JPH0539248A - Triarylamine derivative and its production - Google Patents

Abstract

PURPOSE:To obtain a new triarylamine derivative useful as an organic photoconductive material used for charge transportation layer of electrophotographic photoreceptors, having extremely excellent initial characteristics, especially, being excellent in durability and capable of sufficiently satisfying practical required performance. CONSTITUTION:A compound expressed by formula I (R1 and R2 are H2, lower alkyl, lower alkoxy or halogen), e.g. N,N,N',N'-tetraphenyl-19,10-diaminophenan- threne. The compound can be produced (a) by reacting a compound expressed by formula II (X is halogen) with 9,10-phenanthrenequinone or (b) by reacting a compound expressed by formula III with 9,10-phenanthrenequinone to give a compound expressed by formula IV, derivatizing the compound expressed by formula IV to a compound expressed by formula V and then reacting the compound expressed by formula V again with a compound expressed by formula II. This compound has extremely excellent initial characteristics such as antistatic properties, sensitivity or residual potential, compared with conventional organic photo-conductive materials. Further, the compound is free from deterioration of performance against coronas discharge or visible light even after repeatedly used and especially, being excellent in durability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel triarylamine derivative useful as an organic photoconductive material used in a charge transport layer of an electrophotographic photoreceptor and a method for producing the same.

[0002]

2. Description of the Related Art The electrophotographic system invented by Carlson (U.S. Pat. No. 2,297,691) is one of image forming methods and is also called xerography. This principle is obtained by first charging a photoconductor by corona discharge, then exposing it to a light image to obtain an electrostatic latent image, and then applying colored toner to the electrostatic latent image to develop it. Transfer the toner image onto paper. The characteristics required for the use as such an electrophotographic photoreceptor are as follows: 1) sufficient charge at corona receptive potential in the dark, 2) high ability to retain charged potential, and 3) occurrence of charge generation substance. Charge carriers can be efficiently injected and rapidly transported.

Conventionally, inorganic photoconductive materials such as selenium, cadmium sulfide and zinc oxide have been used as photoconductive materials for electrophotography. These inorganic photoconductive materials have advantages such as high durability and a large number of printable sheets, but have some drawbacks such as high manufacturing cost, poor processability, and toxicity. Problems related to pollution are pointed out such as showing.

In order to solve these problems, research on electrophotographic photoreceptors using organic photoconductive materials has been actively conducted in recent years. Organic photoconductive materials have many advantages such as light weight, variety of shapes, low cost, and no pollution, and many organic compounds have been proposed. For example, hydrazone derivatives (US Pat. No. 3,717, No. 462, JP-A-54-5
9,143, US Pat. No. 4,150,978), triarylpyrazoline derivatives (US Pat. No. 3,820,
989, JP-A-51-93,224, JP-A-55-
108,667), arylamine derivatives (U.S. Pat. No. 3,180,730, JP-A-55-144,250).
No. 56-119,132), stilbene derivatives (58-190,953, 59-19, 59-19).
No. 5,658) and other organic photoconductors are known. However, in the present circumstances, the electrophotographic photoreceptor using these organic photoconductors in the charge transport layer is not always satisfactory in chargeability, sensitivity and residual potential, and further excellent It has been desired to develop a charge transport material having a charge transport function and capable of long-term use.

[0005]

DISCLOSURE OF THE INVENTION In view of such a situation, the inventors of the present invention have conducted earnest research on organic photoconductors having excellent suitability for use to solve the problems of the prior art, and as a result, The present invention has been completed by discovering a useful new triarylamine derivative and a method for producing the same.

[0006]

That is, the gist of the present invention is a triarylamine derivative represented by the following general formula [1] [Formula 9] and a method for producing the same.

[0007]

[Chemical 9]

(Wherein R ₁ and R ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, and R ₁ and R ₂ may be the same or different). The triarylamine derivative represented by the formula [1] is a novel compound. There are two methods for synthesizing the triarylamine derivative shown in the present invention, which will be described in detail below. First, as the first synthesis method, the general formula [2],

[0009]

[Chemical 10]

It can be synthesized by reacting a halobenzene derivative represented by the formula (wherein R ₁ and R ₂ are the same as above) with 9,10-diaminophenanthrene. Hereinafter, this synthesis method is referred to as synthesis method A. To explain this synthetic method in more detail, the basic reaction for obtaining the triarylamine derivative of the present invention is represented by the following reaction scheme 1.

[0011]

[Chemical 11]

(In the formula, R ₁ and R ₂ are the same as above.) That is, 9,10-diaminophenanthrene obtained by a known method (Chem. Ber., 35, 27).
38 (1902), Chem. Ber. , 41,368
4 (1908)) and a halobenzene derivative in a nitrogen atmosphere in an organic solvent or in the absence of a solvent in the presence of a base and a catalyst at a predetermined temperature for a predetermined time to react with the corresponding thoria represented by the general formula [1]. The reel amine derivative can be synthesized with high quality.

Of the R ₁ and R _{2 represented by} the general formula [1], the general formula [2] and the chemical formula 11, the alkyl group and the alkoxy group are, for example, a methyl group, an ethyl group, a propyl group and a butyl group. Group, methoxy group, ethoxy group,
Examples thereof include bromopoxy group and butoxy group. Examples of the halogen atom used in the present invention include chlorine, bromine, iodine and the like. X represented by the general formula [2]
Examples thereof include chlorine, bromine, iodine and the like.
Examples of the base used in the present invention include inorganic bases such as potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, and pyridine, picoline, triethylamine, N, N-dimethylaniline,
N-methylpyrrolidine, 1,5-diazabicyclo [4.
3,0] Nonene-5 (DBN), 1,5-diazabicyclo [5,4,0] undecene-5 (DBU), 1,4-
Organic bases such as diazabicyclo [2.2.2] octane (DBCO) can be mentioned. Examples of the catalyst used in the present invention include copper powder, copper oxide, copper halides such as cuprous chloride, copper sulfate, and copper acetate.

The solvent used in the present invention may be any solvent which can dissolve the raw material 9,10-diaminophenanthrene and the halobenzene derivative and allow the reaction to occur. For example, aromatic carbonization such as toluene and xylene. Hydrogen and nitrobenzene, dimethyl sulfoxide,
N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-
Aprotic polar solvents such as 2-imidazolidinone, HMPA are preferred. The reaction temperature applied in this synthetic method can be appropriately selected so that the production rate of the triarylamine derivative is the best, and is 80 to 300 ° C.
Especially 150-260 degreeC is preferable. The reaction may be performed under normal pressure, but may be performed under pressure to accelerate the reaction and shorten the reaction time.

Further, the basic reaction of the compound as the second synthetic method is represented by Chemical formula 12.

[0016]

[Chemical formula 12]

(Wherein R ₁ and R ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, and R ₁ and R ₂ may be the same or different). 9,10-phenanthrenequinone (Ann., 166 365, J. Cem. S.
oc. , 97 1661 (1910)) and the general formula [3].
An aniline derivative represented by is reacted in the presence of an acid catalyst,
After the diimino derivative represented by the general formula [4] is reduced, the diamine derivative represented by the general formula [5] is obtained, and the diamine derivative represented by the general formula [5] is reacted with the halobenzene derivative represented by the general formula [2]. Thus, the triarylamine derivative represented by the general formula [1] can be synthesized in high yield. Hereinafter, this synthesis method is referred to as synthesis method B.

General formulas [3], [4], [5] and formula 1
Examples of the alkyl group, the alkoxy group and the halogen atom of R ₁ , R ₂ and X in the compound represented by ₂ include the same ones as those described in the above-mentioned synthesis method A.

The acid catalyst used in the synthesis of the diimino derivative represented by the general formula [4] (Scheme 2) is, for example, concentrated sulfuric acid, organic sulfonic acid such as P-toluenesulfonic acid, or polyphosphoric acid. , TiCl ₄ , ZnCl
Lewis acids such as ₂ , AlCl ₃ , SnCl ₄ and BF ₃ can also be used, for example polystyrene sulfonic acid and Nafion.
Polymeric carriers having a sulfonic acid group bonded thereto are exemplified. The amount used is 2 to 5.0 times mol, preferably 3.0 to 3.5 times mol, based on the raw material.

Examples of the reducing agent used in the synthesis of the diamino derivative represented by the general formula [5] (reaction formula 2) include H ₂ / Pt, H ₂ / Pd, H ₂ / Ni and LiAlH.
₄ , NaBH ₄ , Zn, Sn, and the like. The amount used is 4 to 10.0 times the mol of the raw material, preferably 5
A molar amount of up to 6 times is suitable.

The aniline derivative represented by the general formula [3] used in (Reaction scheme 2) is P-toluidine such as P-toluidine.
When the compound had a position-donating group and had high activity, the product was not the expected compound represented by the general formula [4] but the compound represented by the general formula [5] in which the reduction was further advanced. In such a case, the reduction reaction operation corresponding to the reaction formula 2 can be omitted.

Examples of the base and the catalyst used in the synthesis of the triarylamine derivative represented by the general formula [1] (Scheme 2) are the same as those described in the above-mentioned synthesis method A. The solvent may or may not be used, but when it is used, the diamine derivative represented by the general formula [5] and the general formula [2] are used as raw materials.
Any compound capable of dissolving the halobenzene derivative represented by and allowing the reaction to proceed smoothly can be used.
The ones described in are listed. The reaction temperature in this synthetic method can be appropriately selected so as to maximize the production rate of the target compound represented by the general formula [1], and may be 80 to 30.
0 degreeC, especially 150-260 degreeC are preferable. The reaction may be performed under normal pressure, but may be performed under pressure to accelerate the reaction and shorten the reaction time.

The electrophotographic photoreceptor using the novel triarylamine derivative obtained in the present invention in the charge transport layer is superior in charging property, sensitivity, residual potential and durability as compared with the conventional organic photoconductive material. It is excellent and useful as an organic photoconductive material for electrophotographic photoreceptors.

[0024]

EXAMPLES Examples will be shown below for illustrating the present invention in more detail, but they do not limit the present invention.
Hereinafter, the present invention will be described in detail with reference to Examples.

[0025]

Example 1 N, N, N ′, N′-tetraphenyl-
9,10-Diaminophenanthrene [Compound No. 1]
(Synthesis Method A) 9,10-diaminophenanthrene 2.5 g, iodobenzene 42.5 g, caustic potash 10.8 g, and copper sulfate / 5-hydrate 0.1 g were added, and water was distilled off under a nitrogen stream. While reacting at 245-250 ° C for 12 hours. After the reaction,
The mixture was cooled to room temperature, diluted with ethyl acetate, filtered through Celite, and the residue obtained by concentrating the filtrate under reduced pressure was recrystallized from a mixed solvent of ethyl acetate-toluene to give Compound No. mp 211-212 ° C. as a white powder. ． 4.6 g (yield 75%) of 1 was obtained.

[0026]

Example 2 N, N, N ′, N′-tetra (3-methylphenyl) -9,10-diaminophenanthrene [Compound No. 2] Synthesis (Synthesis Method A) 9,10-diaminophenanthrene 6.0
g, m-iodotoluene 102 g, potassium carbonate 31.9
g, copper powder 0.1 g and cuprous chloride 0.06 g,
The reaction was carried out at 235 to 240 ° C. for 8 hours while distilling off water under a nitrogen stream. After completion of the reaction, the mixture was cooled to room temperature, diluted with ethyl acetate, filtered through Celite, and the residue obtained by concentrating the filtrate under reduced pressure was recrystallized from toluene to give a compound having a melting point of 223 to 224 ° C as pale yellow needle crystals. No. 2 to 14.2
g (yield 86%) was obtained.

[0027]

Example 3 N, N, N ′, N′-tetra (4-methylphenyl) -9,10-diaminophenanthrene [Compound No. 3] Synthesis (Synthesis Method A) 9,10-diaminophenanthrene 5.0
g, P-iodotoluene 85 g, caustic potash 21.6 g,
And 0.1 g of cuprous chloride were added to 40 ml of 1,3-dimethyl-2-imidazolidinone, and the mixture was reacted at 215 to 230 ° C. for 9 hours while distilling water under a nitrogen stream. After the reaction was completed, it was cooled to room temperature and poured into water. The obtained crystals were filtered and recrystallized from toluene to give pale yellow needle crystals having a melting point of 227 to 229 ° C., Compound No. 3 to 13.7 g
(Yield 83%) was obtained.

[0028]

Example 4 N, N, N ′, N′-tetra (3-methylphenyl) -9,10-diaminophenanthrene [Compound No. 2] Synthesis (Synthesis Method B) To 400 ml of toluene, 20 g of 9,10-phenanthrenequinone, 34.4 g of m-toluidine, and 39.8 ml of pyridine were added, and the mixture was cooled to 10 ° C. or lower, and then TiC was added.
The l ₄ 54.6 g was added dropwise a solution prepared by dissolving in toluene 196 ml. After completion of the dropping, reaction was carried out at 20 ° C. for 8 hours. After completion of the reaction, 800 ml of water and 200 ml of ethyl acetate were added, and after liquid separation, the organic layer was concentrated under reduced pressure. 200 ml of ethanol was added to the concentrated liquid, and after heating under reflux, the internal temperature was cooled to room temperature and filtered to give a pale yellow powder with a melting point of 123 to 124.
C, N, N '-[di (3-methylphenyl)]-9,1
22.3 g (yield 60.0%) of 0-phenanthrenequinonediimine was obtained. Next, in 180 ml of ethanol, 1.08 g of nickel chloride, N, N '-[di (3-methylphenyl)]-9,10-phenanthrenequinonediimine 8.
After adding 1 g and cooling to 5 ° C. or lower, 4.8 g of NaBH ₄ was added and reacted at 50 ° C. for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, added with 42 ml of water and 23 ml of concentrated hydrochloric acid, made acidic once, made alkaline with 130 ml of aqueous ammonia, and extracted with 63 ml of chloroform. After liquid separation, the chloroform layer was concentrated under reduced pressure and the obtained residue was recrystallized from ethanol to give pale yellow needle crystals, melting point 198-199.
6.3 g (yield 77%) of 9,10-di (3-methylanilino) phenanthrene at 0 ° C was obtained. Next, a mixture of 2.4 g of m-iodotoluene, 0.71 g of potassium carbonate, 3 mg of cuprous chloride and 0.5 g of 9,10-di (3-methylanilino) phenanthrene was added at 190 ° C. under a nitrogen stream at 30 ° C.
Heated for hours. 40 ml of water and 40 ml of chloroform were added to the reaction mixture, and after liquid separation, the chloroform layer was concentrated under reduced pressure and the obtained residue was recrystallized from n-hexane to give compound No. 3 having a melting point of 223 to 224 ° C. as a pale yellow powder. 0.5 g (yield 71%) of 2 was obtained.

[0029]

Example 5 N, N, N ′, N′-tetra (4-methylphenyl) -9,10-diaminophenanthrene [Compound No. 3] Synthesis (Synthesis Method B) To 720 ml of toluene, 36 g of 9,10-phenanthrenequinone, 61.9 g of p-toluidine and 71.6 ml of pyridine were added, and the mixture was cooled to 10 ° C. or lower, and then TiC was added.
The l ₄ 98.3 g was added dropwise a solution prepared by dissolving in toluene 353 mL. After completion of the dropping, reaction was carried out at 20 ° C. for 8 hours. After completion of the reaction, 1200 ml of water and 350 ml of ethyl acetate were added, and after liquid separation, the organic layer was concentrated under reduced pressure. To the concentrated solution was added 360 ml of ethanol, and the mixture was heated under reflux, the internal temperature was cooled to room temperature, and filtered to give a pale yellow powder with a melting point of 203 to 20.
43.2 g (yield 64.2%) of 9,10-di (4-methylanilino) phenanthrene at 5 ° C was obtained. Next, a mixture of 4.3 g of p-iodotoluene, 1.28 g of potassium carbonate, 5 mg of cuprous chloride and 0.9 g of 9,10-di (4-methylanilino) phenanthrene was heated at 190 ° C. for 30 hours under a nitrogen stream. .. 72 ml of water and 72 ml of chloroform were added to the reaction mixture, and after liquid separation, the chloroform layer was concentrated under reduced pressure and the resulting residue was recrystallized from n-hexane to give compound No. 3 having a melting point of 227 to 229 ° C. as a pale yellow powder.
0.9 g (yield 72%) of 3 was obtained.

Table 1 shows the structure and properties of a new type of triarylamine derivative represented by the general formula [1] synthesized by the method of the present invention.

[0031]

[Chemical 13]

[0032]

[Table 1]

[0033]

[Application example]

[0034]

[Application Example 1] 2 parts of a bisazo compound represented by the following structural formula as a charge generating substance and 2 parts of a polyester resin (trade name: Byron 200 manufactured by Toyobo Co., Ltd.) are dissolved in 10 parts of tetrahydrofuran, and pulverized and mixed in a ball mill for 10 hours. Then, the obtained photoconductive composition was applied onto a laminate film of an aluminum foil having a thickness of 5 μm and a polyester film and dried to obtain a charge generation layer having a thickness of about 0.5 μm.
Next, 3 parts of polycarbonate resin (trade name: Panlite K-1300 manufactured by Teijin Ltd.) and tetrahydrofuran 15
Part of the resin solution, the compound No. 1 of Example 1 was used as a charge transport material. 1 part was dissolved in 2 parts, and this solution was applied onto the charge generation layer using an applicator to form a charge transport layer having a thickness of about 15 μm to prepare an electrophotographic photoreceptor having a photosensitive layer composed of two layers. Electrostatic copying paper test equipment (E, manufactured by Kawaguchi Electric Co., Ltd., E
PA-8100 type), 1-5KV corona discharge
After 0 seconds of charging and charging, dark decay was performed for 10 seconds, the surface potential V ₀ (volt) at this time was measured, and then 2854.
K Time tungsten lamp was irradiated with its surface potential until 1/2 of V ₀ which seek (sec), it was determined sensitivity (half decay exposure E1 / 2). The result is V ₀ = -71
0, E _1/2 = 1.8 lux · sec.

[0035]

[Chemical 14]

[0036]

[Application Examples 2 to 4] Compound No. of Application Example 1 A photoreceptor having a two-layer structure was prepared in the same manner as in Application Example 1 except that 1 was replaced with the triarylamine derivative shown in Table 1, and the surface potential V0 by negative charging and half-exposure were performed in the same manner as in Application Example 1. Quantity E1 /
2 was measured. The results are shown in Table-2.

[0037]

[Table 2]

[0038]

INDUSTRIAL APPLICABILITY The novel triarylamine derivative represented by the above general formula [1] according to the present invention has initial characteristics such as chargeability, sensitivity and residual potential as compared with conventional organic photoconductive materials. It is extremely good, and its characteristics are that it does not deteriorate in repeated use with respect to corona discharge and visible light, and that it is particularly excellent in durability, and it fully satisfies the required practical requirements.

Claims (3)

[Claims] 1. A triarylamine derivative represented by the following general formula [1]. [Chemical 1] (In the formula, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group,
It represents a lower alkoxy group or a halogen atom, and R ₁ and R ₂ may be the same or different. ) 2. A halobenzene derivative represented by the following general formula [2]: (In the formula, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group,
It represents a lower alkoxy group or a halogen atom, and R ₁ and R ₂ may be the same or different. X represents a halogen atom. ) 9,10-diaminophenanthrene is reacted with general formula [1] A method for producing a triarylamine derivative represented by: 3. An aniline derivative represented by the following general formula [3]: (In the formula, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group,
It represents a lower alkoxy group or a halogen atom, and R ₁ and R ₂ may be the same or different. ) After reacting with 9,10-phenanthrenequinone to give a diimine derivative represented by the following general formula [4], (In the formula, R ₁ and R ₂ are the same as above.) The compound is derived into a diamine body represented by the following general formula [5]: (In the formula, R ₁ and R ₂ are the same as above.) The reaction is carried out with a halobenzene derivative represented by the following general formula [2]: embedded image (In the formula, R ₁ and R ₂ are the same as above. X represents a halogen atom.) A method for producing a novel triarylamine derivative represented by the general formula [1]. [Chemical 8]