JPH0632884A - Polycarbonate polymer, its production and electrophotographic sensitized material using the same - Google Patents

Abstract

PURPOSE:To obtain a new polymer having a specific repeating unit and a specific reduced viscosity value by reacting 4,4'-dihydroxyoctafluorobiphenyl, etc., with a carbonic acid ester-forming compound. CONSTITUTION:(A) 4,4'-Dihydroxyoctafluorobiphenyl or this component A and a bihydric phenol of formula I (R<1> and R<2> are Cl, Br, 1-6C alkyl, etc.; (a) and (b) are 0-4; X is single bond; O, S, 1-12C alpha,omega-alkylene, etc.) are reacted with (B) a carbonic acid ester-forming compound (e.g. phosgene) to give the objective polymer having a repeating unit of formula II or repeating units of the formula II and a formula III and 0.2-2.5dl/g reduced viscosity (musp/c) in 0.5g/dl solution in methylene chloride as a solvent at 20 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polycarbonate polymer, a method for producing the same, and an electrophotographic photoreceptor using the same. More specifically, the present invention uses a novel polycarbonate polymer that can be suitably used as a binder resin in a photosensitive layer of an electrophotographic photoreceptor, a material for an EL device, etc., a method for producing the same, and the polycarbonate polymer. The present invention relates to an electrophotographic photoreceptor having excellent printing durability and electrophotographic characteristics manufactured by the method.

[0002]

2. Description of the Related Art Polycarbonate is used as a raw material in various fields, and it has been desired to develop one having higher performance as the fields of application expand.

In recent electrophotographic photosensitive members, a laminated electrophotographic photosensitive member, that is, a photosensitive layer is composed of a charge generating layer (CGL) for generating charges upon exposure and a charge transporting layer (CTL) for transferring charges. A multi-layer organic electrophotographic photoreceptor (OPC) having at least two layers, and a single-layer electrophotographic photoreceptor having a photosensitive layer composed of a single layer in which a charge generating substance and a charge transporting substance are dispersed in a binder resin. Is being used. As the binder resin for the charge transport layer of the laminated electrophotographic photoreceptor and the photosensitive layer of the single-layer electrophotographic photoreceptor,
Polycarbonate resins made from bisphenol A or bisphenol Z are widely used. Polycarbonate resin using bisphenol A or bisphenol Z as a raw material has good compatibility with a charge transporting substance, and therefore, when a photoconductor is produced by using this as a binder resin in a photosensitive layer, good electrical characteristics are obtained. A photoreceptor having relatively high mechanical strength can be obtained.

However, when a charge transport layer is formed by using a polycarbonate resin prepared from bisphenol A or bisphenol Z as a binder resin, it has been revealed that the following problems occur. When a photosensitive layer is applied during preparation of a photoreceptor, the coating liquid may be whitened (gelled) or the photosensitive layer may be easily crystallized depending on the solvent used. In the part where this crystallization has occurred, there is no light attenuation, and it remains as an electric charge or a residual potential and appears as a defect in terms of image quality. A charge transport layer or a photosensitive layer using a polycarbonate resin made of bisphenol A or bisphenol Z as a binder resin has poor adhesion to the base and is easily peeled off, or is scratched due to insufficient surface hardness, or the surface is abraded. There is a drawback that the printing life is shortened. In general, the term “base” refers to a charge generation layer, but in a single-layer type photoreceptor and an inverse layer type photoreceptor, it refers to a conductive substrate. When a charge transport layer and a charge generation layer are sequentially laminated on a conductor such as a positive charging type electrophotographic photoreceptor, the conductor serves as a base, and the conductor is used for the purpose of improving electrophotographic characteristics. When a blocking layer or an intermediate layer is provided between the charge transport layer or the charge transport layer or the charge generation layer and the charge transport layer, these layers serve as a base.

[0005]

The present invention has been made based on the above circumstances. An object of the present invention is to solve the above problems found in a conventional electrophotographic photoreceptor using a polycarbonate resin containing bisphenol A or bisphenol Z as a binder resin for a photosensitive layer, and Whitening (gelation) of coating liquid
Another object of the present invention is to provide a novel polycarbonate polymer which is free from abrasion and has excellent mechanical strength for a long period of time.

The present invention also provides a suitable method for producing the above-mentioned polycarbonate polymer of the present invention and an excellent electronic strength produced by using the above-mentioned polycarbonate polymer, which has excellent mechanical strength such as printing durability and excellent electronic properties. It is an object of the present invention to provide an electrophotographic photosensitive member which can maintain photographic characteristics and is remarkably excellent in practical use.

[0007]

As a result of intensive studies to solve the above problems, the present inventors have found that a specific polycarbonate having an octafluorobiphenyl structure in a repeating unit is a binder resin for an electrophotographic photoreceptor. It has been found that the electrophotographic photosensitive member which is preferably used as the above is excellent in printing durability and electrophotographic characteristics, and the present invention has been completed based on this finding.

That is, the present invention provides the following general formula (I)

[0009]

[Chemical 4] Or a repeating unit (I) represented by the following general formula (II)

[0010]

[Chemical 5] [In the formula, R ¹ and R ² are each independently a chlorine atom, a bromine atom,
Iodine atom, alkyl group having 1 to 6 carbon atoms or 6 to carbon atoms
12 represents a substituted or unsubstituted aryl group, a and b each independently represent an integer of 0 to 4, X is a single bond, -O-, -S
-, - CO -, - SO -, - SO 2 -, - CR 3 R 4 - ( provided that R ³ and R ⁴ 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), 1,1-having 5 to 8 carbon atoms
A cycloalkylene group or an α, ω-alkylene group having 2 to 12 carbon atoms is shown. ] The repeating unit (II)
And a reduced viscosity [η _sp / c] at 20 ° C. of a solution of 0.5 g / dl concentration using methylene chloride as a solvent is 0.2
The present invention provides a polycarbonate polymer characterized in that it is about 2.5 dl / g.

The present invention further provides 4,4'-dihydroxyoctafluorobiphenyl or 4,4'-dihydroxyoctafluorobiphenyl and the following general formula (III) as a method for producing the polycarbonate polymer of the present invention.

[0012]

[Chemical 6] [Wherein R ¹ , R ² and X have the same meanings as described above. ]
The present invention provides a method for producing a polycarbonate polymer, which comprises reacting a dihydric phenol (III) represented by the above with a carbonic acid ester forming compound.

The present invention also provides an electrophotographic photoreceptor having a photosensitive layer provided on a conductive substrate, wherein the polycarbonate polymer of the present invention is used as a binder resin in the photosensitive layer. Provide a photoreceptor.

The polycarbonate polymer of the present invention may be a homopolymer represented by the repeating unit (I),
Further, it may be a copolymer having the repeating unit (I) and the repeating unit (II). Further, it may be a copolymer composed of the repeating unit (I) and two or more kinds of the repeating unit (II).

When the polycarbonate polymer of the present invention has a repeating unit (I) and a repeating unit (II),
The content ratio of the repeating unit represented by the general formula (I) is
The molar ratio to the total of the repeating unit (I) and the repeating unit (II) is 1 mol% or more, and more preferably 10 to 10.
90 mol% is preferable. If this molar ratio is less than 1 mol%, sufficient printing durability and good electrophotographic properties may not be obtained when used as a binder resin in an electrophotographic photoreceptor. Repeating unit (II)
By containing the above unit in the above range, the repeating unit (I)
It becomes more difficult to whiten (crystallize) more than in the case of only.

The polycarbonate polymer of the present invention may have other repeating units other than those mentioned above within the range not impairing the object of the present invention, and may appropriately contain other polycarbonate components and additives. It may be a mixed additive.

The polycarbonate polymer of the present invention comprises 20 parts of a solution containing methylene chloride as a solvent and having a concentration of 0.5 g / dl.
Reduced viscosity [η _sp / c] at 0.2 to 2.5 dl /
g, preferably in the range of 0.3 to 2.0 dl / g. When the reduced viscosity [η _sp / c] is less than 0.2 dl / g, the mechanical strength of the polycarbonate polymer is low, and especially the surface hardness of the layer containing the polycarbonate polymer is insufficient,
The photoreceptor wears and the printing life is shortened. On the other hand, when the reduced viscosity [η _sp / c] exceeds 2.5 dl / g, the solution viscosity of the polycarbonate polymer increases, which makes it difficult to manufacture the photoreceptor by the solution coating method.

The polycarbonate polymer of the present invention is represented by 4,4'-dihydroxyoctafluorobiphenyl or 4,4'-dihydroxyoctafluorobiphenyl and the above general formula (III) according to the production method of the present invention. It can be suitably produced by reacting the dihydric phenol (III) with a carbonic acid ester-forming compound.

In this reaction, various carbonyl ester forming compounds such as phosgene and various carbonyl dihalogenates, haloformates such as chloroformate compounds or carbonic acid ester compounds are used in the presence of a suitable acid binder. It is carried out by a method such as a polycondensation reaction or an ester exchange reaction using a bisaryl carbonate as a carbonic acid ester forming compound.

Specific examples of the dihydric phenol (III) represented by the general formula (III) include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane and 1 , 2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) butane, 2,2-bis (4-) Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 4,4-bis (4-hydroxyphenyl) heptane, 4,4′-dihydroxytetraphenylmethane, 1,1-bis (4-hydroxy) Phenyl)-
1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl)
Sulfide, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-) Hydroxyphenyl) propane, 2- (3-methyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl) -1
-Phenylethane, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-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-tert-butyl-4-hydroxy-3-methylphenyl) ethane,
1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 1,1-bis (2-
tert-Butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4)
-Hydroxy-5-methylphenyl) isobutane, 1,
1-bis (2-tert-butyl-4-hydroxy-5)
-Methylphenyl) heptane, 1,1-bis (2-te
rt-Butyl-4-hydroxy-5-methylphenyl)
-1-phenylmethane, 1,1-bis (2-tert-
Amyl-4-hydroxy-5-methylphenyl) butane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, 2,2-bis (3-chloro) -4-Hydroxyphenyl) propane, 2,2-bis (3-bromo-4)
-Hydroxyphenyl) propane, 2,2-bis (3,3
5-dichloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (3,5-dichloro) -4-Hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 4,4 '
-Dihydroxybiphenyl, 4,4'-dihydroxy-
3,3'-dimethylbiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl, 4,
4'-dihydroxy benzophenone etc. are mentioned. These dihydric phenols may be used alone or in combination of two or more.

Particularly preferably, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxytetraphenylmethane, 1-phenyl-1,1-bis (4
-Hydroxyphenyl) ethane, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-)
4-hydroxyphenyl) propane, 4,4'-dihydroxybiphenyl and 2,2-bis (3-phenyl-4)
-Hydroxyphenyl) propane is used.

The reaction of polycondensation using the above-mentioned carbonyl dihalide, haloformate, carbonic acid ester compound or the like as the carbonic acid ester forming compound in the presence of an acid binder is usually carried out in a solvent.

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. 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.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and 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 amount) of the reaction as in the above. Specifically, the number of moles of 4,4'-dihydroxyoctafluorobiphenyl used, or 4,4'-dihydroxyoctafluorobiphenyl and dihydric phenol (III)
It is preferable to use 2 equivalents or slightly excess amount of the acid binder with respect to the total number of moles of the above (usually 1 mole corresponds to 2 equivalents).

As the solvent, various solvents such as those used in the production of known polycarbonates may be used alone or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. The interfacial polycondensation reaction may be carried out using two kinds of solvents that are immiscible with each other.

Further, in order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt, and to adjust the degree of polymerization,
It is desirable to carry out the reaction by adding a molecular weight modifier such as p-tert-butylphenol or phenylphenol. If desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added.
The reaction is usually performed 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, normal pressure or the self-pressure of the reaction system can be suitably used. 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.

First, a part of the reaction raw material composed of 4,4'-dihydroxyoctafluorobiphenyl or 4,4'-dihydroxyoctafluorobiphenyl and dihydric phenol (III) is reacted with a carbonate ester forming compound. It is also possible to use a two-step method in which an oligomer is produced by adding the remaining reaction raw materials to complete polycondensation. According to such a two-step method, the reaction can be easily controlled, and the molecular weight can be controlled with high accuracy.

The latter 4,4'-dihydroxyoctafluorobiphenyl, or 4,4'-dihydroxyoctafluorobiphenyl and the bisaryl carbonate used in the transesterification method of the dihydric phenol (III) and the bisaryl carbonate include For example, di-p-
Examples thereof include tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. As a reaction type of this method, a melt polycondensation method, a solid phase polycondensation method, and the like are suitable. When carrying out the melt polycondensation method, the above-mentioned two or three kinds of monomers are mixed and reacted in a molten state at high temperature under reduced pressure. The reaction is usually 150 to 350 ° C., preferably 2
It is carried out at a temperature in the range of 00 to 300 ° C. When the solid phase polycondensation method is carried out, the above-mentioned two or three kinds of monomers are mixed, and the polycondensation is carried out by heating to a temperature not higher than the melting point of the produced polycarbonate polymer in the solid state. 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 [η _sp / c] of the obtained polycarbonate polymer can be controlled by various methods such as selection of the reaction conditions and adjustment of the amount of the molecular weight modifier used. it can. Also, in some cases,
The obtained polycarbonate polymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction,
It is also possible to obtain a polycarbonate polymer having a predetermined reduced viscosity [η _sp / c] by subjecting it to crosslinking treatment, partial decomposition treatment, etc.).

The reaction product (crude product) thus obtained can be recovered as a polycarbonate polymer having a desired purity (purification degree) by subjecting it to various post-treatments such as a known separation and purification method.

When a compound having an asymmetric molecule is used as the above-mentioned dihydric phenol (III) in the production of a polycarbonate polymer, the orientation of the obtained polymer may be the same or random depending on the polymerization method. However, the polycarbonate polymer of the present invention includes those in any orientation state.

The present invention also provides an electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate, wherein the polycarbonate polymer of the present invention is used as a binder resin in the photosensitive layer. is there. The electrophotographic photoreceptor of the present invention may be any known electrophotographic photoreceptor of various types as long as the polycarbonate polymer of the present invention is used as a binder resin. In a laminated electrophotographic photoreceptor having at least one charge generation layer and at least one charge transport layer, it is preferably used as a binder resin for the charge transport layer.

The laminated electrophotographic photoreceptor may be one in which a charge transport layer is laminated on the charge generation layer in the photosensitive layer, or one in which a charge generation layer is laminated on the charge transport layer. Good. In addition, a conductive or insulating protective film may be formed on the surface layer as necessary. further,
An adhesive layer for improving the adhesiveness between the layers or an intermediate layer such as a blocking layer that plays a role of blocking charges may be formed.

In the electrophotographic photosensitive member of the present invention, the polycarbonate polymer of the present invention may be used alone or in combination of two or more kinds. Further, if desired, other polycarbonate or the like may be contained as a binder resin component within a range not impairing the object of the present invention. Further, additives such as antioxidants may be included.

As the conductive substrate material used in the electrophotographic photosensitive member of the present invention, various materials such as known materials can be used, and specifically, for example, aluminum,
Conductivity by coating a conductive material such as aluminum, nickel, chromium, palladium, graphite, etc. on a metal plate such as brass, copper, nickel, steel, metal drum or metal sheet, plastic sheet by vapor deposition, sputtering, coating, etc. It is possible to use those that have been subjected to a chemical treatment, those whose metal drum surface has been subjected to a metal oxide treatment such as electrode oxidation, or those whose substrates such as glass, plastic plates, cloth, and paper have been subjected to a conductive treatment. it can.

The charge generating layer of the laminated electrophotographic photosensitive member contains at least a charge generating substance, and this charge generating layer is formed on the substrate which is the base thereof by vacuum deposition, sputtering or the like. It can be obtained by forming a layer formed by binding a charge generating substance using a binder resin on a substrate which is the base or the base. 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 used. ,
A method of coating on a substrate which is a predetermined undercoat and drying it is preferably used.

As the charge generating substance, various substances such as known substances can be used. Specifically, for example, selenium simple substance such as amorphous selenium and trigonal selenium, and selenium such as selenium-tellurium. Alloy, selenium compound such as As ₂ Se ₃ or selenium-containing composition, zinc oxide, CdS-
Inorganic materials composed of Group II and Group IV elements such as Se,
Various inorganic materials such as oxide-based semiconductors such as titanium oxide, silicon-based materials such as amorphous silicon, metal or metal-free phthalocyanines, cyanines, anthracenes, bisazo compounds, pyrene, perylene, pyrylium salts, thiapyrylium salts, polyvinylcarbazole, squares Examples thereof include various organic materials such as a lithium pigment.

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

The binder resin in the charge generating layer is not particularly limited, and various known resins can be used. Specific examples include polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-acetic acid. Vinyl copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate,
Thermoplastic resins such as polyamide, polyketone, polyacrylamide, butyral resin, and polyester, and thermosetting resins such as polyurethane, epoxy resin, and phenol resin can be used.

The polycarbonate polymer of the present invention can be used as the binder resin in the charge generation layer.

Next, the charge transport layer can be obtained by forming a layer obtained by binding a charge transport substance using the polycarbonate polymer of the present invention as a binder resin on a base substrate. .

As the method for forming the charge transport layer, various methods such as a known method can be used. Usually, the charge transport substance is dispersed or dissolved in a suitable solvent together with the polycarbonate polymer of the present invention. A method in which a coating liquid is applied on a substrate serving as a predetermined base and dried is used.

In the charge transport layer, the polycarbonate polymer of the present invention can be used alone, or
Further, two or more kinds may be mixed and used. Further, another binder resin may be used in combination with the polycarbonate polymer of the present invention within a range not impairing the object of the present invention.

Examples of the charge transport material that can be used in the present invention include conventionally used electron transport materials and hole transport materials.

Specific examples of the electron transporting substance include, for example, chloranil, bromanil, 2,3-dichloro-5,6-.
Dicyano-p-benzoquinone, tetracyanoethylene,
Tetracyanoquinodimethane, 2,4,7-trinitro-
9-fluorenone, 2,4,5,7-tetranitro-9
-Fluorenone, 2,4,7-trinitro-9-dicyanomethylenefluorenone, 2,4,5,7-tetranitroxanthone, 2,4,9-trinitrothioxanthone or 3,5-dimethyl-3 ', 5'. There are electron-withdrawing substances such as -di-tert-butyl-4,4'-diphenoquinone and polymers obtained by polymerizing these electron-withdrawing substances. In addition, these may be used individually by 1 type, or may be used together, such as mixing 2 or more types.

As the hole transporting substance, pyrene, N-ethylcarbazole, N-isopropylcarbazole, N
-Methyl-N-phenylhydrazino-3-methylidene-
9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N, N
-Diphenylhydrazino-3-methylidene-10-ethylphenothiazine, N, N-diphenylhydrazino-3
-Methylidene-10-ethylphenoxazine, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, p-diethylaminobenzaldehyde-N-α
-Naphthyl-N-phenylhydrazone, p-pyrrolidinobenzaldehyde-N, N-diphenylhydrazone,
1,3,3-Trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone, p-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 1-phenyl-1,2,3,4- Hydrazones such as tetrahydroquinoline-6-carboxaldehyde-1 ′, 1′-diphenylhydrazone, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-3- ( p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [quinolyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [lepidil (2 )]-3- (p-
Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [6-methoxy-pyridyl (2)]-3- (p-diethylaminostyryl) -5-
(P-Diethylaminophenyl) pyrazoline, 1- [pyridyl (5)]-3- (p-diethylaminophenyl)
Pyrazoline, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3- (p
-Diethylaminostyryl) -4-methyl-5- (p-
Diethylaminophenyl) pyrazolin, 1- [pyridyl (2)]-3- (α-methyl-p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazolin, 1-phenyl-3- (p-diethylaminostyryl)- 4-methyl-5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (α-benzyl-
Pyrazolines such as p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and spiropyrazoline, 2- (p-diethylaminostyryl) -δ-
Oxazole compounds such as diethylaminobenzoxazole, 2- (p-diethylaminophenyl) -4- (p-dimethylaminophenyl) -5- (2-chlorophenyl) oxazole, 2- (p-diethylaminostyryl) -6-diethylaminobenzo Thiazole-based compounds such as thiazole, triarylmethane-based compounds such as bis (4-diethylamino-2-methylphenyl) phenylmethane, 1,1-bis (4-N, N-diethylamino-2)
-Methylphenyl) heptane, polyarylamines such as 1,1,2,2-tetrakis (4-N, N-dimethylamino-2-methylphenyl) ethane, N, N'-diphenyl-N, N'- Bis (methylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (ethylphenyl) benzidine, N, N'-diphenyl-N, N '
-Bis (propylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (butylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (isopropylphenyl) benzidine, N, N ' -Diphenyl-
N, N'-bis (sec-butylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (tert
-Butylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (chlorophenyl) benzidine and other benzidine compounds, or butadiene compounds, triphenylamine, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene , Polyvinyl acridine, poly-9-vinylphenylanthracene, organic polysilane, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin and the like.

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

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

These solvents may be used alone or in combination of two or more as a mixed solvent.

The coating of each layer can be carried out by using various coating devices such as known ones. Specifically, for example, an applicator, a spray coater, a bar coater, a tip coater, a roll coater, a dip coater, a doctor blade, etc. Can be done using.

The photosensitive layer of the single-layer type electrophotographic photoreceptor contains at least the polycarbonate polymer of the present invention, the charge transporting substance and the charge transporting substance. As the method for forming the photosensitive layer, various methods such as a known method can be used. Usually, for example, the charge generating substance and the charge transporting substance are dispersed or dissolved in a suitable solvent together with the polycarbonate polymer of the present invention. It is possible to suitably use a method in which the coating liquid thus obtained is applied on a substrate which is a predetermined undercoat and dried.

Further, to the extent that the object of the present invention is not impaired,
It is also possible to use other binder resins together with the polycarbonate polymer of the present invention.

The electrophotographic photosensitive member of the present invention does not cause whitening (gelation) of the coating liquid during its preparation, and has excellent mechanical strength and electrophotographic characteristics even when it is repeatedly used for a long time. It is a remarkably excellent electrophotographic photosensitive member that maintains the above properties, and can be suitably used in various electrophotographic fields.

[0055]

EXAMPLES The present invention will now be described in detail based on examples, but the present invention is not limited thereto.

Example 1 7.59 g (0.023 mol) of 4,4'-dihydroxyoctafluorobiphenyl as raw material monomers and 2,2
2-bis (4-hydroxyphenyl) propane 42.6
g (0.205 mol), 550 ml of 8% concentration of sodium hydroxide aqueous solution, 400 ml of methylene chloride, 0.15 g of p-tert-butylphenol as a terminal terminator (molecular weight regulator), and 3 ml of 10% triethylamine aqueous solution as a catalyst. The mixture was introduced into an attached reactor, and the polycondensation reaction was carried out by blowing phosgene gas at a rate of 600 ml / min for 15 minutes while vigorously stirring while maintaining the temperature of the reaction solution at around 10 ° C.

After completion of the reaction, 1 liter of methylene chloride was added to the organic phase to dilute it, and the organic phase was washed with water, diluted hydrochloric acid and water in this order, and then poured into methanol to obtain a polycarbonate polymer.

The polycarbonate polymer thus obtained has a concentration of 0.5 g / d in methylene chloride as a solvent.
The reduced viscosity [η _sp / c] of the solution of 1 at 20 ° C is 0.6.
It was 63 dl / g. The viscosity average molecular weight (Mv) of this polycarbonate polymer was 28,000, and the glass transition temperature (Tg) was 155 ° C. ^From the results of ¹ H-NMR spectrum analysis and ¹⁹ F-NMR spectrum analysis, it was confirmed that the obtained polycarbonate polymer was composed of the following repeating units.

[0059]

[Chemical 7] ¹ H-NMR (TMS / CD ₂ Cl ₂ ) δ = 7.23 ppm (dd Ar-H 64 H) 7.28 ppm (dd Ar-H 8 H) 1.70 ppm (s CH ₃ 56 H) ¹⁹ F-NMR (CFCl ₃ / CD ₂ Cl ₂ ) δ = -160ppm (ddd Ar-F 4F) -140ppm (ddd Ar-F 4F)

A tetrahydrofuran solution having a hydrazone compound concentration of 50% by weight was prepared by using a hydrazone compound having the following structure as a charge transporting material to obtain a coating liquid. Even when the coating solution was allowed to stand for one month, no cloudiness, no gel formation was observed. This coating solution is applied by a dip coating method onto a charge generation layer (thickness: about 0.5 μm) made of oxotitanium phthalocyanine formed on a conductive substrate made of aluminum, and dried to form a charge transport layer (thickness: 20 μm). Then, a laminated electrophotographic photosensitive member was produced. The charge transport layer did not crystallize during coating.

The electrophotographic characteristics of the obtained laminated type electrophotographic photosensitive member were evaluated by the electrostatic charging test apparatus EPA-8100.
(Manufactured by Kawaguchi Electric Mfg. Co., Ltd.), corona discharge of −6 kV was performed, and initial surface potential (V ₀ ) and light irradiation (10 Lu) were used.
x) residual potential post (V _R), was performed by measuring the half decay exposure amount (E _1/2). The results are shown in Table 1.

Further, the abrasion resistance of the charge transport layer was evaluated by using a Suga abrasion tester to reciprocate the sample 1200 times on an abrasion paper loaded with a load of 200 g and measuring the abrasion amount. The results are shown in Table 2. Charge transport material (1-phenyl-1,2,3,4-tetrahydroquinoline-6-carboxaldehyde-1 ′,
1'-diphenylhydrazone)

[0063]

[Chemical 8]

Example 2 2,2-bis (4-hydroxyphenyl) propane 74
Phosgene gas was blown into the solution at a rate of 950 ml / min for 15 minutes while cooling while mixing a solution of g dissolved in 550 ml of a 6% concentration aqueous sodium hydroxide solution and 250 ml of methylene chloride. Then, the reaction solution was separated by standing to obtain a methylene chloride solution of an oligomer having a degree of polymerization of 2 to 4 in the organic phase and having a chloroformate group at the molecular end.

Methylene chloride was added to the obtained oligomer solution to bring the total amount to 450 ml, and 42.6 g (0.13 mol) of 4,4'-dihydroxyoctafluorobiphenyl was added to 150 ml of an 8% aqueous sodium hydroxide solution. After mixing, p- is added to this as an end-stopping agent (molecular weight regulator).
3.0 g of tert-butylphenol was added. Then, while vigorously stirring this mixed solution, 1 ml of a 10% triethylamine aqueous solution was added as a catalyst, and the mixture was stirred at room temperature for 1 hour.
The reaction was carried out over time.

After completion of the reaction, 1 liter of methylene chloride was added to the organic phase to dilute it, and the organic phase was washed with water, diluted hydrochloric acid and water in this order and then poured into methanol to obtain a polycarbonate polymer. The polycarbonate polymer thus obtained has a reduced viscosity [η _sp / c] of 0.71 dl at 20 ° C. in a solution of methylene chloride at a concentration of 0.5 g / dl.
/ G. The viscosity average molecular weight (Mv) of this polycarbonate polymer was 30,000, and the glass transition temperature (Tg) was 158 ° C. ^From the results of ¹ H-NMR spectrum analysis and ¹⁹ F-NMR spectrum analysis, it was confirmed that the obtained polycarbonate polymer was composed of the following repeating units.

[0067]

[Chemical 9] A laminated electrophotographic photosensitive member was produced in the same manner as in Example 1 using this polycarbonate polymer. The evaluation results of the stability of the coating liquid and the crystallinity during coating were the same as in Example 1. The evaluation results of electrophotographic characteristics and abrasion resistance are shown in Table 1 and Table 2, respectively.

Comparative Example 1 2,2-bis (4-hydroxyphenyl) propane was used as a monomer raw material and p-tert-butylphenol was used as an end terminating agent to produce a commercially available polycarbonate ([η _sp / c] = 0.76 dl / g)
A laminate type electrophotographic photosensitive member was produced in the same manner as in Example 1. As a result, the coating liquid became cloudy on the 3rd day and a gel was generated. Further, at the time of coating, part of the charge transport layer was crystallized (whitened). The electrophotographic characteristics and abrasion resistance of the obtained laminated electrophotographic photosensitive member are shown in Tables 1 and 2.

[0069]

[Chemical 10]

Comparative Example 2 1,1-bis (4-hydroxyphenyl) cyclohexane was used as a monomer raw material, and p-tert was used as a terminal stopper.
-A commercially available polycarbonate ([η _sp /c]=0.78 dl) having the following structure, produced using butylphenol:
/ G) was used to prepare a laminated electrophotographic photosensitive member in the same manner as in Example 1. As a result, the coating liquid became cloudy on the second day and gel was generated. Further, at the time of coating, part of the charge transport layer was crystallized (whitened). The electrophotographic characteristics and abrasion resistance of the obtained laminated electrophotographic photosensitive member are shown in Tables 1 and 2.

[0071]

[Chemical 11]

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

INDUSTRIAL APPLICABILITY According to the present invention, it can be suitably used as a binder resin in the photosensitive layer of an electrophotographic photosensitive member, and in particular, an electrophotographic photosensitive member excellent in printing durability can be easily realized. As a result, a polycarbonate polymer having a novel structure that can be suitably used in various fields of application of polymer materials such as production of electrophotographic photoreceptors and EL devices can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomohiro Nagao 1280 Kamizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd.

Claims (3)

[Claims] 1. The following general formula (I): The repeating unit (I) represented by: or this repeating unit (I) and the following general formula (II): [In the formula, R ¹ and R ² are each independently a chlorine atom, a bromine atom,
Iodine atom, alkyl group having 1 to 6 carbon atoms or 6 to carbon atoms
12 represents a substituted or unsubstituted aryl group, a and b each independently represent an integer of 0 to 4, X is a single bond, -O-, -S
-, - CO -, - SO -, - SO 2 -, - CR 3 R 4 - ( provided that R ³ and R ⁴ 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), 1,1-having 5 to 8 carbon atoms
A cycloalkylene group or an α, ω-alkylene group having 2 to 12 carbon atoms is shown. ] The repeating unit (II)
And a reduced viscosity [η _sp / c] at 20 ° C. of a solution of 0.5 g / dl concentration using methylene chloride as a solvent is 0.2
A polycarbonate polymer characterized in that it is ˜2.5 dl / g. 2. 4,4'-Dihydroxyoctafluorobiphenyl or 4,4'-dihydroxyoctafluorobiphenyl and the following general formula (III): [In the formula, R ¹ and R ² are each independently a chlorine atom, a bromine atom,
Iodine atom, alkyl group having 1 to 6 carbon atoms or 6 to carbon atoms
12 represents a substituted or unsubstituted aryl group, a and b each independently represent an integer of 0 to 4, X is a single bond, -O-, -S
-, - CO -, - SO -, - SO 2 -, - CR 3 R 4 - ( provided that R ³ and R ⁴ 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), 1,1-having 5 to 8 carbon atoms
A cycloalkylene group or an α, ω-alkylene group having 2 to 12 carbon atoms is shown. ] The dihydric phenol (II
The method for producing a polycarbonate polymer according to claim 1, wherein I) is reacted with a carbonic acid ester-forming compound. 3. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate, wherein as a binder resin in the photosensitive layer,
An electrophotographic photoreceptor comprising the polycarbonate polymer according to claim 1.