JPH08292586A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE: To obtain an electrophotographic photoreceptor having superior electric charge transferring ability and exhibiting such photoreceptor characteristics as high sensitivity and high durability. CONSTITUTION: This electrophotographic photoreceptor has a photosensitive layer contg. a polyamine compd. represented by formula I or II on the electrically conductive substrate. In the formulae I, II, each of R1 -R3 , R6 and R7 is H, lower alkyl, lower alkoxy or optionally substd. phenyl, each of R4 , R5 and R8 is H, lower alkyl, lower alkoxy or Cl and each of A and B is a group represented by formula III, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor having a photosensitive layer containing a specific polyamine compound.

[0002]

2. Description of the Related Art An electrophotographic method is generally a method in which the surface of a photoconductor made of a photoconductive material is charged in the dark, for example, by corona discharge, and then exposed to the light to selectively dissipate the charge in the exposed area. It is a kind of image forming method in which an electrostatic latent image is dispersed to obtain an electrostatic latent image, which is visualized with toner, and then transferred and fixed on paper or the like to obtain an image. As the photoconductor, an inorganic photoconductor containing an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide, or silicon as a main component, and a charge generating agent and a low-molecular weight or high-molecular weight charge transport agent in a binder resin There is an organic photoconductor using an organic compound dispersed in. Inorganic photoconductors have many advantages and have been widely used until now.For example, selenium is difficult to produce, its production cost is high, it is vulnerable to heat and mechanical shock, and its performance deteriorates because it easily crystallizes Resulting in. Zinc oxide and cadmium sulfide have problems in moisture resistance and mechanical strength, and the dye added as a sensitizer is deteriorated by electrification and exposure, resulting in poor durability. Silicon is also difficult to manufacture and uses a highly irritating gas, so it is expensive and sensitive to humidity.

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 are functionally separated. The function-separated type organic photoconductor has been extensively researched and widely used because of its wide choice of materials and the fact that a photoconductor having any desired performance can be produced relatively easily by combining them.

Examples of the charge generating agent include azo compounds,
Many organic compounds such as bisazo compounds, trisazo compounds, tetrakisazo compounds, thiapyrylium salts, squarylium salts, azurenium salts, cyanine dyes, perylene compounds, metal-free or metal phthalocyanine compounds, polycyclic quinone compounds, thioindigo compounds, or quinacridone compounds. Pigments and dyes have been proposed and put into practical use.

As the charge transfer agent, for example, Japanese Patent Publication No. 34-
Oxadiazole compounds described in JP-A-5466, JP-A-56
No. 123544, Oxazole Compound, Japanese Examined Patent Publication No. 5
JP-A 2-41880, Pyrazoline Compound, JP-B-55
-42380 gazette and Japanese Patent Publication No. 61-40104 gazette,
JP-B-62-35673, JP-B-63-3597
No. 6, hydrazone compound, Japanese Patent Publication No. 58-32372
Compounds disclosed in Japanese Patent Publication No. 63-18738, Japanese Patent Publication No. 63-19867, and Japanese Patent Publication No. 3-393.
No. 06 stilbene compound, JP-A-62-3025
For example, there is a butadiene compound disclosed in Japanese Patent No. Organic photoconductors using these charge-transporting materials have excellent properties and some have been put into practical use, but those that sufficiently satisfy the properties required for electrophotographic photoconductors have not yet been obtained. The current situation is not.

[0006]

The charge transfer agent used in the organic photoreceptor has not only the sensitivity and other characteristics as a photoreceptor, but also a chemical stability that withstands light, ozone, and electrical loads. Stability and durability are required so that the sensitivity does not decrease even after repeated use or long-term use. An object of the present invention is to provide an electrophotographic photoreceptor having excellent heat resistance and crystallization resistance, satisfying the characteristics of the photoreceptor and having high sensitivity and high durability.

[0007]

According to the present invention, an electrophotographic photoreceptor having a photosensitive layer containing a polyamine compound represented by the following general formula (1) or general formula (2) is provided. Will be provided. General formula (1)

[0008]

[Chemical 25]

[Wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a substituted or unsubstituted phenyl group, and R ₄ is a hydrogen atom, a lower alkyl group, Represents a lower alkoxy group or chlorine atom, and A represents the following formula

[0010]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

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[Chemical 31]

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[Chemical 33]

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R ₅ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a chlorine atom. ] General formula (2)

[0012]

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[Wherein R ₆ and R ₇ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a substituted or unsubstituted phenyl group, and R ₈ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group. Or represents a chlorine atom,
B is the following formula

[0014]

[Chemical 38]

[Chemical Formula 39]

[Chemical 40]

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[Chemical 43]

[Chemical 44]

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[Chemical 47]

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R ₉ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a chlorine atom. ]

In the present invention, the polyamine compound represented by the general formula (1) or the general formula (2) contained in the photosensitive layer is a novel compound, and these compounds are basically known as the Ullmann reaction. It can be synthesized by a combination of condensation reactions of arylamine and aryl halide.

A method for synthesizing the tetraamine compound represented by the general formula (1) will be described. For example, the following formula

[0018]

[Chemical 49]

[In the formula, R ₄ has the same meaning as in the general formula (1), and X represents a chlorine atom, a bromine atom or an iodine atom. However, R ₄ and X are not chlorine atoms at the same time. ] The 4,4'- dihalogenated biphenyl compound represented by

[0020]

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[In the formula, R ₁ has the same meaning as in the general formula (1). ] It is condensed with an acetanilide compound represented by

[0022]

[Chemical 51]

[In the formula, R ₁ , R ₄ and X have the same meanings as described above. However, R ₄ and X are not chlorine atoms at the same time. ] The 4'-halogenated biphenylyl acetanilide compound represented by this is obtained. This 4'-halogenated biphenylyl acetanilide compound is further represented by the following formula

[0024]

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[In the formula, R ₂ and R ₃ have the same meanings as in the general formula (1). ] After the condensation reaction with the diphenylamine compound represented by

[0026]

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[In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as described above. ] The triphenyl benzidine compound represented by this is obtained. 2 mol of this triphenylbenzidine compound is replaced by 1 mol of the following formula

[0028]

[Chemical 54]

[In the formula, A represents the same meaning as in the general formula (1), and X represents the same meaning as described above. ] The tetraamine compound represented by the general formula (1) of the present invention is obtained by allowing the dihalide represented by the formula to act and condense. On the other hand, the following formula

[0030]

[Chemical 55]

[In the formula, A represents the same meaning as described above. ] When the starting material is a diamino compound represented by the following formula, after acetylating the amino group to give a diacetyl compound, the following formula

[0032]

[Chemical 56]

[In the formula, R ₁ and X have the same meanings as described above. ] It is condensed with a halogenated aryl represented by

[0034]

[Chemical 57]

[In the formula, R ₁ and A have the same meanings as described above. ] The diaryl diamino compound represented by this is obtained. The following formula synthesized from a dihalogenated biphenyl compound and an acetanilide compound in the same manner as described above

[0036]

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[In the formula, R ₂ , R ₄ and X have the same meanings as described above. However, R ₄ and X are not chlorine atoms at the same time. ] The 4'-halogenated biphenylyl acetanilide compound represented by
The following formula

[0038]

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[In the formula, R ₁ , R ₂ , R ₄ and A have the same meanings as described above. ] The tetraamine compound represented by this is obtained. Furthermore, this tetraamine compound has the following formula

[0040]

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[In the formula, R ₃ and X have the same meanings as described above. ] The tetraamine compound represented by the general formula (1) of the present invention can also be obtained by condensing a halogenated aryl represented by: In addition, in the reaction of 4,4′-dihalogenated biphenyl with an acetanilide compound in the condensation reaction, a benzanilide compound may be used instead of the acetanilide compound.

Next, a method for synthesizing the hexaamine compound represented by the general formula (2) will be described. For example, the following formula

[0043]

[Chemical formula 61]

[In the formula, R ₈ has the same meaning as in the general formula (2), and X represents a chlorine atom, a bromine atom or an iodine atom. However, R ₈ and X are not chlorine atoms at the same time. ] The 4,4'- dihalogenated biphenyl compound represented by

[0045]

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[In the formula, R ₆ and R ₇ have the same meaning as in the general formula (2). ] It is condensed with a diphenylamine compound represented by

[0047]

[Chemical formula 63]

[In the formula, R ₆ , R ₇ , R ₈ and X have the same meanings as described above. However, R ₈ and X are not chlorine atoms at the same time. ] The 4'-halogenated biphenylyl diphenylamine compound represented by these is obtained. 4 mol of this 4'-halogenated biphenylyldiphenylamine compound is represented by the following formula:

[0049]

[Chemical 64]

[In the formula, B represents the same meaning as in the general formula (2). ] The hexaamine compound represented by the general formula (2) of the present invention is obtained by allowing 1 mole of the diamine compound represented by

On the other hand, the following formula synthesized from a dihalogenated biphenyl compound and a diphenylamine compound in the same manner as described above

[0052]

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[In the formula, R ₆ , R ₇ , R ₈ and X have the same meanings as described above. However, R ₈ and X are not chlorine atoms at the same time. ] A 4'-halogenated biphenylyl diphenylamine compound represented by the following formula is condensed with 1 mol of acetamide and hydrolyzed to give the following formula:

[0054]

[Chemical formula 66]

[In the formula, R ₆ , R ₇ and R ₈ have the same meanings as described above. ] The triamine compound represented by this is obtained. Further, 2 mol of this triamine compound is added to the following formula

[0056]

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[In the formula, X and B have the same meanings as described above. When B has R ₉ having the same meaning as described above, X and R ₉ are not chlorine atoms at the same time. ] The hexaamine compound represented by the general formula (2) of the present invention can also be obtained by allowing 1 mol of the dihalide represented by the formula to act and condense. In the condensation reaction of 2 mol of the 4′-halogenated biphenylyldiphenylamine compound and 1 mol of acetamide in the condensation reaction, a benzamide compound may be used instead of the acetamide compound.
The condensation reaction of the arylamine and the aryl halide described above is a reaction known as the Ullmann reaction, and is performed without a solvent or in the presence of a solvent. As the solvent, a high boiling point solvent such as nitrobenzene, dichlorobenzene or dimethyl sulfoxide is used. Further, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide and the like are used as a deoxidizing agent. Further, usually, the reaction is carried out using a catalyst such as copper powder or copper halide. The reaction temperature is usually 160 to 230 ° C.

In the general formula (1), R ₁ , R ₂ ,
When R ₃ is a phenyl group having a substituent, or when R ₆ and R ₇ in the general formula (2) are phenyl groups having a substituent, the substituent has 1 to 4 carbon atoms.
Lower alkyl group, a lower alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a benzyl group,
A phenyl group or a halogen atom is included, and when the substituent is a benzyl group or a phenyl group, the number of carbon atoms is 1 to 1.
It may be further substituted with a lower alkyl group having 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms or a halogen atom. Examples of the alkyl group represented by R ₁ , R ₂ , R ₃ , R ₆ and R ₇ include linear or branched alkyl groups having 1 to 4 carbon atoms, and the alkoxy group having 1 to 4 carbon atoms. A straight chain or branched alkoxy group may be mentioned.

The following are specific examples of the polyamine compound represented by the general formula (1) or the general formula (2) contained in the photosensitive layer according to the present invention.

Compound No. 1

[Chemical 68]

Compound No. 2

[Chemical 69]

Compound No. Three

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Compound No. 4

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Compound No. 5

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Compound No. 6

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Compound No. 7

[Chemical 74]

Compound No. 8

[Chemical 75]

Compound No. 9

[Chemical 76]

Compound No. 10

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Compound No. 11

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Compound No. 12

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Compound No. 13

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Compound No. 14

[Chemical 81]

Compound No. Fifteen

[Chemical formula 82]

Compound No. 16

[Chemical 83]

Compound No. 17

[Chemical 84]

Compound No. 18

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Compound No. 19

[Chemical 86]

Compound No. 20

[Chemical 87]

Compound No. 21

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Compound No. 22

[Chemical 89]

Compound No. 23

[Chemical 90]

Compound No. 24

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Compound No. 25

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Compound No. 26

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Compound No. 27

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Compound No. 28

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Compound No. 29

[Chemical 96]

Compound No. 30

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Compound No. 31

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Compound No. 32

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Compound No. 33

[Chemical 100]

Compound No. 34

[Chemical 101]

Compound No. 35

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Compound No. 36

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Compound No. 37

[Chemical 104]

Compound No. 38

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Compound No. 39

[Chemical formula 106]

Compound No. 40

[Chemical formula 107]

Compound No. 41

[Chemical 108]

Compound No. 42

[Chemical 109]

Compound No. 43

[Chemical 110]

Compound No. 44

[Chemical 111]

Compound No. 45

[Chemical 112]

The electrophotographic photoreceptor of the present invention has a photosensitive layer containing one or more of the above polyamine compounds. There are various forms of the photosensitive layer, and any of them may be used as the photosensitive layer of the electrophotographic photosensitive member of the present invention. As a typical example, the photoreceptor is shown in FIGS.

The photosensitive member shown in FIG. 1 comprises a conductive support 1 and a photosensitive layer 2 comprising a polyamine compound, a sensitizing dye and a binder resin. The photoconductor of FIG. 2 is such that a photoconductive layer 21 in which a charge generating substance 4 is dispersed in a charge transport medium 3 composed of a polyamine compound and a binder resin is provided on a conductive support 1. In this photoreceptor, the charge generating substance absorbs light to generate charge carriers, which are then transported by the charge transport medium. In this case, the charge transport material is preferably transparent to the light that generates the charge carriers. Since polyamine compounds have almost no absorption in the visible wavelength range,
The condition that the charge generation material and the absorption wavelength range do not overlap is satisfied.

The photoconductor of FIG. 3 has a photoconductive layer 22 formed by laminating a charge generation layer 5 mainly composed of a charge generation substance 4 and a charge transport layer 3 composed of a polyamine compound and a binder resin on a conductive support 1. It is provided. In this photoreceptor, the charge transport layer 3
The light that has passed through reaches the charge generation layer 5 and the charge generation substance 4
Are absorbed by the carrier and charge carriers are generated. The charge carriers are injected and transported in the charge transport layer 3. The photoreceptor of FIG.
The photosensitive layer 23 in which the charge generating layer 5 and the charge transporting layer 3 of the photoconductor of FIG. Generation and transport of charge carriers can be explained by the same mechanism as described above. The photosensitive member of FIG. 5 has a photosensitive layer 24 in which a protective layer 6 is further laminated on the charge generation layer 5 of the photosensitive member of FIG. 4 for the purpose of improving mechanical strength.

The photoconductor of the present invention as exemplified above is manufactured by a conventional method. For example, the above general formula (1)
Alternatively, the polyamine compound represented by the general formula (2) is dissolved in a suitable solvent together with a binder resin, and if necessary, a charge generating substance, a sensitizing dye, an electron-withdrawing compound or a plasticizer, a pigment, and other additives. Can be prepared by coating a coating solution prepared by adding the above on a conductive support and drying it to form a photosensitive layer of several μ to several tens μ. In the case of a photosensitive layer composed of two layers of a charge generation layer and a charge transport layer, the above-mentioned coating solution is applied onto the charge generation layer, or the charge generation layer is applied onto the charge transport layer obtained by applying the above-mentioned coating solution. It can be manufactured by forming. Further, the photoreceptor thus manufactured may be provided with an adhesive layer, an intermediate layer, and a barrier layer, if necessary.

As the solvent for preparing the coating solution, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone,
Examples thereof include polar organic solvents such as cyclohexanone, acetonitrile, N, N-dimethylformamide and ethyl acetate, aromatic organic solvents such as toluene and xylene, and chlorinated hydrocarbon solvents such as dichloromethane and dichloroethane. A solvent having a high solubility for the polyamine compound and the binder resin is preferably used.

Examples of the sensitizing dye include triarylmethane dyes such as methyl violet, brilliant green, crystal violet and acid violet, xanthene dyes such as rhodamine B, eosin S and rose bengal, and thiazine dyes such as methylene blue. Examples thereof include pyrylium dyes such as benzopyrylium salts, thiapyrylium dyes, and cyanine dyes.

Examples of the electron withdrawing compound which forms a charge transfer complex with a polyamine compound include chloranil, 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 2-chloroanthraquinone and phenanthrenequinone. Quinones, aldehydes such as 4-nitrobenzaldehyde, 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, 2,4,7-trinitrofluorenone, 2,4,4.
Ketones such as 5,7-tetranitrofluorenone, acid anhydrides such as phthalic anhydride and 4-chloronaphthalic anhydride,
Tetracyanoethylene, terephthalalmalenonitrile,
Cyano compounds such as 9-anthrylmethylidenemalenonitrile, 3-benzalphthalide, 3- (α-cyano-p-
Nitrobenzal) -4,5,6,7-tetrachlorophthalide and other phthalides.

Examples of the binder resin include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester and butadiene, polyvinyl acetal, polycarbonate, polyester, polyphenylene oxide, polyurethane, Various resins that are compatible with the polyamine compound, such as cellulose ester, phenoxy resin, silicon resin, epoxy resin and the like can be mentioned. The amount of the binder resin used is usually in the range of 0.4 to 10 times by weight, preferably 0.5 to 3 times by weight, of the polyamine compound.

Further, the photosensitive layer of the present invention may contain a well-known plasticizer for the purpose of improving film-forming property, flexibility and mechanical strength. Examples of the plasticizer include phthalic acid ester, phosphoric acid ester, chlorinated paraffin, methylnaphthalene, epoxy compound, chlorinated fatty acid ester and the like.

Further, as the electroconductive support on which the photosensitive layer is formed, the materials used in known electrophotographic photoconductors can be used. For example, a metal drum such as aluminum, stainless steel or copper, a sheet or a laminate of these metals, a vapor deposition product, a metal powder, carbon black, copper iodide or a conductive substance such as a polymer electrolyte is applied together with an appropriate binder. Conductive treated plastic film,
Examples thereof include a plastic drum, paper, a paper tube, and a plastic film and a plastic drum which are made conductive by containing a conductive substance.

[0115]

The present invention will be described below in detail with reference to examples. Parts in the examples represent parts by weight, and the concentration represents Wt%.

Synthesis Example 1 (Synthesis Example of Compound No. 7) 20.3 g (0.15 mol) of acetanilide and 4,4 ′
73.1 g (0.18 mol) of diiodobiphenyl, 22.1 g (0.16 mol) of anhydrous potassium carbonate, copper powder 2.
16 g (0.034 mol) and 35 ml of nitrobenzene were mixed and reacted at 190 to 205 ° C for 10 hours. The reaction product was extracted with 200 ml of toluene, the insoluble matter was removed by filtration, and the mixture was concentrated to dryness. This was purified by column chromatography (carrier; silica gel, eluent: toluene / ethyl acetate = 6/1), and 40.2 g of N- (4'-iodo-4-biphenylyl) acetanilide (yield 64.8). %) Was obtained. The melting point was 135.0 to 136.0 ° C. Then, N- (4'-iodo-4-biphenylyl) acetanilide 13.2 g (0.032 mol), diphenylamine 6.60 g (0.039 mol), anhydrous potassium carbonate 5.53 g (0.040 mol) And copper powder 0.45g
(0.007 mol) and 10 ml of nitrobenzene were mixed and reacted at 200 to 212 ° C for 15 hours. The reaction product was extracted with 100 ml of toluene, the insoluble matter was removed by filtration, and the mixture was concentrated to give an oily substance. The oily substance was dissolved in 60 ml of isoamyl alcohol, 1 ml of water and 2.64 g (0.040 mol) of 85% potassium hydroxide were added thereto, and 13
Hydrolyzed at 0 ° C. After distilling off isoamyl alcohol by steam distillation, it was extracted with 250 ml of toluene, washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier; silica gel, eluent: toluene / n-hexane = 1/2) to obtain 10.5 g of N, N, N'-triphenylbenzidine (yield 72.2%). Obtained. The melting point is 167.
It was 5 to 168.5 ° C.

Furthermore, 8.66 g (0.021 mol) of N, N, N'-triphenylbenzidine, 4,4'-diiodine
Dobiphenyl 4.06 g (0.01 mol), anhydrous potassium carbonate 2.90 g (0.021 mol), copper powder 0.32 g
(0.005 mol) and 10 ml of nitrobenzene were mixed and reacted at 195 to 210 ° C for 20 hours. The reaction product was extracted with 140 ml of toluene, the insoluble matter was filtered off, and after concentration, 120 ml of n-hexane was added to take out crude crystals. The crude crystals were purified by column chromatography (carrier; silica gel, eluent; toluene / n-hexane = 1).
/ 2), N, N'-bis (4'-diphenylamino-4)
-Biphenylyl) -N, N'-diphenylbenzidine (4.73 g, yield: 48.5%) was obtained. Melting point is 24
The temperature was 2.5 to 243.5 ° C. Elemental analysis value is C ₇₂ H
It was as shown below for ₅₄ N ₄ . Carbon: 88.75
% (88.67%), hydrogen: 5.70% (5.58)
%), Nitrogen: 5.68% (5.75%) (calculated value is shown in parentheses) Infrared absorption spectrum (KBr tablet method)
The characteristic fundamental frequency (cm ^-1 ) of 3028, 1591, 14
It was 88, 1323, 1273 and so on.

Synthesis Example 2 (Synthesis Example of Compound No. 17) 16.2 g (0.12 mol) of acetanilide and 3,3 ′
-Dimethyl-4,4'-diiodobiphenyl 56.4 g
(0.13 mol), anhydrous potassium carbonate 18.0 g (0.
13 mol), 1.71 g (0.027 mol) of copper powder, and 30 ml of nitrobenzene are mixed, and 1 at 192 to 203 ° C is added.
The reaction was carried out for 3 hours. The reaction product was extracted with 160 ml of toluene, the insoluble matter was removed by filtration, and the mixture was concentrated to dryness. This was purified by column chromatography (carrier; silica gel, eluent; toluene / ethyl acetate = 7/1) and N- (3,3 ′).
36.7 g (yield 69.3%) of -dimethyl-4'-iodo-4-biphenylyl) acetanilide was obtained. on the other hand,
1,1-bis (4-aminophenyl) cyclohexane 3
2.0 g (0.12 mol) was dissolved in 100 ml of glacial acetic acid, and 26.6 g (0.26 mol) of acetic anhydride was added dropwise at 40 ° C. After dropping, the mixture was reacted at 60 ° C. for 2 hours, the reaction solution was poured into 600 ml of ice water, and the precipitated crystals were filtered, washed with water and dried. The crystals were recrystallized with a mixed solvent of 80 ml of ethyl acetate and 300 ml of methanol to give 1,1-bis (4-acetylaminophenyl) cyclohexane 27.
0 g (yield; 64.3%) was obtained. Melting point is 270.0 ~
It was 271.0 ° C. The obtained 1,1-bis (4-
Acetylaminophenyl) cyclohexane 21.0 g
(0.06 mol), bromobenzene 20.8 g (0.1
32 mol), anhydrous potassium carbonate 17.4 g (0.125
17) and copper powder 1.9 g (0.03 mol) are mixed,
The reaction was carried out at 0 to 200 ° C for 16 hours. The reaction product was extracted with 300 ml of toluene, the insoluble matter was removed by filtration, and the mixture was concentrated to give an oily substance. The oily substance was dissolved in 100 ml of isoamyl alcohol, added with 1 ml of water and 8.32 g (0.125 mol) of 85% potassium hydroxide, and added at 130 ° C.
It was hydrolyzed. After distilling off isoamyl alcohol by steam distillation, it was extracted with 400 ml of toluene, washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier; silica gel, eluent; toluene / n-hexane = 3.
/ 2), 1-bis (4-anilinophenyl) cyclohexane 18.6 g (yield 74.1%) was obtained.

Next, 10.5 g (0.025 mol) of 1,1-bis (4-anilinophenyl) cyclohexane and N were added.
-(3,3'-dimethyl-4'-iodo-4-biphenylyl) acetanilide 22.9 g (0.052 mol),
And 7.19 g (0.052 mol) of anhydrous potassium carbonate,
Copper powder 0.76g (0.012mol), nitrobenzene 2
0 ml was mixed and reacted at 200 to 208 ° C for 18 hours. The reaction product was extracted with 180 ml of toluene, the insoluble matter was removed by filtration, and the mixture was concentrated to give an oily substance. The oily substance was dissolved in 80 ml of isoamyl alcohol, and 1 m of water was added.
1, and 2.77 g (0.042 mol) of 85% potassium hydroxide was added, and the mixture was hydrolyzed at 130 ° C. After distilling off isoamyl alcohol by steam distillation, it was extracted with 180 ml of toluene, washed with water, dried and concentrated. The concentrate was purified by column chromatography (carrier; silica gel, eluent; toluene / n-hexane = 1/1) and 1,1-bis {p-
[N- (4'-anilino-3,3'-dimethyl-4-biphenylyl) anilino] phenyl} cyclohexane 1
3.3 g (yield 55.1%) was obtained.

11.5 g of this 1,1-bis {p- [N- (4'-anilino-3,3'-dimethyl-4-biphenylyl) anilino] phenyl} cyclohexane
2 mol) was mixed with 5.30 g (0.026 mol) of iodobenzene, 3.46 g (0.025 mol) of anhydrous potassium carbonate, 0.38 g (0.006 mol) of copper powder, and 15 ml of nitrobenzene, and mixed with 198. The reaction was allowed to proceed at ~ 213 ° C for 19 hours. The reaction product was extracted with 150 ml of toluene, the insoluble matter was removed by filtration, and the mixture was concentrated. 120 ml of n-hexane was added to the concentrate, and crude crystals were taken out. The crude crystals were purified by column chromatography (carrier; silica gel, eluent; toluene / n-hexane = 1/3),
1-bis {p- [N- (4'-diphenylamino-3,
5.57 g (yield; 41.7%) of 3'-dimethyl-4-biphenylyl) anilino] phenyl} cyclohexane was obtained. No clear melting point was seen. Elemental analysis value is C ₈₂
It was as shown below as H ₇₂ N ₄ . Carbon: 88.3
7% (88.45%), hydrogen: 6.55% (6.52)
%), Nitrogen: 5.19% (5.03%) (calculated value is shown in parentheses), and the characteristic group frequency (cm ⁻¹ ) of infrared absorption spectrum (KBr tablet method) is 2924, 1509,
It was 1486, 1269 and so on.

Synthesis Example 3 (Synthesis Example of Compound No. 32) 20.3 g (0.12 mol) of diphenylamine and 3,
3'-dimethyl-4,4'-diiodobiphenyl 65.
1 g (0.15 mol), anhydrous potassium carbonate 19.3 g
(0.14 mol), 1.52 g (0.024 mol) of copper powder, and 20 ml of nitrobenzene are mixed to obtain 190-20
The reaction was carried out at 5 ° C for 21 hours. The reaction product is toluene 2
The mixture was extracted with 00 ml, the insoluble matter was removed by filtration, and the mixture was concentrated to dryness. This was purified by column chromatography (carrier; silica gel, eluent; toluene / n-hexane = 2/7),
32.6 g (yield 57.2%) of N- (3,3'-dimethyl-4'-iodo-4-biphenylyl) -N, N-diphenylamine was obtained.

Then, N- (3,3'-dimethyl-4'-
Iodo-4-biphenylyl) -N, N-diphenylamine 24.2 g (0.051 mol), o-tolidine 2.5
5 g (0.012 mol), anhydrous potassium carbonate 6.91 g
(0.050 mol), copper powder 0.64 g (0.001 mol), and nitrobenzene 10 ml are mixed, and 200-21
The reaction was carried out at 2 ° C for 30 hours. The reaction product is toluene 1
The mixture was extracted with 50 ml, the insoluble matter was removed by filtration, and the mixture was concentrated to dryness. The obtained solid is purified by column chromatography (carrier; silica gel, eluent: toluene / n-hexane = 3/4) to give N, N, N ', N'-tetrakis (3,3).
9.48 g of 3'-dimethyl-4'-diphenylamino-4-biphenylyl) -o-tolidine (yield; 49.3)
%) Was obtained. The obtained product melted at 196 to 212 ° C and did not show a clear melting point. Elemental analysis value is C ₁₁₈ H
It was as shown below as ₁₀₀ N ₆ . Carbon: 88.5
3% (88.46%), hydrogen: 6.24% (6.29)
%), Nitrogen: 5.21% (5.25%) (calculated value is shown in parentheses), and the characteristic group frequency (cm ⁻¹ ) of infrared absorption spectrum (KBr tablet method) is 3026, 1589,
1486, 1314, 1270 and so on.

Example 1 Chlorodian blue (charge generating agent No. 1) shown below as a charge generating agent

[0124]

[Chemical 113]

1.5 parts of polyester resin (Byron 2
00, manufactured by Toyobo Co., Ltd.) (18.5 parts of 8% THF solution), placed in an agate pot containing agate balls, and spun for 1 hour with a planetary fine pulverizer (Frits) to disperse. The obtained dispersion liquid was applied onto the aluminum surface of an aluminum vapor-deposited PET film which is a conductive support using a wire bar, and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to give a film thickness of 0. A 3 μm charge generation layer was formed. On the other hand, as a charge transport agent, compound No. 1.5 parts of the tetraamine compound of 7 was added to 18.75 parts of an 8% toluene solution of a polycarbonate resin (Upilon Z-300, manufactured by Mitsubishi Gas Chemical Co., Inc.), and ultrasonic waves were applied to completely dissolve the tetraamine compound. This solution was coated on the charge generation layer with a wire bar and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to form a charge transport layer having a thickness of about 20 μm. 1 was produced. The sensitivity of this photoconductor was measured using an electrostatic copying paper test device (trade name "EPA-8100" manufactured by Kawaguchi Electric Co., Ltd.). First, the photoreceptor is charged by a corona discharge of −8 kV in the dark, and then exposed to 3.0 lux of white light, and the time (seconds) until the surface potential is reduced to half of the initial surface potential is measured. The half-exposure amount E1 / 2 (lux · sec) was determined. The initial surface potential of this photoreceptor was −887 V, and E1 / 2 was 0.89 lux · second.

Examples 2 to 20 In the same manner as in Example 1 except that the charge generating agent and the charge transporting agent (polyamine compound) used in Example 1 were replaced with those shown in Table 1, the photoconductor No. 2 to 20 were produced. still,
The charge generating agent No. shown in Table 1 2 to No. The structure of 4 is shown below.

Charge Generating Agent No. 2

[Chemical 114]

Charge Generating Agent No. Three

[Chemical 115]

Charge Generating Agent No. 4

[Chemical formula 116]

Photoreceptor No. Sensitivity measurement was performed for 2 to 20 in the same manner as in Example 1. The results are shown in Table 2.

[0131]

[Table 1]

[0132]

[Table 2]

Example 21 1.5 parts of α-TiOPc as a charge generating agent was added to 50 parts of a 3% THF solution of polyvinyl butyral resin (S-REC BX-L, manufactured by Sekisui Chemical Co., Ltd.), and an ultrasonic disperser 45 Dispersed for minutes. The obtained dispersion liquid was applied onto the aluminum surface of the aluminum vapor-deposited PET film of the conductive support using a wire bar, dried under normal pressure at 60 ° C. for 2 hours, and further dried under reduced pressure for 2 hours to give a film thickness of 0.2 μm. The charge generation layer of was formed. On the other hand, Compound No. 1.5 parts of the tetraamine compound of 7 was added to 18.75 parts of an 8% toluene solution of a polycarbonate resin (Upilon Z-300, manufactured by Mitsubishi Gas Chemical Co., Inc.) and ultrasonic waves were applied to completely dissolve the tetramine amine compound. . This solution was coated on the charge generation layer with a wire bar and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to form a charge transport layer having a thickness of about 20 μm. 21 was produced.
About this photoconductor Electrostatic copying paper tester (trade name "EP
A-8100 ") was used to measure the sensitivity. First, the photoconductor is charged in the dark by a corona discharge of -8 kV, and then exposed to a monochromatic light of 800 nm with a light amount of 1.0 μW / cm ² , and the amount of energy until the surface potential is reduced to half of the initial surface potential. Obtained, half exposure amount E1 / 2 (μJ / cm
² ) was measured. The initial surface potential of this photoconductor is -736.
At V, E1 / 2 was 0.45 μJ / cm ² .

Example 22 As a charge generating agent, the following trisazo compound was used instead of α-TiOPc.

[0135]

[Chemical 117]

A photoconductor No. 22 was prepared in the same manner as in Example 21 except that was used. When the sensitivity of this photosensitive member was measured in the same manner as in Example 21, the initial surface potential was −
At 863 V, E1 / 2 was 0.49 μJ / cm ² .

Example 23 The following thiapyrylium salt as a charge generating agent

[0138]

[Chemical 118]

0.1 part, Compound No.
32 parts of the hexaamine compound of 32 was added to 125 parts of an 8% toluene solution of a polycarbonate resin (Upilon Z-300, manufactured by Mitsubishi Gas Chemical Co., Inc.), and ultrasonic waves were applied to completely dissolve the thiapyrylium salt and the hexaamine compound. This solution is applied on the aluminum surface of an aluminum vapor-deposited PET film which is a conductive support using a wire bar, and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to form a photosensitive layer having a film thickness of 20 μm. Form the photoconductor No. 23 was produced. The sensitivity of this photoconductor was measured using an electrostatic copying paper tester (trade name "EPA-8100"). First, the photoreceptor is charged by +8 kV corona discharge in the dark, then exposed to 3.0 lux white light, and the time (sec) until the surface potential decreases to half of the initial surface potential is measured. The exposure amount E1 / 2 (lux · second) was determined.
The initial surface potential of this photosensitive member was +869 V, and E1 / 2 was 1.4 lux · sec.

Example 24 The coating liquid of the charge transfer agent used in Example 1 was applied to aluminum vapor-deposited PE.
It was applied on the aluminum surface of the T film using a wire bar and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to form a charge transport layer having a film thickness of 10 μm. On the other hand, the same disazo compound as that used in Example 3 as the charge generating agent 3.
Add 0 parts to 18.5 parts of 8% THF solution of polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.), put it in an agate pot containing agate balls, and rotate for 1 hour with a planetary type fine pulverizer (made by Fritz). And then dispersed. This dispersion contains T
200 ml of HF was added and mixed by stirring to obtain a coating liquid. This coating solution was applied onto the above charge transport layer by spraying and dried under normal pressure at 60 ° C. for 2 hours and further under reduced pressure for 2 hours to form a charge generation layer having a thickness of 0.5 μm. Further, a solution in which an alcohol-soluble polyamide resin is dissolved in isopropanol is applied onto the charge generation layer by spraying, and the solution is dried under normal pressure.
Dry at 0 ° C for 2 hours and then under reduced pressure for 2 hours to obtain a film thickness of 0.5
The photoconductor No. Two
4 was produced. The sensitivity of this photoreceptor was measured in the same manner as in Example 1. The initial surface potential of this photoconductor is + 805V.
The E1 / 2 was 1.5 lux · second.

[0141]

INDUSTRIAL APPLICABILITY The novel polyamine compound of the present invention has an excellent charge transporting ability, and the electrophotographic photoreceptor of the present invention having a photosensitive layer containing these compounds on a conductive support has high efficiency. It exhibits excellent photoconductor characteristics such as sensitivity and high durability, and has the advantage that it can be widely used as an electrophotographic photoconductor.

[Brief description of drawings]

FIG. 1 is a sectional view of a single-layer photoconductor for electrophotography.

FIG. 2 is a cross-sectional view of a single-layer electrophotographic photoreceptor for electrophotography in which a charge generating substance is dispersed.

FIG. 3 is a cross-sectional view of an electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are laminated in this order on a conductive support.

FIG. 4 is a cross-sectional view of an electrophotographic photoreceptor in which a charge transport layer and a charge generation layer are laminated in this order on a conductive support.

FIG. 5 is a sectional view of an electrophotographic photosensitive member provided with a protective layer.

[Explanation of symbols]

 1 Conductive Support 2, 21, 22, 23, 24 Photosensitive Layer 3 Charge Transport Medium, Charge Transport Layer 4 Charge Generating Material 5 Charge Generating Layer 6 Protective Layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsutoshi Anzai 45 Miyukigaoka, Tsukuba-shi, Ibaraki Hodogaya Chemical Industry Co., Ltd. Tsukuba Research Institute

Claims (1)

[Claims] 1. The following general formula (1): [Wherein R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a substituted or unsubstituted phenyl group, and R ₄ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group. Alternatively, it represents a chlorine atom, and A is the following formula: Embedded image [Chemical 4] Embedded image [Chemical 6] [Chemical 7] Embedded image [Chemical 9] [Chemical 10] [Chemical 11] [Chemical 12] And R ₅ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a chlorine atom. ] Or a tetraamine compound represented by the following general formula (2): [Wherein R ₆ and R ₇ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a substituted or unsubstituted phenyl group, and R ₈ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a chlorine atom. And B is the following formula: [Chemical 15] Embedded image [Chemical 17] Embedded image [Chemical 19] Embedded image [Chemical 21] [Chemical formula 22] [Chemical formula 23] [Chemical formula 24] And R ₉ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a chlorine atom. ] A photoconductor for electrophotography, comprising a photosensitive layer containing a polyamine compound selected from the group of hexaamine compounds represented by: