JPH08248650A - Electrophotographic photosensitive material - Google Patents

Abstract

PURPOSE: To maintain excellent photographic property in use for a long time without whitening or gelatinizing coating liquid when a photosensitive material is manufactured by using polycarbonate implemented with urethane combination as binder resin. CONSTITUTION: In an electrophotographic photosensitive material which has a photosensitive layer containing charge generating material, charge transporting material and binder resin on a conductive substrate, the photosensitive layer contains polycarbonate with urethane combination as the binder resin. The polycarbonate with urethane combination used for the binder resin has preferably a reducing viscosity of 0.1-20dl/g at 20 deg.C for 0.5g/dl concentration of solution with methylene chloride as solvent, more preferably 0.2-5dl/g. For the polycarbonate, a chain or ring form can be used and a special end structure or a branch structure can be implemented at the end of polymer by using end stopping agent and branching agent in synthesizing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more specifically, it retains excellent mechanical strength and electrophotographic characteristics for repeated use over a long period of time and is suitable for various electrophotographic fields. The present invention relates to a usable electrophotographic photoreceptor.

[0002]

2. Description of the Related Art In the recent electrophotographic field, a laminated electrophotographic photosensitive member, that is, a photosensitive layer has a charge generating layer (CGL) for generating charges upon exposure and a charge transporting layer (CTL) for transferring charges. And a single-layer type electrophotographic photosensitive member (OPC) of a laminate type having at least two layers, and a single-layer type electrophotographic photosensitive member in which the photosensitive layer is a single layer in which a charge generating substance and a charge transporting substance are dispersed in a binder resin. Proposed and used.

On the other hand, the electrophotographic photosensitive member is required to have predetermined sensitivity, electrical characteristics, and optical characteristics according to the electrophotographic process to which it is applied. In particular, for a photoreceptor that is repeatedly used, the surface layer of the photoreceptor, that is, the layer that is located farthest from the substrate (usually a conductive substrate), is subjected to corona charging, toner development, transfer to paper, and cleaning treatment. At the time of the
Durability against them is required. Specifically, it is required to have durability against abrasion and scratches on the surface due to friction and deterioration of the surface due to ozone generated during corona charging under high temperature. Therefore, in order to meet such demands, the binder resin for the charge transport layer of the laminated electrophotographic photoreceptor or the photosensitive layer of the single-layer electrophotographic photoreceptor has good compatibility with the charge transport substance. In addition, polycarbonate resins made from bisphenol A or bisphenol Z, which have high mechanical strength, have been widely used. However, this bisphenol A and bisphenol Z
Even a polycarbonate resin prepared from the above is not sufficient to satisfy the above requirements.

That is, when a polycarbonate resin containing bisphenol A or bisphenol Z as a raw material is dissolved in a solvent to prepare a coating liquid for forming a photosensitive layer, the coating liquid is whitened or gelled, and the coating liquid is applied. , The photosensitive layer after drying may be crystallized. In the part where this crystallization has occurred, there is no light attenuation, and the charge remains as a residual potential,
It appears as a defect in terms of image quality.

Further, a photoreceptor using a polycarbonate resin containing bisphenol A or bisphenol Z as a raw material is inferior in durability due to abrasion and scratches due to insufficient surface hardness.

[0006]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances, and has the above-mentioned problems found in an electrophotographic photoreceptor using a polycarbonate containing bisphenol A or bisphenol Z as a binder resin. In addition to solving the problems, it has good compatibility with charge transport materials,
An electrophotographic photosensitive member which does not cause whitening or gelation even when dissolved in a solvent, and is made of a polycarbonate having high surface hardness and abrasion resistance and which maintains excellent electrophotographic characteristics for a long period of time. The purpose is to provide.

[0007]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, by using a polycarbonate having a urethane bond, which is a rigid bonding mode, as a binder resin, It was found that an electrophotographic photosensitive member is obtained in which the coating liquid does not whiten or gel during the preparation of the body, and moreover, excellent electrophotographic characteristics and durability are maintained over a long period of use. Based on this, the present invention has been completed.

That is, the present invention relates to an electrophotographic photoreceptor having a photosensitive layer containing a charge generating substance, a charge transporting substance and a binder resin on a conductive substrate, and the photosensitive layer is a polycarbonate having a urethane bond as the binder resin. The present invention provides an electrophotographic photosensitive member characterized by containing: [1] Polycarbonate Having Urethane Bond Polycarbonate having a urethane bond used as a binder resin in the electrophotographic photoreceptor of the present invention is
Usually, the reduced viscosity of a solution having a concentration of 0.5 g / dl in methylene chloride at 20 ° C. is 0.1 to 20 dl / g.
It is preferred that This reduced viscosity is 0.1 dl / g
If it is less than 1, the surface hardness is insufficient and the surface of the electrophotographic photosensitive member is easily worn.
If it exceeds / g, the solution viscosity of the polycarbonate may increase, which may make it difficult to manufacture the photoreceptor by applying the coating liquid. More preferably, 0.2-5 dl / g
Is.

The above-mentioned polycarbonate having a urethane bond used in the present invention may be linear or cyclic, and further, by using an end terminating agent, a branching agent or the like at the time of synthesis, the end of the polymer may be terminated. It may have a special terminal structure or a special branched structure. A preferred example of the polycarbonate used in the present invention contains a repeating unit (I) represented by the following general formula (I) and a repeating unit (II) represented by the following general formula (II) as a main component. There are things.

[0010]

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[Wherein Ar is the following general formula (III):

[0012]

[Chemical 15]

(In the formula, R ⁵⁰ and R ⁵¹ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Represents a group, Y is a single bond, -O-, -CO-,
-S -, - SO -, - SO 2 -, - CR 52 R 53 - (R 52
And R ⁵³ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ), Carbon number 5
11,1-cycloalkylidene group having 11 or 2 to 1 carbon atoms
2 represents an α, ω-alkylene group, and A and B each independently represent an integer of 0 to 4. ) Is a divalent group represented by
Is the following general formulas (IV) to (VIII)

[0014]

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(In the formula, X is a single bond, --O--, --S--,-)
SO -, - SO ₂ -, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, an alkynylene group or an alkylidene group, a substituted or from 3 to 20 carbon atoms Unsubstituted cycloalkylene group, substituted or unsubstituted 2 to 6 carbon atoms
Valent aromatic group, substituted or unsubstituted divalent nitrogen-containing heterocyclic group having 3 to 18 carbon atoms, sulfur-containing heterocyclic group or oxygen-containing heterocyclic group, substituted or unsubstituted having 2 to 20 carbon atoms R ⁵⁴ represents a divalent residue of a substituted amine compound, a divalent residue of a substituted or unsubstituted ester compound, amide compound or sulfide compound having 2 to 20 carbon atoms, or a group consisting of a combination of these divalent groups; , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R
⁶⁰ , R ⁶¹ and R ⁶² are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group or alkynyl group having 2 to 20 carbon atoms, carbon A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 36 carbon atoms, a substituted or unsubstituted nitrogen-containing heterocyclic group having 3 to 18 carbon atoms, and a sulfur-containing hetero group Represents a monovalent residue of a cyclic group or an oxygen-containing heterocyclic group or a substituted or unsubstituted epoxide compound having 2 to 20 carbon atoms, n ¹ and n ² are n ¹
+ N ² = integer satisfying 1 to 6, n ³ is an integer satisfying 0 to 6, n ⁴ and n ⁵ are integers satisfying n ⁴ + n ⁵ = 1 to ⁶ , n ⁶ and n ⁷ Is an integer satisfying n ⁶ + n ⁷ = 1 to 6, n ⁸ and n ¹⁰ are each independently an integer of 0 to 6, and n ⁹ and n ¹¹ are each independently 0 or 1. ) Represents a divalent group. The ratio of the repeating unit (II) to the total moles of the repeating units (I) and (II) in the polycarbonate containing the repeating units represented by the general formulas (I) and (II) as a main component is usually , 1 to 50 mol%, preferably 1 to 30 mol%.

The polycarbonate used in the present invention is
For example, it can be synthesized by reacting a divalent phenol and a divalent amine and / or an aminophenol with a carbonic acid ester forming compound. As the synthetic method, for example, phosgene or the like is used as a carbonic acid ester-forming compound, and polycondensed with the above divalent phenols and divalent amines and / or aminophenols in the presence of a suitable acid binder, or carbonic acid is used. A method in which bisaryl carbonate is used as an ester-forming compound and a transesterification reaction is carried out can be mentioned. Dihydric phenols,
The divalent amines and aminophenols are not particularly limited and may be one type or 2 types from compounds including known ones.
It is possible to arbitrarily select and use one or more species.

For example, the above general formulas (I) and (II)
A polycarbonate which has a repeating unit represented by the following as a main component and is preferably used in the present invention is a divalent phenol represented by the following general formula (IX).

[0018]

[Chemical 17]

(Wherein R ⁵⁰ , R ⁵¹ , Y, A and B have the same meanings as described above), divalent amines and / or aminophenols are represented by the following general formula: (X) to (XIV)

[0020]

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(In the formula, X, R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R
⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , n ¹ , n ² , n ³ , n ⁴ , n
⁵ , n ⁶ , n ⁷ , n ⁸ , n ⁹ , n ¹⁰ and n ¹¹ have the same meanings as described above. ) Is used for manufacturing.
Specific examples of the dihydric phenols (IX) represented by the general formula (IX) include, for example, 4,4′-dihydroxybiphenyl, 3,3′-difluoro-4,4′-dihydroxybiphenyl, 4,4. ′ -Dihydroxy-3,3′-dimethylbiphenyl, 4,4′-dihydroxy-2,2 ′
-Dimethylbiphenyl, 4,4'-dihydroxy-3,
4,4'-dihydroxybiphenyls such as 3'-dicyclohexylbiphenyl; bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl)
Ethane, 1,2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 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, 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) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,
2-bis (2-methyl-4-hydroxyphenyl) propane, 1,1-bis (2-butyl-4-hydroxy-5)
-Methylphenyl) butane, 1,1-bis (2-ter
t-butyl-4-hydroxy-3-methylphenyl) ethane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 1,1-bis (2-tert-butyl-) 4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) isobutane, 1,1-bis (2-tert-butyl-4-hydroxy-) 5-methylphenyl) heptane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -1-phenylmethane, 1,1-bis (4-
Hydroxy-2-methyl-5-tert-pentylphenyl) butane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, 2,2-bis (3 -Chloro-4-
Hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-
Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane (also known as tetrafluorobisphenol A), 2,2-bis (3,5- Dichloro-4-hydroxyphenyl) propane (also known as tetrachlorobisphenol A), 2,2-bis (3,5-dibromo-4)
-Hydroxyphenyl) propane (also known as tetrabromobisphenol A), 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, 1,1
-Bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3- Phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-phenyl-4)
Bis (4-) such as -hydroxyphenyl) cyclohexane
Hydroxyphenyl) alkanes; Bis (4-hydroxyphenyl) ethers such as bis (4-hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether; Bis (4-hydroxyphenyl)
Bis (4-hydroxyphenyl) sulfides such as sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis ( 3-phenyl-4-hydroxyphenyl)
Bis (4-hydroxyphenyl) sulfones such as sulfone; 4,4′-dihydroxybenzophenone and the like.

Among them, the dihydric phenols preferably used are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl). ) −
1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
2,2-bis (4-hydroxy-3-phenylphenyl) propane, 4,4'-dihydroxybiphenyl and bis (4-hydroxyphenyl) sulfone, with 2,2-bis (4-hydroxyphenyl) propane being particularly preferred. Used for.

These dihydric phenols may be used alone or in combination of two or more. 2 above
Examples of X in the general formulas (IX) to (XIV) showing examples of divalent amines and aminophenols will be described below. Regarding the unsubstituted alkylene group having 1 to 20 carbon atoms, the unsubstituted alkenylene group having 2 to 20 carbon atoms, the alkynylene group and the alkylidene group, examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group and a tetramethylene group. , Pentamethylene group, hexamethylene group,
Heptamethylene group, octamethylene group, nonamethylene group, decamethylene group and the like, as the alkenylene group, for example, vinylene group, propenylene group, 1-butenylene group, trans-2-butenylene group, cis-2-butenylene group, etc., Examples of the alkynylene group include ethynylene group and the like, and examples of the alkylidene group include ethylidene group, 1-propylidene group, 2-propylidene group, 1-
Examples thereof include butylidene group, 2-butylidene group, 1-pentylidene group, 2-pentylidene group and 3-pentylidene group. Particularly, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and a hexamethylene group are preferable.

These alkylene groups, alkenylene groups,
The alkynylene group and the substituent of the alkylidene group include, for example, halogen atoms of fluorine, chlorine, bromine and iodine,
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, vinyl group, allyl group and other aliphatic hydrocarbon groups having 1 to 4 carbon atoms, phenyl group, Aromatic hydrocarbon groups having 6 to 12 carbon atoms such as naphthyl group and biphenylyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, 2- An alkyloxy group such as a propenoxy group, an alkenyloxy group and an aryloxy group,
Alkylthio group such as methylthio group and phenylthio group, arylthio group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, isobutyloxycarbonyl group And other groups having a heterocycle such as an alkyloxycarbonyl group and an aryloxycarbonyl group, and a 2- (2-methyl-1-imidazolyl) ethyl group. The above alkylene group, alkenylene group, alkynylene group and alkylidene group may be substituted at any substitutable position with one or more of these substituents.

Examples of the unsubstituted cycloalkylene group having 3 to 20 carbon atoms include cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group and the like. A cyclohexylene group is particularly preferable.
Examples of the substituent of these cycloalkylene groups include halogen atoms of fluorine, chlorine, bromine and iodine, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl. Groups, vinyl groups, allyl groups and other aliphatic hydrocarbon groups having 1 to 4 carbon atoms, phenyl groups, naphthyl groups, biphenylyl groups and other aromatic hydrocarbon groups having 6 to 12 carbon atoms, methoxy groups,
Alkoxyoxy groups such as ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, 2-propenoxy group, alkenyloxy group and aryloxy group, methylthio group, phenylthio group, etc. Alkylthio group such as alkylthio group and arylthio group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group and isobutyloxycarbonyl group. And an aryloxycarbonyl group, 2- (2-methyl-1)
Examples thereof include a group having a heterocycle such as -imidazolyl) ethyl group. The above cycloalkylene group may be substituted with one or more of these substituents at any substitutable position.

Examples of the unsubstituted divalent aromatic group having 6 to 36 carbon atoms include phenylene group, tolylene group, xylylene group, naphthylene group, biphenylylene group and the like. Particularly preferred are a phenylene group, a tolylene group, a xylylene group and a biphenylylene group. Examples of the substituent of these divalent aromatic groups include a halogen atom of fluorine, chlorine, bromine and iodine, a methyl group, an ethyl group, a propyl group,
Isopropyl group, butyl group, sec-butyl group, ter
Aliphatic hydrocarbon group having 1 to 4 carbon atoms such as t-butyl group, isobutyl group, vinyl group and allyl group, aromatic hydrocarbon group having 6 to 12 carbon atoms such as phenyl group, naphthyl group and biphenylyl group, methoxy Group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, te
alkyloxy groups such as rt-butoxy group, isobutoxy group and 2-propenoxy group, alkenyloxy groups and aryloxy groups, alkylthio groups such as methylthio group and phenylthio group and arylthio groups, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group ,
Isopropoxycarbonyl group, butoxycarbonyl group,
alkyloxycarbonyl groups such as sec-butoxycarbonyl group, tert-butoxycarbonyl group, isobutyloxycarbonyl group and aryloxycarbonyl groups, groups having a heterocycle such as 2- (2-methyl-1-imidazolyl) ethyl group Can be mentioned. The above divalent aromatic group may be substituted with one or more of these substituents at any substitutable position.

Examples of the unsubstituted divalent nitrogen-containing heterocyclic group having 3 to 18 carbon atoms, sulfur-containing heterocyclic group and oxygen-containing heterocyclic group include, for example, pyrrolidinediyl group as the nitrogen-containing heterocyclic group. , Pyrrolidinylidene group, piperidinediyl group, piperidinylidene group, piperazinediyl group, piperazinylidene group, pyrrolediyl group, pyrrolidene group, pyridinediyl group, pyridylidene group, pyridazinediyl group, pyridazinylidene group, pyrimidinediyl group, pyrimidinylidene group, pyrazinidylidene group, pyrazinidylidene group, pyrazinidylidene group , Imidazolediyl group, imidazolylidene group, indolediyl group, indolylidene group, triazinediyl group, triazinylidene group, carbazolediyl group, carbazolylidene group, groups represented by the following formulas (1), (2) and (3), As a sulfur-containing heterocyclic group, Fendiyl group, thienylidene group, tetrahydrothiophenediyl group, tetrahydrothienylidene group, benzothiophenediyl group, benzothienylidene group and the like, as an oxygen-containing heterocyclic group, furandiyl group, furylidene group, benzfurandiyl group, benzfurylidene group, Tetrahydrofurandiyl group, tetrahydrofurylidene group, 1,4-dioxanediyl group, 1,4-
Dioxanilidene group, 1,3-dioxanediyl group,
Examples thereof include a 1,3-dioxanylidene group and a group represented by the following formula (4). Particularly, pyrrolidinediyl group, pyrrolidinylidene group, piperidinediyl group, piperidylidene group,
Piperazinediyl group, piperazinylidene group, pyrrolediyl group, pyrrolidene group, imidazolediyl group, imidazolylidene group, triazinediyl group, triazinylidene group, 1,3-dioxanediyl group, 1,3-dioxanilidene group and the following group (4) preferable.

[0028]

[Chemical 19]

Examples of the substituents of these divalent heterocyclic groups include halogen atoms of fluorine, chlorine, bromine and iodine, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group. , Tert-butyl group, isobutyl group, vinyl group, allyl group, etc.
4 aliphatic hydrocarbon group, phenyl group, naphthyl group, biphenylyl group and other aromatic hydrocarbon groups having 6 to 12 carbon atoms, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group , Tert-butoxy, isobutoxy, 2-propenoxy, etc. alkyloxy, alkenyloxy and aryloxy, methylthio, phenylthio, etc. alkylthio and arylthio, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl Group, isopropoxycarbonyl group, butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group,
An alkyloxycarbonyl group such as an isobutyloxycarbonyl group and an aryloxycarbonyl group, 2- (2-
Examples thereof include groups having a heterocycle such as a methyl-1-imidazolyl) ethyl group. The above divalent nitrogen-containing heterocyclic group, sulfur-containing heterocyclic group and oxygen-containing heterocyclic group may be substituted with one or more of these substituents at any substitutable position. Good.

Examples of the divalent residue of the unsubstituted amine compound having 2 to 20 carbon atoms include groups having the following structures.

[0031]

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Examples of the substituent of the divalent residue of these amine compounds include halogen atoms of fluorine, chlorine, bromine and iodine, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group. , Tert-butyl group, isobutyl group, vinyl group, allyl group and other aliphatic hydrocarbon groups having 1 to 4 carbon atoms, phenyl group, naphthyl group,
Aromatic hydrocarbon group having 6 to 12 carbon atoms such as biphenylyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert.
-Butoxy group, isobutoxy group, alkyloxy group such as 2-propenoxy group, alkenyloxy group and aryloxy group, methylthio group, alkylthio group such as phenylthio group and arylthio group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, Isopropoxycarbonyl group, butoxycarbonyl group, sec
An alkyloxycarbonyl group such as a butoxycarbonyl group, a tert-butoxycarbonyl group, an isobutyloxycarbonyl group and an aryloxycarbonyl group, 2-
Examples thereof include groups having a heterocycle such as (2-methyl-1-imidazolyl) ethyl group. 2 of the above amine compounds
The valent residue may be substituted by one or more of these substituents at any substitutable position.

Examples of the divalent residue of the unsubstituted ester compound, amide compound and sulfide compound having 2 to 20 carbon atoms include groups having the following structures.

[0034]

[Chemical 21]

(In the formula, n ¹² and n ¹³ are integers from 1 to 6.) Specific examples of the former two groups represented by the general formula include groups having the following structures. Be done.

[0036]

[Chemical formula 22]

As the substituent of the divalent residue of these ester compound, amide compound and sulfide compound, for example, halogen atom of fluorine, chlorine, bromine and iodine, methyl group, ethyl group, propyl group, isopropyl group, butyl group. Group, sec-butyl group, tert-butyl group, isobutyl group, vinyl group, allyl group, etc., aliphatic hydrocarbon group having 1 to 4 carbon atoms, phenyl group, naphthyl group, biphenylyl group, etc., having 6 to 12 carbon atoms Aromatic hydrocarbon group, methoxy group,
Alkoxyoxy groups such as ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, 2-propenoxy group, alkenyloxy group and aryloxy group, methylthio group, phenylthio group, etc. Alkylthio group such as alkylthio group and arylthio group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group and isobutyloxycarbonyl group. And an aryloxycarbonyl group, 2- (2-methyl-1)
Examples thereof include a group having a heterocycle such as -imidazolyl) ethyl group. Divalent Residue of Ester Compound, Amide Compound or Sulfide Compound The divalent residue of ester compound, amide compound or sulfide compound is substituted at any substitutable position by one or more of these substituents. May be. Further, X may be a divalent group composed of a combination of the above various divalent groups.

Preferred specific examples of the divalent group X include the followings.

[0039]

[Chemical formula 23]

R ⁵⁴ and R in the general formulas (X) to (XIV) showing examples of the above divalent amines and aminophenols.
Examples of ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ and R ⁶² will be described below. Examples of the unsubstituted alkyl group having 1 to 20 carbon atoms and the substituted or unsubstituted alkenyl group and alkynyl group having 2 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. , Heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, benzyl group, vinyl group, allyl group, 1-propenyl group, ethynyl group and the like.
Particularly, a methyl group, an ethyl group, a propyl group and an isopropyl group are preferable.

Substituents for these alkyl, alkenyl and alkynyl groups include, for example, fluorine, chlorine,
Halogen atom of bromine and iodine, methyl group, ethyl group,
Propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, vinyl group,
C6-C12 aliphatic hydrocarbon groups such as allyl groups, etc., phenyl groups, naphthyl groups, biphenylyl groups, etc.
Aromatic hydrocarbon group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, 2-
Alkyloxy group such as propenoxy group, alkenyloxy group and aryloxy group, methylthio group, alkylthio group such as phenylthio group and arylthio group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, sec-butoxycarbonyl group, tert-
Examples thereof include alkyloxycarbonyl groups such as butoxycarbonyl group and isobutyloxycarbonyl group, aryloxycarbonyl groups, and groups having a heterocycle such as 2- (2-methyl-1-imidazolyl) ethyl group. The above alkyl group, alkenyl group and alkynyl group may be substituted at any substitutable position with one or more of these substituents.

Examples of the unsubstituted cycloalkyl group having 3 to 20 carbon atoms include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. A cyclohexyl group is particularly preferable. As the substituent of these cycloalkyl groups, for example, halogen atoms of fluorine, chlorine, bromine and iodine, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-
A butyl group, a tert-butyl group, an isobutyl group, a vinyl group, an allyl group, and the like, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, a biphenylyl group, and the like, having 6 carbon atoms.
12 aromatic hydrocarbon groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, sec-
Butoxy group, tert-butoxy group, isobutoxy group,
Alkyloxy group such as 2-propenoxy group, alkenyloxy group and aryloxy group, alkylthio group such as methylthio group and phenylthio group and arylthio group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group Group, sec-butoxycarbonyl group, ter
Examples thereof include alkyloxycarbonyl groups such as t-butoxycarbonyl group and isobutyloxycarbonyl group, aryloxycarbonyl groups, and groups having a heterocycle such as 2- (2-methyl-1-imidazolyl) ethyl group.
The cycloalkyl group above may be substituted at any substitutable position by one or more of these substituents.

Examples of the unsubstituted aromatic group having 6 to 36 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group and biphenylyl group. Particularly, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group are preferable. As the substituent of these aromatic groups, for example, halogen atoms of fluorine, chlorine, bromine and iodine, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-
A butyl group, a tert-butyl group, an isobutyl group, a vinyl group, an allyl group, and the like, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, a biphenylyl group, and the like, having 6 carbon atoms.
12 aromatic hydrocarbon groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, sec-
Butoxy group, tert-butoxy group, isobutoxy group,
Alkyloxy group such as 2-propenoxy group, alkenyloxy group and aryloxy group, alkylthio group such as methylthio group and phenylthio group and arylthio group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group Group, sec-butoxycarbonyl group, ter
Examples thereof include alkyloxycarbonyl groups such as t-butoxycarbonyl group and isobutyloxycarbonyl group, aryloxycarbonyl groups, and groups having a heterocycle such as 2- (2-methyl-1-imidazolyl) ethyl group.
The above aromatic groups may be substituted with one or more of these substituents at any substitutable position.

The unsubstituted nitrogen-containing heterocyclic group having 3 to 18 carbon atoms, the sulfur-containing heterocyclic group and the oxygen-containing heterocyclic group include
For example, as a nitrogen-containing heterocyclic group, a pyrrolidinyl group, a piperidyl group, a piperazyl group, a pyrrolyl group, a pyridyl group, a pyridinidyl group, a pyrimidinyl group, a pyrazinyl group, an imidazolyl group, an indolyl group, a triazinyl group, a carbazolyl group, etc. As the cyclic group, a thienyl group, a tetrahydrothienyl group, a benzothienyl group and the like, and as the oxygen-containing heterocyclic group, a furyl group, a benzfuryl group, a tetrahydrofuryl group, a 1,4-dioxanyl group, a 1,3-dioxanyl group and the like. Can be mentioned. Particularly, a pyrrolyl group, a piperidyl group, a piperazyl group, a pyrrolyl group, an imidazolyl group, a triazinyl group, and a 1,3-dioxanyl group are preferable.

Examples of the substituents of these nitrogen-containing heterocyclic group, sulfur-containing heterocyclic group and oxygen-containing heterocyclic group include
Fluorine, chlorine, bromine and iodine halogen atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, vinyl group, allyl group, etc. 4 aliphatic hydrocarbon group, phenyl group, naphthyl group, biphenylyl group and other aromatic hydrocarbon groups having 6 to 12 carbon atoms, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group , Tert-butoxy, isobutoxy, 2-propenoxy, etc. alkyloxy, alkenyloxy and aryloxy, methylthio, phenylthio, etc. alkylthio and arylthio, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl Group, isopropoxycarbonyl group, butoxycarbo Le group, sec- butoxycarbonyl group, tert- butoxycarbonyl group, an alkyloxycarbonyl group and an aryloxycarbonyl group such as iso-butyloxycarbonyl group, 2- (2-methyl-1
Examples thereof include a group having a heterocycle such as -imidazolyl) ethyl group. The substituents of the above-mentioned nitrogen-containing heterocyclic group, sulfur-containing heterocyclic group and oxygen-containing heterocyclic group may be substituted at any substitutable position with one or more of these substituents. Good.

Examples of the monovalent residue of the unsubstituted epoxide compound having 2 to 20 carbon atoms include groups having the following structures.

[0047]

[Chemical formula 24]

Examples of the substituent of the monovalent residue of these epoxide compounds include halogen atoms of fluorine, chlorine, bromine and iodine, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group. , Tert
-Butyl group, isobutyl group, vinyl group, allyl group and other aliphatic hydrocarbon groups having 1 to 4 carbon atoms, phenyl group, naphthyl group, biphenylyl group and other aromatic hydrocarbon groups having 6 to 12 carbon atoms, methoxy group , Ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, ter
alkyloxy groups such as t-butoxy group, isobutoxy group and 2-propenoxy group, alkenyloxy groups and aryloxy groups, alkylthio groups and arylthio groups such as methylthio group and phenylthio group, methoxycarbonyl group,
Ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, se
alkyloxycarbonyl groups such as c-butoxycarbonyl group, tert-butoxycarbonyl group, isobutyloxycarbonyl group and aryloxycarbonyl groups, 2
Examples thereof include groups having a heterocycle such as a-(2-methyl-1-imidazolyl) ethyl group. The substituent of the monovalent residue of the above epoxide compound may be substituted at any substitutable position with one or more of these substituents.

Particularly preferred groups as R ^{54 to} R ⁶² are, for example,

[Chemical 25]

And the like. Specific examples of divalent amines and aminophenols that are preferably used for producing the polycarbonate used in the present invention are shown below.

[0051]

[Chemical formula 26]

[0052]

[Chemical 27]

These diamines and aminophenols may be used alone or in combination of two or more. When synthesizing the above-mentioned polycarbonate containing the repeating units represented by the above general formulas (I) and (II) as a main component, divalent amines and aminophenols are mixed with divalent phenols and divalent amines. It is usually preferable to use 1 to 50 mol%, preferably 1 to 30 mol% based on the total mol of aminophenols. If the amount of divalent amines and aminophenols is less than 1 mol%, the introduction of the urethane bond, which is a rigid component, will be insufficient, the effects of the present invention will not be obtained, and the improvement of printing life will be unachievable. May be possible. On the other hand, if the proportion of divalent amines and aminophenols exceeds 50 mol%, the solubility of the polycarbonate in a solvent during preparation of the coating solution and the stability of the solution may decrease.

In addition to the above-mentioned dihydric phenols, divalent amines and aminophenols as raw materials, a branching agent and a terminal terminating agent may be used if necessary. As the branching agent, trivalent or higher valent phenol or carboxylic acid can be used. Examples of branching agents are phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,
4-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 1,
3,5-tris (2-hydroxyphenyl) benzene,
1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis (4,4-) Bis (4-hydroxyphenyl) cyclohexyl) propane, 2,4-bis {2-
(4-Hydroxyphenyl) -2-propyl} phenol, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4- Dihydroxyphenyl) propane, tetrakis (4-hydroxyphenyl) methane,
Tetrakis (4- (4-hydroxyphenylisopropyl) phenoxy) methane, 1,4-bis (4 ', 4 "-
Dihydroxytriphenylmethyl) benzene, 2,4-
Dihydroxybenzoic acid, trimesic acid, cyanuric acid,
3,3-bis (3-methyl-4-hydroxyphenyl)
-2-oxo-2,3-dihydroindole, 3,3-
Bis (4-hydroxyaryl) oxindole, 5
-Chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like can be mentioned.

Of these, phloroglysin, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane and the like are preferably used. As the terminal terminator, a monovalent carboxylic acid and its derivative, or a monovalent phenol can be used.

Specific examples include phenol, α-naphthol, β-naphthol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,
4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, p-ethylphenol, p-propylphenol, p-butylphenol, p-pentylphenol,
p-hexylphenol, p-heptylphenol, p
-Octylphenol, p-nonylphenol, p-decylphenol, p-undecylphenol, p-dodecylphenol, p-isopropylphenol, pt
ert-butylphenol, 2,6-dimethyl-pt
ert-butylphenol, 2-tert-pentyl-
4-methylphenol, 3-methyl-6-tert-butylphenol, 2-methyl-4,6-di-tert-
Butylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-tert-pentylphenol, 2,
4,6-Tri-tert-butylphenol, p-phenylphenol, 2,6-di-tert-butyl-4-
Phenylphenol, 2,6-di-sec-butyl-4
-Methylphenol, o-anisole, m-anisole, p-anisole, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, p-ethoxyphenol , O-aminophenol,
m-aminophenol, p-aminophenol, p-cyanophenol, p-nitrophenol, 3-methyl-
6-isopropylphenol, 2-methyl-5-isopropylphenol, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, Perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, perfluoropentadecanoic acid, perfluorohexadecanoic acid, perfluorooctadecanoic acid, 2H, 2H-perfluoropentanic acid, 2H, 2H- Perfluorohexanoic acid, 2H, 2H
-Perfluoroheptanoic acid, 2H, 2H-perfluorooctanoic acid, 2H, 2H-perfluorononanoic acid, 2
H, 2H-perfluorodecanoic acid, 2H, 2H-perfluoroundecanoic acid, 2H, 2H-perfluorododecanoic acid, 2H, 2H-perfluorotridecanoic acid, 2H,
2H, 3H, 3H-perfluorohexanoic acid, 2H, 2
H, 3H, 3H-perfluoroheptanoic acid, 2H, 2
H, 3H, 3H-perfluorooctanoic acid, 2H, 2
H, 3H, 3H-perfluorononanoic acid, 2H, 2H,
3H, 3H-perfluorodecanoic acid, 2H, 2H, 5H
-Perfluoropentanoic acid, 2H, 2H, 6H-perfluorohexanoic acid, 2H, 2H, 7H-perfluoroheptanoic acid, 2H, 2H, 8H-perfluorooctanoic acid,
2H, 2H, 9H-perfluorononanoic acid, 2H, 2
H, 10H-perfluorodecanoic acid, 2H, 2H, 11
H-perfluoroundecanoic acid, 2H, 2H, 12H-
Perfluorododecanoic acid, 2H, 2H, 13H-perfluoroundecanoic acid, or acid halides thereof, p
-(Perfluoropentyl) phenol, p- (perfluorohexyl) phenol, p- (perfluoroheptyl) phenol, p- (perfluorooctyl) phenol, p- (perfluorononyl) phenol, p-
(Perfluorodecyl) phenol, p- (perfluoroundecyl) phenol, p- (perfluorododecyl) phenol, p- (perfluorotridecyl) phenol, p- (perfluorotetradecyl) phenol, p- (per) Fluoropentadecyl) phenol, p
-(Perfluorobutyloxy) phenol, p- (perfluoropentyloxy) phenol, p- (perfluorohexyloxy) phenol, p- (perfluoroheptyloxy) phenol, p- (perfluorooctyloxy) phenol, p -(Perfluorononyloxy) phenol, p- (perfluorodecyloxy) phenol, p- (perfluoroundecyloxy) phenol, p- (perfluorododecyloxy)
Phenol, p- (perfluorotridecyloxy) phenol, p- (perfluorotetradecyloxy) phenol, p- (perfluoropentadecyloxy) phenol, 4-perfluorooctyl-2,3,5,6
-Tetrafluorophenol, 4-perfluorononyl-2,3,5,6-tetrafluorophenol, 4-perfluorodecyl-2,3,5,6-tetrafluorophenol, 4-perfluoroundecyl-2, 3, 5,
6-tetrafluorophenol, 4-perfluorododecyl-2,3,5,6-tetrafluorophenol, 4
-Perfluorotridecyl-2,3,5,6-tetrafluorophenol, 4-perfluorotetradecyl-
2,3,5,6-tetrafluorophenol, 4-perfluoropentadecyl-2,3,5,6-tetrafluorophenol, p-tert-perfluorobutylphenol, 3-methyl-4-perfluorononylphenol, p -(2- (1H, 1H-perfluorooctyloxy) -1,1,1,3,3,3-hexafluoro-2
-Propyl) phenol, p- (2- (1H, 1H-perfluorononyloxy) -1,1,1,3,3,3-
Hexafluoro-2-propyl) phenol, p- (2
-(1H, 1H-perfluorodecyloxy) -1,
1,1,3,3,3-hexafluoro-2-propyl)
Phenol, p- (2- (1H, 1H-perfluoroundecyloxy) -1,1,1,3,3,3-hexafluoro-2-propyl) phenol, p- (2- (1
H, 1H-perfluorododecyloxy) -1,1,
1,3,3,3-hexafluoro-2-propyl) phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, p- (1H, 1H-perfluoropentyloxy) phenol, p- (1H, 1H-perfluorohexyloxy) phenol, p- (1H,
1H-perfluoroheptyloxy) phenol, p-
(1H, 1H-perfluorooctyloxy) phenol, p- (1H, 1H-perfluorononyloxy) phenol, p- (1H, 1H-perfluorodecyloxy) phenol, p- (1H, 1H-perfluorounoxy) Decyloxy) phenol, p- (1H, 1H-perfluorododecyloxy) phenol, p- (1H, 1H
-Perfluorotridecyloxy) phenol, perfluoropentyl p-hydroxybenzoate, perfluorohexyl p-hydroxybenzoate, perfluoroheptyl p-hydroxybenzoate, perfluorooctyl p-hydroxybenzoate, p-hydroxybenzoic acid Perfluorononyl, perfluorodecyl p-hydroxybenzoate, perfluoroundecyl p-hydroxybenzoate,
Perfluorododecyl p-hydroxybenzoate, (p-
(Hydroxybenzyl) perfluorohexane, (p-hydroxybenzyl) perfluoroheptane, (p-hydroxybenzyl) perfluorooctane, (p-hydroxybenzyl) perfluorononane, (p-hydroxybenzyl) perfluorodecane, (p- Examples thereof include hydroxybenzyl) perfluoroundecane and (p-hydroxybenzyl) perfluorododecane.

Among these, preferably used is p-
(Tert-butyl) phenol, p-phenylphenol, p- (perfluorolononylphenyl) phenol, p- (perfluoroxylphenyl) phenol,
p-tert-perfluorobutylphenol, 1-
(P-hydroxybenzyl) perfluorodecane, p-
(2- (1H, 1H-perfluorotridecyloxy)
-1,1,1,3,3,3-hexafluoropropyl)
Phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, perfluorododecyl p-hydroxybenzoate, p- (1H, 1H-perfluorooctyloxy) phenol, 2H, 2H, 9H-perfluorononanoic acid, etc. Is mentioned.

The terminal terminating agent and the branching agent are used in the presence of the above-mentioned dihydric phenols and divalent amines and / or aminophenols. As a method therefor, the above-mentioned two or three raw material compounds are used. And a method of increasing the molecular weight by coexisting with them from the beginning. After forming an oligomer composed of dihydric phenols or divalent amines and / or aminophenols, both of them are allowed to coexist when the molecular weight is increased. Method for molecular weight conversion After forming an oligomer consisting of dihydric phenols or divalent amines and / or aminophenols, a terminal stopper coexists with the oligomer first to react with the oligomer, and then a branching agent is added. Method of coexisting to make high molecular weight After preparing an oligomer consisting of dihydric phenols or dihydric amines and / or aminophenols, it is first divided into oligomers. Agent coexist reacted with the oligomer, then the method the molecular weight of the coexistence of terminating agent such as,
Various methods can be adopted.

The reaction in which polycondensation is carried out in the presence of an acid binder using various carbonyl dihalides such as phosgene, haloformates such as chloroformates, carbonic acid ester compounds and the like as carbonic acid ester forming compounds, Usually, it is carried out in a solvent. When a gaseous carbonic acid ester-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably adopted.

The proportion of the carbonic acid ester forming compound used is
It may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent amount) of the reaction. Examples of the acid binder include sodium hydroxide,
An alkali metal hydroxide such as potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, an organic base such as pyridine, or a mixture thereof is used.

The ratio of the acid binder to be used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, 2 equivalents or an excess thereof, preferably 2 to the total number of moles of divalent phenols, divalent amines and aminophenols used (usually 1 mole corresponds to 2 equivalents), preferably 2 to
It is preferred to use 10 equivalents of acid binder. 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 include hydrocarbon solvents such as toluene and xylene, and halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene. The interfacial polycondensation reaction may be carried out using two types of solvents that are immiscible with each other.

In order to accelerate the polycondensation reaction, it is desirable to carry out the reaction by adding a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt. If desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added. The reaction is
Usually, it is carried out at a temperature in the range of 0 to 150 ° C, preferably 5 to 40 ° C. The reaction pressure may be any of reduced pressure, normal pressure, and increased pressure, but normally, it can be suitably carried out at normal pressure or the self-pressure of the reaction system. The reaction time depends on the reaction temperature and the like, but is usually 0.5 minutes to 10 hours, preferably about 1 minute to 2 hours.

Further, first, a part of the reaction raw material consisting of dihydric phenols and divalent amines and / or aminophenols is reacted with a carbonic acid ester forming substance to form an oligomer, and then the remaining reaction raw materials are reacted. It is also possible to use a two-step method in which the polycondensation is completed by addition. According to such a two-step method, the reaction can be easily controlled, and the molecular weight can be controlled with high accuracy.

Examples of the latter bisaryl carbonate used in the transesterification method of the bisaryl carbonate with the divalent phenols and / or the divalent amines and / or aminophenols include, for example, diphenyl carbonate, di-p-tolyl carbonate, Phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate and the like can be mentioned.

As the reaction type of this transesterification method,
A melt polycondensation method, a solid phase polycondensation method, etc. are suitable. When the melt polycondensation method is carried out, dihydric phenols and dihydric amines and / or aminophenols are mixed with bisaryl carbonate and reacted in a molten state at high temperature under reduced pressure. The reaction is usually performed at a temperature in the range of 150 to 350 ° C, preferably 200 to 300 ° C. When the solid phase polycondensation method is carried out, the dihydric phenols and the divalent amines and / or aminophenols are mixed with the bisaryl carbonate and heated to a temperature below the melting point of the produced polycarbonate in the solid state. And polycondensation is performed. In any case, at the final stage of the reaction, the degree of pressure reduction is preferably set to 1 mmHg or less, and the phenols derived from the bisaryl carbonate produced by the transesterification reaction are distilled out of the system. Although the reaction time depends on the reaction temperature and the degree of reduced pressure, it is usually about 1 to 4 hours. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon, and if desired, the reaction may be carried out by adding the above-mentioned molecular weight modifier or antioxidant.

The reduced viscosity of the obtained polycarbonate can be controlled within the above range by various methods such as selection of the reaction conditions and adjustment of the amounts of the branching agent and the terminator used. In addition, in some cases, the obtained polycarbonate is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment,
It is also possible to obtain a polycarbonate having a predetermined reduced viscosity by subjecting it to a partial decomposition treatment or the like).

[2] Electrophotographic Photoreceptor The electrophotographic photoreceptor of the present invention contains in the photosensitive layer at least one of the above-mentioned urethane-bonded polycarbonates as a binder resin, a charge generating substance and a charge transporting substance. It is a thing. The electrophotographic photosensitive member of the present invention, as long as such a photosensitive layer is formed on a conductive substrate,
The structure thereof is not particularly limited, and may be any one of various known electrophotographic photoreceptors such as a single layer type and a laminated type, and the photosensitive layer may be at least one charge generation layer and at least one layer. It is preferably used as a binder resin for the charge transport layer in a laminated electrophotographic photosensitive member having one charge transport layer.

In the electrophotographic photosensitive member of the present invention, the above-mentioned polycarbonate may be used alone as a binder resin, or may be used in combination of two or more kinds. If desired, other resin components such as polycarbonate may be contained within a range that does not impair the achievement of the object of the present invention. As the material of the conductive substrate used in the electrophotographic photosensitive member of the present invention, various materials such as known materials can be used, and specifically, aluminum, nickel,
Chromium, palladium, titanium, gold, silver, copper, zinc, stainless steel, molybdenum, indium, platinum, brass, lead oxide, tin oxide, indium oxide, ITO or graphite plates, drums and sheets, and vapor deposition, sputtering, coating, etc. A glass, cloth, paper or plastic film that has been electrically conductive by being coated with
A sheet and a seamless belt, a plastic film laminated with a metal foil such as aluminum, a sheet and a seamless belt, a film-like sheet and a seamless belt of a metal plate, and a metal drum subjected to a metal oxidation treatment such as electrode oxidation can be used. .

The charge generating layer of the laminated electrophotographic photosensitive member contains at least a charge generating substance, and the charge generating layer is vacuum-deposited, sputtered, or CV-coated on the base substrate.
It can be obtained by forming a layer of the charge generating substance by the D method or the like, or by forming a layer obtained by binding the charge generating substance using a binder resin on the underlying layer. As the method for forming the charge generation layer using the binder resin, various methods such as a known method can be used. Usually, for example, a coating liquid in which the charge generation substance is dispersed or dissolved together with the binder resin in a suitable solvent. Is preferably applied on a layer serving as a predetermined base and dried.

As the charge generating substance, various substances such as known substances can be used. Specifically, selenium simple substance such as amorphous selenium and trigonal selenium, tellurium simple substance,
Selenium alloys such as selenium-tellurium alloys and selenium-arsenic alloys, selenium compounds such as As ₂ Se ₃ or selenium-containing compositions, alloys such as zinc oxide, cadmium sulfide, antimony sulfide, zinc sulfide, CdS-Se, 12th Inorganic materials made of Group 16 and Group 16 elements, oxide semiconductors such as titanium oxide, various inorganic materials such as silicon-based materials such as amorphous silicon, and metal-free phthalocyanines such as τ-type metal-free phthalocyanine and χ-type metal-free phthalocyanine Pigment, α-type copper phthalocyanine, β-type copper phthalocyanine, γ-type copper phthalocyanine, ε-type copper phthalocyanine, X-type copper phthalocyanine, A-type titanyl phthalocyanine, B-type titanyl phthalocyanine, C-type titanyl phthalocyanine, D-type titanyl phthalocyanine, E-type titanyl Phthalocyanine, F-type titanyl phthalocyanine H type titanyl phthalocyanine,
G-type titanyl phthalocyanine, K-type titanyl phthalocyanine, L-type titanyl phthalocyanine, M-type titanyl phthalocyanine, N-type titanyl phthalocyanine, titanyl phthalocyanine showing a strong diffraction peak at a black angle 2θ of 27.3 ± 0.2 degrees in an X-ray diffraction pattern. Metal phthalocyanine pigments, cyanine dyes, anthracene pigments, bisazo pigments, pyrene pigments, polycyclic quinone pigments, quinacridone pigments, indigo pigments, perylene pigments, pyrylium dyes, thiapyrylium dyes, polyvinylcarbazole, squarium pigments, anthanthrone pigments, Benzimidazole pigment, azo pigment, thioindigo pigment, bisbenzimidazole pigment, quinoline pigment, lake pigment, oxazine pigment, dioxazine pigment, triphenylmethane pigment, azurenium dye , Squarium dye, triarylmethane dye, xanthine dye, thiazine dye and the like.

For example, a compound represented by the following general formula is preferably used.

[0072]

[Chemical 28]

[Wherein Z ¹ , Z ² , Z ³ and Z ⁴ are each independently two carbon atoms on the pyrrole ring together with an aromatic hydrocarbon ring or heterocycle which may have a substituent. Represents an atomic group capable of forming, and M represents a metal atom or a metal compound which may have two hydrogen atoms or a ligand. ]

[0074]

[Chemical 29]

[Wherein Ar ⁶ represents a t-valent residue having a conjugated system which may contain an aromatic hydrocarbon ring or a heterocycle, t is a positive number of 1 or more, and Cp is an aromatic group. Represents a coupler residue having a group hydroxyl group, and when t is 2 or more,
Each Cp may be the same or different. ]

[0076]

Embedded image

[Wherein X ² , X ³ , X ⁴ and X ⁵ each independently represent an oxygen atom, a sulfur atom or a selenium atom, and R ¹⁶ and R ¹⁷ are an alkyl group having 1 to 12 carbon atoms or It represents an aryl group, and X ² or X ³ and R ¹⁶ and X ⁴ or X ⁵ and R ¹⁷ may form a heterocyclic ring which may have a substituent. Examples of the fluorene-based disazo pigment are as follows.

[0078]

[Chemical 31]

[0079]

Embedded image

[0080]

[Chemical 33]

The following are examples of perylene pigments.

[0082]

Embedded image

[0083]

Embedded image

Examples of polycyclic quinone pigments are as follows.

[0085]

Embedded image

Examples of the anthanthrone pigment are as follows.

[0087]

Embedded image

Examples of the dibenzpyrenequinone pigment are as follows.

[0089]

[Chemical 38]

Examples of pyranthrone pigments are as follows.

[0091]

[Chemical Formula 39]

These pigments may be used alone or in admixture of two or more. The thickness of the charge generation layer is 0.0
1 to 2.0 μm is preferable, and 0.1 to 0.8 μm is more preferable. If it is less than 0.01 μm, it is difficult to uniformly form the charge generation layer, and if it exceeds 2.0 μm, the electrophotographic characteristics tend to deteriorate. The binder resin used in the charge generating layer is not particularly limited, and various known resins can be used. Specifically, polystyrene, polyvinyl chloride, polyvinyl acetate,
Vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate, polyurethane, epoxy resin, phenol resin, polyamide, polyketone, polyacrylamide, butyral resin, polyester, vinylidene chloride-vinyl chloride copolymer Polymer, methacrylic resin, polystyrene, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene -Alkyd resin, poly-N-vinylcarbazole, polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, Cellulose, nitrocellulose, carboxy-methylcellulose, vinylidene chloride polymer latex, acrylonitrile-butadiene copolymer, vinyltoluene-styrene copolymer, soybean oil modified alkyd resin, nitrated polystyrene, polymethylstyrene, polyisoprene, polythio Thermosetting resins such as carbonate, polyarylate, polyhaloarylate, polyallyl ether, polyvinyl acrylate, melamine resin, polyether resin, benzoguanamine resin, epoxy acrylate resin, urethane acrylate resin and polyester acrylate can be used.

The above polycarbonate having a urethane bond may be used as the binder resin in the charge generation layer. Next, the charge transport layer can be obtained by forming a layer formed by binding a charge transport substance with a binder resin on a layer serving as a base (for example, a charge generation layer). As a method for forming the charge transport layer, various methods such as a known method can be used. Usually, a coating solution prepared by dispersing or dissolving the charge transport material together with the polycarbonate in a suitable solvent is used. The method of coating on the layer to be the base of, and drying is used.
The compounding ratio of the charge transport material and the polycarbonate in the charge transport layer is preferably 20:80 to 80:20 by weight,
More preferably, it is 30:70 to 70:30.

In the charge transport layer, the above-mentioned polycarbonate having a urethane bond may be used alone or in combination of two or more. Further, other resins such as those mentioned as the binder resin used for the charge generation layer may be used in combination with the above polycarbonate-based copolymer within a range that does not impair the achievement of the object of the present invention.

As the charge transport substance, various substances such as known substances can be used. For example, carbazole compound, indole compound, imidazole compound, oxazole compound, pyrazole compound, oxadiazole compound, pyrazoline compound, thiadiazole compound,
Aniline compounds, hydrazone compounds, aromatic amine compounds, aliphatic amine compounds, stilbene compounds, fluorenone compounds, quinone compounds, quinodimethane compounds, thiazole compounds, triazole compounds, imidazolone compounds, imidazolidine compounds, bisimidazolidine compounds, oxazolone compounds , Benzothiazole compound, benzimidazole compound, quinazoline compound, benzofuran compound, acridine compound, phenazine compound, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9
-Vinylphenylanthracene, pyrene-formaldehyde resin, ethylcarbazole resin, or a polymer having these in the main chain or side chain is used, and preferably a compound represented by the following general formula is used.

[0096]

[Chemical 40]

[Wherein Ar ¹ , Ar ² and Ar ³ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, or a carbon number. 6 to 12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic hetero group Represents a cyclic group, Ar ¹ and Ar ² , Ar ² and Ar ³
And Ar ³ and Ar ¹ may form a ring. ]

[0098]

Embedded image

[Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group or an arylamino group. Group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycycle Represents a formula hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, and a, b, c and d are 0 to 5 each independently
Is an integer. ]

[0100]

Embedded image

[Wherein Ar ¹ and Ar ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, or a carbon number 6-12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic hetero group It represents a cyclic group, and Ar ¹ and Ar ² may form a ring. R ¹ is a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group,
Alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted having 6 to 12 carbon atoms Represents an aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, R ⁵ Represents an ethylene group or an ethenylene group, and e is an integer of 0-4. ]

[0102]

[Chemical 43]

[Wherein Ar ¹ and Ar ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, or a carbon number. 6 to 12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic hetero group It represents a cyclic group, and Ar ¹ and Ar ² may form a ring. R ¹ is a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group,
Alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted having 6 to 12 carbon atoms Represents an aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, R ⁶ And R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and e is an integer of 0 to 4. ]

[0104]

[Chemical 44]

[In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted alkyl group having 7 to 13 carbon atoms. Or an unsubstituted aralkyl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic hetero group Represents a cyclic group or a condensed polycyclic heterocyclic group, Ar
⁶ and Ar ⁷ are each independently a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl compound having 6 to 12 carbon atoms, a polycyclic hydrocarbon, a substituted or unsubstituted condensed compound. Represents a divalent residue of a polycyclic hydrocarbon, a heterocyclic compound, a polycyclic heterocyclic compound or a condensed polycyclic heterocyclic compound, wherein Ar ¹ and Ar ² and Ar ³ and Ar ⁴ may form a ring. Good. ]

[0106]

Embedded image

[In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 13 carbon atoms. Aralkyl group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group Or a condensed polycyclic heterocyclic group, Ar ¹ and Ar ²
And Ar ³ and Ar ⁴ may form a ring. R ⁸ and R ⁹ are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group,
Alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted having 6 to 12 carbon atoms Represents an aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, e and f is 0 to 4 independently
Is an integer. ]

[0108]

Embedded image

[Wherein Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 13 carbon atoms] Aralkyl group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group Or a condensed polycyclic heterocyclic group, Ar ¹ and Ar ²
And Ar ³ and Ar ⁴ may form a ring. R ¹ , R ² and R ³ are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, and a carbon number of 1 to 1. A substituted or unsubstituted alkyl group having 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted It represents a condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, and e, f and g are each independently an integer of 0 to 4. X ¹ is -O-, -S-, -Se
-, - Te -, - CR 10 R 11 -, - SiR 10 R 11 -, -
NR ¹⁰ - or -PR ¹⁰ - (wherein, each independently R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom, an alkylamino group, an arylamino group, aralkylamino group, having 1 to 10 carbon atoms
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group,
It represents a substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or fused polycyclic heterocyclic group. ) Represents. ]

[0110]

[Chemical 47]

[Wherein Ar ¹ and Ar ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, or a carbon number. 6-12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic hetero group It represents a cyclic group, and Ar ¹ and Ar ² may form a ring. R ¹ is a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group,
Alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted having 6 to 12 carbon atoms Represents an aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, and a is It is an integer of 0-5. ]

[0112]

Embedded image

[Wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted alkyl group having 7 to 13 carbon atoms] Or an unsubstituted aralkyl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic hetero group Represents a cyclic group or a condensed polycyclic heterocyclic group, R ¹
And R ² are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, a substituted or unsubstituted C 1-10 group. Substituted alkyl group, C7-13 substituted or unsubstituted aralkyl group, C6-12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic carbon group Represents a hydrogen group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, Ar ¹ and Ar ² and Ar
³ and Ar ⁴ may form a ring. f and e are each independently an integer of 0 to 4. ]

[0114]

[Chemical 49]

[In the formula, Ar ¹ is a hydrogen atom and has 1 to 1 carbon atoms.
A substituted or unsubstituted alkyl group having 0 to 7 carbon atoms
Substituted or unsubstituted aralkyl group having 6 to 12 carbon atoms
, A substituted or unsubstituted aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group And R ¹ , R ² and R ³ are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, a carbon atom. A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, substituted or An unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic heterocyclic group, n is 0 or 1, a, b and c are each independently It is an integer of 0-5. ]

[0116]

Embedded image

[In the formula, Ar ¹ , Ar ² and Ar ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms. Group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed Represents a polycyclic heterocyclic group, R ¹ and R ³ are each independently cyano group, halogen atom, carboxyl group, acyl group, hydroxyl group, nitro group, amino group, alkylamino group, arylamino group, aralkyl Amino group,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substitution Or an unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic heterocyclic group, wherein R ² ′ is a hydrogen atom, a cyano group, a halogen atom or a carboxyl group. Group, acyl group, hydroxyl group,
Nitro group, amino group, alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, and 6 to carbon atoms 12 substituted or unsubstituted aryl groups, polycyclic hydrocarbon groups, substituted or unsubstituted condensed polycyclic hydrocarbon groups, heterocyclic groups, polycyclic heterocyclic groups or condensed polycyclic heterocyclic groups Represents a group, n is 0 or 1, e is an integer of 0 to 4, and h is an integer of 0 to 3. ]

[0118]

[Chemical 51]

[Wherein Ar ¹ and Ar ² are each independently a hydrogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms. A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic group. It represents a cyclic heterocyclic group, and Ar ¹ and Ar ² may form a ring. ]

[0120]

Embedded image

[Wherein Ar ¹ , Ar ² and Ar ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms. A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic group. It represents a cyclic heterocyclic group, and Ar ¹ and Ar ² may form a ring. ]

[0122]

Embedded image

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁸ and R ⁹
Are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group,
Alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted having 6 to 12 carbon atoms Represents an aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, a, b, c, d, i and j are each independently an integer of 0-5. ]

[0124]

[Chemical 54]

[Wherein Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 13 carbon atoms] Aralkyl group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group Or a condensed polycyclic heterocyclic group, Ar ⁶ is a substituted or unsubstituted alkylene group having 1 to ⁶ carbon atoms or a substituted or unsubstituted aryl compound having 6 to 12 carbon atoms, a polycyclic hydrocarbon, A substituted or unsubstituted condensed polycyclic hydrocarbon, heterocyclic compound, polycyclic heterocyclic compound or divalent residue of condensed polycyclic heterocyclic compound, wherein Ar ¹ and Ar ² and Ar
³ and Ar ⁴ may form a ring, and n is 0 or 1. ]

[0126]

[Chemical 55]

[Wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 13 carbon atoms] Aralkyl group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group Alternatively, it represents a condensed polycyclic heterocyclic group. ] Specifically, the following compounds are used.

[0128]

[Chemical 56]

[0129]

[Chemical 57]

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

[0133]

[Chemical formula 61]

[0134]

Embedded image

[0135]

[Chemical formula 63]

[0136]

[Chemical 64]

[0137]

Embedded image

[0138]

[Chemical formula 66]

[0139]

Embedded image

[0140]

[Chemical 68]

[0141]

[Chemical 69]

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

[Chemical 74]

[0147]

[Chemical 75]

[0148]

[Chemical 76]

[0149]

Embedded image

[0150]

Embedded image

[0151]

Embedded image

[0152]

Embedded image

[0153]

[Chemical 81]

[0154]

[Chemical formula 82]

[0155]

[Chemical 83]

[0156]

[Chemical 84]

[0157]

Embedded image

[0158]

[Chemical 86]

[0159]

[Chemical 87]

[0160]

Embedded image

[0161]

[Chemical 89]

[0162]

[Chemical 90]

[0163]

Embedded image

[0164]

Embedded image

[0165]

Embedded image

[0166]

Embedded image

[0167]

Embedded image

[0168]

[Chemical 96]

[0169]

Embedded image

[0170]

Embedded image

[0171]

Embedded image

[0172]

[Chemical 100]

[0173]

[Chemical 101]

The above charge transport materials may be used alone or in admixture of two or more. The thickness of the charge transport layer is 5
100 μm is preferable, and 10 to 30 μm is more preferable. If it is less than 5 μm, the initial potential will be low and 100
If it exceeds μm, the electrophotographic characteristics tend to deteriorate.
A well-known subbing layer as commonly used can be provided between the conductive substrate and the photosensitive layer. As the undercoat layer,
Fine particles of titanium oxide, aluminum oxide, zirconia, titanic acid, zirconic acid, lead lanthanum, titanium black, silica, lead titanate, barium titanate, tin oxide, indium oxide, silicon oxide, etc., polyamide resin, phenol resin, casein, Melamine resin, benzoguanamine resin, polyurethane resin, epoxy resin, cellulose,
Components such as nitrocellulose, polyvinyl alcohol, and polyvinyl butyral resin can be used. These fine particles and resins can be used alone or in admixture of two or more. Especially when fine particles are used, the resin is adsorbed on the fine particles and a smooth film can be obtained. Therefore, it is desirable to use the fine particles and the resin together. The binder resin can be used for the undercoat layer. Further, the above polycarbonate can also be used.

The thickness of the undercoat layer is usually 0.01-10.
It is 0 μm, preferably 0.01 to 1.0 μm. If the thickness is less than 0.01 μm, it may be difficult to uniformly form the undercoat layer, and if it is more than 10.0 μm, the electrophotographic properties may deteriorate. Further, a known blocking layer which is usually used can be provided between the conductive substrate and the photosensitive layer. The binder resin can be used in the blocking layer. The thickness of the blocking layer is usually 0.01 to 20.0 μm, preferably 0.1 to 10.0 μm. This thickness is 0.01
If it is less than μm, it may be difficult to uniformly form the blocking layer, and if it exceeds 20.0 μm, the electrophotographic properties may deteriorate.

In the electrophotographic photosensitive member of the present invention, a protective layer may be laminated on the photosensitive layer. The thickness of the protective layer is 0.01 to
20 μm is possible, and more preferably 0.1 to 10 μm.
m. The binder resin can be used for the protective layer. The protective layer may contain a conductive material such as the above-mentioned charge generating substance, charge transporting substance, additive, metal and oxides, nitrides, salts, alloys and carbon thereof.

Further, in order to improve the performance of the electrophotographic photoreceptor of the present invention, a binder, a plasticizer, a curing catalyst, a fluidizing agent, a pinhole control agent, an electrophotographic agent are added to the charge generation layer and the charge transport layer. In addition to the spectral sensitivity sensitizer (sensitizing agent) for improving sensitivity and the spectral sensitivity sensitizer, the purpose is to prevent an increase in residual potential, a decrease in charging potential, and a decrease in sensitivity with repeated use. Additives such as various chemical substances, antioxidants, surfactants, anti-curl agents, leveling agents and the like can be added.

Specific examples of the binder include silicone resin, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polystyrene resin, polymethacrylate resin, polyacrylamide resin, polybutadiene resin, polyisoprene. Resin, melamine resin, benzoguanamine resin, polychloroprene resin, polyacrylonitrile resin, ethyl cellulose resin, nitrocellulose resin, urea resin, phenol resin, phenoxy resin, polyvinyl butyral resin, formal resin, vinyl acetate resin, vinyl acetate / vinyl chloride copolymer Examples include coalescing and polyester carbonate resins. Further, a heat and / or light curable resin can also be used. In any case, there is no particular limitation as long as it is an electrically insulating resin that can form a film in a normal state.

The binder is 5 to 20 relative to the charge transport material.
It is preferable to add 0% by weight, and 10 to 100% by weight
Is more preferable. If it is less than 5% by weight, the film of the photosensitive layer tends to be non-uniform and the image quality tends to be poor. If it exceeds 20% by weight, the sensitivity tends to decrease and the residual potential tends to increase. Specific examples of the plasticizer include biphenyl, biphenyl chloride, o-terphenyl, halogenated paraffin,
Dimethyl naphthalene, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethylene glycol phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate, dimethyl glycol phthalate, methyl naphthalene, benzophenone , Polypropylene, polystyrene, various fluorohydrocarbons, and the like.

Specific examples of the curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid and the like. Examples of the fluidizing agent include modaflow and acronal 4F. Examples of the pinhole control agent include benzoin and dimethyl phthalate.

The plasticizer, curing catalyst, fluidizing agent, and pinhole control agent are preferably used in an amount of 5% by weight or less based on the charge transport material. Specific examples of the sensitizing dye include triphenylmethane dyes such as methyl violet, crystal violet, night blue, and Victoria blue, erythrosine, rhodamine B, rhodamine 3R, acridine orange, and flapeosin. Acridine dyes, thiazine dyes represented by methylene blue, methylene green, etc., oxazine dyes represented by capri blue, meldra blue, etc., and other cyanine dyes, merocyanine dyes, styryl dyes, pyrylium salt dyes, thiopyrylium salt dyes, etc. .

An electron-accepting substance may be added to the photosensitive layer for the purpose of improving sensitivity and reducing residual potential to fatigue during repeated use. Examples of the electron acceptor include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, and anhydrous Pyromellitic acid, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide, Chloranil, bromanil, benzoquinone, 2,3-dichlorobenzoquinone, dichlorodicyanoparabenzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone,
1-chloroanthraquinone, dinitrotroanthraquinone, 4-nitrobenzophenone, 4,4-nitrobenzophenone, 4-nitrobenzalmalondinitrile, α-
Ethyl cyano-β- (p-cyanophenyl) acrylate, 9-anthracenylmethylmalondinitrile, 1-
Cyano- (p-nitrophenyl) -2- (p-chlorophenyl) ethylene, 2,7-dinitrofluorenone,
2,4,7-trinitrofluorenone, 2,4,5,7
-Tetranitrofluorenone, 9-fluorenylidene [dicyanomethylene malononitrile], polynitro-9
-Fluorenylidene- [dicyanomethylene malonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid , Phthalic acid, mellitic acid, and other compounds with high electron affinity.

This electron-accepting substance may be added to either the charge-transporting layer or the charge-generating layer, and is usually 0.01 to 200% by weight, more preferably 0.1 to 200% by weight based on the charge-transporting substance or the charge-generating substance. ˜50% by weight. In order to improve the surface property, tetrafluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluorodichloroethylene resin. Also, a copolymer thereof or a fluorine-based graft polymer may be used.

These surface modifiers are contained in the binder resin in an amount of 0.1 to 60% by weight, preferably 5 to 40% by weight.
It is blended by weight%. If it is less than 0.1% by weight, surface modification such as abrasion resistance, surface durability and reduction of surface energy is not sufficient, and if it is more than 60% by weight, electrophotographic properties may be deteriorated. Examples of the antioxidant include hindered phenol-based antioxidants, aromatic amine-based antioxidants, hindered amine-based antioxidants, sulfide-based antioxidants, organic phosphoric acid-based antioxidants and the like.

These antioxidants are usually used in an amount of 0.01 to 10% by weight, more preferably 0.1 to 10% by weight based on the charge transport material.
2% by weight is blended. The following are examples of hindered phenolic antioxidants.

[0186]

Embedded image

[0187]

Embedded image

[0188]

[Chemical 104]

The following are examples of aromatic amine antioxidants.

[0190]

Embedded image

As the hindered amine antioxidant,
There are the following examples.

[0192]

[Chemical formula 106]

Examples of the sulfide antioxidants are as follows.

[0194]

[Chemical formula 107]

Examples of the organic phosphoric acid type antioxidant are as follows.

[0196]

[Chemical 108]

Examples of the antioxidant having a hindered phenol structural unit and a hindered amine structural unit in the molecule are as follows.

[0198]

[Chemical 109]

These additives may be used alone or in combination of two or more. These additives may be added to the protective layer, the undercoat layer and the blocking layer. The charge generation layer, specific examples of the solvent used in the formation of the charge transport layer, for example, benzene, toluene, xylene, aromatic solvents such as chlorobenzene, acetone, methyl ethyl ketone, ketone such as cyclohexanone, methanol, Ethanol, alcohols such as isopropanol, ethyl acetate, esters such as ethyl cellosolve, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane and tetrachloroethane, ethers such as tetrahydrofuran and dioxane,
Examples thereof include dimethylformamide, dimethylsulfoxide, diethylformamide and the like.

These solvents may be used alone or in combination of two or more.
As a method of forming a photoreceptor, the charge generating substance, the charge transporting substance, the additive and the binder resin are dispersed in a solvent,
Alternatively, the dissolved solution is applied to a substrate as a predetermined base, a layer, a dip coating method, an electrostatic coating method, a powder coating method, a spray coating method, a roll coating method, an applicator coating method, a spray coater coating method, a bar coater coating method. , Roll coater coating method,
Coating using dip coater coating method, doctor blade coating method, wire bar coating method, knife coater coating method, attritor coating method, spinner coating method, bead coating method, blade coating method, curtain coating method, etc. It can be dried and formed.

As the dispersion method, a ball mill, an ultrasonic wave, a paint shaker, a red devil, a sand mill,
A mixer, an attritor or the like can be used. Also in the single-layer type electrophotographic photoreceptor, the binder resin can be used in the photosensitive layer. The charge generating substance and the charge transporting substance described above can be used for the photosensitive layer of the single-layer type photoreceptor. Further, the above-mentioned additives may be used in order to improve the electrophotographic characteristics of the photosensitive layer. Also a protective layer,
An undercoat layer and a blocking layer may be provided.

The film thickness of the single-layer type photoreceptor is usually 5 to 100 μm.
Is preferable, and 8-50 micrometers is more preferable. If it is less than 5 μm, the initial potential tends to be low, and if it exceeds 50 μm, the electrophotographic properties tend to deteriorate. The ratio by weight of the charge generating substance: polycarbonate in the photosensitive layer of the single-layer type electrophotographic photosensitive member is preferably 20:80 to 80: 2.
It is 0, more preferably 30:70 to 60:40.
The ratio by weight of the charge transport material: polycarbonate is preferably 20:80 to 80:20, more preferably 30:70 to 70:30. The ratio of the charge generating substance to the charge transporting substance by weight is preferably 2
0:80 to 70:30, more preferably 30:70 to
It is 60:40.

It is also possible to use other resins in combination with the polycarbonate of the present invention within the range that does not impair the achievement of the object of the present invention. The layer structure of the photosensitive layer of the electrophotographic photosensitive member of the present invention is preferably such that the above-mentioned layer containing polycarbonate serves as the surface layer of the photosensitive layer. The electrophotographic photosensitive member of the present invention thus obtained is a photosensitive member having a high surface hardness and maintaining excellent printing durability and good cleaning property for a long period of time, and can be used in copying machines (monochrome, multicolor, Full color; analog, digital), printer (laser, LED, liquid crystal shutter), FAX, plate making machine, and various other electrophotographic fields can be suitably used.

When the electrophotographic photosensitive member of the present invention is used, corona discharge (corotron, scotron), contact charging (charging roll, charging brush) or the like is used as the charger. The exposure is performed by a halogen lamp, a fluorescent lamp, a laser (semiconductor, He-Ne), an LED, and a photoconductor internal exposure method. As the developing process, a dry developing method such as cascade developing, two-component magnetic brush developing, one-component insulating toner developing, and one-component conductive toner developing, a wet developing method, or the like is used. In the transfer step, an electrostatic transfer method such as corona transfer, roller transfer, belt transfer, a pressure transfer method, or an adhesive transfer method is used. For fixing, heat roller fixing, radiant flash fixing, oven fixing, pressure fixing and the like are used. A brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, etc. are used for cleaning and charge removal.

[0205]

The present invention will be described in more detail below with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples. Synthesis Example 1 Polycarbonate containing urethane bond (PC-
Synthesis of 1) 2,2-bis (4-hydroxyphenyl) propane 74
550 ml of 6% by weight aqueous sodium hydroxide solution
A solution of phosgene gas (95 ml) was mixed with 250 ml of methylene chloride while stirring with cooling.
Bubbling was carried out for 15 minutes at a rate of 0 ml / min. Then, the reaction solution was allowed to stand to separate the organic layer, and bisphenol A (2,2-bis (4
A methylene chloride solution of polycarbonate of -hydroxyphenyl) propane) was obtained.

Methylene chloride was added to the methylene chloride solution to bring the total amount to 450 ml, and the mixture was mixed with 150 ml of an 8% by weight aqueous sodium hydroxide solution, and 9.0 g of piperazine and p-tert- as a molecular weight regulator were added thereto. Butylphenol 3.0 g was added. Next, while vigorously stirring this mixed solution, 2 ml of a 7 wt% concentration triethylamine aqueous solution was added as a catalyst, and the reaction was carried out at 28 ° C. for 1.5 hours with stirring. After completion of the reaction, the reaction product was diluted with 1 liter of methylene chloride, then twice with 1.5 liter of water, once with 1 liter of 0.01 N hydrochloric acid, and with water 1 liter.
It was washed with liter twice in this order, the organic layer was put into methanol, and the precipitated polymer was filtered and dried to obtain 77 g of polycarbonate (PC-1).

Polycarbonate thus obtained
0.5g / dl solution using methylene chloride as a solvent
Viscosity at 20 ° C [η_sp/ C] is 0.73 dl
/ G. The reduced viscosity was measured by the self-made company
Using the kinematic viscosity measuring device VMR-042,
It was measured by a Cubbellode modified viscometer (RM type). Obtained
Spectrum analysis of polycarbonate (PC-1)
The result of is 3030cm^-1, 1590cm^-1, 830c
m^-1Absorption of benzene ring, 1730cm ^-1In carbon
Absorption by To group, 1650 cm^-1Absorption by amide group
Is found, having a carbonate bond and a urethane bond
Was confirmed. The obtained polycarbonate (PC-
The copolymer composition of 1) is¹Determined by 1 H-NMR analysis.
From these analysis results, polycarbonate (PC-1)
Contains the following repeating units with the following composition:
won.

[0208]

[Chemical 110]

Synthesis Example 2 Synthesis of Urethane Bond-Containing Polycarbonate (PC-2) By the same procedure as in Synthesis Example 1 except that 9.0 g of piperazine was changed to 4.5 g of piperazine and 12.1 g of bisphenol A in Synthesis Example 1. Polycarbonate (PC-2) having the following structure ([η _sp /c]=0.72d
81 g of 1 / g) were obtained. This polycarbonate (PC-
When the structure and composition of 2) were confirmed by IR spectrum analysis, absorption similar to that of the polycarbonate obtained in Synthesis Example 1 was observed, and it was found to have the following structure and composition.

[0210]

[Chemical 111]

Synthesis Example 3 Synthesis of Polycarbonate Containing Urethane Bond (PC-3) Synthesis Example 1 except that 9.0 g of piperazine was changed to 21.8 g of 1,3-bis (4-piperidyl) propane in Synthesis Example 1. By the same operation, polycarbonate (PC-3) having the following structure ([η _sp /c]=0.62 dl
/ G) 84g was obtained.

IR of this polycarbonate (PC-3)
The result of the spectrum analysis is 3030 cm ^-1 , 1590c
m ^-1, the absorption of the benzene ring to 830 cm ^-1, 1730 cm
^-1 for absorption by carbonate groups, absorption was observed by an amide group 1650 cm ^-1, to have a carbonate bond and urethane bond was observed. The copolymer composition of the obtained polycarbonate (PC-3) was determined by ¹ H-NMR analysis. From these analysis results, it was found that the polycarbonate (PC-3) contains the following repeating units with the following composition.

[0213]

[Chemical 112]

Synthesis Example 4 Synthesis of urethane bond-containing polycarbonate (PC-4) Synthesis Example 1 except that 9.0 g of piperazine was changed to 20.7 g of 1,4-bis (3-aminopropyl) piperazine in Synthesis example 1. By the same operation as described above, polycarbonate (PC-4) ([η _sp /c]=0.6 having the following structure
82 g (0 dl / g) was obtained.

IR of this polycarbonate (PC-4)
The result of the spectrum analysis is 3030 cm ^-1 , 1590c
m ^-1, the absorption of the benzene ring to 830 cm ^-1, 1730 cm
^-1 for absorption by carbonate groups, absorption was observed by an amide group 1650 cm ^-1, to have a carbonate bond and urethane bond was observed. The copolymer composition of the obtained polycarbonate (PC-4) was determined by ¹ H-NMR analysis. From these analysis results, it was found that the polycarbonate (PC-4) contained the following repeating units with the following composition.

[0216]

[Chemical 113]

Synthesis Example 5 Synthesis of Polycarbonate Containing Urethane Bond (PC-5) The same procedure as in Synthesis Example 1 was repeated except that 9.0 g of piperazine was changed to 11.4 g of 4-aminophenol in Synthesis Example 1. Structure polycarbonate (PC-
5) 79 g of ([η _sp /c]=0.71 dl / g) were obtained. Result of IR spectrum analysis of this polycarbonate ^{(PC-5), 3030cm -1} , 1590cm -1, 8
Absorption of the benzene ring to 30 cm ^-1, absorption by carbonate groups to 1730 cm ^-1, absorption was observed by an amide group 1650 cm ^-1, to have a carbonate bond and urethane bond was observed. The copolymer composition of the obtained polycarbonate (PC-5) was determined by ¹ H-NMR analysis. From these analysis results, polycarbonate (P
It was found that C-5) contained the following repeating unit with the following composition.

[0218]

[Chemical 114]

Synthesis Example 6 Synthesis of Polycarbonate Containing Urethane Bond (PC-6) By the same operation as in Synthesis Example 1, except that 9.0 g of piperazine was changed to 7.7 g of 1,3-diaminopropane in Synthesis Example 1. Polycarbonate (PC
-6) 77 g of ([η _sp /c]=0.58 dl / g) were obtained. Result of IR spectrum analysis of this polycarbonate ^{(PC-6), 3030cm -1} , 1590cm -1, 8
Absorption of the benzene ring to 30 cm ^-1, absorption by carbonate groups to 1730 cm ^-1, absorption was observed by an amide group 1650 cm ^-1, to have a carbonate bond and urethane bond was observed. The copolymer composition of the obtained polycarbonate (PC-6) was determined by ¹ H-NMR analysis. From these analysis results, polycarbonate (P
It was found that C-6) contained the following repeating unit with the following composition.

[0220]

[Chemical 115]

Synthesis Example 7 Synthesis of Urethane Bond-Containing Polycarbonate (PC-7) By the same operation as in Synthesis Example 1 except that 9.0 g of piperazine was changed to 9.2 g of 1,3-diaminobutane in Synthesis Example 1. Polycarbonate (PC-
7) (78) ([η _sp /c]=0.55 dl / g) was obtained. Result of IR spectrum analysis of this polycarbonate ^{(PC-7), 3030cm -1} , 1590cm -1, 8
Absorption of the benzene ring to 30 cm ^-1, absorption by carbonate groups to 1730 cm ^-1, absorption was observed by an amide group 1650 cm ^-1, to have a carbonate bond and urethane bond was observed. The copolymer composition of the obtained polycarbonate (PC-7) was determined by ¹ H-NMR analysis. From these analysis results, polycarbonate (P
It was found that C-7) contained the following repeating unit with the following composition.

[0222]

[Chemical formula 116]

Example 1 (C-1) was used as the charge transport material, (PC-1) was used as the binder resin, and C-1: PC-1: methylene chloride = 1: 1: 8 (weight ratio). A solution was prepared and used as a coating liquid. Even when the coating solution was allowed to stand for 1 month, no cloudiness or gel formation was observed. A dispersion liquid of oxotitanium phthalocyanine: butyral resin: methylene chloride = 1: 1: 38 (weight ratio) was applied on a conductive substrate made of aluminum by a dip coating method, and an oxotitanium phthalocyanine layer (about 0.5 μm) was charged. Formed as a generation layer,
The above-mentioned coating liquid was applied onto the charge generation layer by a dip coating method and dried to form a charge transport layer having a thickness of about 20 μm, to prepare a laminated electrophotographic photoreceptor. The charge transport layer did not crystallize during coating.

[0224]

[Chemical 117]

The electrophotographic characteristics of the obtained electrophotographic photosensitive member were evaluated by using an electrostatic charging tester EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.) to carry out corona discharge of -6 kV to obtain an initial surface potential (V ₀ ), Light irradiation (10 Lux) 5
The residual potential (V _R ) and the half-exposure amount (E _1/2 ) after 2 seconds were measured. The results are shown in Table 1. Furthermore, the abrasion resistance of the charge transport layer was evaluated using a Suga abrasion tester NUS-ISO-3 type (manufactured by Suga Test Instruments Co., Ltd.). The test conditions were evaluated by reciprocating the sample of the above laminated electrophotographic photosensitive member 1200 times on a worn paper loaded with 200 g and measuring the change in the amount of decrease. Table 2 shows the results.

Example 2 A photoconductor was prepared in the same manner as in Example 1 except that PC-2 was used instead of PC-1 used in Example 1, and the initial surface potential (V ₀ ), Light irradiation (10 Lux) 5
The residual potential (V _R ) after half a second, the half-exposure amount (E _1/2 ) and the amount of decrease in the charge transport layer due to abrasion were measured. The results are shown in Tables 1 and 2.

Example 3 A photoconductor was prepared in the same manner as in Example 1 except that PC-3 was used instead of PC-1 used in Example 1, and the initial surface potential (V ₀ ), Light irradiation (10 Lux) 5
The residual potential (V _R ) after half a second, the half-exposure amount (E _1/2 ) and the amount of decrease in the charge transport layer due to abrasion were measured. The results are shown in Tables 1 and 2.

Example 4 A photoconductor was prepared in the same manner as in Example 1 except that PC-4 was used instead of PC-1 used in Example 1, and the initial surface potential (V ₀ ), Light irradiation (10 Lux) 5
The residual potential (V _R ) after half a second, the half-exposure amount (E _1/2 ) and the amount of decrease in the charge transport layer due to abrasion were measured. The results are shown in Tables 1 and 2.

Example 5 A photoconductor was prepared in the same manner as in Example 1 except that PC-5 was used in place of PC-1 used in Example 1, and the initial surface potential (V ₀ ), Light irradiation (10 Lux) 5
The residual potential (V _R ) after half a second, the half-exposure amount (E _1/2 ) and the amount of decrease in the charge transport layer due to abrasion were measured. The results are shown in Tables 1 and 2.

Example 6 A photoreceptor was prepared in the same manner as in Example 1 except that PC-6 was used in place of PC-1 used in Example 1, and the initial surface potential (V ₀ ), Light irradiation (10 Lux) 5
The residual potential (V _R ) after half a second, the half-exposure amount (E _1/2 ) and the amount of decrease in the charge transport layer due to abrasion were measured. The results are shown in Tables 1 and 2.

Example 7 A photoreceptor was prepared in the same manner as in Example 1 except that PC-7 was used in place of PC-1 used in Example 1, and the initial surface potential (V ₀ ), Light irradiation (10 Lux) 5
The residual potential (V _R ) after half a second, the half-exposure amount (E _1/2 ) and the amount of decrease in the charge transport layer due to abrasion were measured. The results are shown in Tables 1 and 2.

Comparative Example 1 Using bisphenol Z as a raw material, a polycarbonate (reduced viscosity: 0.84 dl / g) consisting of the following repeating units was used as a binder resin, and (C-
An electrophotographic photosensitive member was produced in the same manner as in Example 1 using 1). The results are shown in Tables 1 and 2.

[0233]

[Chemical 118]

[0234]

[Table 1]

[0235]

[Table 2]

[0236]

INDUSTRIAL APPLICABILITY The electrophotographic photoreceptor of the present invention uses polycarbonate, which is resistant to crystallization and gelation and has excellent abrasion resistance, as a binder resin in the photosensitive layer. In the coating liquid does not whiten (gel), the adhesiveness between the conductive substrate and the photosensitive layer and the abrasion resistance of the surface of the photoconductor are improved, and the life of the electrophotographic photoconductor can be prolonged, Excellent electrophotographic characteristics can be maintained even after repeated use for a long time.

Claims (9)

[Claims] 1. An electrophotographic photosensitive member comprising a conductive substrate and a photosensitive layer containing a charge generating substance, a charge transporting substance and a binder resin, wherein the photosensitive layer is a binder resin.
An electrophotographic photoreceptor containing a polycarbonate having a urethane bond. 2. The electrophotographic photosensitive member according to claim 1, wherein a solution of polycarbonate having a concentration of 0.5 g / dl in methylene chloride as a solvent has a reduced viscosity at 20 ° C. of 0.1 to 20 dl / g. 3. A polycarbonate having a urethane bond contains a repeating unit (I) represented by the following general formula (I) and a repeating unit (II) represented by the following general formula (II) as a main component. The electrophotographic photosensitive member according to claim 1. Embedded image [In the formula, Ar represents the following general formula (III): (In the formula, R ⁵⁰ and R ⁵¹ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. , Y is a single bond, -O-, -CO-, -S-, -S.
_{O -, - SO 2 -,} - CR 52 R 53 - (R 52 and R ⁵³ each independently represent a hydrogen atom, a trifluoromethyl group, 1 to 4 carbon atoms
Is an alkyl group having 6 to 6 or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. ), 1, 1 having 5 to 11 carbon atoms
-Cycloalkylidene group or α, ω- having 2 to 12 carbon atoms
It represents an alkylene group, and A and B each independently represent an integer of 0-4. ) Is a divalent group represented by the formula (1) and W is represented by the following general formulas (IV) to (VIII): (In the formula, X is a single bond, -O-, -S-, -SO-, -S.
O ₂ —, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, an alkynylene group or an alkylidene group, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms An alkylene group,
A substituted or unsubstituted divalent aromatic group having 6 to 36 carbon atoms, a substituted or unsubstituted divalent nitrogen-containing heterocyclic group having 3 to 18 carbon atoms, a sulfur-containing heterocyclic group or an oxygen-containing heterocycle Formula group, divalent residue of substituted or unsubstituted amine compound having 2 to 20 carbon atoms, divalent residue of substituted or unsubstituted ester compound, amide compound or sulfide compound having 2 to 20 carbon atoms or these 2 R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ represents a group consisting of a combination of valent groups.
And R ⁶² each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group or alkynyl group having 2 to 20 carbon atoms, and 3 to 20 carbon atoms. Or a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aromatic group having 6 to 36 carbon atoms, a substituted or unsubstituted nitrogen-containing heterocyclic group having 3 to 18 carbon atoms, a sulfur-containing heterocyclic group, or An oxygen-containing heterocyclic group or a monovalent residue of a substituted or unsubstituted epoxide compound having 2 to 20 carbon atoms, n ¹ and n ² are n ¹ + n ² = 1 to
6 is an integer that satisfies 6, n ³ is an integer of 0 to 6,
n ⁴ and n ⁵ are integers satisfying n ⁴ + n ⁵ = 1 to 6,
n ⁶ and n ⁷ are integers satisfying n ⁶ + n ⁷ = 1 to 6,
n ⁸ and n ¹⁰ are each independently an integer of 0 to 6, and n ⁹ and n ¹¹ are each independently 0 or 1. ) Represents a divalent group. ] 4. Ar is represented by: And W is The electrophotographic photoreceptor according to claim 3, wherein 5. Ar is represented by: And W is The electrophotographic photoreceptor according to claim 3, wherein 6. Ar is represented by: And W is The electrophotographic photoreceptor according to claim 3, wherein 7. Ar is represented by: And W is The electrophotographic photoreceptor according to claim 3, wherein 8. Ar is And W is The electrophotographic photoreceptor according to claim 3, wherein 9. A polycarbonate containing a repeating unit (I) and a repeating unit (II) as a main component, wherein the ratio of the repeating unit (II) to the total moles of the repeating unit (I) and the repeating unit (II) is 1 to 50. The electrophotographic photosensitive member according to any one of claims 4 to 8, wherein the electrophotographic photosensitive member is in a mol%.