JP3422140B2 - Organic electronic device using charge-transporting polyester resin randomly copolymerized - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to relates to a novel random copolymer polymerized charge transporting polyester resin electronic photoreceptors using.

[0002]

2. Description of the Related Art Charge-transporting polymers typified by polyvinylcarbazole (PVK) are photoconductive materials for electrophotographic photoconductors, or Proceedings of the 36th Joint Lecture on Applied Physics, 31p-K-12 (1990). ), Etc., and is promising as an organic electroluminescent device material. These are used together to form a layer and are used as a charge transport layer. As a material for forming the charge transport layer, a charge transporting polymer represented by PVK and a charge transporting low molecular weight compound are dispersed in the polymer. A low molecular weight dispersion system is well known. Further, in an organic electroluminescence device, it is general to use a low-molecular charge transport material by vapor deposition. Among them, the low molecular dispersion type has a wide variety of materials,
Since it is easy to obtain a highly functional product, it has become the mainstream in electrophotographic photoreceptors. With respect to electrophotographic photoreceptors, in recent years, with the high performance of organic photoreceptors, they have come to be used in high-speed copying machines and printers. The performance is not sufficient, and it is earnestly desired to further extend the life of the organic photoconductor. One of the important factors that determines the life of the organophotoreceptor is wear of the charge transport layer.
Current organic photoreceptors are generally of the so-called laminated type in which a charge transport layer is laminated on a charge generation layer.
Therefore, the charge transport layer is often the surface layer,
Regarding the current mainstream low molecular weight dispersion type charge transport layer, it is becoming possible to obtain sufficiently satisfactory performance in terms of electrical characteristics, but since the low molecular weight compound is dispersed in the binder resin and used. However, there is a drawback that the mechanical performance inherent to the binder resin is deteriorated, and that it is essentially weak in terms of wear.

On the other hand, charge-transporting polymers are currently being actively studied because they have the potential to greatly improve the above-mentioned drawbacks. For example, U.S. Pat. No. 4,806,4
No. 43 discloses a polycarbonate obtained by polymerizing a specific dihydroxyarylamine and bischloroformate, and US Pat. No. 4,806,444 discloses a specific dihydroxyarylamine and phosgene. Polycarbonates from the polymerization of are disclosed. Further, US Pat. No. 4,801,517 discloses a polycarbonate obtained by polymerizing a bishydroxyalkylarylamine and bischloroformate or phosgene, and US Pat. No. 4,937,1.
No. 65 and No. 4,959,288 describe a polycarbonate produced by polymerization of a specific dihydroxyarylamine or bishydroxyalkylarylamine and bischloroformate, or a polyester produced by polymerization of a bisacyl halide. It is disclosed. Further, US Pat. No. 5,034,296 discloses a polycarbonate or polyester of arylamine having a specific fluorene skeleton, and US Pat. No. 4,983,482 discloses polyurethane. Has been done. Furthermore, Japanese Patent Publication Sho 59-2890
Japanese Patent Publication No. 3 discloses a polyester having a specific bisstyrylbisarylamine as a main chain. Also, JP-A-61-20953 and JP-A-1-134456.
JP, JP-A-1-134457, JP, 1-1
JP-A-34462, JP-A-4-133605, JP-A-4-133066 and the like disclose polymers having pendant charge-transporting substituents such as hydrazone and triarylamine, and a photoconductor using the same. Is also proposed. In particular, polymers having a tetraarylbenzidine skeleton are available in “The Sixth International Congress on
Advances in Non-impact Printing Technologies, 306,
(1990). ”, It has high mobility and is highly practical.

[0004]

The charge transporting polymer is required to have various properties such as solubility, mobility, and matching of oxidation potential. In order to meet these requirements, a substituent is introduced. It is common practice to control the physical properties. Since the ionization potential of the charge transporting polymer is almost determined by the charge transporting polymer, it is important that the ionization potential of the charge transporting polymer can be controlled. The monomers that are the starting materials for the triarylamine polymer shown above are (1) dihydroxyarylamine and (2)
There are two types of bishydroxyalkylarylamines. However, the dihydroxyarylamine is
Since it has an aminophenol structure, it is easily oxidized and is difficult to purify. Further, particularly when the structure has a para-hydroxy substitution, it becomes more unstable, but it is difficult to change the position of the substituent and control the ionization potential. Further, since the aromatic ring has a structure in which oxygen is directly substituted, there is a problem in that the electron withdrawing property thereof tends to cause uneven distribution of charge, and mobility tends to decrease. On the other hand, bishydroxyalkylarylamine has no effect on the electron withdrawing property of oxygen due to the methylene group, but it is difficult to synthesize a monomer. That is, in the reaction of diarylamine or diarylbenzidine with 3-bromoiodobenzene, since both bromine and iodine are reactive, the product is likely to be a mixture, resulting in a decrease in yield. In addition, there is a problem that alkyllithium and ethylene oxide used for converting bromine into lithium are highly dangerous and highly toxic and require careful handling.

In order to solve the above-mentioned problems, the inventors of the present invention first investigated a charge-transporting polymer and found that a novel alternating copolymerization represented by the following general formula (IV) or (V) was used. A performance charge transport polymer was proposed.

[Chemical 3] [In the formula, Y and Z each represent a divalent hydrocarbon group, and A represents a structure represented by formula (I-1) or (I-2). B and B'are each independently a group -O.
_{- (Y'-O) m '} -H or a group -O- (Y'-O)
_{m '-CO-Z'-CO-} OR' ( wherein, R 'is a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group,
A substituted or unsubstituted aralkyl group, Y ′ and Z ′ each represent a divalent hydrocarbon group, and m ′ represents 1 to 1
It means an integer of 5. ), M is an integer of 1 to 5, p is 5
It means an integer of 5000. The charge-transporting polymer has excellent properties as compared with conventional ones and is highly practical, but it has the general formula (I
The polymer represented by V) has a high ratio of the portion having a charge transport function (portion A) and has a problem that it is easily affected by discharge products such as ozone. In addition, the general formula (V)
The polymer represented by is a charge transporting functional portion (A portion).
Since the ratio of A decreases, the resistance to discharge products such as ozone increases, but since the manufacturing method is alternating copolymerization and the ratio of A and Z is constant, the ratio of A becomes too low and mobility increases. However, there is a problem in that it is difficult to obtain a polymer having a high molecular weight. Further, in consideration of application to various devices, it is necessary to increase the degree of freedom in device design, and it is required that mechanical properties, oxidation resistance, charge injection properties, etc. can be freely controlled.

The present invention has been made to solve the above-mentioned problems in the prior art. That is,
An object of the present invention is to provide an electrophotographic photosensitive member using a novel charge transporting polyester resin which has a large degree of freedom in mechanical properties, oxidation resistance, charge injection property and the like and can be easily manufactured.

[0007]

Means for Solving the Problems As a result of intensive investigations by the present inventors on charge-transporting polymers, at least one of the structures represented by the following general formula (I-1) or (I-2) And at least one dicarboxylic acid component represented by the following general formula (II) as a partial structure of a repeating unit, and a random copolymerized charge transporting polyester resin, more specifically, the general formula (I-1 ) Or (I-
At least one of the structures represented by 2) and the general formula (II)
A random copolymer represented by the following general formula (III) containing at least one dicarboxylic acid component represented by It was found that the ratio of the parts can be easily changed, and further, mechanical properties, oxidation resistance, charge injection property, etc. can be easily controlled by appropriately selecting the structures of the A part and the Z part. In addition, the method for producing the charge-transporting polyester resin includes a dicarboxylic acid derivative having a structure represented by the general formula (I-1) or (I-2) and a dicarboxylic acid derivative having a structure represented by the general formula (II). The present invention has been completed by finding that it can be easily obtained by simply mixing an acid derivative in a desired ratio and polymerizing it.

[0008] electronic photosensitive member of the present invention, at least one structure represented by the following general formula (I-1) or (I-2), a dicarboxylic acid represented by the following general formula (II) It is characterized by having a photosensitive layer containing at least one of the components as a partial structure of a repeating unit and containing a random copolymerized charge transporting polyester resin.

[0009]

[Chemical 4] (In the formula, R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a halogen atom,
Alternatively, it represents a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent aromatic group. T is carbon number 1
10 represents a divalent hydrocarbon group which may be branched.
k and l are 0 or 1, respectively. ) -O-CO-Z-CO-O- (II) (Z represents a divalent hydrocarbon group.)

The charge-transporting polyester resin contained in the electrophotographic photoreceptor of the present invention is preferably a random copolymer represented by the following general formula (III).

[Chemical 5] [In formula, A shows the structure represented by the said General formula (I-1) or (I-2), Y and Z show a divalent hydrocarbon group. m is an integer of 1 to 5, q is an integer of 1 or more, and r is 1 to
It means an integer of 3500. However, q + r is 5 to 50
Is an integer of 00, and 0.3 ≦ q / (q + r) <1. ]

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail. In the present invention, as the charge-transporting polyester resin used in the electrophotographic photoreceptor, a specific example of T in the structure represented by the general formula (I-1) or (I-2) contained as a partial structure of the repeating unit is shown. An example of such a structure is shown below. In the above general formula, the arylamine skeleton may be bonded to either side.
-2r indicates that the arylamine skeleton is attached on the right side of the structure T-2, and T-2l indicates on the left side of the structure T-2.

[0012]

[Chemical 6]

[0013]

[Chemical 7] In the charge-transporting polyester resin, the compound represented by the general formula (I-
Specific examples of X in the structure represented by 1) or (I-2) include those selected from the following groups (1) to (7).

[0014]

[Chemical 8] [In the formula, R ₅ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
A substituted or unsubstituted phenyl group or a substituted or unsubstituted aralkyl group, wherein R _{6 to} R ₁₂ are a hydrogen atom or a carbon number 1
To C4 alkyl group, C1 to C4 alkoxy group, substituted or unsubstituted phenyl group, substituted or unsubstituted aralkyl group, halogen atom, and a is 0 or 1.
Examples of V include those selected from the following groups (8) to (17).

[0015]

[Chemical 9] (In the formula, b means an integer of 1 to 10 and c means an integer of 1 to 3.)]

In the charge-transporting polyester resin represented by the general formula (III) used in the present invention, Y and Z include those selected from the following groups (18) to (24).

[Chemical 10] (In the formula, R ₁₃ and R ₁₄ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, a halogen atom. , D and e mean an integer of 1 to 10, f and g mean an integer of 0 to 2, and h
And i is 0 or 1. V has the same meaning as described above. )

Examples of the partial structural formula of the unit represented by the general formula (I-1) contained as the partial structure of the repeating unit in the charge-transporting polyester resin of the present invention are shown in Table 1 below.
5 to 5 and examples of the partial structure of the unit represented by formula (I-2) are shown in Tables 6 to 10 below, but the present invention is not limited thereto. In the present invention, specific examples of the charge transporting polyester resin represented by the general formula (III) are shown in Tables 11 to 14 below, but the present invention is not limited thereto.

Specific examples of the partial structural formula of the unit represented by the general formula (I-1) (Tables 1 to 5)

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

[Table 5]

Specific examples of the partial structure of the unit represented by formula (I-2) (Tables 6 to 10)

[Table 6]

[0024]

[Table 7]

[0025]

[Table 8]

[0026]

[Table 9]

[0027]

[Table 10]

Specific examples of the charge transporting polyester resin represented by the general formula (III) (Tables 11 to 14)

[Table 11]

[0029]

[Table 12]

[0030]

[Table 13]

[0031]

[Table 14]

The monomer used in the production of the above charge transporting polymer of the present invention can be easily synthesized by reacting arylamine or diarylbenzidine with halogenated carboalkoxyalkylbenzene. Regarding the synthesis of the charge transporting material having an alkylenecarboxylic acid ester group, after introducing a chloromethyl group in JP-A-5-80550, a Grignard reagent is formed with Mg and converted into a carboxylic acid with carbon dioxide, followed by esterification. How to do is described. However, in this method, since the chloromethyl group has high reactivity, it cannot be introduced in the initial stage of the raw material. Therefore, after forming a skeleton such as triarylamine or tetraarylbenzidine, for example, the methyl group introduced in the initial stage of the raw material is converted to a chloromethyl group, or an unsubstituted one is used in the raw material stage. It is necessary to directly chloromethylate or introduce a formyl group, reduce it to a hydroxymethyl group, and then convert it to a chloromethyl group with thionyl chloride or the like.

However, the charge-transporting material having a skeleton such as triarylamine or tetraarylbenzidine has a very high reactivity, so that a substitution reaction to an aromatic ring is likely to occur, and therefore the introduced methyl group is not used. Conversion to a chloromethyl group is virtually impossible. Further, in the raw material stage, an unsubstituted one is used, and in the method of directly chloromethylating, the chloromethyl group can be introduced only in the para position with respect to the nitrogen atom. Further, the method of introducing a formyl group and then introducing it into a chloromethyl group has a long reaction step. On the other hand, the method of obtaining a monomer by reacting arylamine or diarylbenzidine with halogenated carboalkoxyalkylbenzene is excellent in that it is easy to change the position of the substituent and control the ionization potential. It is possible to control the ionization potential of the charge-transporting polymer. The charge-transporting monomer used in the present invention can be easily introduced with various substituents and is chemically stable, so that it is easy to handle, and the above-mentioned problems are solved.

The charge-transporting random copolymerized polyester resin of the present invention has the following structural formula (VI-1) or (VI-2).
By using at least one kind of the charge transporting monomer represented by and at least one kind of the dicarboxylic acid derivative represented by the following structural formula (VII), for example, “Experimental Chemistry Course 4th Edition”
It can be synthesized by polymerizing by a known method described in Volume 28 and the like.

[Chemical 11] [In the formula, R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a halogen atom,
Alternatively, it represents a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent aromatic group. T is carbon number 1
10 represents a divalent hydrocarbon group which may be branched.
k and l are 0 or 1, respectively. E represents a hydroxyl group, a halogen atom, or a group —O—R ₁₅ . (However, R ₁₅ represents an alkyl group, a substituted or unsubstituted aryl group, or an aralkyl group.)]

That is, the charge-transporting polyester resin of the present invention can be synthesized as follows. (1) When E is a hydroxyl group When E is a hydroxyl group, dihydric alcohols represented by HO- (YO) _m- H are converted into structural formulas (VI-1) and (VI-
2) and compounds represented by (VII) [hereinafter, referred to as "(VI-
1) + (VI-2) + (VII) ". ], And is polymerized using an acid catalyst. As the acid catalyst, sulfuric acid,
Those used in ordinary esterification reactions such as toluenesulfonic acid and trifluoroacetic acid can be used, and 1/1000 to 1/10 parts by weight, preferably 1/1000 to 1 / part, relative to 1 part by weight of the charge transporting monomer. Used in the range of 50 parts by weight. In order to remove water generated during the polymerization, it is preferable to use a solvent that can form an azeotrope with water, toluene,
Chlorobenzene, 1-chloronaphthalene and the like are effective, and in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, relative to 1 part by weight of (VI-1) + (VI-2) + (VII). Used in. The reaction temperature can be set arbitrarily, but it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water generated during the polymerization. After the reaction, if a solvent is not used, it is dissolved in a solvent that can dissolve it. When a solvent is used, the reaction solution as it is is added dropwise to an alcohol such as methanol or ethanol, or a poor solvent in which a polymer such as acetone is difficult to dissolve, and a charge transporting polymer is deposited to form a charge transporting polymer. After separation, wash thoroughly with water or organic solvent and dry. Further, if necessary, the reprecipitation treatment of dissolving in a suitable organic solvent, dropping in a poor solvent and precipitating the charge transporting polymer may be repeated. The reprecipitation treatment is preferably carried out with a mechanical stirrer or the like while efficiently stirring. The solvent that dissolves the charge transporting polymer during the reprecipitation treatment is (VI-1) +
It is used in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 1 part by weight of (VI-2) + (VII).
The poor solvent is (VI-1) + (VI-2) + (VII) 1
1 to 1000 parts by weight, preferably 10 parts by weight
It is used in the range of up to 500 parts by weight.

(2) When E is a halogen atom When E is a halogen atom, HO- (YO) _m- H
The dihydric alcohol represented by (VI-1) + (VI-
2) + (VII) is mixed in an approximately equivalent amount and polymerized using an organic basic catalyst such as pyridine or triethylamine. The organic basic catalyst is used in the range of 1 to 10 equivalents, preferably 2 to 5 equivalents, relative to 1 equivalent of (VI-1) + (VI-2) + (VII). As the solvent, methylene chloride, tetrahydrofuran (THF), toluene, chlorobenzene, 1-
Chloronaphthalene is effective, and (VI-1) + (VI-
2) + 1 to 1 part by weight of (VII), 1 to 100 parts by weight,
It is preferably used in the range of 2 to 50 parts by weight. The reaction temperature can be set arbitrarily. After the polymerization, it is reprecipitated and purified as described above. Further, in the case of a dihydric alcohol having a high acidity such as bisphenol, an interfacial polymerization method can also be used. That is, dihydric alcohols are added to water,
After adding an equivalent amount or more of the base to dissolve it, vigorously stirring it with the divalent alcohol and an equivalent amount of (VI-1) + (VI-2)
Polymerization can be carried out by adding a solution of + (VII). At this time, 1 to 10 parts by weight of water is used for 1 part by weight of dihydric alcohol.
It is used in an amount of 00 parts by weight, preferably 2 to 500 parts by weight. As a solvent for dissolving (VI-1) + (VI-2) + (VII), methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1-chloronaphthalene and the like are effective. The reaction temperature can be set arbitrarily,
In order to accelerate the reaction, it is effective to use a phase transfer catalyst such as ammonium salt or sulfonium salt. The phase transfer catalyst is 0.1 to 10 parts by weight, preferably 0.2 to 10 parts by weight with respect to 1 part by weight of (VI-1) + (VI-2) + (VII).
Used in the range of 5 parts by weight.

(3) When E is --O--R ₁₅ When E is --O--R _15, a dihydric alcohol represented by HO-(YO) _m --H is added in excess. Inorganic acids such as sulfuric acid and phosphoric acid, titanium alkoxides, acetates or carbonates such as calcium and cobalt, and oxides of zinc and lead are heated as catalysts to be synthesized by transesterification.
The dihydric alcohol is used in the range of 2 to 100 equivalents, preferably 3 to 50 equivalents, relative to (VI-1) + (VI-2) + (VII). The catalyst is (VI-1) + (VI-2) + (VI
It is used in the range of 1/10000 to 1 part by weight, preferably 1/1000 to 1/2 part by weight, relative to 1 part by weight of I). The reaction is carried out at a reaction temperature of 200 to 300 ° C. and the group —O
After completion of transesterification from —R ₁₅ to the group —O— (Y—O) _m —H, 0.01 to 100 mmHg in order to promote polymerization by elimination of HO— (Y—O) _m —H. It is preferable to reduce the pressure to 0.05 to 20 mmHg and to carry out the reaction. In addition, it is azeotropic with HO- (YO) _m- H
It is also possible to use a high-boiling solvent such as -chloronaphthalene to carry out the reaction while azeotropically removing HO- (YO) _m- H under normal pressure.

Of the above-mentioned methods for synthesizing the charge-transporting polyester resin, the method (3) is most preferable because it is easy to obtain a high molecular weight polymer. Further, the monomer ratio [(VI-1) + (VI-2)] / [(VI-1) + (VI-
2) + (VII)] is too low in mobility, so that the polymer cannot be practically used alone, and it is necessary to add a low molecular weight compound or another polymer charge transport material.
0.3 ≦ [(VI-1) + (VI-2)] / [(VI-1) +
(VI-2) + (VII)] <1, preferably 0.4 ≦ [(VI
-1) + (VI-2)] / [(VI-1) + (VI-2) +
(VII)] <1, more preferably 0.5 ≦ [(VI-1) +
(VI-2)] / [(VI-1) + (VI-2) + (VII)] <
Set to 1. If the polymerization degree p of the charge transporting polymer is too low, the film formability is poor, and a strong film is difficult to obtain, and if it is too high, the solubility in a solvent is low and the processability is deteriorated. It is used in the range of, preferably 10 to 3000, more preferably 15 to 1000.

The novel charge transporting polymer of the present invention is an electron
Used in photographic photoreceptors . In the electrophotographic photoreceptor of the present invention, the charge transporting polymer may contain an insulating polymer compatible with it. INDUSTRIAL APPLICABILITY The novel charge transporting polymer of the present invention can be applied to an electrophotographic photoreceptor or an organic electroluminescence device. Specifically, electricity of a photosensitive layer containing the charge-transporting polymer on the support structure
Ru is used as a child photoreceptor. In particular, the general formula (I
-1) or at least one type of the structure represented by (I-2) and at least one type of the dicarboxylic acid component represented by the general formula (II) in the surface layer of the electrophotographic photoreceptor. You can list what is contained. Further, as a charge transporting material in the photosensitive layer, at least one or more structures represented by the general formula (I-1) or (I-2) and at least one dicarboxylic acid component represented by the general formula (II) are used. An electrophotographic photoreceptor containing a phthalocyanine compound crystal as a charge-transporting polymer and a charge-generating material contained therein can be cited as a preferable example.

In the electrophotographic photoreceptor of the present invention, the phthalocyanine crystal used in combination with the charge-transporting polymer is a halogenated gallium phthalocyanine crystal disclosed in JP-A-5-98181 or JP-A-5-98181. -140472 gazette and Unexamined-Japanese-Patent No. 5-1.
Halogenated tin phthalocyanine crystals disclosed in JP-A-40473, hydroxygallium phthalocyanine crystals disclosed in JP-A-5-263007 and JP-A-5-279591, and JP-A-4-189873.
The oxytitanium phthalocyanine hydrate crystals disclosed in Japanese Patent Application Laid-Open No. 5-43813 and Japanese Patent Application Laid-Open No. 5-43813 can be used, whereby an electrophotographic photosensitive member having particularly high sensitivity and excellent repeated stability can be obtained.

As the chlorogallium phthalocyanine crystal used in the present invention, as disclosed in Japanese Unexamined Patent Publication No. 5-98181, a chlorogallium phthalocyanine crystal produced by a known method is used in an automatic mortar, a planetary mill, and a vibration machine. It can be produced by mechanically dry pulverizing with a mill, a CF mill, a roll mill, a sand mill, a kneader or the like, or by performing a wet pulverization treatment with a solvent using a ball mill, a mortar, a sand mill, a kneader or the like after dry pulverizing. As the solvent used in the above treatment, aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.),
Aliphatic polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.),
Esters (acetic acid esters, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ethers (diethyl ether, tetrahydrofuran, etc.), mixed systems of several types, mixed systems of water and these organic solvents, etc. Can be given. The solvent used is 1 to 200 parts, preferably 10 to 100 parts, relative to chlorogallium phthalocyanine. Processing temperature is 0 ℃
~ The boiling point of the solvent or less, preferably in the range of 10 ~ 60 ℃. Further, at the time of crushing, it is possible to use a grinding aid such as sodium chloride and sodium sulfate. The grinding aid is 0.5 to 20 with respect to the pigment.
It may be used twice, preferably 1 to 10 times.

Dichlorotin phthalocyanine crystals are disclosed in JP-A-5-140472 and JP-A-5-14047.
As disclosed in Japanese Patent Laid-Open No. 3 (1993), it can be obtained by pulverizing dichlorotin phthalocyanine crystals produced by a known method in the same manner as the above-mentioned chlorogallium phthalocyanine and treating with a solvent. The hydroxygallium phthalocyanine crystal is obtained by dissolving a chlorogallium phthalocyanine crystal produced by a known method in an acid or alkaline solution, as disclosed in JP-A-5-263007 and JP-A-5-279591. Decomposition or acid pasting, to synthesize hydroxygallium phthalocyanine crystals, directly subjected to solvent treatment, or hydroxygallium phthalocyanine crystals obtained by synthesis, ball mill with a solvent, mortar,
It can be produced by performing a wet pulverization treatment using a sand mill, a kneader or the like, or by performing a dry pulverization treatment without using a solvent and then performing a solvent treatment. As the solvent used in the above treatment, aromatics (toluene,
Chlorobenzene, etc., amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), aliphatic polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (Benzyl alcohol, phenethyl alcohol, etc.), esters (acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide,
Examples include ethers (diethyl ether, tetrahydrofuran, etc.), a mixed system of several kinds, a mixed system of water and these organic solvents, and the like. The solvent used is 1 to 200 parts, preferably 10 to 100 parts, relative to hydroxygallium phthalocyanine. The processing temperature is 0 to 1
The temperature is 50 ° C., preferably room temperature to 100 ° C. Further, at the time of crushing, it is possible to use a grinding aid such as sodium chloride and sodium sulfate. The grinding aid is used in an amount of 0.5 to 20 times, preferably 1 to 10 times that of the pigment.

The oxytitanium phthalocyanine crystal is
JP-A-4-189873 and JP-A-5-438
As disclosed in Japanese Patent No. 13, the oxytitanium phthalocyanine produced by a known method is acid pasted, or salt milled with an inorganic salt using a ball mill, a mortar, a sand mill, a kneader or the like. , Oxytitanium phthalocyanine crystal having a relatively low crystallinity, which has a peak at 27.2 ° in X-ray diffraction spectrum, is directly subjected to solvent treatment, or together with the solvent, ball mill, mortar, sand mill, kneader, etc. It can be manufactured by carrying out a wet pulverization process. As the acid used for acid pasting, sulfuric acid is preferable, and the one having a concentration of 70 to 100%, preferably 95 to 100% is used, and the dissolution temperature is
It is set in the range of -20 to 100 ° C, preferably 0 to 60 ° C. The amount of concentrated sulfuric acid is 1 to 100 times, preferably 3 to 100 times the weight of the oxytitanium phthalocyanine crystal.
The range is set to 50 times. As the solvent to be deposited,
Water or a mixed solvent of water and an organic solvent is used in an arbitrary amount, and a mixed solvent of water and an alcohol solvent such as methanol or ethanol, or a mixture of water and an aromatic solvent such as benzene or toluene. Solvents are particularly preferred. The temperature for precipitation is not particularly limited, but in order to prevent heat generation,
It is preferable to cool with ice or the like. Further, the ratio of the oxytitanium phthalocyanine crystal and the inorganic salt is 1 by weight.
/0.1 to 1/20, and the range of 1 / 0.5 to 1/5 is preferable. As the solvent used in the above solvent treatment, aromatics (toluene, chlorobenzene, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), halogenated hydrocarbons (dichloromethane, chloroform, trichloroethane, etc.), and Is a mixed system of several types,
Examples include mixed solvents of water and these organic solvents. The solvent used is 1 to 100 times, preferably 5 to 50 times, the amount of oxytitanium phthalocyanine. The treatment temperature is room temperature to 100 ° C., preferably 50 to
Set in the range of 100 ° C. The grinding aid is 0.
5 to 20 times, preferably 1 to 10 times may be used.

Next, the electrophotographic photosensitive member will be described.
As the conductive support, metals such as aluminum, nickel, chromium and stainless steel, and plastics provided with a thin film of aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, ITO, etc. Examples thereof include films and the like, paper coated or impregnated with a conductivity-imparting agent, and plastic films. These conductive supports are used in a suitable shape such as a drum shape, a sheet shape, and a plate shape, but are not limited thereto. Further, if necessary, the surface of the conductive support can be subjected to various treatments within a range that does not affect the image quality. For example, surface oxidation treatment, chemical treatment, coloring treatment, or irregular reflection treatment such as graining can be performed. Further, an undercoat layer may be further provided between the conductive support and the charge generation layer.
This undercoat layer prevents injection of charges from the conductive support to the photosensitive layer during charging of the photosensitive layer having a laminated structure, and also causes the photosensitive layer to be integrally adhered and held to the conductive support. It exhibits an action as an adhesive layer, or an action to prevent reflection of light from the conductive support, depending on the case.

The binder resin used for the undercoat layer is polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, chloride resin. Vinylidene resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin,
Known materials such as polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compounds, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds, and silane coupling agents can be used. The thickness of the undercoat layer is 0.01 to 10 μm, preferably 0.05 to 2 μm. Further, as the coating method used when providing the undercoat layer, a usual method such as a blade coating method, a Mayer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. Can be used.

Further, in the charge transport layer, the charge transport composition polymer of the present invention may be used alone, and known binder resins and other hydrazone charge transport materials, triarylamine charge transport materials, and stilbene charge transport materials may be used. You may use together with a charge transport material etc. The binder resin, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, Vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-
Known resins such as N-vinylcarbazole and polysilane can be used, but the resin is not limited to these. Among these binder resins, the following structural formulas (VIII) to (XII
When the polycarbonate resin represented by I) or the polycarbonate resin obtained by copolymerizing them is used, the compatibility is good, a uniform film is obtained, and particularly good properties are exhibited. The compounding ratio (weight ratio) is as follows: charge transporting polymer: binder resin = 1
The range of 0: 0 to 8:10 is preferable. When mixed with another charge transporting material, the range of charge transporting polymer + binder resin: charge transporting material = 10: 0 to 10: 8 is preferable.

[0047]

[Chemical 12] (In the formula, n is a degree of polymerization of 50 to 3,000)

The above-mentioned phthalocyanine crystal is preferably used as the charge generating material in the charge generating layer, but any known charge generating material such as bisazo pigment, phthalocyanine pigment, squarylium pigment, perylene pigment, dibromoanthanthrone and the like can be used. can do. The binder resin used for the charge generation layer can be selected from a wide range of insulating resins. It can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, polysilane. Preferred binder resins include polyvinyl butyral resins, polyarylate resins (polycondensates of bisphenol A and phthalic acid, etc.), polycarbonate resins,
Insulation of polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, etc. However, the present invention is not limited to these. These binder resins may be used alone or in 2
A mixture of two or more species can be used. The compounding ratio (weight ratio) of the charge generating material and the binder resin is 10: 1 to 1: 1.
A range of 0 is preferred. As a method for dispersing these, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. Further, during this dispersion, the particles are 0.5 μm or less, preferably 0.
It is effective to set the particle size to 3 μm or less, and more preferably 0.15 μm or less. Further, as a solvent used for dispersing these, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran. Ordinary organic solvents such as methylene chloride, methylene chloride, chloroform, chlorobenzene, and toluene can be used alone or in combination of two or more.

[0049]

EXAMPLES The present invention will be described below with reference to examples. In addition, "part" in an Example etc. means a "weight part." Synthesis Example 1 N, N-bis [3- (2-ethoxycarbonylethyl)]
Phenyl] -3,4-xylidine (the structure of A part is represented by partial structure 3 and the terminal is a diethyl ester) Synthesis of 3,4-xylidine 6 g, ethyl 3-iododihydrocinnamate 34 g, potassium carbonate 19 g, copper sulfate Pentahydrate 5
20 ml of g and n-tridecane was put into a 100 ml flask and heated and reacted at 230 ° C. for 10 hours under a nitrogen stream. After the reaction, cool to room temperature, dissolve in 50 ml of toluene,
The insoluble matter was filtered, and the filtrate was purified by silica gel column chromatography using toluene. This gave 20 g of oily N, N-bis [3- (2-ethoxycarbonylethyl) phenyl] -3,4-xylidine.

Synthesis Example 2 N, N'-diphenyl-N, N'-bis [3- (2-ethoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4,4'-diamine (A part) Is represented by the partial structure 6, and the terminal is a diethyl ester). Synthesis of N, N′-diphenylbenzidine 10.77 g, ethyl 3-iododihydrocinnamate 23.0 g, potassium carbonate 11.61 g, copper sulfate pentahydrate 1.0 g of the product and 20 ml of n-tridecane were placed in a 100 ml flask, and heated and reacted at 230 ° C. for 1 hour under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 50 ml of toluene, the insoluble matter was filtered, and the filtrate was purified by silica gel column chromatography using toluene. This gives an oily N, N'-diphenyl-N, N'-bis [3- (2-ethoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4,
19.6 g of 4'-diamine was obtained.

Synthesis Example 3 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1, 1'-biphenyl] -4,4'-diamine (the structure of the A part is a partial structure 1
The synthesis of N- (3,4-dimethylphenyl) -N- [4- (2-
45 g of methoxycarbonylethyl) phenyl] amine,
4,4'-diiodo-3,3'-dimethylbiphenyl 3
0 g, potassium carbonate 27 g, copper sulfate pentahydrate 5 g, n-
Add 20 ml of tridecane to a 1000 ml flask,
The mixture was heated and reacted at 230 ° C. for 5 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 200 ml of toluene, the insoluble matter was filtered, and the filtrate was purified by silica gel column chromatography using toluene. Recrystallized from a mixed solvent of ethyl acetate and ethanol to give 3,3'-dimethyl-
N, N'-bis (3,4-dimethylphenyl) -N,
38 g of N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4,4'-diamine was obtained as a pale yellow powder.

Synthesis Example 4 3,3'-Dimethyl-N, N'-bis (4-methoxyphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1 ' -Biphenyl]-
Synthesis of 4,4'-diamine (the structure of A part is shown as partial structure 22 and the terminal is dimethyl ester) N- (4-methoxyphenyl) -N- [4- (2-methoxycarbonylethyl) phenyl] amine 5.0 g,
4,4'-diiodo-3,3'-dimethylbiphenyl 3.4 g, potassium carbonate 2.9 g, copper sulfate pentahydrate 0.
5 g and 5 ml of n-tridecane were placed in a 100 ml flask, and heated and reacted at 230 ° C. for 15 hours under a nitrogen stream. After the reaction, cool to room temperature, dissolve in 20 ml of toluene,
The insoluble matter was filtered, and the filtrate was purified by silica gel column chromatography using toluene. This gives a pale yellow oily 3,3'-dimethyl-N, N'-bis (4-methoxyphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1 '. 5.3 g of -biphenyl] -4,4'-diamine were obtained.

Synthesis Example 5 N, N'-bis (3,4-dimethylphenyl) -N,
N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1 ': 4', 1 "-terphenyl]-
Synthesis of 4,4 "-diamine (the structure of A part is represented by partial structure 31 and the terminal is dimethyl ester) N- (3,4-dimethylphenyl) -N- [4- (2-
Methoxycarbonylethyl) phenyl] amine 5.0
g, 4,4 ″ -diiodo-1,1 ′: 4 ′, 1 ″ -terphenyl 3,8 g, potassium carbonate 2.9 g, copper sulfate pentahydrate 1.0 g, and n-tridecane 10 ml in a 200 ml flask. And heated at 230 ° C. for 5 hours in a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 20 ml of toluene, the insoluble matter was filtered, and the filtrate was purified by silica gel column chromatography using toluene. Recrystallization from acetone gave N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1 ': 4', 1 ″-
3.7 g of terphenyl] -4,4 ″ -diamine was obtained as a pale yellow powder (melting point: 146 to 147 ° C.).

Synthesis Example 6 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonylmethyl) phenyl]-[1, 1'-biphenyl] -4,4'-diamine (the structure of the A part is a partial structure 1
8 and the terminal is dimethyl ester) synthesis N- (3,4-dimethylphenyl) -N- [4- (2-
Methoxycarbonylmethyl) phenyl] amine 9.0
g, 4,4'-diiodo-3,3'-dimethylbiphenyl 6.2 g, potassium carbonate 5.5 g, copper sulfate pentahydrate 1.0 g, and n-tridecane 10 ml were placed in a 200 ml flask and placed under a nitrogen stream. The reaction was carried out by heating at 230 ° C. for 5 hours. After the reaction, the mixture was cooled to room temperature, dissolved in 40 ml of toluene, the insoluble matter was filtered, and the filtrate was purified by silica gel column chromatography using toluene. Recrystallized from a mixed solvent of ethyl acetate and ethanol to give 3,3'-
Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonylmethyl) phenyl]-[1,1'-biphenyl] -4,
7.1 g of 4'-diamine was obtained as a pale yellow powder. (Melting point is 179-181 ° C).

Synthesis Example 7 N, N'-diphenyl-N, N'-bis [4- (4-ethoxycarbonylethylphenyl) phenyl]-[1,
1'-biphenyl] -4,4'-diamine (the structure of the A portion is represented by the partial structure 48, and the terminal is a diethyl ester)
Synthesis of N, N'-diphenylbenzidine 10.0 g, 4-ethoxycarbonylethyl-4'-iodobiphenyl 24.
0 g, potassium carbonate 11 g, copper sulfate pentahydrate 1.0 g,
30 ml of n-tridecane was placed in a 200 ml flask, and heated and reacted at 230 ° C. for 1 hour under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 10 ml of toluene, the insoluble matter was filtered, and the filtrate was purified by silica gel column chromatography using toluene. Thereby, oily N, N'-diphenyl-N, N'-bis [4- (4-ethoxycarbonylethylphenyl) phenyl]-[1,
1'-biphenyl] -4,4'-diamine 16.6 g
Obtained.

Synthetic Example 8 30 parts of 1,3-diiminoisoindoline and 9.1 parts of gallium trichloride were put in 230 parts of quinoline and reacted at 200 ° C. for 3 hours, then the product was filtered and acetone was added. ,
After washing with methanol and then drying the wet cake,
28 parts of chlorogallium phthalocyanine crystal was obtained. 3 parts of the obtained chlorogallium phthalocyanine crystal was dry-ground for 3 hours in an automatic mortar (Lab-Mill UT-21 type, manufactured by Yamato Scientific Co., Ltd.), and 0.5 part was mixed with 60 parts of glass beads (1 mmφ) at room temperature. After milling in 20 parts of benzyl alcohol for 24 hours, the glass beads were separated by filtration, washed with 10 parts of methanol, dried, and powder X-ray diffraction spectrum showed 2θ ± 0.2 ° = 7.4 °, 1
Chlorogallium phthalocyanine crystals having strong diffraction peaks at 6.6 °, 25.5 ° and 28.3 ° were obtained. This is CG-1.

Synthesis Example 9 50 g of phthalonitrile and 27 g of anhydrous stannic chloride
Was added to 350 ml of 1-chlornaphthalene, and 195
After reacting at ℃ for 5 hours, the product was filtered and
It was washed with chloronaphthalene, acetone, methanol, and then with water, and dried under reduced pressure to obtain 18.3 g of dichlorotin phthalocyanine crystal. 5 g of the obtained dichlorotin phthalocyanine crystal was added to 10 g of salt and agate ball (20
(mmφ) 500g and put in an agate pot, 400r with a planetary ball mill (P-5 type, Fritsch)
After crushing with pm for 10 hours, it was thoroughly washed with water and dried.
0.5g of it is added with 15g of THF and glass beads (1mm
φ) After milling with 30 g at room temperature for 24 hours,
The glass beads were separated by filtration, washed with methanol and dried, and the powder X-ray diffraction spectrum showed 2θ ± 0.2 ° = 8.5.
Dichlorotin phthalocyanine crystals having strong diffraction peaks at °, 11.2 °, 14.5 ° and 27.2 ° were obtained. This is designated as CG-2.

Synthesis Example 10 3 parts of the chlorogallium phthalocyanine crystal obtained in Synthesis Example 8 was dissolved in 60 parts of concentrated sulfuric acid at 0 ° C., and then the above solution was added dropwise to 450 parts of distilled water at 5 ° C. to recrystallize the crystal. It was deposited.
After washing with distilled water, diluted ammonia water, etc., and drying, 2.
5 parts of hydroxygallium phthalocyanine crystals were obtained.
After crushing the crystals for 5.5 hours in an automatic mortar, 0.5
After milling 24 parts with 15 parts of dimethylformamide and 30 parts of glass beads having a diameter of 1 mm for 24 hours, crystals were separated, washed with methanol and dried, and powder X-ray diffraction spectrum showed 2θ ± 0.2 ° = 7.5 °. 9.9 °, 12.5
°, 16.3 °, 18.6 °, 25.1 ° and 28.3
A hydroxygallium phthalocyanine crystal having a strong diffraction peak at ° was obtained. This is designated as CG-3.

Synthesis Example 11 30 parts of 1,3-diiminoisoindoline and 17 parts of titanium tetrabutoxide were put in 200 parts of 1-chloronaphthalene and reacted at 190 ° C. for 5 hours under a nitrogen stream, and then the product was filtered. Separately, it was washed with aqueous ammonia, water, and acetone to obtain 40 parts of oxytitanium phthalocyanine. 5 parts of the obtained oxytitanium phthalocyanine crystal and 10 parts of sodium chloride were placed in an automatic mortar (Lab-Mill).
UT-21 type, manufactured by Yamato Scientific Co., Ltd.) was pulverized for 3 hours.
Then, it was thoroughly washed with distilled water and dried to obtain 4.8 parts of oxytitanium phthalocyanine crystal. The obtained oxytitanium phthalocyanine crystal had a clear peak at 2θ ± 0.2 ° = 27.3 ° in the powder X-ray diffraction spectrum. 2 parts of the obtained oxytitanium phthalocyanine crystal was stirred in a mixed solvent of 20 parts of distilled water and 2 parts of monochlorobenzene at 50 ° C. for 1 hour, filtered, thoroughly washed with methanol, and dried to obtain powder X-rays. Oxytitanium phthalocyanine hydrate crystal having a strong diffraction peak at 2θ ± 0.2 ° = 27.3 ° in the diffraction spectrum was obtained. This is designated as CG-4.

Synthesis Example 12 (Synthesis of Charge Transporting Polyester Resin (16)) 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- ( 2-Methoxycarbonylethyl) phenyl]-[1,1′-biphenyl] -4,4′-diamine 15.0 g, dimethyl sebacate 3.0 g, ethylene glycol 30.0 g and tetrabutoxy titanium 0.1 g in 300 ml. The mixture was placed in a flask and heated under reflux for 3 hours under a nitrogen stream. 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl)
-N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4,4 '
0.5 mm after confirming that the diamine has been consumed
230g while decompressing to Hg and distilling off ethylene glycol
The mixture was heated to ° C and the reaction was continued for 3 hours. Then, the mixture was cooled to room temperature, dissolved in 200 ml of methylene chloride, the insoluble matter was filtered, and the filtrate was added dropwise to 1400 ml of ethanol while stirring to precipitate a polymer. The polymer obtained is filtered, washed thoroughly with ethanol and then dried,
6.5 g of polymer was obtained. When the molecular weight was measured by GPC, it was Mw = 1.45 × 10 ⁵ (in terms of styrene). (Polymerization degree q = about 160, r = about 105). The IR spectrum is shown in FIG.

Synthesis Example 13 (Synthesis of Charge Transporting Polyester Resin (17)) 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- ( 2-Methoxycarbonylethyl) phenyl]-[1,1′-biphenyl] -4,4′-diamine 15.0 g, dimethyl terephthalate 3.0 g, ethylene glycol 30.0 g and tetrabutoxytitanium 0.1 g in 300 ml. The mixture was placed in a flask and heated under reflux for 3 hours under a nitrogen stream. 3,3'-
Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4,
After confirming that the 4'-diamine was consumed, 0.5
While reducing the pressure to mmHg and distilling off ethylene glycol, 2
It was heated to 35 ° C. and the reaction was continued for 2.5 hours. Then, the mixture was cooled to room temperature, dissolved in 200 ml of methylene chloride, the insoluble matter was filtered, and the filtrate was added dropwise to 1400 ml of ethanol while stirring to precipitate a polymer. The obtained polymer was filtered, sufficiently washed with ethanol, and then dried to obtain 17.0 g of a polymer. When the molecular weight was measured by GPC, it was Mw = 1.40 × 10 ⁵ (in terms of styrene). (Polymerization degree q = about 150, r = about 12
0). The IR spectrum is shown in FIG.

Synthesis Example 14 (Synthesis of Charge Transporting Polyester Resin (15)) 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- ( 2-Methoxycarbonylethyl) phenyl]-[1,1′-biphenyl] -4,4′-diamine 15.0 g, dimethyl adipate 3.0 g, ethylene glycol 30.0 g and tetrabutoxytitanium 0.1 g in 300 ml. The mixture was placed in a flask and heated under reflux for 3 hours under a nitrogen stream. 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl)
-N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4,4 '
0.5 mm after confirming that the diamine has been consumed
235 while reducing the pressure to Hg and distilling off ethylene glycol
The mixture was heated to ° C and the reaction was continued for 3 hours. Then, the mixture was cooled to room temperature, dissolved in 200 ml of methylene chloride, the insoluble matter was filtered, and the filtrate was added dropwise to 1400 ml of ethanol while stirring to precipitate a polymer. The polymer obtained is filtered, washed thoroughly with ethanol and then dried,
7.0 g of polymer was obtained. When the molecular weight was measured by GPC, it was Mw = 1.30 × 10 ⁵ (in terms of styrene). (Polymerization degree q = about 145, r = about 125). The IR spectrum is shown in FIG.

Tables 11 to 1 show combinations of the charge transporting monomer and the dicarboxylic acid represented by the general formula (II).
A charge transporting polyester resin was synthesized in the same manner, except that the charge transfer polyester resin was changed as shown in FIG.

Example 1 A zirconium compound (trade name: Organix Z) was formed on a 30 mmφ aluminum cylindrical substrate that had been subjected to honing treatment.
C540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 100 parts of a silane compound (trade name: A1110, manufactured by Nippon Unicar Co., Ltd.), and a solution of 400 parts of i-propanol and 200 parts of butanol was applied by a dip coating method, and then at 150 ° C.
Was heated and dried for 10 minutes to form an undercoat layer having a film thickness of 0.5 μm. Chlorogallium phthalocyanine crystal 10
Parts were mixed with 10 parts of polyvinyl butyral resin (trade name: S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 500 parts of n-butyl acetate, and treated with a glass shaker for 1 hour in a paint shaker to be dispersed, and then obtained. The coating solution is applied onto the above-mentioned undercoat layer by a dip coating method,
Heat dried at 0 ° C. for 10 minutes. Next, 5 parts of the charge transporting polyester resin (16) was mixed with monochlorobenzene 3
The coating liquid obtained by dissolving in 8 parts was applied onto an aluminum cylindrical substrate having a charge generation layer formed thereon by a dip coating method, and dried by heating at 120 ° C. for 1 hour to give a film thickness of 15
A μm charge transport layer was formed.

The electrophotographic characteristics of the electrophotographic photosensitive member thus obtained were measured by a laser beam printer (XP-1
1, high temperature and high humidity (35 ° C, 80
% RH), print test is performed under the environment of
The image quality after copying 000 sheets was evaluated. The results are shown in Table 15.
Shown in.

Examples 2 to 24 Electrophotography in the same manner as in Example 1 except that the combination of the charge generating material and the charge transporting material (charge transporting polyester resin) was changed as shown in Table 15. A photoconductor was prepared and evaluated. The results are shown in Table 15.

Reference Example 1 (Synthesis of Alternate Copolymer) N, N'-diphenyl-N, N'-bis [3- (2-ethoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4 , 4'-diamine 1.03 g, ethylene glycol 2.0 g and tetrabutoxy titanium 0.0
6 g was put into a 50 ml flask and heated under reflux for 3 hours under a nitrogen stream. N, N'-diphenyl-N, N'-bis [3- (2-ethoxycarbonylethyl) phenyl]-
After confirming that [1,1′-biphenyl] -4,4′-diamine was consumed, the pressure was reduced to 0.5 mmHg and ethylene glycol was distilled off. Then cool to room temperature,
A solution prepared by dissolving 20 ml of methylene chloride and 0.30 g of isophthalic acid dichloride in 10 ml of methylene chloride was added dropwise. Furthermore, triethylamine 0.61g was added and it heated and refluxed for 30 minutes. After adding 0.3 ml of methanol and heating under reflux for another 30 minutes, the insoluble matter was filtered and 300 ml of ethanol was added dropwise while stirring.
The polymer was precipitated. The polymer obtained by filtration was again dissolved in 50 ml of THF, and 300 ml of water was added dropwise while stirring to precipitate the polymer. This was thoroughly washed with water and dried to obtain 0.52 g of polymer. When the molecular weight of the thus obtained polymer was measured by GPC, it was Mw = 1.60 × 10 ⁴ (in terms of styrene) and the degree of polymerization p was about 20.

Reference Example 2 (Synthesis of Alternating Copolymer) 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonyl) 50 g of ethyl) phenyl]-[1,1′-biphenyl] -4,4′-diamine, 4.0 g of ethylene glycol and 0.1 g of tetrabutoxytitanium are added.
The mixture was placed in a ml flask and heated under reflux for 3 hours under a nitrogen stream. 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1'-biphenyl]- After confirming that 4,4′-diamine was consumed, the pressure was reduced to 0.5 mmHg and the temperature was raised to 230 ° C. while distilling off ethylene glycol, and the reaction was continued for 3 hours. Then, the mixture was cooled to room temperature, dissolved in 50 ml of methylene chloride, the insoluble matter was filtered off, and the filtrate was added dropwise to 250 ml of stirred ethanol to precipitate a polymer. After filtering the obtained polymer and thoroughly washing with ethanol,
It was dried to obtain 1.9 g of polymer. When the molecular weight of the polymer thus obtained was measured by GPC, it was Mw = 1.23 × 10 ⁵ (in terms of styrene). (Polymerization degree p = about 160)

Comparative Examples 1 and 2 An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the charge transporting polymers synthesized in Reference Examples 1 and 2 were used. The results are shown in Table 15.

[0070]

[Table 15]

[0071]

The electrophotographic photosensitive member of the present invention is a random copolymer obtained by using a monomer having a specific structural unit, and the mechanical properties can be improved by appropriately selecting the partial structure of the monomer. Since a novel high molecular weight charge-transporting polyester resin, which can easily control characteristics, oxidation resistance, charge injection property, etc., is used as a charge-transporting material, it has an advantage that the degree of freedom in device design is large. The electrophotographic photosensitive member of the present invention has high photosensitivity and excellent repeatability.

[Brief description of drawings]

FIG. 1 is an IR spectrum diagram of a charge-transporting polyester resin of Synthesis Example 12.

FIG. 2 is an IR spectrum diagram of a charge-transporting polyester resin of Synthesis Example 13.

FIG. 3 is an IR spectrum diagram of a charge-transporting polyester resin of Synthesis Example 14.

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-7-199503 (JP, A) JP-A-5-232727 (JP, A) JP-A-7-13376 (JP, A) JP-A-5- 295096 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 5/00 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. The following general formula (I-1) or (I-2):
And at least one structure represented by the following general formula (II)
Contained in the partial structure of at least one and repeating units of the dicarboxylic acid component represented, that having a photosensitive layer containing a random copolymer polymerized charge transporting polyester resin
Electrophotographic photosensitive member, wherein a call. [Chemical 1] (In the formula, R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a halogen atom,
Alternatively, it represents a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent aromatic group. T is carbon number 1
10 represents a divalent hydrocarbon group which may be branched.
k and l are 0 or 1, respectively. ) —O—CO—Z—CO—O— (II) (In the formula, Z represents a divalent hydrocarbon group.) 2. A charge-transporting polyester resin comprising at least one type of structure represented by the general formula (I-1) or (I-2) and a dicarboxylic acid component represented by the general formula (II). The electrophotographic photograph according to claim 1, which is a random copolymer represented by the following general formula (III) containing at least one of the above as a partial structure of a repeating unit.
Photoconductor . [Chemical 2] [In formula, A shows the structure represented by the said General formula (I-1) or (I-2), Y and Z show a divalent hydrocarbon group. m is an integer of 1 to 5, q is an integer of 1 or more, and r is 1 to
It means an integer of 3500. However, q + r is 5 to 50
Is an integer of 00, and 0.3 ≦ q / (q + r) <1. ] 3. X in the structure represented by formula (I-1) or (I-2) is a biphenylene group or 3,
An electrophotographic image according to claim 1 or 2, further comprising a charge-transporting polyester resin containing a partial structure of a repeating unit which is a 3'-dimethylbiphenylene group.
Photoconductor . 4. The above general formula (I-1) or (I-2)
And at least one structure represented by the general formula (II)
A charge-transporting polyester resin that contains at least one dicarboxylic acid component represented by the formula (1) as a partial structure of a repeating unit and is randomly copolymerized, and a substantially insulating insulating resin that is compatible with the charge-transporting polyester resin. The electrophotographic photosensitive member according to claim 1, further comprising a polymer.
Body . 5. A random copolymerized charge transporting polyester.
A tellurium resin is contained in the surface layer.
1. The electrophotographic photosensitive member according to 1 . 6. A halo as a charge generating material in a photosensitive layer.
Gallium gallium phthalocyanine crystal, Sulfur halide
Tarocyanine crystals, hydroxygallium phthalocyanine
Contains crystals or oxytitanium phthalocyanine crystals
The electrophotographic photosensitive member according to claim 1, wherein