JPH08295655A - Triphenylamine derivative, charge transport material and photosensitizer for electrophotograph using the same - Google Patents

Abstract

PURPOSE: To obtain a new derivative having properties such as excellent solubility into a binder polymer, not depositing crystals nor generating pinholes, and exhibiting high carrier transport, and useful for obtaining an excellent photosensitizing material. CONSTITUTION: This triphenylaime derivative is expressed by formula I (R<1> , R<2> , R<3> , R<4> , R<5> and R<6> are each H, an alkyl, an alkoxy, a phenoxy, a halogen or an aryl; (m) and (n) are each 0 or 1), e.g. 4,4',4"-tris(4,4-disphenyl-1,3- butadienyl)triphenylamine. The derivative is blended with a triphenylamine derivative of formula II (R<7> , R<8> , R<9> , R<10> , R<11> , R<12> and R<13> are each H, an alkyl, an alkoxy, a phenoxy, a halogen or an aryl; (m) and (n) are each 0 or 1) to obtain a charge transport material. Further, a charge generating layer and a charging transport layer are layered on an electroconductive substrate containing the charge transport material to obtain a photosensitizer of a laminated type for electrophotograph.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the following general formula (1):

[Chemical 10] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or Represents an optionally substituted aryl group, m and n each represent 0 or 1), a novel triphenylamine derivative represented by: The present invention relates to an electrophotographic photoreceptor containing a charge transport material.

The present invention also provides the following general formula (6):

[Chemical 11] Wherein or different even R ⁷ to R ¹³ are each the same hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or a substituted aryl group that may be substituted, l ₁ And l ₂ represents 0 or 1. Z is a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom, an aryl group which may have a substituent or the following general formulas (7a), (7b) and (7c).

[Chemical 12] (In the formula, R ^{10 to} R ¹³ , l ₁ and l ₂ have the same meanings as in the general formula (6), and R ′ and R ″ may be the same or different, and each is a hydrogen atom or a lower atom. (It represents an alkyl group, an alkoxy group, a phenoxy group, a halogen atom or an aryl group which may be substituted, and l ₃ represents 0 or 1.)
The group of is shown. ] It is related with the manufacturing method of the triphenylamine derivative including the novel triphenylamine derivative of the said General formula (1) represented by this.

The present invention further relates to the above-mentioned general formula (1) and /
Alternatively, the following general formula (4) useful as an intermediate for the production of the triphenylamine derivative represented by the general formula (6)

[Chemical 13] [In the formula, R ⁷ , R ⁸ and R ⁹ may be the same or different and each is a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, an aryl group which may have a substituent or a halogen. And Y represents a formyl group, a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or an aryl group which may have a substituent. ] It is related with the manufacturing method of the polyformyl substituted triphenylamine derivative represented by these.

[0004]

2. Description of the Related Art Recently, as an inorganic photoconductive material,
Amorphous silicon, amorphous selenium, cadmium sulfide, zinc oxide, etc. are used, but they are expensive because they are difficult to manufacture, or they are toxic and may cause problems from the viewpoint of environmental protection. On the other hand, as the organic photoconductor, in particular, a form in which the photoconductor is functionally separated into a charge generation material and a charge transport material has been actively proposed (for example,
U.S. Pat. No. 3,791,826). In this method,
A high-sensitivity electrophotographic photoconductor can be obtained by using a substance having a high generation efficiency of carriers (the carrier indicates an electric charge, the same applies hereinafter) as a charge generating material and combining a substance having a high charge transporting ability as a charge transporting material. there is a possibility.

Among them, what is required of the charge transport material is that the carriers generated in the charge generating material by the light irradiation under the application of an electric field are efficiently received, the carriers are rapidly moved in the photosensitive layer, and the surface charges are quickly eliminated. That is. The speed at which carriers move per unit electric field is called carrier mobility. High carrier mobility means that carriers move fast in the charge transport layer. This carrier mobility is specific to the charge transport material, and therefore, it is necessary to use a material with high carrier mobility in order to achieve high carrier mobility, but it is said that it has reached a sufficient level yet. The current situation is that I cannot say that.

Further, when the charge transport material is dissolved in an organic solvent together with the binder polymer and applied, it is necessary to form a uniform organic thin film without crystal precipitation or pinhole formation in the coating film. This is because a high electric field is applied to the obtained thin film, which may cause dielectric breakdown or noise when microcrystals or pinholes are generated. Further, even if the characteristics of both the charge generating substance and the charge transporting substance are good, the injection of carriers from the charge generating substance to the charge transporting substance, that is, the injection of charges from the charge generating layer to the charge transporting layer is efficiently performed. This is very important. This charge injection is due to the characteristics of the interface between the charge generating substance (or charge generating layer) and the charge transporting substance (or charge transporting layer) and is not uniform among various substances. As described above, since various conditions are required for the charge transport material, charge transport materials having various properties have been developed.

Conventionally, as a charge transporting material, for example, the following formula (A) is disclosed in JP-A-60-174749.

Embedded image A styryl compound represented by is proposed.

Further, Japanese Unexamined Patent Publication No. 60-175052 discloses the following general formula (B):

[Chemical 15] (In the formula, R ¹ represents an alkyl group containing a substituted alkyl group or an aryl group containing a substituted aryl group, R ² represents a hydrogen atom, an alkyl group containing a substituted alkyl group or an aryl group containing a substituted aryl group, and Ar Represents an aryl group including a substituted aryl group.) Has been proposed.

Compounds similar to the above compound (B) are disclosed in JP-A-62-120346 and JP-A 1-21.
7357, JP-A-4-57056 and JP-A-4-292663.

On the other hand, Japanese Patent Publication No. 6-93124 discloses that
A styryl compound represented by the following formula (C) has been proposed.

Embedded image (In the formula, R ¹ , R ³ , and R ⁵ each represent hydrogen, an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and the aryl group, the aralkyl group, or the heterocyclic group may have a substituent. R ² , R ⁴ , and R ⁶ each represent an aryl group, an aralkyl group, or a heterocyclic group, and each group may have a substituent, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ may together form a ring, and R ⁷ , R ⁸ and R ⁹ represent hydrogen, an alkyl group, an alkoxy group, an aralkyl group or an aryl group.)

Compounds similar to the above (C) are disclosed in JP-A-63-
It is also proposed in Japanese Laid-Open Patent Publication No. 163361 and Japanese Laid-Open Patent Publication No. 6-332206. Further, a hydrazone compound represented by the following formula (D) is disclosed in JP-A-4-292663.

[Chemical 17] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group or an aryl group, and an alkyl group, an alkoxy group,
Both the aralkyl group and the aryl group may have a substituent. Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and an alkyl group, an aryl group, an aralkyl group and Any of the heterocyclic groups may have a substituent. l, m and n represent 0 or 1. However, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ must not be hydrogen atoms. ) The demand for charge transport materials is expanding more and more, and accordingly, newer materials capable of meeting various conditions are required.

For example, Japanese Patent Application Laid-Open No. 4-57056 describes that some of the crystals are precipitated at the time of producing the photoconductor because of poor solubility of the following compound (E).

Embedded image

Further, Japanese Patent Application Laid-Open No. 6-332206 describes that cracks occur in the charge transport layer composed of the following compound (F) and a binder polymer.

[Chemical 19]

Further, in Japanese Patent Laid-Open No. 2-226159, the following general formula G

Embedded image [In the formula, X represents an aryl group, an arylene group, a heterocyclic group, a diarylamino group or a triarylamino group which may have a substituent, and Y represents the following group.

[Chemical 21] Represents a group selected from or a single bond, n is 0 or 1, m
Represents an integer of 1, 2 or 3. R ₁ and R ₂ may be the same or different and each represents an alkyl group which may have a substituent, an aryl group, an aralkyl group, a cyano group, a nitro group or a halogen atom, and R ₃ represents a substituent. Represents an alkyl group, an aryl group or an aralkyl group which may have. ], The compound is a complex compound in which two phenyl groups are bonded by Y to form another ring.

The various triphenylamine derivatives used as the above-mentioned known charge-transporting materials can be used as the corresponding triphenylamine derivatives as described in, for example, "Jikken Kagaku Koza", Vol. 14, page 688 (published by Maruzen). An iminium intermediate obtained by reacting a compound having a phenylamine basic skeleton with a Wielsmeier reagent prepared from a halogenating agent such as phosphorus oxychloride and a formylating agent such as N, N-dimethylformamide is used as an aqueous alkaline solution. It can be produced by reacting a formyl-substituted triphenylamine derivative produced by a method such as hydrolysis with a predetermined phosphite.

However, in the case of the above method, when a monoiminium salt is produced by reacting triphenylamine with 1 equivalent of the Wiersmeier's reagent, the nucleophilicity of this salt is extremely reduced, and thus the monoiminium salt is reacted with the second Wiersmeier's reagent. It becomes difficult to form diiminium salt efficiently.
Therefore, the synthesis of triphenylamine monoaldehyde can be easily achieved, but the synthesis of triphenylamine diformyl is difficult, and even if a large amount of Wiersmeier reagent is present or the reaction time is prolonged, the yield is high. Is very low. For example, in JP-A-7-173112, 4,4 '
It has been shown that the yield of -diformyltriphenylamine is 39.5% and the yield of 4-methyl-4,4'-diformyltriphenylamine is only 11.8%.

Bouanane et al. Give 4,4'- by reacting triphenylamine with a usual Wiersmeier reaction.
Diformyltriphenylamine was reported to be obtained in a yield of 75% (CR Hebd. Seances Acad. Sci., Se.
r. C, Vol.279, No.5, p187-190), in the additional test by the present inventor, it was not possible to obtain 4,4′-diformyltriphenylamine in such a high yield. Further, it is very disadvantageous in the formation of a triiminium salt that has reacted with the third Wiersmeier reagent, and the synthesis of a triformyl derivative of triphenylamine is very difficult. in this way,
Up to now, a method for synthesizing a 4,4′-diformyltriphenylamine derivative and a 4,4 ′, 4 ″ -triformyltriphenylamine derivative in good yield has not been known.

[0018]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a charge transport material which is stable when formed into a film,
It is an object of the present invention to provide a new material that can exhibit high carrier mobility and is excellent in various characteristics when an electrophotographic photoreceptor is formed. Another object of the present invention is to provide an electrophotographic photoreceptor containing a new material having the above characteristics as a charge transport material.

Another object of the present invention is to provide an efficient method for producing a novel charge transport material having the above characteristics, and the present invention also produces the above novel charge transport material. It is an object of the present invention to provide an improved method for producing an intermediate substance useful for the above.

[0020]

Under these circumstances, the present inventors have conducted various studies on various compounds, and as a result, one phenyl group of triphenylamine has a substituent of a diphenylbutadienyl skeleton. The following general formula (1) has a diphenylbutadienyl skeleton substituent or a diphenylvinyl skeleton substituent on the other two phenyl groups.

[Chemical formula 22] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or The present invention has been completed by finding that a novel triphenylamine derivative represented by an aryl group which may have a substituent, m and n are 0 or 1) can solve the above problems.

That is, the present inventors have found that the triphenylamine derivative of the general formula (1) has good solubility in the binder polymer, does not cause crystal precipitation or pinhole formation, and has high carrier mobility. The present invention has been completed by discovering that the above-mentioned properties can be exhibited, and that the photoconductor using the same has high sensitivity and low residual potential.

The present invention has the following general formula (1):

[Chemical formula 23] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or Represents an aryl group which may have a substituent, and m and n represent 0 or 1).

The present invention also provides a novel triphenylamine derivative of the above general formula (1) and the following general formula (2)

[Chemical formula 24] (In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, It represents an aryl group which may have a halogen atom or a substituent.
And n are 0 or 1. ) A charge transporting material characterized by containing a mixture with a triphenylamine derivative.

The present invention also provides the following general formula (3):

[Chemical 25] (In the formula, R ⁷ , R ⁸ and R ⁹ may be the same or different from each other and represent a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, an aryl group which may have a substituent or a halogen atom. ) In the presence of an acid selected from the group consisting of a Lewis acid and a protic acid, with a Wiermeier reagent prepared from a halogenating agent and an N-substituted formamide, and then alkaline. The following general formula (4) can be obtained by hydrolysis with an aqueous solution.

[Chemical formula 26] (In the formula, R ⁷ , R ⁸ and R ⁹ have the same meanings as in the general formula (3), and Y has a formyl group, a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or a substituent. A polyformyl-substituted triphenylamine derivative represented by the following general formula (5a) is obtained. (5b) or (5c)

[Chemical 27] (Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R, R ′ and R ″
Are the same or different and each represents a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or an aryl group which may have a substituent. l ₁ , l ₂ and l ₃ represent 0 or 1, when each is 0, A represents a hydrogen atom, and when 1 is 1, A, B
Bind together to form a single bond. ) And a phosphite compound represented by the following general formula (6)

[Chemical 28] [Wherein R ^{7 to} R ¹³ , R ′, R ″, l ₁ , l ₂ and l
₃ has the same meaning as in the general formulas (5a), (5b) and (5c), and Z may have a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or a substituent. An aryl group or the following general formula (7a),
(7b), (7c)

[Chemical 29] (In the formula, R ^{10 to} R ¹³ , and l ₁ , l ₂ and l ₃ have the same meanings as those in the general formulas (5a), (5b), (5c) and (6)). Indicates. ] It is related with the manufacturing method of the triphenylamine derivative represented by these.

In the present invention, the polyformyl-substituted triphenylamine derivative represented by the general formula (4) is a diformyl-substituted triphenylamine derivative in which the substituent Y is a hydrogen atom, and the substituent Y is a formyl group. Which is a mixture of triformyl-substituted triphenylamine derivatives, wherein the triphenylamine derivative represented by the general formula (6) is
The above-mentioned general formula (6), wherein the triphenylamine derivative in which the substituent Z is a hydrogen atom and the triphenylamine derivative in which the substituent Z is a group represented by the general formula (7) are mixed. ) Relates to a method for producing a triphenylamine derivative.

The present invention also has the following general formula (3):

Embedded image (In the formula, R ⁷ , R ⁸ and R ⁹ may be the same or different from each other and represent a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, an aryl group which may have a substituent or a halogen atom. In the presence of an acid selected from the group consisting of a Lewis acid and a protic acid, a triphenylamine derivative represented by) is reacted with a Wielsmeier reagent prepared from a halogenating agent and an N-substituted formamide to form a reaction product. The following general formula (4) is characterized in that the product is then hydrolyzed with an alkaline aqueous solution.

[Chemical 31] (In the formula, R ⁷ , R ⁸ and R ⁹ have the same meanings as in the general formula (3), and Y has a formyl group, a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or a substituent. An aryl group which may be present) is represented by the formula (3).

In the present invention, the Lewis acid used when the triphenylamine derivative represented by the general formula (3) is reacted with the Wiersmeier reagent is zinc chloride, zinc bromide,
Selected from the group consisting of boron trifluoride, aluminum chloride, titanium tetrachloride and tin chloride, wherein the protonic acid is selected from hydrogen chloride and hydrogen bromide. The present invention relates to a method for producing a polyformyl-substituted triphenylamine derivative.

In the present invention, the Wielsmeier reagent is at least one halogenating agent selected from phosphorus oxychloride, phosgene and thionyl chloride, and at least one halogenated reagent selected from N, N-dimethylformamide and N-methylformamide. The present invention relates to a method for producing a polyformyl-substituted triphenylamine derivative represented by the general formula (4), which is prepared from the N-substituted formamide of

In the present invention, the reaction of the triphenylamine derivative represented by the general formula (3) with the Wiersmeier reagent uses at least one reaction solvent selected from toluene, xylene, chlorobenzene and dichlorobenzene. The general formula (4) is characterized in that
Relates to a method for producing a polyformyl-substituted triphenylamine derivative represented by:

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the compound of the general formula (1) of the present invention may be the same or different. , A hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or an aryl group which may have a substituent, and the lower alkyl group includes an alkyl group having 1 to 4 carbon atoms,
Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and the like, and a methyl group or an ethyl group is particularly preferable. Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the aryl group which may have a substituent, a phenyl group, a p-tolyl group, 2,
Examples thereof include a phenyl group substituted with a lower alkyl group such as 4-dimethylphenyl group, a phenyl group substituted with a lower alkoxy group such as p-methoxyphenyl group, and a phenyl group substituted with a halogen atom such as p-chlorophenyl group. Specific preferred examples of the compound of the general formula (1) of the present invention are shown in Table 1 below.
The compounds shown in Table 2 and Table 3 may be mentioned, but the present invention is not limited thereto.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

The abbreviations in the table have the following meanings. 4-Me: a methyl group substituted at the 4-position of a phenyl group 3-Me: a methyl group substituted at the 3-position of a phenyl group 4-Cl: a chlorine atom substituted at the 4-position of a phenyl group 4-MeO: phenyl Methoxy group substituting at 4-position of group 4-F: Fluorine atom substituting at 4-position of phenyl group The abbreviations used in each compound described later in the present specification have the same meanings as described above. Show.

In the general formula (1) of the present invention, m = n =
1, (R ¹ , R ² ) = (R ³ , R ⁴ ) = (R ⁵ , R ⁶ ).
A compound represented by R ¹ , R ² and R ³ , R ⁴ and R ⁵ , R
^The triphenylamine derivative (1a) in which ⁶ is the same can be synthesized according to reaction formula 1.

Embedded image (In the formula, R ¹ , R ² and R have the same meanings as described above.) Incidentally, R is particularly preferably a methyl group or an ethyl group.

That is, 4,4 ', 4 "-triformyltriphenylamine (4a) and 3,3-diarylallylphosphorous acid dialkyl ester (5) in an amount three times or more the molar amount thereof are added in the presence of a base. It can be easily produced by reacting at room temperature to a temperature of about 80 ° C. As the base, sodium hydroxide, sodium amide and sodium methoxide, sodium-tert-butoxide, potassium-tert.
-A metal alkoxide such as butoxide is used. As the solvent, lower alcohols such as methanol and ethanol,
Ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane, toluene,
Hydrocarbons such as xylene, dimethyl sulfoxide, N, N
An aprotic polar solvent such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or a mixture thereof can be used.

The compound represented by the general formula (4) is used in the production of the novel triphenylamine derivative represented by the general formula (1) in the present invention (the above reaction formula 1) and also serves as an intermediate for the production of the compound (2). The polyformyl-substituted triphenylamine derivative represented by the formula (1) is obtained by adding the triphenylamine derivative represented by the general formula (3) to the presence of an acid selected from the group consisting of a Lewis acid and a protic acid. Below, it is produced by reacting with the Wiersmeier reagent and then hydrolyzing it with an alkaline aqueous solution. For example, the following synthetic scheme (a Vilsmeier reagent prepared from N, N-dimethylformamide and phosphorus oxychloride is used) will be described as an example.

[0039]

[Chemical 33]

As can be seen from the above reaction formula, when the triphenylamine compound (a) is subjected to the Wiersmeier reaction, if the reaction is carried out without a catalyst, the monoiminium salt (b) is obtained.
At this point, the reaction almost stopped, so that the hydrolyzate was mostly monoformyl-substituted product (C). However, when a Lewis acid or a protonic acid is present as a catalyst, the reaction of forming a diiminium salt (d) proceeds, and when the amount of Wiersmeier reagent is increased and the reaction time is extended, a triiminium salt (e) is formed. As a result, the di-formyl-substituted product (f) and / or the tri-formyl-substituted product (to) can be obtained as a hydrolysis product, either alone or as a mixture. The di-formyl-substituted product (f) obtained here is useful as a production intermediate for the compound included in the general formula (2) in the charge transport material of the present invention, and a tri-formyl-substituted product obtained in the same manner. The body (g) is a production intermediate of the compound included in the general formula (1). Therefore, the triformyl-substituted product (to) and the mixture of the triformyl-substituted product (to) and the diformyl-substituted product (f) obtained according to the above reaction are both used as intermediates for producing a compound to be contained in the charge transport material of the present invention. It is useful.

As the substituents R ⁷ , R ⁸ and R ⁹ of the triphenylamine derivative (a) used as a raw material for producing the polyformyl-substituted triphenylamine derivative (f) and (g), a hydrogen atom and a carbon number are used. 1 to 4 branched or straight-chain alkyl group, lower alkoxy group such as methoxy group and ethoxy group, phenoxy group, aryl group which may have a substituent such as phenyl group, orthotolyl, methatril and paratolyl group, fluorine, chlorine , Halogen elements such as bromine and iodine, and the like. The substitution positions are R ⁷ , R
⁸ is the meta position of the amino group, and R ⁹ may be in the ortho position, meta position, or para position with respect to the amino group.
In order to obtain the compounds (e) and (g), it is preferably in the meta position with respect to the amino group.

Examples of the N-substituted formamide to be a formylating agent include N, N-dimethylformamide, N-methylformanilide, N-formylmorpholine and N, N.
-Diisopropylformamide and the like can be mentioned, but N, N-dimethylformamide and N-methylformanilide are preferable. Further, as a halogenating agent which reacts with these N-substituted formamides to form Wiersmeier's reagent, phosphorus oxychloride, phosgene, oxalyl chloride, thionyl chloride, triphenylphosphine-
Examples thereof include bromine complex and hexachlorotriphosphazatriene, with phosphorus oxychloride, phosgene and thionyl chloride being preferred. The solvent used may be any solvent inert to the reaction, such as toluene, xylene and other hydrocarbon solvents, methylene chloride, 1,2-dichloroethane, chlorobenzene, chlorinated solvents such as dichlorobenzene, diethyl ether, diisopropyl ether, etc. 1,
Examples include ether solvents such as 4-dioxane,
A mixed solvent of these may be used.

The reaction was carried out by adding 2 N-substituted formamide in a solvent.
From which 8 to 8 equivalents were weighed and 2 to 8 equivalents of the halogenating reagent were added dropwise to prepare the Wiersmeier reagent, then 1 equivalent of the triphenylamine derivative was added, and further 1 equivalent or more of a Lewis acid or protic acid was added. You can do it. When synthesizing a diformyl-substituted compound, the N-substituted formamide and the halogenating reagent are preferably about 2 to 4 times the amount of triphenylamine. When a triformyl-substituted product is synthesized, the N-substituted formamide and the halogenating reagent are preferably about 5 to 7 times as much as triphenylamine.
It is sufficient that the amount of the catalyst is 1 to 2 times that of triphenylamine. If the amount is less than this, the progress of the reaction is insufficient, and if the amount is large, it is economically disadvantageous. Further, the catalyst, the triphenylamine derivative, and the N-substituted formamide may be charged in advance in a solvent, and the halogenating agent may be added thereto. The reaction can be carried out at room temperature to 150 ° C, preferably 50 to 90 ° C.

In the case of synthesizing the diformyl-substituted product, the reaction can be carried out at this temperature for 20 to 30 hours to obtain a diiminium salt of triphenylamine. Further, in the case of synthesizing a triformyl-substituted product, further reaction is carried out for a total of 40 to 60 hours to obtain a triiminium salt of triphenylamine. These iminium salts are hydrolyzed with an aqueous alkaline solution of sodium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate or the like to give a 4,4'-diformyltriphenylamine derivative or 4,4'-diformyltriphenylamine derivative. Each of these can be led to a 4 ', 4 "-triformyltriphenylamine derivative.
According to the production method of the present invention, it becomes possible to synthesize 4,4′-diformyltriphenylamine derivative and 4,4 ′, 4 ″ -triformyltriphenylamine derivative in a good yield, and Since the reagent is relatively inexpensive, it can be manufactured industrially.

The 3,3-diarylallyl phosphite dialkyl ester (5) used in the above-mentioned reaction formula 1 can be obtained according to the following reaction formula 3.

Embedded image

That is, the benzophenone derivative (8) is reacted with (i) methylmagnesium chloride (MeMgCl), and (ii) the resulting alcohol is dehydrated in the presence of an acid to give 1,1-diarylethylene ( 9)
Get. As the acid, PTSA (p-toluenesulfonic acid) or the like which is usually used in a dehydration reaction can be used.

Here, 1,1-diarylethylene (9) can also be obtained by the reaction formula 4. That is, except that a substituted phenylmagnesium bromide is used instead of methylmagnesium chloride as the starting compound of the acetophenone derivative (10), the above (i)
It can be obtained by carrying out the same reaction as in (ii).

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Then, 1,1-diarylethylene (9) was added to paraformaldehyde (CH ₂ O) in acetic acid according to the method described in JP-A-49-75564.
Reaction with _n and hydrogen chloride gives the 3,3-diarylallyl chloride (11). Further, this 3,3-diarylallyl chloride (11) is allowed to react with trialkylphosphite P (OR) ₃ to obtain 3,3-diarylallylphosphorous acid diethyl ester (5). Here, as the trialkyl phosphite, for example, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite and the like can be used.

On the other hand, in the general formula (1) of the present invention, m =
n = 1, (R ¹ , R ² ) = (R ⁵ , R ⁶ ) ≠ (R ³ , R
^The compound represented by ⁴ ), that is, the triphenylamine derivative (1b) in which R ¹ and R ² are the same as R ⁵ and R ⁶ but different from R ³ and R ⁴ , can be synthesized according to Reaction Formula 5. it can.

Embedded image

4,4 ', 4 "-triformyltriphenylamine (4a) and a double molar amount of 3,3-diarylallylphosphorous acid dialkyl ester (5) are reacted in the presence of a base to give 4, 4'-bis (4 "', 4"'-diaryl-1 "", 3 "'-butadienyl)-
By synthesizing 4 ″ -formyltriphenylamine (12) and reacting with a 3,3-diarylallyl allyl phosphite dialkyl ester (5 ′) different from the above (5), the objective compound of the present invention is obtained. (1b) can be synthesized. On the other hand, in the general formula (1) of the present invention, m =
1, n = 0, (R ¹ , R ² ) = (R ⁵ , R ⁶ ) ≠
The triphenylamine derivative (1c) represented by (R ³ , R ⁴ ) can be synthesized according to reaction formula 6.

[0051]

Embedded image

That is, 4,4 'shown in the above reaction formula (5)
-Bis (4 "", 4 ""-diaryl-1 "",
3 ′ ″-Butadienyl) -4 ″ -formyltriphenylamine (12) and an equivalent amount of diarylmethylphosphorous acid dialkyl ester (5 ″) are reacted to synthesize the desired compound (1c) of the present invention. It is possible.
Diarylmethylphosphorous acid dialkyl ester (5 ″)
Is the corresponding diarylmethyl chloride, or bromide and trialkyl phosphite directly, or toluene,
It is obtained by heating in a solvent such as xylene.

On the other hand, in the general formula (1) of the present invention, m
= N = 0, (R ¹ , R ² ) = (R ³ , R ⁴ ) ≠ (R ⁵ ,
The triphenylamine derivative (1d) represented by R ⁶ ) can be synthesized according to reaction formula 7.

[Chemical 38]

4,4 ', 4 "-Triformyltriphenylamine (4a) and a double molar amount of diarylmethylphosphorous acid dialkyl ester (5") are reacted in the presence of a base to give 4,4'- Bis (2 "", 2 ""-diarylvinyl) -4 "-formyltriphenylamine (1
By synthesizing 3) and reacting this with 3,3-diarylallyl phosphite dialkyl ester (5), the desired compound of the present invention (1d) can be synthesized.

The following general formula (2) which can be used as a charge transporting material of the present invention as a mixture with the novel triphenylamine derivative represented by the above general formula (1).

[Chemical Formula 39] (In the formula, R ^{7 to} R ¹³ may be the same or different and each represents a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or an aryl group which may have a substituent. Preferred examples of the triphenylamine derivative represented by m and n are 0 or 1.), but are not limited to those shown in Tables 4 to 6 below. .

Generally, in the substituents R ^{7 to} R ¹³ in the general formula (2), the lower alkyl group is an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, se
Examples thereof include a c-butyl group and an isobutyl group, with a methyl group or an ethyl group being particularly preferable. Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Moreover, as the aryl group which may have a substituent, a phenyl group, p-
Examples thereof include a phenyl group substituted with a lower alkyl group such as a tolyl group and a 2,4-dimethylphenyl group, a phenyl group substituted with a lower alkoxy such as a p-methoxyphenyl group, and a phenyl group substituted with a halogen atom such as a p-chlorophenyl group. .

The triphenylamine derivative of the general formula (2) adopts the same reaction method as the above reaction formulas 1 to 7 described as the method for producing the triphenylamine derivative of the general formula (1). Can be manufactured.

[0058]

[Table 4]

[0059]

[Table 5]

[0060]

[Table 6]

A method for preparing a mixture of the novel triphenylamine derivative represented by the general formula (1) and the triphenylamine derivative represented by the general formula (2), which can be used in the charge transport material of the present invention. There is no particular limitation. It can be prepared by mixing two types of triphenylamine derivatives of the general formula (1) and the general formula (2), which are separately produced according to the reaction methods shown in the above reaction formulas 1 to 7.
Further, for example, the above-mentioned general formula (4) produced in the process of producing the novel triphenylamine derivative of the general formula (1)
The polyformyl-substituted triphenylamine derivative intermediate represented by the formula (4) is a diformyl-substituted triphenylamine derivative in which the substituent Y in the general formula (4) is a hydrogen atom, and the substituent Y
Is obtained as a mixture with a triformyl-substituted triphenylamine derivative having a formyl group, the intermediate mixture is directly reacted with the phosphite compound represented by the general formula (5) to give the above-mentioned general formula A mixture of two kinds of triphenylamine derivatives represented by (1) and the general formula (2) can be prepared. In addition, it may be prepared according to another manufacturing method capable of preparing a mixture of the above two kinds of triphenylamine derivatives.

For example, when the compound of the general formula (1) and the compound of the general formula (2) are mixed to form the charge transport material of the present invention, combinations as shown in the following Tables 7 to 10 are listed. However, the present invention is not limited to this.

[0063]

[Table 7]

[0064]

[Table 8]

[0065]

[Table 9]

[0066]

[Table 10]

High carrier mobility can be obtained by using the novel triphenylamine derivative of the general formula (1) of the present invention as a charge transport material. Further, the novel triphenylamine derivative of the general formula (1) of the present invention can be used in a wide range of fields such as organic electroluminescence (EL). The charge transporting material containing the triphenylamine derivative represented by the general formula (1) of the present invention or the mixture of the novel triphenylamine derivative and the triphenylamine derivative represented by the general formula (2) is electrophotographically photographed. A high-sensitivity electrophotographic photoreceptor can be obtained by using it in the photosensitive layer of the photoreceptor.

Specifically, the electrophotographic photosensitive member of the present invention comprises the compound (1) of the present invention as a charge transporting material of an electrophotographic photosensitive member having a charge generating layer and a charge transporting layer functionally separated on a conductive support. Used for the charge transport layer. The electrophotographic photosensitive member of the present invention may have a single layer containing the compound of the general formula (1) of the present invention as a charge generating agent and a charge transporting agent provided on a conductive support.

A charge transport layer using the compound of the general formula (1) of the present invention as a charge transport material is a compound of the general formula (1) of the present invention.
Or a mixture of the compound of the general formula (1) and the compound of the general formula (2) is directly deposited on the conductive support or the charge generation layer, or the compound of the general formula (1) of the present invention or It is formed by coating a solution of a mixture of the compounds of the general formulas (1) and (2) and a binder in a suitable solvent on a conductive support or a charge generating layer and drying. . On the other hand, the monolayer containing the charge generating agent and the compound of the general formula (1) of the present invention is a solution or dispersion of the charge generating agent and the compound of the general formula (1) of the present invention together with a binder in a suitable solvent. It is formed by applying the obtained solution to a conductive support and drying it.

Examples of the binder include polyacrylate, polymethacrylate, polyamide, acrylic resin, acrylonitrile resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, phenol resin, epoxy resin, polyester, alkyd resin, polycarbonate,
Examples thereof include polyurethane, polystyrene and copolymers thereof. In addition to such an insulating polymer, an organic photoconductive polymer such as polyvinylcarbazole, polyvinylanthracene, or polyvinylene can be used.

It is particularly preferable to use polycarbonate among these binders. As a polycarbonate that can be preferably used, a bisphenol A type polycarbonate represented by the following structural formula (for example, Upilon E series manufactured by Mitsubishi Gas Chemical Co., Inc.) and a bisphenol Z type polycarbonate resin (for example, manufactured by Mitsubishi Gas Chemical Co., Inc.) Polycarbonate Z series) or a copolymerized polycarbonate containing bisphenol A, bisphenol Z, and biphenol carbonate as structural units disclosed in JP-A-4-179996.

[0072]

[Chemical 40]

Specific examples of the biphenol copolymerized polycarbonate include, for example, a bisphenol A / biphenyl type polycarbonate resin represented by the following structure (here, n / n + m = 0.1 to 0.9 is preferable). Can be 0.85.

[0074]

Embedded image

(In formulas H to L, R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, an alkyl group or an aryl group, and R ^14
14 and R ¹⁵ may be cyclically bonded. R ¹⁶ , R ¹⁷ ,
R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R
²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and n and m represent the number of moles of each repeating unit described above. There is. )

Further, in addition to the above-mentioned polycarbonate, the polycarbonate whose repeating unit is represented by the following structural formula, which is disclosed in JP-A-6-21412, can be used.

Embedded image

Further, polycarbonate having a repeating unit represented by the following structure, which is disclosed in JP-A-6-222581, can also be used.

[Chemical 43] (In the formula, R ³² , R ³³ and R ³⁴ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an arylalkyl group.) Specifically, What is shown in the table of.

[0078]

[Table 11]

The compounding ratio of these binders to the compound (1) of the present invention is such that the charge transport substance is 1 per 100 parts by weight of the binder.
0 to 1000 parts by weight, preferably 30 to 500 parts by weight,
More preferably, 40 to 200 parts by weight can be added.

The solvent to be used is not particularly limited, but an organic solvent can be used, and alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, N, N-dimethylformamide and N, N-dimethyl are used. Amides such as acetamide, sulfoxides such as dimethyl sulfoxide,
Ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, esters such as ethyl acetate and methyl acetate, methylene chloride, chloroform,
Aliphatic halogenated hydrocarbons such as 1,2-dichloroethane, dichloroethylene, carbon tetrachloride and trichloroethylene, or aromatic compounds such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene are used alone or in the form of a mixture thereof. be able to.

The conductive support used in the photoreceptor of the present invention is a sheet or drum of foil or plate of metal or alloy such as copper, aluminum, silver, iron, zinc and nickel. , Or those obtained by vacuum deposition or electrolytic plating of these metals on a plastic film or cylinder, or a layer of a conductive compound such as a conductive polymer, indium oxide or tin oxide on a support such as glass, paper or a plastic film. Those provided by coating or vapor deposition are used.

The coating can be carried out by using a coating method such as a dip coating method, a spray coating method, a spinner coating method, a Meyer bar coating method, a blade coating method, a roller coating method or a curtain coating method. Drying is preferably performed by drying at room temperature and then heat drying. It is preferable that the heat drying is carried out at a temperature of 30 to 200 ° C. for 5 minutes to 2 hours with or without air blowing.

Further, the charge transport layer in the present invention may contain other charge transport materials and various additives, if necessary. Other charge transport materials include
For example, JP-B-55-42380 and JP-A-60-340.
Hydrazone compounds represented by the following general formula (I) described in JP-A No. 61-23154, etc., and trihydrazine compounds represented by the following general formula (II) described in JP-B-58-32372. Phenylamine dimers, U.S. Pat. No. 3,873,312 and the like, distyryl-based compounds represented by the following general formula (III), other tetraphenylbutadiene-based compounds, α-phenylstilbene, polyvinylcarbazole, triphenylmethane and the like, but are not limited thereto. Not something.

[0084]

[Chemical 44] (In the formula, R ₁ and R ₂ represent the same or different lower alkyl groups, optionally substituted aryl groups, and optionally substituted aralkyls, and R ₃ and R ₄ are the same. Or they may be different, a lower alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent which may have a substituent. It represents a heterocyclic group, and R ₃ and R ₄ may be bonded to each other to form a ring, wherein R ₅ has a hydrogen atom, a lower alkyl group, an aryl group which may have a substituent or a substituent. Optionally aralkyl, a lower alkoxy group, or a halogen atom.
₅ and R ₁ or R ₂ may be bonded to each other to form a ring. )

[0085]

Embedded image (In the formula, R _{1 to} R ₁₂ may be the same or different and may be a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, an aryl group which may have a substituent, or a halogen. Indicates an atom.)

[0086]

Embedded image (In the formula, R _{1 to} R ₄ may be the same or different and represent a lower alkyl group or an aryl group which may have a substituent, and
₁ and Ar ₃ may be the same or different and each represents a phenyl group which may be substituted with one or more groups selected from a lower alkyl group, a lower alkoxy group, an aryloxy group and a halogen atom. Ar ₂ has a monocyclic or polycyclic aromatic ring having 4 to 14 carbon atoms which may have the same substituents as Ar ₁ and Ar ₃ , or has the same substituent as Ar ₁ and Ar _3. Optionally represents a heterocycle. )

Examples of various additives include, for example, biphenyl compounds (for example, those disclosed in JP-A-6-332206), m-terphenyl, plasticizers such as dibutyl phthalate, silicone oil, and graft type silicone polymers. Surface lubricants such as various fluorocarbons,
Potential stabilizers such as dicyanovinyl compounds and carbazole derivatives, monophenol antioxidants such as 2-tert-butyl-4-methoxyphenol and 2,6-di-tert-butyl-4-methylphenol, bisphenol antioxidants Agents, amine-based antioxidants such as 4-diazabicyclo [2,2,2] octane, salicylic acid-based antioxidants, and tocopherols.

The thickness of the resulting charge transport layer is 5 to 40 μm.
m, preferably 10 to 30 μm. The charge transport layer obtained as described above is electrically connected to the charge generation layer to receive the charge carriers injected from the charge generation layer in the presence of an electric field, and at the same time, to charge these charge carriers into the photosensitive layer. Can have the function of transporting to the surface. At this time, the charge transport layer may be laminated on or below the charge generation layer, but is preferably laminated on the charge generation layer.
A protective layer can be applied and formed on the photosensitive layer thus produced, if necessary. In addition, an undercoat layer having a barrier function and an adhesive function can be provided between the conductive support and the photosensitive layer. Examples of the material for forming the undercoat layer include polyvinyl alcohol, nitrocellulose, casein, ethylene-acrylic acid copolymer, polyamide such as nylon, polyurethane, gelatin, aluminum oxide and the like. The thickness of the undercoat layer is 0.1 to 5 μm,
It is preferably 0.5 to 3 μm.

As the charge generation layer, an inorganic charge generation material such as selenium, selenium-tellurium or amorphous silicon,
Pyrylium salt dyes, thiapyrylium salt dyes, azurenium salt dyes, thiacyanine dyes, cationic dyes such as quinocyanine dyes, squalium salt pigments, phthalocyanine pigments, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments Polycyclic quinone pigments such as pigments, indigo pigments, quinacridone pigments, azo pigments, pyrrolopyrrole pigments, and other organic charge generating materials may be used alone or in combination and used as a vapor deposition layer or coating layer. it can. Among the above-mentioned organic charge generating substances, Chem. Re is particularly preferable.
v. 1993, 93, p.449-486. Specifically, a phthalocyanine pigment is preferable.

Particularly, as the phthalocyanine pigment, alkoxytitanium phthalocyanine (Ti (O
R) ₂ Pc), oxotitanium phthalocyanine (Ti
OPc), copper phthalocyanine (CuPc), metal-free phthalocyanine (H ₂ Pc), hydroxygallium phthalocyanine (HOGaPc), vanadyl phthalocyanine (V
OPc), chloroindium phthalocyanine (ClIn
Pc). More specifically, as TiOPc, α-type TiOPc, β-type TiOPc, γ-type-T
Examples include iOPc, m-type-TiOPc, Y-type-TiOPc, A-type TiOPc, B-type-TiOPc, and TiOPc amorphous. As H ₂ Pc, α-type-H ₂ Pc,
Examples include β-type-H ₂ Pc, τ-type-H ₂ Pc, and x-type-H ₂ Pc.

Azo pigments are also preferred. Examples of the azo pigment include a monoazo compound, a bisazo compound and a trisazo compound, and specifically, an azo compound represented by the following structural formula is preferable.

[Chemical 47]

Further, a perylene compound or a polycyclic quinone compound represented by the following structural formula is also preferable.

Embedded image Other than these materials, any material can be used as long as it absorbs light and generates charges with high efficiency.

As described above, an electrophotographic photoreceptor containing the triphenylamine derivative (1) of the compound of the present invention in the charge transport layer can be obtained. As described above, the triphenylamine derivative (1) of the compound of the present invention, that is, the compounds listed in Tables 1 to 3 is stable when formed into a film, can exhibit high carrier mobility, and can be used in electrophotography. It is also an excellent material in terms of various characteristics when a photoconductor is formed.

[0094]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The measuring instruments and measuring conditions used in the examples are shown below. (1) ¹ H-NMR equipment: AM-400 manufactured by Bruker Co.
Model device (400MHz) Solvent: CDCl ₃ Internal standard substance: Tetramethylsilane (2) MASS Equipment: Hitachi M-80B (manufactured by Hitachi, Ltd.) (3) HPLC column: Intersil ODS-2 Pump: Hitachi L-6000 Pump Detection Instrument: Hitachi C-4000 UV Detector Integrator: Hitachi D-2000 Chromato-Integrat
or

Example 1 4,4 ′, 4 ″ -tris (4 ″ ″, 4 ″ ″-diphenyl-1 ″ ″, 3 ″ ″-butadienyl) triphenylamine (Exemplified Compound 1, m = N = 1, R ¹ = R ² =
Synthesis of R ³ = R ⁴ = R ⁵ = R ⁶ = H)

(1) 1,1-diphenylethylene (9
Synthesis of a) Magnesium 3 in a nitrogen stream was added to a 2 liter reaction flask.
1.6 g (1.3 mol) and 50 ml of dry THF were charged, a small amount of iodine and ethyl bromide were added, and after confirming the reaction start, 600 ml of dry THF was added with stirring, and methyl chloride gas was blown therein. The blowing amount and cooling were controlled so that the temperature was maintained at 30 to 40 ° C. After 2 hours, the heat generation stopped and magnesium disappeared. The blowing of methyl chloride gas was stopped, and the mixture was stirred at the same temperature for 1 hour to complete the preparation of Grineer. Next, benzophenone (8a, R ¹ = R ² = H) 18
A mixed solution of 2.22 g (1.1 mol) and 364 ml of dry THF was added dropwise at 35 to 40 ° C. for 30 minutes, and the mixture was further stirred at the same temperature for 15 hours to complete the reaction. Under ice cooling, cooling 10%
It was poured into 1400 g of an aqueous solution of ammonium chloride, stirred for 30 minutes, allowed to stand, separated, washed with brine, dried over magnesium sulfate and concentrated to give 200.23 g of crude carbinol (theoretical yield from benzophenone was 98.6%. ) Got.

Crude carbinol (200.23 g), toluene (400 ml) and paratoluenesulfonic acid (PTSA) (1 g) were charged in a 1-liter reaction flask, and subjected to azeotropic dehydration for 2 hours under reflux of toluene (94 to 116 ° C.). After cooling, it was washed with water, washed with 2% soda ash, washed with water, dried over magnesium sulfate and concentrated to give crude 1,1-diphenylethylene (9a, R
¹ = R ² = H) 190.09 g was obtained. Crude 1,1-diphenylethylene (9a) was distilled using a Claisen with Vigreux to give 1,1-diphenylethylene (9a) 174.0.
6 g was obtained. b. p. The yield is 96.5% from 103 ° C./1 mmHg benzophenone.

(2) Synthesis of 3,3-diphenylallyl chloride (11a, R ¹ = R ² = H) In a 300 ml reaction flask, 54.13 g (0.3 mol) of 1,1-diphenylethylene (9a) and acetic acid were added. 108.2
6 g and 13.51 g (0.45 mol) of paraformaldehyde were charged, and 13.67 g (0.375 mol) of hydrogen chloride was blown thereinto with stirring at 30 ° C. for 3.5 hours. The reaction temperature was kept at 30 ° C by cooling because it generated a weak heat. The blowing of hydrogen chloride was stopped, the mixture was stirred at the same temperature for 2 hours, and then left standing overnight. The reaction solution was poured into 200 ml of water, extracted with 200 ml of toluene, washed with water, washed with 2% soda ash, washed with water,
Dry over magnesium sulfate, concentrate and concentrate crude chloride 68.
42 g was obtained. Distilled in a Claisen with Bigelow, 5
7.51 g was obtained.

B. p. 120-132 ° C / 1 mmHg Yield; 79% from 8a The spectral data of this product is as follows. Mass spectrum (m / e); 228 (M ⁺ ), 193
178,115 ¹ H-NMR spectrum (400 MHz, δ; ppm in
CDCl ₃ ); 4.11 (2H, d, J = 8.0H
z), 6.23 (1H, t, J = 8.0 Hz), 7.2
1-7.41 (10H, m)

(3) Synthesis of 3,3-diphenylallyl phosphite diethyl ester (5a, R ¹ = R ² = H, R = Et) 3,3-diphenylallyl chloride (11a) 40.7
5 g (0.155 mol), triethyl phosphite 9
4.48 g (0.569 mol) was stirred under reflux for 24 hours. The disappearance of 3,3-diphenylallyl chloride (11a) was confirmed, and the reaction was terminated. After cooling, it was distilled with a Claisen with a vigreux to obtain 55.39 g.

B. p. 170 to 203 ° C./1 mmHg Theoretical yield 99% The spectral data of this product is as follows. Mass spectrum (m / e); 330 (M ⁺ ), 193
115 ¹ H-NMR spectrum (400 MHz, δ; ppm in
CDCl ₃ ); 1.31 (6H, t, J = 7.0H
z), 2.71 (2H, dd, J = 7.9 Hz, J = 2)
2.4 Hz), 4.08 (6H, dt, J = 7.1H
z, J = 7.6 Hz), 6.12 (1H, q, J = 7.
9 Hz, J = 7.6 Hz), 7.22-7.38 (10
H, m)

(4) Synthesis of 4,4 ', 4 "-triformyltriphenylamine (4a) In a 2 liter reaction flask, 150 g (0.61 mol) of triphenylamine and N, N-dimethylformamide were added in a nitrogen stream. Charge 268 g (3.67 mol) and 500 g of a toluene solution, and phosphoryl trichloride 562.5 g
(3.67 mol) was added dropwise. Two hours after the completion of the dropping, 166.7 g (1.22 mol) of zinc chloride was added. 80
The mixture was stirred at 0 ° C for 2 days. After cooling, 500 g of water was added dropwise while cooling. Further, 100 g of toluene was added, and 1314.59 g of sodium carbonate was gradually added until it became alkaline. After heating at 60 ° C. for 3 hours, it was extracted with toluene. The extract was washed with water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off to obtain 185.6 g of a solid product.
When recrystallized with a mixed solvent of isopropanol / toluene (4/1 wt), 164.6 g of a mixture of a diformyl body and a triformyl body was obtained (diformyl body: triformyl body = 85.6: 14.4 molar ratio). Crude product 165.
134.95 g of 10 g was purified and separated by silica gel chromatography (eluent: toluene / ethyl acetate = 8.3), and then recrystallized (solvent isopropanol / toluene = 1.5).
/ 1 wt), 4,4 ', 4 "-triformyltriphenylamine (4a) was obtained at 15.09 g in a yield of 7.5%.

M. p. 247-248 ° C mass spectrum (m / e); 329 (M ⁺ ), 301,
271,243,167,141,115,77,41 ¹ H-NMR spectrum (400 MHz, δ; ppm in
CDCl ₃ ); 7.25 (d, J = 8.6 Hz, 6
H), 7.85 (d, J = 8.7 Hz, 6H), 9.9
5 (s, 3H)

(5) 4,4 ′, 4 ″ -tris (4 ″ ″, 4 ″ ″-diphenyl-1 ″ ″,
Synthesis of 3 ″ ″-butadienyl) triphenylamine 0.44 g (1.2 mmol) of 4,4 ′, 4 ″ -triformyltriphenylamine (4a), 3,3-diphenylallyl phosphite diethyl ester ( 5) (R ¹ = R ²
= H, R = ethyl) 1.80 g (5.4 mmol)
It was dissolved in 2 ml of DMF and 0.73 g (6.5 mmol) of potassium-tert-butoxide was gradually added at room temperature. After that, stir at 50 ° C for 1 day, and mix the mixture for 120 m.
Poured into 1 of methanol. The precipitate was collected by filtration, dissolved in 100 ml of benzene, and washed with water. The organic layer was dried over magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography (eluent: benzene) to obtain 1.0 g of crystals. This was recrystallized from toluene to give 0.47 g of 4,4 ′, 4 ″ -tris (4 ″ ″, 4 ″ ″-diphenyl-1 ″ ″,
3 ′ ″-butadienyl) triphenylamine was obtained.

Yield 45.3% m.p. p. 189-190 ° C Mass spectrum (m / e); 857 (M ⁺ ), 666
369, 313, 289, 265, 239, 202 ¹ H-NMR spectrum (400 MHz, δ; ppm in
CDCl ₃ ); 6.76 (d, J = 15.1 Hz, 3
H), 6.78 (dd, J = 15.0 Hz, J = 10.
7Hz, 3H), 6.87 (d, J = 10.7Hz, 3
H), 6.93 (d, J = 8.6 Hz, 6H), 7.1
5 (d, J = 8.7 Hz, 6H), 7.20-7.42
(M, 30H)

Example 2 4,4 ', 4 "-Tris [4"', 4 "'-di (p-tolyl) -1"",3"'-butadienyl]
Triphenylamine (Exemplified Compound 2, m = n = 1, R ¹
= R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = 4-Me)

(1) Synthesis of 1,1-di (p-tolyl) ethylene (9b, R ¹ = R ² = 4-Me) Nitrogen gasification, 15.6 g in 1 liter reaction flask.
(0.65 mol) magnesium and 20 ml THF were added, the reaction was started with a small amount of ethyl iodide and iodine, and p
-Bromotoluene 111.15 g (0.65 mol) of T
HF 500 ml solution was added dropwise at room temperature to 40 ° C. for 2 hours,
The Grineer reagent was prepared. To this was added 83.75 g (0.625 mol) of p-methylacetophenone (10a) TH.
A solution of F200 ml was added dropwise at the same temperature for 3 hours. Three
The mixture was stirred at room temperature for 1 hour and then refluxed for 4 hours. Cool, 5
It was hydrolyzed by pouring it into 1 liter of a% sulfuric acid water. It was extracted with toluene, washed with soda ash, washed with water, and concentrated. To this, 300 ml of toluene and 0.5 g of PTSA were added, and the mixture was refluxed and stirred for 4 hours for dehydration by boiling. It was washed with soda ash, washed with water, and concentrated.
Crude 1,1-di (p-tolyl) ethylene (9b) was distilled by Claisen equipped with vigreux to obtain 98.5 g. b. p. The theoretical yield is 75.8% from 120-121 ° C / 1 mmHg p-methylacetophenone.

(2) Synthesis of 3,3-di (p-tolyl) allyl chloride (11b, R ¹ = R ² = 4-Me) 3,3-diphenylallyl chloride (11a) in (2) of Example 1 ), 1,1-di (p-
Triyl) ethylene (9b) 70.5 g (0.337 mol), paraformaldehyde 15.1 (0.505 mol) to 3,3-di (p-tolyl) allyl chloride (1
1b) 58.7 g (bp 153-173 ° C./1 mm)
Hg, theoretical yield 67.9%) was obtained. This was recrystallized from hexane to obtain 49.0 g.

M. p. 66 ° C theoretical yield 56.7% The spectrum data of 3,3-di-p-tolylallyl chloride (11b) is as follows. Mass spectrum (m / e); 256 (M ⁺ ), 221,
206,165,129 ¹ H-NMR spectrum (40
0 MHz, δ; ppm in CDCl ₃ ); 2.33 (3
H, s), 2.39 (3H, s), 4.13 (2H,
d, J = 8.1 Hz), 6.17 (1H, t, J = 8.
1 Hz), 7.01-7.24 (8H, m)

(3) 3,3-di (p-tolyl) allyl phosphite diethyl ester (5b, R ¹ = R ² = 4-Me,
Synthesis of R = Et In the same manner as in the synthesis of Example 1 (3) 3,3-diphenylallyl phosphite diethyl ester ((5) R ¹ = R ² = H, R = Et), 3,3-di ( 35.0 g (0.1365 mol) of p-tolyl) allyl chloride (8b) was reacted with 68 g (0.409 mol) of triethylphosphite to obtain 49.3 g as a distillation residue. This was recrystallized from hexane to give 29.9 g of 3,3-di (p-tolyl).
Allyl phosphite diethyl ester (5b, R ¹ = R ² = 4
-Me, R = Et) was obtained.

Theoretical yield 61.16% m.p. p. 56.0 ° C. The spectral data of this product are as follows. Mass spectrum (m / e); 358 (M ⁺ ), 314,
221,129 ¹ H-NMR spectrum (400 MHz, δ; ppm in
CDCl ₃ ); 1.30 (6H, t, J = 7.1H
z), 2.32 (3H, s), 2.39 (3H, s),
2.71 (2H, dd, J = 7.9 Hz, J = 22.4
Hz), 4.07 (4H, q, J = 7.1 Hz, J =
8.1 Hz), 6.05 (1H, dd, J = 7.9H)
z, J = 15.2 Hz), 7.06-7.19 (8H,
m)

(4) 4,4 ′, 4 ″ -tris [4 ″ ″, 4 ″ ″-di (p-tolyl) -1 ″ ″,
Synthesis of 3 "'-butadienyl] triphenylamine 4,4', 4" -triformyltriphenylamine (4a) 0.4 g (1.2 mmol), 3,3-di (p
-Tolyl) allyl phosphorous acid diethyl ester (5b, R ¹
= R ² = 4-Me, R = Et) 1.96 g (5.5 mmol), DMF 12 ml, potassium-tert-butoxide 1.22 g (10.9 mmol) were reacted in the same manner as in Example 1 (5). And post-treatment was carried out.
69 g of 4,4 ', 4 "-tris [4"',
4 ″ ″-di (p-tolyl) -1 ″ ″, 3 ″ ″-butadienyl] triphenylamine was obtained.

Yield 60.3% m.p. p. 155-156 ° C Mass spectrum (m / e); 942, 722, 632
307,279,229,202 ¹ H-NMR spectrum (400 MHz, δ; ppm in
CDCl ₃ ); 2.35 (s, 9H), 2.40
(S, 9H), 6.59-6.67 (m, 3H), 6.
76-6.83 (m, 6H), 6.93 (d, J = 8.
6Hz, 6H), 7.09 (d, J = 8.3Hz, 6
H), 7.12-7.30 (m, 24H), and 6.20-6.38 as minor peaks.
(M) was observed.

Example 3 4,4'-bis (4 "'", 4 "'-diphenyl-
1 "", 3 ""-butadienyl] -4 "-
[4 ″ ″ ″, 4 ″ ″ ″-di (p-tolyl)-
1 ''',3''' - butadienyl] triphenylamine (Exemplified Compound 5, m = n = 1, R 1 = R 2 = R 5 = R
^{6 = H, R 3 = R} 4 = 4-Me) Synthesis of

(1) 4,4′-bis (4 ″ ″,
4 ″ ″-diphenyl-1 ″ ″, 3 ″ ″-butadienyl) -4 ″ -formyltriphenylamine (12
Synthesis of a) 4,4 ′, 4 ″ -triformyltriphenylamine (4a) 2.0 g (6.1 mmol), 3,3-diphenylallyl phosphite diethyl ester (5b, R ¹ = R ²
= H, R = Et) 4.0 g (12.1 mmol) of 15
Dissolved in ml DMF, 1.5 g (13.4 mmol)
Of potassium-tert-butoxide were gradually added. After stirring overnight at room temperature, it was poured into 100 ml of water. The mixture was extracted twice with toluene, the organic layer was dried over magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography (eluent: benzene) to give 1.24.
g oil was obtained. By crystallizing this with a mixed solvent consisting of acetonitrile and ethyl acetate,
1.03 g of 4,4'-bis (4 "', 4"'-diphenyl-1 "', 3"'-butadienyl)-
4 ″ -formyltriphenylamine (12a) was obtained.

Yield 24.9% m.p. p. 179-181 ° C. The spectral data of this product are as follows. Mass spectrum (m / e); 681 (M ⁺ ), 505,
203 ¹ H-NMR spectrum (400 MHz, δ; ppm in
CDCl ₃ ); 6.69 (d, J = 14.1 Hz, 2
H), 6.85 (dd, J = 27.1 Hz, J = 10.
9Hz, 2H), 6.87 (d, J = 3.1Hz, 2
H), 6.99-7.06 (m, 6H), 7.21-
7.44 (m, 24H), 7.66 (d, J = 8.8H
z, 2H), 9.82 (s, l)

(2) 4,4'-bis (4 "',
4 ″ ″-diphenyl-1 ″ ″, 3 ″ ″-butadienyl) -4 ″-[4 ″ ″, 4 ″ ″-di (p-tolyl) -1 ″ ″, 3 ″ ″ Synthesis of'-butadienyl] triphenylamine 4,4'-bis (4 "'", 4 "'-diphenyl-
1.4 g (2.1 mmol) of 1 ″ ″, 3 ″ ″-butadienyl) -4 ″ -formyltriphenylamine (12a), 3,3-di (p-tolyl) allyl phosphorous acid diethyl ester ( (5) R ¹ = R ² = 4-Me, R = Et)
885 mg (2.5 mmol) was dissolved in 10 ml DMF and potassium tert-butoxide 280 mg
(2.5 mmol) was gradually added and reacted overnight. The same post-treatment as in (5) of Example 1 was carried out to give 1.11 g of 4,4'-bis (4 "', 4"'-diphenyl-).
1 "", 3 ""-butadienyl) -4 "-
[4 ″ ″ ″, 4 ″ ″ ″-di (p-tolyl)-
1 ′ ″ ″, 3 ″ ″ ″-butadienyl] triphenylamine was obtained.

Yield 61.1% m.p. p. 133-135 ° C. The spectral data of this product are as follows. Mass spectrum (m / e); 885 (M ⁺ ), 44 ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δppm); 2.35 (s, 3H), 2.40 (s, 3)
H), 6.59-6.70 (m, 3H), 6.73-
6.83 (m, 4H), 6.87 (d, J = 10.8H
z, 2H), 6.90-7.00 (m, 6H), 7.0
9 (d, J = 8.0 Hz, 2H), 7.12-7.43
(M, 32H) In addition to this, 6.20-6.35 as a minor peak.
(M) was observed.

Example 4 4,4'-bis (4 "'", 4 "'-diphenyl-
1 "", 3 ""-butadienyl) -4 "-
(2 ″ ″ ″, 2 ″ ″ ″-diphenylvinyl) -triphenylamine (Exemplified compound 21, m = 1, n = 0, R
¹ = R ² = R ⁵ = R ⁶ == H, R ³ = R ⁴ = H)

4,4'-bis (4 "', 4"'-diphenyl-1 "', 3"'-butadienyl)-
4 ″ -formyltriphenylamine (12a) 1.7
7 g (2.6 mmol), diethyl diphenylmethyl phosphite ((5 ″) R ³ ═R ⁴ ═H, R = Et) 1.0 g
(3.3 mmol), potassium-tert-butoxide (400 mg, 3.6 mmol), and DMF (10 ml) were treated in the same manner as in Example 1 (5) to give 2.01 g of 4,4 ′.
-Bis (4 "", 4 ""-diphenyl-1 "",
3 ″ ″-butadienyl) -4 ″-(2 ″ ″ ″,
2 ′ ″ ″-diphenylvinyl) -triphenylamine was obtained.

Yield 92.9% m.p. p. 127-128 ° C Mass spectrum (m / e); 832 (M ⁺ ), 831
667 ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δ ppm); 6.65 (d, J = 15.0 Hz, 2
H), 6.72-6.95 (m, 13H), 7.12-
7.43 (m, 34H)

Example 5 4,4'-bis (2 "', 2"'-diphenylvinyl) -4 "-(4"'",4"'"-diphenyl-1""" ′, 3 ″ ′ ″ ′-Butadienyl) -triphenylamine (Exemplified compound 41, m = n = 0, R ¹ ═R ²
= R ⁵ = R ⁶ = R ³ = R ⁴ = H)

(1) 4,4'-bis (2 ''',
Synthesis of 2 ″ ″-diphenylvinyl) -4 ″ -formyltriphenylamine (13a) 4,4 ′, 4 ″ -triformyltriphenylamine (4a) 2.0 g (6.1 mmol), diphenyl Diethyl methyl phosphite ((5 ″) R ³ = R ⁴ = H, R = E
t) 3.7 g (12.2 mmol), potassium-ter
1.4 g (12.5 mmol) of t-butoxide, DMF
20 ml was treated in the same manner as in Example 3 (1) to obtain 728 mg.
Of crude 13a was obtained. Crystallization from ethyl acetate yielded 558 mg of 4,4'-bis (2 "', 2"'-
Diphenylvinyl) -4 ″ -formyltriphenylamine (13a) was obtained.

Yield 14.5% m.p. p. 159-161 ° C Mass spectrum (m / e); 629 (M ⁺ ), 315,
179 ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δppm); 6.84 (d, J = 8.7Hz, 4H),
6.90-6.97 (m, 6H), 6.98 (d, J =
8.7 Hz, 2H), 7.20-7.38 (m, 20
H), 7.64 (d, J = 8.8Hz, 2H), 9.7
9 (s, 1H)

(2) 4,4'-bis (2 ''',
2 ""-diphenylvinyl) -4 "-
(4 ″ ″ ″, 4 ″ ″ ″-diphenyl-1 ″ ″ ″,
Synthesis of 3 ″ ″ ″-butadienyl) -triphenylamine 4,4′-bis (2 ″ ″, 2 ″ ″-diphenylvinyl) -4 ″ -formyltriphenylamine (13a)
1.53 g (2.4 mmol), 3,3-diphenylallyl phosphorous acid diethyl ester ((5) R ¹ = R ² = H,
R = Et) 963 mg (2.9 mmol), potassium-
tert-butoxide 350 mg (3.1 mmol),
10 ml of DMF was treated in the same manner as in Example 1 (5),
1.66 g of 4,4'-bis (2 "", 2 ""-diphenylvinyl) -4 "-(4""", 4 """
-Diphenyl-1 "'", 3 "'"-butadienyl) -triphenylamine was obtained.

Yield 84.7% m.p. p. 140-142 ° C. Mass spectrum (m / e); 805,629,268 ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δ ppm); 6.64 (d, J = 15.0 Hz, 1
H), 6.73-6.81 (m, 5H), 6.82-
6.93 (m, 10H), 7.12-7.19 (m, 5
H), 7.20-7.43 (m, 26H) In addition to this, as a minor peak, 6.23 (t, J = 1).
1.6 Hz) and 6.35 (d, J = 11.6 Hz) were observed.

Example 6 4,4'-bis (2 "', 2"'-diphenylvinyl) -4 "-[4"'",4"'"-di (p-tolyl) -1 "'", 3 "'"-butadienyl] -triphenylamine (Exemplified compound 45, m = n = 0, R ¹
= R ² = R ³ = R ⁴ = H, R ⁵ = R ⁶ = 4-Me)

1.58 g (2.5 mmol) of 4,4'-bis (2 "", 2 ""-diphenylvinyl) -4 "-formyltriphenylamine (13a), 3,3-
Di (p-tolyl) allyl phosphite diethyl ester ((5) R ¹ = R ² = 4-Me, R = Et) 1.0 g
(2.8 mmol), potassium-tert-butoxide (340 mg, 3.0 mmol) and DMF (10 ml) were treated in the same manner as in Example 1 (5) to give 1.72 g of 4,4′-.
Bis (2 "", 2 ""-diphenylvinyl)-
4 ″-[4 ″ ″ ″, 4 ″ ″ ″-di (p-tolyl)
-1 ″ ″ ″, 3 ″ ″ ″-butadienyl] -triphenylamine was obtained.

Yield 82.2% m.p. p. 131-133 ° C. Mass spectrum (m / e); 834 (M ⁺ ), 833
629,416,179 ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δppm); 2.35 ((s, 3H), 2.41 (s,
3H), 6.58-6.65 (m, 1H), 6.75-
6.92 (m, 13H), 7.08-7.37 (m, 3
1H)

Synthesis Example 1 4,4 ′, 4 ″ -Tris (2 ″ ″, 2 ″ ″-diphenylvinyl) -triphenylamine (Comparative Compound 1)
Synthesis of 4,4 ′, 4 ″ -triformyltriphenylamine (4a) 622 mg (1.89 mmol), diphenylmethylphosphorous acid diethyl ester ((5 ″) R ³ ═R ⁴ =
H, R = Et) 1.9 g (6.25 mmol), DMF
10 ml, potassium-tert-butoxide 1.0 g
(8.9 mmol) was reacted in the same manner as in Example 1, 5
After the post-treatment, 0.80 g of 4,4 ', 4''
-Tris (2 "", 2 ""-diphenylvinyl)-
Triphenylamine was obtained. Yield 54.2% m.p. p. 196-197 ° C

[Chemical 49]

Synthesis Example 2 Synthesis of 1,1-diphenyl-4- (p-di-n-propylaminophenyl) -1,3-butadiene (Comparative Compound 2) p-di-n-propylaminobenzaldehyde 2.05
g (10.0 mmol), 3,3-diphenylallyl phosphite diethyl ester ((5), R ¹ = R ² = H, R =
Et) 3.6 g (10.9 mmol), potassium-te
1.3 g (11.6 mmol) rt-butoxide, DM
F15 ml was treated as in Example 1 (5) to give 2.35.
g of 1,1-diphenyl-4- (p-di-n-propylaminophenyl) -1,3-butadiene was obtained. Yield 73.8%, m.p. p. 94.5-95.2 ° C

Embedded image

Various types of 4, represented by the general formula (4),
4'-diformyltriphenylamine derivative and 4,
The 4 ', 4 "-triformyltriphenylamine derivative was prepared according to the following method. In addition, in Examples 7 to 10 and Comparative Example 1, p was used as an internal standard substance in order to quantify the product in the Wiersmeier reaction of 4-methyltriphenylamine by high performance liquid chromatography.
-The reaction was carried out with terphenyl.

Example 7 Wiersmeier reaction of 4-methyltriphenylamine in the presence of zinc chloride: 5-methyltriphenylamine (5.18 g, 2) in a 300 ml reaction flask in a nitrogen stream.
0.0 mmol) and N, N-dimethylformamide 5.
85 g (80 mmol) and 35 g of a toluene solution were charged, and 12.27 g (80.0 mmo) of phosphoryl trichloride.
l) was added dropwise. In addition, 0.461 g (2.0 mmol) of p-terphenyl was added as an internal standard. End of dripping 2
After a period of time, 2.73 g (20.0 mmol) of zinc chloride was added. After stirring at 90 ° C. for 30 hours, 100 g of water was added dropwise while cooling. Further, 100 g of toluene was added, and sodium carbonate was gradually added until it became alkaline. After heating at 60 ° C. for 3 hours, it was extracted with toluene. After washing with water and saturated saline, drying over magnesium sulfate and evaporation of the solvent gave a solid. The raw material, 4-methyltriphenylamine, had completely disappeared. The product of high performance liquid chromatography was quantified using p-terphenyl as an internal standard substance. The results are shown in Table 1.
Shown in 2.

Example 8 Wiersmeier Reaction of 4-Methyltriphenylamine in the Presence of Zinc Bromide: Performed except that 4.50 g (20.0 mmol) of zinc bromide was used in place of the zinc chloride of Example 7. The reaction was carried out in the same manner as in Example 7, and the product was quantified by high performance liquid chromatography. The results are shown in Table 12.

Example 9 Wiersmeier reaction in the presence of boron trifluoride diethyl ether complex of 4-methyltriphenylamine: 2.84 g (20.20 g) of boron trifluoride diethyl ether complex in place of zinc chloride of Example 7. 0 mmol) was used, and the reaction was performed in the same manner as in Example 7, and the product was quantified by high performance liquid chromatography. The results are shown in Table 12.

Example 10 Wiersmeier Reaction of 4-Methyltriphenylamine in the Presence of Hydrogen Chloride: Example 7 except that hydrogen chloride gas was bubbled in for about 60 hours at about 20 ml / min instead of the zinc chloride of Example 7. The reaction was performed in the same manner as in, and the product was quantified by high performance liquid chromatography. The results are shown in Table 12.

Comparative Example 1 Wiersmeier reaction of 4-methyltriphenylamine in the absence of a catalyst: The reaction was performed in the same manner as in Example 1 except that the Lewis acid was not added, and the reaction was performed.
The product was quantified by high performance liquid chromatography.
The results are shown in Table 12.

[0138]

[Table 12]

As is clear from Table 12, the yield of 4-methyl-4 ', 4 "-diformyltriphenylamine (A) was remarkably increased by carrying out the Wiersmeier reaction in the presence of a Lewis acid and a protic acid. You can see that it will improve.

Example 11 Synthesis of 4-methyl-4 ', 4 "-diformyltriphenylamine: N, 5N in a reaction flask under nitrogen stream.
N-dimethylformamide 488.1 (6.68 mol) and toluene 1200 g were added, and phosphorus oxychloride 93 was added.
0.8 g (6.07 mol) was added dropwise at 5 to 10 ° C over 2 hours. After stirring at the same temperature for 1 hour, 400 g (1.52 mol) of 4-methyltriphenylamine and 8 of toluene were added.
00 g of the mixed solution was added dropwise from 10 ° C. to room temperature for 1 hour.
After the dropwise addition, 206.85 g (1.52 mol) of anhydrous zinc chloride was added, and the reaction was carried out at 80 to 81 ° C. for 30 hours (1% or less of monoformyl compound was confirmed by HPLC). After cooling to about 40 ° C., it was poured into 8 liters of cold water. Soda ash 1500g
After neutralizing with, the mixture was extracted with stirring at 55 to 60 ° C. for 1 hour. After Celite filtration, the filtrate is separated and washed with water (8 liters x 2 times, pH
7) I did. It was dried over anhydrous magnesium sulfate and concentrated to obtain 520.8 g of residue. This was recrystallized from isopropanol / toluene = 9/1 (wt) to give 4-methyl-4 ',
413.6 g of 4 ″ -diformyltriphenylamine
Obtained. m. p. 153-135 ° C. Theoretical yield 85.
7%.

Example 12 Synthesis of 4-ethyl-4 ', 4 "-diformyltriphenylamine: To a 300 ml reaction flask, in a nitrogen stream, 50 ml of toluene and 2.5 g of zinc chloride (18.3 mmo).
l), 5.0 g of 4-ethyltriphenylamine (18.
3 mmol) and N, N-dimethylformamide 5.6.
6 g (77.5 mmol) was weighed and 11.5 g (75.0 mmol) of phosphoryl trichloride was gradually added dropwise. After completion of dropping, the mixture was stirred at 90 ° C. for 30 hours, and then water 100
g was added dropwise while cooling. In addition, 100 g of toluene
Was added, and sodium carbonate was gradually added to the mixture until it became alkaline. After heating at 60 ° C. for 3 hours, it was extracted with toluene. The extract was washed with water and saturated saline, dried over MgSO ₄ , and the solvent was distilled off. The residue was subjected to silica gel column chromatography (eluent toluene / ethyl acetate = 10 /
Separation in 1) gives 0.97 g (17.6%) of 4-ethyl-4'-formyltriphenylamine and 4.93 g.
(81.8%) of 4-ethyl-4 ', 4 "-diformyltriphenylamine was obtained. The obtained 4-ethyl-4'-formyltriphenylamine was crystallized from methanol to give 0.72 g (13.1%). The results are shown in Table 13. The physical properties of the product are as follows.

4-Ethyl-4'-formyltriphenylamine m.p. p. 81.82 ° C. mass spectrum; 301 (M ⁺ ), 286. ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δppm); 1.23 (t, J = 7.6Hz, 3H),
2.65 (q, J = 7.6 Hz, 2H), 6.98
(D, J = 8.8 Hz, 2H), 7.09 (d, J =
8.5 Hz, 2H), 7.13 to 7.20 (m, 5
H), 7.30 to 7.36 (m, 2H), 7.65
(D, J = 8.9 Hz, 2H), 9.80 (s, 1H) 4-ethyl-4 ′, 4 ″ -diformyltriphenylamine m.p. p. 103-104 ° C. mass spectrum; 329,314,167,105 ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δppm); 1.28 (t, J = 7.6Hz, 3H),
2.70 (q, J = 7.6 Hz, 2H), 7.08
(D, J = 8.4 Hz, 2H), 7.17 (d, J =
8.7 Hz, 4 H), 7.23 (d, J = 8.4 Hz,
2H), 7.76 (d, J = 8.7Hz, 4H), 9.
90 (s, 2H)

Comparative Example 2 The same operation as in Example 12 was carried out without adding zinc chloride.
The results are shown in Table 13.

Example 13 Synthesis of 2-methyl-4 ', 4 "-diformyltriphenylamine: 5-methyltriphenylamine 5 g (1
9.3 mmol), N, N-dimethylformamide 6.
14 g (84.0 mmol), phosphorus oxychloride 12.5
g (81.5 mmol), zinc chloride 2.7 g (19.8)
mmol) and 100 ml of toluene were reacted, post-treated and isolated in the same manner as in Example 12. The results are shown in Table 13. The physical properties of the product are as follows. 2-Methyl-4'-formyltriphenylamine m.p. p. Mass spectrum: 287 (M ⁺ ), 180,167 ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δppm); 2.05 (s, 3H), 6.88 (q, J
= 8.7 Hz, 2H), 7.07 to 7.17 (m, 4
H), 7.21 to 7.26 (m, 2H), 7.26 to
7.33 (m, 3H), 7.67 (d, J = 8.9H
z, 2H), 9.79 (s, 1H) 2-methyl-4 ', 4 "-diformyltriphenylamine m.p. p. 121 to 122 ° C. mass spectrum; 315 (M ⁺ ), 286, 271,
56, 243, 210, 180, 167. ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δppm): 2.03 (s, 3H), 7.12 (d, J
= 8.6 Hz, 4H), 7.12 to 7.17 (m, 1
H), 7.28 to 7.36 (m, 3H), 7.77.
(D, J = 8.8 Hz, 4H), 9.88 (s, 2
H).

Comparative Example 3 The same operation as in Example 13 was performed without adding zinc chloride.
The results are shown in Table 13.

Example 14 Synthesis of 4-methoxy-4 ', 4 "-diformyltriphenylamine: 5 g of 4-methoxytriphenylamine
(18.16 mmol), N, N-dimethylformamide 5.66 g (77.5 mmol), phosphorus oxychloride 1
1.5 g (75.0 mmol), 2.5 g of zinc chloride (1
8.3 mmol) and 100 ml of toluene were reacted, post-treated and isolated in the same manner as in Example 12. The results are shown in Table 13.
Shown in The physical properties of the product are as follows. 4-methoxy-4'-formyltriphenylamine m.p. p. 73-74 ° C Mass spectrum: 315 (M ⁺ ), 288,230,1
29 ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δppm): 3.80 (s, 3H), 6.89 (d, J
= 9.0 Hz, 2H), 6.94 (d, J = 8.7H)
z, 2H), 7.12 (d, J = 9.1Hz, 2H),
7.16 (m, 3H), 7.32 (m, 2H), 7.6
4 (d, J = 8.9 Hz, 2H), 9.78 (s, 1
H) 4-methoxy-4 ', 4 "-diformyltriphenylamine m. p. 113-114 ° C. mass spectrum (m / e); 331 (M ⁺ ), 316.
259,230 ¹ H-NMR spectrum (400 MHz, δ; ppm in
_{CDCl 3); 3.85 (3H,} s), 6.94 (2
H, d, J = 9.0 Hz), 7.12 (2H, d, J =
9.0 Hz), 7.17 (4H, d, J = 8.7H)
z), 7.56 (4H, d, J = 8.7Hz), 9.8
8 (2H, s)

Comparative Example 4 The same operation as in Example 14 was carried out without adding zinc chloride.
The results are shown in Table 13.

[0148]

[Table 13] As is clear from Table 13, the yield of diformyltriphenylamine is remarkably improved by carrying out the Wiersmeier reaction in the presence of a Lewis acid.

Example 15 4,4'-Diformyltriphenylamine and 4,4 ',
Synthesis of 4 ″ -triformyltriphenylamine: 150 g (0.61 mol) of triphenylamine, 268 g (3.67 mol) of N, N-dimethylformamide and a toluene solution of 5 in a 2-liter reaction flask in a nitrogen stream.
00g was charged, and phosphoryl trichloride 562.5g (3.
67 mol) was added dropwise. Two hours after the completion of the dropping, 166.7 g (1.22 mol) of zinc chloride was added. 2 at 80 ° C
The solution was stirred for one day. After cooling, 500 g of water was added dropwise while cooling. Further, 100 g of toluene was added, and 1314.59 g of sodium carbonate was gradually added until it became alkaline. After heating at 60 ° C. for 3 hours, it was extracted with toluene.
The extract was washed with water and saturated brine, dried over magnesium sulfate, and the solvent was distilled off to obtain 185.6 g of a solid product. When recrystallized with a mixed solvent of isopropanol / toluene (4/1 wt), 164.6 g of a mixture of a diformyl body and a triformyl body was obtained. 13 out of 165.10 g of crude product
4.95 g of silica gel chromatography (eluent;
After purification and separation with toluene / ethyl acetate = 8.3) and recrystallization (solvent isopropanol / toluene = 1.5 / 1 wt), 122.6 g of 4,4′-diformyltriphenylamine was obtained. . m. p. 148-149
C, yield 67.4%. Also, 4,4 ′, 4 ″ -triformyltriphenylamine was 15.09 g, and the yield was 7.5%.
Obtained in. m. p. 247-248 ° C

Comparative Example 5 44.74 g (0.612 mol) of N, N-dimethylformamide and dichloroethane 2 were placed in a 1-liter reaction flask.
00 ml was charged, and 93.82 g (0.612 mol) of phosphorus oxychloride was added dropwise at 5 to 10 ° C. for 30 minutes. Then, triphenylmine 50g (0.204mol) 200m
A solution of 1 in dichloroethane was added at room temperature over 30 minutes. The mixture was stirred at room temperature for 12 hours and further refluxed for 24 hours. After cooling, N, N-dimethylformamide 44.74.
g (0.612 mol), phosphorus oxychloride 93.82 g
(0.612 mol) was further added, and the mixture was stirred under reflux for 24 hours. After repeating this operation 3 times, it was poured into 4 liters of ice water, 1 liter of toluene was added, and the mixture was neutralized with sodium carbonate. The mixture was stirred at 65 ° C. for 1 hour, separated, washed with water, dried and concentrated to obtain 56.6 g. The crystals were recrystallized twice from isopropyl alcohol to obtain 24.3 g (theoretical yield: 39.5%) of 4,4'-diformyltriphenylamine.

Comparative Example 6 110.52 g (1.51 g) was added to a 3 liter reaction flask.
Mol) N, N-dimethylformamide with 757 ml
Of 1,2-dichloroethane was added to the mixture at 0 to 5 ° C for 23
1.84 g (1.51 mol) of phosphorus oxychloride was added dropwise over 1 hour. Then, the mixture was stirred at room temperature for 1 hour, and 126.17 g (0.504 mol) of 1,2-triphenylamine was added.
Dichloroethane solution (505 ml) at 0-5 ° C. 1
It dripped over time. Then at room temperature for 1 hour under reflux 2
Reacted for 6 hours. After cooling, N, N-dimethylformamide 110.52 g (1.5 mol), phosphorus oxychloride 23
1.84 g (1.51 mol) was added, and the mixture was stirred under reflux for 26
I went on time. After repeating this operation three more times, the mixture was poured into 10 liters of ice water to obtain 1823 g of sodium carbonate.
Neutralized with. The solution was stirred at 50-60 ° C for 1 hour,
Chloroform was added and the layers were separated. Wash the organic layer twice with water,
It was dried over magnesium sulfate and then concentrated. The residue was purified by silica gel column chromatography (eluent; benzene / ethyl acetate = 9/1) to obtain 1.3 g of crystals. When recrystallized from a mixed solvent of acetonitrile and ethyl acetate, 0.52 g of 4,4 ', 4 "-
Triformyltriphenylamine was obtained. Yield 0.5%

As can be seen from Example 15 and Comparative Examples 5 and 6, 4,4'-diformyltriphenylamine and 4,4 ', 4' were obtained in good yield by carrying out the Wiersmeier reaction in the presence of a Lewis acid. ′ -Triformyltriphenylamine can be synthesized.

Example 16 Synthesis of 4-bromo-4 ', 4 "-diformyltriphenylamine: 10.0 g of 4-bromotriphenylamine
(30.4 mmol), N, N-dimethylformamide 9.79 g (133.9 mmol), phosphorus oxychloride 1
8.67 g (121.8 mmol), zinc chloride 4.15
g (30.4 mmol) and 100 ml of toluene were reacted, post-treated and isolated in the same manner as in Example 12. The results are shown in Table 14. The physical properties of the product are as follows. 4-Bromo-4'-formyltriphenylamine m.p. p. 119-120 ° C Mass spectrum (m / e); 353, 351, 322
271,243,167,141,115 ¹ H-NMR spectrum (400 MHz, δ; ppm in
_{CDCl 3); 7.03 (m,} 4H), 7.12~
7.21 (m, 3H), 7.35 (m, 2H), 7.4
3 (d, J = 8.9 Hz, 2H), 7.69 (d, J =
8.9 Hz, 2H), 9.84 (s, 1H) 4-Bromo-4 ', 4 "-diformyltriphenylamine m.p. p. 201.5-202.5 ° C Mass spectrum (m / e); 381, 379, 271,
241,167 ¹ H-NMR spectrum (400 MHz, δ; ppm in
CDCl ₃ ); 7.05 (d, J = 8.8 Hz, 2
H), 7.18 (d, J = 8.7 Hz, 4H), 7.5
1 (d, J = 8.9 Hz, 2H), 7.78 (d, J =
8.8Hz, 4H), 9.90 (s, 2H)

Comparative Example 7 The same operation as in Example 16 was carried out without adding zinc chloride.
The results are shown in Table 14.

Example 17 Synthesis of 4-p-tolyl-4 ', 4 "-diformyltriphenylamine: 4-p-tolyltriphenylamine 1
0.0 g (29.5 mmol), N, N-dimethylformamide 9.47 g (129.6 mmol), phosphorus oxychloride 18.06 g (117.8 mmol), zinc chloride 4.02 g (29.5 mmol), toluene 100 ml
Was subjected to the same reaction, post-treatment, and isolation operations as in Example 13. The results are shown in Table 14. The physical properties of the product are as follows. 4-p-tolyl-4'-formyltriphenylamine mass spectrum; 363, 334, 243, 167, 1
49 ¹ H-NMR spectrum (400 MHz, CDCl ₃ ,
δppm); 2.39 (s, 3H), 7.07 (d, J
= 8.7 Hz, 2H), 7.16 to 7.27 (m, 7
H), 7.36 (m, 2H), 7.48 (d, J = 8.
2Hz, 2H), 7.54 (d, J = 8.7Hz, 2
H), 7.69 (d, J = 8.9 Hz, 2H), 9.8
1 (s, 1H) 4-p-tolyl-4′-4 ″ -diformyltriphenylamine m.p. p. 197-198 ° C. Mass spectrum (m / e); ¹ H-NMR spectrum (400 MHz, δ; ppm in
_{CDCl 3); 2.42 (s,} 3H), 7.19~
7.28 (m, 8H), 7.49 (d, J = 8.2H
z, 2H), 7.59 (d, J = 8.7Hz, 2H),
7.79 (d, J = 8.8 Hz, 4H), 9.90
(S, 2H)

Comparative Example 8 The same operation as in Example 17 was carried out without adding zinc chloride.
The results are shown in Table 14.

[0157]

[Table 14]

Example 18 Synthesis of Exemplified Compound 1 and Exemplified Compound (2) -57 Mixture (1) 4,4'-Diformyltriphenylamine and 4,4'-diformyltriphenylamine
Synthesis of 4 ', 4 "-triformyltriphenylamine mixture In a 2 liter reaction flask under nitrogen stream 100.0 g
(0.41 mol) triphenylamine, 214.5 g
(2.93 mol) of N, N-dimethylformamide and 500 g of toluene were weighed out, and 24 to 53 ° C. and 30
375 g (2.45 mol) of phosphorus oxychloride was slowly added dropwise over the course of a minute. Subsequently, 111.1 g (0.82 mol) of zinc chloride was added, and the mixture was stirred at 80 ° C. for 57 hours. The mixture was poured into 2 liters of ice water and 500 g of toluene was added.
721.7 g of sodium carbonate was gradually added, and the solution was adjusted to pH.
I set it to 11. The mixture was extracted with stirring at 60 ° C for 30 minutes, and after separating the layers, the toluene layer was washed with water (three times). Dry the toluene layer (Na ₂
SO ₄ ), concentrated to give 133.9 g of solid. When this was recrystallized with a mixed solvent consisting of 240 g of toluene and 536 g of 2-propanol, 111.
6 g of crystals were obtained. From ¹ H-NMR, this product shows that 4,4'-diformyltriphenylamine and 4,4 ',
It was a mixture of 4 ″ -triformyltriphenylamine, and the ratio was 74.4 mol% and 25.6 mol%. Melting point 141-143 ° C, 184-192 ° C

(2) Exemplified Compound 1 and Exemplified Compound (2)-
57 Synthesis of mixture 4,4 'synthesized in (1) in a 1 liter reaction flask
-Diformyltriphenylamine and 4,4 ', 4 "-
Mixture of triformyltriphenylamine (molar ratio 7
4.4: 25.6) 50 g, diethyl 3,3-diphenylallyl phosphite 145.4 g (0.44 mol), N,
Charge 250 ml of N-dimethylformamide, 59 g
(0.526 mol) potassium-t-butoxide was added slowly. After reacting at 50 ° C. for 8 hours, the mixture was mixed with water 2.
Poured into 5 liters. The precipitate was taken out by vacuum filtration, dissolved in 730 g of toluene, and washed with water (twice).
did. The toluene was concentrated, and the crude product was purified by silica gel column chromatography (eluent: toluene) to obtain 127.6 g of crystals. This was recrystallized from a mixed solvent of toluene and heptane to give 77.2.
A mixture of g of Exemplified Compound 1 and Exemplified Compound (2) -57 was obtained. By high performance liquid chromatography analysis,
The molar ratio of this product was 71.4: 28.6. Melting point 123-125 ° C

Application Examples 1 to 3 parts of chlorsian blue (CDB) and a polycarbonate resin (Upilon E-200 manufactured by Mitsubishi Gas Chemical Co., Inc.)
0) 1 part was mixed with 30 parts of dichloroethane as a solvent and kneaded with a ball mill for 5 hours. The obtained pigment dispersion liquid was applied onto a sheet obtained by vapor-depositing aluminum on a polyethylene terephthalate (PET) film by using a wire bar, and 4
The charge carrier generating layer was formed in a thickness of about 1 μm by drying at 5 ° C. for 3 hours. Further, 1 part each of the exemplified compounds 1, 21, and 41 and 1 part of a polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.) were mixed and dissolved in 8 parts of dichloroethane. This liquid was applied onto the charge carrier generating layer with a doctor blade and dried at 80 ° C. for 3 hours to prepare photoconductors 1 to 3.

The electrophotographic characteristics of the electrophotographic photosensitive member thus obtained were measured by an electrostatic recording tester SP-428 type Elect.
It was measured by a static method using a rostatic Paper Analyzer (manufactured by Kawaguchi Denki Seisakusho). That is,
A 6 kV corona discharge was carried out for 5 seconds to charge the surface, the surface potential V ₀ (unit: −V) was measured, and the surface potential was kept for 5 seconds in a dark place. Exposure amount required to attenuate the electric potential in half, that is, half-electrical light amount E _1/2 (lux seconds), and illuminance 5
Surface residual potential V after illuminating with light for 10 seconds
_R10 (-V) was determined. The results are shown in Table 15.

Application Comparative Example 1 Photosensitive member 4 was prepared in the same manner as in Application Examples 1 to 3 except that Comparative Compound 1 was used in place of Exemplified Compounds 1, 21, and 41, and electrophotographic characteristics were measured. The results are shown in Table 15.
Here, the fact that the surface residual potential V _R10 has a high value causes a decrease in image density or smearing. Therefore, the smaller V _R10 is, the better.
When 1 is used, the surface residual potential V _R10 is 0,
8 and 6, while Comparative Compound 1 was used,
Since V _R10 is also 102, it is clear that the compound of the present invention is excellent.

Application Examples 4 to 9 Oxotitanium phthalocyanine (TiOPc) was vacuum-deposited at 10 ⁻⁶ torr to a thickness of about 0.8 μm on an aluminum thin film deposited on a polyester film to form a charge carrier generation layer. . Further exemplified compounds 1, 2,
5, 21, 41, 45 1 part each, polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.) 1
Parts were mixed and dissolved in 8 parts of dichloroethane. This liquid was applied onto the charge carrier generating layer with a doctor blade and dried at 80 ° C. for 3 hours to prepare photoconductors 5-10. Application example 1
The electrophotographic characteristics were measured in the same manner as in 3. The results are shown in Table 15.

Application Comparative Example 2 Exemplified compounds 1, 2, 5 used in Application Examples 4 to 9,
Photosensitive member 11 was prepared in the same manner as in Application Examples 4 to 9 except that Comparative Compound 2 was used instead of 21, 41 and 45, and the electrophotographic characteristics were measured. The results are shown in Table 15. When the exemplified compounds 1, 2, 5, 21, 45 are used, V _R10 is 0.
In the case of using Exemplified Compound 41, V _R10 is 4
On the other hand, when Comparative Compound 2 was used, V
There is also _R10 of 58, which clearly shows that the compound of the present invention is excellent.

Application Examples 10 to 12 1 part of τ type metal-free phthalocyanine (τ-H ₂ Pc) and 1 part of butyral resin (Polyvinyl butyral BM-1 of Sekisui Chemical Co., Ltd.) were used in a ball mill with 30 parts of tetrahydrofuran as a solvent. Kneaded for hours. The obtained pigment dispersion was applied onto a sheet obtained by vapor-depositing aluminum on a polyethylene terephthalate (PET) film, and dried at 50 ° C. for 2 hours to form a charge carrier generation layer. Further, Example 3,
1 part of each of the exemplified compounds 5, 21, and 41 synthesized in 5, 6 and 1 part of a polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.) was used as dichloroethane 8
Mix and dissolve in parts. This liquid was applied onto the charge carrier generating layer with a doctor blade and dried at 80 ° C. for 2 hours to prepare photoconductors 12 to 14. The electrophotographic characteristics of the thus obtained photoreceptor were measured in the same manner as in Application Examples 1 to 3. The results are shown in Table 16.

Application Comparative Example 3 Photosensitive member 15 was prepared in the same manner as in Application Examples 10 to 12 except that Comparative Compound 2 was used instead of Exemplified Compounds 5, 21, and 41. The electrophotographic characteristics were measured in the same manner as in Application Examples 1 to 3, and the results are shown in Table 16. Here, the higher the surface potential V _{0, the} clearer the contrast, but if V ₀ is too low, a sufficient function as a photoreceptor cannot be obtained. When the exemplified compounds 5, 21, and 41 of the present invention were used, V ₀ was 826, 1238, and 1184, respectively, whereas when the comparative compound 2 was used, V ₀ was 67, which is clear. It can be seen that the compound of the present invention is excellent.

[0167]

[Table 15]

[0168]

[Table 16]

Application Examples 13 to 14 1 part of x-type metal-free phthalocyanine (x-H ₂ Pc) and 1 part of butyral resin (Polyvinyl butyral BM-1 of Sekisui Chemical Co., Ltd.) were used in a ball mill with 30 parts of tetrahydrofuran as a solvent. Kneaded for hours. The obtained pigment dispersion was applied onto a sheet obtained by vapor-depositing aluminum on a polyethylene terephthalate (PET) film, and dried at 50 ° C. for 2 hours to form a charge carrier generation layer. Further, 1 part each of the exemplified compounds 21 and 41 and 1 part of a polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.) were mixed and dissolved in 8 parts of dichloroethane. This liquid was applied onto the charge carrier generating layer with a doctor blade and dried at 80 ° C. for 3 hours to prepare photoconductors 16 and 17. The electrophotographic characteristics of the thus obtained photoreceptor were measured in the same manner as in Application Examples 1 to 3. The results are shown in Table 16.

Application Examples 15 to 17 A binder resin solution prepared by dissolving 1 part of butyral resin (polyvinyl butyral BM-1 of Sekisui Chemical Co., Ltd.) in 30 parts of tetrahydrofuran was added to JP-A-63-20365.
1 part of crystalline oxotitanium phthalocyanine (TiOPc crystals) produced according to the publication was added and dispersed with glass beads for 2 hours using a vibrating mill. This dispersion was applied onto a sheet obtained by vapor-depositing aluminum on a polyethylene terephthalate (PET) film using a wire bar and dried to prepare a charge carrier generation layer of about 0.5 μm. Furthermore, each of the exemplified compounds 5, 21, and 41 is 1
Parts and 1 part of a polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.) were mixed and dissolved in 8 parts of dichloroethane. This solution was applied onto the above charge carrier generating layer with a doctor blade and dried at 80 ° C. for 3 hours, and then the photoconductor 18 to
20 was produced. The electrophotographic characteristics of the thus obtained photoreceptor were measured in the same manner as in Application Examples 1 to 3. The results are shown in Table 16.

Application Comparative Example 4 Photosensitive member 21 was prepared in the same manner as in Application Examples 15 to 17 except that Comparative Compound 2 was used instead of Exemplified Compounds 5, 21, and 41. The electrophotographic characteristics were measured in the same manner as in Application Examples 1 to 3, and the results are shown in Table 16. Exemplary compounds 5 and 2 of the present invention
1, 41 is used, V ₀ is 300, 7 respectively.
66,832, V ₀ was 70 when the comparative compound 2 was used, which clearly shows that the compound of the present invention is excellent. Further, a high value of the half-electron amount E _1/2 indicates that the sensitivity is poor, but when the exemplified compounds 5, 21, 41 of the present invention are used, E _1/2 is 0.6 respectively. , 0.6, 0.8, whereas in the case of using the comparative compound 2, E _1/2 was 12.0, which clearly shows that the compound of the present invention is excellent.

Application Examples 18-20 1 part of the bisazo pigment (P) and 1 part of a polycarbonate resin (Upilon E-2000 manufactured by Mitsubishi Gas Chemical Co., Inc.) were kneaded in a ball mill for 5 hours with 30 parts of dichloroethane as a solvent. The obtained pigment dispersion is applied onto a polyethylene terephthalate (PET) film on which aluminum is vapor-deposited using a wire bar and dried at 45 ° C. for 3 hours to form a charge carrier generation layer having a thickness of about 1 μm. It was Further, 1 part each of Exemplified Compounds 5, 21, and 41 and 1 part of a polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.) were mixed and dissolved in 8 parts of dichloroethane. This liquid was applied onto the charge carrier generating layer with a doctor blade and dried at 80 ° C. for 3 hours to prepare photoconductors 22 to 24. These electrophotographic characteristics were measured, and the results are shown in Table 17.

[0173]

[Table 17]

Application Examples 21 to 24 1 part each of Exemplified Compounds 5, 21, 41 and 45 and 1 part polycarbonate resin were mixed and dissolved in 8 parts dichloroethane. This solution was applied with a doctor blade onto a sheet obtained by vapor-depositing aluminum on a polyethylene terephthalate (PET) film, and dried at 80 ° C. for 3 hours.
Further, a semitransparent gold electrode was vapor-deposited on the charge transport layer to measure the charge carrier mobility. The carrier mobility was measured using a nitrogen gas laser with a pulse half width of 0.9 nsec and a wavelength of 337 nm as a light source, and a time-of-flight method (Satoshi Tanaka, Yasuhiro Yamaguchi, Masaaki Yokoyama: Electrophotography, 29, 366 (1
990). The measurement results at 25 ° C. and 25 V / μm are shown in Table 18.

Application Comparative Example 5 Comparative Compound 2 in place of Exemplified Compounds 5, 21, 41 and 45
Films were prepared and carrier mobilities were measured in the same manner as in Application Examples 21 to 24 except that was used. The results are shown in Table 1.
8 shows.

[0176]

[Table 18] As is clear from Table 18, the compound of the present invention has higher carrier mobility than the comparative compound.

Application Examples 25 and 26 In the same manner as in Application Examples 4 to 9, oxotitanium phthalocyanine (TiOPc) was vacuum-deposited at a thickness of about 0.8 μm at 10 ⁻⁶ torr to prepare a charge carrier generating layer. 1 part each of the exemplified compounds 21 and 41 as a charge transport material, and a bisphenol A / biphenyl type copolycarbonate resin represented by the following structural formula (Idemitsu Kosan (polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.) 1 part (manufactured by K.K.) was mixed and dissolved in 8 parts of dichloroethane. This solution is applied onto the charge carrier generating layer with a doctor blade and dried at 80 ° C. for 3 hours to form a photoconductor 25, 2.
6 was produced.

[Chemical 51]

Electrophotographic characteristics of the photoconductors 25 and 26 were measured in the same manner as in Application Examples 1 to 3. The results are shown in Table 19.

[0179]

[Table 19]

Application Examples 27 and 28 In the same manner as in Application Examples 10 to 12, charge carrier generating layers of τ-type metal-free phthalocyanine (τ-H ₂ Pc) were formed. Furthermore, 1 part each of Exemplified Compounds 21 and 41, a polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.)
Instead of bisphenol A used in Application Examples 25 and 26
1 part of a / biphenyl type copolycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd.) was mixed and dissolved in 8 parts of dichloroethane. This liquid was applied onto the charge generation layer with a doctor blade and dried at 80 ° C. for 3 hours to prepare photoconductors 27 and 28. The charge photographic characteristics were measured in the same manner as in Application Examples 1 to 3. The results are shown in Table 20.

Application Examples 29 and 30 The x-type metal-free phthalocyanine (x-H ₂ Pc) charge carrier generating layer was formed in the same manner as in Application Examples 13 and 14. Further, 1 part each of Exemplified Compounds 21 and 41, bisphenol A / biphenyl type copolycarbonate resin (Idemitsu Kosan Co., Ltd.) used in Application Examples 25 and 26 in place of the polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.). 1 part) was mixed and dissolved in 8 parts of dichloroethane. This liquid was applied onto the charge generation layer with a doctor blade and dried at 80 ° C. for 3 hours to prepare photoconductors 29 and 30. Next, the electrophotographic characteristics of the photoconductors 29 to 30 were measured in the same manner as in Application Examples 1 to 3. The results are shown in Table 20.

Application Examples 31 and 32 In the same manner as in Application Examples 15 to 17, charge carrier generating layers using crystalline oxotitanium phthalocyanine (TiOPc crystal) were prepared. Further, 1 part each of Exemplified Compounds 21 and 41, bisphenol A / biphenyl type copolycarbonate resin (Idemitsu Kosan Co., Ltd.) used in Application Examples 25 and 26 in place of the polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.). Made) 1 part dichloroethane 8
Mix and dissolve in parts. This liquid was applied onto the charge generation layer with a doctor blade and dried at 80 ° C. for 3 hours to prepare photoconductors 31 and 32. The electrophotographic characteristics of the thus obtained photoreceptor were measured in the same manner as in Application Examples 1 to 3. The results are shown in Table 20.

[0183]

[Table 20]

Application Examples 33 and 34 In the same manner as in Application Examples 18 to 20, charge carrier generating layers using the bisazo pigment (P) were prepared. Further exemplified compound 2
1 part of each of 41 and 41, bisphenol A / biphenyl type copolycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd.) used in Application Examples 25 and 26 in place of the polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.) 1 Parts were mixed and dissolved in 8 parts of dichloroethane. This solution is applied onto the charge carrier generating layer with a doctor blade and the temperature is adjusted to 3 at 80 ° C.
After being dried for an hour, photoconductors 33 and 34 were prepared, and the electrophotographic characteristics were measured. The results are shown in Table 21.

[0185]

[Table 21]

Application Examples 35 and 36 Instead of the polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.) in Application Examples 21 to 24, the bisphenol A / biphenyl type copolycarbonate resin (Idemitsu Idemitsu) used in Application Examples 25 and 26 is used. Kosan Co., Ltd.) 1
A charge transport layer was formed in the same manner as in Application Examples 21 to 24 except that the parts were used and dried at 80 ° C. for 3 hours. Application example 21-
Similarly to 24, the charge carrier mobility was measured by the time-of-flight method. Charge carrier mobility is 25 ° C, 25V /
Table 22 shows the measurement results in μm. As is clear from Table 22, the compound of the present invention shows high carrier mobility.

[0187]

[Table 22]

Application Example 37 Instead of using 1 part of Exemplified Compound 1 of Application Example 1, a mixed charge transport material comprising 0.4 part of Exemplified Compound 41 and 0.6 part of a hydrazone compound represented by the following formula (U) is used. A photoconductor 35 was prepared in the same manner as in Application Example 1 except that the electrophotographic characteristics were evaluated. The results are shown in Table 23.

Embedded image

Application Example 38 Application Example except that a mixed charge transport material consisting of 0.4 part of Exemplified Compound 41 and 0.6 part of hydrazone compound (U) was used instead of using 1 part of Exemplified Compound 5 of Application Example 10. Example 10
A photoconductor 36 was prepared in the same manner as in 1. and the electrophotographic characteristics were evaluated. The results are shown in Table 23.

Application Example 39 Instead of using 1 part of Exemplified Compound 21 of Application Example 13, 0.4 parts of Exemplified Compound 41 and 0.6 parts of hydrazone compound (U) were used.
Example 1 except that a mixed charge transport material consisting of parts is used
A photoconductor 37 was prepared in the same manner as in Example 3 and evaluated for electrophotographic characteristics. The results are shown in Table 23.

Application Example 40 Application Example except that a mixed charge transport material consisting of 0.4 parts of Exemplified Compound 41 and 0.6 part of hydrazone compound (U) was used instead of using 1 part of Exemplified Compound 5 of Application Example 15. Example 15
A photoconductor 38 was prepared in the same manner as in 1. and the electrophotographic characteristics were evaluated. The results are shown in Table 23.

Application Examples 41 to 43 Instead of the polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.), the bisphenol A / biphenol type copolymerized polycarbonate resin used in Application Example 25 (manufactured by Idemitsu Kogyo Co., Ltd.) is used. Photoreceptors 39, 4 were made of the same materials as in Application Examples 37, 38, 39, respectively, except that they were used.
0 and 41 were prepared and evaluated for electrophotographic characteristics.
The results are shown in Table 23.

Application Example 44 Instead of using 1 part of Exemplified Compound 1 of Application Example 1, a mixed charge transport material consisting of 0.4 part of Exemplified Compound 41 and 0.6 part of a hydrazone compound represented by the following formula (V) is used. A photoreceptor 42 was prepared in the same manner as in Application Example 1 except that the electrophotographic characteristics were evaluated. The results are shown in Table 23.

Embedded image

Application Example 45 Application Example except that a mixed charge transport material consisting of 0.4 part of Exemplified Compound 41 and 0.6 part of hydrazone compound (V) was used instead of using 1 part of Exemplified Compound 5 of Application Example 10. Example 10
A photoconductor 43 was prepared in the same manner as in 1. and the electrophotographic characteristics were evaluated. The results are shown in Table 24.

Application Example 46 Application Example except that a mixed charge transport material consisting of 0.4 part of Exemplified Compound 41 and 0.6 part of hydrazone compound (V) was used instead of using 1 part of Exemplified Compound 5 of Application Example 15. Example 15
A photoconductor was prepared in the same manner as in 1. and the electrophotographic characteristics were evaluated. The results are shown in Table 24.

Application Example 47 The bisphenol A / biphenol type copolymerized polycarbonate resin (manufactured by Idemitsu Kogyo Co., Ltd.) used in Application Example 25 was used in place of the polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.). A photoreceptor 45 was prepared using the same materials as in Application Example 44 except for the above, and the electrophotographic characteristics were evaluated. The results are shown in Table 24.

Application Example 48 Compound 41 is an example of the mixed charge transport material in Application Example 43.
A photoconductor 46 was prepared using the same materials except that 0.4 parts and 0.6 parts of the hydrazone compound (V) were used, and the electrophotographic characteristics were evaluated. The results are shown in Table 24.

Application Example 49 Instead of using 1 part of Exemplified Compound 1 of Application Example 1, a mixed charge transport material comprising 0.4 part of Exemplified Compound 41 and 0.6 part of a hydrazone compound represented by the following formula (W) is used. A photoreceptor 47 was prepared in the same manner as in Application Example 1 except that it was not used, and the electrophotographic characteristics were evaluated. The results are shown in Table 25.

[Chemical 54]

Application Example 50 Application Example except that a mixed charge transport material consisting of 0.4 part of Exemplified Compound 41 and 0.6 part of hydrazone compound (W) was used instead of using 1 part of Exemplified Compound 5 of Application Example 10. Example 10
A photoconductor 48 was prepared in the same manner as in 1. and the electrophotographic characteristics were evaluated. The results are shown in Table 25.

Application Example 51 Instead of using 1 part of Exemplified Compound 21 of Application Example 13, 0.4 part of Exemplified Compound 41 and 0.6 part of hydrazone compound (W) were used.
Example 1 except that a mixed charge transport material consisting of parts is used
A photoconductor 49 was prepared in the same manner as in Example 3 and evaluated for electrophotographic characteristics. The results are shown in Table 25.

Application Example 52 Application Example 52 was repeated except that a mixed charge transport material consisting of 0.4 parts of Exemplified Compound 41 and 0.6 part of hydrazone compound (W) was used instead of using 1 part of Exemplified Compound 5 of Application Example 15. Example 15
A photoconductor 50 was prepared in the same manner as in 1. and the electrophotographic characteristics were evaluated. The results are shown in Table 25.

Application Examples 53 to 56 In place of the polycarbonate resin (Polycarbonate Z manufactured by Mitsubishi Gas Chemical Co., Inc.), the bisphenol A / biphenol type copolymerized polycarbonate resin (manufactured by Idemitsu Kogyo Co., Ltd.) used in Application Example 25 is used. Application example 4 except that
Photoreceptor 5 using the same material as 9, 50, 51, 52
1, 52, 53 and 54 were produced and evaluated for electrophotographic characteristics. The results are shown in Table 25.

[0203]

[Table 23]

[0204]

[Table 24]

[0205]

[Table 25]

Application Examples 57-60 Instead of using 1 part of Exemplified Compound 1 of Application Example 1, 0.4 part of Exemplified Compound 1 and 0.6 part of Exemplified Compound (2) -57,
Exemplified Compound 1 0.3 parts and Exemplified Compound (2) -57
0.7 parts, Exemplified Compound 1 0.2 parts and Exemplified Compound (2)-
57 Photoreceptor 5 in the same manner as in Application Example 1 except that a mixed charge transport material composed of 57 0.8 parts, Exemplified Compound 1 0.1 part, and Exemplified Compound (2) -57, 0.9 part was used.
5, 56, 57 and 58 were produced and the electrophotographic characteristics were evaluated. The results are shown in Table 26.

Application Examples 61 to 64 Instead of using 1 part of Exemplified Compound 5 of Application Example 15, 0.4 part of Exemplified Compound 1 and Exemplified Compound (2) -57 0.6
Part, Exemplified Compound 1 0.3 parts and Exemplified Compound (2) -57
0.7 part, Exemplified Compound 1 0.2 part, Exemplified Compound (2) -57 0.8 part, Exemplified Compound 1 0.1 part and Exemplified Compound (2) -57 0.9 part Photoconductors 59, 60, 61, and 62 were produced in the same manner as in Application Example 15 except that the above was used, and the electrophotographic characteristics were evaluated. The results are shown in Table 26.

Application Example 65 Except that 1 part of Exemplified Compound 1 of Application Example 1 is used, a mixed charge transport material consisting of 0.5 parts of Exemplified Compound 41 and 0.5 parts of Exemplified Compound (2) -57 is used. A photoconductor 63 was prepared in the same manner as in Application Example 1 and evaluated for electrophotographic characteristics. The results are shown in Table 27.

Application Example 66 Except that 1 part of Exemplified Compound 1 of Application Example 4 is used and a mixed charge transport material consisting of 0.5 parts of Exemplified Compound 41 and 0.5 part of Exemplified Compound (2) -57 is used. A photoconductor 64 was prepared in the same manner as in Application Example 1 and evaluated for electrophotographic characteristics. The results are shown in Table 27.

Application Example 67 Instead of using 1 part of Exemplified Compound 5 of Application Example 10, 0.5 part of Exemplified Compound 41 and Exemplified Compound (2) -57 0.5
A photoconductor 65 was prepared in the same manner as in Application Example 1 except that the mixed charge transport material consisting of parts was used, and the electrophotographic characteristics were evaluated. The results are shown in Table 27.

Application Example 68 Instead of using 1 part of Exemplified Compound 21 of Application Example 13, 0.5 part of Exemplified Compound 41 and Exemplified Compound (2) -57.
Application Example 1 except that a mixed charge transport material consisting of 5 parts was used
A photoconductor 66 was produced in the same manner as in 1. and evaluated for electrophotographic characteristics. The results are shown in Table 27.

Application Example 69 Except that 1 part of Exemplified Compound 1 of Application Example 1 is used and a mixed charge transport material consisting of 0.4 parts of Exemplified Compound 1 and 0.6 part of Exemplified Compound (2) -76 is used. A photoconductor 67 was prepared in the same manner as in Application Example 1 and evaluated for electrophotographic characteristics.
The results are shown in Table 28.

Application Example 70 Except that 1 part of Exemplified Compound 5 of Application Example 15 is used and a mixed charge transport material of 0.4 part of Exemplified Compound 1 and 0.6 part of Exemplified Compound (2) -76 is used. A photoconductor 68 was prepared in the same manner as in Application Example 1 and evaluated for electrophotographic characteristics. The results are shown in Table 28.

Application Example 71 Instead of using 1 part of Exemplified Compound 1 of Application Example 1, 0.4 parts of Exemplified Compound 1 and 0.6 part of Exemplified Compound (2) -33 are used, and a mixed charge transport material is used. A photoconductor 69 was prepared in the same manner as in Example 1 and evaluated for electrophotographic characteristics. Table 2 shows the results
9 shows.

Application Example 72 Instead of using 1 part of Exemplified Compound 21 of Application Example 13, 0.4 parts of Exemplified Compound 1 and Exemplified Compound (2) -33 0.6
A photoconductor 70 was prepared in the same manner as in Application Example 13 by using the mixed charge transporting material in some parts, and the electrophotographic characteristics were evaluated. The results are shown in Table 29.

Application Example 73 A photoconductor 71 was prepared using the same materials as in Application Example 71 except that the bisphenol A / biphenol type copolycarbonate resin used in Application Example 25 was used in place of the polycarbonate resin. The electrophotographic properties were evaluated. The results are shown in Table 29.

Application Example 74 Instead of using 1 part of Exemplified Compound 1 of Application Example 1, 0.4 parts of Exemplified Compound 1 and 0.6 part of Exemplified Compound (2) -1 are used to prepare a mixed charge transport material. A photoconductor 72 was produced in the same manner as in No. 1 and evaluated for electrophotographic characteristics. The results are shown in Table 30.
Shown in

Application Example 75 Instead of using 1 part of Exemplified Compound 5 of Application Example 10, 0.4 parts of Exemplified Compound 1 and 0.6 part of Exemplified Compound (2) -1 are used, and a mixed charge transport material is used. A photoconductor 73 was produced in the same manner as in No. 10, and electrophotographic characteristics were evaluated. The results are shown in Table 30.

Application Example 76 0.4 part of Exemplified Compound 1, Exemplified Compound (2) -57
Using 0.6 part, a photoconductor 74 was prepared in the same manner as in Application Example 21, and the carrier mobility was measured. The results are shown in Table 31.

Application Example 76- (1) 0.8 part of Exemplified Compound (1), Exemplified Compound (2) -57
Was used in the same manner as in Application Example 21, and the carrier mobility was measured. The results are shown in Table 31.

[0221]

[Table 26]

[0222]

[Table 27]

[0223]

[Table 28]

[0224]

[Table 29]

[0225]

[Table 30]

[0226]

[Table 31]

Application Example 77 0.15 g of oxotitanium phthalocyanine (TiOPc) used in Application Example 15, 3.5 g of polycarbonate (Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.), 1.35 g of Exemplified Compound 41 and 31.5 g of dichloroethane were dispersed. Using glass beads as a means, dispersion was carried out for 5 hours. The dispersion was filtered through a 200 mesh filter to separate it from the beads. This dispersion was applied onto a polyethylene terephthalate (PET) film on which aluminum was vapor-deposited using a doctor blade.
A photoconductor 75 was prepared by drying in an oven at 80 ° C. for 3 hours. The single-layer type photoconductor thus obtained was
It was negatively charged by V corona discharge, and electrophotographic characteristics were measured by the same method as in Application Example 1. The results are shown in Table 32.

Application Comparative Example 7 Instead of Exemplified Compound 41, as Comparative Compound 3, triphenylamine (TPA, manufactured by Tokyo Chemical Industry Co., Ltd.) was used which was recrystallized from a mixed solvent of toluene and hexane. Example 7 except that a melting point of 127 ° C.) was used.
A single-layer type photosensitive member 76 was prepared in the same manner as in No. 7, and electrophotographic characteristics were measured by the same method as in Application Example 1. The results are shown in Table 32.

Application Example 78 The same as Application Example 77 except that the x-type metal-free phthalocyanine (x-H ₂ Pc) used in Application Example 3 was used in place of oxotitanium phthalocyanine (TiOPc) which is a charge generating substance. A single-layer type photoconductor 77 was prepared by using the above method, negatively charged, and then electrophotographic characteristics were evaluated in the same manner as in Application Example 1. The results are shown in Table 32.

Application Comparative Example 8 A single-layer type photosensitive member 78 was prepared from the same materials as in Application Example 78 except that Comparative Compound 3 was used in place of Exemplified Compound 41, and electrophotographic characteristics were measured in the same manner. The results are shown in Table 32.
Shown in

Application Example 79 The single-layer type photoconductor 75 manufactured in Application Example 77 was charged by performing corona discharge of +6 kV for 5 seconds, and the surface potential V ₀ (unit: V) was measured. After holding for 2 seconds, a tungsten lamp is irradiated with light having an illuminance of lux, and the exposure amount required to attenuate the surface potential by half, that is, a half electric light amount E _1/2 (lux · sec), and a light having an illuminance of 5 lux is 10 The surface residual potential V _R10 (V) after the second irradiation was determined. The results are shown in Table 33.

Application Comparative Example 9 The electrophotographic characteristics were evaluated in the same manner as in Application Example 79 by positively charging the single-layer type photoreceptor 76 manufactured in Application Comparative Example 7 by corona discharge of +6 kV. The results are shown in Table 33.

Application Example 80 The single-layer type photoreceptor 77 manufactured in Application Example 78 was positively charged by a corona discharge of +6 kV, and electrophotographic characteristics were evaluated in the same manner as in Application Example 79. The results are shown in Table 33.

Application Comparative Example 10 The single-layer type photoreceptor 78 manufactured in Application Comparative Example 8 was positively charged by a corona discharge of +6 kV, and electrophotographic characteristics were evaluated in the same manner as in Application Example 79. The results are shown in Table 33.

[0235]

[Table 32]

[0236]

[Table 33]

As can be seen from Tables 32 and 33, when the compound of the present invention is used as a single-layer type photoreceptor, it has a clearly better sensitivity and a lower residual potential than the comparative compound regardless of whether it is charged positively or negatively. ing.

Application Example 81 Instead of using 1 part of Exemplified Compound 1 of Application Example 4, a mixed charge transport material consisting of 0.4 part of Exemplified Compound 1 and 0.6 part of the following compound (Xa) was used. A photoconductor 79 was prepared in the same manner as in Application Example 4 except that a bisphenol A / biphenol type copolycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd.) was used in place of the polycarbonate Z manufactured by Gas Chemical Co., Ltd. Photographic properties were evaluated.
The results are shown in Table 34.

[0239]

[Chemical 55]

Application Example 82 Similar to Application Example 31 except that a mixed charge transport material consisting of 0.5 part of Exemplified Compound 1 and 0.5 part of Compound (Xb) is used instead of using 1 part of Exemplified Compound 21 or 41. Then, a photoconductor 80 was produced and the electrophotographic characteristics were evaluated. The results are shown in Table 3.
4 shows.

[0241]

[Table 34]

Application Example 83 Application Example except that a mixed charge transport material consisting of 0.4 part of Exemplified Compound 1 and 0.6 part of the following compound (Y) was used instead of using 1 part of Exemplified Compound 1 of Application Example 1. A photoconductor 81 was prepared in the same manner as in Example 1 and evaluated for electrophotographic characteristics. The results are shown in Table 3.
5 shows.

[0243]

[Chemical 56]

Application Example 84 Application Example except that a mixed charge transport material consisting of 0.4 parts of Exemplified Compound 1 and 0.6 part of the following compound (Y) was used instead of using 1 part of Exemplified Compound 1 of Application Example 4. A photoconductor 82 was prepared in the same manner as in No. 4, and the electrophotographic characteristics were evaluated. The results are shown in Table 3.
5 shows.

Application Example 85 Application Example except that a mixed charge transport material consisting of 0.4 parts of Exemplified Compound 1 and 0.6 part of the following compound (Y) was used instead of using 1 part of Exemplified Compound 5 of Application Example 10. A photoconductor 83 was prepared in the same manner as in No. 10, and electrophotographic characteristics were evaluated. The results are shown in Table 35.

[0246]

[Table 35]

[0247]

As described above, the triphenylamine derivative (1) of the present invention and the mixture thereof with the compound (2) are
An industrially superior material that has excellent performance as a charge transport material, and therefore can exhibit high carrier mobility when used as an electrophotographic photoreceptor, and has various characteristics such as high sensitivity and no residual potential. Is. Further, the production method of the present invention can provide an industrially advantageous method capable of producing the triphenylamine derivative (1) and / or the compound (2) in a high yield.

Continued Front Page (72) Inventor Toshimitsu Hagiwara 1-4-11 Nishi-Hachiman, Hiratsuka-shi, Kanagawa Takasago International Corp.

Claims (12)

[Claims] 1. The following general formula (1): (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or Represents a aryl group which may have a substituent, and m and n represent 0 or 1). 2. A charge-transporting material containing the novel triphenylamine derivative according to claim 1. 3. A novel triphenylamine derivative represented by the general formula (1) according to claim 1 and the following general formula (2): (In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, It represents an aryl group which may have a halogen atom or a substituent.
And n are 0 or 1. ) A charge-transporting material containing a mixture with a triphenylamine derivative represented by 4. The claim 1 according to claim 2 or claim 3.
An electrophotographic photoreceptor containing the charge transport material according to the item 1. 5. A laminated electrophotographic photosensitive member comprising a conductive support and a charge generation layer and a charge transport layer provided on the conductive support, wherein the charge transport material according to any one of claims 2 and 3 is contained. An electrophotographic photoconductor characterized by: 6. A single-layer type electrophotographic photoreceptor comprising a charge generating material and a charge transporting material on a conductive support, containing the charge transporting material according to any one of claims 2 and 3. An electrophotographic photoconductor characterized by: 7. The following general formula (3): (In the formula, R ⁷ , R ⁸ and R ⁹ may be the same or different from each other and represent a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, an aryl group which may have a substituent or a halogen atom. .) In the presence of an acid selected from the group consisting of a Lewis acid and a protic acid, with a Wiermeier reagent prepared from a halogenating agent and an N-substituted formamide, and then Hydrolysis with an alkaline aqueous solution gives the following general formula (4): (In the formula, R ⁷ , R ⁸ and R ⁹ have the same meanings as in the general formula (3), and Y has a formyl group, a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or a substituent. A polyformyl-substituted triphenylamine derivative represented by the following general formula (5a) is obtained. (5b), (5c) (In the formula, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R, R ′ and R ″
May be the same or different, and a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group,
The aryl group which may have a halogen atom or a substituent is shown. l ₁ , l ₂ and l ₃ represent 0 or 1, and when each is 0, A represents a hydrogen atom, and when 1 is bonded, A and B bond together to form a single bond. ) And a phosphite compound represented by the following general formula (6): IN FORMULA, R < ⁷ >, R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R < ¹¹ >, R < ¹² >, R < ¹³ >, L < ₁ > AND L < ₂ > REPRESENT THE SAME MEANING AS THE FORMULA (5a) AND (5b), AND A hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom, an aryl group which may have a substituent, or the following general formulas (7a) and (7
b), (7c) (Wherein R ^{10 to} R ¹³ , R ′, R ″, l ₁ , l ₂ and l
₃ has the same meaning as in the general formulas (5a), (5b) and (5c). ) Represents a group represented by. ] The manufacturing method of the triphenylamine derivative represented by these. 8. The manufacturing method according to claim 7,
In the polyformyl-substituted triphenylamine derivative represented by the general formula (4), the substituent Y is a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or an aryl which may have a substituent. A di-formyl-substituted triphenylamine derivative that is a group and a triformyl-substituted triphenylamine derivative in which the substituent Y is a formyl group, and the triphenylamine derivative represented by the general formula (6) is A triphenylamine derivative in which the group Z is a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, a halogen atom or an aryl group which may have a substituent, and the substituent Z is represented by the general formula (7).
The preparation of the triphenylamine derivative represented by the general formula (6) according to claim 7, which is a mixture of triphenylamine derivatives which are groups represented by a), (7b) or (7c). Method. 9. The following general formula (3): (In the formula, R ⁷ , R ⁸ and R ⁹ may be the same or different from each other and represent a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group, an aryl group which may have a substituent or a halogen atom. In the presence of an acid selected from the group consisting of a Lewis acid and a protic acid, a triphenylamine derivative represented by) is reacted with a Wielsmeier reagent prepared from a halogenating agent and an N-substituted formamide to form a reaction product. The product is then hydrolyzed with an alkaline aqueous solution, and is represented by the following general formula (4): (In the formula, R ⁷ , R ⁸ and R ⁹ have the same meanings as in the general formula (3), and Y has a formyl group, a hydrogen atom, a lower alkyl group, an alkoxy group, a phenoxy group or a substituent. Which represents a good aryl group or a halogen atom). 10. The production method according to claim 9, wherein the Wiersmeier reagent is phosphorus oxychloride,
It is prepared from at least one halogenating agent selected from phosgene and thionyl chloride and at least one N-substituted formamide selected from N, N-dimethylformamide and N-methylformamide. A method for producing a polyformyl-substituted triphenylamine derivative represented by the general formula (4) according to claim 9. 11. The reaction of the triphenylamine derivative represented by the general formula (3) with the Wiersmeier reagent is carried out using at least one reaction solvent selected from toluene, xylene, chlorobenzene and dichlorobenzene. 9. The method according to claim 9 and claim 10, characterized in that
A method for producing a polyformyl-substituted triphenylamine derivative represented by the general formula (4) according to any one of items 1 to 4. 12. The reaction between the triphenylamine derivative represented by the general formula (3) and the Wiersmeier reagent in the presence of a Lewis acid and / or a protonic acid is performed by zinc chloride, zinc bromide, boron trifluoride. , A Lewis acid consisting of aluminum chloride, titanium tetrachloride and tin chloride, and a protic acid consisting of hydrogen chloride and hydrogen bromide, in the presence of at least one selected from the group consisting of:
A method for producing a polyformyl-substituted triphenylamine derivative represented by the general formula (4) according to any one of claims 9 to 11.