JP2003202687A - Electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor free of impairment of electrophotographic properties such as potential by electrification and residual potential and excellent also in repetition stability. <P>SOLUTION: The electrophotographic photoreceptor has a photosensitive layer containing one or more of the indane compounds of formula [1] as a charge transport material and an organic additive for an electrophotographic photoreceptor containing one or more atoms selected from nitrogen, oxygen, phosphorus and sulfur. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor. More specifically, the present invention relates to an electrophotographic photosensitive member which has small changes in charging potential and residual potential even after repeated use and has excellent durability.

[0002]

2. Description of the Related Art Conventionally, selenium,
Inorganic photoconductive materials such as zinc oxide, cadmium sulfide, and silicon have been widely used. While these inorganic materials have many advantages, they also have various drawbacks. For example, selenium has the drawback that it is difficult to manufacture and it is easily crystallized by heat or mechanical impact.Zinc oxide and cadmium sulfide have problems in moisture resistance and mechanical strength, and they are charged by a dye added as a sensitizer. Also, there are drawbacks such as deterioration of exposure and exposure, and lack of durability. Silicon is also expensive to manufacture due to difficult manufacturing conditions and the use of highly irritating gas. In addition, selenium and cadmium sulfide have toxicity problems.

In recent years, organic photoreceptors using various organic compounds have been studied and widely used for the purpose of overcoming the drawbacks of these inorganic photoreceptors. Organic photoreceptors include a single-layer photoreceptor in which a charge generating agent and a charge transporting agent are dispersed in a binder resin, and a laminated photoreceptor in which a charge generating layer and a charge transporting layer have different functions. A characteristic of such a photoconductor, which is called a function-separated type, is that materials suitable for each function can be selected from a wide range, and many studies have been carried out because a photoconductor having arbitrary performance can be easily produced. Has been promoted.

As described above, in order to satisfy the requirements for the basic performance and high durability required for the electrophotographic photoreceptor, the development of new materials, their combination, etc.
Although various improvements have been made, the current situation is that sufficient ones have not been obtained yet.

[0005]

However, although the organic material has many advantages that the inorganic material does not have, an organic material which does not sufficiently satisfy all the properties required for the electrophotographic photoreceptor has not been obtained. Is the current situation. That is, deterioration of image quality is caused by a decrease in charging potential, an increase in residual potential, a change in sensitivity, and the like due to repeated use. The cause of this deterioration is not fully understood, but some factors are charge transport due to ozone generated during charging by corona discharge, active gas such as NOX, exposure, and ultraviolet rays and heat contained in static elimination light. It is possible to decompose the agent. In order to suppress the above deterioration, for example, JP-A-1-44
Japanese Patent Application Laid-Open No. 946-846 describes a combination of a hydrazone compound and an antioxidant, and Japanese Patent Application Laid-Open No. 1-118845 describes a combination of a butadiene compound and an antioxidant.
Those having good initial sensitivity do not sufficiently improve deterioration due to repeated use, and those having little deterioration due to repeated use have problems in initial sensitivity and chargeability. As described above, it is the current situation that these conventional techniques have not yet achieved sufficient effects.

Therefore, an object of the present invention is to provide an electrophotographic photosensitive member having high sensitivity and low residual potential in the initial stage, stable to ozone, light, heat, etc. and less fatigue deterioration even after repeated use. To do.

[0007]

The present invention provides the following general formula [1] on a conductive support.

[0008]

[Chemical 15]

[In the formula, Ar1 represents a substituted or unsubstituted aryl group, Ar2 represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group or a substituted or unsubstituted Represents an anthrylene group, W represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, X represents a substituted or unsubstituted aryl group, the following general formula [2]

[0010]

[Chemical 16]

A monovalent group represented by or the following general formula [3]

[0012]

[Chemical 17]

(Wherein R 1 represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, R 2 represents a hydrogen atom, a halogen atom or a lower alkyl group, and Y represents a hydrogen atom or a substituted or unsubstituted aryl group. , M and n represent an integer of 0 to 4). ] A photosensitive layer containing one or more kinds of indane compounds represented by the following and an organic additive for an electrophotographic photoreceptor containing one or more kinds of atoms selected from nitrogen, oxygen, phosphorus and sulfur. An electrophotographic photosensitive member characterized by having. By containing the photosensitive layer of the present invention, a highly durable electrophotographic photoreceptor having stable electrophotographic characteristics such as charging potential and residual potential can be provided.

In the present invention, the organic additive for an electrophotographic photoreceptor containing one or more kinds of atoms selected from the above-mentioned nitrogen, oxygen, phosphorus and sulfur is represented by the following general formula [4]. An organic phosphite compound, a triphenylated phosphorus compound represented by the general formula [5], a thioether compound represented by the general formula [6], a hydroquinone compound represented by the general formula [7], A benzotriazole compound represented by the general formula [8], a benzotriazole-alkylenebisphenol compound represented by the general formula [9], a hydroxybenzophenone compound represented by the general formula [10], and a general formula [11]. To a hindered phenol compound represented by [12], a hindered amine compound represented by a general formula [13], and a salicylate compound represented by a general formula [14] Is one or more are al selected, relative indane compound electrophotographic photoreceptor organic additive is represented by the general formula [1], 0.05
It is characterized by containing 30% by weight.

[0015]

[Chemical 18]

(In the general formula [4], R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an allyl group or a substituted group. Alternatively, it represents an unsubstituted aryl group.
However, R ₃ , R ₄ , and R ₅ are not hydrogen atoms at the same time. )

[0017]

[Chemical 19]

(In the general formula [5], R ₆ , R ₇ , R ₈ and R
₉ , R ₁₀ and R ₁₁ may be the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group or an alkyl group. )

[0019]

[Chemical 20]

(In the general formula [6], R ₁₂ and R ₁₃ may be the same or different and may be a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an allyl group or a substituted or unsubstituted aryl group. Represents.)

[0021]

[Chemical 21]

(In the general formula [7], R ₁₄ , R ₁₅ , R
₁₆ and R _{17, which} may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an allyl group or a substituted or unsubstituted aryl group. )

[0023]

[Chemical formula 22]

(In the general formula [8], R ₁₈ and R ₁₉ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an allyl group or a substituted or unsubstituted group. Represents the aryl group of.)

[0025]

[Chemical formula 23]

(In the general formula [9], T represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or an aralkyl group, and R ₂₀ represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or Represents an aralkyl group, R ₂₁ represents a hydrogen atom, an alkyl group or an aryl group, and R ₂₂ and R ₂₃ may be the same or different and represent an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.)

[0027]

[Chemical formula 24]

(In the general formula [10], R ₂₄ and R ₂₅ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an allyl group or a substituted or unsubstituted group. Represents the aryl group of.)

[0029]

[Chemical 25]

(In the general formula [11], R ₂₆ represents a lower alkyl group, and R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ may be the same or different and each is a hydrogen atom or a substituted or unsubstituted lower alkyl group. Or represents a substituted or unsubstituted lower alkoxy group.)

[0031]

[Chemical formula 26]

(In the general formula [12], R ₃₁ represents a lower alkyl group, and R ₃₂ , R ₃₃ and R ₃₄ may be the same or different, and are a hydrogen atom, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted lower alkyl group. Represents an unsubstituted lower alkoxy group, q represents an integer of 2 to 4, E represents an oxygen atom or an aliphatic divalent group when q = 2, and an aliphatic trivalent group when q = 3 Represents a group or an aromatic trivalent group, and when q = 4 represents an aliphatic tetravalent group.)

[0033]

[Chemical 27]

(In the general formula [13], R ₃₅ , R ₃₆ , R
₃₇ and R _{38, which} may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and Z represents an atomic group necessary for forming a nitrogen-containing heterocycle. . Further, in the set of R ₃₅ and R _{36 and} the set of R ₃₇ and R ₃₈ , one of them may be incorporated into Z to form a double bond. u and j represent organic residues. )

[0035]

[Chemical 28]

(In the general formula [14], R ₃₉ and R ₄₀ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an allyl group or a substituted or unsubstituted group. Represents the aryl group of.)

The electrophotographic photoreceptor of the present invention contains one or more kinds of the above-mentioned indane compound and further contains one or more kinds of atoms selected from the above-mentioned nitrogen, oxygen, phosphorus and sulfur. It has a photosensitive layer containing one or more organic additives for photographic photoreceptors (hereinafter abbreviated as "additives").

Specific examples of the charge transfer agent of the indane compound represented by the general formula [1] include the following.

(Charge transport material No. 1)

[Chemical 29]

(Charge transport material No. 2)

[Chemical 30]

(Charge transport material No. 3)

[Chemical 31]

(Charge transport material No. 4)

[Chemical 32]

(Charge transport material No. 5)

[Chemical 33]

(Charge transport material No. 6)

[Chemical 34]

(Charge transport material No. 7)

[Chemical 35]

(Charge transport material No. 8)

[Chemical 36]

(Charge transport material No. 9)

[Chemical 37]

(Charge transport material No. 10)

[Chemical 38]

(Charge transport material No. 11)

[Chemical Formula 39]

(Charge transport material No. 12)

[Chemical 40]

(Charge transport material No. 13)

[Chemical 41]

(Charge transport material No. 14)

[Chemical 42]

(Charge transport material No. 15)

[Chemical 43]

(Charge transport material No. 16)

[Chemical 44]

(Charge transport material No. 17)

[Chemical formula 45]

(Charge transport material No. 18)

[Chemical formula 46]

(Charge transport material No. 19)

[Chemical 47]

(Charge transport material No. 20)

[Chemical 48]

(Charge transport material No. 21)

[Chemical 49]

(Charge transport material No. 22)

[Chemical 50]

(Charge transport material No. 23)

[Chemical 51]

(Charge transport material No. 24)

[Chemical 52]

(Charge transport material No. 25)

[Chemical 53]

(Charge transport material No. 26)

[Chemical 54]

(Charge transport material No. 27)

[Chemical 55]

(Charge transport material No. 28)

[Chemical 56]

(Charge transport material No. 29)

[Chemical 57]

(Charge transport agent No. 30)

[Chemical 58]

[0069]

Various forms of the photosensitive layer exist, and any of them can be adopted as the photosensitive layer of the electrophotographic photosensitive member of the present invention. As a typical example, those photoreceptors are shown in FIGS.

In FIGS. 1 and 2, a stack of a charge generating layer 2 containing a charge generating substance as a main component and a charge transporting layer 3 containing a charge transporting substance and a polycarbonate resin as a main component is laminated on a conductive support 1. A photosensitive layer 4 composed of a body is provided. At this time, as shown in FIGS. 3 and 4, the photosensitive layer 4 may be provided via an undercoat layer 5 provided on the conductive support for adjusting the electric charge, and the protective layer 8 is provided as the outermost layer. It may be provided. Further, in the present invention, as shown in FIGS. 5 and 6, the photosensitive layer 4 obtained by dissolving or dispersing the charge generating substance 7 in the layer 6 containing the charge transporting substance as a main component is formed on the conductive support 1. It may be provided directly or via the undercoat layer 5.

The photoreceptor of the present invention can be manufactured by a conventional method as follows. For example, the indane compound represented by the general formula [1] and the general formulas [4] to [1
4] is dissolved in an appropriate solvent together with the binder resin in a suitable solvent, and if necessary, a charge generating substance, an electron-withdrawing compound or a plasticizer, a pigment, and other additives are added to prepare a coating solution. adjust. This coating liquid is applied on a conductive support,
A photoreceptor can be manufactured by drying to form a photosensitive layer having a thickness of several μm to several tens of μm. In the case of a photosensitive layer comprising two layers of a charge generation layer and a charge transport layer, the indane compound represented by the general formula [1] and the general formulas [4] to [1]
4] is dissolved in an appropriate solvent together with the binder resin and an antioxidant, and a coating solution prepared by adding a plasticizer, a pigment and other additives is applied onto the charge generation layer. Or
Alternatively, it can be produced by forming a charge generation layer on the charge transport layer obtained by applying the above coating solution. Further, an undercoat layer and a protective layer may be provided on the photoconductor thus manufactured, if necessary.

The constituent materials used in the present invention are as follows. First, specific examples of the additives represented by the general formulas [4] to [14] are shown below, but the additives are not limited to these.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

[0076]

[Table 4]

[0077]

[Table 5]

[0078]

[Table 6]

[0079]

[Table 7]

[0080]

[Table 8]

[0081]

[Table 9]

[0082]

[Table 10]

[0083]

[Table 11]

[0084]

[Table 12]

[0085]

[Table 13]

[0086]

[Table 14]

[0087]

[Table 15]

[0088]

[Table 16]

[0089]

[Table 17]

[0090]

[Table 18]

[0091]

[Table 19]

[0092]

[Table 20]

In the photoconductor of the present invention, the ratio of the additive is 0.05 based on the indane compound represented by the general formula [1].
~ 30% by weight. A preferable amount of the additive is 0.1 to 20% by weight based on the indane compound represented by the general formula [1].

As the electroconductive support on which the photosensitive layer of the present invention is formed, the materials used in known electrophotographic photoreceptors can be used. Aluminum, aluminum alloy, stainless steel, copper, zinc, vanadium, molybdenum, chrome,
Titanium, nickel, indium, metal drums such as gold and platinum, sheets or laminates of these metals, vapor deposits, metal powder, carbon black, copper iodide, and polymer electrolyte conductive substances are applied together with an appropriate binder. It is possible to use a plastic film, a plastic drum, paper, a paper tube, or a plastic film or a plastic drum that has been made conductive by containing a conductive substance.

If desired, an undercoat layer containing a resin or a resin and a pigment may be provided between the conductive support and the photosensitive layer. The pigment dispersed in the undercoat layer is
Although generally used powder may be used, white with almost no absorption in the near infrared, or a powder close to this is desirable in consideration of high sensitivity. Examples of such pigments include metal oxides represented by titanium oxide, zinc oxide, tin oxide, indium oxide, zirconium oxide, alumina, silica, and the like, which have no hygroscopicity and little environmental change. desirable.

As the resin used for the undercoat layer, considering the fact that the photosensitive layer is coated therewith with a solvent, a resin having a high solvent resistance to a general organic solvent is desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymerized nylon and methoxymethylated nylon, and three-dimensional network structures such as polyurethane, melamine resin, and epoxy resin. The curable resin and the like are used.

The charge generating layer in the present invention comprises a charge generating agent, a binder resin, and additives which are added as necessary. Examples of the method for producing the charge generating layer include a coating method, a vapor deposition method and a CVD method. To be

As charge generating agents, various crystal forms of titanyl phthalocyanine and Cu-Kα have X-ray diffraction spectra with diffraction angles 2θ ± 0.2 ° of 9.3, 10.6, 1
Titanyl phthalocyanine having strong peaks at 3.2, 15.1, 20.8, 23.3, 26.3, diffraction angle 2θ
± 0.2 ° is 7.5, 10.3, 12.6, 22.5,
Titanyl phthalocyanine having strong peaks at 24.3, 25.4, and 28.6 and a diffraction angle 2θ ± 0.2 ° of 9.
Titanyl phthalocyanine having a strong peak at 6, 24. 1 and 27.2, metal-free phthalocyanine of various crystal types such as τ type and X type, copper phthalocyanine, aluminum phthalocyanine, zinc phthalocyanine, α type, β type, Y
Phthalocyanine-based pigments such as oxotitanyl phthalocyanine, cobalt phthalocyanine, hydroxygallium phthalocyanine, chloroaluminum phthalocyanine, and chloroindium phthalocyanine. Azo pigments having a triphenylamine skeleton (described in JP-A No. 53-132347), azo pigments having a carbazole skeleton (described in JP-A No. 53-95033), azo pigments having a fluorene skeleton (JP-A No. 54-22834), azo pigments having an oxadiazole skeleton (described in JP-A-54-12742), azo pigments having a bisstilbene skeleton (described in JP-A-54-17733), Azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728), azo pigments having a distyrylbenzene skeleton (described in JP-A-53-133445), and azo pigments having a distyrylcarbazole skeleton ( JP-A-54-17734), azo pigments having a distyryl oxadiazole skeleton (JP-A-54-17934). No. 4-2129), an azo pigment having a stilbene skeleton (described in JP-A-53-138229), and a trisazo pigment having a carbazole skeleton (JP-A-57-195767 and 57-195768). ), An azo pigment having an anthraquinone skeleton (described in JP-A-57-202545), and a bisazo pigment having a diphenylpolyene skeleton (JP-A-59-1298).
57, 62-267363, 64-79753.
No. 3, Japanese Patent Publication No. 3-34503, and No. 4-52459). Perylene pigments such as perylene anhydride and perylene imide. Anthraquinone derivative, anthanthrone derivative, dibenzpyrenequinone derivative,
Polycyclic quinone pigments such as pyranthrone derivatives, violanthrone derivatives and isobiolanthrone derivatives. Diphenylmethane and triphenylmethane pigments. Cyanine and azomethine pigments. Indigoid pigments, bisbenzimidazole pigments, azurenium salts, pyrylium salts,
Examples include thiapyrylium salt, benzopyrylium salt, and squarylium salt. These may be used alone or as a mixture of two or more as necessary.

The binder resin used in the charge generation layer is not particularly limited, and examples thereof include polycarbonate, polyarylate, polyester, polyamide, polyethylene, polystyrene, polyacrylate, polymethacrylate, polyvinyl butyral, polyvinyl acetal, polyvinyl. Formal, polyvinyl alcohol,
Examples thereof include polyacrylonitrile, polyacrylamide, styrene-acrylic copolymer, styrene-maleic anhydride copolymer, acrylonitrile-butadiene copolymer, polysulfone, polyether sulfone, silicone resin and phenoxy resin. These may be used alone or as a mixture of two or more as necessary.

Examples of the additives used in this case as required include, for example, antioxidants, ultraviolet absorbers, dispersants,
Examples thereof include adhesives and sensitizers. The thickness of the charge generation layer manufactured using the above materials is 0.1 to 2.0.
μm, and preferably 0.1 to 1.0 μm. The charge-transporting layer in the present invention comprises a charge-transporting agent, a binder resin, and optionally an electron-accepting substance and an additive, which are dissolved in a solvent,
It can be formed by coating it on the charge generation layer, the conductive support, or the undercoat layer and then drying it.

As the binder resin for the charge transport layer, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester butadiene, polyvinyl acetal, polycarbonate (special Kaisho 60-172044,
JP-A-62-247374, JP-A-63-14826
3, JP-A-2-254459), polyesters, polyphenylene oxides, polyurethane cellulose esters, phenoxy resins, silicon resins, epoxy resins, and other various resins that are compatible with the charge transport agent and additives. . These may be used alone or as a mixture of two or more as necessary. The amount of the binder resin used is usually in the range of 0.4 to 10 times by weight, preferably 0.5 to 5 times by weight that of the charge transport agent. Specific examples of particularly effective resins include "Iupilon Z" (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and "bisphenol A".
-Biphenol copolycarbonate "(made by Idemitsu Kosan Co., Ltd.)
Polycarbonate resins such as

The solvent used for the charge transport layer is not particularly limited as long as it dissolves the charge transport agent, the binder resin, the electron accepting substance and the additive, and examples thereof include:
Tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, cyclohexanone, acetonitrile, N, N
-Use polar organic solvents such as dimethylformamide and ethyl acetate, aromatic organic solvents such as toluene, xylene and chlorobenzene, and chlorinated hydrocarbon solvents such as chloroform, trichloroethylene, dichloromethane, 1,2-dichloroethane and carbon tetrachloride. be able to. These may be used alone or as a mixture of two or more as necessary.

The photosensitive layer of the present invention may contain an electron accepting substance for the purpose of improving sensitivity, reducing residual potential, or reducing fatigue during repeated use. Examples of such an electron-accepting substance include succinic anhydride, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, and 3
-Nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene , P-nitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bromanil, dichlorodicyano-p-benzoquinone, anthraquinone,
Dinitroanthraquinone, 2,3-dichloro-1,4-
Naphthoquinone, 1-nitroanthraquinone, 2-chloroanthraquinone, phenanthrenequinone, terephthalalmalenonitrile, 9-anthrylmethylidene malenonitrile, 9-fluorenylidene malononitrile, polynitro-9-fluorenylidene malononitrile, 4 -Nitrobenzaldehyde, 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, 4-chloronaphthalic anhydride, 3-benzalphthalide, 3-
(Α-Cyano-p-nitrobenzal) -4,5,6,7
-Tetrachlorophthalide, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid,
3,5-dinitrosalicylic acid, phthalic acid, meritic acid,
Other compounds having a high electron affinity can be given.

If necessary, a surface protective layer may be provided on the surface of the photoreceptor. As a material to be used, a resin such as polyester or polyamide, or a mixture of these resins with a metal or a metal oxide capable of adjusting electric resistance can be used. It is desirable that this surface protective layer be as transparent as possible in the wavelength region of light absorption of the charge generating agent.

[0105]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Parts in the examples represent parts by weight, and concentrations represent%.

[Example 1] 1 part by weight of an alcohol-soluble polyamide (Amilan CM-4000, manufactured by Toray) was dissolved in 13 parts by weight of methanol. After adding 5 parts by weight of titanium oxide (Taipaque CR-EL, made by Ishihara Sangyo Co., Ltd.) and dispersing with a paint shaker for 8 hours to prepare a coating solution for the undercoat layer, a wire bar is formed on the aluminum surface of the aluminum-deposited PET film Was applied and dried to form an undercoat layer having a thickness of 1 μm.

Next, the diffraction angles 2θ ± 0.2 ° in the X-ray diffraction spectrum of Cu-Kα are 9.6, 24.1, 27.
Titanyl phthalocyanine having a strong peak at 2 (charge generating agent No. 1)

[0108]

[Chemical 59]

1.5 parts of polyvinyl butyral resin (S-REC BL-S, manufactured by Sekisui Chemical Co., Ltd.) was added to 50 parts of a 3% cyclohexanone solution, and the mixture was dispersed by an ultrasonic disperser for 1 hour. The obtained dispersion was applied onto the undercoat layer using a wire bar, and then dried at 110 ° C. under normal pressure for 1 hour to form a charge generation layer having a thickness of 0.6 μm. On the other hand, 5.3 parts of Exemplified Compound I- (6) as an additive and the following indane compound as a charge transport agent (charge transport agent N
o. 1)

[0110]

[Chemical 60]

100 parts of polycarbonate resin (Upilon Z, manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
Was added to 962 parts of a 13.0% tetrahydrofuran solution of 1. and ultrasonic waves were applied to completely dissolve the additive and the indane compound. This solution was coated on the above charge generation layer with a wire bar and dried under atmospheric pressure at 110 ° C. for 30 minutes to give a film thickness of 20 μm.
A charge transport layer of m was formed to prepare a photoconductor.

Example 2 A photoreceptor was prepared in the same manner as in Example 1 except that Exemplified Compound III- (6) was used instead of Exemplified Compound I- (6).

Example 3 A photoconductor was prepared in the same manner as in Example 1 except that Exemplified Compound IV- (8) was used instead of Exemplified Compound I- (6) in Example 1.

Example 4 A photoreceptor was prepared in the same manner as in Example 1 except that Exemplified Compound VI- (5) was used instead of Exemplified Compound I- (6).

Example 5 A photoconductor was prepared in the same manner as in Example 1 except that Exemplified Compound X- (6) was used instead of Exemplified Compound I- (6) in Example 1.

[Embodiment 6] Charge generator No. 1, the diffraction angle 2θ ± 0.2 ° in the X-ray diffraction spectrum of Cu-Kα is 7.5, 10.
3, 12.6, 22.5, 24.3, 25.4, 28.
Titanyl phthalocyanine having a strong peak at 6 (charge generator No. 2),

Charge transport material No. 1 instead of using indane compound (charge transfer agent No. 2)

[0118]

[Chemical formula 61]

A photoconductor was prepared in the same manner as in Example 2 except that was used.

Example 7 Compound Exemplified in Example 6
Instead of using III- (6), exemplary compound III- (10)
A photoconductor was produced in the same manner as in Example 6 except that was used.

[Embodiment 8] Charge generator No. 1, the diffraction angle 2θ ± 0.2 ° in the X-ray diffraction spectrum of Cu-Kα is 9.3, 10.
6, 13.2, 15.1, 20.8, 23.3, 26.
Titanyl phthalocyanine having a strong peak at 3 (charge generator No. 3),

Charge Transfer Agent No. 1 instead of using indane compound (charge transfer agent No. 3)

[0123]

[Chemical formula 62]

A photoconductor was prepared in the same manner as in Example 2 except that was used.

Example 9 Compound Exemplified in Example 8
A photoconductor was prepared in the same manner as in Example 8 except that the exemplified compound VI- (5) was used instead of III- (6).

[Example 10] The charge transfer material No. 3 instead of using indane compound (charge transfer agent No. 4)

[0127]

[Chemical formula 63]

A photoconductor was prepared in the same manner as in Example 8 except that was used.

[Example 11] Instead of using the exemplified compound III- (6) in Example 10, the exemplified compound VI-
A photoconductor was produced in the same manner as in Example 10 except that (5) was used.

[Example 12] The charge transfer material No. 3 instead of using indane compound (charge transfer agent No. 5)

[0131]

[Chemical 64]

A photoconductor was prepared in the same manner as in Example 8 except that was used.

[Example 13] 10 parts by weight of an alcohol-soluble polyamide (Amilan CM-8000, manufactured by Toray) was dissolved in 190 parts by weight of methanol, and then coated and dried using a wire bar on the aluminum surface of an aluminum vapor-deposited PET film,
An undercoat layer having a thickness of 1 μm was formed.

Next, the following τ-type metal-free phthalocyanine (charge-generating agent No. 4) was used as the charge-generating agent.

[0135]

[Chemical 65]

1.5 parts of polyvinyl butyral resin (S-REC BL-S, manufactured by Sekisui Chemical Co., Ltd.) was added to 50 parts of a 3% cyclohexanone solution, and the mixture was dispersed for 1 hour with an ultrasonic disperser. The obtained dispersion was applied onto the undercoat layer using a wire bar, and then dried at 110 ° C. under normal pressure for 1 hour to form a charge generation layer having a thickness of 0.6 μm. On the other hand, Exemplified compound VI- (5), 5.3 parts as an additive and the following indane compound (charge transfer agent N
o. 6)

[0137]

[Chemical formula 66]

100 parts of polycarbonate resin (Upilon Z, manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
Was added to 962 parts of a 13.0% tetrahydrofuran solution of 1. and ultrasonic waves were applied to completely dissolve the additive and the indane compound. This solution was coated on the above charge generation layer with a wire bar and dried under atmospheric pressure at 110 ° C. for 30 minutes to give a film thickness of 20 μm.
A charge transport layer of m was formed to prepare a photoconductor.

[Embodiment 14] Charge generator No. 4, instead of using X-type metal-free phthalocyanine (charge generator No. 5),

Charge Transfer Agent No. 6 instead of using indane compound (charge transfer agent No. 7)

[0141]

[Chemical formula 67]

A photoconductor was prepared in the same manner as in Example 13 except that was used.

[Example 15] In Example 6, the charge transfer material No. Instead of using No. 2, charge transfer agent No. 2 and an indane compound (charge transport material No. 8),

[0144]

[Chemical 68]

A photoconductor was prepared in the same manner as in Example 6 except that the mixture of 8: 2 by weight was used.

Example 16 Instead of using Exemplified Compound III- (6) in Example 15, Exemplified Compound VI-
A photoconductor was produced in the same manner as in Example 16 except that (5) was used.

[Example 17] The charge transfer material No. Instead of using No. 4, charge transfer agent No. 4 was used. 4 and indane compound (charge transport material No. 9),

[0148]

[Chemical 69]

A photoconductor was prepared in the same manner as in Example 10 except that the mixture of 8: 2 by weight was used.

Example 18 Instead of using the exemplified compound III- (6) in Example 17, the exemplified compound VI-
A photoconductor was produced in the same manner as in Example 17 except that (5) was used.

Example 19 The following bisazo pigment (charge generating agent No. 6) was used as the charge generating agent.

[0152]

[Chemical 70]

1.0% and 5% of polyvinyl butyral resin (S-REC BL-S, manufactured by Sekisui Chemical Co., Ltd.)
8.6 parts of cyclohexanone solution was added to cyclohexanone 83
In addition to the parts, pulverization and dispersion treatment was performed with a ball mill for 48 hours. The obtained dispersion liquid is aluminum vapor deposition P which is a conductive support.
A wire bar was used to coat and dry the aluminum surface of the ET film to form a charge generation layer having a thickness of 0.8 μm. On the other hand, 5.3 parts of Exemplified Compound III- (6) as an additive and Charge Transfer Agent No. 3 as a charge transfer agent. 7,100 parts were added to 962 parts of a 13.0% tetrahydrofuran solution of a polycarbonate resin (Iupilon Z, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and ultrasonic waves were applied to completely dissolve the additive and the indane compound. This solution was applied onto the above charge generation layer with a wire bar and dried under atmospheric pressure at 110 ° C. for 30 minutes to form a charge transport layer having a film thickness of 20 μm to prepare a photoreceptor.

[Embodiment 20] Charge generator No. The following bisazo pigment (charge generating agent No. 7) was used in place of 6

[0155]

[Chemical 71]

A photoconductor was prepared in the same manner as in Example 19 except that the above was used. [Example 21] The following bisazo pigment (charge generating agent No. 8) as a charge generating agent

[0157]

[Chemical 72]

1.0 part and 8.6 parts of a 5% tetrahydrofuran solution of polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) were added to 83 parts of tetrahydrofuran, and pulverized and dispersed by a ball mill for 48 hours. The obtained dispersion was applied on the aluminum surface of an aluminum vapor-deposited PET film as a conductive support using a wire bar and dried to form a charge generation layer having a thickness of 0.8 μm. On the other hand, 5.3 parts of Exemplified Compound III- (6) as an additive and Charge Transfer Agent No. 3 as a charge transfer agent. 1,100 parts of a 13.0% solution of polycarbonate resin (Iupilon Z, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) in tetrahydrofuran 96
Two parts were added and ultrasonic waves were applied to completely dissolve the additive and the indane compound. This solution was applied onto the above charge generation layer with a wire bar and dried under atmospheric pressure at 110 ° C. for 30 minutes to form a charge transport layer having a film thickness of 20 μm to prepare a photoreceptor.

[Embodiment 22] Charge generator No. The following trisazo pigment (charge generating agent No. 9) instead of using No. 8

[0160]

[Chemical formula 73]

A photoconductor was prepared in the same manner as in Example 21 except that the above was used.

Comparative Example 1 A comparative photoreceptor was prepared in the same manner as in Example 1 except that the exemplified compound I- (6) was omitted.

[Comparative Example 2] Compound exemplified in Example 6
A comparative photoconductor was prepared in the same manner as in Example 6 except that III- (6) was omitted.

Comparative Example 3 A comparative photoconductor was prepared in the same manner as in Example 17, except that the Exemplified Compound III- (6) was omitted from Example 17.

[Comparative Example 4] A comparative photoconductor was prepared in the same manner as in Example 19 except that the exemplified compound III- (6) was omitted.

[Examples 1 to 18 and Comparative Examples 1 to 3] The photoconductors manufactured in Examples 1 to 18 and Comparative Examples 1 to 3 were measured by a photosensitive drum characteristic measuring device (trade name "ELYSIA-II" Trek Japan ( (Manufactured by K.K.) was used for electrophotographic characteristic evaluation. First, the photoreceptor was subjected to a corona discharge of −5.5 kV in the dark, and then the charging potential V0 was measured when the 70lux erase lamp was turned on. Then image exposure 7
The residual potential Vr was determined by exposing with monochromatic light of 80 nm-30 μW. Next, this photoconductor is placed in a room under fluorescent lamp illumination.
After exposure to ppm ozone gas for 5 days, charging potential V0 and residual potential Vr were measured in the same manner as before exposure. The results are shown in [Table 11].

[0167]

[Table 21]

[Examples 19 to 22, Comparative Example 4] Example 1
9 to 22 and the photoconductors manufactured in Comparative Example 4 with a photosensitive drum characteristic measuring device (trade name "ELYSIA-II" Trek.
Electrophotographic characteristics were evaluated using Japan Co., Ltd. First, the photoreceptor was subjected to corona discharge of −4.8 kV in a dark place, and subsequently, the charging potential V0 was measured when the 70lux erase lamp was turned on. Image exposure 40
It was exposed to white light of lux to determine the residual potential Vr. Next, after exposing this photoreceptor to 20 ppm ozone gas for 5 days in a room under fluorescent lighting, in the same manner as before exposure,
The charging potential V0 and the residual potential Vr were measured. The results are shown in [Table 1
2].

[0169]

[Table 22]

[0170]

As described above, according to the present invention, by combining an indane compound having a specific structure as a charge transporting agent and an organic type additive for an electrophotographic photoreceptor having a specific structure, the charge potential and It is possible to provide an electrophotographic photoreceptor having a small change in residual potential and excellent durability.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing the layer structure of a function-separated type electrophotographic photoreceptor.

FIG. 2 is a schematic cross-sectional view showing a layer structure of a function-separated type electrophotographic photoreceptor.

FIG. 3 is a schematic cross-sectional view showing a layer structure of a function-separated type electrophotographic photoreceptor in which an undercoat layer is provided between a charge generation layer and a conductive support.

FIG. 4 is a schematic cross-sectional view showing the layer structure of a function-separated electrophotographic photoreceptor in which an undercoat layer is provided between a charge transport layer and a conductive support, and a protective layer is provided on the charge generation layer. is there.

FIG. 5 is a schematic cross-sectional view showing the layer structure of a function-separated electrophotographic photoreceptor in which an undercoat layer is provided between a charge generation layer and a conductive support, and a protective layer is provided on a charge transport layer. is there.

FIG. 6 is a schematic cross-sectional view showing the layer structure of a single-layer type electrophotographic photoconductor.

FIG. 7 is a schematic cross-sectional view showing the layer structure of a single-layer type electrophotographic photoreceptor in which an undercoat layer is provided between a photosensitive layer and a conductive support.

[Explanation of symbols]

1 Conductive support 2 Charge generation layer 3 Charge transport layer 4 Photosensitive layer 5 Undercoat layer 6 Charge transport material-containing layer 7 Charge generation material 8 protective layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masaki Okubo             Hodogaya 45, Miyukigaoka, Tsukuba City, Ibaraki Prefecture             Gakkou Co., Ltd. Tsukuba Research Center F-term (reference) 2H068 AA14 AA15 AA16 AA17 AA20                       AA35 BA16 BA60

Claims (3)

[Claims] 1. A conductive film having the following general formula [1] on a conductive support: [In the formula, Ar1 represents a substituted or unsubstituted aryl group, Ar2 represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group or a substituted or unsubstituted anthrylene group. And W represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group,
X is a substituted or unsubstituted aryl group, represented by the following general formula [2] Or a monovalent group represented by the following general formula [3] (In the formula, R1 represents a hydrogen atom, a lower alkyl group or a lower alkoxy group, R2 represents a hydrogen atom, a halogen atom or a lower alkyl group, Y represents a hydrogen atom or a substituted or unsubstituted aryl group, and m and n represents an integer of 0 to 4) and represents a monovalent group. ] One or more kinds of indane compounds represented by the following, nitrogen, oxygen,
An electrophotographic photoreceptor comprising a photosensitive layer containing an organic additive for an electrophotographic photoreceptor containing at least one atom selected from phosphorus and sulfur. 2. The organic phosphorous additive for an electrophotographic photoreceptor containing at least one atom selected from nitrogen, oxygen, phosphorus, and sulfur, which is represented by the following general formula [4]: Acid ester compounds, triphenylated phosphorus compounds represented by the general formula [5], thioether compounds represented by the general formula [6], hydroquinone compounds represented by the general formula [7], and general formula [7] 8], a benzotriazole compound represented by the general formula [9], a benzotriazole-alkylenebisphenol compound represented by the general formula [9], a general formula [1
0], a hydroxybenzophenone compound, a hindered phenol compound represented by the general formulas [11] to [12], a hindered amine compound represented by the general formula [13], and a general formula [14]. 1 to 2 or more selected from the salicylate compounds described above, and the organic additive for an electrophotographic photoreceptor is 0.05 to 30% by weight with respect to the indane compound represented by the general formula [1]. %, The photoconductor for electrophotography according to claim 1. [Chemical 4] (In the general formula [4], R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an allyl group or a substituted or unsubstituted group. Represents an aryl group of R
₃ , R ₄ and R ₅ are not hydrogen atoms at the same time. ) [Chemical 5] (In the general formula [5], R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ ,
R ₁₁ may be the same or different and represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group or an alkyl group. ) [Chemical 6] (In the general formula [6], R ₁₂ and R ₁₃ may be the same or different and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an allyl group or a substituted or unsubstituted aryl group. ) [Chemical 7] (In the general formula [7], R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group,
It represents an allyl group or a substituted or unsubstituted aryl group. ) [Chemical 8] (In the general formula [8], R ₁₈ and R ₁₉ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted alkenyl group, an allyl group or a substituted or unsubstituted aryl group. ) [Chemical 9] (In the general formula [9], T represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or an aralkyl group, and R ₂₀ represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or an aralkyl group. And R ₂₁ represents a hydrogen atom, an alkyl group or an aryl group, and R ₂₂ and R ₂₃ may be the same or different and represent an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.) (In the general formula [10], R ₂₄ and R ₂₅ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an allyl group or a substituted or unsubstituted aryl group. Is represented.) (In the general formula [11], R ₂₆ represents a lower alkyl group,
R ₂₇ , R ₂₈ , R ₂₉ , and R ₃₀ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted lower alkyl group, or a substituted or unsubstituted lower alkoxy group. ) [Chemical 12] (In the general formula [12], R ₃₁ represents a lower alkyl group,
R ₃₂ , R ₃₃ and R _{34, which} may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted lower alkyl group or a substituted or unsubstituted lower alkoxy group, and q is 2 to
Represents an integer of 4, E represents an oxygen atom or an aliphatic divalent group when q = 2, represents an aliphatic trivalent group or an aromatic trivalent group when q = 3, and q = When 4, it represents an aliphatic tetravalent group. ) [Chemical 13] (In the general formula [13], R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈
May be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and Z represents an atomic group necessary for forming a nitrogen-containing heterocycle. Further, in the set of R ₃₅ and R _{36 and} the set of R ₃₇ and R ₃₈ , one of them may be incorporated into Z to form a double bond. u and j represent organic residues. ) [Chemical 14] (In the general formula [14], R ₃₉ and R ₄₀ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an allyl group or a substituted or unsubstituted aryl group. Represents.) 3. The organic additive for electrophotographic photoreceptors represented by the general formulas [4] to [14] is 0.1 to 20% by weight based on the indane compound represented by the general formula [1]. The electrophotographic photosensitive member according to claim 1 or 2, wherein the electrophotographic photosensitive member is contained.