JP3267115B2 - Random copolymerized charge-transporting polyester resin and method for producing 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 charge transporting device which is applicable to various organic electronic devices such as an electrophotographic photosensitive member, an organic EL device, an organic conductive material and the like which have excellent wear resistance and a long life. The present invention relates to a novel polyester resin having properties and a method for producing the same.

[0002]

2. Description of the Related Art A charge transporting polymer represented by polyvinyl carbazole (PVK) is a photoconductive material for a photoreceptor for electrophotography, or a preprint of the 36th Alliance Lecture Meeting on Applied Physics, 31p-K-12 (1990). ), Etc. are promising organic electroluminescent device materials. These form a layer together and are used as a charge transporting layer. As a material for forming the charge transporting layer, a charge transporting polymer represented by PVK and a low molecular weight compound having a charge transporting property are dispersed in the polymer. Low molecular dispersion systems are well known. In general, a low-molecular charge transporting material is deposited and used in an organic electroluminescent device. Among them, the low molecular dispersion type has a variety of materials,
Since it is easy to obtain high-performance ones, it has become mainstream especially in electrophotographic photosensitive members. In recent years, electrophotographic photoconductors have been used in high-speed copiers and printers with the advancement of organic photoconductors. The performance is not sufficient, and it is desired that the organic photoreceptor has a longer life. One of the important factors that determines the life of an organic photoreceptor is the wear of the charge transport layer.
Current organic photoreceptors are mainly of the so-called stacked type in which a charge transport layer is laminated on a charge generation layer,
Therefore, the charge transport layer often becomes the surface layer,
Regarding the charge transport layer of the low molecular weight dispersion system, which is the current mainstream, it is becoming possible to obtain satisfactory performance with regard to the electrical characteristics.However, since the low molecular weight compound is dispersed in the binder resin and used. However, the mechanical performance inherent to the binder resin is reduced, and the wear is essentially weak.

[0003] On the other hand, charge transporting polymers have been actively studied at present because of the possibility of remarkably improving the above-mentioned disadvantages. For example, US Pat. No. 4,806,4
No. 43 discloses a polycarbonate obtained by polymerization of a specific dihydroxyarylamine and bischloroformate, and US Pat. No. 4,806,444 discloses a specific dihydroxyarylamine and phosgene. Polycarbonate by polymerization of is disclosed. U.S. Pat. No. 4,801,517 discloses a polycarbonate obtained by polymerizing bishydroxyalkylarylamine with bischloroformate or phosgene.
No. 65 and 4,959,288 disclose a polycarbonate obtained by polymerization of a specific dihydroxyarylamine or bishydroxyalkylarylamine and bischloroformate, or a polyester obtained by polymerization of a bisacyl halide. It has been disclosed. Further, U.S. Pat. No. 5,034,296 discloses a polycarbonate or polyester of an arylamine having a specific fluorene skeleton, and U.S. Pat. No. 4,983,482 discloses polyurethane. Have been. Furthermore, Japanese Patent Publication No. 59-2890
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-A-1-1-1
JP-A-34462, JP-A-4-1330065, JP-A-4-133066 and the like disclose a polymer having a pendant charge-transporting substituent such as hydrazone or triarylamine, and a photoreceptor using the same. Has also been proposed. In particular, polymers having a tetraarylbenzidine skeleton are referred to as “The Sixth International Congress on
Advances in Non-impact Printing Technologies, 306,
(1990). ”, High mobility and high practicality.

[0004]

SUMMARY OF THE INVENTION First, the present inventors have
The charge-transporting polymer was studied and the following general formula (IV)
Or, a novel alternating copolymerized high performance charge transporting polymer represented by (V) was proposed.

Embedded image [Wherein, Y and Z each represent a divalent hydrocarbon group, and A represents a structure represented by the general formula (I-1) or (I-2), or a general formula (I-1) Or, in the structure represented by (I-2),-(CH ₂ ) _n -has 1 to 1 carbon atoms.
It shows 10 divalent hydrocarbon groups which may be branched. B and B 'each independently represent a group -O- (Y'-
_{O) m} '-H or a group _{-O- (Y'-O) m'} -CO-
Z'-CO-OR '(where R' represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, and Y 'and Z' are each a divalent carbon atom. M represents an integer of 1 to 5; m represents an integer of 1 to 5; and p represents an integer of 5 to 5000. The charge-transporting polymer has excellent properties as compared with conventional ones and has high practicality.
The polymer represented by V) has a problem that the ratio of the charge transporting functional portion (portion A) is high and the polymer is easily affected by a discharge product such as ozone. The general formula (V)
Is a charge transporting functional part (part A)
, The resistance to discharge products such as ozone is increased, but the production method is alternating copolymerization, and the ratio of A and Z is constant. However, there is a problem that it is easy to cause a decrease in the molecular weight and it is difficult to obtain a high molecular weight compound. Further, in consideration of application to various devices, it is necessary to increase the degree of freedom in device design, and it is required to be able to freely control mechanical characteristics, oxidation resistance, charge injection properties, and the like.

[0005] 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 a novel polyester resin having excellent abrasion resistance and having a long life and charge transportability. Another object of the present invention is to provide a novel charge transporting polyester resin which has a high degree of freedom in mechanical properties, oxidation resistance, charge injecting property and the like and is easy to produce. Another object of the present invention is to provide a method for producing a novel charge transporting polyester resin which can be easily synthesized by a simple method.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the charge transporting polymer and found that 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 repeating unit partial structure, and randomly copolymerized charge-transporting polyester resin. More specifically, general formula (I-1) ) Or (I-
At least one of the structures represented by 2) and a compound represented by the general formula (II):
By forming a random copolymer represented by the following general formula (III) containing at least one kind of dicarboxylic acid component represented by the following formula as a partial structure of a repeating unit, the A portion in the copolymer and Z It has been found that the ratio of the portions can be easily changed, and that the mechanical properties, oxidation resistance, charge injection properties, and the like can be easily controlled by appropriately selecting the structure of the A portion and the Z portion. 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 inventors have found that the compound can be easily obtained only by mixing an acid derivative in a desired ratio and polymerizing the acid derivative, thereby completing the present invention.

The novel charge-transporting polyester resin of the present invention comprises at least one of the structures represented by the following general formulas (I-1) and (I-2) and a dicarboxylic acid represented by the following general formula (II) It contains at least one acid component as a partial structure of a repeating unit and is random copolymerized.

Embedded image (Wherein, 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, X represents a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent aromatic group. k is 0 or 1, and n represents an integer of 1 to 5. ) -O-CO-Z-CO-O- (II) (wherein, Z represents a divalent hydrocarbon group.) Further, the charge-transporting polyester resin is represented by the general formula (I-1) or A compound represented by the following general formula (III) containing, as a partial structure of a repeating unit, at least one kind of a structure represented by (I-2) and at least one kind of a dicarboxylic acid component represented by the above formula (II). It is preferably a random copolymer represented.

Embedded image [In the formula, A represents a structure represented by the general formula (I-1) or (I-2), and Y and Z each represent a divalent hydrocarbon group. m is an integer of 1 to 5, q is an integer of 1 or more, r is 1 to
It means an integer of 3500. However, q + r is 5 to 50
It is an integer of 00, and 0.3 ≦ q / (q + r) <1. Further, the method for producing the charge-transporting random copolymerized polyester resin of the present invention is characterized in that at least one of the above general formula (I-
A dicarboxylic acid ester having a structure represented by 1) or (I-2), at least one dicarboxylic acid ester having a structure represented by the general formula (II), and H-
It is characterized by being synthesized by a transesterification reaction using a diol having a structure represented by (OY) _m -OH.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described in detail. In the charge-transporting polyester resin of the present invention, X in the structure represented by the above general formula (I-1) or (I-2) contained as a partial structure of a repeating unit specifically includes the following groups Examples selected from (1) to (7).

Embedded image [Wherein, 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; R _{6 to} R _{12 each} represent a hydrogen atom,
A represents 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, or a halogen atom;
V is selected from the following groups (8) to (17).

[0009]

Embedded image (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) of the present invention, examples of Y and Z include those selected from the following groups (18) to (24).

Embedded image (Wherein, R ₁₃ and R ₁₄ 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 d and e each represent an integer of 1 to 10, f and g each represent an integer of 0 to 2, and h
And i is 0 or 1. V has the same meaning as described above. )

In the charge transporting polyester resin of the present invention, examples of the partial structural formula of the unit represented by the general formula (I-1) contained as a partial structure of the repeating unit are shown in Table 1 below.
3, and examples of the partial structure of the unit represented by the general formula (I-2) are shown in Tables 4 and 5 below, but the present invention is not limited to these. In the present invention, specific examples of the compound of the charge transporting polyester resin represented by the general formula (III) are shown in the following Tables 6 to 8, but the present invention is not limited to these.

Specific examples of the partial structure of the unit represented by formula (I-1) (Tables 1 to 3)

[Table 1]

[0013]

[Table 2]

[0014]

[Table 3]

Specific examples of the partial structure of the unit represented by formula (I-2) (Tables 4 and 5)

[Table 4]

[0016]

[Table 5]

Specific examples of the charge transporting polyester resin represented by the general formula (III) (Tables 6 to 8)

[Table 6]

[0018]

[Table 7]

[0019]

[Table 8]

The charge-transporting polyester resin obtained by random copolymerization of the present invention comprises at least one charge-transporting monomer represented by the following structural formula (VI-1) or (VI-2), It can be synthesized by polymerizing at least one of the dicarboxylic acid derivatives represented by VII) by a known method described in, for example, “Experimental Chemistry Lecture, 4th Edition”, volume 28, and the like.

Embedded image [Wherein, R _{1 to} R ₄ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a halogen atom,
X represents a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent aromatic group. k is 0 or 1, and n represents an integer of 1 to 5. 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, a dihydric alcohol represented by HO- (YO) _m -H is converted into a compound represented by the structural formula (VI-1) or (VI-
Compounds represented by (2) and (VII) [hereinafter, "(VI-
1) + (VI-2) + (VII) ". ] And polymerized using an acid catalyst. As the acid catalyst, sulfuric acid,
What is used for a usual esterification reaction, such as toluenesulfonic acid and trifluoroacetic acid, can be used, and is 1/10000 to 1/10 parts by weight, preferably 1/1000 to 1/100 with respect 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 capable of azeotropic with water, toluene,
Chlorobenzene, 1-chloronaphthalene and the like are effective, and are in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight based on 1 part by weight of (VI-1) + (VI-2) + (VII). Used in The reaction temperature can be arbitrarily set, but the reaction is preferably performed at the boiling point of the solvent in order to remove water generated during the polymerization. After completion of the reaction, if no solvent is used, the solvent is dissolved in a soluble solvent. When a solvent is used, the reaction solution is directly dropped into a poor solvent in which a polymer such as alcohols such as methanol and ethanol or acetone is difficult to dissolve, thereby precipitating a charge transporting polymer, and forming a charge transporting polymer. After being separated, it is sufficiently washed with water or an organic solvent and dried. Further, if necessary, the re-precipitation treatment of dissolving in a suitable organic solvent and dropping it into a poor solvent to precipitate a charge transporting polymer may be repeated. In the case of the reprecipitation treatment, it is preferable to carry out the stirring with a mechanical stirrer or the like while efficiently stirring. The solvent for dissolving the charge transporting polymer in 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 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
Are converted to (VI-1) + (VI-
2) Mix almost equivalent amount with + (VII) and polymerize 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 100 parts by weight with respect to 1 part by weight of + (VII)
Preferably it is used in the range of 2 to 50 parts by weight. The reaction temperature can be set arbitrarily. After the polymerization, reprecipitation treatment and purification are performed as described above. 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 dissolving by adding an equivalent or more of a base, an equivalent of (VI-1) + (VI-2) is equivalent to a dihydric alcohol with vigorous stirring.
Polymerization can be carried out by adding a solution of + (VII). At this time, water is added in an amount of 1 to 10 with respect to 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 promote the reaction, it is effective to use a phase transfer catalyst such as an ammonium salt or a sulfonium salt. The phase transfer catalyst is used in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 10 parts by weight, based on 1 part by weight of (VI-1) + (VI-2) + (VII).
Used in the range of 5 parts by weight.

[0023] (3) when when E is -O-R ₁₅ E is -O-R ₁₅ is excessively added dihydric alcohol represented by HO- _(Y-O) m -H It can be synthesized by transesterification by heating using an inorganic acid such as sulfuric acid or phosphoric acid, an acetate or carbonate such as titanium alkoxide, calcium and cobalt, or an oxide of zinc or lead as a catalyst.
The dihydric alcohol is used in an amount of 2 to 100 equivalents, preferably 3 to 50 equivalents, based on (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, per 1 part by weight of I). The reaction is carried out at a reaction temperature of 200 to 300 ° C.
-R ₁₅ from group -O- _(Y-O) transesterification after the end of the m -H is, HO- _(Y-O) to promote polymerization by elimination of m -H, 0.01~100mmHg, The reaction is preferably performed under reduced pressure of 0.05 to 20 mmHg. Further, 1 which can be azeotropic with HO- (YO) _m -H
The reaction can also be carried out using a high-boiling solvent such as -chloronaphthalene under normal pressure while removing HO- (YO) _m -H by azeotropic distillation.

Among the above-mentioned methods for synthesizing the charge-transporting polyester resin, the method (3) is most preferable because a high molecular weight polymer is easily obtained. Further, the monomer ratio [(VI-1) + (VI-2)] / [(VI-1) + (VI-
If 2) + (VII)] is too low, the mobility is reduced, and the polymer alone cannot be used practically, and a low-molecular compound or other high-molecular charge transport material needs to be added.
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 hardly obtained. On the other hand, if the polymerization degree p is too high, the solubility in a solvent becomes low and the processability deteriorates. And is preferably set to 10 to 3000, more preferably 15 to 1000.

[0025]

The present invention will be described below by way of examples. In the examples and the like, “parts” means “parts by weight”. Synthesis Example 1 N, N-bis [3- (2-ethoxycarbonylethyl)
Synthesis of phenyl] -3,4-xylysine (the structure of A portion is represented by partial structure 3 and the terminal is diethyl ester) 6 g of 3,4-xylidine, 34 g of ethyl 3-iododihydrocinnamate, 19 g of potassium carbonate, copper sulfate Pentahydrate 5
g and 20 ml of n-tridecane were placed in a 100 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 and dissolved in 50 ml of toluene.
The insolubles were filtered, and the filtrate was purified by silica gel column chromatography using toluene. As a result, 20 g of oily N, N-bis [3- (2-ethoxycarbonylethyl) phenyl] -3,4-xylidine was obtained. The IR spectrum is shown in FIG.

Synthesis Example 2 N, N'-diphenyl-N, N'-bis [3- (2-ethoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4,4'-diamine (part A Is represented by the partial structure 5, and the terminal is diethyl ester) Synthesis of 10.77 g of N, N'-diphenylbenzidine, 23.0 g of ethyl 3-iododihydrocinnamate, 11.61 g of potassium carbonate, copper sulfate pentahydrate The product (1.0 g) and n-tridecane (20 ml) were placed in a 100 ml flask, and heated and reacted at 230 ° C. for 1 hour in a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 50 ml of toluene, insolubles were filtered, and the filtrate was purified by silica gel column chromatography using toluene. Thereby, oily N, N'-diphenyl-N, N'-bis [3- (2-ethoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4,
19.6 g of 4'-diamine was obtained. FIG. 2 shows the IR spectrum.

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 portion is a partial structure 1
3. Synthesis of N- (3,4-dimethylphenyl) -N- [4- (2-
Methoxycarbonylethyl) phenyl] amine 45 g,
4,4'-diiodo-3,3'-dimethylbiphenyl 3
0 g, potassium carbonate 27 g, copper sulfate pentahydrate 5 g, n-
Put 20 ml of tridecane into 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, insolubles were 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. FIG. 3 shows the IR spectrum.

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 portion is represented by partial structure 16 and the terminal is dimethyl ester) N- (4-methoxyphenyl) -N- [4- (2-methoxycarbonylethyl) phenyl] amine 5.0 g,
3.4 g of 4,4'-diiodo-3,3'-dimethylbiphenyl, 2.9 g of potassium carbonate, 0.1 g of copper sulfate pentahydrate.
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, the mixture was cooled to room temperature, dissolved in 20 ml of toluene,
The insolubles were filtered, and the filtrate was purified by silica gel column chromatography using toluene. Thus, pale yellow oily 3,3'-dimethyl-N, N'-bis (4-methoxyphenyl) -N, N'-bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1 ' -Biphenyl] -4,4'-diamine (5.3 g) was obtained. Its IR
The spectrum is shown in FIG.

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 portion is represented by partial structure 22 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, n-tridecane 10 ml in a 200 ml flask And reacted under heating at 230 ° C. for 5 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 20 ml of toluene, insolubles were filtered, and the filtrate was purified by silica gel column chromatography using toluene. After recrystallization from acetone, 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: 146-147 ° C.).
The spectrum is shown in FIG.

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 portion is a partial structure 1
Synthesis of 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 solution was cooled to room temperature, dissolved in 40 ml of toluene, insolubles were 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: 179-181C). Fig. 6 shows the IR spectrum.
Shown in

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 partial structure 30, and the terminal is diethyl ester)
Synthesis of 10.0 g of N, N'-diphenylbenzidine, 4-ethoxycarbonylethyl-4'-iodobiphenyl
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, insolubles were 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,
16.6 g of 1'-biphenyl] -4,4'-diamine
Obtained. FIG. 7 shows the IR spectrum.

Example 1 (Synthesis of charge transporting polyester resin (CTP-14)) 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 The mixture was placed in a 300 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] -4,4 '
0.5 mm after confirming that the diamine has been consumed
The pressure was reduced to Hg, and the ethylene glycol was distilled off.
C. and continued the reaction for 3 hours. Thereafter, the mixture was cooled to room temperature, dissolved in 200 ml of methylene chloride, the insoluble matter was filtered, and the filtrate was dropped into 1400 ml of ethanol while stirring to precipitate a polymer. The obtained polymer was filtered, washed thoroughly with ethanol, dried, and dried.
6.5 g of polymer were obtained. When the molecular weight was measured by GPC, it was Mw = 1.45 × 10 ⁵ (in terms of styrene). (Degree of polymerization q = about 160, r = about 105). IR
The spectrum is shown in FIG.

Example 2 (Synthesis of charge-transporting polyester resin (CTP-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 terephthalate 3.0 g, ethylene glycol 30.0 g and tetrabutoxy titanium 0.1 g The mixture was placed in a 300 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] -4,
After confirming that the 4'-diamine was consumed, 0.5
The pressure was reduced to mmHg and ethylene glycol was distilled off.
Heated to 35 ° C. and continued the reaction for 2.5 hours. Thereafter, the mixture was cooled to room temperature, dissolved in 200 ml of methylene chloride, the insoluble matter was filtered, and the filtrate was dropped into 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). FIG. 9 shows the IR spectrum.

Example 3 (Synthesis of charge transporting polyester resin (CTP-13)) 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) The mixture was placed in a 300 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] -4,4 '
0.5 mm after confirming that the diamine has been consumed
The pressure was reduced to Hg and the ethylene glycol was distilled off while 235.
C. and continued the reaction for 3 hours. Thereafter, the mixture was cooled to room temperature, dissolved in 200 ml of methylene chloride, the insoluble matter was filtered, and the filtrate was dropped into 1400 ml of ethanol while stirring to precipitate a polymer. The obtained polymer was filtered, washed thoroughly with ethanol, dried, and dried.
7.0 g of polymer were 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). IR
The spectrum is shown in FIG.

Further, charge-transporting polyester resins were similarly synthesized by changing the combination of the charge-transporting monomer and the dicarboxylic acid represented by the general formula (II) as shown in Tables 6 to 8.

Application Example 1 A zirconium compound (trade name: ORGATICS Z) is placed on a honing-treated 30 mmφ aluminum cylindrical substrate.
A solution consisting of 100 parts of C540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 10 parts of a silane compound (trade name: A1110, manufactured by Nippon Unicar), 400 parts of i-propanol and 200 parts of butanol is applied by a dip coating method, and then applied at 150 ° C.
For 10 minutes to form an undercoat layer having a thickness of 0.5 μm. Chlorogallium phthalocyanine crystal 10
Part was mixed with 10 parts of polyvinyl butyral resin (trade name: Esrec BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 500 parts of n-butyl acetate, and treated with a glass shaker for 1 hour using a paint shaker to obtain a dispersion. The applied coating solution was applied on the undercoat layer by a dip coating method.
Heat drying at 10 ° C. for 10 minutes. Next, 5 parts of a charge transporting polyester resin (CTP-14) are dissolved in 38 parts of monochlorobenzene, and the obtained coating solution is applied by dip coating on an aluminum cylindrical substrate on which a charge generation layer is formed. At 120 ° C. for 1 hour to form a charge transport layer having a thickness of 15 μm.

The electrophotographic characteristics of the thus obtained electrophotographic photosensitive member were measured using a laser beam printer (XP-1).
1. Fuji Xerox Co., Ltd.) at room temperature and humidity (20 ° C, 40
% RH), a print test was performed, and the image quality after 2000 copies was evaluated. Table 9 shows the results.

Application Examples 2 to 10 The charge transporting polyester resin (CTP) in Application Example 1
-14) An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Application Example 1, except that 5 parts of the charge-transporting polyester resin shown in Table 9 was used instead of 5 parts. Table 9 shows the results.

Comparative Example 1 (Synthesis of Alternating Copolymer) N, N'-diphenyl-N, N'-bis [3- (2-ethoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4 1.03 g of 4,4'-diamine, 2.0 g of ethylene glycol and 0.0 of tetrabutoxytitanium
6 g was placed in a 50 ml flask, and heated and refluxed 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 of 0.30 g of isophthalic acid dichloride dissolved in 20 ml of methylene chloride was added dropwise to 20 ml of methylene chloride. Further, 0.61 g of triethylamine was added, and the mixture was heated under reflux for 30 minutes. After adding 0.3 ml of methanol and heating under reflux for further 30 minutes, the insoluble matter was filtered, and 300 ml of ethanol was added dropwise while stirring,
The polymer was precipitated. After filtration, the obtained polymer was again dissolved in 50 ml of THF, and 300 ml of water was added dropwise while stirring to precipitate the polymer. After being sufficiently washed with water, it was dried to obtain 0.52 g of a polymer. When the molecular weight was measured by GPC, Mw = 1.60 × 10
⁴ (in terms of styrene), and the degree of polymerization p was about 20.

[0040]

[Table 9]

[0041]

The charge-transporting polyester resin of the present invention is a random copolymer obtained using a monomer having a specific structural unit. Properties, oxidation resistance,
It is a novel substance that can easily control charge injection properties and the like. Therefore, it is useful as a charge transport material for producing organic electronic devices such as electrophotographic photoreceptors. The method for producing a charge-transporting polyester resin of the present invention can easily obtain a high-molecular-weight polymer from the above-mentioned monomer in a high yield.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the compound of Synthesis Example 1.

FIG. 2 is an IR spectrum of the compound of Synthesis Example 2.

FIG. 3 is an IR spectrum of the compound of Synthesis Example 3.

FIG. 4 is an IR spectrum of the compound of Synthesis Example 4.

FIG. 5 is an IR spectrum of the compound of Synthesis Example 5.

FIG. 6 is an IR spectrum of the compound of Synthesis Example 6.

FIG. 7 is an IR spectrum of the compound of Synthesis Example 7.

FIG. 8 shows the charge transporting polyester resin (C
It is an IR spectrum figure of TP-14).

FIG. 9 shows the charge transporting polyester resin (C
It is an IR spectrum figure of TP-15).

FIG. 10 is an IR spectrum of the charge-transporting polyester resin (CTP-13) of Example 3.

Claims (3)

(57) [Claims] 1. The following general formula (I-1) or (I-2)
And at least one structure represented by the following general formula (II)
A charge-transporting polyester resin which contains at least one dicarboxylic acid component represented by the following formula as a partial structure of a repeating unit, and is randomly copolymerized. Embedded image (Wherein, 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, X represents a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent aromatic group. k is 0 or 1, and n represents an integer of 1 to 5. ) -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 of the structures represented by the above general formula (I-1) or (I-2) and a dicarboxylic acid component represented by the above general formula (II) The charge-transporting polyester resin according to claim 1, which is a random copolymer represented by the following general formula (III) containing at least one of the following as a partial structure of a repeating unit. Embedded image [In the formula, A represents a structure represented by the general formula (I-1) or (I-2), and Y and Z each represent a divalent hydrocarbon group. m is an integer of 1 to 5, q is an integer of 1 or more, r is 1 to
It means an integer of 3500. However, q + r is 5 to 50
It is an integer of 00, and 0.3 ≦ q / (q + r) <1. ] 3. At least one of the above general formulas (I-1)
Or a dicarboxylic acid ester having a structure represented by (I-2), at least one dicarboxylic acid ester having a structure represented by the general formula (II), and H- (O-
The method for producing a charge-transporting random copolymerized polyester resin according to claim 1, wherein the compound is synthesized by a transesterification reaction using a diol having a structure represented by Y) _m— OH.