Electrophotographic photoreceptor

FIELD OF THE INVENTION
The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor comprising a charge transporting material containing at least one triphenylamine compound represented by general formula (1) and at least one compound selected from the group consisting of a hydrazone compound represented by general formula (2), a hydrazone compound represented by general formula (3), a triphenylamine dimer compound (N,N,N',N'-tetraphenylbenzidine compound) represented by general formula (4) and a distyryl compound represented by general formula (5): ##STR2## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a halogen atom or a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; and n represents 0 or 1; ##STR3## wherein R.sup.8, R.sup.9 and R.sup.10, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; ##STR4## wherein R.sup.11, R.sup.12 and R.sup.13, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and R.sup.11 or R.sup.12 may form a nitrogen-containing heterocycle unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom, together with R.sup.13 ; R.sup.14 represents a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, a benzyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, or a naphthylmethyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and may form a nitrogen-containing heterocycle unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom, together with R.sup.11, R.sup.12 or R.sup.13 ; and R.sup.15 and R.sup.16 each represents a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, a naphthyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, or a benzyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and R.sup.15 and R.sup.16 may form together a nitrogen-containing heterocycle unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom; ##STR5## wherein R.sup.17, R.sup.18, R.sup.19 and R.sup.20, which may be the same or different, each represents a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; o, p, q and r each represents 0, 1 or 2; and R.sup.21 and R.sup.22, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; ##STR6## wherein R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31 and R.sup.32, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and the central phenyl group may be substituted by two ethylene groups at the o-, p- of m-positions.
BACKGROUND OF THE INVENTION
Organic photoconductive materials are excellent in mass productivity and incur little risk of causing pollution problems when discarded, compared with inorganic photoconductive materials such as selenium alloys, cadmium sulfide and zinc oxide. They have therefore been widely used as photoreceptors for copying machines or printers utilizing electrophotographic systems. In particular, the function separation type laminated photoreceptors are high in material selectivity and easy in functional design, compared with the monolayer type photoreceptors, so that applied research and development thereof in many fields have been made. The function separation type laminated photoreceptors comprises charge generating layers for generating carriers (charge) by light and charge transporting layers for efficiently transporting the carriers generated in the charge generating layers and neutralizing surface charge, and have the possibility of providing electrophotographic photoreceptors high in electrophotographic characteristics such as charging characteristics, sensitivity and residual potential.
Of these, the characteristics of charge transporting materials constituting the charge transporting layers require efficient receiving of the carriers generated in the charge generating layers, rapid transportation of the carriers in the photoreceptor layers and rapid neutralization of surface charge. For example, charge transporting materials such as hydrazone compounds (JP-A-59-223432 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") and JP-A-60-173112), triphenylamine compounds (JP-A-7-173112), distyryl compounds (JP-A-63-269158), triphenylamine dimer compounds (N,N,N',N'-tetraphenylbenzidine compounds) (Denshi Shasin Gakkai Shi (Journal of Electrophotographic Society) 30, 16-21 (1991) and heterocyclic compounds such as poly-N-vinylcarbazole and oxadiazole are already known. When they are used alone, however, some compounds are liable to suffer from light fatigue and cause an increase in residual potential in repeated use. Further, there are still many unsolved problems with respect to the compatibility with binder polymers, and the like.
On the other hand, it has been attempted that specified compounds selected from the known charge transporting materials are used in combination. For example, mixtures of hydrazone compounds and tetraphenylbutadiene compounds (JP-A-63-223755), and mixtures of distyrene compounds and butadiene compounds (JP-A-3-252861) are known. The former discloses that the problem of the light fatigue phenomenon is solved, and the latter discloses that the problem of prevention of a decrease in residual potential is solved. However, even such photoreceptors are not sufficiently high in light sensitivity yet.
Further, use of two positive hole transporting materials, poly(N-vinylcarbazole) and N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1-biphenyl)-4,4'-diamine, as a mixture is described in J. Phys. Chem. 88 (20), 4714-4717 (1984). However, it was observed that combined use of the two materials more reduced the mobility at certain mixing ratios than single use of each material. Accordingly, in some cases, even if two kinds of compounds selected as charge transporting materials both independently exhibit high mobility, they result in decreased performance of the charge transporting materials, leading to the failure to sufficiently keep the characteristics necessary for electrophotographic photoreceptors.
As described above, for the charge transporting materials obtained by mixing two kinds of compounds, ones satisfying all various desirable characteristics such as high charging performance in the dark, high static charge keeping ability, high mobility of charge generated in light irradiation and formation ability of charge transporting layers which are high in solubility in binder polymers and homogeneous have not necessarily been obtained yet at present.
Accordingly, in the charge transporting materials, it has been expected to obtain materials in which the above-mentioned disadvantages are overcome, higher carrier mobility can be exhibited, and various excellent characteristics can be expressed even when the electrophotographic photoreceptors are formed, and the electrophotographic photoreceptors comprising the charge transporting materials having such excellent characteristics have been desired.
SUMMARY OF THE INVENTION
The present inventors have made intensive studies to discover highly sensitive electrophotographic photoreceptors which can form homogeneous, stable charge transporting layers and satisfy various characteristics, giving attention to the characteristics of triphenylamine compounds high in carrier mobility. As a result, the present inventors have discovered that a system in which triphenylamine compounds are combined with hydrazone compounds, triphenylamine dimer compounds (N,N,N',N'-tetraphenylbenzidine compounds) or distyryl compounds which are good in solubility in binders does not reduce carrier mobility, is low in residual potential and can express highly sensitive photoreceptor performance. Further, the present inventors have discovered that electrophotographic photoreceptors produced by using charge transporting materials consisting of mixtures of triphenylamine compounds and hydrazone compounds, triphenylamine dimer compounds (N,N,N',N'-tetraphenylbenzidine compounds) or distyryl compounds also show no light fatigue even after use for a long period of time, do not increase residual potential, do not cau, images, and have highly sensitive, excellent light response thus completing the present invention.
That is, the present invention provides an electrophotographic photoreceptor comprising a charge transporting material containing at least one triphenylamine compound represented by general formula (1) and at least one compound selected from the group consisting of a hydrazone compound represented by general formula (2), a hydrazone compound represented by general formula (3), a triphenylamine dimer compound (N,N,N',N'-tetraphenylbenzidine compound) represented by general formula (4) and a distyryl compound represented by general formula (5): ##STR7## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a halogen atom or a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; and n represents 0 or 1; ##STR8## wherein R.sup.8, R.sup.9 and R.sup.10, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; ##STR9## wherein R.sup.11, R.sup.12 and R.sup.13, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and R.sup.11 or R.sup.12 may form a nitrogen-containing heterocycle unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom, together with R.sup.13 ; R.sup.14 represents a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, a benzyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, or a naphthylmethyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and may form a nitrogen-containing heterocycle unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom, together with R.sup.11, R.sup.12 or R.sup.13 ; and R.sup.15 and R.sup.16 each represents a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, a naphthyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, or a benzyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and R.sup.15 and R.sup.16 may form together a nitrogen-containing heterocycle unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom; ##STR10## wherein R.sup.17, R.sup.18, R.sup.19 and R.sup.20, which may be the same or different, each represents a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; o, p, q and r each represents 0, 1 or 2; and R.sup.21 and R.sup.22, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; ##STR11## wherein R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31 and R.sup.32, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and the central phenyl group may be substituted by two ethylene groups at the o-, p- or m-positions.

BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1(a) to 1(c) are sectional views showing layer structures of electrophotographic photoreceptors;
FIG. 2 is a graph showing the carrier mobility of electrophotographic photoreceptors in Example 127;
FIG. 3 is a graph showing the carrier mobility of electrophotographic photoreceptors in Example 128;
FIG. 4 is a graph showing the carrier mobility of electrophotographic photoreceptors in Example 129;
FIG. 5 is a graph showing the carrier mobility of electrophotographic photoreceptors in Example 130;
FIG. 6 is a graph showing the carrier mobility of electrophotographic photoreceptors in Example 131;
FIG. 7 is a graph showing the carrier mobility of electrophotographic photoreceptors in Example 132;
FIG. 8 is a graph showing the carrier mobility of electrophotographic photoreceptors in Example 133;
FIG. 9 is a graph showing the carrier mobility of electrophotographic photoreceptors in Comparative Example 54;
FIG. 10 is a graph showing the carrier mobility of electrophotographic photoreceptors in Comparative Example 55;
FIG. 11 is a graph showing the carrier mobility of electrophotographic photoreceptors in Comparative Example 56;
FIG. 12 is a graph showing the carrier mobility of electrophotographic photoreceptors in Comparative Example 57;
FIG. 13 is a graph showing the carrier mobility of electrophotographic photoreceptors in Comparative Example 58; and
FIG. 14 is a graph showing the carrier mobility of electrophotographic photoreceptors in Comparative Example 59.

DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the triphenylamine compounds represented by general formula (1) described above can be obtained, for example, by the method described in JP-A-7-173112.
In general formula (1) described above, substituent groups R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a halogen atom or a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom.
Preferably, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 or 2 carbon atoms, a methoxy group, a chlorine atom, a bromine atom, a phenyl group or p-tolyl group.
Of these, examples of the lower alkyl groups having 1 and 2 carbon atoms include methyl and ethyl, and methyl is particularly preferred.
In the present invention, preferred examples of the triphenylamine compounds represented by general formula (1) described above include but are not limited to compounds shown in Tables 1, 2 and 3 given below. The abbreviations used in Tables 1, 2 and 3 have the following meanings, respectively. The abbreviations hereinafter used in compounds in this specification also have the same meanings. The numeral indicates the position of a substituent group in a phenyl group (for example, 4-Me means a methyl group substituted at the 4-position of a phenyl group).
Me: Methyl group
Et: Ethyl group
F: Fluorine atom
Cl: Chlorine atom
Br: Bromine atom
I: Iodine atom
OMe: Methoxy group
OEt: Ethoxy group
p-Tol: p-Tolyl group
Ph: Phenyl group
.alpha.-Np: .alpha.-Naphthyl group
Bn: Benzyl group
nPr: n-Propyl group
iPr: Isopropyl group
iBu: Isobutyl group
O-nPr: n-Propoxy group
O-nBu: n-Butoxy group
O-iPr: Isopropoxy group
O-iBu: Isobutoxy group
p-MeOPh: p-Methoxyphenyl group
TABLE 1__________________________________________________________________________General Formula (1)Examplecompound n R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7__________________________________________________________________________1 0 H H H H H H H2 0 H H H H H 2-Me 2-Me3 0 H H H H H 3-Me 3-Me4 0 H H H H 4-Me H H5 0 H H H H 4-Me 2-Me 2-Me6 0 H H H H 4-OMe H H7 0 H H H H 4-OMe 2-Me 2-Me8 0 H H H H 4-(p-Tol) H H9 0 H H H H 4-(p-Tol) 2-Me 2-Me10 0 H H H H 4-Br H H11 0 H H H H 4-Br 3-Me 3-Me12 0 H H H H 4-Cl H H13 0 H H H H 4-Cl 3-Me 3-Me14 0 H H 4-Me 4-Me H H H15 0 H H 4-Me 4-Me 3-Me H H16 0 3-Me 3-Me H H H H H17 0 3-Me 3-Me H H 3-Me H H18 0 3-Me 3-Me 4-Me 4-Me H H H19 0 3-Me 3-Me 4-Me 4-Me 3-Me H H20 0 4-Me 4-Me 4-Me 4-Me H H H__________________________________________________________________________
TABLE 2__________________________________________________________________________General Formula (1)Examplecompound n R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7__________________________________________________________________________21 1 H H H H H H H22 1 H H H H H 2-Me 2-Me23 1 H H H H 2-Me H H24 1 H H H H 4-Me H H25 1 H H H H 4-Me 3-Me 3-Me26 1 H H H H 4-OMe H H27 1 H H H H 4-OMe 3-Me 3-Me28 1 H H H H 4-(p-Tol) H H29 1 H H H H 4-(p-Tol) 2-Me 2-Me30 1 H H 3-Me 3-Me H H H31 1 H H 3-Me 3-Me 4-Me H H32 1 H H 4-Me 3-Me H H H33 1 H H 4-Me 4-Me 4-Me H H34 1 H H 4-Me 4-Me 4-Br H H35 1 H H 4-Me 4-Me 4-Br 3-Me 3-Me36 1 H H 4-Cl 4-Cl H H H37 1 H H 4-Cl 4-Cl 4-Me H H38 1 H 4-Me H 4-Me H H H39 1 H 4-Me H 4-Me 4-Me H H40 1 3-Me 3-Me 4-Me 4-Me H H H__________________________________________________________________________
TABLE 3__________________________________________________________________________General Formula (1)Examplecompound n R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7__________________________________________________________________________41 1 3-Me 3-Me 4-Me 4-Me 2-Me H H42 1 4-Me 4-Me 4-Me 4-Me H H H43 1 4-Me 4-Me 4-Me 4-Me H 2-Me 2-Me44 1 4-Me 4-Me 4-Me 4-Me H 3-Me 3-Me45 1 4-Me 4-Me 4-Me 2-Me 2-Me H H46 1 4-Me 4-Me 4-Me 4-Me 4-Me 3-Me 3-Me47 1 4-Me 4-Me 4-Me 4-Me 4-Me H H48 1 4-Me 4-Me 4-Me 4-Me 4-Me 2-Me 2-Me49 1 4-Me 4-Me 4-Me 4-Me 4-Et 3-Me 3-Me50 1 4-Me 4-Me 4-Me 4-Me 4-Et H H51 1 4-Me 4-Me 4-Me 4-Me 4-Et 2-Me 2-Me52 1 4-Me 4-Me 4-Me 4-Me 4-OEt H H53 1 4-Me 4-Me 4-Me 4-Me 4-(p-Tol) H H54 1 4-Me 4-Me 4-Me 4-Me 4-Br H H55 1 4-Me 4-Me 4-OMe 4-OMe H H H56 1 4-Me 4-Me 4-Cl 4-Cl H H H57 1 4-OMe 4-OMe 4-OMe 4-OMe H H H58 1 4-OMe 4-OMe 4-OMe 4-OMe 4-Me H H59 1 4-Cl 4-Cl 4-Cl 4-Cl H H H60 1 4-Cl 4-Cl 4-Cl 4-Cl 4-Me H H__________________________________________________________________________
For the compounds represented by general formula (2) described above in the present invention, substituent groups R.sup.8, R.sup.9 and R.sup.10 in general formula (2), which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom.
Preferably, R.sup.8, R.sup.9 and R.sup.10, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a methoxy group or a chlorine atom.
Of these, examples of the lower alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, and methyl and ethyl are particularly preferred.
Preferred examples of the hydrazone compounds represented by general formula (2) described above in the present invention include but are not limited to compounds shown in Table 4 given below.
The abbreviations used in Table 4 have the same meanings as given above. The numeral indicates the position of a substituent group in a phenyl group (for example, 4-Me means a methyl group substituted at the 4-position of a phenyl group).
TABLE 4______________________________________General Formula (2)Examplecompound R.sup.8 R.sup.9 R.sup.10______________________________________61 H H H62 H H 2-Me63 H H 3-Me64 H H 2-OMe65 4-Me H H66 4-Me H 2-Me67 4-Me H 2-Et68 4-Me H 2-nPr69 2-Me H H70 4-Me 4-Me H71 4-Me 4-Me 2-Me72 4-Me 4-Me 2-nPr73 4-OMe H H74 4-OMe H 2-Me75 4-OMe 4-OMe H76 4-OMe 4-OMe 2-Cl77 4-OMe 4-OMe 2-Cl78 4-Cl H H79 4-Cl H 2-Me80 4-Cl 4-Cl H______________________________________
The hydrazone compounds represented by general formula (3) described above in the present invention can be obtained by reacting corresponding aldehydes with hydrazine compounds in inactive organic solvents, for example, according to the method described in JP-A-60-255854.
In general formula (3) described above, R.sup.11, R.sup.12 and R.sup.13, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and R.sup.11 or R.sup.12 may form a nitrogen-containing heterocycle unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom, together with R.sup.13. R.sup.14 represents a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, a benzyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, or a naphthylmethyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and may form a nitrogen-containing heterocycle unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom, together with R.sup.11, R.sup.12 or R.sup.13. R.sup.15 and R.sup.16 each represents a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, a naphthyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, or a benzyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and R.sup.15 and R.sup.16 may form together a nitrogen-containing heterocycle unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, an aryl group or a halogen atom.
Preferably, R.sup.11, R.sup.12 and R.sup.13, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a chlorine atom or a bromine atom, and R.sup.11 or R.sup.12 may form a single bond together with R.sup.13. R.sup.14 represents a lower alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted by a methoxy group, or a benzyl group, and may form an alkylene group having 2 or 3 carbon atoms together with R.sup.13. R.sup.15 and R.sup.16 each represents a methyl group, a phenyl group, a naphthyl group or a benzyl group, and R.sup.15 and R.sup.16 may form together an indoline ring, a carbazole ring or a 1,2,3,4-tetrahydroquinoline ring each of which may be substituted by a lower alkyl group having 1 to 4 carbon atoms or methoxy group.
Of these, examples of the lower alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, and methyl and ethyl are particularly preferred.
Further, the phenyl groups which may be substituted by lower alkyl groups having 1 to 4 carbon atoms or methoxy groups include, for example, phenyl, phenyl groups substituted by lower alkyl groups having 1 to 4 carbon atoms such as p-tolyl and 2,4-dimethylphenyl, and phenyl groups substituted by methoxy groups such as p-methoxyphenyl.
In general formula (3) described above in the present invention, R.sup.11 or R.sup.12 may form a single bond together with R.sup.13. For example, when R.sup.11 or R.sup.12 which is at the 2-position of a phenyl group forms a single bond together with R.sup.13 which is at the 2-position of a phenyl group, a carbazole ring is formed together with a nitrogen atom.
R.sup.14 may form an alkylene group having 2 or 3 carbon atoms together with R.sup.13. For example, when R.sup.14 forms an ethylene group together with R.sup.13 which is at the 2-position of a phenyl group, an indoline ring is formed together with a nitrogen atom. When R.sup.14 forms a propylene group together with R.sup.13, a 1,2,3,4-tetrahydroquinoline ring is formed together with a nitrogen atom.
The lower alkyl groups having 1 to 4 carbon atoms by which indoline rings, carbazole rings or 1,2,3,4-tetrahydroquinoline rings may be substituted include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, and methyl is particularly preferred.
Preferred examples of the hydrazone compounds represented by general formula (3) described above in the present invention include but are not limited to compounds shown in Tables 5 to 7 given below.
The abbreviations used in Tables 5 to 7 have the same meanings as given above. The numeral indicates the position of a substituent group in a phenyl group, and N indicates a nitrogen atom (for example, (2,2)-(single bond) means that the 2-position of a phenyl group is linked by a single bond to the 2-position of a phenyl group, and (N, 2)--(--(CH.sub.2).sub.3 --) means that a nitrogen atom is linked by a propylene chain to the 2-position of a phenyl group).
Further, (a) to (j) are represented by the following formulas: ##STR12##
TABLE 5______________________________________General Formula (3)Examplecompound R.sup.11 R.sup.12 R.sup.13 R.sup.14 R.sup.15 R.sup.16______________________________________81 H H H Ph Ph Ph82 H H H Ph Ph Me83 H H H Ph Ph .alpha.-Np84 H H H Ph (a)85 H H H Ph (b)86 H H H Ph (c)87 H (2,2)-(single bond) Et Ph Ph88 H (2,2)-(single bond) Et (b)89 H (2,2)-(single bond) Et (a)90 H (2,2)-(single bond) Et (c)91 H H (N,2)-(-(CH.sub.2).sub.3 -) Ph Ph92 H H (N,2)-(-(CH.sub.2).sub.3 -) Ph Me93 H 4-Me H p-Tol Ph Ph94 H 4-Me H Ph Ph Me95 H 4-OMe H Ph (a)96 H 4-Br H Ph (b)97 2-Me 4-Me H p-Tol Ph .alpha.-Np98 H 4-Et H p-Tol Ph Ph99 H H H H P-Tol Me100 H H H Ph (d)______________________________________
TABLE 6______________________________________General Formula (3)Examplecompound R.sup.11 R.sup.12 R.sup.13 R.sup.14 R.sup.15 R.sup.16______________________________________101 H H H Ph (b)102 H H H Ph (e)103 H (2,2)-(single bond) i-Pr Ph Ph104 H (2,2)-(single bond) Et (b)105 H (2,2)-(single bond) Et Bn Ph106 H H (N,2)-(-(CH.sub.2).sub.3 -) (b)107 H H (N,2)-(-(CH.sub.2).sub.3 -) (e)108 H H H Bn Ph Ph109 H H H Ph Bn Ph110 H H H Ph (f)111 H (2,2)-(single bond) Et (f)112 H H H Bn Bn Ph113 H 4-OEt H p-Tol Ph Ph114 H 4-Cl H Ph p-Tol Me115 H 4-Me H Ph (d)116 H 4-OMe H Ph (g)117 H 4-OMe H p-MeOPh (e)118 H (2,2)-(single bond) i-Pr Ph p-Tol119 4-Br (2,2)-(single bond) Et (h)120 H (2,2)-(single bond) Et Bn p-Tol______________________________________
TABLE 7______________________________________General Formula (3)Examplecompound R.sup.11 R.sup.12 R.sup.13 R.sup.14 R.sup.15 R.sup.16______________________________________121 H 4-Me (N,2)-(-(CH.sub.2).sub.3 -) (h)122 H H (N,2)-(-(CH.sub.2).sub.3 -) (i)123 H 4-Me 3-Me Bn Ph Ph124 H 4-OMe H p-Tol Bn Ph125 2-OMe 4-Me H p-MeOPh (f)126 H (2,2)-(single bond) Et (j)127 H 4-Me H Bn Bn Ph128 H H H Me Ph Ph______________________________________
The triphenylamine dimer compounds (N,N,N',N'-tetraphenylbenzidine compounds) represented by general formula (4) described above in the present invention can be obtained, for example, by reacting corresponding diarylamines with diiodobiphenyl derivatives in inactive organic solvents Denshi Shasin Gakkai Shi (Journal of Electrophotographic Society) 30, 16-21 (1991)).
In general formula (4) described above in the present invention, substituent groups R.sup.17, R.sup.18, R.sup.19 and R.sup.20, which may be the same or different, each represents a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; o, p, q and r each represents 0, 1 or 2; and R.sup.21 and R.sup.22, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom.
Preferably, R.sup.17 R.sup.18, R.sup.19 and R.sup.20, which may be the same or different, each represents a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; o, p, q and r each represents 0, 1 or 2; and R.sup.21 and R.sup.22, which may be the same or different, each represents a hydrogen atom, a methyl group, a methoxy group or a chlorine atom.
Of these, examples of the lower alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, and methyl and ethyl are particularly preferred.
The lower alkoxyl groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy and butoxy, and methoxy and ethoxy are particularly preferred.
The halogen atoms include, for example, fluorine, chlorine, bromine and iodine.
Preferred examples of the triphenylamine dimer compounds (N,N,N',N'-tetraphenylbenzidine compounds) represented by general formula (4) described above in the present invention include but are not limited to compounds shown in Tables 8 to 10 given below.
The abbreviations used in Tables 8 to 10 have the same meanings as given above.
TABLE 8__________________________________________________________________________General Formula (4)Examplecompound o R.sup.17 p R.sup.18 q R.sup.19 r R.sup.20 R.sup.21 R.sup.22__________________________________________________________________________129 0 -- 0 -- 0 -- 0 -- H H130 1 4-Me 0 -- 1 4-Me 0 -- H H131 1 3-Me 0 -- 1 3-Me 0 -- H H132 2 2-Me 0 -- 2 2-Me 0 -- H H 4-Me 4-Me133 0 -- 0 -- 0 -- 0 -- Me Me134 1 4-Me 0 -- 1 4-Me 0 -- Me Me135 1 3-Me 0 -- 1 3-Me 0 -- Me Me136 2 2-Me 0 -- 2 2-Me 0 -- Me Me 4-Me 4-Me137 1 4-Me 1 4-Me 1 4-Me 1 4-Me H H138 1 4-Me 1 3-Me 1 4-Me 1 3-Me H H139 1 3-Et 0 -- 1 3-Et 0 -- H H140 1 4-Et 0 -- 1 4-Et 0 -- H H141 1 4-Et 0 -- 1 4-Et 0 -- H H142 2 3-Me 1 4-Et 2 3-Me 1 4-Et H H 4-Me 4-Me143 2 3-Me 1 4-Et 2 3-Me 1 4-Et Me Me 4-Me 4-Me144 1 4-Me 1 4-Me 1 4-Me 1 4-Me Me Me145 1 4-nPr 0 -- 1 4-nPr 0 -- H H146 1 3-nBu 0 -- 1 3-Me 0 -- H H147 1 4-iPr 0 -- 1 4-iPr 0 -- H H148 1 4-iBu 0 -- 1 4-iBu 0 -- Me Me__________________________________________________________________________
TABLE 9__________________________________________________________________________General Formula (4)Examplecompound o R.sup.17 p R.sup.18 q R.sup.19 r R.sup.20 R.sup.21 R.sup.22__________________________________________________________________________149 1 4-OMe 0 -- 1 4-OMe 0 -- H H150 1 4-OMe 0 -- 1 4-Me 0 -- H H151 1 3-Me 0 -- 1 4-OMe 0 -- H H152 1 4-Me 1 4-OMe 1 4-OMe 1 4-OMe H H153 1 4-OMe 0 -- 1 4-OMe 0 -- Me Me154 1 4-OMe 0 -- 1 4-Me 0 -- Me Me155 1 3-Me 0 -- 1 4-Me 0 -- Me Me156 1 4-Me 1 4-OMe 1 4-Me 1 4-OMe Me Me157 1 3-OMe 0 -- 1 3-OMe 0 -- H H158 1 4-OMe 1 3-Me 1 4-OMe 1 3-Me H H159 1 3-OEt 0 -- 1 3-OEt 0 -- H H160 1 4-OEt 0 -- 1 4-OEt 0 -- H H161 1 4-OMe 0 -- 1 4-Me 0 -- Me Me162 2 3-OMe 0 -- 2 3-OMe 0 -- H H 4-OMe 4-OMe163 2 3-OMe 0 -- 2 3-OMe 0 -- Me Me 4-OMe 4-OMe164 1 4-Me 1 4-Me 1 4-Me 1 4-Me OMe OMe165 1 4-O-nPr 0 -- 1 4-O-nPr 0 -- H H166 1 3-O-nBu 0 -- 1 4-Me 0 -- H H167 1 4-O-iPr 0 -- 1 4-O-iPr 0 -- H H168 1 4-O-iBu 0 -- 1 4-O-iBu 0 -- Me H__________________________________________________________________________
TABLE 10__________________________________________________________________________General Formula (4)Examplecompound o R.sup.17 p R.sup.18 q R.sup.19 r R.sup.20 R.sup.21 R.sup.22__________________________________________________________________________169 1 4-Cl 0 -- 1 4-Cl 0 -- H H170 1 4-Me 1 4-Cl 1 4-Me 1 4-Cl H H171 1 3-Me 1 4-Cl 1 3-Me 1 4-Cl H H172 2 2-Me 1 4-Cl 2 2-Me 1 4-Cl H H 4-Me 4-Me173 1 4-Br 0 -- 1 4-Br 0 -- H H174 1 4-Me 1 4-Br 1 4-Me 1 4-Br H H175 1 3-Me 1 4-Br 1 3-Me 1 4-Br H H176 2 2-Me 1 4-Br 2 2-Me 1 4-Br H H 4-Me 4-Me177 1 4-F 0 -- 1 4-F 0 -- H H178 1 4-Me 1 4-F 1 4-Me 1 4-F H H179 1 3-Me 1 4-F 1 3-Me 1 4-F H H180 2 2-Me 1 4-F 2 2-Me 1 4-F H H 4-Me 4-Me181 1 4-Et 1 4-I 1 4-Et 1 4-I Me Me182 1 4-OMe 1 4-Cl 1 4-OMe 1 4-Cl H H183 2 3-OMe 1 4-Br 2 3-OMe 1 4-Br Me Me 4-OMe 4-OMe184 1 4-Me 1 4-Me 1 4-Me 1 4-Me Cl Cl185 1 4-Me 0 -- 1 4-Cl 0 -- H H186 1 3-Me 0 -- 1 4-Cl 0 -- H H187 1 2-Me 0 -- 1 2-Me 0 -- H H188 1 4-Me 0 -- 1 4-F 0 -- H H__________________________________________________________________________
The distyryl compounds represented by general formula (5) in the present invention can be obtained, for example, according to the method described in JP-A-63-269158.
In general formula (5) described above, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31 and R.sup.32, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and the central phenyl group may be substituted by two ethylene groups at the o-, p- or m-positions.
Preferably, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31 and R.sup.32, which may be the same or different, each represents a hydrogen atom, a lower alkyl group having 1 or 2 carbon atoms, a methoxy group, a chlorine atom or a bromine atom, and the central phenyl group may be substituted by two ethylene groups at the o-, p- or m-positions.
Of these, examples of the lower alkyl groups having 1 and 2 carbon atoms include methyl and ethyl.
Preferred examples of the distyryl compounds represented by general formula (5) described above in the present invention include but are not limited to compounds shown in Tables 11 to 16 given below.
TABLE 11__________________________________________________________________________General Formula (5)Examplecompound R.sup.23 R.sup.24 R.sup.25 R.sup.26 R.sup.27 R.sup.28 R.sup.29 R.sup.30 R.sup.31 R.sup.32 *__________________________________________________________________________189 H H H H H H H H H H (p)190 3-Me H H H H H 3-Me H H H (p)191 2-Me H H H H H 2-Me H H H (p)192 4-Me H H H H H 4-Me H H H (p)193 4-Me H 4-Me H H H 4-Me H 4-Me H (p)194 2-Me 4-Me H H H H 2-Me 4-Me H H (p)195 2-Me 4-Me 4-Me H H H 2-Me 4-Me 4-Me H (p)196 4-Me H 2-Me H H H 4-Me H 2-Me H (p)197 2-Me 4-Me 2-Me 4-Me H H 2-Me 4-Me 2-Me 4-Me (p)198 2-Me 4-Me 2-Me H H H 2-Me 4-Me 2-Me H (p)199 H H H H 2-Me 2-Me H H H H (p)200 4-Me H H H 2-Me 2-Me 4-Me H H H (p)201 4-Me H 4-Me H 2-Me 2-Me 4-Me H 4-Me H (p)202 4-Me H 2-Me 4-Me 2-Me 2-Me 4-Me H 2-Me 4-Me (p)203 4-Me H 2-Me H 2-Me 2-Me 4-Me H 2-Me H (p)204 2-Me 4-Me 2-Me 4-Me 2-Me 2-Me 2-Me 4-Me 2-Me 4-Me (p)205 H H H H 3-Me 3-Me H H H H (p)206 4-Me H H H 3-Me 3-Me 4-Me H H H (p)207 4-Me H 4-Me H 3-Me 3-Me 4-Me H 4-Me H (p)208 4-Me H 2-Me 4-Me 3-Me 3-Me 4-Me H 2-Me 4-Me (p)__________________________________________________________________________ *: substituting position
TABLE 12__________________________________________________________________________General Formula (5)Examplecompound R.sup.23 R.sup.24 R.sup.25 R.sup.26 R.sup.27 R.sup.28 R.sup.29 R.sup.30 R.sup.31 R.sup.32 *__________________________________________________________________________209 4-Et H H H H H 4-Et H H H (p)210 3-Et H H H H H 3-Et H H H (p)211 2-Et H H H H H 2-Et H H H (p)212 4-Cl H H H H H 4-Cl H H H (p)213 4-Br H H H H H 4-Br H H H (p)214 2-Me 4-Me 4-Br H H H 2-Me 4-Me 4-Br H (p)215 2-Me 4-Me 4-Cl H H H 2-Me 4-Me 4-Cl H (p)216 4-F H H H H H 4-F H H H (p)217 2-Me 4-Me 4-Me H H H 4-Me H 4-Me H (p)218 2-Me 4-Me 4-Me H H H 4-Me H H H (p)219 H H H H H H 2-Me 4-Me H H (p)220 4-Me H 4-Me H 2-Me H 4-Me H 4-Me H (p)221 4-OMe H H H H H 4-OMe H H H (p)222 4-OMe H 2-Me 4-Me H H 4-OMe H 2-Me 4-Me (p)223 4-OMe H 2-Me H H H 4-OMe H 2-Me H (p)224 2-OMe 4-Me 2-Me 4-Me H H 2-OMe 4-Me 2-Me 4-Me (p)225 4-OMe H 4-Me H H H 4-OMe H 4-Me H (p)226 2-OMe 5-Me H H H H 2-OMe 5-Me H H (p)227 3-OMe H H H H H 3-OMe H H H (p)228 4-OMe H 4-Me H 2-Me 2-Me 4-OMe H 4-Me H (p)__________________________________________________________________________ *: substituting position
TABLE 13__________________________________________________________________________General Formula (5)Examplecompound R.sup.23 R.sup.24 R.sup.25 R.sup.26 R.sup.27 R.sup.28 R.sup.29 R.sup.30 R.sup.31 R.sup.32 *__________________________________________________________________________229 H H H H H H H H H H (m)230 3-Me H H H H H 3-Me H H H (m)231 2-Me H H H H H 2-Me H H H (m)232 4-Me H H H H H 4-Me H H H (m)233 4-Me H 4-Me H H H 4-Me H 4-Me H (m)234 2-Me 4-Me H H H H 2-Me 4-Me H H (m)235 2-Me 4-Me 4-Me H H H 2-Me 4-Me 4-Me H (m)236 4-Me H 2-Me H H H 4-Me H 2-Me H (m)237 2-Me 4-Me 2-Me 4-Me H H 2-Me 4-Me 2-Me 4-Me (m)238 2-Me 4-Me 2-Me H H H 2-Me 4-Me 2-Me H (m)239 H H H H 2-Me 2-Me H H H H (m)240 4-Me H H H 2-Me 2-Me 4-Me H H H (m)241 4-Me H 4-Me H 2-Me 2-Me 4-Me H 4-Me H (m)242 4-Me H 2-Me 4-Me 2-Me 2-Me 4-Me H 2-Me 4-Me (m)243 4-Me H 2-Me H 2-Me 2-Me 4-Me H 2-Me H (m)244 2-Me 4-Me 2-Me 4-Me 2-Me 2-Me 2-Me 4-Me 2-Me 4-Me (m)245 H H H H 3-Me 3-Me H H H H (m)246 4-Me H H H 3-Me 3-Me 4-Me H H H (m)247 4-Me H 4-Me H 3-Me 3-Me 4-Me H 4-Me H (m)248 4-Me H 2-Me 4-Me 3-Me 3-Me 4-Me H 2-Me 4-Me (m)__________________________________________________________________________ *: substituting position
TABLE 14__________________________________________________________________________General Formula (5)Examplecompound R.sup.23 R.sup.24 R.sup.25 R.sup.26 R.sup.27 R.sup.28 R.sup.29 R.sup.30 R.sup.31 R.sup.32 *__________________________________________________________________________249 4-Et H H H H H 4-Et H H H (m)250 3-Et H H H H H 3-Et H H H (m)251 2-Et H H H H H 2-Et H H H (m)252 4-Cl H H H H H 4-Cl H H H (m)253 4-Br H H H H H 4-Br H H H (m)254 2-Me 4-Me 4-Br H H H 2-Me 4-Me 4-Br H (m)255 2-Me 4-Me 4-Cl H H H 2-Me 4-Me 4-Cl H (m)256 4-F H H H H H 4-F H H H (m)257 2-Me 4-Me 4-Me H H H 4-Me H 4-Me H (m)258 2-Me 4-Me 4-Me H H H 4-Me H H H (m)259 H H H H H H 2-Me 4-Me H H (m)260 4-Me H 4-Me H 2-Me H 4-Me H 4-Me H (m)261 4-OMe H H H H H 4-OMe H H H (m)262 4-OMe H 2-Me 4-Me H H 4-OMe H 2-Me 4-Me (m)263 4-OMe H 2-Me H H H 4-OMe H 2-Me H (m)264 2-OMe 4-Me 2-Me 4-Me H H 2-OMe 4-Me 2-Me 4-Me (m)265 4-OMe H 4-Me H H H 4-OMe H 4-Me H (m)266 2-OMe 5-Me H H H H 2-OMe 5-Me H H (m)267 3-OMe H H H H H 3-OMe H H H (m)268 4-OMe H 4-Me H 2-Me 2-Me 4-OMe H 4-Me H (m)__________________________________________________________________________ *: substituting position
TABLE 15__________________________________________________________________________General Formula (5)Examplecompound R.sup.23 R.sup.24 R.sup.25 R.sup.26 R.sup.27 R.sup.28 R.sup.29 R.sup.30 R.sup.31 R.sup.32 *__________________________________________________________________________269 H H H H H H H H H H (o)270 3-Me H H H H H 3-Me H H H (o)271 2-Me H H H H H 2-Me H H H (o)272 4-Me H H H H H 4-Me H H H (o)273 4-Me H 4-Me H H H 4-Me H 4-Me H (o)274 2-Me 4-Me H H H H 2-Me 4-Me H H (o)275 2-Me 4-Me 4-Me H H H 2-Me 4-Me 4-Me H (o)276 4-Me H 2-Me H H H 4-Me H 2-Me H (o)277 2-Me 4-Me 2-Me 4-Me H H 2-Me 4-Me 2-Me 4-Me (o)278 2-Me 4-Me 2-Me H H H 2-Me 4-Me 2-Me H (o)279 H H H H 2-Me 2-Me H H H H (o)280 4-Me H H H 2-Me 2-Me 4-Me H H H (o)281 4-Me H 4-Me H 2-Me 2-Me 4-Me H 4-Me H (o)282 4-Me H 2-Me 4-Me 2-Me 2-Me 4-Me H 2-Me 4-Me (o)283 4-Me H 2-Me H 2-Me 2-Me 4-Me H 2-Me H (o)284 2-Me 4-Me 2-Me 4-Me 2-Me 2-Me 2-Me 4-Me 2-Me 4-Me (o)285 H H H H 3-Me 3-Me H H H H (o)286 4-Me H H H 3-Me 3-Me 4-Me H H H (o)287 4-Me H 4-Me H 3-Me 3-Me 4-Me H 4-Me H (o)288 4-Me H 2-Me 4-Me 3-Me 3-Me 4-Me H 2-Me 4-Me (o)__________________________________________________________________________ *: substituting position
TABLE 16__________________________________________________________________________General Formula (5)Examplecompound R.sup.23 R.sup.24 R.sup.25 R.sup.26 R.sup.27 R.sup.28 R.sup.29 R.sup.30 R.sup.31 R.sup.32 *__________________________________________________________________________289 4-Et H H H H H 4-Et H H H (o)290 3-Et H H H H H 3-Et H H H (o)291 2-Et H H H H H 2-Et H H H (o)292 4-Cl H H H H H 4-Cl H H H (o)293 4-Br H H H H H 4-Br H H H (o)294 2-Me 4-Me 4-Br H H H 2-Me 4-Me 4-Br H (o)295 2-Me 4-Me 4-Cl H H H 2-Me 4-Me 4-Cl H (o)296 4-F H H H H H 4-F H H H (o)297 2-Me 4-Me 4-Me H H H 4-Me H 4-Me H (o)298 2-Me 4-Me 4-Me H H H 4-Me H H H (o)299 H H H H H H 2-Me 4-Me H H (o)300 4-Me H 4-Me H 2-Me H 4-Me H 4-Me H (o)301 4-OMe H H H H H 4-OMe H H H (o)302 4-OMe H 2-Me 4-Me H H 4-OMe H 2-Me 4-Me (o)303 4-OMe H 2-Me H H H 4-OMe H 2-Me H (o)304 2-OMe 4-Me 2-Me 4-Me H H 2-OMe 4-Me 2-Me 4-Me (o)305 4-OMe 4-Me H H H H 4-OMe H 4-Me H (o)306 2-OMe 5-Me H H H H 2-OMe 5-Me H H (o)307 3-OMe H H H H H 3-OMe H H H (o)308 4-OMe H 4-Me H 2-Me 2-Me 4-OMe H 4-Me H (o)__________________________________________________________________________ *: substituting position
The charge transporting material according to the present invention contains a mixture of the triphenylamine compound represented by general formula (1) described above and at least one compound selected from the group consisting of the hydrazone compound represented by general formula (2) described above, the hydrazone compound represented by general formula (3) described above, the triphenylamine dimer compound (N,N,N',N'-tetraphenylbenzidine compound) represented by general formula (4) described above and the distyryl compound represented by general formula (5) described above. There is no particular limitation on a method for preparing the mixture of both the compounds.
The mixing ratio of the compounds, namely the mixing ratio of the triphenylamine compound (1) to at least one compound selected from the group consisting of the hydrazone compound (2), the hydrazone compound (3), the triphenylamine dimer compound (N,N,N',N'-tetraphenylbenzidine compound) (4) and the distyryl compound (5), can be from 5% to 95% by weight, and preferably from 5% to 50% by weight, because some triphenylamine compound is poor in solubility in a binder.
The charge transporting layer can be formed by coating a conductive support or the charge generating layer with a solution in which the triphenylamine compound represented by general formula (1) described above, at least one compound selected from the group consisting of the hydrazone compound represented by general formula (2) described above, the hydrazone compound represented by general formula (3) described above, the triphenylamine dimer compound (N,N,N',N'-tetraphenylbenzidine compound) represented by general formula (4) described above and the distyryl compound represented by general formula (5) described above, and a binder are dissolved in an appropriate solvent, and drying it. The binders usually affect not only electric characteristics such as charging properties and sensitivity of the photoreceptors, but also binding strength of the photosensitive layers and mechanical properties such as hardness and abrasion resistance to influence the durability of the photoreceptors. Furthermore, the binders affect viscosity of the coating liquid, dispersion stability of the charge generating materials and production conditions. Accordingly examples of the binders used in the present invention include polycarbonates, polyesters, polystyrene, polyacrylates, polymethacrylates, polyamides, acrylic resins, vinyl chloride resins, vinyl acetate resins, epoxy resins, polyurethanes, copolymers thereof and mixtures thereof. In addition to such insulating polymers, organic photoconductive polymers such as polyvinylcarbazole, polyvinylanthracene and polysilane can also be used.
Of these binders, polycarbonates are particularly preferably used. The polycarbonates include bisphenol methane type polycarbonates represented by the following formula (H): ##STR13## wherein R.sup.33 and R.sup.34 each independently represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and may form together an alicyclic group unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a phenyl group or a halogen atom; R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41 and R.sup.42 each independently represents a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; and n represents an integer.
Specific examples of the polycarbonates include bisphenol A type polycarbonates represented by the following formula (H-1) (for example, Yupilon E series manufactured by Mitsubishi Gas Chemical Co., Inc.), bisphenol Z type polycarbonate resins represented by the following formula (H-2) (for example, Polycarbonate Z series manufactured by Mitsubishi Gas Chemical Co., Inc.), polycarbonates represented by the following formula (H-3) or (H-4), mixtures thereof and copolymers thereof. These polycarbonates preferably have relatively high molecular weight so that cracks or flaws are hard to develop when formed into the photoreceptors. ##STR14##
Examples of the copolymers include copolymers in which the monomer units represented by formula (H) are appropriately combined, and a bisphenol/biphenol type copolymerized polycarbonate resin (JP-A-4-179961) represented by the following formula (J) is preferably used: ##STR15## wherein R.sup.33 and R.sup.34 each independently represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and may form together an alicyclic group unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a phenyl group or a halogen atom; R.sup.35, R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41 and R.sup.42 each independently represents a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47, R.sup.48, R.sup.49 and R.sup.50 each independently represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a halogen atom or a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, and may each independently cyclically bind; and m and n each represents an integer.
Further, specific examples of the bisphenol type copolymerized polycarbonate include bisphenol/biphenol type copolymerized polycarbonate resins represented by the following formulas (J-1), (J-2), (J-3) and (J-4) (the ratio of m to n may be any). ##STR16##
In addition to the above-mentioned polycarbonates, the polycarbonates further include polycarbonates having repeating units represented by the following formulas (JP-A-6-214412 and JP-A-6-222581): ##STR17## wherein R.sup.51, R.sup.52 and R.sup.53 each independently represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, a halogen atom, a 3- to 8-membered carbon atom-containing alicyclic groups unsubstituted or substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, a phenyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, a naphthyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, a benzyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom, or a naphthylmethyl group which may be substituted by a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a halogen atom; and n represents an integer.
These binders may be mixed with the charge transporting materials used in the present invention at any ratio. Usually, the charge transporting materials are added in an amount of 10 to 1,000 parts by weight, and preferably in an amount of 25 to 500 parts by weight, per 100 parts by weight of binder.
Although the film thickness of the resulting charge transporting materials is generally 2 .mu.m to 40 .mu.m, it is preferably 5 .mu.m to 30 .mu.m.
The organic solvents used in forming such charge transporting layers include ketones such as methyl ethyl ketone and cyclohexanone, amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether, esters such as ethyl acetate and methyl acetate, aliphatic halogen hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, dichloroethylene, carbon tetrachloride, trichloroethylene and trichloroethane, aromatic compounds such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, and mixtures thereof.
The charge transporting layers obtained as described above are electrically connected to the charge generating layers, and have the functions of receiving carriers injected from the charge generating layers in the presence of the electric field and being able to transport the carriers to surfaces of the photoreceptors. In this case, the charge transporting layers may be formed either on or under the charge generating layers disposed on conductive substrates. However, it is desirable that the charge transporting layers are formed on the charge generating layers.
With respect to the charge generating layers, materials selected from inorganic charge generating materials such as selenium, selenium-tellurium and amorphous silicon; cationic dyes such as pyrylium salt dyes, thiapyrylium salt dyes, azulenium salt dyes, thiacyanine dyes and quinocyanine dyes; polycyclic quinone pigments such as squarylium salt pigments, phthalocyanine pigments, anthoanthrone pigments, dibenz-pyrenequinone pigments and pyranthrone pigments; and organic charge generating materials such as indigo pigments, quinacridone pigments, azo pigments and pyrrolopyrrole pigments can be used alone or in combination as deposited layers or coated layers. Of the organic charge generating materials as described above, organic charge generating materials described in Chem. Rev. 93, 449-486 (1993) are particularly preferred. Specifically, phthalocyanine pigments are preferred.
In particular, the phthalocyanine pigments include oxotitanium phthalocyanine (TiOPc), copper phthalocyanine (CuPc), metal-free phthalocyanine (H.sub.2 PC), hydroxygallium phthalocyanine (HOGaPc), vanadyl phthalocyanine (VOPc) and chloroindium phthalocyanine (ClInPc). More particularly, TiOPc includes .alpha.-TiOPc, .beta.-TiOPc, .gamma.-TiOPc, m-TiOPc, Y-TiOPc, A-TiOPc, B-TiOPc, amorphous TiOPc and dimethylethylene glycoside titanium phthalocyanine. H.sub.2 Pc includes .alpha.-H.sub.2 Pc, .beta.-H.sub.2 Pc, .tau.-H.sub.2 Pc, .tau..sub.2 -H.sub.2 Pc and X-H.sub.2 Pc. Mixed crystals of these phthalocyanine pigments (for example, JP-A-6-148917 and JP-A6-271786) can also be suitably used.
Further, the azo compounds include various monoazo pigments, bisazo pigments, trisazo pigments and tetrakisazo pigments, and the compounds represented by the following structural formulas are preferred. ##STR18##
Further, the perylene compound represented by the following structural formula (S) or the polycyclic quinone compound represented by the following structural formula (T) are also preferred. ##STR19##
In addition to these, any materials can be used as long as they are materials absorbing light and generating charge at high efficiency.
The conductive supports used in the photoreceptors of the present invention include foils or plates of metals such as copper, aluminum, silver, iron, zinc and nickel or alloys thereof formed into the sheet form or the drum form, plastic films or cylinders over which these metals are vacuum deposited or electrolytically plated, or supports such as glass, paper and plastic films over which layers of conductive compounds such as conductive polymers, indium oxide and tin oxide are provided by coating or vapor deposition.
Coating can be conducted by use of coating methods such as dip coating, spray coating, spinner coating, wire bar coating, blade coating, roller coating and curtain coating.
Drying is preferably conducted by the method of heating at room temperature, followed by heat drying. It is preferred that the heat drying is generally performed at a temperature of 30.degree. C. to 200.degree. C. for 5 minutes to 4 hours in still or forced air.
In order to improve the durability of the photoreceptors, ultraviolet absorbers, antioxidants and other additives are used in the photosensitive layers in the present invention as required. The various additives include, for example, plasticizers such as biphenyl compounds disclosed in JP-A-6-332206, m-di-tert-butylphenyl and dibutyl phthalate, surface lubricants such as silicone oil, graft type silicone polymers and various fluorocarbons, potential stabilizers such as dicyanovinyl compounds and carbazole derivatives, monophenol antioxidants such as 2-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-methylphenol, bisphenol antioxidants, polymeric phenol antioxidants, amine antioxidants such as 4-diazabicyclo�2,2,2!octane, salicylic acid antioxidants, dilauryl-3,3-thiodiamine antioxidants, phosphorus antioxidants, hindered amine light stabilizers such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, and dl-.alpha.-tocopherol (vitamin E).
On the photosensitive layers thus prepared, protective layers can be formed by coating as required. Underlayers having the barrier function and the adhesive function can also be provided between the conductive supports and photosensitive layers. Materials for forming the underlayers include polyvinyl alcohol, nitrocellulose, casein, ethylene-acrylic acid copolymers, polyamides such as nylon, polyurethanes, gelatin and aluminum oxide. The film thickness of the underlayers is 0.1 .mu.m to 5 .mu.m, and preferably 0.5 .mu.m to 3 .mu.m.
As described above, the charge transporting material can be obtained which contains at least one triphenylamine compound represented by general formula (1) and at least one compound selected from the group consisting of the hydrazone compound represented by general formula (2), the hydrazone compound represented by general formula (3), the triphenylamine dimer compound represented by general formula (4) and the distyryl compound represented by general formula (5). The electrophotographic photoreceptor (shown in FIG. 1(a) or 1(b)) can be obtained in which the charge transporting layer containing said charge transporting material and the above-mentioned charge generating layer are laminated with each other to form the photosensitive layer, and the electrophotographic photoreceptor (shown in FIG. 1(c)) in which the above-mentioned charge generating material is dissolved (molecularly dispersed) in the charge transporting layer containing said charge transporting material or mixed therewith in the form of fine grain dispersion to form the photosensitive layer.
The present invention will be described with reference to examples below, but these are not to be construed as limiting the invention. It is to be understood that changes and variations may be made without departing from the spirit and the scope of the present invention.
Abbreviations used in the examples are as follows:
V.sub.0 : Initial surface charge potential (unit: -volt, hereinafter described as -V)
V.sub.1 : Surface potential after keeping in the dark for 5 seconds (unit: -V)
E.sub.1/2 : Half-exposure (unit: lux.multidot.second, hereinafter described as lux.multidot.s)
E.sub.1/6 : Exposure necessary for attenuating the surface potential V.sub.1 to 1/6 (unit: lux.multidot.s)
V.sub.R10 : Surface residual potential after light irradiation for 10 seconds (unit: -V) Comparative
Compounds used in the examples have the following structures: ##STR20##
EXAMPLES 1 TO 7 AND COMPARATIVE EXAMPLES 1 AND 2
Oxotitanium phthalocyanine (TiOPc) was vacuum deposited at 10.sup.-6 Torr to a thickness of about 0.8 .mu.m on an aluminum thin film deposited on a polyester film to form a charge generating layer. Further, one part of the test compounds in each example shown in Table 17 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z-200, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the above-mentioned charge generating layer with a-doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor.
The electrophotographic characteristics of the electrophotographic photoreceptors thus obtained were measured by the static system using an electrostatic paper analyzer Model EPA-8200 (manufactured by Kawaguchi Electric Works). That is, the photoreceptors were exposed to the corona discharge of -6 kV to charge them, and the surface potential V.sub.0 was measured. They were kept in the dark for 5 seconds (surface potential V.sub.1), followed by irradiation of light having an illuminance of 5 luxes with a halogen lamp. Then, the exposure necessary for decreasing the surface potential to 1/2 or 1/6 (E.sub.1/2 or E.sub.1/6) was measured. Subsequently, after irradiation of light having an illuminance of 5 luxes for 10 seconds, the surface residual potential V.sub.R10 was determined.
In Comparative Example 1, comparative compound 1 was used in place of one of the test compounds, and in Comparative Example 2, only example compound 47, a triphenylamine compound, was used.
Results thereof are shown in Table 18.
TABLE 17______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example 1 Example compound 1 H-2 Dichlo- TiOPc (0.4 part) (1 part) roethane Deposited Example compound 63 (0.6 part)Example 2 Example compound 21 H-2 Dichlo- TiOPc (0.5 part) (1 part) roethane Deposited Example compound 63 (0.5 part)Example 3 Example compound 42 H-2 Dichlo- TiOPc (0.4 part) (1 part) roethane Deposited Example compound 61 (0.6 part)Example 4 Example compound 21 H-2 Toluene TiOPc (0.5 part) (1 part) Deposited Example compound 63 (0.5 part)Example 5 Example compound 21 H-2 Tetrahy- TiOPc (0.5 part) (1 part) drofuran Deposited Example compound 63 (0.5 part)Example 6 Example compound 47 H-2 Tetrahy- TiOPc (0.4 part) (1 part) drofuran Deposited Example compound 61 (0.6 part)Example 7 Example compound 47 H-2 Dioxane TiOPc (0.4 part) (1 part) Deposited Example compound 61 (0.6 part)Compara- Comparative comp- H-2 Dichlo- TiOPctive Ex- ound 1 (0.4 part) (1 part) roethane Depositedample 1 Example compound 63 (0.6 part)Compara- Example compound 47 H-2 Dichlo- TiOPctive Ex- (1.0 part) (1 part) roethane Depositedample 2______________________________________
TABLE 18______________________________________ ##STR21## ##STR22## ##STR23## ##STR24## ##STR25##______________________________________Example 1 932 603 12 0.83 2.51Example 2 971 671 11 0.72 1.98Example 3 789 398 3 0.75 2.61Example 4 923 756 0 1.33 3.33Example 5 1072 951 0 1.19 2.82Example 6 1118 988 11 1.15 2.73Example 7 1009 815 0 1.11 2.51Comparative 924 624 55 1.14 6.91Example 1Comparative UnmeasurableExample 2______________________________________
As apparent from Table 18, it has become clear that the photoreceptors of the present invention prepared by use of the test compounds of Examples 1 to 7 were low in residual potential and also low in E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 1 prepared by use of comparative compound 1.
For the photoreceptor of Comparative Example 2 prepared by use of example compound 47 alone, cracks developed in the photoreceptor layer after film formation.
EXAMPLES 8 TO 13 AND COMPARATIVE EXAMPLE 3
A charge generating layer was prepared in the same manner as with Examples 1 to 7. A photoreceptor was prepared and the electrophotographic characteristics thereof were measured in the same manner as with Examples 1 to 7 with the exception that the test compounds in each example shown in Table 19 were used in an amount of one part in place of the compounds shown in Table 17 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) was used in place of the polycarbonate resin represented by formula (H-2).
In Comparative Example 3, comparative compound 1 was used in place of one of the test compounds.
Results thereof are shown in Table 20.
TABLE 19______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example 8 Example compound 21 J-1 Dichlo- TiOPc (0.5 part) (1 part) roethane Deposited Example compound 61 (0.5 part)Example 9 Example compound 1 J-1 Tetrahy- TiOPc (0.4 part) (1 part) drofuran Deposited Example compound 63 (0.6 part)Example Example compound 1 J-1 Dioxane TiOPc10 (0.4 part) (1 part) Deposited Example compound 63 (0.6 part)Example Example compound 42 J-1 Tetrahy- TiOPc11 (0.3 part) (1 part) drofuran Deposited Example compound 61 (0.7 part)Example Example compound 42 J-1 Dioxane TiOPc12 (0.3 part) (1 part) Deposited Example compound 63 (0.7 part)Example Example compound 47 J-1 Tetrahy- TiOPc13 (0.4 part) (1 part) drofuran Deposited Example compound 63 (0.6 part)Compara- Comparative comp- J-1 Dichlo- TiOPctive Ex- ound 1 (0.4 part) (1 part) roethane Depositedample 3 Example compound 63 (0.6 part)______________________________________
TABLE 20______________________________________ ##STR26## ##STR27## ##STR28## ##STR29## ##STR30##______________________________________Example 8 835 478 4 0.75 2.42Example 9 1018 869 0 1.07 2.48Example 10 963 729 1 1.20 2.85Example 11 992 864 0 1.10 2.57Example 12 999 830 4 1.21 2.83Example 13 1028 896 0 1.14 2.73Comparative 921 569 44 0.94 5.95Example 3______________________________________
As apparent from Table 20, it has become clear that the photoreceptors of the present invention of Examples 8 to 13 were low in residual potential-and also low in E.sub.1/16, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 3 prepared by use of comparative compound 1.
EXAMPLES 14 TO 17 AND COMPARATIVE EXAMPLE 4
According to the method described in JP-A-1-291256, 40 parts of crystalline oxytitanyl phthalocyanine was added to a binder resin solution obtained by dissolving 35 parts of a butyral resin (trade name: Polyvinyl Butyral BL-1, manufactured by Sekisui Chemical Co., Ltd.) in 1,425 parts of tetrahydrofuran, and dispersed together with glass beads by use of a vibrating mill for 2 hours. This dispersion was applied with a wire bar onto a sheet in which aluminum was deposited over a polyethylene terephthalate (PET) film, and dried to form a charge generating layer.
One part of the test compounds in each example shown in Table 12 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 4, comparative compound 1 was used in place of one of the test compounds.
Results thereof are shown in Table 22.
TABLE 21______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example Example compound 1 H-2 Dichlo- TiOPc14 (0.5 part) (1 part) roethane Crystal Example compound 63 (0.5 part)Example Example compound 47 H-2 Dichlo- TiOPc15 (0.4 part) (1 part) roethane Crystal Example compound 63 (0.6 part)Example Example compound 21 H-2 Tetrahy- TiOPc16 (0.5 part) (1 part) drofuran Crystal Example compound 63 (0.5 part)Example Example compound 47 H-2 Tetrahy- TiOPc17 (0.3 part) (1 part) drofuran Crystal Example compound 61 (0.7 part)Compara- Comparative comp- H-2 Dichlo- TiOPctive Ex- ound 1 (0.4 part) (1 part) roethane Crystalample 4 Example compound 63 (0.6 part)______________________________________
TABLE 22______________________________________ ##STR31## ##STR32## ##STR33## ##STR34## ##STR35##______________________________________Example 14 821 429 2 0.49 1.39Example 15 693 463 2 0.37 0.80Example 16 775 540 0 0.36 0.86Example 17 697 479 1 0.30 0.63Comparative 718 285 48 1.25 48.70Example 4______________________________________
As apparent from Table 22, it has become clear that the photoreceptors of the present invention of Examples 14 to 17 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 4.
EXAMPLES 18 AND 19 AND COMPARATIVE EXAMPLE 5
A charge generating layer was prepared in the same manner as with Examples 14 to 17. A photoreceptor was prepared and the electrophotographic characteristics thereof were measured in the same manner as with Examples 14 to 17 with the exception that the test compounds in each example shown in Table 23 were used in an amount of one part in place of the compounds shown in Table 21 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) was used in place of the polycarbonate resin represented by formula (H-2).
In Comparative Example 5 as a control, comparative compound 1 was used in place of one of the test compounds.
Results thereof are shown in Table 24.
TABLE 23______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example Example compound 47 J-1 Dichlo- TiOPc18 (0.4 part) (1 part) roethane Crystal Example compound 63 (0.6 part)Example Example compound 1 J-1 Tetrahy- TiOPc19 (0.3 part) (1 part) drofuran Crystal Example compound 63 (0.7 part)Compara- Comparative comp- J-1 Dichlo- TiOPctive Ex- ound 1 (0.4 part) (1 part) roethane Crystalample 5 Example compound 63 (0.6 part)______________________________________
TABLE 24______________________________________ ##STR36## ##STR37## ##STR38## ##STR39## ##STR40##______________________________________Example 18 732 336 3 0.42 1.16Example 19 702 421 2 0.34 0.95Comparative 712 247 35 1.19 31.02Example 5______________________________________
As apparent from Table 24, it has become clear that the photoreceptors of the present invention prepared in Examples 18 and 19 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 5 prepared by use of comparative compound 1.
EXAMPLES 20 TO 27 AND COMPARATIVE EXAMPLE 6
One part of chlorodian blue (CDB) and one part of a polycarbonate resin (trade name: Yupilon E-2000, manufactured by Mitsubishi Gas Chemical Co., Inc.) were kneaded in a ball mill for 5 hours, using 30 parts of dichloroethane as a solvent. The resulting pigment dispersion was applied with a wire bar onto a sheet in which aluminum was deposited over a polyethylene terephthalate carrier generating layer to a thickness of about 1 .mu.m.
One part of the test compounds in each example shown in Table 25 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge carrier generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor.
The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Example 1.
In Comparative Example 6, comparative compound 1 was used in place of one of the test compounds.
Results thereof are shown in Table 26.
TABLE 25______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example Example compound 1 H-2 Dichlo- CDB20 (0.4 part) (1 part) roethane Example compound 63 (0.6 part)Example Example compound 21 H-2 Dichlo- CDB21 (0.5 part) (1 part) roethane Example compound 63 (0.5 part)Example Example compound 42 H-2 Dichlo- CDB22 (0.3 part) (1 part) roethane Example compound 61 (0.7 part)Example Example compound 47 H-2 Dichlo- CDB23 (0.4 part) (1 part) roethane Example compound 63 (0.6 part)Example Example compound 21 H-2 Toluene CDB24 (0.5 part) (1 part) Example compound 63 (0.5 part)Example Example compound 21 H-2 Tetrahy- CDB25 (0.5 part) (1 part) drofuran Example compound 63 (0.5 part)Example Example compound 47 H-2 Tetrahy- CDB26 (0.3 part) (1 part) drofuran Example compound 63 (0.7 part)Example Example compound 47 H-2 Tetrahy- CDB27 (0.4 part) (1 part) drofuran Example compound 63 (0.6 part)Compara- Comparative comp- H-2 Dichlo- CDBtive Ex- ound 1 (0.4 part) (1 part) roethaneample 6 Example compound 63 (0.6 part)______________________________________
TABLE 26______________________________________ ##STR41## ##STR42## ##STR43## ##STR44## ##STR45##______________________________________Example 20 860 666 14 3.71 9.02Example 21 1003 857 5 3.65 8.28Example 22 812 695 0 3.71 8.51Example 23 1033 905 6 3.62 8.06Example 24 889 773 3 3.75 8.23Example 25 751 647 0 4.12 8.95Example 26 651 560 0 4.39 9.46Example 27 988 859 1 3.72 8.07Comparative 931 792 32 4.25 10.78Example 6______________________________________
As apparent from Table 26, it has become clear that the photoreceptors of the present invention of Examples 20 to 27 were low in residual potential and also low in E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 6 prepared by use of comparative compound 1.
EXAMPLES 28 TO 30 AND COMPARATIVE EXAMPLE 7
Chlorodian blue (CDB) was used as an electrophotographic material similary to Examples 20 to 27. One part of the test compounds in each example shown in Table 27 as charge transporting materials and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in an organic solvent. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Example 1.
In Comparative Example 7, comparative compound 1 was used in place of one of the test compounds. The test compounds of Comparative Example 7 were dissolved by mixing, together with the bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1), using 8 parts of dichloroethane as the organic solvent. The resulting solution was applied onto the CDB-containing charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor.
Results thereof are shown in Table 28.
TABLE 27______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example Example compound 47 J-1 Dichlo- CDB28 (0.4 part) (1 part) roethane Example compound 63 (0.6 part)Example Example compound 1 J-1 Tetrahy- CDB29 (0.3 part) (1 part) drofuran Example compound 63 (0.7 part)Example Example compound 47 J-1 Tetarhy- CDB30 (0.4 part) (1 part) drofuran Example compound 63 (0.6 part)Compara- Comparative comp- J-1 Dichlo- CDBtive Ex- ound 1 (0.4 part) (1 part) roethaneample 7 Example compound 63 (0.6 part)______________________________________
TABLE 28______________________________________ ##STR46## ##STR47## ##STR48## ##STR49## ##STR50##______________________________________Example 28 1219 753 0 3.07 6.32Example 29 712 594 1 3.77 8.33Example 30 806 655 1 2.98 6.11Comparative 916 773 33 4.21 10.48Example 7______________________________________
As apparent from Table 28, it has become clear that the photoreceptors of the present invention were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor prepared by use of comparative compound 1.
EXAMPLES 31 TO 33 AND COMPARATIVE EXAMPLE 8
One part of x-form metal-free phthalocyanine (x-H.sub.2 Pc) and one part of a butyral resin (Polyvinyl Butyral BL-1, manufactured by Sekisui Chemical Co., Ltd.) were kneaded in a ball mill for 5 hours, using 30 parts of tetrahydrofuran as a solvent. The resulting pigment dispersion was applied onto a sheet in which aluminum was deposited over a polyethylene terephthalate (PET) film, and dried at 50.degree. C. for 2 hours.
Further, one part of the test compounds in each example shown in Table 29 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 8, comparative compound 1 was used in place of one of the test compounds.
Results thereof are shown in Table 30.
TABLE 29______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example Example compound 1 H-2 Dichlo- x-H.sub.2 Pc31 (0.5 part) (1 part) roethane Example compound 63 (0.5 part)Example Example compound 47 H-2 Dichlo- x-H.sub.2 Pc32 (0.4 part) (1 part) roethane Example compound 63 (0.6 part)Example Example compound 47 H-2 Tetarhy- x-H.sub.2 Pc33 (0.4 part) (1 part) drofuran Example compound 63 (0.6 part)Compara- Comparative comp- H-2 Dichlo- x-H.sub.2 Pctive Ex- ound 1 (0.4 part) (1 part) roethaneample 8 Example compound 63 (0.6 part)______________________________________
TABLE 30______________________________________ ##STR51## ##STR52## ##STR53## ##STR54## ##STR55##______________________________________Example 31 968 727 7 1.53 3.28Example 32 980 790 2 1.56 3.21Example 33 723 479 1 0.93 1.91Comparative 1042 834 45 1.84 5.16Example 8______________________________________
As apparent from Table 30, it has become clear that the photoreceptors of the present invention of Examples 31 to 33 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 8.
EXAMPLE 34
In a charge generating layer, x-form metal-free phthalocyanine (x-H.sub.2 Pc) was used. The test compounds shown in Table 31 as charge transporting materials and a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in an organic solvent. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as with Examples 1 to 7.
Results thereof are shown in Table 32.
TABLE 31__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 34 Example compound 42 J-1 Tetrahy- x-H.sub.2 Pc (0.4 part) (1 part) drofuran Example compound 63 (0.6 part)__________________________________________________________________________
TABLE 32______________________________________ ##STR56## ##STR57## ##STR58## ##STR59## ##STR60##______________________________________Example 34 775 621 7 3.23 7.74______________________________________
EXAMPLES 35 TO 38 AND COMPARATIVE EXAMPLE 9
One part of .tau.-form metal-free phthalocyanine (.tau.-H.sub.2 Pc) and one part of a butyral resin (trade name: Polyvinyl Butyral BL-1, manufactured by Sekisui Chemical Co., Ltd.) were kneaded in a ball mill for 5 hours, using 30 parts of tetrahydrofuran as a solvent. The resulting pigment dispersion was applied onto a sheet in which aluminum was deposited over a polyethylene terephthalate (PET) film, and dried at 50.degree. C. for 2 hours.
Further, one part of the test compounds in each example shown in Table 33 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 9, comparative compound 1 was used in place of one of the test compounds.
Results thereof are shown in Table 34.
TABLE 33______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example Example compound 1 H-2 Dichlo- .tau.-H.sub.2 Pc35 (0.5 part) (1 part) roethane Example compound 63 (0.5 part)Example Example compound 1 H-2 Dichlo- .tau.-H.sub.2 Pc36 (0.4 part) (1 part) roethane Example compound 63 (0.6 part)Example Example compound 21 H-2 Dichlo- .tau.-H.sub.2 Pc37 (0.5 part) (1 part) roethane Example compound 63 (0.5 part)Example Example compound 47 H-2 Tetrahy- .tau.-H.sub.2 Pc38 (0.4 part) (1 part) drofuran Example compound 63 (0.6 part)Compara- Comparative comp- H-2 Dichlo- .tau.-H.sub.2 Pctive Ex- ound 1 (0.4 part) (1 part) roethaneample 9 Example compound 63 (0.6 part)______________________________________
TABLE 34______________________________________ ##STR61## ##STR62## ##STR63## ##STR64## ##STR65##______________________________________Example 35 594 278 7 0.84 3.94Example 36 934 752 20 1.73 3.88Example 37 665 344 5 0.85 2.46Example 38 703 531 0 0.86 1.69Comparative 596 290 43 1.53 35.64Example 9______________________________________
As apparent from Table 34, it has become clear that the photoreceptors of the present invention of Examples 35 to 38 were low in residual potential and also low in E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 9 prepared by use of comparative compound 1.
EXAMPLES 39 AND 40
In a charge generating layer, .tau.-form metal-free phthalocyanine (.tau.-H.sub.2 Pc) was used. One part of the test compounds in each example shown in Table 35 as charge transporting materials and a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in an organic solvent. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
Results thereof are shown in Table 36.
TABLE 35__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 39 Example compound 1 J-1 Tetrahy- .tau.-H.sub.2 Pc (0.3 part) (1 part) drofuran Example compound 61 (0.7 part)Example 40 Example compound 42 J-1 Tetrahy- .tau.-H.sub.2 Pc (0.4 part) (1 part) drofuran Example compound 61 (0.6 part)__________________________________________________________________________
TABLE 36______________________________________ ##STR66## ##STR67## ##STR68## ##STR69## ##STR70##______________________________________Example 39 620 354 7 0.84 2.44Example 40 640 355 5 0.77 1.85______________________________________
EXAMPLE 41 AND COMPARATIVE EXAMPLE 10
One part of a bisazo pigment represented by formula (O) and one part of a polycarbonate resin (trade name: Yupilon E-2000, manufactured by Mitsubishi Gas Chemical Co., Inc.) were kneaded in a ball mill for 5 hours, using 30 parts of dichloroethane as a solvent. The resulting pigment dispersion was applied with a wire bar onto a sheet in which aluminum was deposited over a polyethylene terephthalate (PET) film, and dried at 50.degree. C. for 3 hours to form a charge carrier generating layer to a thickness of about 1 .mu.m.
Further, one part of the test compounds in each example shown in Table 37 and a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in dichloroethane. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors were measured in the same manner as with Examples 1 to 7.
In Comparative Example 10, comparative compound 1 was used in place of one of the test compounds. One part of the test compounds of Comparative Example 10 was dissolved by mixing, together with one part of the bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1), using 8 parts of dichloroethane as the organic solvent. The resulting solution was applied onto the bisazo (O)-containing charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor.
Results thereof are shown in Table 38.
TABLE 37__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 41 Example compound 47 J-1 Dichlo- Bisazo (0.4 part) (1 part) roethane (O) Example compound 63 (0.6 part)Comparative Comparative compound 1 J-1 Dichlo- BisazoExample 10 (0.4 part) (1 part) roethane (O) Example compound 63 (0.6 part)__________________________________________________________________________
TABLE 38______________________________________ ##STR71## ##STR72## ##STR73## ##STR74## ##STR75##______________________________________Example 41 1019 803 93 2.95 6.00Comparative 850 750 120 4.50 Unmeas-Example 10 urable______________________________________
As apparent from Table 38, it has become clear that the photoreceptor of the present invention of Example 41 was low in residual potential and also low in E.sub.1/2 providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 10 prepared by use of comparative compound 1. It was impossible to measure E.sub.1/6.
EXAMPLES 42 AND 43 AND COMPARATIVE EXAMPLE 11
One part of copper phthalocyanine (CuPc) and one part a butyral resin (Polyvinyl Butyral BL-1, manufactured by Sekisui Chemical Co., Ltd.) were kneaded in a ball mill for 5 hours, using 30 parts of tetrahydrofuran as a solvent. The resulting pigment dispersion was applied onto a sheet in which aluminum was deposited over a polyethylene terephthalate (PET) film, and dried at 50.degree. C. for 2 hours.
Further, one part of the test compounds in each example shown in Table 39 and one part of a polycarbonate resin represented by formula (H-2) (Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 11, comparative compound 1 was used in place of one of the test compounds.
Results thereof are shown in Table 40.
TABLE 39______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example Example compound 1 H-2 Dichlo- CuPc42 (0.4 part) (1 part) roethane Example compound 63 (0.6 part)Example Example compound 42 H-2 Dichlo- CuPc43 (0.3 part) (1 part) roethane Example compound 61 (0.7 part)Compara- Comparative comp- H-2 Dichlo- CuPctive Ex- ound 1 (0.4 part) (1 part) roethaneample 11 Example compound 63 (0.6 part)______________________________________
TABLE 40______________________________________ ##STR76## ##STR77## ##STR78## ##STR79## ##STR80##______________________________________Example 42 1026 891 14 2.48 5.49Example 43 1022 893 9 2.35 5.16Comparative 979 792 50 2.84 8.12Example 11______________________________________
As apparent from Table 40, it has become clear that the photoreceptors of the present invention of Examples 42 and 43 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 11 prepared by use of comparative compound 1.
EXAMPLE 44 AND COMPARATIVE EXAMPLE 12
A charge generating layer was prepared in the same manner as with Examples 42 and 43. One part of the test compounds in each example shown in Table 41 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the above-mentioned charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 12, comparative compound 1 was used in place of one of the test compounds.
Results thereof are shown in Table 42.
TABLE 41__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 44 Example compound 47 J-1 Dichlo- CuPc (0.4 part) (1 part) roethane Example compound 63 (0.6 part)Comparative Comparative compound 1 J-1 Dichlo- CuPcExample 12 (0.4 part) (1 part) roethane Example compound 63 (0.6 part)__________________________________________________________________________
TABLE 42______________________________________ ##STR81## ##STR82## ##STR83## ##STR84## ##STR85##______________________________________Example 44 987 824 6 2.60 5.61Comparative 1071 918 59 2.79 7.54Example 12______________________________________
As apparent from Table 42, it has become clear that the photoreceptor of the present invention of Example 44 was low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 12 prepared by use of comparative compound 1.
EXAMPLES 45 TO 47 AND COMPARATIVE EXAMPLE 13
A charge generating layer was prepared in the same manner as with Examples 1 to 7. A photoreceptor was prepared and the electrophotographic characteristics thereof were measured in the same manner as with Examples 1 to 7 with the exception that the test compounds in each example shown in Table 43 were used in an amount of one part in place of the compounds shown in Table 17.
In Comparative Example 13, example compound 63 (0.5 part) and example compound 128 (0.5 part) were used.
Results thereof are shown in Table 44.
TABLE 43__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 45 Example compound 21 H-2 Dichlo- TiOPc (0.5 part) (1 part) roethane Deposited Example compound 85 (0.5 part)Example 46 Example compound 21 H-2 Dichlo- TiOPc (0.5 part) (1 part) roethane Deposited Example compound 91 (0.5 part)Example 47 Example compound 21 H-2 Dichlo- TiOPc (0.5 part) (1 part) roethane Deposited Example compound 128 (0.5 part)Comparative Example compound 63 H-2 Dichlo- TiOPcExample 13 (0.5 part) (1 part) roethane Deposited Example compound 128 (0.5 part)__________________________________________________________________________
TABLE 44______________________________________ ##STR86## ##STR87## ##STR88## ##STR89## ##STR90##______________________________________Example 45 1121 1044 11 1.47 4.01Example 46 1197 876 39 2.06 7.59Example 47 1130 1041 22 1.42 3.92Comparative 1338 1228 258 2.33 Unmea-Example 13 surable______________________________________
As apparent from Table 44, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 45 to 47 were low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 13 prepared by use of example compound 63 (0.5 part) and example compound 128 (0.5 part).
In Comparative Example 13, it was impossible to measure E.sub.1/6 because of insufficient light attenuation.
EXAMPLES 48 TO 51 AND COMPARATIVE EXAMPLES 14 and 15
According to the method described in JP-A-1-291256, 40 parts of crystalline oxytitanyl phthalocyanine was added to a binder resin solution obtained by dissolving 35 parts of a butyral resin (trade name: Polyvinyl Butyral EL-1, manufactured by Sekisui Chemical Co., Ltd.) in 1,425 parts of tetrahydrofuran, and dispersed together with glass beads by use of a vibrating mill for 2 hours. This dispersion was applied with a wire bar onto a sheet in which aluminum was deposited over a polyethylene terephthalate (PET) film, and dried to form a charge generating layer.
One part of the example compounds in each example shown in Table 45 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 14, example compound 63 (0.4 part) and example compound 85 (0.6 part) were used. On the other hand. in Comparative Example 15, only example compound 47, a triphenylamine compound, was used,
Results thereof are shown in Table 46.
TABLE 45__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 48 Example compound 47 H-2 Dichlo- TiOPc (0.4 part) (1 part) roethane Crystal Example compound 81 (0.6 part)Example 49 Example compound 47 H-2 Dichlo- TiOPc (0.4 part) (1 part) roethane Crystal Example compound 85 (0.6 part)Example 50 Example compound 47 H-2 Dichlo- TiOPc (0.4 part) (1 part) roethane Crystal Example compound 93 (0.6 part)Example 51 Example compound 47 H-2 Dichlo- TiOPc (0.4 part) (1 part) roethane Crystal Example compound 99 (0.6 part)Comparative Example compound 63 H-2 Dichlo- TiOPcExample 14 (0.4 part) (1 part) roethane Crystal Example compound 85 (0.6 part)Comparative Example compound 47 H-2 Dichlo- TiOPcExample 15 (1.0 part) (1 part) roethane Crystal__________________________________________________________________________
TABLE 46______________________________________ ##STR91## ##STR92## ##STR93## ##STR94## ##STR95##______________________________________Example 48 1468 681 0 0.29 0.54Example 49 1083 678 2 0.32 0.73Example 50 1015 664 0 0.29 0.86Example 51 1166 756 3 0.30 0.64Comparative 1065 756 267 0.80 Unmea-Example 14 surableComparative UnmeasurableExample 15______________________________________
As apparent from Table 46, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 48 to 51 were low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 14 prepared by use of example compound 63 (0.4 part) and example compound 85 (0.6 part).
In Comparative Example 14, it was impossible to measure E.sub.1/6 because of insufficient light attenuation.
In Comparative Example 15 in which the triphenylamin compound was singly used, cracks developed in a photoreceptor film.
EXAMPLE 52 AND COMPARATIVE EXAMPLE 16
A charge generating layer was prepared in the same manner as with Examples 48 to 51. A photoreceptor was prepared in the same manner as with Examples 48 to 51 with the exception that the example compounds in each example shown in Table 47 were used in an amount of one part in place of the compounds shown in Table 45 and a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) was used in place of the polycarbonate resin represented by formula (H-2), and the electrophotographic characteristics thereof were measured in the same manner as with Examples 1 to 7
In Comparative Example 16, comparative compound 1 was used in place of one of the example compounds.
Results thereof are shown in Table 48.
TABLE 47__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 52 Example compound 47 J-1 Dichlo- TiOPc (0.4 part) (1 part) roethane Crystal Example compound 93 (0.6 part)Comparative Comparative compound 1 J-1 Dichlo- TiOPcExample 16 (0.4 part) (1 part) roethane Crystal Example compound 93 (0.6 part)__________________________________________________________________________
TABLE 48______________________________________ ##STR96## ##STR97## ##STR98## ##STR99## ##STR100##______________________________________Example 52 626 232 4 0.20 0.47Comparative 990 784 18 0.71 1.86Example 16______________________________________
As apparent from Table 48, it has become clear that the photoreceptor of the present invention prepared by use of the example compounds of Example 52 was low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 16 prepared by use of comparative compound 1.
EXAMPLES 53 TO 56 AND COMPARATIVE EXAMPLE 17
A charge generating layer was prepared in the same manner as with Examples 20 to 27.
One part of the example compounds in each example shown in Table 49 as charge transporting materials and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z. manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 17, example compound 63 (0.4 part) and example compound 85 (0.6 part) were used.
Results thereof are shown in Table 50.
TABLE 49__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 53 Example compound 47 H-2 Dichlo- CDB (0.4 part) (1 part) roethane Example compound 81 (0.6 part)Example 54 Example compound 47 H-2 Dichlo- CDB (0.4 part) (1 part) roethane Example compound 82 (0.6 part)Example 55 Example compound 47 H-2 Dichlo- CDB (0.4 part) (1 part) roethane Example compound 93 (0.6 part)Example 56 Example compound 47 H-2 Dichlo- CDB (0.4 part) (1 part) roethane Example compound 99 (0.6 part)Comparative Example compound 63 H-2 Dichlo- CDBExample 17 (0.4 part) (1 part) roethane Example compound 85 (0.6 part)__________________________________________________________________________
TABLE 50______________________________________ ##STR101## ##STR102## ##STR103## ##STR104## ##STR105##______________________________________Example 53 1581 1384 7 3.08 6.72Example 54 1425 1187 0 3.55 7.55Example 55 1487 1309 0 2.83 5.94Example 56 1651 1424 0 3.37 7.52Comparative 1133 910 54 4.42 11.28Example 17______________________________________
As apparent from Table 50, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 53 to 56 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 17 prepared by use of example compound 63 (0.4 part) and example compound 85 (0.6 part).
EXAMPLES 57 AND 58 AND COMPARATIVE EXAMPLE 18
A charge generating layer was prepared in the same manner as with Examples 20 to 27.
One part of the example compounds in each example shown in Table 51 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 18, example compound 63 (0.4 part) and example compound 81 (0.6 part) were used.
Results thereof are shown in Table 52.
TABLE 51__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 57 Example compound 47 J-1 Dichlo- CDB (0.4 part) (1 part) roethane Example compound 81 (0.6 part)Example 58 Example compound 47 J-1 Dichlo- CDB (0.4 part) (1 part) roethane Example compound 93 (0.6 part)Comparative Example compound 63 J-1 Dichlo- CDBExample 18 (0.4 part) (1 part) roethane Example compound 81 (0.6 part)__________________________________________________________________________
TABLE 52______________________________________ ##STR106## ##STR107## ##STR108## ##STR109## ##STR110##______________________________________Example 57 936 839 7 3.32 7.28Example 58 897 802 1 2.88 6.21Comparative 1160 979 189 5.29 Unmea-Example 18 surable______________________________________
As apparent from Table 52, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 57 and 58 were low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 18 prepared by use of example compound 63 (0.4 part) and example compound 81 (0.6 part).
In Comparative Example 18, it was impossible to measure E.sub.1/6 because of insufficient light attenuation.
EXAMPLES 59 TO 61 AND COMPARATIVE EXAMPLE 19
A charge generating layer was prepared in the same manner as with Examples 31 to 33.
One part of the example compounds in each example shown in Table 53 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 19, example compound 63 (0.4 part) and example compound 85 (0.6 part) were used.
Results thereof are shown in Table 54.
TABLE 53__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 59 Example compound 47 H-2 Dichlo- x-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 81 (0.6 part)Example 60 Example compound 47 H-2 Dichlo- x-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 85 (0.6 part)Example 61 Example compound 47 H-2 Dichlo- x-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 109 (0.6 part)Comparative Example compound 63 H-2 Dichlo- x-H.sub.2 PcExample 19 (0.4 part) (1 part) roethane Example compound 85 (0.6 part)__________________________________________________________________________
TABLE 54______________________________________ ##STR111## ##STR112## ##STR113## ##STR114## ##STR115##______________________________________Example 59 1318 956 0 1.22 2.54Example 60 1618 1379 0 1.60 3.35Example 61 1509 1235 0 1.42 2.91Comparative 488 290 232 Unmea- Unmea-Example 19 surable surable______________________________________
As apparent from Table 54, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 59 to 61 were low in residual potential, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 19 prepared by use of example compound 63 (0.4 part) and example compound 85 (0.6 part).
In Comparative Example 19, it was impossible to measure E.sub.1/2 and E.sub.1/6 because of insufficient light attenuation.
EXAMPLE 62 TO 64 AND COMPARATIVE EXAMPLE 20
A charge generating layer was prepared in the same manner as with Examples 35 to 38.
One part of the example compounds in each example shown in Table 55 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 20, example compound 63 (0.4 part) and example compound 82 (0.6 part) were used.
Results thereof are shown in Table 56.
TABLE 55__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 62 Example compound 47 H-2 Dichlo- .tau.-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 82 (0.6 part)Example 63 Example compound 47 H-2 Dichlo- .tau.-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 93 (0.6 part)Example 64 Example compound 47 H-2 Dichlo- .tau.-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 109 (0.6 part)Comparative Example compound 63 H-2 Dichlo- .tau.-H.sub.2 PcExample 20 (0.4 part) (1 part) roethane Example compound 82 (0.6 part)__________________________________________________________________________
TABLE 56______________________________________ ##STR116## ##STR117## ##STR118## ##STR119## ##STR120##______________________________________Example 62 1392 933 0 0.90 1.87Example 63 1054 528 0 0.68 1.33Example 64 1161 751 0 0.89 1.73Comparative 400 189 68 5.22 Unmea-Example 20 surable______________________________________
As apparent from Table 56, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 62 to 64 were low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 20 prepared by use of example compound 63 (0.4 part) and example compound 82 (0.6 part).
In Comparative Example 20, it was impossible to measure E.sub.1/6 because of insufficient light attenuation.
EXAMPLES 65 TO 67 AND COMPARATIVE EXAMPLE 21
A charge generating layer was prepared in the same manner as with Example 41.
Further, one part of the example compounds in each example shown in Table 57 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 21, example compound 63 (0.4 part) and example compound 85 (0.6 part) were used.
Results thereof are shown in Table 58.
TABLE 57______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example Example compound 47 J-1 Dichlo- Bisazo65 (0.4 part) (1 part) roethane (O) Example compound 81 (0.6 part)Example Example compound 47 J-1 Dichlo- Bisazo66 (0.4 part) (1 part) roethane (O) Example compound 82 (0.6 part)Example Example compound 47 J-1 Dichlo- Bisazo67 (0.4 part) (1 part) roethane (O) Example compound 85 (0.6 part)Compara- Example compound 63 J-1 Dichlo- Bisazotive Ex- (0.4 part) (1 part) roethane (O)ample 21 Example compound 85 (0.6 part)______________________________________
TABLE 58______________________________________ ##STR121## ##STR122## ##STR123## ##STR124## ##STR125##______________________________________Example 65 1306 1009 12 1.69 2.91Example 66 1396 1195 0 1.75 3.25Example 67 1505 1176 6 2.16 3.97Comparative 721 499 37 2.08 4.74Example 21______________________________________
As apparent from Table 58, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 65 to 67 were low in residual potential and also low in E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 21 prepared by use of example compound 63 (0.4 part) and example compound 85 (0.6 part).
EXAMPLE 68 AND COMPARATIVE EXAMPLE 22
A charge generating layer was prepared in the same manner as with Examples 42 and 43.
Further, one part of the example compounds in each example shown in Table 59 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 22, example compound 63 (0.4 part) and example compound 82 (0.6 part) were used.
Results thereof are shown in Table 60.
TABLE 59__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 68 Example compound 47 H-2 Dichlo- CuPc (0.4 part) (1 part) roethane Example compound 82 (0.6 part)Comparative Example compound 63 H-2 Dichlo- CuPcExample 22 (0.4 part) (1 part) roethane Example compound 82 (0.6 part)__________________________________________________________________________
TABLE 60______________________________________ ##STR126## ##STR127## ##STR128## ##STR129## ##STR130##______________________________________Example 68 1562 1359 4 2.64 5.90Comparative 1059 971 221 3.83 Unmea-Example 22 surable______________________________________
As apparent from Table 60, it has become clear that the photoreceptor of the present invention prepared by use of the example compounds of Example 68 was low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 22 prepared by use of example compound 63 (0.4 part) and example compound 82 (0.6 part).
In Comparative Example 22, it was impossible to measure E.sub.1/6 because of insufficient light attenuation.
EXAMPLES 69 AND 70 AND COMPARATIVE EXAMPLE 23
A charge generating layer was prepared in the same manner as with Example 68.
One part of the example compounds in each example shown in Table 61 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 23, example compound 63 (0.4 part) and example compound 93 (0.6 part) were used.
Results thereof are shown in Table 62.
TABLE 61__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 69 Example compound 47 J-1 Dichlo- CuPc (0.4 part) (1 part) roethane Example compound 81 (0.6 part)Example 70 Example compound 47 J-1 Dichlo- CuPc (0.4 part) (1 part) roethane Example compound 93 (0.6 part)Comparative Example compound 63 J-1 Dichlo- CuPcExample 23 (0.4 part) (1 part) roethane Example compound 93 (0.6 part)__________________________________________________________________________
TABLE 62______________________________________ ##STR131## ##STR132## ##STR133## ##STR134## ##STR135##______________________________________Example 69 667 584 6 2.67 5.99Example 70 883 769 2 2.51 5.77Comparative 898 733 149 2.79 Unmea-Example 23 surable______________________________________
As apparent from Table 62, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 69 and 70 were low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 23 prepared by use of example compound 63 (0.4 part) and example compound 93 (0.6 part).
In Comparative Example 23, it was impossible to measure E.sub.1/6 because of insufficient light attenuation.
EXAMPLE 71 AND COMPARATIVE EXAMPLE 24
An underlayer, a charge generating layer and a charge transporting layer are successively formed on an aluminum drum by a dip coating method to prepare an OPC (organic photoconductor) having a film thickness of 20 .mu.m.
For the charge generating layer, a dispersion was used which was obtained by adding 40 parts of crystalline oxytitanyl phthalocyanine to a binder resin solution obtained by dissolving 35 parts of a butyral resin (trade name: Polyvinyl Butyral BL-1, manufactured by Sekisui Chemical Co., Ltd.) in 1,425 parts of tetrahydrofuran, and dispersing it together with glass beads by use of a vibrating mill for 2 hours, according to the method described in JP-A-1-291256.
For the charge generating layer, a solution was used which was obtained by dissolving 0.2 part of example compound 47, 0.8 part of example compound 81 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) in 8 parts of dichloroethane by mixing.
After standing of this coating solution in the dark for 2 months, a photoreceptor was prepared similarly.
The electrophotographic characteristics were measured with a Cynthia 99HC (manufactured by Gentec Co., Ltd.).
The retention was determined from the ratio of a reduced amount of charge potential from an initial charge potential to a surface potential after 5 seconds in the dark to the initial charge potential, when a photoreceptor was charged by corona discharge. The half-exposure E.sub.1/2 (.mu.J/cm.sup.2) was calculated by determining a time taken until a surface potential reached one-half (-300 V) of an initial surface potential (-600 V). Further, E.sub.1 oo is an irradiation energy necessary for attenuating the initial surface potential (-600 V) to -100 V.
In Comparative Example 24, a solution was used which was obtained by dissolving one part of example compound 81 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z. manufactured by Mitsubishi Gas Chemical Co., Inc.) in 8 parts of dichloroethane by mixing.
Results thereof are shown in Table 63.
TABLE 63__________________________________________________________________________ Initial Characteristics After standing for 2 monthsCharge Trans- Retention E.sub.1/2 E.sub.100 Retention E.sub.1/2 E.sub.100porting material (%) (.mu.J/cm.sup.2) (.mu.J/cm.sup.2) (%) (.mu.J/cm.sup.2) (.mu.J/cm.sup.2)__________________________________________________________________________Example 71 Example compound 47 89.5 0.22 0.63 89.1 0.22 1.59 Example compaund 81Comparative Example compound 81 90.1 0.22 2.40 89.1 0.24 5.31Example 24__________________________________________________________________________
As apparent from Table 63, the photoreceptor of the present invention obtained in Example 71 was small in changes in characteristics before and after standing of the coating solution, compared with the photoreceptor obtained by use of example compound 81 alone in Comparative Example 24. Thus, the photoreceptor in which example compound 47 was mixed with example compound 81 could increase the stability of the coating solution.
EXAMPLES 72 TO 75 AND COMPARATIVE EXAMPLES 25 AND 26
A charge generating layer was prepared in the same manner as with Examples 1 to 7. A photoreceptor was prepared and the electrophotographic characteristics thereof were measured in the same manner as with Examples 1 to 7 with the exception that the test compounds in each example shown in Table 64 were used in an amount of one part in place of the compounds shown in Table 17.
In Comparative Example 25, comparative compound 1 was used in place of one of the example compounds, and in Comparative Example 26, only comparative compound 1 was used.
Results thereof are shown in Table 65.
TABLE 64______________________________________Test Compound Organic Charge Gene-(Amount Used) Polymer Solvent rating Layer______________________________________Example Example compound 1 H-2 Dichlo- TiOPc72 (0.4 part) (1 part) roethane Deposited Example compound 132 (0.6 part)Example Example compound 21 H-2 Dichlo- TiOPc73 (0.5 part) (1 part) roethane Deposited Example compound 132 (0.5 part)Example Example compound 47 H-2 Tetrahy- TiOPc74 (0.4 part) (1 part) drofuran Deposited Example compound 131 (0.6 part)Example Example compound 47 H-2 Dichlo- TiOPc75 (0.4 part) (1 part) roethane Deposited Example compound 152 (0.6 part)Compara- Comparative comp- H-2 Dichlo- TiOPctive Ex- ound 1 (0.4 part) (1 part) roethane Depositedample 25 Example compound 132 (0.6 part)Compara- Comparative comp- H-2 Dichlo- TiOPctive Ex- ound 1 (1 part) (1 part) roethane Depositedample 26______________________________________
TABLE 44______________________________________ ##STR136## ##STR137## ##STR138## ##STR139## ##STR140##______________________________________Example 72 1175 909 3 0.56 1.39Example 73 792 515 21 0.67 2.11Example 74 1805 1658 0 1.14 2.61Example 75 844 591 8 0.43 0.87Comparative 1175 1012 82 1.57 5.73Example 25Comparative UnmeasurableExample 26______________________________________
As apparent from Table 65, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 72 to 75 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 25 prepared by use of comparative compound 1.
In the photoreceptor of Comparative Example 26 prepared by use of example compound 47 alone, cracks developed after film formation and drying, resulting in the failure of measurement.
EXAMPLES 76 TO 78 AND COMPARATIVE EXAMPLE 27
A charge generating layer was prepared in the same manner as with Examples 1 to 7.
Further, one part of the example compounds in each example shown in Table 66 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In comparative Example 27, comparative compound 1 was used in place of the triphenylamine compound (1) of the example compounds.
Results thereof are shown in Table 67.
TABLE 66__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 76 Example compound 47 J-1 Toluene TiOPc (0.4 part) (1 part) Deposited Example compound 131 (0.6 part)Example 77 Example compound 47 J-1 Dioxane TiOPc (0.5 part) (1 part) Deposited Example compound 131 (0.5 part)Example 78 Example compound 47 J-1 Tetrahy- TiOPc (0.4 part) (1 part) drofuran Deposited Example compound 131 (0.6 part)Comparative Comparative compound 1 J-1 Dichlo- TiOPcExample 27 (0.4 part) (1 part) roethane Deposited Example compound 132 (0.6 part)__________________________________________________________________________
TABLE 67______________________________________ ##STR141## ##STR142## ##STR143## ##STR144## ##STR145##______________________________________Example 76 675 549 4 1.35 3.29Example 77 1000 899 0 1.16 2.78Example 78 1004 918 0 1.07 2.48Comparative 1140 989 66 1.45 4.63Example 27______________________________________
As apparent from Table 67, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 76 to 78 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 27 prepared by use of comparative compound 1.
EXAMPLES 79 TO 81 AND COMPARATIVE EXAMPLE 28
A charge generating layer was prepared in the same manner as with Examples 14 to 17.
Further, one part of the example compounds in each example shown in Table 68 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 28, comparative compound 1 was used in place of the triphenylamine compound (1) of the example compounds.
Results thereof are shown in Table 69.
TABLE 68__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 79 Example compound 21 H-2 Dichlo- TiOPc (0.5 part) (1 part) roethane Deposited Example compound 132 (0.5 part)Example 80 Example compound 47 H-2 Tetrahy- TiOPc (0.4 part) (1 part) drofuran Deposited Example compound 131 (0.6 part)Example 81 Example compound 47 H-2 Dichlo- TiOPc (0.5 part) (1 part) roethane Deposited Example compound 152 (0.5 part)Comparative Comparative compound 1 H-2 Dichlo- TiOPcExample 28 (0.4 part) (1 part) roethane Deposited Example compound 132 (0.6 part)__________________________________________________________________________
TABLE 69______________________________________ ##STR146## ##STR147## ##STR148## ##STR149## ##STR150##______________________________________Example 79 876 532 0 0.33 0.64Example 80 1060 734 0 0.29 0.56Example 81 586 238 10 0.26 0.53Comparative 714 389 75 0.75 Unmea-Example 28 surable______________________________________
As apparent from Table 69, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 79 to 81 were low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 28 prepared by use of comparative compound 1.
In Comparative Example 28, it was impossible to measure E.sub.1/6 because of insufficient light sensitivity.
EXAMPLE 82 AND COMPARATIVE EXAMPLE 29
A charge generating layer was prepared in the same manner as with Examples 14 to 17. Further, a photoreceptor was prepared in the same manner as with Examples 48 to 51 with the exception that the example compounds in each example shown in Table 70 were used in an amount of one part in place of the compounds shown in Table 45 and a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) was used in an amount of one part in place of the polycarbonate resin represented by formula (H-2). The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 29, comparative compound 1 was used in place of the triphenylamine compound (1) of the example compounds.
Results thereof are shown in Table 71.
TABLE 70__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 82 Example compound 47 J-1 Dichlo- TiOPc (0.4 part) (1 part) roethane Deposited Example compound 131 (0.6 part)Comparative Comparative compound 1 J-1 Dichlo- TiOPcExample 29 (0.4 part) (1 part) roethane Deposited Example compound 132 (0.6 part)__________________________________________________________________________
TABLE 67______________________________________ ##STR151## ##STR152## ##STR153## ##STR154## ##STR155##______________________________________Example 82 821 539 0 0.35 0.70Comparative 604 166 59 7.82 Unmea-Example 29 surable______________________________________
As apparent from Table 71, it has become clear that the photoreceptor of the present invention prepared by use of the example compounds of Example 82 was low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 29 prepared by use of comparative compound 1.
In Comparative Example 29, it was impossible to measure E.sub.1/6 because of insufficient light sensitivity.
EXAMPLES 83 AND 84 AND COMPARATIVE EXAMPLE 30
A charge generating layer was prepared in the same manner as with Examples 20 to 27.
Further, one part of the example compounds in each example shown in Table 72 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 30, comparative compound 1 was used in place of the triphenylamine compound (1) of the example compounds.
Results thereof are shown in Table 73.
TABLE 72__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 83 Example compound 1 H-2 Dichlo- CDB (0.6 part) (1 part) roethane Example compound 132 (0.4 part)Example 84 Example compound 47 H-2 Tetrahy- CDB (0.4 part) (1 part) drofuran Example compound 131 (0.6 part)Comparative Comparative compound 1 H-2 Dichlo- CDBExample 30 (0.4 part) (1 part) roethane Example compound 132 (0.6 part)__________________________________________________________________________
TABLE 73______________________________________ ##STR156## ##STR157## ##STR158## ##STR159## ##STR160##______________________________________Example 83 1022 886 0 4.14 9.15Example 84 800 691 0 3.56 7.52Comparative 1094 912 95 4.71 15.35Example 30______________________________________
As apparent from Table 73, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 83 and 84 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 30 prepared by use of comparative compound 1.
EXAMPLES 85 AND 86 AND COMPARATIVE EXAMPLE 31
Chlorodian blue (CDB) was used as a charge generating material similarly to Examples 20 to 27. One part of the example compounds in each example shown in Table 74 as charge transporting materials and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of an organic solvent. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 31, comparative compound 1 was used in place of the triphenylamine compound (1) of the example compounds.
Results thereof are shown in Table 75.
TABLE 74__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 85 Example compound 47 J-1 Toluene CDB (0.6 part) (1 part) Example compound 131 (0.4 part)Example 86 Example compound 47 J-1 Dioxane CDB (0.3 part) (1 part) Example compound 131 (0.7 part)Comparative Comparative compound 1 J-1 Dichlo- CDBExample 31 (0.4 part) (1 part) roethane Example compound 132 (0.6 part)__________________________________________________________________________
TABLE 75______________________________________ ##STR161## ##STR162## ##STR163## ##STR164## ##STR165##______________________________________Example 85 796 705 0 3.85 8.27Example 86 798 683 0 3.02 6.34Comparative 868 738 34 4.46 10.81Example 31______________________________________
As apparent from Table 75, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 85 and 86 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 31 prepared by use of comparative compound 1.
EXAMPLES 87 TO 90 AND COMPARATIVE EXAMPLE 32
A charge generating layer was prepared in the same manner as with Examples 31 to 33.
Further, one part of the example compounds in each example shown in Table 76 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 32, comparative compound 1 was used in place of the triphenylamine compound (1) of the example compounds.
Results thereof are shown in Table 77.
TABLE 76__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 87 Example compound 1 H-2 Dichlo- x-H.sub.2 PC (0.5 part) (1 part) roethane Example compound 132 (0.5 part)Example 88 Example compound 21 H-2 Dichlo- x-H.sub.2 Pc (0.5 part) (1 part) roethane Example compound 132 (0.5 part)Example 89 Example compound 47 H-2 Dichlo- x-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 131 (0.6 part)Example 90 Example compound 47 H-2 Dichlo- x-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 152 (0.6 part)Comparative Comparative compound 1 H-2 Dichlo- x-H.sub.2 PcExample 32 (0.4 part) (1 part) roethane Example compound 132 (0.6 part)__________________________________________________________________________
TABLE 77______________________________________ ##STR166## ##STR167## ##STR168## ##STR169## ##STR170##______________________________________Example 87 1094 947 0 1.54 3.10Example 88 1113 993 0 1.70 3.46Example 89 1135 759 0 1.54 3.09Example 90 1037 934 0 1.10 1.09Comparative 904 652 77 1.49 12.95Example 32______________________________________
As apparent from Table 77, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 87 to 90 were low in residual potential and also low in E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 32 prepared by use of comparative compound 1.
EXAMPLES 91 TO 93 AND COMPARATIVE EXAMPLE 33
A charge generating layer was prepared by use of x-form metal-free phthalocyanine (x-H.sub.2 Pc) in the same manner as with Examples 31 to 33.
Further, one part of the example compounds in each example shown in Table 78 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 33, comparative compound 1 was used in place of the triphenylamine compound (1) of the example compounds.
Results thereof are shown in Table 79.
TABLE 78__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 91 Example compound 47 J-1 Toluene x-H.sub.2 Pc (0.4 part) (1 part) Example compound 131 (0.6 part)Example 92 Example compound 47 J-1 Dioxane x-H.sub.2 Pc (0.5 part) (1 part) Example compound 131 (0.5 part)Example 93 Example compound 42 J-1 Tetrahy- x-H.sub.2 Pc (0.5 part) (1 part) drofuran Example compound 131 (0.5 part)Comparative Comparative compound 1 J-1 Dichlo- x-H.sub.2 PcExample 33 (0.4 part) (1 part) roethane Example compound 132 (0.6 part)__________________________________________________________________________
TABLE 79______________________________________ ##STR171## ##STR172## ##STR173## ##STR174## ##STR175##______________________________________Example 91 699 472 0 0.96 1.81Example 92 584 310 0 0.64 1.31Example 93 598 391 0 0.86 1.74Comparative 837 597 55 1.35 6.40Example 33______________________________________
As apparent from Table 79, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 91 to 93 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 33 prepared by use of comparative compound 1.
EXAMPLES 94 AND 95 AND COMPARATIVE EXAMPLE 34
A charge generating layer was prepared in the same manner as with Examples 35 to 38.
Further, one part of the example compounds in each example shown in Table 80 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 34, comparative compound 1 was used in place of the triphenylamine compound (1) of the example compounds.
Results thereof are shown in Table 81.
TABLE 80__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 94 Example compound 47 H-2 Tetrahy- .tau.-H.sub.2 Pc (0.5 part) (1 part) drofuran Example compound 131 (0.5 part)Example 95 Example compound 52 H-2 Dichlo- .tau.-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 152 (0.6 part)Comparative Comparative compound 1 H-2 Dichlo- .tau.-H.sub.2 PcExample 34 (0.4 part) (1 part) roethane Example compound 132 (0.6 part)__________________________________________________________________________
TABLE 81______________________________________ ##STR176## ##STR177## ##STR178## ##STR179## ##STR180##______________________________________Example 94 1295 948 0 0.86 1.65Example 95 807 587 4 0.54 0.93Comparative 623 332 76 1.63 Unmea-Example 34 surable______________________________________
As apparent from Table 81, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 94 and 95 were low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 34 prepared by use of comparative compound 1.
In Comparative Example 34, it was impossible to measure E.sub.1/6 because of insufficient light sensitivity.
EXAMPLE 96 AND COMPARATIVE EXAMPLE 35
A charge generating layer was prepared by use of .tau.-form metal-free phthalocyanine (.tau.-H.sub.2 Pc) in the same manner as with Examples 39 and 40.
One part of the example compounds in each example shown in Table 82 as charge transporting materials and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 35, comparative compound 1 was used in place of the triphenylamine compound (1) of the example compounds.
Results thereof are shown in Table 83.
TABLE 82__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 96 Example compound 42 J-1 Tetrahy- .tau.-H.sub.2 Pc (0.3 part) (1 part) drofuran Example compound 131 (0.7 part)Comparative Comparative compound 1 J-1 Dichlo- .tau.-H.sub.2 PcExample 35 (0.4 part) (1 part) roethane Example compound 132 (0.6 part)__________________________________________________________________________
TABLE 83______________________________________ ##STR181## ##STR182## ##STR183## ##STR184## ##STR185##______________________________________Example 96 806 679 0 1.08 2.12Comparative 597 315 63 1.42 Unmea-Example 35 surable______________________________________
As apparent from Table 83, it has become clear that the photoreceptor of the present invention prepared by use of the example compounds of Example 96 was low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 35 prepared by use of comparative compound 1.
In Comparative Example 35, it was impossible to measure E.sub.1/6 because of insufficient light sensitivity.
EXAMPLE 97
A charge generating layer was prepared in the same manner as with Examples 42 and 43.
Further, one part of the example compounds shown in Table 84 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as with Examples 1 to 7.
Results thereof are shown in Table 85.
TABLE 84__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 97 Example compound 47 H-2 Dichlo- CuPc (0.4 part) (1 part) roethane Example compound 131 (0.6 part)__________________________________________________________________________
TABLE 85______________________________________ ##STR186## ##STR187## ##STR188## ##STR189## ##STR190##______________________________________Example 97 1047 873 0 2.38 4.89______________________________________
EXAMPLE 98
A charge generating layer was prepared by use of copper phthalocyanine (CuPc) in the same manner as with Examples 42 and 43.
Further, one part of the example compounds shown in Table 86 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as with Examples 1 to 7.
Results thereof are shown in Table 87.
TABLE 86__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 98 Example compound 21 J-1 Dichlo- CuPc (0.4 part) (1 part) roethane Example compound 131 (0.6 part)__________________________________________________________________________
TABLE 87______________________________________ ##STR191## ##STR192## ##STR193## ##STR194## ##STR195##______________________________________Example 98 1054 932 0 2.55 5.37______________________________________
EXAMPLES 99 AND 100
A charge generating layer was prepared in the same manner as with Example 41.
Further, one part of the example compounds in each example shown in Table 88 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
Results thereof are shown in Table 89.
TABLE 88__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 99 Example compound 47 H-2 Dichlo- Bisazo (0.4 part) (1 part) roethane (O) Example compound 152 (0.6 part)Example 100 Example compound 52 H-2 Dichlo- Bisazo (0.4 part) (1 part) roethane (O) Example compound 152 (0.6 part)__________________________________________________________________________
TABLE 89______________________________________ ##STR196## ##STR197## ##STR198## ##STR199## ##STR200##______________________________________Example 99 716 362 8 3.65 6.55Example 100 659 328 5 2.98 5.27______________________________________
As apparent from Tables 85, 87 and 89, it has become clear that the photoreceptosr of the present invention prepared by use of the example compounds of Examples 97 to 100 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics.
EXAMPLE 101
A mixture of 0.4 part of example compound 47 and 0.6 part of example compound 131 was dissolved by heating at various ratios in 2.0 g of a polymer solution comprising one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) and 8 parts of tetrahydrofuran. After dissolution, it was observed whether crystals were precipitated or not when the solution was allowed to stand in the dark at room temperature. When the mixture of example compound 47 (0.4 part) and example compound 131 (0.6 part) was added in an amount of 0.4 g or more, the precipitation of crystals was observed.
COMPARATIVE EXAMPLE 3.6
Only example compound 47 was dissolved by heating in 2.0 g of a polymer solution comprising one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z. manufactured by Mitsubishi Gas Chemical Co., Inc.) and 8 parts of tetrahydrofuran, similarly to Example 101. After dissolution, it was observed whether crystals were precipitated or not when the solution was allowed to stand in the dark at room temperature. When example compound 47 was added in an amount of 0.15 g or more, the precipitation of crystals was observed.
Example 101 and Comparative Example 36 have proved that the solubility in the binder polymer was improved in the case where example compound 131 was mixed with example compound 47, compared with the case where only example compound 47 was used.
EXAMPLES 102 TO 104 AND COMPARATIVE EXAMPLES 37 AND 38
A charge generating layer was prepared in the same manner as with Examples 1 to 7. Further, a photoreceptor was prepared in the same manner as with Examples 1 to 7 with the exception that the example compounds in each example shown in Table 90 were used in an amount of one part in place of the compounds shown in Table 17.
In Comparative Example 37, comparative compound 1 was used in place of the triphenylamine compound of the example compounds. In Comparative Example 38, only the triphenylamine compound (example compound 47) was used.
Results thereof are shown in Table 91.
TABLE 90__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 102 Example compound 1 H-2 Dichlo- TiOPc (0.5 part) (1 part) roethane Deposited Example compound 229 (0.5 part)Example 103 Example compound 47 H-2 Dichlo- TiOPc (0.5 part) (1 part) roethane Deposited Example compound 235 (0.5 part)Example 104 Example compound 47 H-2 Dichlo- TiOPc (0.4 part) (1 part) roethane Deposited Example compound 269 (0.6 part)Comparative Comparative compound 1 H-2 Dichlo- TiOPcExample 37 (0.5 part) (1 part) roethane Deposited Example compound 235 (0.5 part)Comparative Example compound 47 H-2 Dichlo- TiOPcExample 38 (1.0 part) (1 part) roethane Deposited__________________________________________________________________________
TABLE 91______________________________________ ##STR201## ##STR202## ##STR203## ##STR204## ##STR205##______________________________________Example 102 844 620 21 0.58 2.23Example 103 980 764 21 0.57 1.39Example 104 979 746 3 0.69 1.62Comparative 1293 1082 339 2.15 Unmea-Example 37 surableComparative UnmeasurableExample 38______________________________________
As apparent from Table 91, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 102 to 104 were low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 37 prepared by use of comparative compound 1.
In Comparative Example 37, it was impossible to measure E.sub.1/6 because of insufficient light sensitivity. In the photoreceptor of Comparative Example 38, cracks developed after film formation and drying, resulting in the failure of measurement.
EXAMPLE 105 AND COMPARATIVE EXAMPLE 39
A charge generating layer was prepared in the same manner as with Examples 1 to 7.
Further, a photoreceptor was prepared in the same manner as with Examples 1 to 7 with the exception that the example compounds in each example shown in Table 92 were used in an amount of one part in place of the compounds shown in Table 17 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) was used in place of the polycarbonate resin represented by formula (H-2). The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 39, comparative compound 1 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 93.
TABLE 92__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 105 Example compound 47 J-1 Dichlo- TiOPc (0.4 part) (1 part) roethane Deposited Example compound 269 (0.6 part)Comparative Comparative compound 1 J-1 Dichlo- TiOPcExample 39 (0.5 part) (1 part) roethane Deposited Example compound 235 (0.5 part)__________________________________________________________________________
TABLE 93______________________________________ ##STR206## ##STR207## ##STR208## ##STR209## ##STR210##______________________________________Example 105 917 700 71 0.82 14.50Comparative 933 592 88 1.19 21.09Example 39______________________________________
As apparent from Table 93, it has become clear that the photoreceptor of the present invention prepared by use of the example compounds of Example 105 was low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 39 prepared by use of comparative compound 1.
EXAMPLES 106 AND 107 AND COMPARATIVE EXAMPLE 40
A charge generating layer was prepared in the same manner as with Examples 20 to 27.
Further, one part of the example compounds in each example shown in Table 94 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 40, comparative compound 1 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 95.
TABLE 94__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 106 Example compound 1 H-2 Dichlo- CDB (0.5 part) (1 part) roethane Example compound 229 (0.5 part)Example 107 Example compound 47 H-2 Dichlo- CDB (0.4 part) (1 part) roethane Example compound 235 (0.6 part)Comparative Comparative compound 1 H-2 Dichlo- CDBExample 40 (0.5 part) (1 part) roethane Example compound 235 (0.5 part)__________________________________________________________________________
TABLE 95______________________________________ ##STR211## ##STR212## ##STR213## ##STR214## ##STR215##______________________________________Example 106 1041 967 12 5.93 14.64Example 107 999 870 12 3.68 8.30Comparative 1324 1141 129 5.16 16.28Example 40______________________________________
As apparent from Table 95, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 106 and 107 were low in residual potential and also low in E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 40 prepared by use of comparative compound 1.
EXAMPLE 108 AND COMPARATIVE EXAMPLE 41
Chlorodian blue (CDB) was used as a charge generating material similarly to Examples 20 to 27.
Further, one part of the example compounds in each example shown in Table 96 as charge transporting materials and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of dichloroethane. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 41, comparative compound 1 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 97.
TABLE 96__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 108 Example compound 1 J-1 Dichlo- CDB (0.5 part) (1 part) roethane Example compound 241 (0.5 part)Comparative Comparative compound 1 J-1 Dichlo- CDBExample 41 (0.5 part) (1 part) roethane Example compound 234 (0.5 part)__________________________________________________________________________
TABLE 97______________________________________ ##STR216## ##STR217## ##STR218## ##STR219## ##STR220##______________________________________Example 108 985 896 18 5.52 13.00Comparative 1077 930 127 5.50 21.71Example 41______________________________________
As apparent from Table 97, it has become clear that the photoreceptor of the present invention prepared by use of the example compounds of Example 108 was low in residual potential and also low in E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 41 prepared by use of comparative compound 1.
EXAMPLES 109 TO 111 AND COMPARATIVE EXAMPLE 42
A charge generating layer was prepared in the same manner as with Examples 35 to 38.
Further, one part of the example compounds in each example shown in Table 98 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z. manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 42, comparative compound 1 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 99.
TABLE 98__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 109 Example compound 1 H-2 Dichlo- .tau.-H.sub.2 Pc (0.5 part) (1 part) roethane Example compound 229 (0.5 part)Example 110 Example compound 14 H-2 Dichlo- .tau.-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 234 (0.6 part)Example 111 Example compound 47 H-2 Dichlo- .tau.-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 269 (0.6 part)Comparative Comparative compound 1 H-2 Dichlo- .tau.-H.sub.2 PcExample 42 (0.5 part) (1 part) roethane Example compound 235 (0.5 part)__________________________________________________________________________
TABLE 99______________________________________ ##STR221## ##STR222## ##STR223## ##STR224## ##STR225##______________________________________Example 109 908 762 0 0.73 1.37Example 110 808 682 10 0.67 1.23Example 111 1002 876 12 0.74 1.39Comparative 1411 1203 255 1.16 Unmea-Example 20 surable______________________________________
As apparent from Table 99, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 109 to 111 were low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 42 prepared by use of comparative compound 1.
In Comparative Example 42, it was impossible to measure E.sub.1/6 because of insufficient light sensitivity.
EXAMPLE 112 AND COMPARATIVE EXAMPLE 43
A charge generating layer was prepared by use of .tau.-form metal-free phthalocyanine (.tau.-H.sub.2 Pc) in the same manner as with Examples 35 to 38.
One part of the example compounds in each example shown in Table 100 as charge transporting materials and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 43, comparative compound 1 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 101.
TABLE 100__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 112 Example compound 1 J-1 Dichlo- .tau.-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 241 (0.6 part)Comparative Comparative compound 1 J-1 Dichlo- .tau.-H.sub.2 PcExample 43 (0.4 part) (1 part) roethane Example compound 234 (0.6 part)__________________________________________________________________________
TABLE 101______________________________________ ##STR226## ##STR227## ##STR228## ##STR229## ##STR230##______________________________________Example 112 808 676 22 0.63 1.18Comparative 1072 933 37 0.87 2.16Example 43______________________________________
As apparent from Table 101, it has become clear that the photoreceptor of the present invention prepared by use of the example compounds of Example 112 was low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 43 prepared by use of comparative compound 1.
EXAMPLES 113 AND 114 AND COMPARATIVE EXAMPLE 44
A charge generating layer was prepared in the same manner as with Examples 14 to 17.
Further, one part of the example compounds in each example shown in Table 102 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z. manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 44, comparative compound 1 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 103.
TABLE 102__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 113 Example compound 14 H-2 Dichlo- TiOPc (0.4 part) (1 part) roethane Deposited Example compound 235 (0.6 part)Example 114 Example compound 47 H-2 Dichlo- TiOPc (0.4 part) (1 part) roethane Deposited Example compound 234 (0.6 part)Comparative Comparative compound 1 H-2 Dichlo- TiOPcExample 44 (0.5 part) (1 part) roethane Deposited Example compound 235 (0.5 part)__________________________________________________________________________
TABLE 103______________________________________ ##STR231## ##STR232## ##STR233## ##STR234## ##STR235##______________________________________Example 113 745 399 15 0.31 0.64Example 114 866 501 5 0.37 0.89Comparative 655 205 37 2.43 48.72Example 44______________________________________
As apparent from Table 103, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 113 and 114 were low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 44 prepared by use of comparative compound 1.
EXAMPLE 115 AND COMPARATIVE EXAMPLE 45
A charge generating layer was prepared in the same manner as with Examples 48 to 51.
Further, a photoreceptor was prepared in the same manner as with Examples 48 to 51 with the exception that the example compounds in each example shown in Table 104 were used in an amount of one part in place of the compounds shown in Table 45 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) was used in place of the polycarbonate resin represented by formula (H-2). The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 45, comparative compound 1 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 105.
TABLE 104__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 115 Example compound 47 J-1 Dichlo- TiOPc (0.5 part) (1 part) roethane Deposited Example compound 234 (0.5 part)Comparative Comparative compound 1 J-1 Dichlo- TiOPcExample 45 (0.5 part) (1 part) roethane Deposited Example compound 234 (0.5 part)__________________________________________________________________________
TABLE 105______________________________________ ##STR236## ##STR237## ##STR238## ##STR239## ##STR240##______________________________________Example 115 626 383 19 0.49 1.51Comparative 915 528 45 0.66 4.00Example 45______________________________________
As apparent from Table 105, it has become clear that the photoreceptor of the present invention prepared by use of the example compounds of Example 115 was low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 45 prepared by use of comparative compound 1.
EXAMPLES 116 TO 118 AND COMPARATIVE EXAMPLE 46
A charge generating layer was prepared in the same manner as with Examples 31 to 33.
Further, one part of the example compounds in each example shown in Table 106 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 46, comparative compound 1 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 107.
TABLE 106__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 116 Example compound 47 H-2 Dichlo- x-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 235 (0.6 part)Example 117 Example compound 47 H-2 Dichlo- x-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 241 (0.6 part)Example 118 Example compound 41 H-2 Dichlo- x-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 269 (0.6 part)Comparative Comparative compound 1 H-2 Dichlo- x-H.sub.2 PcExample 46 (0.5 part) (1 part) roethane Example compound 235 (0.5 part)__________________________________________________________________________
TABLE 107______________________________________ ##STR241## ##STR242## ##STR243## ##STR244## ##STR245##______________________________________Example 116 1152 1065 6 1.05 2.11Example 117 1232 1091 1 1.13 2.19Example 118 1030 911 2 1.04 1.96Comparative 1372 1293 379 2.48 Unmea-Example 46 surable______________________________________
As apparent from Table 107, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 116 to 118 were low in residual potential and also low in E.sub.1/2, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 46 prepared by use of comparative compound 1.
In Comparative Example 46, it was impossible to measure E.sub.1/6 because of insufficient light sensitivity.
EXAMPLE 119 AND COMPARATIVE EXAMPLES 47 AND 48
A charge generating layer was prepared by use of x-form metal-free phthalocyanine (x-H.sub.2 Pc) in the same manner as with Examples 20 to 27.
Further, one part of the example compounds in each example shown in Table 108 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 47, comparative compound 1 was used in place of the triphenylamine compound of the example compounds, and in Comparative Example 48, example compound 63 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 109.
TABLE 108__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 119 Example compound 52 J-1 Dichlo- x-H.sub.2 Pc (0.4 part) (1 part) roethane Example compound 269 (0.6 part)Comparative Comparative compound 1 J-1 Dichlo- x-H.sub.2 PcExample 47 (0.4 part) (1 part) roethane Example compound 234 (0.6 part)Comparative Example compound 63 J-1 Dichlo- x-H.sub.2 PcExample 48 (0.5 part) (1 part) roethane Example compound 234 (0.5 part)__________________________________________________________________________
TABLE 109______________________________________ ##STR246## ##STR247## ##STR248## ##STR249## ##STR250##______________________________________Example 119 964 868 4 1.22 2.51Comparative 1184 1077 40 1.65 4.20Example 47Comparative 1024 923 63 1.51 4.52Example 48______________________________________
As apparent from Table 109, it has become clear that the photoreceptor of the present invention prepared by use of the example compounds of Example 119 was low in residual potential and also low in E.sub.1/2 and E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 47 prepared by use of comparative compound 1 and the photoreceptor of Comparative Example 48 prepared by use of example compound 63 (0.5 part) and example compound 234 (0.5 part).
EXAMPLES 120 AND 121 AND COMPARATIVE EXAMPLE 49
A charge generating layer was prepared in the same manner as with Example 41.
Further, one part of the example compounds in each example shown in Table 110 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 8 parts of dichloroethane by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 49, comparative compound 1 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 111.
TABLE 110__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 120 Example compound 14 H-2 Dichlo- Bisazo (0.4 part) (1 part) roethane (O) Example compound 235 (0.6 part)Example 121 Example compound 47 H-2 Dichlo- Bisazo (0.4 part) (1 part) roethane (O) Example compound 269 (0.6 part)Comparative Comparative compound 1 H-2 Dichlo- BisazoExample 49 (0.5 part) (1 part) roethane (O) Example compound 235 (0.5 part)__________________________________________________________________________
TABLE 111______________________________________ ##STR251## ##STR252## ##STR253## ##STR254## ##STR255##______________________________________Example 120 804 585 53 5.11 10.71Example 121 921 696 85 7.56 15.22Comparative 806 542 108 4.07 Unmea-Example 49 surable______________________________________
As apparent from Table 111, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 120 and 121 were low in residual potential, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 49 prepared by use of comparative compound 1.
In Comparative Example 49, it was impossible to measure E.sub.1/6 because of insufficient light sensitivity.
EXAMPLES 122 AND 123 AND COMPARATIVE EXAMPLE 50
A charge generating layer was prepared by use of a bisazo pigment represented by formula (O) in the same manner as with Example 41.
Further, one part of the example compounds in each example shown in Table 112 and one part of a bisphenol A/biphenol copolymerized polycarbonate resin represented by formula (J-1) (manufactured by Idemitsu Kosan Co., Ltd.) were dissolved in 8 parts of an organic solvent by mixing. This solution was applied onto the charge generating layer with a doctor blade, and dried at 80.degree. C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptors thus obtained were measured in the same manner as with Examples 1 to 7.
In Comparative Example 50, comparative compound 1 was used in place of the triphenylamine compound of the example compounds.
Results thereof are shown in Table 113.
TABLE 112__________________________________________________________________________ Test Compound Organic Charge Gene- (Amount Used) Polymer Solvent rating Layer__________________________________________________________________________Example 122 Example compound 1 J-1 Dichlo- Bisazo (0.4 part) (1 part) roethane (O) Example compound 241 (0.6 part)Example 123 Example compound 14 J-1 Dichlo- Bisazo (0.4 part) (1 part) roethane (O) Example compound 235 (0.6 part)Comparative Comparative compound 1 J-1 Dichlo- BisazoExample 50 (0.5 part) (1 part) roethane (O) Example compound 234 (0.5 part)__________________________________________________________________________
TABLE 113______________________________________ ##STR256## ##STR257## ##STR258## ##STR259## ##STR260##______________________________________Example 122 882 697 46 4.72 10.24Example 123 785 604 12 4.56 8.36Comparative 924 717 94 3.79 12.62Example 50______________________________________
As apparent from Table 113, it has become clear that the photoreceptors of the present invention prepared by use of the example compounds of Examples 122 and 123 were low in residual potential and also low in E.sub.1/6, providing excellent electrophotographic characteristics, compared with the photoreceptor of Comparative Example 50 prepared by use of comparative compound 1.
EXAMPLE 124
A mixture of 0.4 part of example compound 47 and 0.6 part of example compound 234 was dissolved by heating at various ratios in 2.0 g of a polymer solution comprising one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) and 8 parts of tetrahydrofuran. After dissolution, it was observed whether crystals were precipitated or not when the solution was allowed to stand in the dark at room temperature. When the mixture of example compound 47 and example compound 234 was added in an amount of 0.4 g or more, the precipitation of crystals was observed.
COMPARATIVE EXAMPLE 51
Only example compound 47 was dissolved by heating in 2.0 g of a polymer solution comprising one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) and 8 parts of tetrahydrofuran, similarly to Example 124. After dissolution, it was observed whether crystals were precipitated or not when the solution was allowed to stand in the dark at room temperature. When example compound 47 was added in an amount of 0.15 g or more, the precipitation of crystals was observed.
Example 124 and Comparative Example 51 have proved that the solubility in the binder polymer was improved in the case where example compound 234 was mixed with example compound 47, compared with the case where only example compound 47 was used.
EXAMPLES 125 AND 126 AND COMPARATIVE EXAMPLES 52 AND 53
An underlayer, a charge generating layer and a charge transporting layer are successively formed on an aluminum drum by a dip coating method to prepare a photoreceptor drum having a film thickness of 20 .mu.m.
For the charge generating layer, a dispersion was used which was obtained by adding 40 parts of crystalline oxytitanyl phthalocyanine to a binder resin solution obtained by dissolving 35 parts of a butyral resin (trade name: Polyvinyl Butyral BL-1, manufactured by Sekisui Chemical Co., Ltd.) in 1,425 parts of tetrahydrofuran, and dispersing it together with glass beads by use of a vibrating mill for 2 hours, according to the method described in JP-A-1-291256.
For the charge generating layer, in Example 125, a solution was used which was obtained by dissolving 0.2 part of example compound 47, 0.8 part of example compound 63 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) in 8 parts of dichloroethane by mixing, and further dissolving 0.1 part of .alpha.-tocopherol therein by mixing as an antioxidant.
In Example 126, a solution was used which was obtained by dissolving a mixture of 0.4 part of example compound 47 and 0.6 part of example compound 63, one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) in 9 parts of dichloroethane by mixing.
After standing of this coating solution in the dark for 2 months, a photoreceptor was prepared similarly.
The electrophotographic characteristics were measured with a Cynthia 99HC (manufactured by Gentec Co., Ltd.).
The retention was determined from the ratio of a reduced amount of charge potential from an initial charge potential to a surface potential after 5 seconds in the dark to the initial charge potential, when a photoreceptor was charged by corona discharge. The half-exposure E.sub.1/2 (.mu.J/cm.sup.2) was calculated by determining a time taken until a surface potential reached one-half (-300 V) of an initial surface potential (-600 V). Further, E.sub.100 is an irradiation energy necessary for attenuating the initial surface potential (-600 V) to -100 V.
In Comparative Example 52, a solution was used which was obtained by dissolving one part of example compound 63 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z. manufactured by Mitsubishi Gas Chemical Co., Inc.) in 8 parts of dichloroethane by mixing, and further dissolving 0.1 part of .alpha.-tocopherol therein by mixing as an antioxidant.
In Comparative Example 53, a solution was used which was obtained by dissolving one part of example compound 47 and one part of a polycarbonate resin represented by formula (H-2) (trade name: Polycarbonate Z, manufactured by Mitsubishi Gas Chemical Co., Inc.) in 8 parts of dichloroethane by mixing Results thereof are shown in Table 114.
TABLE 114__________________________________________________________________________ Initial Characteristics After Standing for 2 Months Retention E.sub.1/2 E.sub.100 Retention E.sub.1/2 E.sub.100 (%) (.mu.J/cm.sup.2) (.mu.J/cm.sup.2) (%) (.mu.J/cm.sup.2) (.mu.J/cm.sup.2)__________________________________________________________________________Example 125 Antioxidant 95.3 0.14 0.60 95.6 0.14 0.77 UsedComparative Antioxidant 90.1 0.22 0.60 94.8 0.16 1.05Example 52 UsedExample 12 Antioxidant 95.9 0.13 0.56 95.4 0.13 0.60 Not usedComparative Antioxidant 94.0 0.14 0.67 95.1 0.14 0.78Example 52 Not used__________________________________________________________________________
As apparent from Table 114, the photoreceptors of the present invention obtained in Examples 125 and 126 was small in changes in characteristics before and after standing of the coating solutions, compared with the photoreceptors obtained by use of example compound 63 alone in Comparative Example 52 and example compound 47 alone in Comparative Example 53. Thus, the photoreceptors of Examples 125 and 126 in which example compound 47 was mixed with example compound 63 could increase the stability of the coating solution.
EXAMPLES 127 TO 133 AND COMPARATIVE EXAMPLES 54 TO 64
One part of a mixed charge transporting material in which the example compounds in each of Examples 127 to 133 shown in Table 115 were mixed at 8 to 11 kinds of ratios and one part of a polycarbonate resin represented by structural formula (H-2) were dissolved in 8 parts of dichloroethane by mixing. Each of these solutions was applied with a doctor blade onto a sheet in which aluminum was deposited over a polyethylene terephthalate (PET) film, and dried at 80.degree. C. for 3 hours. When one part of example compound 47 alone was used, cracks developed in a photoreceptor film on standing after film formation.
Further, a translucent gold electrode was deposited over each of these 8 kinds of charge transporting layers, and the charge carrier mobility was measured for each layer. The measurement of the carrier mobility was made by the time-of-flight method (Toshiaki Tanaka, Yasuhiro Yamaguchi and Masaaki Yokoyama, Denshi Shashin (Electrophotography) 29, 366 (1990)) using a nitrogen gas laser having a pulse half width of 0.9 nsec. and a wavelength of 337 nm as a light source. Results measured at 25.degree. C. at 25 V/.mu.m are shown in FIGS. 2 to 8.
Similarly, in each of Comparative Examples 54 to 56 in Table 116, the measurement was made in the same manner as with Examples 127 to 133, using one part of a charge transporting material in which each of comparative compounds 1 to 3 was mixed with example compound 47 at 9 or 10 kinds of ratios. Results thereof are shown in FIGS. 9 to 11.
Further, in Comparative Example 57, the measurement was made in the same manner as with Examples 127 to 133, using one part of a charge transporting material in which comparative compound 4 was mixed with example compound 81 at 8 kinds of ratios. Results thereof are shown in FIG. 12.
Furthermore, in Comparative Example 58, the measurement was made in the same manner as with Examples 127 to 133, using one part of a charge transporting material in which comparative compound 4 was mixed with example compound 131 at 10 kinds of ratios. Results thereof are shown in FIG. 13.
Still further, in Comparative Example 59, the measurement was made in the same manner as with Examples 127 to 133, using one part of a charge transporting material in which comparative compound 1 was mixed with example compound 195 at 8 kinds of ratios. Results thereof are shown in FIG. 14.
The term "carrier mobility" means the moving speed of a carrier per unit electric field (V/cm). That the carrier mobility is high is that a carrier rapidly moves in a charge transporting layer. The carrier mobility is inherent in a charge transporting material, and indicated by cm.sup.2 /V.multidot.s.
TABLE 115__________________________________________________________________________ Mixing Ratio of Example Compounds (unit: part by__________________________________________________________________________ weight)Example 127 (8 kinds)Example compound 47 0 0.2 0.4 0.6 0.8 0.9 0.95 1.0Example compound 63 1 0.8 0.6 0.4 0.2 0.1 0.05 0.0Example 128 (10 kinds)Example compound 47 0 0.05 0.1 0.2 0.4 0.6 0.8 0.9 0.95 1.0Example compound 81 1 0.95 0.9 0.8 0.6 0.4 0.2 0.1 0.05 0.0Example 129 (10 kinds)Example compound 47 0 0.05 0.1 0.2 0.4 0.6 0.8 0.9 0.95 1.0Example compound 82 1 0.95 0.9 0.8 0.6 0.4 0.2 0.1 0.05 0.0Example 130 (11 kinds)Example compound 47 0 0.05 0.1 0.2 0.4 0.6 0.7 0.8 0.9 0.95 1.0Example compound 93 1 0.95 0.9 0.8 0.6 0.4 0.3 0.2 0.1 0.05 0.0Example 131 (10 kinds)Example compound 47 0 0.05 0.1 0.2 0.4 0.6 0.8 0.9 0.95 1.0Example compound 109 1 0.95 0.9 0.8 0.6 0.4 0.2 0.1 0.05 0.0Example 132 (10 kinds)Example compound 47 0 0.05 0.1 0.2 0.4 0.6 0.8 0.9 0.95 1.0Example compound 132 1 0.95 0.9 0.8 0.6 0.4 0.2 0.1 0.05 0.0Example 133 (10 kinds)Example compound 47 0 0.05 0.1 0.2 0.4 0.6 0.8 0.9 0.95 1.0Example compound 195 1 0.95 0.9 0.8 0.6 0.4 0.2 0.1 0.05 0.0__________________________________________________________________________
TABLE 116__________________________________________________________________________ Mixing Ratio of Example Compounds (unit: part by__________________________________________________________________________ weight)Comparative Example 54 (10 kinds)Example compound 47 0 0.05 0.1 0.2 0.4 0.6 0.8 0.9 0.95 1.0Comparative compound 1 1 0.95 0.9 0.8 0.6 0.4 0.2 0.1 0.05 0.0Comparative Example 55 (10 kinds)Example compound 47 0 0.05 0.1 0.2 0.4 0.6 0.8 0.9 0.95 1.0Comparative compound 2 1 0.95 0.9 0.8 0.6 0.4 0.2 0.1 0.05 0.0Comparative Example 56 (9 kinds)Example compound 47 0 0.05 0.2 0.4 0.6 0.8 0.9 0.95 1.0Comparative compound 1 0.95 0.8 0.6 0.4 0.2 0.1 0.05 0.0Comparative Example 57 (8 kinds)Example compound 81 0 0.2 0.4 0.6 0.8 0.9 0.95 1.0Comparative compound 4 1 0.8 0.6 0.4 0.2 0.1 0.05 0.0Comparative Example 58 (10 kinds)Example compound 131 0 0.05 0.1 0.2 0.4 0.6 0.8 0.9 0.95 1.0Comparative compound 4 1 0.95 0.9 0.8 0.6 0.4 0.2 0.1 0.05 0.0Comparative Example 59 (8 kinds)Example compound 195 0 0.2 0.4 0.6 0.8 0.9 0.95 1.0Comparative compound 1 1 0.8 0.5 0.4 0.2 0.1 0.05 0.0__________________________________________________________________________
FIG. 2 shows that a combination of the triphenylamine compound represented by general formula (1) and the hydrazone compound represented by general formula (2) according to the present invention exhibited a high mobility value of 10.sup.-6 cm.sup.2 /V.multidot.s or more without a lowering, even when the content of the triphenylamine compound was 5 to 95% by weight.
On the other hand, as apparent from FIG. 9, a combination of the triphenylamine compound represented by general formula (1) and comparative compound 1 only exhibited a mobility value similar to that of comparative compound 1 low in mobility, when the content of the triphenylamine compound was 5 to 95% by weight.
As apparent from FIGS. 10 and 11, when the triphenylamine compound represented by general formula (1) was combined with comparative compound 2 or comparative compound 3, the curves were convex downward, showing that the mobility of the mixtures was lower than that of the triphenylamine compound and the comparative compounds almost all over the regions, although the mobility of the comparative compounds was high.
From the results described above, it has become clear that only a combination of the triphenylamine compound represented by general formula (1) and the hydrazone compound represented by general formula (2) gave a charge transporting material having high mobility.
Further, FIGS. 3 to 6 show that combinations of the triphenylamine compounds represented by general formula (1) and the hydrazone compounds represented by general formula (3) according to the present invention exhibited a high mobility value of 10.sup.-6 cm.sup.2 /V.multidot.s or more without a lowering, even when the content of the triphenylamine compounds was 5 to 95% by weight.
On the other hand, as apparent from FIG. 9, a combination of the triphenylamine compound represented by general formula (1) and comparative compound 1 only exhibited a mobility value similar to that of comparative compound 1 low in mobility, when the contest of the triphenylamine compound was 5 to 95% by weight.
As apparent from FIGS. 10 and 11, when the triphenylamine compound represented by general formula (1) was combined with comparative compound 2 or comparative compound 3, the curves were convex downward, showing that the mobility of the mixtures was lower than that of the triphenylamine compound and the comparative compounds almost all over the regions, although the mobility of the comparative compounds was high.
FIG. 12 shows that even when the hydrazone compound represented by general formula (2) was combined with comparative compound 4, the mobility of the mixture was significantly lowered by mixing, although the mobility of each compound was high.
From the results described above, it has become clear that only a combination of the triphenylamine compound represented by general formula (1) and the hydrazone compound represented by general formula (3) gave a charge transporting material having high mobility.
Furthermore, FIG. 7 shows that a combination of the triphenylamine compound represented by general formula (1) and the triphenylamine diner compound represented by general formula (4) according to the present invention exhibited a high mobility value of 10.sup.-5 cm.sup.2 /V.multidot.s or more without a lowering, even when the content of the triphenylamine compound was 5 to 95% by weight.
On the other hand, as apparent from FIG. 9, a combination of the triphenylamine compound represented by general formula (1) and comparative compound 1 only exhibited a mobility value similar to that of comparative compound 1 low in mobility, when the content of the triphenylamine compound was 5 to 95% by weight.
As apparent from FIGS. 10 and 11, when the triphenylamine compound represented by general formula (1) was combined with comparative compound 2 or comparative compound 3, the curves were convex downward, showing that the mobility of the mixtures was lower than that of the triphenylamine compound and the comparative compounds almost all over the regions, although the mobility of the comparative compounds was high.
From the results described above, it has become clear that only a combination of the triphenylamine compound represented by general formula (1) and the triphenylamine dimer compound represented by general formula (4) gave a charge transporting material having high mobility.
FIG. 8 shows that a combination of the triphenylamine compound represented by general formula (1) and the distyryl compound represented by general formula (5) according to the present invention exhibited a high mobility value of 10.sup.-5 cm.sup.2 /V.multidot.s or more without a lowering, all over the content regions of the triphenylamine compound.
On the other hand, as apparent from FIG. 9, a combination of the triphenylamine compound represented by general formula (1) and comparative compound 1 only exhibited a mobility value similar to that of comparative compound 1 low in mobility, when the content of the triphenylamine compound was 5 to 95% by weight.
As apparent from FIGS. 10 and 11, when the triphenylamine compound represented by general formula (1) was combined with comparative compound 2 or comparative compound 3, the curves were convex downward, showing that the mobility of the mixtures was lower than that of the triphenylamine compound and the comparative compounds almost all over the regions, although the mobility of the comparative compounds was high.
As apparent from FIG. 14, when the distyryl compound represented by general formula (5) was combined with comparative compound 1, a mobility value similar to that of comparative compound 1 low in mobility was only obtained all over the regions.
From the results described above, it has become clear that only a combination of the triphenylamine compound represented by general formula (1) and the distyryl compound represented by general formula (5) gave a charge transporting material having high mobility.
The charge transporting materials obtained by the present invention can improve the carrier mobility without an increase in concentration, and the electrophotographic photoreceptors comprising said charge transporting materials have excellent electrophotographic characteristics such as good sensitivity and low residual potential. Accordingly, they are very useful.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Number	Date	Country
8-202736	Jul 1996	JPX
8-276873	Sep 1996	JPX
8-353817	Dec 1996	JPX
8-925756	Jan 1997	JPX

Number	Name	Date	Kind
5486439	Sakakibara et al.	Jan 1996
5567560	Hagiwara et al.	Oct 1996

Electrophotographic photoreceptor

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