AU604429B2 - Photosensitive member for electrophotography - Google Patents

Description

~-i W~OMMI^NWEALTH OF AUSTRALIA S F Ref: 117176 PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class Complete Spec Priority: Related Art: ification Lodged: Accepted: Published: Name and Address of Applicant: Canon Kabushiki Kaisha 3-30-2 Shimomaruko Ohta-ku Tokyo

JAPAN

Address for Service: Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: Photosensitive Member for Electrophotography The following statement is a full description of this invention, including the best method of performing it known to me/us t r I, i ~c I Sr 5845/5

II

-I-

ABSTRACT OF THE DISCLOSURE A photosensitive member for electrophotography, including an electroconductive substrate and a photosensitive layer disposed thereon, wherein the photosensitive layer comprises a triarylamine compound represented by the following general formula or

(II):

Ar 1 N-Ar 3 (I) Ar 2

R

1

R

2 Ar 4

(II)

Ar wherein Ar 1 and Ar 2 respectively denote a biphenyl group capable of having a substituent; Ar 3 denotes a phenyl group capable of having a substituent or an t: S' aromatic heterocyclic group capable of having a substituent; Ar 4 and Ar 5 respectively denote a benzene ring or aromatic fused-ring hydrocarbon group capable of having a substituent; R 1 and R 2 respectively denote i a hydrogen atom, alkyl, alkoxyl or halogen atom; and at least one of Ar 4 and Ar 5 is an aromatic fused-ring I I Sl hydrocarbon group.

44 a A *4 a a yu01 7/1073 i T -1 PHOTOSENSITIVE MEMBER FOR ELECTROPHOTOGRAPHY FIELD OF THE INVENTION AND RELATED ART The present invention relates to a photosensitive member for electrophotography, particularly to a photosensitive member for electrophotography comprising a low-molecular weight organic photoconductor capable of providing improved electrophotographic characteristics.

Hitherto, there have been proposed a large number of organic photoconductive polymers to be used for electrophotographic photosensitive members, such as polyvinyl carbazole. These conventional organic polymers are superior to inorganic photoconductive materials in lightness (in weight), film-forming property, etc., but are inferior to the latter in sensitivity, durability, stability to environmental change, mechanical strength, etc.

On the other hand, there have been proposed 20 several low-molecular weight organic photoconductive materials such as hydrazone compound Patent 4,150,987), triaryl pyrazoline compound Patent 3,837,851), and 9-styryl anthracene (Japanese Laid-Open Patent Application (JP-A, KOKAI) Nos. 94828/1976 and 25 94829/1976).

In a case where the conventional low-molecular weight organic photoconductors represented by those as Ii I Ii I I II ic I r

I.

o 00 00 0 00 0 0 00D 0 00)

I_

described above are used, the above-mentioned defect in film-forming property, which has conventionally posed a problem in the field of the organic photoconductive polymer, may be obviated by appropriately selecting a binder to be used in combination therewith. However, these conventional organic photoconductors cannot provide a sufficient sensitivity.

In such a viewpoint, there has recently been proposed a laminate-type structure wherein the photosensitive layer is function-separated into a charge generation layer and a charge transport layer.

The electrophotographic photosensitive member comprising such a photosensitive layer may be improved in sensitivity to visible light, charge retentivity, surface strength, etc.

As the charge-transporting substance constituting the above-mentioned charge transport layer, a large number of organic compounds have heretofore been proposed. Examples thereof include: 20 pyrazoline compounds (Japanese Laid-Open Patent Application No. 72231/1977), hydrazone compounds (U.S.

Patent 842,431 and Japanese Laid-Open Patent Application No. 52063/1980), triphenylamine compounds (Japanese Laid-Open Patent Application Nos. 195254/1982 25 and 58445/1979), stilbene compounds (Japanese Laid-Open Patent Application Nos. 151955/1979 and 198043/1983), carbazole compounds (Japanese Laid-Open Patent 4 4 4 4 i 4 4, 4414 4I 4 1 0 o 0 0 4 4 4 44 -3- Application Nos. 150128/1979 and 58451/1988), benzothiophene compounds (Japanese Laid-Open Patent Application No. 110835/1979), etc.

However, in the electrophotographic photosensitive member using the conventional lowmolecular weight organic compound as the chargetransporting substance, the sensitivity and other electrophotographic characteristics are not necessarily sufficient, and the light part potential and dark part potential are liable to show a considerable change, when charging and exposure operations are conducted repetitively.

Accordingly, with respect to such an electrophotographic photosensitive member, there is still room for improvement.

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member which has solved the above-mentioned various problems encountered in the conventional photosensitive member.

Another object of the present invention is to provide an electrophotographic photosensitive member using a novel organic photoconductor which may easily S 25 be produced, is relatively inexpensive and is excellent in durability.

0° According to the present invention, there is .71

I

-4provided a photosensitive member for electrophotography, comprising an electroconductive substrate and a photosensitive layer disposed thereon, wherein the photosensitive layer comprises a triarylamine compound represented by the following general formula or

(II):

N-Ar 3 3 Ar 2

R

1 R 2 Ar 4

K

(II)

Ar wherein Ar, and Ar 2 respectively denote a biphenyl group capable of having a substituent; Ar 3 denotes a phenyl group capable of having a substituent or an aromatic heterocyclic group capable of having a substituent; Ar 4 and Ar 5 respectively denote a benzene ring or aromatic fused-ring hydrocarbon group capable of having a substituent; R 1 and R 2 respectively denote a hydrogen atom, alkyl, alkoxyl or halogen atom; and at least one of Ar 4 and Ar 5 is an aromatic fused-ring hydrocarbon group.

These and other objects, features and 25 advantages of the present invention will become more apparent upon a consideration of the following description of the preferred embodiments of the present I I IIC I S 5- 1 4 *446 O 4 4o 44 44 0 4o 4 4a 0 t invention taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 and 2 show infrared absorption spectra of Compound Example Nos. 2 and 26, respectively, according to the KBr tablet method.

DETAILED DESCRIPTION OF THE INVENTION In the above general formula Arl and Ar 2 respectively denote a biphenyl group capable of having a substituent. Specific examples of such a substituent may include alkyl groups such as methyl, ethyl and propyl; alkoxy groups such as methoxy, ethoxy and propoxy; halogen atoms such as fluorine, chlorine and bromine; etc. Ar, may be the as or different from Ar 2 Ar 3 denotes a phenyl group capable of having a substituent, or an aromatic heterocyclic group such as pyridyl, quinolyl, thienyl or furyl capable of having a substituent. Specific examples of such a substituent may include: alkyl groups such as methyl, ethyl and propyl; alkoxy groups such as methoxy, ethoxy and propoxy; aryloxy groups such as phenoxy and naphthoxy; aromatic groups such as phenyl and naphthyl; halogen atoms such as fluorine, chlorine and bromine; etc.

In the above general formula Ar, and Ar 2 respectively denote a benzene ring or aromatic c I r I C CC I' C C 0 I II il

-C-

condensed-ring (or fused-ring) hydrocarbon group capable of having a substituent. At least one of Arl and Ar 2 is an aromatic condensed ring hydrocarbon group. Specific examples of such an aromatic condensed ring hydrocarbon may include naphthalene, anthracene, phenanthrene, chrysene and naphthacene. Specific examples of such a substituent which Ar 1 and Ar 2 may have include: alkyl groups such as methyl, ethyl and propyl; alkoxy groups such as methoxy, ethoxy and propoxy; halogen atoms such as fluorine, chlorine and bromine; etc. Ar 1 may be the as or different from Ar 2 R1 and R 2 respectively denote a hydrogen atom; an alkyl group such as methyl, ethyl and propyl; an alkoxy group such as methoxy, ethoxy and propoxy; a halogen atom such as fluorine, chlorine and bromine; etc. R 1 may be the as or different from R 2 Representative examples of the compound represented by the above-mentioned formula are described hereinbelow.

SI

4 4 S0: 0 0 00 o -7- <Compound Examples> (1) 00 0-0 N 4 C0 00 N-OC2 3 00c 00

C

005 I C 81404; 25 4840 44 40 4 8* 8 8 04 I 88 00 CR3 NQ0 00CH 3 I mmrp-- 00 N-Q -OCH 3 5000\1 00z N C~-C 3

H

7 OCH 3 0 (9) 00

NQ

0 0 0 N-7 00 I IC (I I II C I C C C 4* -9-

CE

3 OCH 3 N--0 (12) N4 O-OC 2

%H

CH3QQ 0 06 0 0 0 00 0 000 0c~t 6 0 00 0000 (13)

CH

3 0 0 NnO 00 0 (14) 00-l 000 0 0 0 0 0 00 0

C

2

H

5 0 0

C

2

H

5 0 0 Br 01 0 0 00

NQ\I

(17)

CH

3 O0 00", (18' 0 0

NO~C

2 0 (19)

NQA

ci 0 0

CE

3 ocr 0 to t 3 0 0 3403 4 0 Go 33 0 34 3 00 0C 2

H

00 25 0 0 -11 (21) n-C 3

H

7 (22) 0-0 (23) 0 0 00/

-D

(24) CH 3 CH 3

QQD

0 0

CH

3

Q

3 00 0 0 7 -12- Representative examples of the compound represented by the above-mentioned formula (IT) are described hereinbelow.

<Compound Examples>~ (26) 0 0 (27) ClQ NC, D (28)

CH

3 Q N_

O

04 14 ''44 44 44 4 I 4$ 4 054 4844 4,4' 4.4' 4 II 44 0 4 04 4 4 o 44 4 0 044440 4440 0 04 44 4 44 4 4 0 8 4, 04 (29)

CH

3 O0D_ (30) 06 C2

H

N<OJ

-13- (31 000, (32)

CH

3

CR

3

NYD©

(33) n-C 4

H

9 -4 0 x N-O tIt Is It I I 'It' II II

I

(34) 0 OCR 3

CRN

3 I*t~ I I C II. I

II

I I I I II

CR

3 C CII CO C I CC C S C C .5 C I I I I SI Noo

D

-1 4- (36) Cl 0 0

CH

3 0 (37) C 2 )Hr 0 (38)0 0 0 0

N

(39) C H0 0 0 O Br t, I 0 it t..

(41

CH

3 0 (42) N C 1 0 (43) (44) 0 0CH 3 N

CH

3 4 4 4 4 4 I__I QWW___ ~ll L1II~-r-i I -16- The above-mentioned Compound Examples may be synthesized in the following manner.

<Synthesis of Compound Example No. 2> 23.5 g (83.9 mmol) of 4-iodobiphenyl, 3.0 g (28.0 mmol) of p-toluidine, 11.6 g (83.9 mmol) of anhydrous potassium carbonate, and 15 g of copper powder were added to 50 ml of nitrobenzene, and refluxed for 12 hours under heating and stirring.

After the reaction mixture was cooled, the reaction mixture was subjected to filtration by suction, and the nitrobenzene was removed from the resultant filtrate under reduced pressure. Ethanol was added to the residue to precipitate crude crystals.

The crude crystals were subjected to separation to be purified by using a silica gel column, whereby 7.80 g (yield 66.7 of the intended Compound Example showing a melting point of 187.0 188.0 OC was obtained.

Elemental analysis (C 31

H

25

N)

Calculated value 90.47 6.12 3.40 Observed value 90.45 6.16 3.39 Figure 1 shows an infrared absorption spectrum chart obtained by measuring the thus obtained compound 25 by a KBr tablet (or pellet) method.

<Synthesis of Compound Example No. 26> 5.75 g (20.5 mmol) of 4-iodobiphenyl, 3.0 g a tat a a c o a a aa a. a *1 U

C

(i t -17- (13.7 mmol) of N-phenyl-L-naphthylamine, 2.83 g (20.5 mmol) of anhydrous potassium carbonate, and 1.5 g of copper powder were added to 30 ml of nitrobenzene, and refluxed for 10 hours under heating and stirring.

After the reaction mixture was cooled, the reaction mixture was subjected to filtration by suction, and then the nitrobenzene was removed from the resultant filtrate under reduced pressure. The residue was subjected to separation to be purified by using a silica gel column, whereby 3.3 g (yield 65 of the intended Compound Example (26) showing a melting point of 176.5 177.5 °C was obtained.

Elemental analysis (C 28

H

21

N)

Calculated value 90.53 5.70 3.77 Observed value 90.48 5.76 3.76 Figure 2 shows an infrared absorption spectrum chart obtained by measuring the thus obtained compound i by a KBr tablet (or pellet) method.

As described above, the compound according to the present invention may easily be synthesized Sinexpensively. The other compounds according to the present invention may be synthesized in a similar manner as described in the above-mentioned Synthesis Examples.

tIIn a preferred embodiment of the present invention, the photosensitive layer is function- 4' -18separated into a charge generation layer and a charge transport layer, and the charge transport layer comprises the compound represented by the abovementioned general formula or (II) as a chargetransporting substance.

The charge transport layer according to the present invention may preferably be formed by dissolving the above-mentioned compound of the formula or (II) in an appropriate solvent together with a binder, applying the resultant coating liquid such as solution onto a predetermined surface, and drying the resultant coating.

Examples of the binder to be used for forming the charge transport layer may include: polyarylate resins, polysulfone resins, polyamide resins, acrylic resins, acrylonitrile resins, methacrylic resins, vinyl chloride resins, vinyl acetate resins, phenol resins, f t8 epoxy resins, polyester resins, alkyd resins, 4 polycarbonate, polyurethane, or copolymer resins S 20 containing two or more of the recurring units of these resins, such as styrene-butadiene copolymers, styreneacrylonitrile copolymers, styrene-maleic acid o 0 copolymers, etc. Also, other than such insulating polymers, organic photoconductive polymers such as o0 25 polyvinylcarbazole, polyvinylanthracene and polyvinylpyrene may be used.

In the charge transport layer, the charge- In the charge transport layer, the charge- 6 04 34 6 4C 4 I4t I -19transporting substance may preferably be used in an amount of 10 500 wt. parts, more preferably 50 200 wt. parts, per 100 wt. parts of the binder.

The charge transport layer is electrically connected to the charge generation layer as described hereinafter, and has a function of receiving charge carriers injected from the charge generation layer in the presence of an electric field and of transporting these charge carriers to the surface of the charge transport layer. In such an embodiment, the charge transport layer may be disposed on the charge generation layer, or may be disposed under the charge generation layer. The charge transport layer may preferably be disposed on the charge generation layer.

It is not preferred that the charge transport layer has too large a thickness, since there is a certain limit to the thickness thereof suitable for the transport of Sthe charge carriers. In general, the charge transport layer may preferably have a thickness of 5 microns, more preferably 10 30 microns.

The organic solvent to be used in the abovei mentioned formation of the charge transport layer may t vary depending on the kind of the binder used therefor, 4i, and may preferably be se.ected from those which do not substantially dissolve the charge generation layer or a primer (or undercoat layer) as described hereinafter.

Specific examples of such an organic solvent a It at 4 t 4 a 4 t4 may include: alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, methyl ethyl i ketone, and cyclohexanone; amides such as N,Ndimethylformamide and N,N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, and ethylene glycol monomethyl ether; esters such as methyl acetate and ethyl acetate; aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, and trichloroethylene; aromatic compounds such as benzene, toluene, xylene, monochlorobenzene, and dichlorobenzene; etc.

The coating may be effected by various coating I methods such as dip coating, spray coating, wire bar coating, and blade coating. The drying should preferably be conducted in the sequence of drying at room temperature to a "tack-free" state and then heat drying. In general, the heat drying may preferably be conducted for a time in the range of 5 minutes to 2 hours at a temperature of 30 OC to 200 OC under i quiescent condition or under blowing.

The charge transport layer according to the a present invention can further contain an additive selected from various species thereof. Examples of ,s a 25 such an additive may include: plasticizers such as diphenyl, m-terphenyl and dibutyl phthalates; surfacelubricating agents such as silicone oil, graft-type titslubricating agents such as silicone oil, graft-type t t t I g_ I -21silicone polymers, and various fluorocarbons; potential stabilizing agents such as dicyanovinyl compounds and carbazole derivatives; anti-oxidizing agents such as I -carotene, Ni complexes, and 1,4-diazabicyclo[2,2,2]octane; etc.

The charge generation layer may comprise a charge-generating substance. Specific examples of the charge-generating substance may include: inorganic charge-generating substances such as selenium, selenium-tellurium, and amorphous silicon; and organic charge-generating substances including: cationic dyes such as pyrylium dye, thiapyrylium dye, azulenium dye, thiacyanine dye, and quinocyanine dye; polycyclic quinone pigments such as squarium salt dye, phthalocyanine pigment, anthanthrone pigment, dibenzpyrene-quinone pigment, and pyranthrone pigment; indigo pigment; quinacridone pigment; azo pigment; etc.

II SThese charge-generating substances may be used singly or as a combination of two or more species. The charge generation layer may be formed by using such a chargegenerating substance in the form of a vapor deposition layer or coating layer.

Among the above-mentioned charge-generating 0 "a substances, the azo pigment particularly includes oa a 25 various types. Representative structures of the azo a Q pigment preferably used in the present invention are 0 0 described hereinbelow. When the azo pigment is c tI -22represented by a general formula including the following central skeleton A: A{N=N-Cp wherein Cp denotes a coupler portion (or coupler moiety) and n is 2 or 3, specific examples of the central skeleton A include those comprising the following structures: t" o 0 020 0000 S 0 0 o 0 S0 o 0 0 0 o 0. o 0 0 0 00 0 0 C0 0 0 0 0 O qi i -23- A-1 2. R.

-66.

Cl, OCH 3 H, CN) A- 2 A- 3 R R lo H, CN) A-4 0, S R: H, CH 3 ,J Cl) 0, S R: H, CH 3 1 Cl) cc,.

R

R

t c A- 6 cc c S S C C CI 4 *84454 4 4 4644 48 44 4 44 4 4 48 44

RR

H, CH 3 1 Cl, x -24- A-7 0 A-8 ~N 0 N>K A- 9 0, S) 0, S) 0 >CH=CH 0-

N

N-N

O-CH=CH-( 11 1-CH=CH 0 0, S) A-i 1

I

A

R

N

0 N> 0C x 00f-O H, CH 3 A- 12 CH 2 0, S 1 so0 2 .A-13 0 00 c c Ct c A-1 4 0,1 S) A- 0 A-i 6 N-N N-N 0, S) A-i 7 2 A- 18 A-i19 -Q CH=N-N=CH 0t t I 72 -26- A-

R

A-21 H, CH 3 A-22 0 0 Specific examples of the coupler portion Cp include those having the following structures: 444, 4454 Cp- 1 HO CONH 0q 0R H, halogen atom, alkoxy, alkyl, nitro group, etc.

n =1 or 2) Cp- 2 4 1 4 4 44 4 I I I 44 44,44.

4 4 I I 44 4 61 4 t 4 4 4 41 Cp-3 HO CONHR -0 0CCNNC- CH 3 1 C 2 H 5 C 3 H 7 alkyl or KICR) R' H, halogen atom, alkoxy, alkyl, nitro group, etc.) Mnnbb -27- Cp-4

H

0 HN- 0

CO

0U H, halogen atom, alkoxyl,alkyl, nitro group, etc.) 0

N-R

alkyl, aryl, etc.) Cp-6

HO

N

or 0 N)9 0 0 I 25 Cp-7 HO, CONH

-O

(Rif R 2 H, halogen atom, alkoxy, alkyl, nitro group, etc.

n =1or 2) 'tIe 11 41 I 1.1 1 4 I I It

I,

i -28- SThe above-mentioned central skeleton A and i coupler Cp may appropriately be combined to form a i pigment as a charge-generating substance.

i The charge generation layer may be formed by i 5 vapor-depositing such a charge-generating substance by means of a vacuum vapor deposition device, or by i applying a dispersion containing such a charge- I generating substance dispersed therein, together with an appropriate binder as desired.

i 10 The binder to be used for forming the charge generation layer may be selected from a wide variety of insulating resins or alternatively from organic i photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene. There may i 15 preferably be used the insulating resin such as polyvinyl butyral, polyarylates polycondensation product between bisphenol A and phthalic acid), j polycarbonate, polyester, phenoxy resin, acrylic resin, Spolyacrylamide resin, polyamide, polyvinyl pyridine, s 20 cellulose resin, urethane resin, epoxy resin, casein, S polyvinyl alcohol, and polyvinyl pyrrolidone.

The resin may preferably be contained in the charge generation layer in an amount of 5 80 wt. I more preferably 10 40 wt. Specific examples of the organic solvent usable in the coating of the charge generation layer may include: alcohols such as methanol, ethanol, and

I

r -29- !i S i isopropanol; ketones such as acetone, methyl ethyl *ketone, and cyclohexanone; amides such as N,Ni; dimethylformamide and N,N-dimethylacetamide; sulfoxides i H such as dimethyl sulfoxide; ethers such as i :i I 5 tetrahydrofuran, dioxane, and ethylene glycol i monomethyl ether; esters such as methyl acetate and ethyl acetate; aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, 1 carbon tetrachloride, and trichloroethylene; aromatic S10 compounds such as benzene, toluene, xylene, 'i monochlorobenzene, and dichlorobenzene; etc.

The charge generation layer may preferably i contain the above-mentioned charge-generating substance in an amount as large as possible, so that it may provide a sufficient absorbance. Further, the charge generation layer may preferably be a thin layer having S a thickness of 5 microns or below, more preferably 0.01 1 micron so that it may inject charge carriers generated therein into the charge transport layer within the lifetime of the charge carriers. This may be attributable to facts such that most of the incident t- 4 light quantity may preferably be absorbed into the charge generation layer to generate a large number of 44 4 k 4 charge carriers, and that the thus generated charge 4444 S 25 carriers may preferably be injected into the charge transport layer without deactivation due to recombination or trapping thereof.

1 The above-mentioned photosensitive layer having a laminate structure comprising a charge generation layer and a charge transport layer may be disposed on an electroconductive substrate.

The electroconductive substrate may be a substrate which per se has an electroconductivity such as those of aluminum, aluminum alloy, copper, zinc, and stainless steel; alternatively, the above-mentioned metal substrate or a substrate of a plastic coated with, a vacuum vapor-deposited layer of aluminum, aluminum alloy, indium oxide, tin oxide or indium oxide-tin oxide alloy, or a mixture of an electroconductive powder (such as aluminum powder, titanium oxide, tin oxide, zinc oxide, carbon black and S 15 silver particles) and an appropriate binder; a substrate of paper or plastic impregnated with electroconductive particles, or a plastic substrate S' coated with an electroconductive polymer layer. The i electroconductive substrate may be in any form such as sheet, drum, etc.

J Between the electroconductive substrate and 1i the photosensitive layer, there can be formed a primer or undercoat layer having a barrier function and an l adhesive function. The primer layer may comprise, S 25 casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide nylon S 6, nylon 66, nylon 610, copolymer nylon, r- 1 -31i alkoxymethylated nylon, etc.), polyurethane, gelatin, K or aluminum oxide. The thickness of the primer layer K should preferably be 0.1 5 microns, particularly i to 3 microns.

In the electrophotographic photosensitive i member according to the present invention, a protective layer can further be disposed on the photosensitive layer. Such a protective layer may comprise a resin, or a resin and an electroconductive material dispersed therein.

In another embodiment of the present invention, a pigment or dye having a photoconductivity may be used as a sensitizer. Examples of such a dye or pigment include: the above-mentioned disazo pigment, pyrylium dye, thiapyrylium dye, selenapyrylium dye, Sbenzopyrylium dye, benzothiapyrylium dye, naphthopyrylium dye, and naphthothiapyrylium dye, as I described in U.S. Patent 3,554,745; 3,567,438; and i 3,586,500.

In a still another embodiment of the present invention, an eutectic (crystal) complex comprising a pyrylium dye (as disclosed in U.S. Patent 3,684,502) and an electrically insulating polymer comprising an alkylidene-diarylene portion may be used as a sensitizer. Such an eutectic complex may be formed by dissolving 4-[4-bis(2-chloroethyl)aminophenyl]-2,6diphenylthiapyrylium perchlorate and poly(4,4'- 9. i'- -32isopropylidene diphenylene carbonate) in a halogenated hydrocarbon-type solvent dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, bromobenzene, 1,2-dichlorobenzene, etc.), and then adding a non-polar solvent ji hexane, octane, decane, 2,2,4-trimethylbenzene, ligroin, etc.) to the resultant mixture so as to I produce a particulate eutectic complex. In such an j 10 embodiment, the electrophotographic photosensitive member may include a binder such as styrene-butadiene I copolymer, silicone resin, vinyl resin, vinylidene ;chloride-acrylonitrile copolymer, styrene-acrylonitrile copolymer, vinyl acetate-vinyl chloride copolymer, polyvinyl butyral, polymethyl methacrylate, poly-Nbutyl methacrylate, polyester, cellulose ester, etc.

i The electrophotographic photosensitive member j according to the present invention may be used not only for ordinary copying machines but also in the fields related to electrophotography such as laser printers, j CRT printers and electrophotographic plate-making.

i The present invention will be described in more detail with reference to Examples.

Example 1 5 g of a disazo pigment represented by the following formula: ii j -33- -HNOC OH CH HO CONH- N=N 0 N=N 0 Nl Cl and a solution obtained by dissolving 2 g of a butyral resin (butyral degree: 63 mol. in 100 ml of cyclohexanone were dispersed for 24 hours by means of a sand mill to prepare a coating liquid. The thus prepared coating liquid was applied onto an aluminum sheet by means of a wire bar to form a charge generation layer having a thickness (after drying) of 0.2 micron.

Then, 10 g of the above-mentioned Compound Example No. 6 as a charge-transporting substance, and S 15 10 g of a polycarbonate resin (weight-average molecular weight 20,000) were dissolved in 70 g of monochlorobenzene to prepare a coating liquid. The coating liquid was applied onto the above-mentioned charge generation layer by means of a wire bar to form a charge transport layer having a thickness (after drying) of 20 microns, whereby an electrophotographic photosensitive member having a laminate structure was prepared.

The thus prepared photosensitive member was S 25 charged by using corona KV) according to a static 4t,' method by means of an electrostatic copying paper 4 tester (Model: SP-428, mfd. by Kawaguchi Denki K.K.) i t-34i and retained in a dark place for 1 sec. Thereafter, H the photosensitive member was exposed to light at an illuminance of 20 lux, to evaluate the charging i characteristic. In order to evaluate the charging characteristic, the surface potential (V 0 the potential (V 1 obtained after a dark decay of 1 sec, 1 and the exposure quantity (E 1 2 required for i decreasing the potential V 1 to 1/2 thereof were Smeasured.

Further, in order to measure the variations in light part potential and dark part potential in repetitive use, the photosensitive member prepared in this instance was bonded to the cylinder for a photosensitive drum to be used for a plain paper copying (PPC) machine (NP-3525, mfd. by Canon and subjected to a copying test of 5000 sheets. Thus, the light part potential (VL) and dark part potential (VD) were measured in the initial stage and after the copying of 5000 sheets to evaluate variations therein.

i i 20 The initial VD and VL were set to -700 V and -200 V, Srespectively.

The results are shown in the following Table L1.

Table 1 v v E Initial potential Potential after 0 1 1/2 copying of 5000 (lux.sec) sheets J V D -700 -691 Example 1 -697 -692 1.4 V L -200 -207 -36- Example 2 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that Compound Example (29) was used as the chargetransporting substance instead of the Compound Example used in Example 1.

The electrophotographic characteristic of the thus obtained photosensitive member were measured in the same manner as in Example 1.

The results are shown in the following Table 2.

i Table 2 Initial potential Potential after copying of 5000 sheets (V) -692 -211 i -38- Examples 3 11 Nine species of photosensitive members were prepared in the same manner as in Example 1 except that Compound Examples (20) and (23) were respectively used as the chargetransporting substance instead of the Compound Example used in Example 1, and that a pigment having the following formula was used as the charge-generating substance.

-HNOCHNOC OH N-N HO CONHCONH 0 N=N- I LK N=N O 0 The electrophotographic characteristics of the thus obtained photosensitive members were measured in the same manner as in Example 1.

The results are shown in the following Table 3.

CC C t

CC

Table 3 Example Compound vo0 v E 12 Initial potential Potential after copying of 5000 sheets Example (lux.sec) VD VL VD VL (V) 3 697 695 1.2 -700 -200 -691 -210 4 700 696 1.0 -700 -200 -697 -208 698 694 1.0 -700 -200 -692 -217 6 696 689 1.3 -700 -200 -690 -214 7 (10) 702 695 1.5 -700 -200 -687 -220 8 700 695 1.1 -700 -200 -692 -209 cont.

:1 Table 3 cont.

9 (15) 699 694 1.4 -700 -200 -693 -213 (20) 697 693 1.2 -700 -200 -690 -210 11 (23) 701 697 1.2 -700 -200 -692 -218 11 (23) 701 697 1.2 -700 -200 -692 -218 i

__J

I

-41- Examples 12 17 Six species of photosensitive members were prepared in the same manner as in Example 1 except that Compound Examples (43) and (44) were respectively used as the charge-transporting substance instead of the Compound Example (29) used in Example 2, and that the pigment used in Examples 3 11 was used as the charge-generating substance.

The electrophotographic characteristic of the thus obtained photosensitive members were measured in the same manner as in Example 1.

The results are shown in the following Table 4.

I

t Table 4 m~aple 0 E 1 2 Initial potential Potential after copying of 5000 sheets Example (lux.sec) VD VL VD VL (V) 12 (26) 699 694 1.3 -700 -200 691 210 13 (28) 700 692 1.2 -700 -200 687 213 14 (33) 698 691 1.3 -700 -200 693 209 (39) 697 690 1.1 -700 -200 688 204 16 (43) 701 694 1.4 -700 -200 695 211 17 (44) 696 688 1.1 -700 -200 694 208 i -43- Comparative Examples 1 For the purpose of comparison, five species of photosensitive members were prepared in the same manner as in Example 1 except that the following Comparative Compound Examples 1 5 were respectively used as the charge-transporting substance.

i The electrophotographic characteristics of the thus obtained photosensitive members were measured in the same manner as in Example 1.

The results are shown in the following Table <Comparative Compound Examples> (1) (disclosed in Japanese Laid-Open Patent Appln. No. 195254/1982) h 20 (2) o iCH CH 0 0 N N (disclosed in Japanese Laid-Open Patent Appln. No. 58445/1979) P I- _L -44- 3

O

CH

0 (disclosed in Japanese Laid-Open Patent Appln. No. 198043/1983) (4) (disclosed in Japanese Laid-Open Patent Appln. No. 195254/1982)

CH

3

CH

3 N0N (disclosed in Japanese Laid-Open Patent Appln. No. 58445/1979) 0 o 0 0 0 a 0 0 0 o00 0 0 0 0 0 a 00 0 0 0 0 0 0 0 0 0 0 0 CG 00 Ce co 00 0 0) 4 00 000 00 0 0 0 0 0 0 00 00 0 0.0 C 0 0, 0 00 00 0 0 0 0 0 0 0 .0C Table E Initial potential 'Ptential after copying of 5000 sheets EComp.e CORPun 0 1 E1/2 E-cml opud (lux.sec) VD() V V D(V) VL (V) 1 1 697 694 3.4 -700 -200 -651 -315 2 2 699 693 2.9 -700 -200 -680 -289 3 3 701 694 2.4 -700 -200 -681 -301 4 4 700 690 3.0 -700 -200 -665 -310 5 699 693 2.9 -700 -200 -680 -289 -46- As apparent from the results as described above, the compound according to the present invention provided photosensitive member providing a better sensitivity and better potential stability in successive copying, as compared with those of Comparative Examples.

Examples 18 and 19 A coating liquid obtained by dissolving 5 g of a methoxymethylated nylon resin (number-average molecular weight 32,000) and 10 g of an alcoholsoluble copolymer nylon resin (number-average molecular weight 29,000) in 95 g of methanol was applied onto an aluminum substrate by means of a wire bar to form a primer layer having a thickness of 1 micron (after drying).

Then, 10 g of a charge-generating substance represented by the following formula:

C

2

H

5 C 2

H

-HNOC OH 0 HO CONH 0 0 N=N 0 O Cl Cl a butyral resin (butyral degree: 63 mol. and 200 g of dioxane were dispersed for 48 hours by means of a -47ball mill disperser to prepare a dispersion. The thus prepared dispersion was applied onto the abovementioned primer layer by a blade coating method to form a charge generation layer having a thickness (after drying) of 0.15 micron.

Then, 10 g of the above-mentioned Compound Example No. 3 and 10 g of a polymethyl methacrylate resin (weight-average molecular weight 50,000) were dissolved in 70 g of monochlorobenzene to prepare a coating liquid. The coating liquid was applied onto the above-mentioned charge generation layer by a blade coating method to form a charge transport layer having a thickness (after drying) of 19 microns, whereby an electrophotographic photosensitive member was prepared (Example 18).

The thus prepared photosensitive member was charged by using corona discharge KV) so as to have j an initial potential of V0, left standing in a dark i place for 1 sec, and thereafter the surface potential 20 thereof (V 1 was measured. In order to evaluate the I sensitivity, the exposure quantity (E 1 PJ/cm 2 irequired for decreasing the potential V 1 after the dark decay to 1/2 thereof was measured. The light source used herein was laser light (output: 5 mW, emission wavelength: 780 nm) emitted from a ternary semiconductor comprising gallium/aluminum/arsenic.

The results were as follows: -48-

V

0 -701 V

V

1 -693 V E1/2: 0.51 pJ/cm 2 Separately, the above-mentioned procedure was repeated except that Compound Example No. 41 was used as the charge-transporting substance contained in the charge transport layer, thereby to prepare another electrophotographic photosensitive member. The thus prepared photosensitive member was evaluated in the same manner as described above (Example 19).

The results were as follows:

V

0 -700 V V1: -694 V E1/2: 0.54 pJ/cm 2 Each of the above-mentioned photosensitive member was assembled in a laser beam printer (trade name: LBP-CX, mfd. by Canon as an electrophotographic printer equipped with the abovementioned semiconductor laser using a reversal development system, and subjected to actual image formation.

The image formation conditions used herein were as follows: surface potential after primary charging: -700 V 25 surface potential after image exposure: -150 V (exposure quantity: 2.0 pJ/cm 2 transfer potential: +700 V IL q-WM -49polarity of developer: negative process speed: 50 mm/sec developing condition (developing bias): -450 V image exposure scanning system: image scan exposure prior to the primary charging: 50 lux.sec (whole surface exposure using red light) The image formation was effected by linescanning the laser beam corresponding to character and image signals. As a result, good prints were obtained with respect to the characters and images, when each of the above-mentioned two photosensitive members was used.

Further, when successive image formation of fit 3,000 sheets was conducted, good prints were stably obtained from the initial stage to 3,000 sheets, in a case where each of the above-mentioned two photosensitive members was used.

Examples 20 and 21, Comparative Examples 6 and 7 g of oxytitanium phthalocyanine and a solution obtained by dissolving 5 g of a phenoxy resin in 485 g of dioxane were dispersed for 2 hours by means of a ball mill. The thus prepared dispersion was applied onto an aluminum sheet by means of a wire bar and then dried at 80 °C for 2 hours to form a charge 25 generation layer having a thickness of 0.5 micron.

'got Then, 10 g of the above-mentioned Compound Example No. 7, and 10 g of a bisphenol Z-type polycarbonate resin (weight-average molecular weight 50,000) were dissolved in 70 g of monochlorobenzene to prepare a coating liquid. The coating liquid was applied onto the above-mentioned charge generation layer by means of a wire bar and then dried at 110 °C for one hour to form a charge transport layer having a thickness of 19 microns, whereby an electrophotographic photosensitive member was prepared (Example The thus obtained photosensitive member was evaluated in the same manner as in Example 18.

The above-mentioned procedure was repeated except that Compound Example No. 28 was used for forming the charg- transport layer thereby to prepare a photosensitive member (Example 21), which was then evaluated in the same manner as described above.

Further, the above-mentioned procedure was repeated except that the following Comparative Compound Examples 6 and 7 were respectively used for forming the charge transport layer (Comparative Examples 6 and 7), which were then evaluated in the same manner as described above.

<Comparative Compound Examples> N- n-C4-H t 25 14« -51 (7)

CH

3

N

N O CH The thus obtained results are shown in the following Table 6.

I L Table 6 Compound V 0 V, E1/ 2 (uJ/cm 2 Example 1/2 Example 20 -699 -693 0.61 Example 21 (28) -697 -693 0.62 Comparative (Comparative) Example 6 6 -700 -692 3.96 Comparative (Comparative) Example 7 7 -698 -681 1.95 1 -53- Examples 22 and 23 3 g of 4-(4-dimethylaminophenyl)-2,6diphenylthiapyrilium perchlorate, and 5 g of Compound Example No. 18 as a charge-transporting substance, and 5 g of a polyester resin (weight-average molecular weight 49,000) were mixed with 50 g of a solvent comprising toluene and dioxane and dispersed for 6 hours by means of a ball mill. The thus prepared dispersion was applied onto an aluminum sheet by means of a wire bar and then dried at 100 OC for 2 hours to form a photosensitive layer having a thickness of microns, whereby an electrophotographic photosensitive member was prepared.

The thus obtained photosensitive member was evaluated in the same manner as in Example 1 (Example 22).

Separately, the above-mentioned procedure was repeated except that Compound Example No. 43 was used as the charge-transporting substance contained in the charge transport layer, thereby to prepare another electrophotographic photosensitive member. The thus prepared photosensitive member was evaluated in the same manner an described above (Example 23).

The thus obtained results are shown in the following Table 7.

c Table 7 Examples 24 and An aqueous ammonia solution of casein (comprising 11.2 g of casein, 1 g of 28 ammonia water, and 222 ml of water) was applied onto an aluminum plate by means of a wire bar to form a primer layer having a thickness of 1 micron (after drying).

On the primer layer, a charge transport layer and a charge generation layer were successively formed in the same manner as in Example 4, whereby an electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the laminate structure was different (Example 24).

The charging characteristics of the thus obtained photosensitive member were evaluated in the same manner as in Example 1 except that the charging polarity was positive.

The above procedure was repeated except that the charge transport layer was formed in the same manner as in Example 13 (Example The thus obtained results are shown in the following Table 8.

Table 8 i -57- Examples 26 and 27 A 5 methanol solution of a soluble nylon (6- 66-610-12 quaternary copolymer nylon) was applied onto an aluminum substrate to form a primer layer having a thickness of 0.5 micron (after drying).

Then, 5 of a pigment represented by the Sfollowing formula: Q-HNOC OH HO CONH- CH Q N=N- -CH=CQ -N=N Q CH CN 0 was dispersed in 95 ml of tetrahydrofuran for 20 hours by means of a sand mill to prepare a dispersion.

Separately, 5 g of the above-mentioned Compound Example No. 14 as a charge-transporting substance, and 10 g of a bisphenol Z-type polycarbonate resin (weight-average molecular weight 50,000) were dissolved in 30 ml of monochlorobenzene to prepare a solution. The solution was then added to the abovementioned dispersion, and further dispersed by means of a sand mill for 2 hours, thereby to prepare a coating liquid. The thus prepared coating liquid was applied onto the above-mentioned primer layer by means of a wire bar and dried to form a photosensitive layer having a thickness of 20 microns (after drying), whereby an electrophotographic photosensitive member j -58was prepared.

The electrophotographic characteristics of the thus obtained photosensitive member were evaluated in the same manner as in Example 1 (Example 26).

The above procedure was repeated except that Compound Example No. 32 was used as the chargetransporting substance (Example 27).

The thus obtained results are shown in the following Table 9.

Table 9 Exapl Cmpled v0 V E 1 2 (lux.sec) Example xCmpun

V

0

()V

26 (14) -700 -L13.0 27 (32) -701 -690 3.2 Sib.-

Claims (9)

1. A photosensitive member for electrophoto- graphy, comprising an electroconductive substrate and a i photosensitive layer disposed thereon, wherein the photosensitive layer comprises a triarylamine compound represented by the following general formula or (II): Arl NA-Ar 3 (I) Ar 2 R 1 R 2 Ar4 N (II) Ar wherein Ari and Ar 2 respectively denote a biphenyl group capable of having a substituent; Ar 3 denotes a phenyl group capable of having a substituent or an aromatic heterocyclic group capable of having a substituent; Ar 4 and Ar 5 respectively denote a benzene ring or aromatic fused-ring hydrocarbon group capable of having a substituent; RI and R 2 respectively denote a hydrogen atom, alkyl, alkoxyl or halogen atom; and at least one of Ar 4 and Ar 5 is an aromatic fused-ring hydrocarbon group.

2. A member according to Claim 1, wherein the photosensitive layer has a laminate structure 1 -61- comprising a charge generation layer and a charge transport layer.

3. A member according to Claim 2, which comprises the electroconductive substrate, and the charge generation layer and the charge transport layer in this order on the substrate.

4. A member according to Claim 2, which comprises the electroconductive substrate, and the charge transport layer and the charge generation layer in this order on the substrate.

A member according to Claim 2, wherein the charge transport layer comprises the compound represented by the formula or and an insulating polymer or organic photoconductive polymer.

6. A member according to Claim 2, wherein the charge transport layer comprises the compound represented by the formula or an insulating polymer or organic photoconductive polymer, and at least one species selected from the group consisting of a plasticizer, a surface lubricating agent, a potential stabilizing agent, and an anti-oxidizing agent.

7. A member according to Claim 2, wherein the I -62- charge generation layer comprises an organic charge- generating substance and an insulating resin.

8. A member according to Claim 1, which further comprises a primer layer disposed between the electroconductive substrate and the photosensitive layer.

9. A member according to Claim 1, which further comprises a protective layer disposed on the photosensitive layer. DATED this TWENTY NINTH day of DECEMBER 1989 Canon Kabushiki Kaisha Patent Attorneys for the Applicant SPRUSON FERGUSON