JP3496541B2 - Charge transporting polyester and organic electronic device using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel charge transporting polyester and an organic electronic device using the same, particularly an electrophotographic photoreceptor.

[0002]

2. Description of the Related Art Charge-transporting polymers typified by polyvinylcarbazole (PVK) are known as photoconductive materials for electrophotographic photoconductors and proceedings of the 36th Joint Lecture on Applied Physics, 31p-K-12 (1990). It is promising as a material for an organic electroluminescence device as described in the above. These materials form a layer together and are used as a charge transport layer. As a material for forming the charge transport layer, PVK is used.
Well-known are the charge-transporting polymers represented by (1) and low-molecular-weight dispersion systems in which a charge-transporting low-molecular compound is dispersed in the polymer. Further, as the organic electroluminescent element, it is general to use a low molecular weight charge transport material by vapor deposition. Among them, the low molecular dispersion type is predominant especially in electrophotographic photoreceptors because of the variety of materials and the ease of obtaining highly functional ones.

With respect to electrophotographic photoreceptors, in recent years, as the performance of organic photoreceptors has increased, they have come to be used in high-speed copying machines and printers. When used in a printer, the current performance is not always sufficient, and further longevity is particularly desired. One of the important factors that determines the life of the organophotoreceptor is the abrasion of the surface layer. The current organic photoreceptor is
A so-called laminated type in which a charge transport layer is laminated on a charge generation layer is mainly used, and therefore the charge transport layer often serves as a surface layer. Currently, the mainstream low molecular weight dispersion type charge transport layer is being obtained with sufficiently satisfactory electric properties, but since the low molecular weight compound is dispersed in the binder resin, There is a drawback that the mechanical performance inherent to the resin to be coated is deteriorated and that it is essentially weak in terms of wear. On the other hand, the charge-transporting polymer may significantly improve the above-mentioned drawbacks,
Currently being actively researched. For example, US Pat.
806,443 discloses polycarbonates by polymerization of certain dihydroxyarylamines and bischloroformates and is described in US Pat. No. 4,80.
No. 6,444 discloses polycarbonates by polymerization of certain dihydroxyarylamines with phosgene. Further, US Pat. No. 4,801,517 discloses a polycarbonate obtained by polymerizing a bishydroxyalkylarylamine with bischloroformate or phosgene, and US Pat. No. 4,937,
165 and U.S. Pat. No. 4,959,288 disclose polycarbonates by polymerization of certain dihydroxyarylamines or bishydroxyalkylarylamines with bischloroformates, and by polymerization with bisacyl halides. Polyesters are disclosed. Furthermore, US Pat. No. 5,034,296 discloses polycarbonates and polyesters of arylamines having a specific fluorene skeleton, and US Pat. No. 4,983,482 discloses polyurethanes. ing. Furthermore, Japanese Patent Publication Sho 59-289
No. 03 discloses a polyester having a specific bisstyrylbisarylamine as a main chain. Further, JP-A-61-20953, JP-A-1-134456, JP-A-1-134457 and JP-A-1-134.
In Japanese Patent Laid-Open No. 462, Japanese Patent Laid-Open No. 4-133065, Japanese Patent Laid-Open No. 4-133066, etc., a polymer having pendant charge-transporting substituents such as hydrazone and triarylamine and a photoreceptor using the same are proposed. Has been done. In particular, a polymer having a tetraarylbenzidine skeleton is referred to as "The Sixth International
al Congress on Advances i
n Non-impact Printing Tec
hnologies. 306, (1990) ”, it is highly mobile and 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 satisfy 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 monomer, it is important that the ionization potential of the charge transporting monomer can be controlled. The monomers that are the raw materials for the above-mentioned triarylamine polymers can be roughly classified into dihydroxyarylamines and bishydroxyalkylarylamines.
However, since dihydroxyarylamine has an aminophenol structure, it is easily oxidized and is difficult to purify. Further, particularly in the case of a para-hydroxy substituted structure, 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 a bias in the charge distribution and the mobility tends to decrease. On the other hand, bishydroxyalkylarylamine does not affect the electron withdrawing property of oxygen due to the methylene group, but it is difficult to synthesize a monomer. That is, in the case of synthesizing by reacting diarylamine or diarylbenzidine with 3-bromoiodobenzene, both bromine and iodine are reactive, so that the product is likely to be a mixture, leading to a decrease in yield. In addition, there is a problem that alkyllithium and ethylene oxide used for lithiating a bromine compound are highly dangerous and toxic and require careful handling.

In order to solve this problem, the inventors of the present invention have made extensive studies as to a charge transporting polymer, and as a result, disclosed in JP-A-8-253568 and JP-A-8-212640.
JP-A-8-208820 and JP-A-9-208820.
No. 110974 discloses a novel high performance charge transporting polymer. The materials described in these publications are alternating copolymer charge-transporting polymers represented by the following general formula (III) or (IV). H- (O-Y) _r- O [CO-A-CO-O- (Y-O) _r ] _p- H (III) B- [CO-A-CO-O- (Y-O) _r-. -CO-Z-CO-O- (Y-O) _r ] CO-A-CO-B '(IV) [In the formula, Y and Z each represent a divalent hydrocarbon group, and A is the following. Represents a divalent group represented by the formula,

[Chemical 2] (R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
It represents a halogen atom, an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent organic group. a, b, k and m each represent an integer of 0 or 1, and T represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be branched. ) B and B'are each independently a group -O- (YO) _r.
-H or group -O- (Y-O) _r -CO-Z-CO-O
R '(wherein R'represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, Y and Z each represent a divalent hydrocarbon group, r Represents an integer of 1 to 5), and r is 1
Represents an integer of 5 and p represents an integer of 5 to 5000. ]

This charge-transporting polymer showed excellent characteristics as compared with conventional ones and was highly practical, but it was not sufficient to meet the demand for higher speed.
As a result of studying this point, in the charge-transporting polymer of alternating copolymerization represented by the above general formulas (III) and (IV), the part responsible for charge transport is only the part of the group A, and the charge-transporting function is It was found that the demand for higher speed cannot be met because the ratio of the portion (the portion of the base A) is reduced.
That is, it is well known that in a low molecular weight charge transport material, the charge transport ability increases as the concentration in the charge transport layer increases, and also in the charge transporting polymer, the concentration of the charge transport functional portion increases. By doing so, it is considered that higher functionality is possible. However, because it is difficult to control the availability of monomers as the raw material of the polymer, or the polymerization method and the polymerization conditions, for example, even the portion corresponding to the groups Y, B and B'in the general formula (III) or (IV) is reached. Polymers incorporating charge transport functional moieties have not been investigated.

Accordingly, it is an object of the present invention to provide a novel high performance charge transporting polyester which is easy to manufacture. Another object of the present invention is to provide an organic electronic device using the charge-transporting polyester, particularly an electrophotographic photoreceptor.

[0008]

Means for Solving the Problems As a result of earnest studies on the above problems, the present inventors have found that a monomer having a partial structure of a dicarboxylic acid component represented by the following general formula (I) can be easily reduced. It is possible to synthesize a monomer having a partial structure of a diol component represented by the following general formula (II),
Using these monomers, at least one kind of the structure represented by the following general formula (I) and at least one kind of the structure represented by the following general formula (II) are contained as a partial structure of the repeating unit. As a result, they have found that a high performance charge transporting polyester resin can be synthesized, and completed the present invention.

Therefore, the charge-transporting polyester of the present invention is represented by at least one of the structures represented by the following general formula (I) as the dicarboxylic acid component and the following general formula (II) as the diol component. At least one of the structures
And at least one species as a partial structure of a repeating unit, and the weight average molecular weight thereof is preferably 10,000 to 300,000. -CO- (T) a-A- (T) a-CO- (I) -O- (T) b-A '-(T) b-O- (II) [wherein A and A'are , Each represents a divalent group represented by the following formula.

[0010]

[Chemical 3] (R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
It represents a halogen atom, an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent organic group. a, b, k and m each represent an integer of 0 or 1, and T represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be branched. )] The organic electronic device of the present invention is characterized by containing the above charge-transporting polyester in a charge-transporting functional film, and is preferably an electrophotographic photoreceptor having a photosensitive layer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Specific structural examples of T in the above general formulas (I) and (II) are shown below. The arylamine skeleton may be bonded to either side, for example,
The description "T-2r" indicates that the arylamine skeleton is bonded to the right side of the structure T-2, and the description "T-21" indicates that the arylamine skeleton is bonded to the left side of the structure T-2.

[0012]

[Chemical 4]

[0013]

[Chemical 5]

Examples of the group X include those selected from the following groups (1) to (7).

[Chemical 6]

[In the formula, R ₄ represents a hydrogen atom or a carbon number of 1 to 4
Represents an alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, R _{5 to} R ₁₀ represent 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, and c is 0
Or means 1. Further, the group V is the following group (8)-
The one selected from (17) is shown.

[0016]

[Chemical 7] (In the formula, d means an integer of 1 to 10, and e is 1 to 3
Means an integer of. )]

Examples of the structures represented by the above general formulas (I) and (II) are shown in Table 1 to Table 7 and Table 8 to Table 14, respectively, but the polyester in the present invention is limited thereto. is not. (Specific examples of general formula (I))

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

[0022]

[Table 6]

[0023]

[Table 7]

(Specific examples of general formula (II))

[Table 8]

[0025]

[Table 9]

[0026]

[Table 10]

[0027]

[Table 11]

[0028]

[Table 12]

[0029]

[Table 13]

[0030]

[Table 14]

The dicarboxylic acid component monomer used in the production of the charge transporting polymer of the present invention can be easily synthesized by reacting arylamine or diarylbenzidine with halogenated carboalkoxyalkylbenzene. Further, the diol component can be synthesized by reducing the obtained dicarboxylic acid component monomer with lithium aluminum hydride, sodium borohydride or the like.

Regarding the synthesis of the charge-transporting material having an alkylenecarboxylic acid ester group, see JP-A-5-80550.
Japanese Patent Laid-Open Publication No. 2003-242242 describes a method of introducing a chloromethyl group, forming a Grignard reagent with Mg, converting it into a carboxylic acid with carbon dioxide, and then performing esterification. However, in this method, since the reactivity of the chloromethyl group is high, it cannot be introduced from the initial stage of the raw material. Therefore, after forming a skeleton such as triarylamine or tetraarylbenzidine, for example, the methyl group introduced at the initial stage of the raw material is converted to a chloromethyl group, or an unsubstituted one is used at 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, charge-transporting materials having a skeleton such as triarylamine and tetraarylbenzidine are so highly reactive that they tend to undergo a substitution reaction to an aromatic ring. Therefore, the introduced methyl group is replaced with a chloromethyl group. It is virtually impossible to convert to. 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 problem that the reaction step is long. 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. This method enables control of 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.
It is easy to handle and alleviates the above-mentioned problems.

The charge-transporting polyester resin of the present invention is
Using at least one or more kinds of monomers represented by the following general formula (V) and at least one kind of monomers represented by the following general formula (VI), for example, Fourth Edition Experimental Chemistry Course 2
It can be synthesized by polymerizing by the method described in Vol. When synthesizing using a plurality of monomers, in order to control the polymerization reaction and increase the molecular weight, all monomers having a partial structure of a dicarboxylic acid component and all monomers having a partial structure of a diol component, It is preferable that the functional groups are the same. For example, if the functional group is a methyl ester group, it is preferable to use one in which all the monomers have a methyl ester group.

E-CO- (T) a- (A)-(T) a-CO-E (V) HO- (T) b-A '-(T) b-OH (VI) [wherein A, A ′, T, a and b have the same meanings as described above, and E is a hydroxyl group, a halogen atom,
Alternatively, it represents a group —O—R ₁₁ . (However, R ₁₁ represents an alkyl group, a substituted or unsubstituted aryl group, or an aralkyl group.)]

Next, the synthesis of the charge transporting polyester of the present invention will be described. The charge-transporting polyester may be synthesized only from the monomer represented by the general formula (V) and the monomer represented by the general formula (VI), and if necessary, in order to improve flexibility, strength and the like. A monomer having no charge transporting component other than the monomers represented by the general formulas (V) and (VI) can be mixed and used. Examples of the monomer having no charge transport component include those represented by the following formula. E-CO-R
_{12 -CO-E (VII) HO} -R 13 -OH (VIII) ( wherein, E is has the same meanings as defined above, R ₁₂ represents an alkylene group or a divalent aromatic radical, R ₁₃ represents an alkylene group or a divalent aromatic group which may be bonded via an oxygen atom.) When these monomers are used, the following structure is included in the partial structure of the repeating unit. become. If these monomers are used, their content is 50% by weight.
The following is preferable, and 30% by weight or less is more preferable.

—CO—R ₁₂ —CO— (IX) —O—R ₁₃ —O— (X) Specifically, as the dicarboxylic acid component, isophthalic acid,
Terephthalic acid, adipic acid, their acid chlorides and bismethyl esters can be used, and as the diol component, ethylene glycol, propylene glycol, diethylene glycol, bisphenol and the like can be used.

(1) When E is a hydroxyl group When E is a hydroxyl group, the diol component monomer and the dicarboxylic acid component monomer are mixed in approximately equivalent amounts and polymerized using an acid catalyst. As the acid catalyst, sulfuric acid, toluenesulfonic acid, trifluoroacetic acid, or the like used in ordinary esterification reaction can be used, and 1/10000 to 1/10 parts by weight, preferably 1 part by weight to 1 part by weight of the dicarboxylic acid component monomer. Is used in the range of 1/1000 to 1/50 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, and toluene, chlorobenzene, 1-chloronaphthalene, etc. are effective, and relative to 1 part by weight of the generated polymer, 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, 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 capable of dissolving it. When a solvent is used, the reaction solution as it is, is dripped into a poor solvent in which alcohols such as methanol and ethanol, and polyesters such as acetone are difficult to dissolve, and the charge transporting polymer is deposited to form the charge transporting polyester. After separation, it is thoroughly washed with water or an organic solvent and dried. Further, if necessary, the reprecipitation treatment of dissolving in a suitable organic solvent and dropping in a poor solvent to precipitate the charge transporting polyester may be repeated. The reprecipitation treatment is preferably carried out with a mechanical stirrer while efficiently stirring. The solvent for dissolving the charge-transporting polyester in the reprecipitation treatment is 1 to 1 with respect to 1 part by weight of the produced polyester.
It is used in an amount of 00 parts by weight, preferably 2 to 50 parts by weight. The poor solvent is 1 to 1000 parts by weight, preferably 10 to 50 parts by weight, relative to 1 part by weight of the polyester produced.
Used in the range of 0 parts by weight.

(2) When E is Halogen When E is halogen, the diol component monomer and the dicarboxylic acid component monomer are mixed in approximately equivalent amounts and polymerized using an organic basic catalyst such as pyridine or triethylamine. The organic basic catalyst is one of the dicarboxylic acid component monomers.
It is used in 1-10 equivalents, preferably 2-5 equivalents, relative to equivalents. As the solvent, methylene chloride, tetrahydrofuran (THF), toluene, chlorobenzene, 1-
Chloronaphthalene is effective and is used in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, relative to 1 part by weight of the produced polyester. The reaction temperature can be set arbitrarily. After the polymerization, it is reprecipitated and purified as described above.

In the case of a dihydric alcohol having a high acidity such as bisphenol, an interfacial polymerization method can be used. That is, the diol component monomer can be polymerized by adding it to water, adding an equivalent amount or more of a base to dissolve it, and then adding a solution of the diol component monomer and an equivalent amount of the dicarboxylic acid component monomer with vigorous stirring. At this time, water is used in the range of 1 to 1000 parts by weight, preferably 2 to 500 parts by weight, relative to 1 part by weight of the diol component monomer. As a solvent for dissolving the dicarboxylic acid component monomer, methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1
-Chloronaphthalene is effective. The reaction temperature can be set arbitrarily, and it is effective to use a phase transfer catalyst such as an ammonium salt or a sulfonium salt in order to accelerate the reaction. The phase transfer catalyst is one of the dicarboxylic acid component monomers.
0.1 to 10 parts by weight, preferably 0.
It is used in the range of 2 to 5 parts by weight.

(3) When E is --O--R ₁₁ When E is --O--R ₁₁ , when the diol component monomer is substantially non-volatile, the diol component monomer is almost equivalent to the dicarboxylic acid component monomer. Is volatile, is added in an equivalent amount or more to the dicarboxylic acid component monomer, sulfuric acid,
Inorganic acids such as phosphoric acid, acetates or carbonates such as titanium alkoxide, calcium and cobalt, and oxides of zinc and lead can be used as catalysts for heating and transesterification. When the diol component monomer is volatile, 2 per 1 equivalent of the dicarboxylic acid component monomer is used.
To 100 equivalents, preferably 3 to 50 equivalents.
1 part by weight of the produced polyester is used as the catalyst.
/ 10,000 to 1 part by weight, preferably 1/1000 to 1
/ 2 parts by weight. The reaction temperature is 200 to 3
It is carried out at 00 ° C., and in order to accelerate the polymerization, 0.01 to 100
It is preferable to reduce the pressure to about mmHg, preferably 0.05 to 20 mmHg for reaction. Further, the reaction may be carried out while azeotropically removing the diol component monomer under normal pressure by using a high boiling point solvent such as 1-chloronaphthalene which is azeotropic with the diol component monomer.

Of these synthesizing methods, the method (3) is most preferable because a high molecular weight polyester can be easily obtained.
If the degree of polymerization p of the charge-transporting polyester is too low, the film-forming property is poor, and a strong film is difficult to obtain. If it is too high, the solubility in a solvent is low and the processability is poor.
Is used in the range of 500 to 500, preferably 10 to 300,
More preferably, it is set to 15-100. The weight average molecular weight (GPC method: styrene conversion) was 10,000.
0 to 300,000, preferably 15,000 to 200,000, more preferably 50,000 to 1
It is set in the range of 0,000. Further, in the structures represented by the formulas A and A ′, k represents an integer selected from 0 or 1, but when k is 1, the bias of charge distribution in the charge transport component is less likely to occur, and high transportability is obtained. It is preferable because it can be obtained.

It can be applied to the charge-transporting polyester of the present invention, an electrophotographic photoreceptor or an organic electroluminescent element, and may be used alone, or it may contain an insulating polymer compatible with it. May be.

Specifically, an organic electronic device having a structure in which a layer containing the above charge transporting polyester is provided on a support is used as an organic electronic device. A typical example of the organic electronic device is an electrophotographic photosensitive member having a photosensitive layer, and in particular, one containing the charge transporting polyester of the present invention in the surface layer of the electrophotographic photosensitive member. . In addition, a photosensitive layer containing the charge-transporting polyester of the present invention as a charge-transporting material and a known charge-generating material, particularly an electrophotographic photoreceptor containing a phthalocyanine compound crystal can be mentioned as a preferable example.

As the phthalocyanine crystal used in combination with the above charge-transporting polyester in the electrophotographic photoreceptor of the present invention, there is disclosed in Japanese Patent Laid-Open No. 5-98181.
Halogenated gallium phthalocyanine crystal disclosed in JP-A-5-140472 and JP-A-5-140472
-140473, halogenated tin phthalocyanine crystals, JP-A-5-263007 and JP-A-5-279591, hydroxygallium phthalocyanine crystals, JP-A-4-189.
The oxytitanium phthalocyanine hydrate crystals disclosed in Japanese Patent Application No. 873 and Japanese Patent Application Laid-Open No. 5-43813 are cited, and by using them, particularly high sensitivity,
It is possible to obtain an electrophotographic photosensitive member having excellent repeated stability.

As the chlorogallium phthalocyanine crystal used in the present invention, as disclosed in Japanese Patent Laid-Open No. 5-98181, a chlorogallium phthalocyanine crystal produced by a known method is used in an automatic mortar, a planetary mill, and a vibration. It can be produced by mechanically dry pulverizing with a mill, CF mill, roller mill, sand mill, kneader or the like, or by performing wet pulverization treatment with a solvent using a ball mill, mortar, sand mill, kneader or the like after dry pulverizing. .
The solvent used in the above treatment is aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), aliphatic polyhydric compounds. Alcohols (ethylene glycol, glycerin,
Polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetate ester, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ethers (diethyl ether, tetrahydrofuran, etc.) Further, a mixed system of several kinds and a mixed system of water and these organic solvents can be mentioned. The solvent used is 1 to 200 parts, preferably 10 to 100 parts, relative to chlorogallium phthalocyanine. The treatment temperature is 0 ° C to the boiling point of the solvent or less, preferably 10 to 60 ° 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 may be used in an amount of 0.5 to 20 times, preferably 1 to 10 times the amount of the pigment.

Dichlorotin phthalocyanine crystals are disclosed in JP-A-5-140472 and JP-A-5-14047.
As disclosed in Japanese Patent Laid-Open No. 3 (1999), 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 disclosed in JP-A-5-263007 and 5-2.
As disclosed in Japanese Patent No. 79591, a chlorogallium phthalocyanine crystal produced by a known method is subjected to hydrolysis or acid pasting in an acid or alkaline solution to synthesize a hydroxygallium phthalocyanine crystal, which is directly synthesized. Solvent treatment, or
A hydroxygallium phthalocyanine crystal obtained by synthesis is wet-milled with a solvent using a ball mill, a mortar, a sand mill, a kneader or the like, or is produced by performing a dry pulverization treatment without a solvent and then a solvent treatment. You can Examples of the solvent used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), and aliphatic polyhydric compounds. Polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetic acid ester,
Butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ethers (diethyl ether, tetrahydrofuran, etc.), a mixed system of several kinds, and a mixed system of water and these organic solvents. The solvent used is 1 to 200 parts, preferably 10 to 100 parts, relative to hydroxygallium phthalocyanine.
Used in part range. The treatment temperature is 0 to 150 ° 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 the amount of the pigment.

The oxytitanium phthalocyanine crystal is
JP-A-4-189873 and JP-A-5-4381
As disclosed in Japanese Patent No. 3, gazette, oxytitanium phthalocyanine crystals produced by a known method are acid pasted, or a ball mill, a mortar,
27. In the X-ray diffraction spectrum, salt milling was performed with an inorganic salt using a sand mill, a kneader or the like.
Oxytitanium phthalocyanine crystals having a peak at 2 and relatively low crystallinity are directly solvent-treated, or wet-milled with a solvent using a ball mill, mortar, sand mill, kneader or the like. It can be manufactured by As the acid used for acid pasting, sulfuric acid is preferable, and the concentration is 70 to 100.
%, Preferably 95 to 100%, and the melting temperature is set in the range of −20 to 100 ° C., preferably 0 to 60 ° C. The amount of concentrated sulfuric acid is set in the range of 1 to 100 times, preferably 3 to 50 times, the weight of the oxytitanium phthalocyanine crystal. As the solvent to be precipitated, water or a mixed solvent of water and an organic solvent is used in an arbitrary amount, and 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 it is preferably cooled with ice or the like in order to prevent heat generation. Further, the ratio of the oxytitanium phthalocyanine crystal and the inorganic salt is 1 / 0.1 by weight.
The range of 1/20 to 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 Examples include mixed systems of several kinds, mixed systems of water and these organic solvents, and the like. The solvent used is
1 to 100 for oxytitanium phthalocyanine
Double, preferably 5 to 50 times. The treatment temperature is set in the range of room temperature to 100 ° C, preferably 50 to 100 ° C. The grinding aid is 0.5 to 20 times as much as the pigment,
Preferably, it may be used 1 to 10 times.

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, paper coated with 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. An undercoat layer may be further provided between the conductive support and the charge generation layer. This undercoat layer prevents the injection of charges from the conductive support to the photosensitive layer during charging of the photosensitive layer having a laminated structure, and also adheres the photosensitive layer to the conductive support in an integrated manner. It exhibits a function as a layer, or an antireflection function of light of the conductive support in some cases.

As the binder used for the undercoat layer, polyethylene resin, polypropylene resin, acrylic resin,
Methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester Resin, nitrocellulose, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compound, titanium chelate compound,
Known materials such as 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.

In the charge transport layer, the charge transporting polyester 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 material etc. When using a binder resin, specifically, 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-N- Known resins such as vinylcarbazole and polysilane can be used, but the resin is not limited to these. Of these binder resins, the following structural formula (XI)
A polycarbonate resin represented by (XVI), and
When a 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 preferably in the range of charge transporting polyester: binder resin = 10: 0 to 8:10. Also,
When mixed with another charge transporting material, charge transporting polyester + binder resin: charge transporting material = 10: 0 to 10:
A range of 8 is preferred. The thickness of the charge transport layer is 5 to 5
0 μm, preferably 10 to 40 μm is suitable. Further, as a coating method used when providing the charge transport layer, a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method,
Bead coating method, air knife coating method,
A usual method such as a curtain coating method can be used.

[0053]

[Chemical 8] (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 a bisazo pigment, a phthalocyanine pigment, a squarylium pigment, a perylene pigment, and dibromoanthanthrone can be used. Can be used.

The binder resin used for the charge generation layer can be selected from a wide range of insulating resins. In addition, poly-N-vinylcarbazole, polyvinyl anthracene,
It can also be selected from organic photoconductive polyesters such as polyvinylpyrene and polysilane. Preferred binder resins include polyvinyl butyral resins, polyarylate resins (polycondensates of bisphenol A and phthalic acid, etc.), polycarbonate resins, polyester resins, phenoxy resins, vinyl chloride-vinyl acetate copolymers, polyamide resins, acrylic resins. Insulating resins such as, but not limited to, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, and polyvinyl pyrrolidone resin can be used. These binder resins may be used alone or in combination of two or more.

The compounding ratio (weight ratio) of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10.
As a method for dispersing these, a usual method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method can be used. Further, during this dispersion, it is effective that the particles have a particle size of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. Further, as the solvent used for dispersing these, methanol, ethanol, n-propanol, n-
Butanol, benzyl alcohol, methyl cellosolve,
Ordinary organic solvents such as ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene can be used alone or in combination of two or more. . The thickness of the charge generation layer is 0.01 to 10 μm, preferably 0.05 to 5 μm. Further, as the coating method used when the charge generating layer is provided, 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, and a curtain coating method can be used. Can be used.

[0057]

EXAMPLES The present invention will be described below with reference to examples. For example, the monomer used for producing the charge transporting polyester can be synthesized as follows. Synthesis Example 1 N, N-bis (3- (2- (ethoxycarbonyl) ethyl) phenyl) -3,4-xylidine (the partial structure is (I
-3) of which both ends are ethylesters) 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 in a 1000 ml flask, and heated and reacted at 230 ° C. for 10 hours under a nitrogen stream.
After the reaction, the mixture was cooled to room temperature, dissolved in 500 ml of toluene, the insoluble matter was filtered, and the filtrate was produced by silica gel column chromatography using toluene. 20 g of oily N, N-bis (3- (2- (ethoxycarbonyl) ethyl) phenyl) -3,4-xylidine was obtained.

Synthesis Example 2 N, N'-diphenyl-N, N'-bis (3- (2-
(Ethoxycarbonyl) ethyl) phenyl)-[1,
Synthesis of 1'-biphenyl] -4,4'-diamine (partial structure is represented by (I-6), both ends are ethyl ester) N, N'-diphenylbenzidine 10.77 g, 3-iododihydrocinnamic acid 23.0 g of ethyl, 11.61 g of potassium carbonate, 1.0 g of copper sulfate pentahydrate, and 20 ml of n-tridecane were put into 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, insoluble matter was filtered, and the filtrate was produced by silica gel column chromatography using toluene. 19.6 g of oily N, N'-diphenyl-N, N'-bis (3- (2- (ethoxycarbonyl) ethyl) phenyl)-[1,1'-biphenyl] -4,4'-diamine was obtained. It was

Synthesis Example 3 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[ 1,1'-biphenyl] -4,4'-diamine (partial structure is (I-19)
, And both ends are methyl ester) N- (3,4-dimethylphenyl) -N- (4- (2-
(Methoxycarbonyl) ethyl) phenyl) amine 45
g, 4,4′-diiodo-3,3′-dimethylbiphenyl 30 g, potassium carbonate 27 g, copper sulfate pentahydrate 5 g,
20 ml of n-tridecane was put into a 1000 ml flask, and heated and reacted at 230 ° C. for 5 hours in a nitrogen stream. After the reaction, cool to room temperature, dissolve in 200 ml of toluene,
The insoluble matter was filtered off, the filtrate was purified by silica gel column chromatography using toluene, and recrystallized from a mixed solvent of ethyl acetate and ethanol to give 3,3′-dimethyl-N,
N'-bis (3,4-dimethylphenyl) -N, N'-
38 g of bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1,1'-biphenyl] -4,4'-diamine was obtained as a pale yellow powder (melting point: 161.5).
~ 163 ° C).

Synthesis Example 4 3,3'-Dimethyl-N, N'-bis (4-methoxyphenyl) -N, N'-bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1, Synthesis of 1'-biphenyl] -4,4'-diamine (a partial structure is represented by (I-22) and both ends are methyl ester) N- (4-methoxyphenyl) -N- (4- (2- (Methoxycarbonyl) ethyl) 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 n-tridecane (5 ml) were placed in a 100 ml flask and placed under a nitrogen stream. Heat reaction was carried out at 230 ° C. for 15 hours. 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. Light yellow oily 3,3'-dimethyl-N, N'-bis (4-methoxyphenyl) -N, N'-bis (4- (2- (methoxycarbonyl) ethyl) 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- (methoxycarbonyl) ethyl) phenyl)-[1,1 ': 4', 1 "-terphenyl] -4,4" -diamine (partial structure is (I-31) , And both ends are methyl ester) N- (3,4-dimethylphenyl) -N- (4- (2-
(Methoxycarbonyl) ethyl) 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 to 200 g.
It was put in a ml flask and heated and reacted at 230 ° C. for 5 hours under a nitrogen stream. After the reaction, cool to room temperature and add 20 m of toluene.
l, the insoluble matter was filtered off, the filtrate was purified by silica gel column chromatography using toluene, and recrystallized from acetone to give N, N'-bis (3,4-dimethylphenyl) -N. , N'-bis (4- (2- (methoxycarbonyl) ethyl) 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-methoxycarbonylmethyl) phenyl)-[1,1 ' -Biphenyl]-
Synthesis of 4,4′-diamine (partial structure is represented by (I-18) and both ends are methyl ester) 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. Recrystallize 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: 179-181 ° C).

Synthesis Example 7 N, N'-diphenyl-N, N'-bis (4- (4-
Synthesis of (2- (ethoxycarbonyl) ethyl) phenyl) phenyl)-[1,1'-biphenyl] -4,4'-diamine (partial structure is shown by (I-52), both ends are ethyl ester) N, N'-diphenylbenzidine 1
0.0 g, 4- (2- (ethoxycarbonyl) ethyl)
-4'-iodobiphenyl 24.0 g, potassium carbonate 1
1 g, copper sulfate pentahydrate 1.0 g, n-tridecane 30 m
1 in a 200 ml flask and 230 ° C under nitrogen flow
The mixture was heated and reacted for 1 hour. 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 produced by silica gel column chromatography using toluene. Oily N, N'-diphenyl-N, N'-bis (4
-(4- (2- (ethoxycarbonyl) ethyl) phenyl) phenyl)-[1,1'-biphenyl] -4,4 '
-16.6 g of diamine were obtained.

Synthesis Example 8 N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) -biphenyl-4-amine (partial structure is shown by (I-2), both ends are methyl ester) Synthesis of N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) amine 25.0 g, 4-iodobiphenyl 20.5 g, potassium carbonate 12.0 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 3 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 100 ml of toluene, the insoluble matter was filtered, and the filtrate was produced by silica gel column chromatography using toluene. Recrystallization from a mixed solvent of acetone and ethanol gave N, N-bis (4
-(2- (methoxycarbonyl) ethyl) phenyl)-
24.5 g of biphenyl-4-amine was obtained as a pale yellow powder (melting point: 92-93 ° C).

Synthesis Example 9 1,2-bis (4- (N- (4- (2- (methoxycarbonyl) ethyl) phenyl) -N- (4-phenylphenyl) amino) phenyl) ethane (partial structure is ( I-4
4) in which both terminals are methyl ester) N- (4- (2- (methoxycarbonyl) ethyl) phenyl) -N- (4-phenylphenyl) amine 5.0
g, 1,2-bis (4-iodophenyl) ethane 3.0
g, potassium carbonate 2.1 g, copper sulfate pentahydrate 0.2 g,
10 ml of n-tridecane was placed in a 100 ml flask, and heated and reacted at 230 ° C. for 3 hours 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 produced by silica gel column chromatography using toluene. Recrystallization from a mixed solvent of acetone and ethanol gave 1,2-bis (4- (N- (4
-(2- (methoxycarbonyl) ethyl) phenyl)-
3.6 g of N- (4-phenylphenyl) amino) phenyl) -ethane were obtained as a pale yellow powder (melting point: 157).
~ 159 ° C).

Synthesis Example 10 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis (4- (2- (hydroxyethyl) phenyl))-[1 , 1'-biphenyl]-
Synthesis of 4,4'-diamine (partial structure is represented by (II-18) and hydroxyl groups at both ends) 3,3'-Dimethyl-N, N'- synthesized in Synthesis Example 6
Bis (3,4-dimethylphenyl) -N, N'-bis ((4-methoxycarbonylmethyl) phenyl)-
[1,1'-biphenyl] -4,4'-diamine 10.
0 g and 50 ml of tetrahydrofuran were placed in a 100 ml flask and dissolved, and 1.2 g of lithium aluminum hydride was gradually added to this solution. After the reaction was completed, methanol and water were added to consume excess lithium aluminum hydride, and the purified precipitate was filtered. Water was further added to the filtrate, extraction was performed with toluene, and the toluene phase was thoroughly washed with water. This was dried over sodium sulfate and recrystallized from ethyl acetate and methanol to give 3,3'-dimethyl-
N, N'-bis (3,4-dimethylphenyl) -N,
7.0 g of N'-bis (4- (2- (hydroxyethyl) phenyl))-[1,1'-biphenyl] -4,4'-diamine was obtained (melting point: 214-216 ° C).

Synthesis Example 11 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis (4- (3- (hydroxypropyl) phenyl))-[1 , 1'-biphenyl]
Synthesis of 4,4'-diamine (partial structure is represented by (II-19) and hydroxyl groups at both ends) 3,3'-Dimethyl-N, N'-synthesized in Synthesis Example 3
10.0 g of bis (3,4-dimethylphenyl) -N, N'-bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1,1'-biphenyl] -4,4'-diamine was added. Except that it was used, in the same manner as in Synthesis Example 10,
3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis (4- (3- (hydroxypropyl) phenyl))-[1,1'-biphenyl]
7.2 g of -4,4'-diamine was obtained (melting point: 182
~ 184 ° C).

Synthesis Example 12 N, N'-diphenyl-N, N'-bis (4- (4-
(2- (hydroxyethyl) phenyl) phenyl)-
Synthesis of [1,1′-biphenyl] -4,4′-diamine (partial structure is represented by (II-52) and hydroxyl groups at both ends) N, N′-diphenyl-N synthesized in Synthesis Example 7 , N '
-Bis (4- (4- (2- (ethoxycarbonyl) ethyl) phenyl) phenyl)-[1,1'-biphenyl]
N, N'-diphenyl-N, N 'was prepared in the same manner as in Synthesis Example 10 except that 10.0 g of -4,4'-diamine was used.
-Bis (4- (4- (2- (hydroxyethyl) phenyl) phenyl)-[1,1'-biphenyl] -4,4 '
6.5 g of diamine were obtained (melting point 143-145)
C).

Synthesis Example 13 1,3-Diiminoisoindoline (30 parts) and gallium trichloride (9.1 parts) were added to 230 parts of quinoline, and the mixture was reacted at 200 ° C. for 3 hours. ,
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 filtered off, washed with 10 parts of methanol and dried to obtain a powder X-ray diffraction spectrum of 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 14 50 g of phthalonitrile and 27 g of anhydrous stannic chloride
Was added to 350 ml of 1-chlornaphthalene, and 195
After reacting at 5 ° C for 5 hours, the product was filtered off, and 1-
After washing with chloronaphthalene, acetone, methanol, and then water, it was 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) 500 g, put in an agate pot, and use a planetary ball mill (P-5 type, manufactured by Fritsch) to 400
After crushing at rpm for 10 hours, it was thoroughly washed with water and dried. 0.5 g of it was added with 15 g of THF and glass beads (1
(mmφ) 30 g at room temperature for milling for 24 hours, then the glass beads are filtered off, washed with methanol, dried and powder X-ray diffraction spectrum shows 2θ ± 0.2 ° =
Dichlorotin phthalocyanine crystals having strong diffraction peaks at 8.5 °, 11.2 °, 14.5 ° and 27.2 ° were obtained. This is designated as CG-2.

Synthesis Example 15 3 parts of the chlorogallium phthalocyanine crystal obtained in Synthesis Example 3 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,
After milling 5 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 16 1,3-Diiminoisoindoline (30 parts) and titanium tetrabutoxide (17 parts) were added to 200 parts of 1-chloronaphthalene, and the mixture was reacted at 190 ° C. for 5 hours under a nitrogen stream, and the product was filtered. Then, 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, manufactured by Yamato Scientific Co., Ltd.) was used for milling 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 a powder X-ray. 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.

Example 1 N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) -biphenyl-4- synthesized in Synthesis Example 8
6.0 g (12.2 mmol) of amine, 11,3'-dimethyl-N, N'-bis (3,4-synthesized in Synthesis Example 11)
Dimethylphenyl) -N, N'-bis (4- (3- (hydroxypropyl) phenyl))-[1,1'-biphenyl] -4,4'-diamine 8.37 g (12.2 mm)
ol) and 0.1 g of tetrabutoxy titanium 0.1 g
The flask was put in a flask and the temperature was gradually raised to 200 ° C. over 1 hour under a nitrogen stream. When the generation of methanol was completed, the pressure was reduced to 1 mmHg, and the reaction was further performed for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, dissolved in 30 ml of methylene chloride, and insoluble matter was filtered. 5 ml of 1-N hydrochloric acid in this solution
Was added, and the mixture was vigorously stirred for 30 minutes, washed thoroughly with water, and then 200 ml of isopropanol was added dropwise while stirring.
The polymer was precipitated. The polymer obtained is filtered, washed thoroughly with isopropanol and then dried, 13.
5 g of polymer was obtained. When the molecular weight was measured by GPC, it was Mw = 5.05 × 10 ⁴ (in terms of styrene). The IR spectrum is shown in FIG.

Example 2 N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) -biphenyl-4- synthesized in Synthesis Example 8
6.0 g of amine, 3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) synthesized in Synthesis Example 11
-N, N'-bis (4- (3- (hydroxypropyl))
Phenyl))-[1,1'-biphenyl] -4,4'-
8.37 g of diamine, 30 ml of p-cymene, and 0.1 g of tetrabutoxytitanium were placed in a 100 ml flask,
The mixture was heated under reflux for 4 hours under a nitrogen stream. After completion of the reaction, the mixture was cooled to room temperature, 30 ml of methylene chloride was further added, and the insoluble matter was filtered. 5 ml of 1-N hydrochloric acid was added to this solution,
After stirring vigorously for 30 minutes, washing thoroughly with water, 300 ml of isopropanol was added dropwise while stirring to precipitate a polymer. The obtained polymer was filtered, sufficiently washed with isopropanol, and then dried to obtain 13.8 g of a polymer. When the molecular weight was measured by GPC, M
It was w = 7.05 × 10 ⁴ (styrene conversion). IR
The spectrum was similar to that of FIG.

Example 3 In place of 6.0 g of N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) -biphenyl-4-amine, 3,3'-dimethyl synthesized in Synthesis Example 3 was used. -N,
N'-bis (3,4-dimethylphenyl) -N, N'-
1 in the same manner as in Example 1 except that 9.06 g of bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1,1'-biphenyl] -4,4'-diamine was used.
5.4 g of polymer was obtained. When the molecular weight was measured by GPC, it was Mw = 1.36 × 10 ⁵ (in terms of styrene). The IR spectrum is shown in FIG.

Example 4 N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) -biphenyl-4- synthesized in Synthesis Example 8
6.0 g of amine, 11 synthesized in Synthesis Example 3,3′-dimethyl-N, N′-bis (3,4-dimethylphenyl)-
N, N'-bis (4- (3- (hydroxypropyl) phenyl))-[1,1'-biphenyl] -4,4'-diamine 7.8 g, ethylene glycol 1.0 g and tetrabutoxy titanium 0 0.1 g was put into a 100 ml flask and gradually heated to 200 ° C. over 1 hour under a nitrogen stream. After that, the pressure is reduced to 1 mmHg, and the temperature is further increased to 230 ° C for 2
Reacted for hours. After completion of the reaction, the mixture was cooled to room temperature, dissolved in 30 ml of methylene chloride, and insoluble matter was filtered. 5 ml of 1-N hydrochloric acid was added to this solution, and the mixture was vigorously stirred for 30 minutes, thoroughly washed with water, and then 200 ml of isopropanol was added dropwise while stirring to precipitate a polymer. The obtained polymer was filtered, sufficiently washed with isopropanol, and then dried to obtain 12.3 g of a polymer. When the molecular weight was measured by GPC, Mw = 8.05 × 10
^{It was 4} (styrene conversion).

Examples 5 to 15 Polymers were synthesized in the same manner as in Example 1 except that combinations of dicarboxylic acid ester and diol were as shown in Table 1 and 12.2 mmol of dicarboxylic acid ester and diol were used respectively. The results are shown in Table 15.

[0078]

[Table 15]

Comparative Example 1 3,3'-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4 synthesized in Synthesis Example 3
-(2-Methoxycarbonylethyl) phenyl]-
[1,1'-biphenyl] -4,4'-diamine 15.
0 g, dimethyl terephthalate 3.0 g, ethylene glycol 30.0 g and tetrabutoxy titanium 0.1 g were placed in a 300 ml flask and heated under reflux for 3 hours under a nitrogen stream. 3,3'-dimethyl-N, N'-bis (3,3
4-Dimethylphenyl) -N, N'-bis [4- (2-
Methoxycarbonylethyl) phenyl]-[1,1'-
After confirming that the biphenyl] -4,4′-diamine was consumed, the pressure was reduced to 0.5 mmHg and the temperature was raised to 235 ° C. while distilling off ethylene glycol, and the reaction was continued for 2.5 hours. Then, cool to room temperature and add 20 methylene chloride.
Dissolve in 0 ml, filter the insoluble matter, and filter the filtrate with ethanol 1
400 ml was added dropwise 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, Mw = 1.4
It was 0 × 10 ⁵ (converted to styrene).

Comparative Example 2 A polymer was synthesized in the same manner as in Comparative Example 1 except that dimethyl sebacate was used instead of dimethyl terephthalate. Comparative Example 3 Comparative Example 1 except that dimethyl terephthalate was not added.
A polymer was synthesized in the same manner as in.

Example 16 A zirconium compound (trade name: Organix ZC) was formed on a 20 mmφ stainless steel cylindrical substrate subjected to honing treatment.
540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 100 parts of a silane compound (trade name: A1110, manufactured by Nippon Junker Co.), 400 parts of i-propanol and 200 parts of butanol are applied by a dip coating method, and the solution is applied at 150 ° C. for 10 minutes. It was heated and dried for a minute to form an undercoat layer having a thickness of 0.5 μm. Polyvinyl butyral resin (trade name: S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.) was added to 10 parts of CG-1.
After mixing with 0 parts and 500 parts of n-butyl acetate and treating with glass beads for 1 hour with a paint shaker to disperse, the obtained coating solution is applied onto the above-mentioned undercoat layer by a dip coating method, and at 100 ° C. Heat dried for 10 minutes. 5 parts of the charge transporting polymer obtained in Example 1 was dissolved in 38 parts of monochlorobenzene, and the obtained coating solution was applied onto a stainless steel cylindrical substrate having a charge generating layer formed thereon by a dip coating method, It was heated and dried at 120 ° C. for 1 hour to form a charge transport layer having a film thickness of 23 μm.

The electrophotographic characteristics of the electrophotographic photosensitive member thus obtained were measured using a laser beam printer test model-1 (A-4 lateral direction, 1 minute / minute) manufactured by Fuji Xerox Co., Ltd.
Two sheets were subjected to a print test under a normal environment (20 ° C., 50% RH) to evaluate the image quality of the first sheet and 2000 sheets. The light amount was adjusted using a filter according to the sensitivity of the charge generating material. The results are shown in Table 16.

Examples 17 to 30 and Comparative Examples 4 to 6 Electrophotographic photoreceptors were prepared and evaluated in the same manner as in Example 4, except that the combination of the charge generating material and the charge transporting polymer was changed as shown in Table 16. The results are shown in Table 16.

[0084]

[Table 16]

[0085]

Industrial Applicability The charge-transporting polyester of the present invention is a novel substance, and as is clear from the results of the above-mentioned examples, it can be easily obtained as a high molecular weight polymer and is suitable for electrophotography. It is a useful material for organic electronic devices such as photoconductors. The electrophotographic photoreceptor using the charge-transporting polyester of the present invention has good sensitivity and excellent repeated stability.

[Brief description of drawings]

FIG. 1 is an IR spectrum of the charge-transporting polyester synthesized in Example 1.

2 is an IR spectrum of the charge-transporting polyester synthesized in Example 3. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mieko Seki 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Xerox Co., Ltd. (56) References JP-A-9-110974 (JP, A) JP-A-9-62019 ( JP, A) JP-A-8-211640 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63/91

Claims (8)

(57) [Claims] 1. A dicarboxylic acid component having at least one structure represented by the following general formula (I), and a diol component having at least one structure having a structure represented by the following general formula (II). , A charge-transporting polyester characterized by containing each as a partial structure of a repeating unit. -CO- (T) a-A- (T) a-CO- (I) -O- (T) b-A '-(T) b-O- (II) [wherein A and A'are , Each represents a divalent group represented by the following formula. [Chemical 1] (R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
It represents a halogen atom, an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent organic group. a, b, k and m each represent an integer of 0 or 1, and T represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be branched. )] 2. A weight average molecular weight of 10,000 to 30.
The charge-transporting polyester according to claim 1, which is 10,000. 3. The charge according to claim 1, wherein the dicarboxylic acid component comprises only the structure represented by the general formula (I) and the diol component comprises only the structure represented by the general formula (II). Transportable polyester. 4. The charge-transporting polyester according to claim 1, wherein the group X is a biphenylene group, a 3,3′-dimethylbiphenylene group or a terphenylene group. 5. An organic electronic device comprising the charge-transporting polyester according to any one of claims 1 to 4 in a charge-transporting functional film. 6. The organic electronic device according to claim 5, wherein the organic electronic device comprises an electrophotographic photosensitive member having a photosensitive layer. 7. An organic electronic device according to claim 5, wherein the charge-transporting polyester according to any one of claims 1 to 4 is contained in a surface layer of an electrophotographic photosensitive member. 8. The organic electronic device comprises an electrophotographic photoreceptor having a photosensitive layer, and the charge transporting polyester according to any one of claims 1 to 4 is used as a charge transporting material in the photosensitive layer. 8. The organic electronic device according to claim 5, wherein the generating material contains a gallium phthalocyanine crystal, a halogenated tin phthalocyanine crystal, a hydroxygallium phthalocyanine crystal, or an oxytitanium phthalocyanine crystal.