JPH0862871A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE: To make a photoreceptor usable in a copying machine, a printer, etc., and to prevent the rise of residual potential at the time of repeating electrification, exposure, and discharge by incorporating a specified triphenylamine deriv. CONSTITUTION: A triphenylamine deriv. represented by formula I is incorporated. In the formula I, Ar1 is a group represented by formula II the bonding position is not limited, each of R1 and R2 is an alkyl or alkoxy, m is an integer of 1-5, n is an integer of 0-5 and Ar2 is an optionally substd. phenyl, an optionally substd. condensed polycyclic residue or an optionally substd. hetero ring. In the formula II,. each of R3 -R6 is an optionally substd. alkyl, aralkyl, aryl or halogen, each of p and q is an integer of 0-4, each of r and s is an integer of 0-3 and X is stad. or unstatd. 5- to 7-membered hyrocarbon ring or a hetero ring. The resultant photoreceptor has high sensitivity and durability and undergoes a slight change in potential by electrification. Even when the photoreceptor is incorporated into a high-speed copying mechine, a high-speed printer, etc., and is repeatedly used, residual potential can be reduced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrylamine compound and an electrophotographic photosensitive member, and more particularly to a styryl suitable as the carrier transporting material in the electrophotographic photosensitive member having a photosensitive layer containing a carrier generating substance and a carrier transporting substance. The present invention relates to a compound and an electrophotographic photoreceptor.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic photoreceptor, a photoreceptor containing an inorganic photoconductor such as selenium, zinc oxide, cadmium sulfide or silicon as a main component has been widely known. However, these are not always satisfactory in properties such as thermal stability and durability, and have problems in production and handling.

On the other hand, a photoreceptor having a photosensitive layer containing an organic photoconductive compound as a main component is relatively easy to manufacture, inexpensive, easy to handle, and generally a selenium photoreceptor. The thermal stability is superior. As such an organic photoconductor compound, poly-N-vinylcarbazole is well known, and a charge transfer complex formed from this and a Lewis acid such as 2,4,7-trinitro-9-fluorenone is a main component. A photoconductor having a photosensitive layer is already put into practical use.

On the other hand, there is known a photoconductor having a laminated type or single layer type function-separated type photosensitive layer in which the carrier generating function and the carrier transporting function of the photoconductor are shared by separate substances. For example, a photoconductor having a photosensitive layer composed of a carrier generation layer composed of an amorphous selenium thin layer and a carrier transport layer containing poly-N-vinylcarbazole as a main component has already been put into practical use.

However, poly-N-vinylcarbazole is
It lacks flexibility, its coating film is hard and brittle, and it is prone to cracking and film peeling, and the photoreceptor using this film has poor durability. Therefore, if a plasticizer is added to remedy this drawback, the residual potential becomes large in the electrophotographic process, and the residual potential is accumulated with repeated use, and fogging is gradually increased and the copy image is damaged.

Since a low molecular weight organic photoconductive compound generally has no film forming ability, it is used in combination with an appropriate binder, and the physical properties or photosensitivity of the film are selected by selecting the kind and composition ratio of the binder. However, the types of organic photoconductive compounds having high compatibility with the binder are limited. Actually, there are few kinds of binders that can be used for the construction of the photosensitive layer of the electrophotographic photosensitive member.

For example, as described in US Pat. No. 3,189,447
2,5-Bis (p-diethylaminophenyl) -1,3,4-oxadiazole has low compatibility with binders commonly used as the material of the photosensitive layer of an electrophotographic photoreceptor, such as polyester and polycarbonate. That is, when the photosensitive layer is formed by mixing in a ratio necessary for adjusting the electrophotographic characteristics, crystals of oxadiazole start to precipitate at a temperature of 50 ° C. or higher, and the electrophotographic characteristics such as charge retention and sensitivity. Has the drawback that

On the other hand, the diarylalkane derivative described in US Pat. No. 3,820,989 has few compatibility problems with the binder, but has little stability to light, and the repetitive transfer type electrophotography in which this is repeatedly charged and exposed. When used for the photoconductor of No. 1, there is a drawback that the sensitivity of this photosensitive layer is gradually lowered.

US Pat. No. 3,274,000, Japanese Patent Publication No. 47-36
No. 428 describes different types of phenothiazine derivatives, but they all have the drawbacks of low photosensitivity and low stability during repeated use.

Further, JP-A-58-65440 and JP-A-58-190953
The stilbene compounds described in JP-A No. 63-149652 and JP-A No. 63-149652 have relatively good charge retention and sensitivity, but they are not satisfactory in durability against repeated use.

In particular, the following two problems have been problems.

1) In a high-speed copying machine having a high linear velocity, the cycle of charging, exposure, and static elimination becomes short, so that the residual potential greatly increases during repeated copying.

2) In the case of a reversal development printer, it has been found that the exposure potential (VL) rises at a low temperature, and the charging potential (VH) drops with repeated use.

As described above, the present situation is that no carrier transporting substance having practically satisfactory characteristics for producing an electrophotographic photosensitive member has been found yet.

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a compound and an electrophotographic photoreceptor which are suitable as a carrier transporting material for a highly sensitive and durable photoreceptor which can be used in a copying machine, a printer and the like. It is in.

Further, other objects of the present invention are as follows (1) and (2).

(1) In a copying machine with a high linear velocity, charging
To provide a compound suitable for a carrier generating substance for a photoconductor and an electrophotographic photoconductor that do not increase in residual potential even after repeated exposure and charge elimination.

(2) When incorporated into a reversal development printer and used repeatedly, the exposure potential (VL) is low even at repeated use.
To provide a compound and an electrophotographic photosensitive member suitable as a carrier generating substance for a photosensitive member, in which the charging potential (VH) does not decrease with repeated use.

[0019]

The above-mentioned object of the present invention is to realize the above-mentioned general formulas [A], [B],
It is achieved by an electrophotographic photoreceptor containing a compound represented by [C] or [D].

(A-1) An electrophotographic photoreceptor containing a triphenylamine derivative represented by the following general formula [A].

[0021]

[Chemical 17]

[In the formula, Ar ₁ represents the following group. The bonding position is not limited.

[0023]

[Chemical 18]

R ₁ and R ₂ represent alkyl and alkoxy.

M represents an integer of 1 to 5 and n represents an integer of 0 to 5.

R _{3 to} R ₆ each represent substituted or unsubstituted alkyl, aralkyl, aryl or halogen.

P and q represent an order of 0 to 4, r and s represent an integer of 0 to 3.

Ar ₂ is substituted / unsubstituted phenyl, substituted / unsubstituted
It represents an unsubstituted fused polycyclic residue and a substituted / unsubstituted heterocycle.

X represents a saturated or unsaturated 5- to 7-membered hydrocarbon ring or heterocycle. (A-2) The compound represented by the general formula [A] is a compound represented by the following general formula [a] (A
The electrophotographic photosensitive member according to -1).

[0030]

[Chemical 19]

[In the formula, Ar ₁ represents the following group.

[0032]

Embedded image

R ₁ and R ₂ represent CH ₃ and C ₂ H ₅ , and R ₃ and R ₄
Represents alkyl, aralkyl and aryl.

M is an integer of 1 to 3, n is an integer of 0 to 3, p is an integer of 0 to 3, and q is an integer of 0 to 1.

Y represents O and S.

Ar ₂ represents substituted / unsubstituted phenyl and naphthyl. (B-1) An electrophotographic photoreceptor containing a phenylamine derivative represented by the following general formula [B].

[0037]

[Chemical 21]

[In the formula, Ar ₁ represents the following group. The bonding position is not limited.

[0039]

[Chemical formula 22]

R _{1 to} R ₄ each represent substituted or unsubstituted alkyl, aralkyl, aryl or halogen.

M, n, r and s represent integers of 0 to 3.

Ar ₂ represents substituted or unsubstituted phenyl, condensed polycycle, or heterocycle.

Ar ₃ represents a substituted / unsubstituted condensed polycycle.

Ar ₄ represents substituted or unsubstituted phenyl or condensed polycycle.

X represents a saturated or unsaturated 5- to 7-membered hydrocarbon ring or heterocycle. (B-2) The compound represented by the general formula [B] is a compound represented by the following general formula [b] (B
The electrophotographic photosensitive member according to -1).

[0046]

[Chemical formula 23]

[In the formula, Ar ₁ represents the following group. R ₀ represents alkyl or aralkyl, and p represents an integer of 0-4. ]

[0048]

[Chemical formula 24]

R ₁ and R ₂ represent an alkyl, aralkyl or aryl group.

M represents an integer of 0 to 3, and n represents an integer of 0 to 1.

Y represents O and S.

Ar ₂ represents substituted or unsubstituted phenyl.

Ar ₄ represents substituted or unsubstituted phenyl or naphthyl.

Y represents O and S.

(C-1) An electrophotographic photoreceptor containing an amine derivative represented by the following general formula [C].

[0056]

[Chemical 25]

[In the formula, Ar ₁ represents the following group. The bonding position is not limited.

[0058]

[Chemical formula 26]

R _{1 to} R ₄ each represent substituted or unsubstituted alkyl, aralkyl, aryl or halogen.

P, q, r and s represent integers of 0-3.

Ar ₂ is a substituted / unsubstituted phenyl,
Represents a fused polycycle or heterocycle.

Ar ₃ represents a substituted / unsubstituted fused polycycle.

Ar ₄ and Ar ₅ represent substituted / unsubstituted phenyl and condensed polycycle.

X represents a saturated or unsaturated 5- to 7-membered hydrocarbon ring or heterocycle. (C-2) The compound represented by the general formula [C] is a compound represented by the following general formula [c] (C
The electrophotographic photosensitive member according to -1).

[0065]

[Chemical 27]

[In the formula, Ar ₁ represents the following group.

[0067]

[Chemical 28]

Ar ₂ represents a substituted or unsubstituted phenyl, and A
r ₄ and Ar ₅ represent substituted or unsubstituted phenyl and condensed polycycle.

R ₃ and R ₄ represent substituted / unsubstituted alkyl, aralkyl and aryl.

P and q represent an integer of 0 to 3.

Y represents O and S. (D-1) An electrophotographic photoreceptor containing an amine derivative represented by the following general formula [D].

[0072]

[Chemical 29]

[In the formula, Ar ₁ represents the following group. The bonding position is not limited.

[0074]

[Chemical 30]

R ₁ represents alkyl or alkoxy.

M represents an integer of 1 to 4.

R _{3 to} R ₆ each represent substituted or unsubstituted alkyl, aralkyl, aryl or halogen.

P and q are integers of 0 to 4, and r and s are integers of 0 to 3.

Ar ₂ represents a substituted / unsubstituted phenyl, a substituted / unsubstituted fused polycyclic residue, or a substituted / unsubstituted heterocycle.

Ar ₃ and Ar ₄ represent substituted / unsubstituted phenyl and substituted / unsubstituted fused polycyclic residue.

X represents a saturated or unsaturated 5- to 7-membered hydrocarbon ring or heterocycle. (D-2) The compound represented by the general formula [D] is a compound represented by the following general formula [d] (D
The electrophotographic photosensitive member according to -1).

[0082]

[Chemical 31]

[In the formula, Ar ₁ represents the following groups.

[0084]

[Chemical 32]

R ₁ represents alkyl.

Ar ₂ , Ar ₃ and Ar ₄ are the same as in the general formula [D].

M is an integer of 1 to 4, p is an integer of 0 to 3, q
Represents an integer of 0 to 3.

R ₃ and R ₄ represent alkyl, aralkyl and aryl.

Y represents O and S. The compounds of the above general formulas [A] to [D] of the present invention are represented by the following A
It has the characteristics of C to C and is suitable as a carrier transport material for an electrophotographic photoreceptor.

(A). The sensitivity and durability are high, and the fluctuation of the charging potential is small, so when incorporated in a copying machine or printer and used repeatedly, there are no image defects or image defects such as white spots, black spots, fog, and density loss. Images can be obtained.

(B). Moreover, when incorporated in a high-speed copying machine or printer and repeatedly used, the residual potential also becomes small, so that a good image without image defects or image defects can be obtained.

(C). Since it is an amine compound, it is easy to synthesize.

[A] Specific Compound N of the General Formula [A]
o.A-1 to A-25 are exemplified below.

(Exemplified Compound)

[0095]

[Chemical 33]

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

Next, synthetic examples of the compound of the general formula [A] will be described.

(Synthesis Example: Synthesis of Exemplified Compound A-1)

[0102]

[Chemical 38]

Synthetic Scheme 1 An outline of the synthesis of Exemplified Compound A-1 is shown in Synthetic Scheme 1.

[Synthesis to Intermediate 5] Using 4-biphenylcarboxylic acid chloride 1 (manufactured by Aldrich) as a starting material, a known method (Beil 5, II, 618, JP-A-5-11250).
8 and the like), and intermediate 5 was synthesized. The total yield from 1 to 5 was 51%. The melting point was 55-56 ° C.

[Synthesis up to Intermediate 9] Aniline 6 (manufactured by Kanto Chemical Co., Inc.) and p-iodotoluene 7 (manufactured by Tokyo Kasei Co.) were used as starting materials, and Intermediate 9 was prepared according to a known method (Japanese Patent Publication No. 4-66023). Was synthesized. The total yield from 6 to 9 is
It was 81%. The melting point was 102-103 ° C.

[Synthesis of Exemplified Compound A-1] Potassium t-butoxide (manufactured by Kanto Chemical Co., Inc.) 5.
4 g (0.048 mol) and 50 ml of N, N-dimethylformamide (manufactured by Kanto Kagaku Co., Ltd.) were added, and stirring was started under a nitrogen stream.

Next, 14.4 g (0.038 mol) of intermediate 5 and 10.0 g (0.032 mol) of intermediate 9 were placed in a 100 ml beaker,
Add 50 ml of N, N-dimethylformamide (Kanto Chemical Co., Inc.) and dissolve. Add dropwise to this solution and the solution in the 200 ml four-headed flask described above. At this time, keep the internal temperature at 20 to 30 ° C. After dropping, the mixture is stirred at room temperature for 2 hours.

For the post-treatment, 400 ml of methanol was poured into the reaction solution under ice cooling to precipitate crystals. The crystals are suction filtered and dried. The crude crystals were subjected to a 1 kg SiO ₂ column chromatogram, and toluene-n-hexane = 1
The / 10 eluate is crystallized from acetone-methanol,
12.6 g (0.024 mol) of the target Exemplified Compound A-1,
Obtained in 75% yield. The melting point was 120-122 ° C.

The structure is FAB-MS spectrum, M ⁺
And the elemental analysis values are in good agreement with the calculated values, it was confirmed that the compound was Exemplified Compound A-1.

[0110] [B] Next, specific examples of the compound represented by the general formula [B] will be given.

[0111]

[Chemical Formula 39]

[0112]

[Chemical 40]

[0113]

Embedded image

[0114]

Embedded image

[0115]

[Chemical 43]

[0116]

[Chemical 44]

[0117]

[Chemical formula 45]

Next, a synthesis example of the compound represented by the general formula [B] will be described.

(Synthesis Example: Synthesis of Exemplified Compound B-1)

[0120]

[Chemical formula 46]

Synthetic Scheme 1 An outline of the synthesis of Exemplified Compound B-1 is shown in Synthetic Scheme 1.

[Synthesis up to Intermediate 5] Using 4-biphenylcarboxylic acid chloride 1 (manufactured by Aldrich) as a starting material, a known method (Beil 5, II, 618, JP-A-5-11250).
8 and the like), and intermediate 5 was synthesized. The total yield from 1 to 5 was 51%. The melting point was 55-56 ° C.

[Synthesis to Intermediate 9] A known method using aniline 6 (manufactured by Kanto Chemical Co., Inc.) and 2-naphthyl bromide (manufactured by Aldrich Co.) as starting materials (JP-A-2-154267).
According to the above, Intermediate 9 was synthesized. The total yield from 6 to 9 was 83%. The melting point was 109-110 ° C.

[Synthesis of Exemplified Compound B-1] Potassium t-butoxide (manufactured by Kanto Chemical Co., Inc.) 5.
Add 3 g (0.047 mol) and 50 ml of N, N-dimethylformamide (manufactured by Kanto Chemical Co., Inc.) and start stirring under a nitrogen stream.

Next, 14.1 g (0.037 mol) of Intermediate 5 and 10.0 g (0.031 mol) of Intermediate 9 were placed in a 100 ml beaker,
Add 50 ml of N, N-dimethylformamide (Kanto Chemical Co., Inc.) and dissolve. This solution is added dropwise to the solution in the 200 ml four-headed flask described above. At this time, keep the internal temperature at 20 ° to 30 ° C.
After dropping, the mixture is stirred at room temperature for 2 hours.

For the post-treatment, 400 ml of methanol was poured into the reaction solution under ice cooling to precipitate crystals. The crystals are suction filtered and dried. The crude crystals were subjected to a 1 kg SiO ₂ column chromatogram, and toluene / n-hexane = 1
The / 10 eluate was crystallized in acetone-methanol to give 1.9 g (0.022 mol) of the desired exemplary compound B-1 in a yield of 70.
Earned in%. The melting point was 125-127 ° C.

The structure is FAB-MS spectrum, M ⁺
And the elemental analysis values are in good agreement with the calculated values, it was confirmed that the compound was Exemplified Compound B-1.

[0128] Specific examples of the compound represented by the general formula [C] will be given.

[0129]

[Chemical 47]

[0130]

[Chemical 48]

[0131]

[Chemical 49]

[0132]

Embedded image

[0133]

[Chemical 51]

[0134]

[Chemical 52]

[0135]

Embedded image

Next, synthetic examples of the compound represented by the general formula [C] will be described.

(Synthesis Example: Synthesis of Exemplified Compound C-1)

[0138]

[Chemical 54]

Synthetic Scheme 1 An outline of the synthesis of Exemplified Compound C-1 is shown in Synthetic Scheme 1.

[Synthesis until Intermediate 5] 4-Biphenylcarboxylic acid chloride 1 (manufactured by Aldrich) is used as a starting material, and a known method (Beil 5, II, 618, JP-A-5-11250) is used.
8 and the like), and intermediate 5 was synthesized. The total yield from 1 to 5 was 51%. The melting point was 55-56 ° C.

[Synthesis until Intermediate 9] 1-naphthylamine (manufactured by Tokyo Kasei) and p-iodotoluene 7 (manufactured by Tokyo Kasei) are used as starting materials, and a known method (Japanese Patent Publication No. 4-66023).
According to the above, Intermediate 9 was synthesized. The total yield from 6 to 9 was 90%. The melting point was 110 ° -111 ° C.

[Synthesis of Exemplified Compound C-1] Potassium t-butoxide (manufactured by Kanto Chemical Co., Inc.) 4.
7 g (0.042 mol) and 50 ml of N, N-dimethylformamide (manufactured by Kanto Kagaku Co., Ltd.) were added, and stirring was started under a nitrogen stream.

Next, 12.9 g (0.034 mol) of Intermediate 5 and 10.0 g (0.028 mol) of Intermediate 9 were placed in a 100 ml beaker,
Add 50 ml of N, N-dimethylformamide (Kanto Chemical Co., Inc.) and dissolve. This solution is added dropwise to the solution in the 200 ml four-headed flask described above. At this time, keep the internal temperature at 20 ° to 30 ° C. After dropping, the mixture is stirred at room temperature for 2 hours.

For the post-treatment, 400 ml of methanol was poured into the reaction solution under ice cooling to precipitate crystals. The crystals are suction filtered and dried. This crude crystal was subjected to a 1 kg SiO ₂ column chromatogram, and toluene-n-hexane = 1 /
The 9-eluted portion was crystallized with acetone-methanol to give 14.0 g (0.024 mol) of the desired exemplary compound C-1 in a yield of 8
Obtained at 7%. The melting point was 126-127 ° C.

The structure is FAB-MS spectrum, M ⁺
And that the elemental analysis values agree well with the calculated values, it was confirmed that the compound was Exemplified compound C-1.

[0146] Specific examples of the compound represented by the general formula [D] will be given.

[0147]

[Chemical 55]

[0148]

[Chemical 56]

[0149]

[Chemical 57]

[0150]

[Chemical 58]

[0151]

Embedded image

[0152]

Embedded image

[0153]

[Chemical formula 61]

Next, synthetic examples of the compound represented by the general formula [D] will be described.

(Synthesis Example: Synthesis of Exemplified Compound D-1)

[0156]

Embedded image

Synthetic Scheme 1 An outline of the synthesis of Exemplified Compound D-1 is shown in Synthetic Scheme 1.

[Synthesis up to Intermediate 5] 4-Biphenylcarboxylic acid chloride 1 (manufactured by Aldrich) is used as a starting material, and a known method (Beil 5, II, 618, JP-A-5-11250) is used.
8 and the like), and intermediate 5 was synthesized. The total yield from 1 to 5 was 51%. The melting point was 55-56 ° C.

[Synthesis to Intermediate 9] m-Toluidine 6
(Kanto Chemical Co., Ltd.) and P-iodotoluene 7 (Tokyo Kasei Co., Ltd.) as starting materials, a known method (Japanese Patent Publication No. 4-66023).
According to the above, Intermediate 9 was synthesized. The total yield from 6 to 9 was 85%. The melting point was 95-96 ° C.

[Synthesis of Exemplified Compound D-1] Potassium t-butoxide (manufactured by Kanto Chemical Co., Inc.) 5.
4 g (0.048 mol) and 50 ml of N, N-dimethylformamide (manufactured by Kanto Kagaku Co., Ltd.) were added, and stirring was started under a nitrogen stream.

Next, 12.0 g (0.038 mol) of intermediate 5 and 10.0 g (0.032 mol) of intermediate 9 were placed in a 100 ml beaker,
Add 50 ml of N, N-dimethylformamide (Kanto Chemical Co., Inc.) and dissolve. This solution is added dropwise to the solution in the 200 ml four-headed flask described above. At this time, keep the internal temperature at 20 ° C to 30 ° C. After dropping, the mixture is stirred at room temperature for 2 hours.

For the post-treatment, 400 ml of methanol was poured into the reaction solution under ice cooling to precipitate crystals. The crystals are suction filtered and dried. The crude crystals were subjected to a 1 kg SiO ₂ column chromatogram, and toluene-n-hexane = 1
The / 8 elution part was crystallized with acetone-methanol,
10.0 g (0.018 mol) of the target Exemplified Compound D-1 was obtained with a yield of 56%. The melting point was 112 ° -113 ° C.

The structure is FAB-MS spectrum, M ⁺
And the elemental analysis values are in good agreement with the calculated values, it was confirmed that the compound was Exemplified Compound D-1.

[0164] An electrophotographic photoreceptor containing the compound of the above general formula [A], [B], [C] or [D] as a carrier transporting substance has the layer structure shown in FIGS. 1 (1) to 1 (6). be able to.

That is, in FIGS. 1A and 1B, a carrier generating layer 2 containing a carrier generating substance as a main component and a carrier transporting substance according to the present invention as a main component are contained on a conductive support 1. A photosensitive layer 4 composed of a laminated body with the carrier transport layer 3 is provided.

As shown in (3) and (4) of the same drawing, the photosensitive layer 4 may be provided via the intermediate layer 5 provided on the conductive support 1. Thus, when the photosensitive layer 4 has a two-layer structure, a photoreceptor having excellent electrophotographic characteristics can be obtained.

Further, in the present invention, as shown in FIGS. 1 (5) and 1 (6), the photosensitive layer 4 formed by dispersing the carrier-generating substance in the layer 6 containing the carrier-transporting substance as the main component.
May be provided directly on the conductive support 1 or via the intermediate layer 5.

In the present invention, the protective layer 7 may be provided as the outermost layer as indicated by the phantom line in FIG. 1 (4).

The compounds of the general formulas [A] to [D] in the present invention have poor coating forming ability by themselves, so that various binders are combined to form a photosensitive layer.

Any binder can be used as the binder used here, but it is hydrophobic and has a high dielectric constant.
It is preferable to use an electrically insulating film-forming polymer.

Examples of such high molecular weight polymers include, but are not limited to, the followings.

(P-1) Polycarbonate (P-2) Polyester (P-3) Methacrylic resin (P-4) Acrylic resin (P-5) Polyvinyl chloride (P-6) Polyvinylidene chloride (P-7) Polystyrene (P-8) Polyvinyl acetate (P-9) Styrene-butadiene copolymer (P-10) Vinylidene chloride-acrylonitrile copolymer (P-11) Vinyl chloride-vinyl acetate copolymer (P-12) Chloride Vinyl-vinyl acetate-maleic anhydride copolymer (P-13) Silicone resin (P-14) Silicone-alkyd resin (P-15) Phenol formaldehyde resin (P-16) Styrene-alkyd resin (P-17) Poly -N-Vinylcarbazole (P-18) Polyvinyl butyral (P-19) Polyvinyl formal These binder resins are independent. It can be used as a mixture of two or more.

The carrier transporting material (CTM) that can be used in combination in the present invention is not particularly limited, and examples thereof include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives and imidazolone derivatives. , Imidazolidine derivative, bisimidazolidine derivative, styryl compound, hydrazone compound, pyrazoline derivative, amine derivative, oxazolone derivative, benzothiazole derivative, benzimidazole derivative, quinazoline derivative,
Examples thereof include benzofuran derivative, acridine derivative, phenazine derivative, aminostilbene derivative, poly-N-vinylcarbazole, poly-1-vinylpyrene and poly-9-vinylanthracene.

The CTM used in the present invention is preferably one which is excellent in the ability to transport holes generated upon irradiation with light to the support side, and is also suitable for combination with the organic pigment described later used in the present invention.

Examples of the carrier-generating substance used in the carrier-generating layer of the photosensitive layer according to the present invention include the following (1) Azo dyes such as monoazo dyes, bisazo dyes and trisazo dyes (2) perylene Perylene dyes such as acid anhydrides and perylene imides (3) Indigo dyes such as indigo and thioindigo (4) Polycyclic quinones such as anthraquinone, pyrenequinone and flavanthrons (5) Quinacridone dyes (6) Bis Benzimidazole dye (7) Induslone dye (8) Squarerium dye (9) Cyanine dye (10) Azulenium dye (11) Triphenylmethane dye (12) Amorphous silicon (13) Metal phthalocyanine, none Phthalocyanine pigments such as metal phthalocyanine (14) Selenium, selenium- Lulu, selenium - arsenic (15) CdS, CdSe (16) pyrylium salt dyes and thiapyrylium salt dyes, and the like, may be used alone or in combination of two or more.

In the electrophotographic photoreceptor according to the present invention,
As the CGM, it is preferable to use an organic pigment such as a fluorenone-based bisazo pigment, a fluorenylidene-based bisazo pigment, a polycyclic quinone pigment, a perylene derivative, or titanyl phthalocyanine. When these organic pigments are used in the present invention, the effects which are remarkably improved in terms of sensitivity, durability and image quality are exhibited.

The fluorenone bisazo pigment usable in the present invention is represented by the general formula [F ₁ ], and its specific example (F ₁ -1)
~ F ₁ -24), but not limited thereto.

[0178]

[Chemical formula 63]

In the general formula [F ₁ ], X ₁ and X ₂ each represent a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a hydroxy group or a substituted or unsubstituted amino group. p and q each represent an integer of 0, 1 or 2, and when p and q are 2, X ₁ and X ₂ may be the same or different groups.

Further, in A, Ar represents a fluorinated hydrocarbon group or an aromatic carbocyclic group having a substituent or an aromatic heterocyclic group. Z represents a non-metal atom group necessary for forming a substituted or unsubstituted aromatic carbocycle or a substituted or unsubstituted aromatic heterocycle.

M and n each represent an integer of 0, 1 or 2. However, m and n do not become 0 at the same time.

[0182]

[Chemical 64]

[0183]

[Chemical 65]

The fluorenone bisazo pigment represented by the following general formula [F ₁ ] that can be used in the present invention is easily synthesized by a known method, for example, the method of Japanese Patent Application No. 62-304862. .

The fluorenylidene type bisazo pigment which can be used in the present invention is represented by the following general formula [F ₂ ].

[0186] Examples of useful bisazo pigment of the present invention represented by the general formula [F _2], may be, for example, those represented by the below structural formula (F ₂ -1~F ₂ -7) However, this does not limit the bisazo pigment that can be used in the present invention.

[0187]

[Chemical formula 66]

Y represents a substituted or unsubstituted aromatic group.

R ₁ is a hydrogen atom, a substituted or unsubstituted four groups described below; an alkyl group, an amino group, a carbamoyl group, a carboxy group or an ester group thereof, or a cyano group.

R ₂ is a substituted or unsubstituted group consisting of 3 groups; an alkyl group, an aralkyl group and an aryl group.

Q ₂ and Q ₃ represent a hydrogen atom, a cyano group, an alkyl group, a substituted or unsubstituted aromatic group, a halogen atom, a vinyl group, an acyl group or an ester group. Also Q ₂ and Q ₃
May be linked with other atomic groups to form a ring.

P ₁ and P ₂ represent a hydrogen atom, a halogen, a methyl group or a methoxy group.

[0193]

Embedded image

[0194]

[Chemical 68]

The polycyclic quinone pigment that can be used in the present invention is represented by the following general formulas [Q ₁ ] to [Q ₃ ].

Specific examples of the polycyclic quinone pigments represented by the following general formulas [Q ₁ ] to [Q ₃ ] that can be used in the present invention are shown below, but the invention is not limited thereto.

[0197] a later street Taking specific examples of compounds of anthanthrone pigment represented by the general formula [Q _1] (Q ₁ -1~Q ₁ -6).

[0198] a later street Taking specific examples of the compound di-benz pyrene quinone pigments represented by the general formula [Q _2] (Q ₂ -1~Q ₂ -5).

[0199] Aru Taking specific examples of compounds of pyranthrone pigments represented by the general formula [Q _3] (Q ₃ -1~Q ₃ -4) and later of the street.

[0200]

[Chemical 69]

In each formula, X represents a halogen atom, a nitro group, a cyano group, an acyl group or a carboxy group, and n is 0 to 0.
The integer of 4 and m represent the integer of 0-6.

[0202]

Embedded image

[0203]

Embedded image

[0204]

Embedded image

General formula [Q ₁ ] which can be used in the present invention:
The polycyclic quinone pigment represented by [Q ₃ ] can be easily synthesized by a known method.

The perylene derivative usable in the present invention is represented by the following general formula [P] and can be synthesized by the synthesis method described in JP-A No. 4-186364.

[0207]

Embedded image

The oxytitanyl phthalocyanine usable in the present invention is represented by the general formula [TP] described below.

[0209]

[Chemical 74]

In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent H, Cl or Br, and n, m, l and k each independently represent 0 to 0.
Represents an integer of 4.

As the materials usable in the present invention, those having different crystal forms disclosed in the following patents are known. For example, JP-A 61-239248, 62-670943, and 62-2.
72272, 63-116158 or 64-17066, JP-A-2-28
No. 265, No. 2-215866 and the like.

As the dispersion medium of the organic pigment usable in the present invention, there are known dispersion media such as methyl ethyl ketone.

In the present invention, the photosensitive layer may contain one or more known electron-accepting substances. The addition ratio of the electron-accepting substance is a weight ratio of the organic pigment used in the present invention: the electron-accepting substance = 100: 0.01 to 20
0, preferably 100: 0.1 to 100. Further, the addition ratio of the electron-accepting substance is an important ratio: total CTM: electron-accepting substance = 100: 0.01-100, preferably 100: 0.1-50.

Organic amines can be added to the photosensitive layer for the purpose of improving the charge generation function of CGM (carrier generating substance), and it is particularly preferable to add a secondary amine. These compounds are disclosed in JP-A-59-218447 and JP-A-62-8160.
No.

Further, in the photosensitive layer, for example, an antioxidant as disclosed in JP-A-63-18354 can be added for the purpose of preventing ozone deterioration. The amount of antioxidant added is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, and particularly preferably 5 to 25 parts by weight, based on 100 parts by weight of CTM.

In addition, the photoreceptor according to the present invention may further contain an ultraviolet absorber or the like for the purpose of protecting the photosensitive layer, if necessary, and may also contain a dye for correcting color sensitivity.

An intermediate layer may be provided between the photosensitive layer and the support, and this intermediate layer functions as an adhesive layer or a blocking layer.

In the present invention, when the photosensitive layer has a two-layer structure as shown in FIG. 1, the CGL (carrier generation layer) is directly or optionally an adhesive layer on the conductive support or CTL (carrier transport layer). Alternatively, it can be formed by the following method after providing an intermediate layer such as a blocking layer.

(1) Vacuum evaporation method (2) Method of applying a solution of CGM dissolved in a suitable solvent (3) CGM is made into fine particles in a dispersion medium by a ball mill, sand grinder or the like, and if necessary, a binder. A method of applying a dispersion obtained by mixing and dispersing with.

That is, specifically, a vapor deposition method such as vacuum deposition, a sputtering method, a CVD method or a coating method such as a dipping method, a spray method, a blade method, or a roll method is arbitrarily used.

The thickness of the CGL thus formed is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm.

Also, the CTL can be formed by the same method as the CGL. Although the thickness of the CTL can be changed as necessary, it is usually preferably 5 to 60 μm.

The composition ratio in this CTL is preferably 0.1 to 5 parts by weight of the binder with respect to 1 part by weight of the CTM of the present invention, but when forming the photosensitive layer 4 in which fine particle CGM is dispersed, CGM1 is used. It is preferable to use the binder in an amount of 5 parts by weight or less with respect to parts by weight.

Further, when the CTL is constructed as a dispersion type in the binder, it is preferable to use the binder in the range of 5 parts by weight or less to 1 part by weight of CGM.

The electrophotographic photosensitive member according to the present invention has the above-mentioned constitution and, as will be apparent from the examples described later, is excellent in charging property, sensitivity property, image forming property and the like, and is particularly used repeatedly. There is little fatigue deterioration even when doing,
It has excellent durability.

Further, the electrophotographic photoreceptor according to the present invention can be widely used not only in electrophotographic copying machines but also in other application fields such as lasers, cathode ray tubes (CRTs), and photoreceptors of printers using light emitting diodes (LEDs) as light sources. You can In addition to such a photoreceptor, EL (electroluminescence) and the like can be applied to the compound of the present invention.

[0227]

EXAMPLES Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

The example embodiments of each group and each set were different only in the CTMs of the samples and the comparisons shown in the tables attached to each group, and the contents of the corresponding Example Nos given to each group were exactly the same, and The evaluation contents were the same.

Example A-1 The intermediate layer was formed as follows.

As a CGM, 1 part of a perylene derivative (general formula [P]) and 50 parts of 1,2-dichloroethane as a dispersion medium were dispersed by using a sand mill, and this was laminated on a polyester base on which aluminum was vapor-deposited to form the following intermediate layer. After the formation, was coated using a wire bar to form a carrier generation layer having a film thickness of 0.3 μm. Next, 1 part of CTM and polycarbonate resin "Iupilon Z200" (manufactured by Mitsubishi Gas Chemical Co., Inc.) 1.3
Double and a minute amount of silicone oil "KF-54" (manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in 10 parts of 1,2-dichloroethane was applied using a blade coating machine and dried, and then a CTL having a film thickness of 23 μm
Was formed. The photoconductor A-1 thus obtained was produced.

(Formation of Intermediate Layer) ε-Amino-caproic acid,
Polyamide copolymerized with adipic acid and N- (β-aminoethyl) piperazine in a monomer composition of 1: 1: 1
30 g was added to 800 ml of methanol EL standard (Kanto Chemical Co., Inc.) 200 ml heated to 50 ° C. This was used for dip coating to form an intermediate layer having a thickness of 0.6 μm.

Examples A-2 and A-3 The photoreceptor A-2 of the present invention was prepared in the same manner as in Example A-1 except that CGM and CTM in Example A-1 were changed as shown in Table 1. , A-3 were produced.

Comparative Examples A-1 and A-2 CTM was compared with Comparative Compound A in Example A-1 as shown in Table 1 below.
Comparative photoconductors A-1 and A-2 were prepared in the same manner as in Example A-1, except that -1 and A-2 were used instead.

Example A-4 Y-type oxytitanium phthalocyanine (YT) was added to CGM.
iOPC) [Journal of the Electrophotographic Society 250 (2), 29 (2) , 1990]
Intermediate layer-C in the same manner as in Example A-1 except that
A GL-CTL was sequentially laminated to prepare a photoconductor.

Examples A-5 and A-6 Photoreceptors A-5 and A-5 were prepared in the same manner as in Example A-4, except that CTM was changed to the exemplified compounds shown in Table 2 below.
A-6 was produced.

Comparative Examples A-3 and A-4 As shown in Table 2 below, comparison was made in the same manner as in Example A-4 except that CTM was changed to Comparative Compounds R-1 and R-2 in Example A-4. A photoconductor was prepared.

(Comparative Compound Example)

[0238]

[Chemical 75]

[0239]

[Table 1]

[0240]

[Table 2]

(Evaluation Example 1) Copier U-BI manufactured by Konica
X5076 remodeling machine (Battery electrode changed to negative charge, exposure amount 4.65lu
x), the linear velocity was changed to three levels of 240, 330, and 440 mm / sec, and the residual potential Vr when charging and exposing were repeated 20,000 times
Was measured. The results are shown in Table 3 below. The photoreceptor using the CTM of the present invention showed an excellent high-speed property as compared with the photoreceptor using the comparative compound when the linear velocity was increased without increasing the residual potential. . The initial blank sheet potential (Vw) is shown in Table 3.
It was the street. It has been found that the comparative photoreceptor does not exhibit as good properties as those of the present invention.

[0242]

[Table 3]

(Evaluation example 2) Digital copy manufactured by Konica
Using Konica 8028, the unexposed portion potential VH and the exposed portion potential VL were measured at room temperature (25 ° C) and low temperature (10 ° C).
The results are shown in Table 4 below.

[0244]

[Table 4]

It can be seen that all of the materials in the present invention exhibit good characteristics at both room temperature and low temperature, whereas the materials used for comparison have particularly high VL at low temperatures and insufficient characteristics.

Similarly, the results of performance tests conducted using the compounds of the present invention belonging to the general formulas [B], [C] and [D] are shown.

The method was carried out as follows in the same manner as in the case of the general formula [A].

[Prepared Sample Photoreceptor] In the same manner as in the case of the general formula [A], CGM was prepared by using the compound P and the Y-type TiOPC, and represented by the following general formulas [B], [C], and [D]. The ones shown in the table were prepared.

Photoreceptors relating to the general formula [B].

[0250]

[Table 5]

[0251]

[Table 6]

Photoreceptors relating to the general formula [C].

[0253]

[Table 7]

[0254]

[Table 8]

Photoreceptors relating to the general formula [D].

[0256]

[Table 9]

[0257]

[Table 10]

[Performance Test and Results] (Evaluation Example 1) Using a modified machine of copying machine U-BIX5076 manufactured by Konica Corporation (changing the charging electrode to negative charging, exposure amount 4.65 lux),
The fine speed was changed to three stages of 240, 330, and 440 mm / sec, and the residual potential Vr was measured when the charging and exposure were repeated 20,000 times. The results are shown in Tables 11 to 13 below, and the photoconductor using the CTM of the present invention showed an excellent high-speed property as compared with the photoconductor using the comparative compound when the linear velocity was faster and the residual potential did not increase. It was
The initial blank sheet potential (Vw) is shown in Tables 11 to 13.

[0259]

[Table 11]

[0260]

[Table 12]

[0261]

[Table 13]

(Evaluation Example 2) Digital copy manufactured by Konica
Using Konica 8028, the unexposed portion VH and the exposed portion potential VL were measured at room temperature (25 ° C) and low temperature (10 ° C). The results are shown in Tables 14 to 16 below.

[0263]

[Table 14]

[0264]

[Table 15]

[0265]

[Table 16]

[0266]

EFFECTS OF THE INVENTION In a high-speed copying machine with a high linear velocity, the residual potential does not rise even after repeated charging, exposure and static elimination, and even when repeatedly used when incorporated in a digital machine for reversal development, It is possible to obtain a photoconductor in which the exposure potential (VL) does not rise even at low temperatures and the charging potential (VH) does not drop after repeated use.

[Brief description of drawings]

1 (1) to (6) are cross-sectional views of an example of an electrophotographic photosensitive member according to the present invention.

[Explanation of symbols]

1 Support 2 Carrier Generation Layer 3 Carrier Transport Layer 5 Intermediate Layer 6 Layer Containing Carrier Generation Substance and Carrier Transport Substance

Claims (8)

[Claims] 1. An electrophotographic photoreceptor containing a triphenylamine derivative represented by the following general formula [A]. Embedded image [In the formula, Ar ₁ represents the following group. The bonding position is not limited. Embedded image R ₁ and R ₂ represent alkyl and alkoxy. m is 1
Is an integer of 5 and n is an integer of 0 to 5. R _{3 to} R ₆ each represent substituted or unsubstituted alkyl, aralkyl, aryl, or halogen. p and q represent an order of 0 to 4, r and s represent an integer of 0 to 3. Ar ₂ represents a substituted / unsubstituted phenyl, a substituted / unsubstituted fused polycyclic residue, or a substituted / unsubstituted heterocycle. X is an atomic group forming a saturated or unsaturated 5- to 7-membered hydrocarbon ring or heterocycle. ] 2. The electrophotographic photosensitive member according to claim 1, wherein the compound represented by the general formula [A] is a compound represented by the following general formula [a]. [Chemical 3] [In the formula, Ar ₁ represents the following group. [Chemical 4] R ₁ and R ₂ represent CH ₃ and C ₂ H ₅ , and R ₃ and R ₄ represent alkyl, aralkyl and aryl. m is an integer from 1 to 3,
n represents an integer of 0 to 3. p is an integer of 0 to 3, q is 0
Represents an integer of 1. Y represents O and S. Ar ₂ represents substituted / unsubstituted phenyl and naphthyl. ] 3. An electrophotographic photoreceptor containing a phenylamine derivative represented by the following general formula [B]. [Chemical 5] [In the formula, Ar ₁ represents the following group. The bonding position is not limited. [Chemical 6] R _{1 to} R ₄ each represent substituted or unsubstituted alkyl, aralkyl, aryl, or halogen. m, n, r, s is 0
Represents an integer of 3; Ar ₂ represents a substituted / unsubstituted phenyl, fused polycycle or heterocycle, and Ar ₃ represents a substituted / unsubstituted fused polycycle. Ar ₄ each represents a substituted / unsubstituted phenyl or a condensed polycycle. X is 5 between saturated and unsaturated
Represents a 7-membered hydrocarbon ring and heterocycle. ] 4. The electrophotographic photosensitive member according to claim 1, wherein the compound represented by the general formula [B] is a compound represented by the following general formula [b]. [Chemical 7] [In the formula, Ar ₁ represents the following group. R ₀ represents alkyl or aralkyl, and p represents an integer of 0-4. Embedded image R ₁ and R ₂ represent an alkyl group, an aralkyl group, or an aryl group, m is an integer of 0 to 3, and n is an integer of 0 to 1. Y represents O and S. Ar ₂ represents substituted or unsubstituted phenyl, A
r ₄ represents substituted or unsubstituted phenyl or naphthyl. Y represents O and S. 5. An electrophotographic photoreceptor containing an amine derivative represented by the following general formula [C]. [Chemical 9] [In the formula, Ar ₁ represents the following group. The bonding position is not limited. [Chemical 10] R _{1 to} R ₄ each represent substituted or unsubstituted alkyl, aralkyl, aryl, or halogen. p, q, r, s are 0
Represents an integer of 3; Ar ₂ represents a substituted / unsubstituted phenyl, fused polycycle, or heterocycle, and Ar ₃ represents a substituted / unsubstituted fused polycycle. Ar ₄ and Ar ₅ represent substituted / unsubstituted phenyl and condensed polycycle. X represents a saturated or unsaturated 5- to 7-membered hydrocarbon ring or heterocycle. ] 6. The electrophotographic photosensitive member according to claim 1, wherein the compound represented by the general formula [C] is a compound represented by the following general formula [c]. [Chemical 11] [In the formula, Ar ₁ represents the following group. [Chemical 12] Ar ₂ represents a substituted / unsubstituted phenyl, and Ar ₄ and Ar ₅ represent a substituted / unsubstituted phenyl and a condensed polycycle. R ₃ and R ₄ represent substituted / unsubstituted alkyl, aralkyl and aryl.
p and q represent the integer of 0-3. Y represents O and S. ] 7. An electrophotographic photoreceptor containing an amine derivative represented by the following general formula [D]. [Chemical 13] [In the formula, Ar ₁ represents the following group. The bonding position is not limited. Embedded image R ₁ represents alkyl or alkoxy. m represents an integer of 1 to 4. R _{3 to} R ₆ each represent substituted or unsubstituted alkyl, aralkyl, aryl, or halogen. p, q
Is an integer of 0 to 4, r and s are integers of 0 to 3. Ar ₂ represents a substituted / unsubstituted phenyl, a substituted / unsubstituted condensed polycyclic residue, or a substituted / unsubstituted heterocycle. Ar ₃ and Ar ₄ represent a substituted / unsubstituted phenyl and a substituted / unsubstituted fused polycyclic residue.
X represents a saturated or unsaturated 5- to 7-membered hydrocarbon ring or heterocycle. ] 8. The electrophotographic photosensitive member according to claim 1, wherein the compound represented by the general formula [D] is a compound represented by the following general formula [d]. [Chemical 15] [In the formula, Ar ₁ represents the following group. Embedded image R ₁ represents alkyl, Ar ₂ , Ar ₃ and Ar ₄ are the same as those in the general formula [D]. m is an integer of 1 to 4, p is an integer of 0 to 3, and q is 0.
Represents an integer of 3. R ₃ and R ₄ are alkyl, aralkyl,
Represents aryl. Y represents O and S. ]