JPS63193152A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To increase the sensitivity of a photosensitive body, to decrease the residual potential thereof and to improve the durability thereof by incorporating a specific trimethylindoline deriv. into an electric charge transfer layer. CONSTITUTION:An electric charge generating layer 3 essentially consisting of an electric charge transfer layer 2 and the charge transfer layer 4 uniformly contg. the N-substd.-2,3,3-trimethylindoline deriv. expressed by the formula are laminated successively on a conductive base. In formula, R denotes a lower alkyl, phenyl; R1 denotes a lower alkyl, phenyl, benzyl; R2 denotes a phenyl. The layer 3 is formed by vacuum deposition of the material 2 or dispersing the material 2 in a binder soln. and coating the soln. on the base. The layer 4 is formed by dissolving the compd. expressed by the formula in a soln. off a binder (e.g.: polycarbonate) and coating the soln. on the layer 3. Then, the photosensitive body having the high sensitivity, the small residual potential and the excellent durability is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an electrophotographic photoreceptor, and more specifically, an electrophotographic photoreceptor comprising a charge generation layer and a charge transport layer provided on a conductive support. The charge transport layer has the following general formula ([) (in the formula, R represents a lower alkyl group or a phenyl group,
R1 is a lower alkyl group, phenyl group or benzyl group, R2 is a phenyl group)
The present invention relates to an alpha photoreceptor characterized by containing a 2,3,3-t'J methylindoline derivative.

[Conventional technology]

In recent years, inorganic photoconductive substances such as selenium and cadmium sulfide are widely known as electrophotographic photosensitive materials, and organic photoconductive substances include yte.
l) Various substances have been proposed including -N-vinylcarbasol and polyvinylanthracene.

Among these, broken-N-vinylcarbazole can be used to form a film by itself, but has the disadvantage of low flexibility and poor durability as an electrophotographic photoreceptor. Therefore, it has been proposed to use a plasticizer to increase flexibility, but while using a plasticizer improves flexibility,
The drawback is that electrophotographic properties such as sensitivity and residual potential are reduced.

On the other hand, in addition to electrophotographic methods that use these materials, methods are gaining popularity in which the two functions of photoconductive materials, namely the generation of charge carriers and the transport of the generated charges, are performed using separate organic compounds. (For example, "Recording Materials Manual," Chapter 2, Photosensitive Materials, published by Trikebbs).

This method is known to yield high sensitivity because a wide range of compounds can be selected that are optimal for the two functions of generating charge carriers and transporting charges. In this method, it is necessary to sequentially stack a compound that generates charges, ie, a charge-generating substance, and a metal compound, ie, charge-generating substance, that transports the generated charges, on the conductive support. In many cases, the compounds used in the charge transport layer are low-molecular organic compounds and do not have film-forming ability. Therefore? Reester resin, vinyl chloride resin, methacrylic resin, ? The film must be formed using a polymeric binder such as recarbonate resin.

In order to rapidly transport the charge carriers generated in the charge generation layer, the charge transport layer must be uniform. Here, the solubility of the charge transport substance in the binder becomes a problem. For those with low solubility, they are dispersed in a binder as silk powder, but in this case it is difficult to obtain a uniform film, and even if dissolved, crystals may precipitate over time. This often results in a significant deterioration of electrophotographic performance.

In addition, when a conventional electrophotographic photoreceptor having a functionally separated type photosensitive layer is repeatedly used in an electrophotographic process, the ability to recover the original charging characteristics decreases, which shortens the life of the photoreceptor. are doing. In other words, if the actual processes of electrophotography, such as charging dark decay, light decay, and cleaning, are repeated many times, there will be some changes in surface charge after charging, a decrease in charge retention ability, a decrease in photosensitivity, and an increase in residual potential. or one or more optical fatigue phenomena occur,
This is a major practical problem because it significantly degrades the performance of electrophotography.

As a result of intensive research to solve the above-mentioned linear problem, the present inventors discovered that tetrahydroquinoline carboxaldehyde enzyme conductor is an excellent charge transport material, and filed a patent application (% patent application). Showa 60-14624
No. 8).

[Problem that the invention seeks to solve]

However, it has been desired to develop a new charge transport material with better physical properties. In other words, it has excellent solubility in polymer binders, high sensitivity, and low residual potential.
Furthermore, there has been a demand for an electrophotographic photoreceptor that exhibits less optical fatigue and excellent durability even when used repeatedly according to an electrophotographic process.

[Means for solving problems]

In order to solve the above problems, the present inventor conducted extensive research focusing on indoline derivatives as charge transport materials, and as a result discovered that a specific indoline derivative satisfies various requirements for electrophotography, and has developed the present invention. It was completed.

That is, the present invention uses N represented by the formula (I), which has good solubility in a polymeric binder and excellent electrophotographic properties.
-Substitution-2,3,3-t! The present invention provides an electrophotographic photoreceptor containing a J methylindoline derivative as a charge generating substance.

The N-substituted-2,3,3-)limethylindoline derivative (I) of the present invention can be prepared according to the reaction formula shown below.
The formyl-substituted product (I) obtained by the Wielsmeier reaction of 3,3-)limethylindoly/(■) is 1,
It is prepared by reaction with 1-substituted hydracine (■).

(If) (I[I)E (IV) (I) Starting material N-substituted-2,3,3-1-limethylindoline (formerly N-lower alkyl-N-phenylhydrazone (formula (V) hydrazone (Vl) by reacting a salt of R=lower alkyl group) or diphenylhydrazone ((■), R=phenyl group) with methyl isozorobyl ketone.
This hydrazone was then passed through acetic acid at high speed to cyclize and form N-
Substituted-3,3-dimethyl-2-methyleneindoline (■
) is synthesized by catalytic hydrogenation using a rhazome catalyst. This reaction formula is abbreviated below.

(V) / (VI) N-substituted-2 represented by the general formula (I) thus obtained
,3,3-) rimetherindoline derivatives exhibit extremely excellent properties as organic photoconductors. In particular, when used as a charge transport material for an electrophotographic photoreceptor, it has excellent bath dissolution properties for polymeric binders, and can provide a photoreceptor with high sensitivity and excellent durability.

Representative examples of the N-substituted-2,3°3-trimethylindoline derivatives represented by the general formula (I) are illustrated below.

The following margin exemplified compounds: Me Me Next, a basic method for producing the electrophotographic photoreceptor of the present invention using the above N-substituted-2,3,3-1 rimetherindoline derivative (I) will be explained. However, of course, the mode of use of the present invention is not limited to this example.

The photoreceptor containing the indoline derivative (I) of the present invention is
On the conductive support 1 shown in FIG. 1, there is provided a photosensitive layer 5 consisting of a charge generation layer 3 mainly composed of a charge generation substance 2 and a charge transport layer 4 uniformly containing an indoline derivative (I). There is. Here, the indoline derivative (I) is used as a charge transport substance, and forms the charge transport layer 4 together with the binder, and the light transmitted through the charge transport layer 4 is transferred to the charge generation substance 2 dispersed in the charge generation layer 3. The charge generating substance 2 generates the charge necessary for light attenuation. The charge transport layer 4 receives this charge injection and transports it. Here, it is a necessary condition that the absorption wavelength regions of the charge generating substance 2 and the indoline derivative (I) do not overlap each other, mainly in the visible region.

This is because in order to efficiently generate charge carriers in the charge generation material 2, it is necessary to transmit light to the surface of the charge generation material. The indoline derivative (I) of the present invention has almost no absorption in the visible region, and when combined with a charge-generating substance that generally absorbs light in the visible region and generates a charge,
One of its characteristics is that it works particularly effectively as a charge transport material.

To produce the photoreceptor shown in FIG. 1, the charge generating substance 2 is vacuum-deposited on the conductive support 1, or fine particles of the charge generating substance 2 are deposited in a suitable solvent in which a binder is dissolved as necessary. After coating and drying the dispersion obtained by dispersing the indoline derivative in It is obtained by coating and drying a solution containing the agent.

Application is performed using conventional means, such as a doctor blade or Maya per.

The thickness of the charge generation layer 3 is 5μ or less, preferably 2μ or less, and the thickness of the charge transport layer 4 is 3 to 50μ, preferably 5μ or less.
~20μ. Further, the metal material (I) of the present invention is contained in the charge transport layer 4 in an amount of 10 to 90% by weight, preferably 30 to 90% by weight.
Weight t% is blended.

4. As the retroactive support 1, a metal plate or metal foil made of aluminum or the like, a plastic film coated with a metal such as aluminum, or paper treated with electrical conductivity is used. As a binder? Lyester resin? Vinyl chloride resin, acrylic resin, methacrylic resin, ? Listyrene resin? Recarbonate resin etc. are used, but among them? Recarbonate resins are preferred.

The charge generating substance 2 may include inorganic materials such as selenium and cadmium sulfide, and CI Pigment Blue 25.
(Color Index Cl21180), CI Pigment Red 41 (CI21200), CI Acid Red 52 (Cl45100), CI Basic Red (
Azo pigments such as CI45210); 7-talocyanine pigments such as CI pigment pull-16 (CI74100); CI Knot Brown 5CI73410), CI
Indigo pigments such as Pat Dye (CI73030);
Perylene pigments such as Argo Scarlet R (manufactured by Bayer AG) and Indance Scarlet R (manufactured by Bayer AG), as well as chlorocyan blue, i.e. 4.4'-
C (3゜3'-dichloro-4,4'-piphenylylene)
bisCazo)]-]bis-3-hydroxy-2-naphthanilide methylsquarium, i.e. 2,4-bis-(2
-methyl-4-dimethylaminophenyl)-1,3-cycloptazoenzoylium-1,3-diolate, hydroxysquarium i.e. 2,4-bis-(2-hydroxy-4-dimethylaminophenyl)-1, Organic pigments such as 3-cycloptazoenzoylium-1,3-diolate are used.

〔Example〕

Next, the present invention will be explained in detail using synthesis examples and examples.

Synthesis Example-1 N, 3.3-)dimethyl-2-methyleneindoline (
(■) in the formula, R=methyl) 282 was added to inzologyl alcohol 100-, and hydrogenation was performed at room temperature using 5% Pd-C0152 as a catalyst (initial pressure 30 o/-). Distill to obtain the target compound 26.2 with a boiling point of 85°C/4as Hy.
F (theoretical yield 92.5%) was obtained. The infrared absorption (IR) spectrum (neat) of this product is shown in FIG. Also, the NMR spectrum of 400MH2 (CDC
l3) is the following passage.

δI)pm: 1.01 (3H, s), 1.18 (3
H, d, J=6.6H2), 1.28(3H,S)
, 2.70 (3H, S), '2. ．． 87 (IH, q, J
= 6.6Hz), 6.51 (IH.

d, J=7.8Hz), 6.72 (IH, dd
, J=7.4°7.7H1), 7.02 (IH,
d, J=7.7Hz), 7.09(IH, dd,
J=7.4, 7.8Hz) Synthesis Example-2 Dimethyl formaldehyde (hereinafter referred to as DMF) 14.
A Guillsmeyer reagent was prepared by adding 30.7 t of phosphorus oxychloride dropwise to 100 ml of 6F dichloroethane at 5 to 10°C. 24.5 N of P, 2, 3゜3
50 ml of a dichloroethane solution of -tetramethylindoline (2a) was added dropwise at 10 to 20°C, and the mixture was reacted at 50°C for 4 hours. Thereafter, a water bath solution prepared by bathing 50 tons of sodium acetate in 300 μm of water was added, and the mixture was stirred at 55° C. for 1 hour for separate water decomposition. The oil was separated, washed with water, and then distilled to obtain the target compound 23 with a boiling point of 142°C/1,5 txxHy.
．． 55' (theoretical yield 82.7%) was obtained. I of this
The R spectrum (neat) is shown in FIG. Also, the NMR spectrum of 400MH2 (CDCl3
) is the following p.

δI)pm: 1.07 (3H,s), 1.19 (
3H, d, J=6.6Hz), 1.30(3H,s
), 2.82 (3H, s), 3.22 (IH, q, J=
6.6Hz), 6.43 (IH, d, J=8, IHz)
, 7.53 (I H, d, J=1.5Hz),
7.57 (IH, dd, J=1.7, 8.1Hz), 1
0.00flH.

S) Synthesis Example-3 Synthesis of Razon (Exemplary Compound-1) Add 1.62 pyricine to 42 N,2,3,3-tetramethyl-5-formylindoline, 4.5 t of zonenylhydrazone hydrochloride, and 20 yrl of ethanol. After stirring under reflux for 2 hours, the mixture was cooled to room temperature. The formed crystals were filtered, and the crystals were soaked in benzene and passed through silica gel chromatography to separate a yellow band. This was concentrated and recrystallized from ethanol to give a crystal with a melting point of 162-3°C.
．． OS' (theoretical yield 68.8%) was obtained. The IR spectrum (KBr) of this product is shown in FIG. Also, the 400 MHz NMR spectrum (CDC2
3) is the following υ.

δppm: 1.04 (3H,s), 1.18 (3
H, d, J=6.5Hz), L 31 (3H, s
), 2-71 (3H+s), 2.94 (IH
, Q, J=6.5Hz), 6.42(IH,d,
J=8.1Hz), 7.13~7.24 (8H,
rn), 7.37-7.42 (5H, m) Synthesis Example-4 Synthesis of monocargoaldehyde=N'-methyl-N'-phenylhydrazone (Exemplary Compound-2) N,2,3.3-tetra 2.03t of methyl-5-formylindoline, 1,22F of phenylmethylhydrazone and 20m of ethanol
0.12% of acetic acid was added, and the mixture was stirred under reflux for 4 hours. Concentration and purification were performed in the same manner as in Synthesis Example 3 to obtain crystals of 1.82 F with a melting point of 86-7°C (theoretical yield 56.0%).
) was obtained.

The IR spectrum (KBr) of this product is shown in FIG. Also, the NMR spectrum of this product at 400 MH2 (
CDC45) has the following policy.

δppm: 1.06 (3H, s), 1.19 (3H,
d, J~6.5Hz), 1.33(3H,s),
2.73 (3H, s), 2.95 (IH, q, J=6
．． 5Hz), 3.38 (3H, s), 6, 48 (I
H, d, J ~8.0 Hz), 6.86~
6.90 (I H, m), 7.29-7.37 (
5H, m), 7.48-7.51 (2H, m) Synthesis Example-5 ((■) In the formula, R = inzolovir) Disperse 50% NaH9,6SJ in dry benzene 80- A solution of 19.4 t of phenylhydrazone and 20-penzea was added thereto over 15 minutes, and then gradually heated to 60°C. Hydrogen gas was generated, and the gas generation stopped after 1 hour of reaction.

To this, inzolovir bromide 27f was added dropwise at 60° C. over 20 minutes, and the mixture was refluxed for 3 hours. After that, methanol was added to decompose it, and then it was poured into water.

After extraction twice with benzene, the benzene layer was washed with water, dried with anhydrous soda carbonate, and distilled under reduced pressure to obtain a boiling point of 126-128℃/
20 yHy of the target compound 23.6 S' (theoretical yield 87.4%) was obtained. Purity was 93.4%.

Synthesis Example-6 A piece of Fe (No. 3) in 500 ml of liquid ammonia
-Added 9H20. After adding sodium 6.92 in small portions, phenylhydrazone 272 was added over 10 minutes. After 1 hour, isopropylbromide 40.6.2
was added dropwise over a period of 40 minutes. After 2 hours, dry ice
The acetone bath was removed and left as it was. The next day, Ether 100-
The ether layer was washed with water, dried over anhydrous sodium carbonate, and then distilled under reduced pressure to obtain the target compound 32.21 (theoretical) with a boiling point of 123-126°C/20 mHy. A yield of 85.9%) was obtained. Purity was 98%.

Synthesis Example - 100% of isopropyl alcohol was added to 35.5% of physopropyl methyl ketone and 319% of N-phenyl-N-inzolobylhydrazone, and the mixture was stirred under reflux for 4 hours. The obtained oil is rectified under reduced pressure to a boiling point of 98-100℃/
5 xuaHy target compound 40.7f (theoretical yield 9
0.3%) was obtained.

Synthesis Example-8 N-phenyl-N-isopropyl hydrazone (32.29 g) of N-isopropyl-2-methylene-3,3-diisozorobyl methyl ketone was refluxed in 300 me of acetic acid for 1 hour. Acetic acid was distilled off under reduced pressure, and an aqueous solution of caustic soda was added to the residue, followed by extraction twice with benzene. After washing the benzene layer with water and drying with magnesium sulfate, this oil was distilled under reduced pressure to obtain the target compound 24.22 (theoretical yield: 70.7%) with a boiling point of 102-103°C/5 wsHy. The IR spectrum (neat) of this product is shown in FIG. Also, the 400 MHz NMR spectrum (
CDCl2) is as follows.

δppm: 1.32 (6H, s), 1.43 (3H
, d , J = 7.1 Hz), 3.85 (IH, s),
3.94 (IH, s), 4.14 (IH, m), 6-6
9~6,75 (2H+m), 705~7,09
(2H, m) Synthesis Example-9 Synthesis of 2-11 2-2-11-2-2-11-2-2-2-11-2-2-ammonium water/indoline ((■) in the formula, R = isozorobyl) Synthesis example-9 N-inpropyl -2-methylene-a, A-y methylindoline 10ft-isozorobyl alcohol 50
-, 0.5 t of 5% Pd-C catalyst was added, and the mixture was stirred overnight at room temperature at an initial pressure of 3 Q Kg/cm"% to perform hydrogenation. The catalyst was filtered off, and the oil was distilled under reduced pressure. boiling point 10
9.2 f of the target compound at 2°C/4 Hf (theoretical yield 9
1%). IR spectrum (neat) of this thing
is shown in Figure 7. Also this 400MH2 NM
The R spectrum (CDCts) is as follows.

δppm: L 05 (3H+s), 1-1
5 (3Ht d + J ~6.5 Hz), 1.
21 (3H, s), λ22 (3H, d, J
~6.6Hz), 1.30 (3H, d, J=7.0Hz
), 3.27 (IH, q.

J=6.5Hz), 3.67 (IH, septet, J=
6.9 Hz), 6.52 (LH, d, J = 7
．． 9Hz), 6.62 (IH.

ddwJ=7.3-7.4Hz), 6.97(IH, d
, J=7.3Hz), 7.01 (IH, dd, J=7.
8,7.3Hz) Synthesis Example-10 N-isopropyl-2,3,3-trimethyl-DMF7
．． 3? A Guillsmeyer reagent was prepared from 15.4 F of phosphorus oxychloride, and 100 ml of 1°2-dichloroethane, and 8.12 t of N-inpropyl-2,3,3=trimethylindoline was reacted with the mixture to obtain Synthesis Example 2. An oily substance having a temperature of 8.78 F was obtained in the same manner. Bath temperature 130℃/1
mHy, the IR spectrum (nea t ) of this product is shown in FIG. Also this 400 MHz NM
The R spectrum (CDC23) is as follows.

δri I) m: 1.16 (3H, d, J = 6.5Hz),
1.17 (3H, s), 1.22 (3H, s), 1.3
1 (3H, d, J=6.9Hz), 1.37 (3
H, d, J = 6.9 Hz), 3.53 (IH, q.

J=6.5Hz), 3.81 (IH, septet, J=6.
9Hz), 6.45 (I H, d, J = 8.2
Hz), 7.50 (IH, d.

J=1.4H2), 7.52 (LH, dd, J=
1.6, 8.2Hz), 9.65 (I H+
s) Synthesis Example-11 Synthesis of N-isozorobyl-2,3,3-)dimethylindoline-5-cargoaldehyde N', N'-diphenylhydrazone (Exemplary Compound-5) N-isopropyl-2,3,3 -trimethyl-5-formylindoline 1
．． 572, diphenylhydrazone hydrochloride 1.5F, and ethanol 10- were added 0.59 ft of bilicin and refluxed for 2 hours. Thereafter, it was allowed to cool to room temperature, the formed crystals were filtered out, and after the same procedure as in Synthesis Example 3, they were recrystallized from ethanol to yield 1.562 crystals with a melting point of 119-120°C (theoretical yield: 57.8 %) was obtained. The IR/l and vector (KBr) of this product are shown in FIG. 400 of this again
The NMR spectrum of MH2 (CDCl2) is as follows.

δppm: 1.11 (3H, s), 1.15 (3H
, d, J=6.5Hz), 1゜24 (3H, d,
J=6.9Hz), 1.25 (3H, s), 1.3
0 (3H, d, J=6.9Hz), 3.34 (
IH, m), 3.70 (IH, m), 6.42 (LH,
m), 7.12-7.19 (8H, m), 7.37-7
．． 41 (5H, m) Synthesis Example-12 Synthesis of N-isozorobyl-2,3,3-trimethylindoline-5-carbaldehyde=N'-methyl-N'-phenylhydrazone (exemplary compound N-isopropyl-2, 3,3-trimethyl-5-formylindoline 2
．． 1.22 t of 03F,72;methylhydrazone was added to 30 m/ml of ethanol, 0.12 t of acetic acid was added, and the mixture was stirred under reflux for 4 hours.

After concentration, it was treated in the same manner as in Synthesis Example 3 and recrystallized twice from ethanol to give crystals 1 and 22 F with a melting point of 77-8°C.
(Theoretical yield: 55.8%). The IR spectrum (xBr) of this product is shown in FIG.

Also, the NMR spectrum of this product at 400 MH2 (c
Dct, ) is as follows.

δppm: 1.12 (3H, s), 1.16 (3H,
d, J=6.5Hz), 1.26(3H, d, J=
6.9Hz), 1.27 (31H, s), 1.32
(3H, d, J=6.9Hz), 3.34-3.3
7 (4H, m), 3.68-3.74 (IH, m)
, 6.48 (IH.

d, J=8.2Hz), 6.85-6.88 (I
H, m), 7.23-7.36 (5H, m), 7.44
(IH, d, J=1.5Hz), 7.50 (IH,
s) Synthesis Example-13 N-phenyl-2-methylene-3,3-zomethylene N,N-diphenylhydrazone hydrochloride 55. IS'
, 22 parts of methyl isozorobyl ketone, and 20 parts of bilysin were added to 300 njl of benzene, stirred under reflux, and azeotropically dehydrated. Production of 4 ml of water was observed in 5 hours. Insoluble matter was removed by decantation and distilled under reduced pressure to a boiling point of 145.
An oil content of 43.19 at ~150°C/3 puHy was obtained.

This oil was added to 200% acetic acid and refluxed for 5 hours. After acetic acid was distilled off under reduced pressure, the mixture was neutralized with an aqueous solution of caustic soda and extracted with benzene. The benzene layer is washed with water and distilled to a boiling point of 1
25-130℃/1ffiJHf crude oil 33? I got it.

Gas chromatography analysis showed 2 peaks, the main peak (78.3%) was the target compound, and the remaining 15%
．． 3% was the side reactant diphenylamine. The target compound 15.1 was generated using silica gel chromatography.
(Theoretical yield: 25.4%). The IR spectrum (neat) of this product is shown in FIG. The 400 MH2 NMR spectrum (CDCt3) of this product is as follows.

δI)I)m: 1.45 (6H, s), 3.87 (
IH, s), 3.95 (L H+ s), 6-47
(I H-d + J = z8 Hz), 6-81
(I H+ d d , J = 7.4 + 76 H
z), 703 (IH, dd, J=7.4, 7.8H
z), 7.16 (IH.

d, J''7.6 Hz), 7.32-7.3
8 (3H9m), 7.46-7.50 (2H,m) Synthesis Example-14 Add 8,6t of N-722-2-methylene-3,3-dimethylindoline to 50ml of methanol, 5 %P
Add 0.52 of d-C catalyst, 200#l/! was placed in an autoclave. Hydrogenation was carried out at an initial pressure of 30 K4/cm 2 and room temperature for 20 hours. The catalyst was filtered off to obtain the target compound 8.
53 f was obtained.

Synthesis Example-15 N-phenyl-2,3,3-trimethyl-5-N-7 dimolar 2,3,3-toIJ methylindoline 8.
4t, DMF 10t, phosphorus oxychloride 15.3f,
It was reacted with Vilsmeier's sample prepared from 1,2-dichloroethane, purified by silica gel column chromatography, and
The target compound 6.5f was obtained. The IR spectrum (neat) of this product is shown in FIG. 40 of this again
The NMR spectrum (CDCts) at 0 MHz is as follows.

δpI)m: 1.16 (3H,d, J=6.5Hz
), 1.21 (3H, s), 1.40 (3H, s),
2.99 (IH, Q, J = 6.5Hz), 6.63 (I
H, d, J = 8.2Hz), 7.21-7.26 (3H
, m), 7.41 = 7.45 (2H, m), 7.50 (
IH, dd, J = 1.6, 8.2Hz), 7.64 (I
H.

d, J=1.6Hz) Synthesis Example-16 Synthesis of phosphorus-5-carbaldehydemethylphenylhydrazine (Exemplary Compound-9) N-phenyl-2,3,3-trimethyl-5-formylindoline 1.4M, N- In addition to 0.69 P'i of phenyl-N-methylhydrazone and 20 - of ethanol, 3 drops of acetic acid were added, and the mixture was stirred under reflux for 3 hours.

Thereafter, the mixture was cooled to 5° C., and the formed crystals were filtered off.

This was recrystallized from acetonitrile to obtain 1.74 tons of crystals (theoretical yield: 71.4%) with a melting point of 131°C.

The IR spectrum (KBr) of this product is shown in FIG. The 400 MH2 NMR spectrum (CDCt, ) of this product is as follows.

δppm: 1.18 (3H, d, J = 6.5I
(z), 1.22 (3H, s), 1.39 (3H, S
), 3.37 (3H, s), 3.86 (IH, q, J=
6.5Hz), 6.69 (IH, d, J=8.2Hz)
, 6.91-6.96 (IH, m), 7.14-7.1
9 (IH, m), 7.23-7.40 (9H, m), 7
．． 50 (LH, s), 7.56 (LH, d, J = 1.6
Hz) Synthesis Example-17 Synthesis of Nylhydrazone (Exemplary Compound-8) N-phenyl-2,3,3-)rifthyl-5-formylindoline 1
．． Add 1.33 t of 59F, zophenylhydrazone hydrochloride to 20 mg of ethanol, add 0.82 t of pyricin,
The mixture was stirred under reflux for 3 hours.

Thereafter, the mixture was cooled and the formed crystals were filtered to obtain 2.372 crystals. This was passed through a short silica gel column and then recrystallized from ethanol-ethyl acetate, with a melting point of 16.
Crystals at 8°C2. ．． 27f (theoretical yield 87, 8%) was obtained. The IR spectrum (KBr) of this product is shown in FIG. The 400 MHz NMR spectrum (CDCl3) of this product is as follows.

δppm: 1.16 (3H, d, J=6.5Hz
), 1.20 (3H, s), 1.37 (3H, S)
, 3.86 (LH, bs), 6.66 (I1 (, d,
J=8.2Hz), 7.12~7.24 (I1H
.

m), 7.35-7.42 (6H, m), 7.50 (I
H,d.

J = 1.7 Hz) Synthesis Example-18 Phosphorus-5-carbaldehyde-N'-phenyl-N'-
Synthesis of benzylhydrazone (exemplary compound - N-phenyl-2,3,3-tri,methyl-5-formylindoline 2.0?, N-phenyl-N-pencylhydrazone hydrochloride 1.82 g in 40 g of ethanol) In addition, bilicin 1.0
2 and treated in the same manner as in Synthesis Example 17 to obtain a melting point of 151.
C. crystals 2,42 (theoretical yield 71.5%) were obtained. The IR spectrum (KBr) of this product is shown in FIG.

Also, the 400 MH2 NMR spectrum (C
DCts) is as follows.

δppm: 1.16 (3H, d, J=6.5Hz), 1
．． 20 (3H, s), 1.37 (3H, s), 3.84
(IH, Q, J=6.5Hz), 5.15 (2H
, s), 6.66 (LH, d, J=8.2Hz)
, 6, 87-6.91 (I H, m), 7.07
~7.11 (LH.

m), 7.15-7.37 (I5H, m), 7.50 (
IH.

d, J=1.6Hz) Example 1 Chlorocyan blue (CBD) or phthalocyanine (Pc) as a charge generating substance 0.2? of,? Licargenate resin (Mitsubishi Gas Chemical Co., Ltd. “Nipilon E”)
-2000J) dichloroethane solution containing 5 g
After adding 20 m of dichloroethane, the mixture was pulverized to less than 1 μm using a vibration mill to prepare a dispersion of the charge carrier-generating pigment.

This was applied onto a polyethylene terephthalate (PET) film on which aluminum was vapor-deposited using a Mayer bar and dried at 45° C. to form a charge carrier generation layer with a thickness of about 1 μm. On this charge carrier generation layer, a charge transport layer coating solution prepared by dissolving 5% by weight of the charge generating substance of the present invention in a dichloroethane solution of 5% by weight of polycarbonate (Nipilon E-2000) was applied using a doctor blade. ,
Apply to a dry film thickness of approximately 15μ, and heat at 45-60°C.
It was dried for 4 hours. The thus obtained electrophotographic photoreceptor films (Products 1 to 14 of the present invention) were subjected to an electrostatic copying paper tester (
Fluctuations in surface potential were measured using an SP-428 model (Kawaguchi Seisakusho #).

The photoreceptor was charged by -6KV corona discharge for 5 seconds, and the surface potential was V. (Unit - Volt), hold it for 5 seconds in a dark place, and then irradiate it with light with an illuminance of 5 lux using a tungsten lamp to obtain the amount of light necessary to attenuate the surface potential by 1/2 and 1/6. That is, the half-reduced exposure iE1/2 (lux/second) and E1/6 (lux/second) and the surface UfJ potential VR20 (volt) after irradiation with light with an illuminance of 5 lux for 20 seconds were determined. The results are shown in Table-1. In addition, the same electronic photoreceptor film was irradiated with 10,000 lux light for 3 seconds, and after static electricity was removed,
Table 2 shows the measured values obtained when the above measurement was repeated 200 times.

Margin Table-1 Table-2 [Effects of the Invention] The N-substituted-2, 3, 3-) IJ methyl indotri-spun conductor of the present invention has properties useful as a material for electrophotographic photoreceptors, such as It has a strong electrostatic charge retention ability.

However, the electrophotographic photoreceptor using the compound of the present invention has the highest demands in the field of electrophotographic processes, such as high sensitivity, low residual potential, little optical fatigue even after repeated use, and excellent durability. It has the following characteristics and is industrially advantageous.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing the structure of the electrophotographic photoreceptor of the present invention. Figures 2 and 3 show N,2,3.3-tetramethylindoline and N,2,3.3-tetramethyl-
It is a drawing showing the IR spectrum of 5-formylindoline. FIG. 4 and FIG. 5 are drawings showing IR spectra of Exemplified Compound-1 and Exemplified Compound-2, respectively. Figures 6, 7 and 8 show N-isozologyl-2-methylene-3,3-dimethylindoline, N-
1 is a drawing showing IR spectra of isopropyl-2,3,3-)dimethylindoline and N-inzologyl-2,3°3-trimethyl-5-formylindoline. FIG. 9 and FIG. 10 are drawings showing the IR spectra of Exemplified Compound-5 and Exemplified Compound-6, respectively. Figures 11 and 12 show N-phenyl-2-
1 is a drawing showing IR spectra of methylene-3,3-dimethylindoline and N-phenyl-2,3,3-trimethyl-5-formylindoline. FIG. 13, FIG. 14, and FIG. 15 are drawings showing the IR spectra of Exemplified Compound-9, Exemplified Compound-8, and Exemplified Compound-10, respectively. Figure 1 above

Claims (1)

[Claims] 1. In an electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are provided on a conductive support, the charge transport layer has the following general formula (I), ▲ mathematical formula, chemical formula, table, etc. ▼(I) (In the formula, R represents a lower alkyl group or a phenyl group,
An electrophotographic photoreceptor characterized by containing an N-substituted-2,3,3-trimethylindoline derivative represented by R_1 represents a lower alkyl group, phenyl group, or benzyl group, and R_2 represents a phenyl group.