereinafter sometimes referred to as a 9-carbazolyl group or 9-carbazolyl); Respective residues (hereinafter referred to as alkyl-9-
It is sometimes referred to as a carbazolyl group or alkyl-9-carbazolyl. ). Some typical examples of these aromatic amino groups [VI] include, for example, 2-methyl-9-carbazolyl group, 3-methyl-9
-carbazolyl group, 4-methyl-9-carbazolyl group,
3-ethyl-9-carbazolyl group, 3-propyl-9-
Carbazolyl group, 3-butyl-9-carbazolyl group, 3
-Pentyl-9-carbazolyl group, 3,6-dimethyl-
9-carbazolyl group, 3,5-dimethyl-9-carbazolyl group, 4,5-dimethyl-9-carbazolyl group, 3,
Examples include 6-diethyl-9-carbazolyl group, 3,6-dipropyl-9-carbazolyl group, 3,6-dibutyl-9-carbazolyl group, and 3,6-dipentyl-9-carbazolyl group. Among these, particularly preferable examples of the aromatic amino group [VI] include a 9-carbazolyl group represented by the following formula [VIa], and a 9-carbazolyl group represented by the following formula [VIb].
] 3,6-dimethyl-9-carbazolyl group, etc. can be mentioned.

[0014]

[C25]

Therefore, the formula [III] or the formula [I
Specific examples of Y in V] include a hydrogen atom and the various aromatic amino groups [V] and [VI] listed above. Among these, hydrogen atoms, diphenylamino groups, bis(4-methylphenyl)amino groups, 9-
Carbazolyl group (formula [VIa]), 3,6-dimethyl-
9-carbazolyl group (formula [VIb]) and the like are preferred.

In the aromatic amino group represented by the above formula [III], the pair of phenyl groups to which R2 and Y are bonded are each independently an unsubstituted phenyl group or the alkyl group exemplified above as R2. Substituted alkylphenyl groups or phenyl groups, or various aromatic amino group-substituted phenyl groups obtained by substituting the aromatic amino group [V] or aromatic amino group [VI] exemplified as Y on these alkylphenyl groups Alternatively, it can be an aromatic amino group-substituted alkylphenyl group. Specific examples of the alkylphenyl group include the various alkylphenyl groups listed above, and the preferred and particularly preferred ones are the same as above.

Specific examples of the aromatic amino group [III] that can be used as X1 and X2 include various types depending on the selection and combination of R2 and Y, as well as R3, as described above. , typical examples include diphenylamino group; bis(4
-methylphenyl)amino group, N-phenyl-N-(4
-methylphenyl)amino group, bis(3-methylphenyl)amino group, bis(4-ethylphenyl)amino group,
Various alkyl-substituted diphenylamino groups such as bis(4-propylphenyl)amino group, bis(4-butylphenyl)amino group, bis(4-pentylphenyl)amino group; bis[4-(diphenylamino)phenyl]amino group, bis[3-(diphenylamino)phenyl]amino group, bis[4-(diphenylamino)-3-methylphenyl]amino group, bis{4-[bis(4-methylphenyl)amino]phenyl}amino group , bis{4-[bis(4
-ethylphenyl)amino]phenyl}amino group, bis{4-[bis(4-propylphenyl)amino]phenyl}amino group, bis{4-[bis(4-butylphenyl)amino]phenyl}amino group, bis {4-[N-(4
-methylphenyl)-N-phenylamino]phenyl}
Amino group, 4-{N-[4-(diphenylamino)phenyl]-N-phenylamino}phenyl group, 4-{N-
Various (diphenylamino group or alkyl-substituted diphenylamino group) substituted diphenylamino groups such as [4-(diphenylamino)phenyl]-N-[4-methylphenyl]amino}phenyl group and the following formula [IIIa] (
However, R3 in the formula is each independently the same as above,
Preferred is a hydrogen atom or a methyl group. ) and various other diphenylamino groups having an unsubstituted or alkyl-substituted 9-carbazolyl group.

[0018]

[C26]

On the other hand, specific examples of the aromatic amino group [IV] that can be used as X1 and X2 are as follows:
As mentioned above, there are various types depending on the selection and combination of R2, Y, and even R3, and among these, specific examples where Y is a hydrogen atom include, for example, 9-carbazolyl group, 2-methyl- 9-carbazolyl group, 3-methyl-9-carbazolyl group, 4-methyl-9-carbazolyl group, 3-ethyl-9-carbazolyl group, 3-propyl-9-carbazolyl group, 3-butyl-9-carbazolyl group, 3-pentyl-9-carbazolyl group, 3,6-dimethyl-9-carbazolyl group, 3,5-dimethyl-9-carbazolyl group, 4,5-dimethyl-9-carbazolyl group, 3,6-diethyl-9- Carbazolyl group, 3,6-dipropyl-9-carbazolyl group, 3,6-dibutyl-9
-carbazolyl group, 3,6-dipentyl-9-carbazolyl group, and the like. In addition, as specific examples of Y not being a hydrogen atom, there are various types in which the carbazole ring of the above-mentioned various carbazolyl phenyl groups is substituted with the above-mentioned various aromatic amino groups [V] and [VI]. An aromatic amino group [IV] can be mentioned. On the other hand, if the aromatic amino group [IV] is classified from the structural point of view, typical ones include the following formula [I
Va] (wherein each E in the formula independently represents a group selected from the above R2 and Y). .

[0020]

[C27]

Particularly preferable groups for X1 and X2 include, for example, diphenylamino group, bis(4-
methylphenyl)amino group, bis[4-(diphenylamino)phenyl]amino group, bis[4-(bis(4-methylphenyl)amino)phenyl]amino group, bis[4
-(9-carbazolyl)phenyl]amino group, i.e. R
A group represented by the formula [IIIa] when 3 is a hydrogen atom, a bis[4-(3,6-dimethyl-9-carbazolyl)phenyl]amino group, that is, a group represented by the formula [IIIa] when R3 is a methyl group
IIIa], the following formula [IVa-1], formula [IVa-2] or formula [IVa-3]

[0022]

[C28]

(However, E in the formula represents a hydrogen atom or a methyl group.) Various groups {namely, 9-carbazolyl group, 3,6-dimethyl-9-carbazolyl group, 3
, 6-bis(9-carbazolyl)-9-carbazolyl group, 3,6-bis(3,6-dimethyl-9-carbazolyl)-9-carbazolyl group, 3,6-bis(diphenylamino)-9-carbazolyl group, 3,6-bis[bis(4
-methylphenyl)amino]-9-carbazolyl, etc.}, and particularly preferable groups for X1 include, in addition to the above, a hydrogen atom and a methyl group.

The repeating unit [I] represented by the above formula [I]
], Z is a direct bond, -O-, -S-, -SO
-, -SO2-, -(CH2)p- (however, p is 2 to 1
It is an integer of 0. ), the above formula [VII] (where q is 4
It is an integer between ~10. ) or the above formula [VIII] (wherein R4 is each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -CF3, or an aryl group having 6 to 12 carbon atoms) ). Here, the polymethylene group represented by -(CH2)p- is a dimethylene group [-CH2CH2-
], trimethylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, and various other polymethylene groups having 2 to 10 carbon atoms. Among these, those with p of about 2 to 4 are usually preferred. Examples of the cycloalkylidene group represented by the formula [VII] include 1,1-cyclopentylidene group, 1,1-cyclohexylidene group, and 1,1-cyclooctylidene group, where q is 4. ~10 (preferably 4-7
Various 1,1-cycloalkylidene groups can be mentioned. Among these, 1,1-cyclopentylidene group (q=4) and 1,1-cyclohexylidene group (q=5) are preferred, with 1,1-cyclohexylidene group being particularly preferred. can be mentioned.

In the group represented by the above formula [VIII], R4 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -CF3, or an aryl group having 6 to 12 carbon atoms. Specific examples of the alkyl group include various alkyl groups having 1 to 5 carbon atoms as exemplified above for R1, linear and branched hexyl groups such as n-hexyl group and isohexyl group, and furthermore cyclopentyl group and methyl group. Examples include alicyclic alkyl groups such as a cyclopentyl group, a cyclopentylmethyl group, and a cyclohexyl group. Among these, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-heptyl group and the like are preferable, and methyl group is particularly preferable.

Regarding R4, examples of the aryl group include various methylphenyl groups such as phenyl group, tolyl group, xylyl group, and trimethylphenyl group, various ethylphenyl groups, various propylphenyl groups, various butylphenyl groups, Various alkylphenyl groups such as various pentylphenyl groups, various hexylphenyl groups, various cyclohexylphenyl groups, various biphenylyl groups such as 4-biphenylyl group, various alkylbiphenyl groups such as methylbiphenylyl group, 1-naphthyl group, 2 - Various alkylnaphthyl groups such as naphthyl group, methylnaphthyl group, ethylnaphthyl group, dimethylnaphthyl group, various alkylanthryl groups such as 1-, 2- or 9-anthryl group, methylanthryl group, various indenyl groups, Various alkylindenyl groups such as methylindenyl groups, various aryl groups in the narrow sense such as various phenanthryl groups, various fluorenyl groups, and various aralkyl groups (i.e., various types in the broad sense) represented by benzyl groups, phenethyl groups, etc. aryl group). Among these various aryl groups, those having about 6 to 8 carbon atoms are usually preferred, and phenyl groups are particularly preferred. A hydrogen atom is also a preferable example of R4.

Among the groups represented by the formula [VIII], particularly preferred examples include, for example, the group represented by the formula [VI
IIa] to formula [VIIIk]

[0028]

[C29] Examples include each group represented by the following.

As for the above-mentioned Z, as a specific example of a preferable group, for example, a 1,1-cyclohexylidene group (formula [V
IIIe]), -C(CH3)2-(formula [VIIIa]
, -C(CH3)Ph-(formula [VIIIb]), -C(
Ph)2-(formula [VIIId]), among others, particularly preferred are, for example, -C(C
Examples include H3)2-(formula [VIIIa], -C(Ph)2-(formula [VIIId]), and the like. Ph represents a phenyl group.

The repeating unit [I] represented by the above formula [I]
] has various structures depending on the selection, combination, etc. of R1, X1, , in which R1, X1, X2 and Z have the same meanings as above) are preferred from the viewpoint of ease of production of polycarbonate, properties as a charge transfer material for electrophotographic photoreceptors, etc. Among these, those in which R1 is a hydrogen atom are particularly preferred. In addition, X1
Particularly preferable groups for and X2 are as described above.

[0031]

embedded image As described above, the repeating unit [I] represented by the general formula [I] may have various structures determined depending on the selection of R1, X1, X2, and Z. Can be done.

In the repeating unit [II] represented by the general formula [II], W1 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. shows. Specific examples of the alkyl group include the various alkyl groups exemplified above for R4. Among them, usually methyl group,
Ethyl group, cyclohexyl group, etc. are preferred, and methyl is particularly preferred. Regarding W1, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atoms, chlorine atoms, etc. are generally preferred, and chlorine atoms are particularly preferred. Further, regarding W1, examples of the aryl group include those exemplified with respect to R4 above. Among these, those having about 6 to 8 carbon atoms are usually preferred, and phenyl groups are particularly preferred. Particularly preferable examples of W1 include a hydrogen atom, a methyl group, a cyclohexyl group, a phenyl group, a fluorine atom, and a chlorine atom. Among these, the most preferred example is when all of W1 are hydrogen atoms.

[0033] In the above formula [II], each k is independently an integer of 1 to 4. This means that the pair of p-phenylene groups shown in the formula [II] are each independently W
This means that it may be unsubstituted p-phenylene when 1 is a hydrogen atom, or a substituted p-phenylene group having 1 to 4 of the various groups exemplified as W1 above other than hydrogen atoms as substituents. . Among these various p-phenylene groups, those in which k is 1 or 2, that is, unsubstituted p-phenylene groups and mono- or di-substituted p-phenylene groups, are usually used.
-phenylene group is preferred, and unsubstituted p-phenylene group is particularly preferred.

[0034] The repeating unit represented by the above formula [II] [
II], Q is a direct bond, -O-, -S-, -
SO-, -SO2 -, -(CH2)n - (however,
n is an integer from 2 to 10. ), a cycloalkylidene group represented by the formula [IX] (where m is an integer of 4 to 10), or a cycloalkylidene group represented by the formula [X] (wherein, W2 each independently represents a hydrogen atom, a carbon number of 1 -6 alkyl group or halogen-substituted alkyl group, or an aryl group having 6 to 12 carbon atoms.

Here, examples of the polymethylene group represented by -(CH2)n- include the various polymethylene groups exemplified for -(CH2)p-. Among these, those in which n is about 2 to 4 are usually preferred. Furthermore, examples of the cycloalkylidene group represented by the above formula [IX] include various 1,1-cycloalkylidene groups exemplified with respect to the cyclohexylidene group represented by the above formula [XII]. Among these,
1,1-cyclopentylidene group (m=4) and 1,1-
Cyclohexylidene groups (m=5) are preferred, and among them, 1,1-cyclohexylidene groups are particularly preferred.

In the group represented by the above formula [X], W2
Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen-substituted alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Examples of this alkyl group include the various alkyl groups exemplified above for W1. Among the alkyl groups mentioned above, W2 is preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-heptyl group, etc., and particularly,
A methyl group is preferred. Regarding W2, the halogen-substituted alkyl group may include one or as many halogen atoms as possible (this halogen atom may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). , preferably a fluorine atom or a chlorine atom, particularly preferably a fluorine atom). Among these halogen-substituted alkyl groups, particularly preferred ones include, for example, CF3-. Furthermore, the aryl group as W2 is:
Various aryl groups exemplified above as W1 can be mentioned. Regarding W2, a particularly preferred aryl group includes, for example, a phenyl group. A hydrogen atom is also one of the preferable examples of W2. Among the groups represented by the formula [X], specific examples of particularly preferable groups include the groups represented by the formulas [VIIIa] to [VIIIk] as exemplified above for the group represented by the formula [VIII]. Examples include groups such as
Among these, formula [VIIIa] to formula [VI
The groups represented by the formula [VIIIa] are preferred, and the groups represented by the formula [VIIIa] are particularly preferred. Said Q
Specific examples of preferable groups include, for example, direct bond, -O-, -S-, -SO2-, -CH2-(
Formula [VIIIk]), -CH2CH2-, 1,1-
Cyclopentylidene group (formula [VIIIf]), 1,1-
Cyclohexylidene group (formula [VIIIe]), -C (C
H3)2-(Formula [VIIIa]), -C(CH3
)Ph-(formula [VIIIb]), -C(CF3)2
-(Formula [VIIIc]), -C(Ph)2-(Formula [VI
IId]), and particularly preferred among them are, for example, 1,1-cyclohexylidene group (formula [VIIIe]), -C(CH3)2-(formula [VIIIe]), -C(CH3)2-(formula [VIIIe]),
VIIIa]), -C(Ph)2- (formula [VIIId]
), etc. can be exemplified. Note that Ph represents a phenyl group.

The polycarbonate of the present invention comprises one or more repeating units represented by the general formula [I] (that is, repeating units [I]), or repeating units [I]
and one or more repeating units represented by the general formula [II] (ie, repeating units [II]). That is, the content ratio of the repeating unit [I] in the polycarbonate of the present invention is determined by the following formula 0<{[I]/( [I]+[II])}≦1, any ratio can be selected. Here, if this ratio is 0, that is, if the polycarbonate does not contain the repeating unit [I], it will not show photoconductivity as it is, and even if a low-molecular charge transfer substance is dispersed and dissolved in it, it will be electrophotographically sensitive. Even if it is used as a charge transport layer of a photosensitive layer of a body, both electrical properties and printing durability cannot be fully satisfied, and the object of the present invention cannot be achieved. That is, one of the important points in the present invention is that the repeating unit [I] has a specific side chain type arylamine type structure.

When the polycarbonate of the present invention is used in a field of application requiring high photoconductivity, such as when used as a charge transfer substance in a charge transport layer of an electrophotographic photoreceptor, the content ratio of the repeating unit [I] molar ratio, usually 0
．． It is preferable to select a range that satisfies the relationship 01≦{[I]/([I]+[II])}≦1, particularly 0.1
It is preferable to select a range that satisfies the relationship: ≦{[I]/([I]+[II])}≦1.

Another important point regarding the polycarbonate of the present invention is that the concentration of the polycarbonate using methylene chloride as a solvent is 0.
Reduced viscosity [ηsp/
C] is 0.1 dl/g or more. If this reduced viscosity [ηsp/C] is less than 0.1 dl/g, the inherent mechanical strength and other properties of polycarbonate, especially the printing durability when used in the charge transport layer of an electrophotographic photoreceptor, are insufficient. I can't get it. The preferred range of reduced viscosity [ηsp/C] is 0.1 to 5 dl/g, particularly preferably 0.3 to 3 dl.
/g.

As described above, the polycarbonate of the present invention having a specific structure and a specific reduced viscosity is a polycarbonate having photoconductivity, and can be used for various purposes, especially for electrophotography as described below. It can be advantageously used as a charge transfer substance and binder resin for photoreceptors.

The polycarbonate of the present invention is not particularly limited as to its general manufacturing method, and can be manufactured by various methods according to known methods using appropriate monomers, but in particular, the following methods can be used. Advantageous production can be achieved by the method of the invention. That is, the method for producing the polycarbonate of the present invention which is practically advantageous is based on the following general formula [XI]

embedded image (wherein, R1, X1, X2 and Z each have the same meaning as in formula [I] above), alone or , the dihydroxyarylamine compound and the following general formula [XII]

[Chemical formula 32] (However, in the formula, W1, Q and k each have the same meaning as in the above formula [II].) This is done by reacting with a compound.

R1 and X1 in the general formula [XI]
, X2 and Z (and Y with respect to X1 and X2
, R2, R3, etc.) are as described above,
These specific examples, preferred examples, particularly preferred examples, etc. are also the same as above. Furthermore, the general formula [XII]
The explanations of W1, Q and k in are as described above, and specific examples, preferable examples, particularly preferable examples, etc. of these are also as follows.
Each is the same as above.

Representative examples of the compound represented by the general formula [XI], that is, the dihydroxyarylamine compound, include the following compounds represented by [XI-1] to [XI-12]. be able to.

[0044]

[Chemical formula 33]

[C34]

[C35]

[C36]

A compound represented by the general formula [XII],
That is, typical examples of the dihydric phenol compound [XII] include 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,
2,2-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
-phenylethane, 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, 2-(3-methyl) -4-hydroxyphenyl)-2-(4-hydroxyphenyl)-1-phenylethane, bis(3-methyl-4-hydroxyphenyl) sulfide, bis(3-methyl-4-hydroxyphenyl) sulfone, bis(3-hydroxyphenyl)-2-(4-hydroxyphenyl)-1-phenylethane, -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-t
ert-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
t-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-dibromo-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, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(
4-hydroxyphenyl) sulfoxide, 1,1,1,
Examples include 3,3,3-hexafluoro-2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenyl-2,2,2-trifluoroethane, etc. be able to. 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 preferably used. As the carbonate ester-forming compound, various compounds commonly used in the field of polycarbonate production can be used. Typical examples include various carbonyl dihalides including phosgene, or haloformates such as chloroformate compounds,
Examples include carbonate ester compounds. Among these, phosgene is particularly preferably used.

In the method of the present invention, one or more of the dihydroxyarylamine compounds [XI] and at least one of the carbonate-forming compounds are reacted, or the dihydroxyarylamine compounds [XI] are reacted with at least one of the carbonate-forming compounds. Polycondensation reaction by reacting one or more of the dihydric phenol compounds [XII] with at least one of the carbonate-forming compounds, or polymerization by transesterification. The polycarbonate of the present invention is produced by carrying out the reaction.

[0047] By appropriately selecting the ratio of the dihydroxyarylamine compound [XI] and the dihydric phenol compound [X] to be used, the ratio of the repeating unit [I] to the repeating unit [II] can be adjusted as desired. . There are no particular limitations on the method of this reaction (reaction atmosphere, conditions, reaction method, operation method, etc.), and generally any known method used in the production of polycarbonate may be used as appropriate. For example, when carbonyl dihalides such as phosgene or haloformates such as chloroformates are used as the carbonate-forming compound, this reaction can be carried out in a suitable solvent in the presence of an acid acceptor.

Examples of the acid acceptor include organic basic compounds such as pyridine, picoline, and lutidine, and basic alkali metal compounds such as alkali metal hydroxides and alkali metal carbonates. As the organic base compound, various compounds other than those mentioned above can be used, but pyridine is usually particularly preferably used mainly from an economical point of view. Various types of alkali metal hydroxides and alkali metal carbonates can be used, but from an economical point of view, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. are usually preferred. used. Among these various acid acceptors, pyridine is usually particularly preferably used.

The proportion of the carbonate-forming compound to be used may be appropriately selected in consideration of the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using a gaseous carbonate ester-forming compound such as phosgene, a method of blowing it into the reaction system can be suitably employed. The proportion of the acid acceptor to be used may also be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, the acid acceptor is used in an amount of 2 equivalents or slightly in excess of the total number of moles of the dihydroxyarylamine compound [XI] and the dihydric phenol compound [XII] used (usually 1 mole corresponds to 2 equivalents). It is preferable to use

As the solvent, various solvents such as those used in the production of known polycarbonates may be used alone or as a mixed solvent. Typical examples of this solvent include hydrocarbon solvents such as xylene, tertiary aromatic amine solvents such as pyridine, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Ru. Among these, pyridine and the like are particularly preferably used. Note that a tertiary aromatic amine solvent such as pyridine can serve both as a solvent in this reaction and as the acid acceptor. Also,
To promote the polycondensation reaction, triethylamine,
Catalysts such as tertiary amines such as pyridine or quaternary ammonium salts may also be used to adjust the degree of polymerization.
The reaction can be carried out by adding a molecular weight regulator such as tert-butylphenol or phenylphenol.

[0051] In this polycondensation reaction, substances that can function as an acid acceptor, a solvent, and a catalyst, such as pyridine, can be suitably used in a form that can function as an acid acceptor, a solvent, and a catalyst. Also from this point of view, pyridine is particularly preferably used. Further, if desired, a small amount of additives such as antioxidants such as sodium sulfite and hydrosulfide may be added. The reaction is usually 0-1
It can be suitably carried out at a temperature of 50°C, preferably in the range of 5 to 50°C. The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure, but usually, the reaction can be suitably carried out at normal pressure or about the own pressure of the reaction system. The reaction time is usually about 0.5 minutes to 10 hours, preferably about 1 minute to 2 hours. As the reaction method, any of a continuous method, a semi-continuous method, a batch method, etc. can be adopted.

Note that the reduced viscosity [ηsp
/C] within the above range can be achieved by various methods such as selection of the reaction conditions and amount of molecular weight modifier used. Further, depending on the case, the obtained polymer may be subjected to appropriate physical treatment (mixing, crosslinking treatment, partial dissolution treatment, etc.) to obtain a polycarbonate having a predetermined reduced viscosity [ηsp/C]. The obtained reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods, and then recovered as a polycarbonate of desired purity (purification degree). As described above, the polycarbonate of the present invention can be efficiently produced with simple operations and as a high-quality polycarbonate.

Next, the electrophotographic photoreceptor of the present invention will be explained. The electrophotographic photoreceptor of the present invention is characterized in that the polycarbonate of the present invention is used as a charge transfer material. That is, as long as the electrophotographic photoreceptor of the present invention utilizes the polycarbonate of the present invention as a charge transfer material,
Not only various types of electrophotographic photoreceptors known in the art, but also any type of electrophotographic photoreceptor may be used.
Preferably, the organic electrophotographic photoreceptor (OPC) is provided with a photosensitive layer having a charge generating layer (CGL) and at least one charge transport layer (CTL).

The polycarbonate of the present invention may be used in any part of the electrophotographic photoreceptor as long as it is used as a charge transport material, but usually at least one charge transport layer contains a charge transport material, preferably a charge transport material. Also used as a binder resin. In the case of a multilayer electrophotographic photoreceptor having two or more charge transport layers, it can be used for one or more of the charge transport layers, but unless otherwise specified, Usually, it is desirable to use it in all of the charge transport layers.

In the electrophotographic photoreceptor of the present invention, the polycarbonate of the present invention may be used alone or in combination of two or more. In addition, if desired, other polycarbonates (for example, conventional dihydric phenols and carbonate esters such as the dihydric phenol compound [XII] represented by the general formula [XII]) may be used within a range that does not impede the object of the present invention. It is also possible to include binder resin components of this type of electrophotographic photoreceptor, such as conventional polycarbonate (such as conventional polycarbonate obtained by reaction with a forming compound). Various additive components such as additives used in charge transport layers of electrophotographic photoreceptors may be included, and other low-molecular or high-molecular charge transport substances may also be added. Note that such additives include, for example, antioxidants,
Stabilizers, dispersibility improvers, ultraviolet absorbers, fillers, viscosity modifiers, adhesives (adhesion) agents, electrical property improvers, etc. can be mentioned.

The coating liquid used for forming the charge transport layer of the electrophotographic photoreceptor of the present invention contains a charge transfer substance, preferably the polycarbonate of the present invention as a charge transfer substance and binder resin component (or a combination thereof as necessary). In addition to various components such as the above-mentioned other binder resin components and the above-mentioned other additives that are added depending on the composition and a suitable solvent or dispersion solvent for dissolving or dispersing them, an anti-gelling agent, etc. is appropriately contained. You can also do that.

The structure of the electrophotographic photoreceptor of the present invention can be similar to the structure of known electrophotographic photoreceptors of this type, or various modifications can be made as necessary. can. For example, when a photosensitive layer on a conductive substrate 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. It's okay. Furthermore, a conductive or insulating protective film may be formed on the surface layer, if necessary. Furthermore, an intermediate layer such as an adhesive layer for improving adhesion between each layer or a blocking layer for blocking charges may be formed. Further, the electrophotographic photoreceptor of the present invention can be produced by various methods such as known methods.

The electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are sequentially provided on a conductive substrate, which is a typical example of the structure of the electrophotographic photoreceptor of the present invention, and a preferred method for producing the same are described below. An example will be explained. As the conductive substrate material used in the electrophotographic photoreceptor of the present invention, various known materials can be used. Specifically, for example, metals such as aluminum, brass, copper, nickel, and steel can be used. A plate or metal sheet, a black sheet coated with a conductive substance such as aluminum, nickel, chromium, palladium, graphite, etc. by vapor deposition, sputtering, coating, etc., or a glass or plastic plate. , cloth, paper, or the like which has been subjected to conductive treatment can be used.

The charge generation layer has at least a charge generation material, and the charge generation layer is formed by forming a layer on the underlying substrate by binding the charge generation material with a binder resin. can get. Various known methods can be used to form the charge generation layer, but usually, for example, a coating solution in which a charge generation material is dispersed or dissolved together with a binder resin in a suitable solvent is mixed with a predetermined coating solution. Apply it on the underlying substrate,
A method such as drying can be suitably used.

Various known charge generating materials can be used as the charge generating material in the charge generating layer. Specifically, for example, amorphous selenium, trigonal selenium, selenium alloys such as selenium-tellurium, etc. , As2 Se3 and other selenides or selenium-containing compositions, zinc oxide, CdS-
Various inorganic materials such as inorganic materials consisting of Group II and Group IV elements of the periodic table such as Se, oxide semiconductors such as titanium oxide, silicon materials such as amorphous silicon, metal or metal-free phthalocyanine, anthracene, and pyrene. , perylene, pyrylium salt, thiapyrylium salt, polyvinylcarbazole, squareium pigment, and various other organic materials. Incidentally, these may be used alone or in combination by mixing two or more thereof.

The binder resin in the charge generation layer is not particularly limited, and various known ones can be used. Specifically, for example, polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate, etc. Polymers, polyvinyl acetal, alkyd resins, acrylic resins, polyacrylonitrile, polycarbonates, polyamides, polyketones, polyacrylamide, butyral resins, thermoplastic resins such as polyesters, thermosetting resins such as polyurethane, epoxy resins, phenolic resins, etc. are used. can do. Note that the polycarbonate of the present invention can also be used as the binder resin in the charge generation layer. These binder resins may be used alone or in combination of two or more as a mixture. The charge transport layer can usually be obtained by forming a layer of the polycarbonate of the present invention (or a layer containing the polycarbonate of the present invention as a main component) on the underlying substrate.

[0062] As a method for forming this charge transport layer, various methods such as known methods can be used, but usually,
A method of applying a coating liquid in which the polycarbonate of the present invention alone or together with other binder resins or the like is dispersed or dissolved in an appropriate solvent onto a predetermined substrate and then drying can be suitably used. . In this charge transport layer, the polycarbonates of the present invention can be used alone or in combination, such as by mixing two or more types. Further, it is also possible to use other charge transfer substances in combination with the polycarbonate of the present invention within a range that does not impede the purpose of the present invention.

Charge transfer substances other than the polycarbonate of the present invention that can be used in the electrophotographic photoreceptor of the present invention include, for example, conventionally used electron transport substances and hole transport substances. Specific examples of this electron transporting substance include chloroanil, bromoanil,
Tetracyanoethylene, tetracyanoquinodimethane, 2
, 4,7-trinitro-9-fluorenone, 2,4,5
, 7-tetranitro-9-flolerenone, 2,4,7-
Trinitro-9-dicyanomethylene fluorenone, 2,
Examples include electron-withdrawing substances such as 4,5,7-tetranitroxanthone and 2,4,9-trinitrothioxanthone, and polymerized polymers of these electron-withdrawing substances. May be used alone or
Two or more types may be mixed and used in combination.

Specific examples of the hole transporting substance include 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,
Hydrazones such as p-diethylaminobenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 2
,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)pyrazoline,
1-[pyridyl(5)]-3-(p-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]-3-(
p-diethylaminostyryl)-5-(p-diethylaminophenyl)pyrazoline, 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-p-diethylaminostyryl)-5-(p -Pyrazolines such as -diethylaminophenyl)pyrazoline and spiropyrazoline, 2-(p-diethylaminostyryl)-
Oxazole compounds such as δ-ethylaminobenzoxazole, 2-(p-diethylaminophenyl)-4-(p-dimethylaminophenyl)-5-(2-chlorophenyl)oxazole, 2-(p-diethylaminostyryl)-6 -thiazole compounds such as diethylaminobenzothiazole, triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)-phenylmethane, 1,1-bis(4-N,N-diethylamino-2-methylphenyl) ) Heptane, polyarylamines such as 1,1,2,2-tetrakis(4-N,N-dimethylamino-2-methylphenyl)ethane, N,N'-
Diphenyl-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(sec-butylphenyl)benzidine, N,N'-diphenyl-N,N'-bis(tert-
butylphenyl)benzidine, N,N'-diphenyl-
Benzidine compounds such as N,N'-bis(chlorophenyl)benzidine, triphenylamine, polyvinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-vinylphenylanthracene, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin These may be used alone or in combination by mixing two or more types.

Specific examples of the solvent used in forming the charge generation layer and the charge transport layer include aromatic solvents such as benzene, toluene, xylene, and chlorobenzene, and ketones such as acetone, methyl ethyl ketone, and cyclohexanone. , alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl acetate and ethyl cellosolve, carbon tetrachloride, carbon tetrabromide, chloroform,
Examples include halogenated hydrocarbons such as dichloromethane and tetrachloroethane, ethers such as tetrahydrofuran and dioxane, dimethylformamide (DMF), dimethylsulfoxide (DMSO), and diethylformamide. These solvents may be used alone or in combination of two or more as a mixed solvent.

[0066] The coating of each layer can be carried out using various coating apparatuses such as those known in the art. Specifically, for example, an applicator, a spray coater, a bar coater, a dip coater, a roll coater, a spin coater, a doctor blade, etc. This can be done using In the manner described above, the electrophotographic photoreceptor of the present invention can be suitably obtained. The electrophotographic photoreceptor of the present invention includes not only a conventional electrophotographic photoreceptor of the type in which a conventional polycarbonate resin or the like is used as a binder resin and a conventional charge transfer substance is dispersed and dissolved therein, but also an improved type of the conventional electrophotographic photoreceptor. Compared to electrophotographic photoreceptors that use polyarylamine (conventional photoconductive polycarbonate) as a charge transfer substance or a charge transfer substance and binder resin, it has excellent printing durability and electrical properties. The electrophotographic photoreceptor has excellent performance and can be advantageously used in various electrophotographic photoreceptor applications.

[Examples] Next, the present invention will be explained 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. Variations and applications are possible.

Example 1 A flask equipped with a mechanical stirrer, a gas inlet tube and a thermometer was charged with the formula [XI-7].

[C37
] A dihydroxyarylamine compound (compound [XI-7]) represented by diphenylbis[3-(9-carbazolyl)-4-hydroxyphenyl]methane (6.
4g; 0.0094mol) and pyridine (50ml)
was introduced into the reaction system, and while the reaction system was maintained at 30 to 40°C under stirring, phosgene gas was introduced into the reaction system at a supply rate of 5 ml/min. After about 1 hour, the reaction solution became highly viscous. Furthermore, after continuing to introduce phosgene gas for 30 minutes,
p-tert-butylphenol dissolved in pyridine (
1.5 g, 0.01 mol) was added. After the reaction is complete,
The reaction mixture was added portionwise to water, yielding a fibrous solid. The resulting solid was separated by filtration and then dried. The reduced viscosity [ηsp/C] of the thus obtained solid product at 20°C of a solution with a concentration of 0.5 g/dl using methylene chloride as a solvent was measured and was found to be 0.
It was 50 dl/g. Moreover, this solid product is 1H
- From NMR spectrum analysis etc., the following formula [I-7]

It was found that it was a polycarbonate consisting of a repeating unit represented by the following formula. Next, a methylene chloride solution containing the polycarbonate obtained above at a concentration of 10% by weight was prepared as a coating solution for forming a charge transport layer. A charge generation layer with a thickness of about 0.5 μm using oxotitanium phthalocyanine as a charge generation material is provided on an aluminum conductive substrate, and then the above coating liquid is applied onto the charge generation layer by dip coating. Thickness 2 by applying and drying
A charge transport layer with a thickness of 0 μm was formed to produce a desired laminated electrophotographic photoreceptor. Next, the electrophotographic properties of this electrophotographic photoreceptor were measured using a static electricity resistance tester [EPA-8100;
(manufactured by Kawaguchi Electric Seisakusho Co., Ltd.) in the following manner. That is, -6 kV corona discharge was performed, and the acceptance potential immediately after corona discharge, the surface potential after 5 seconds in the dark, that is, the initial surface potential (V0), the residual potential (VR) after light irradiation (10 LuX), and the half-decreased exposure dose ( E1/2) was measured. The results are shown in Table 1. Further, regarding this electrophotographic photoreceptor, the abrasion characteristics of the photoreceptor surface (charge transport layer) were examined using a Suga abrasion tester under the following conditions. The results are shown in Table 2. From the results of the above evaluation test regarding electrophotographic properties (for example, Table 1), it is clear that the electrophotographic photoreceptor (i.e., the electrophotographic photoreceptor of the present invention) using the above polycarbonate of the present invention as a charge transfer substance (also a binder resin) An example of the electrophotographic photoreceptor) is a conventional polycarbonate obtained by copolymerizing a conventional hydroxyarylamine compound and diethylene glycol bischloroformate in place of the polycarbonate of the present invention described above. A conventional electrophotographic photoreceptor (Comparative Example 1) prepared by Compared to the conventional electrophotographic photoreceptor produced (Comparative Example 2), the acceptance potential immediately after corona discharge, the surface potential after 5 seconds in the dark (initial surface potential), the residual potential after light irradiation, and the half-reduced exposure amount It was found that the material had excellent electrophotographic properties. Furthermore, the electrophotographic photoreceptor of the present invention has a lower amount of wear than the conventional electrophotographic photoreceptors (Comparative Examples 1 and 2), and has a longer printing life than the above-mentioned conventional electrophotographic photoreceptors (Comparative Examples 1 and 2). It turned out that he has excellent sex.

Example 2 Formula [XI-1] as a monomer

A dihydroxyarylamine compound (compound [XI-1]) represented by the formula 2,2-bis[3-(diphenylamino)-4-hydroxyphenyl]propane (4.
51 g, 0.0080 mol) and 1,1-bis(4-hydroxyphenyl)-1,1-diphenylmethane (0.51 g, 0.0080 mol).
A polycarbonate having the following structural units and composition was obtained in the same manner as in Example 1 except that 70 g, 0.0020 mol) was used.

embedded image The reduced viscosity [ηsp/C] of this polycarbonate measured under the same conditions as in Example 1 is 0.61 d
It was l/g. An electrophotographic photoreceptor was produced using this polycarbonate in the same manner as in Example 1, and evaluated in the same manner. The results regarding the electrophotographic properties of this electrophotographic photoreceptor and the results regarding the wear characteristics of its charge transport layer are shown in Tables 1 and 2, respectively.

Example 3 Formula [XI-6] as a monomer

A dihydroxyarylamine compound (compound [XI-6]) represented by: 2,2-bis{3-[3,6-
Bis(diphenylamino)-9-carbazolyl]-4-
Hydroxyphenyl}propane (6.11g, 0.00
5 mol) and 1,1-bis(4-hydroxyphenyl)
A polycarbonate having the following structural units and composition was obtained in the same manner as in Example 1 except that cyclohexane (1.34 g, 0.005 mol) was used.

embedded image The reduced viscosity [ηsp/C] of this polycarbonate measured under the same conditions as in Example 1 was 0.58 d
It was l/g. An electrophotographic photoreceptor was produced using this polycarbonate in the same manner as in Example 1, and evaluated in the same manner. The results regarding the electrophotographic properties of this electrophotographic photoreceptor and the results regarding the wear characteristics of its charge transport layer are shown in Tables 1 and 2, respectively.

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 diethylene glycol bischloroformate (23. 38g, 0.12
5 mol) and polycarbonate consisting of the following repeating units (reduced viscosity [ηsp/C] = 0.42 dl/g
) was obtained.

embedded image An electrophotographic photoreceptor was prepared in the same manner as in Example 1 using the conventional polycarbonate having this main chain type arylamine structure, and evaluated in the same manner. The results regarding the electrophotographic characteristics of this conventional electrophotographic photoreceptor and the results regarding the abrasion characteristics of its charge transport layer are shown in Tables 1 and 2, respectively.
Shown below.

Comparative Example 2 Conventional bisphenol A as binder resin component
The following formula is used as a charge transfer substance in a proportion of 50% by weight to polycarbonate:

10 of a mixture containing a stilbene compound represented by
An electrophotographic photoreceptor was prepared in the same manner as in Example 1, except that a wt % methylene chloride solution was prepared and used as the coating liquid, and evaluated in the same manner. The results regarding the electrophotographic properties of this conventional electrophotographic photoreceptor and the results regarding the wear characteristics of its charge transport layer are shown in Tables 1 and 2, respectively.

[0072]

[Table 1] Electrophotographic characteristics

[0073]

[Table 2] Wear characteristics *Load 100g, number of reciprocations 300 times

[0074]

According to the present invention, a novel polycarbonate (photoconductive polycarbonate) having a specific structural unit having a side chain (pendant) type arylamine structure can be provided. The photoconductive polycarbonate can be particularly suitably used as a charge transport substance, particularly as a charge transport substance and binder resin, in the charge transport layer of an organic electrophotographic photoreceptor, thereby making it suitable for use as a charge transport substance and binder resin in the charge transport layer of an electrophotographic photoreceptor. High-quality electrophotography that can sufficiently improve performance such as electrical properties and printing durability, and therefore has excellent electrophotographic properties, has a long printing life, and is resistant to damage and has excellent durability. A photoreceptor can be easily realized. Further, according to the present invention, a simple method is used in which a monomer having a specific structure corresponding to the repeating unit of the polycarbonate of the present invention is reacted with a carbonate ester-forming compound. A practically advantageous manufacturing method that can be suitably used can be provided. Further, according to the present invention, by using the polycarbonate of the present invention at least as a charge transport substance in the charge transport layer, particularly as a charge transport substance and binder resin, the electrical properties and printing durability of the charge transport layer can be sufficiently improved. mechanical strength such as surface hardness (printing durability, etc.)
and excellent electrophotographic properties (high sensitivity, prevention of residual potential, etc.)
It is possible to provide an electrophotographic photoreceptor that has significantly improved practical performance, such as maintaining the following characteristics.

Claims (3)

[Claims] Claim 1: A repeating unit [I] represented by the following general formula [I] or the repeating unit [I] and a repeating unit [II] represented by the following general formula [II] [Formula 1]
] {However, in formula [I], R1 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and or an aromatic amino group represented by formula [IV] [Formula 2] [However, R2 is each independently a hydrogen atom or a carbon number 1
~5 alkyl group, Y is a hydrogen atom, an aromatic amino group represented by formula [V], or an aromatic amino group represented by formula [VI] [Formula 3] (R3 is each independently , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ], and X2 is an aromatic amino group represented by the above formula [III] or the above formula [I
V] represents an aromatic amino group represented by X1 and X2
may be the same or different, and Z is a direct bond, -O-, -S-, -SO2-, -(CH2)p
- (however, p is an integer from 2 to 10), the following formula [V
II] [Chemical formula 4] (However, q is an integer of 4 to 10.) or the following formula [VIII] [Chemical formula 5] (However, R4 is each independently hydrogen atom, -CF3, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Further, in formula [II], W1 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Q represents a direct bond, -O- , -S-, -SO-
, -SO2 -, -(CH2)n - (where n is 2
~10 integer. ), a cycloalkylidene group represented by the following formula [IX] [Chemical 6] (wherein m is an integer of 4 to 10), or a cycloalkylidene group represented by the following formula [X] [Chemical 7] (however, W2 is Each independently, hydrogen atom, carbon number 1-
6 alkyl group or halogen-substituted alkyl group, or an aryl group having 6 to 12 carbon atoms. ), and k represents an integer of 1 to 4. }, and the content ratio of the repeating unit [I] is a molar ratio of 0<{[I]/
([I]+[II])}≦1, and the reduced viscosity [ηsp/C] at 20°C of a solution with a concentration of 0.5 g/dl using methylene chloride as a solvent is 0.1 dl.
/g or more. [Claim 2] The following general formula [XI] [Formula 8] {However, in the formula, R1 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X1 represents a hydrogen atom, -5 alkyl group, aromatic amino group represented by formula [III] or aromatic amino group represented by formula [IV] [However, R2 is each independently a hydrogen atom or a carbon number 1~
5 is an alkyl group, and Y is a hydrogen atom, an aromatic amino group represented by formula [V], or an aromatic amino group represented by formula [VI] [Formula 10] (R3 is each independently, ) is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ], and X2 is an aromatic amino group represented by the above formula [III] or the above formula [IV
], X1 and X2 may be the same or different, and Z is a direct bond, -O-, -S-, -SO2-, -(CH2) p-(
However, p is an integer of 2 to 10. ), the following formula [VII
] [Chemical formula 11] (However, q is an integer of 4 to 10.) A cyclohexylidene group represented by the following formula [VIII] [Chemical formula 12] (However, R4 is each independently a hydrogen atom , -CF3, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. }, or the dihydroxyarylamine compound and the following general formula [XII]
[In the formula, W1 is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 6 to 1 carbon atoms]
2 represents an aryl group, Q is a direct bond, -O-, -S
-, -SO-, -SO2 -, -(CH2)n -(
However, n is an integer of 2 to 10. ), the following formula [IX]
[Chemical formula 14] (However, m is an integer of 4 to 10.) or the following formula [X] [Chemical formula 15] (However, W2 is each independently a hydrogen atom, a carbon Number 1~
6 alkyl group or halogen-substituted alkyl group, or an aryl group having 6 to 12 carbon atoms. ), and k represents an integer of 1 to 4. 2. The method for producing polycarbonate according to claim 1, characterized in that the dihydric phenol compound represented by )] is reacted with a carbonate ester-forming compound. 3. An electrophotographic photoreceptor comprising the polycarbonate according to claim 1 as a charge transfer substance.