JPS60143351A - Photosensitive body - Google Patents

Abstract

PURPOSE:To improve sensitivity of a photosensitive body and its stability against UV rays by incorporating a specified amine deriv. and an org. polymer semiconductor having condensed aromatic rings or hetero rings on the side chains in a carrier transfer phase. CONSTITUTION:A photosensitive layer 4 is composed of a carrier generating phase 2, and a carrier transfer phase (CTL)3 contg. an org. polymer semiconductor having condensed aromatic or hetero rings on the side chains, and an amine deriv. represented by the formula in which Ar<1>, Ar<2> are each optionally substd. phenyl, or the like; and Ar<3> is optionally substd. phenyl, naphthyl, heterocyclic, or the like. Here, the phase means a so-called layer and also the phase in which each constituent material is in contact with each other. Since said org. polymer semiconductor is used together with said amine deriv. as a carrier transfer material, light sensitization is effectively executed, a discharging curve has a sharply cut toe, especially, sensitivity in a low electric field is enhanced, and a fog-free good image can be obtained. Since said semiconductor has high light absorptivity, deterioration of the amine deriv. can be prevented and the UV stability of the CTL3 can be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. Industrial Application Field The present invention relates to a photoreceptor, such as an electrophotographic photoreceptor, having a photosensitive layer comprising a carrier generation phase and a carrier transport phase.

2. Prior Art According to conventionally known electrophotographic photoreceptors, a carrier-generating substance (hereinafter referred to as "CGM") that absorbs visible light and generates charge carriers (hereinafter simply referred to as "carriers") is used.
There is a thing. ) containing a carrier generation layer (
Hereafter, it may be referred to as "CGL". ) and this CGL
A carrier transport layer (hereinafter sometimes referred to as "CTL") containing a carrier transport material (hereinafter sometimes referred to as "CTM") that transports either or both of positive and negative carriers generated in .) In this way, the two necessary basic functions of carrier generation and carrier transport are assigned to the separate layers that make up the photosensitive layer. By doing so, the selection range of materials that can be used to form the photosensitive layer is widened, and it becomes possible to independently select materials or material systems that optimally perform each function. In addition, this also allows for the characteristics required in the electrophotographic process, such as high surface potential when charged, high charge retention capacity, high photosensitivity, and high stability during repeated use. It becomes possible to obtain an electrophotographic photoreceptor having excellent characteristics.

The types of CTM constituting the above photosensitive layer are as follows:
For example, amine derivatives (Japanese Patent Application No. 56-8044) have been proposed. Although amine derivatives have various advantages, it has been found that they still contain problems that need to be improved. That is, when an amine derivative is used alone as a C'TM, the tail of the discharge curve is insufficiently cut, the sensitivity in the low electric field region is likely to be low, and the stability against ultraviolet light is insufficient. Since the sensitivity tends to decrease due to irradiation with ultraviolet light, the photoreceptor is likely to be deteriorated by ultraviolet light components when the copying machine is maintained under fluorescent lights or sunlight.

3. Object of the invention The object of the invention is to improve the sensitivity and ultraviolet light stability of a photoreceptor.

4. Structure of the invention and its effects, that is, the present invention provides a photoreceptor having a photoreceptor layer consisting of a carrier generation phase and a carrier transport layer, which has the following general formula (A
) and a polymeric organic semiconductor having a fused aromatic ring or a heterocycle in its side chain are contained in the carrier transport layer.

General formula [A]: [However, in this general formula, Ar", Ar" represents a substituted or unsubstituted phenyl group, and a halogen atom, an alkyl group, a nitro group, or an alkoxy group is used as a substituent.

Ar": represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, fluorenyl group, heterocyclic group,
As the substituent, an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, an aryloxy group, an aryl group, an amino group, a nitro group, a piperidino group, a morpholino group, a naphthyl group, an anthryl group, and a substituted amino group are used. however,
An acyl group, an alkyl group, an aryl group, or an aralkyl group is used as a substituent for the substituted amino group. ] Here, the above-mentioned "phase" includes not only the case where the material forms a so-called layer, but also the case where the constituent substances form a phase in which they are in contact with each other.

According to the present invention, since the above-mentioned polymeric organic semiconductor is used together with the above-mentioned amine derivative as the CTM, the polymeric organic semiconductor has the property of generating photocarriers by absorbing ultraviolet light. Effectively contributes to sensitization.

Therefore, the tail of the discharge curve is well cut, and the sensitivity is improved, especially in the low electric field region. As a result, a conductive or insulating component can be obtained. - When a bias voltage is applied during the component development process, the sharpness of the edge of the image decreases due to the so-called fringing phenomenon, causing blurring.
According to the present invention, such problems are eliminated.

In addition, the polymeric organic semiconductor has a high absorbance in the ultraviolet light region and absorbs most of the ultraviolet light, and has a kind of filter effect on the ultraviolet light, so it can prevent the deterioration of the amine derivative. , can improve the ultraviolet light stability of cTL.

In the present invention, if an electron-accepting substance or a Lewis acid, which will be described later, is added to at least one of CTL and CGL, a charge transfer complex is formed, so that the sensitization effect can be further improved.

5. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples.

First, examples of the amine derivatives of the general formula (A) used as the CTM in the present invention include those having the following structural formula, but the invention is not limited thereto.

(A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) (A-8) (A-9) (A-10) (A-11) (A-12) (A-13) (A-14) Hs0 (A-15) (A-16) (A-17) (A-18) (A-19) (A-2 (+) (A-21> (A-22) (A-23,) (A-24) (A-25) (A-26) (A-27) (A-28) (A-29) ( A-30) (A-31) (A-32) (A-33) In addition, the polymeric organic semiconductor used in combination with the above amine derivative as CTM in the present invention includes:
Examples include, but are not limited to, the following examples: (B-6)-+CH-CH2
+F1 Hi Hz (B-10) (B-11) (B-12) (B-13) C=0 (B-14) (B-15) 1 Js (B-16) (B-17) (B -19) (B-20) Among the polymeric organic semiconductors used in the CTL of the present invention, poly-N-vinylcarbazole or its derivatives are effective, and the poly-N-vinylcarbazole derivatives and the preferably used poly-N-vinylcarbazole derivatives are the most effective. is a carno (sol ring containing various substituents, such as an alkyl group, a nitro group, an amino group, a hydroxy group or
- 0 substituted by a rogene atom Furthermore, in the present invention, any inorganic pigment or organic pigment can be used as the CGM as long as it absorbs visible light and generates free carriers. In addition to inorganic pigments such as amorphous selenium, trigonal selenium, selenium-arsenic alloy, selenium-tellurium alloy, cadmium sulfide, cadmium selenide, cadmium selenide sulfide, mercury sulfide, lead oxide, lead sulfide, the following representative examples Organic dyes such as those shown in may also be used.

(1) Azo dyes such as monoazo dyes, polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbene azo dyes, and thiazole azo dyes (2) Perylene dyes such as perylenic anhydride and perylenic acid imide (3) Anthraquinone derivatives, anthanthrone derivatives, dibenzpyrenequinone derivatives, pyranthrone derivatives,
Anthraquinone to polycyclic quinone dyes such as violanthrone derivatives and inviolanthrone derivatives (4) Indigoid dyes such as indigo derivatives and thioindigo derivatives (5) Heptalocyanine dyes such as metal phthalocyanine and metal-free phthalocyanine (6) Diphenylmethane Carbonium dyes such as triphenylmethane dyes, xanthine dyes and acridine dyes (7) Quinoneimine dyes such as azine dyes, oxazine dyes and thiazine dyes (8) Methine dyes such as cyanine dyes and azomethine dyes (9) Quinoline Nitro dye αυ Nitroso dye Q2 Benzoquinone and naphthoquinone dye 03 Naphthalimide dye I Helinone dye α such as bisbenzimidazole derivative Quinacridone dye Next, the present invention will be specifically explained with reference to the drawings.

The photoreceptor of the present invention is preferably constructed as shown in FIG. That is, CGL 2 containing the above-mentioned CGM as a main component is formed on a conductive support 1, and CTLa containing the above-mentioned styryl compound and polymeric organic semiconductor as main components is laminated on this carrier generation layer 2. , CGL2 and CTLa constitute the photosensitive layer 4.

Here, as the material of the conductive support 1, for example, a sheet of metal such as aluminum, nickel, copper, zinc, palladium, silver, indium, tin, platinum, gold, stainless steel, brass, etc. can be used. The present invention is not limited to these, and for example, as shown in FIG. 2, a conductive layer IB may be provided on an insulating substrate IA to constitute the conductive support 1. In this case, the substrate IA is made of paper, plastic sheet, etc., which is flexible and bendable.
It is appropriate that the material has sufficient strength against stress such as tensile stress. The conductive layer IB can also be provided by laminating metal sheets, vacuum depositing metals, or by other methods.

CGL2 is formed by the above-mentioned CGM alone, by adding an appropriate binder resin to it, or by adding a substance having high mobility for carriers of specific or non-specific polarity (i.e., a carrier transporting substance). can do.

Specific forming methods include a method in which CGM is vacuum-deposited on the support, and a method in which CGM is dissolved or dispersed in a suitable solvent alone or together with a suitable binder resin and then applied and dried. I can do it.

In this latter method, binder resins or carrier transport substances may be added, in which case
The ratio of carrier generating substance: binder resin: carrier transporting substance is 1: (θ~100): (0~
500), particularly i:(o-io):(0-50).

Examples of the solvent or dispersion medium used in the above method include n-butylamine, diethylamine, ethylenediamine, impropaturamine, monoethanolamine, triethanolamine, triethylenediamine, N,N
-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol,
Ethanol, improper tool, ethyl acetate, butyl acetate, dimethyl sulfoxide, and others can be used.

Further, as the binder resin, for example, polyethylene,
Addition polymer resins and polyaddition resins such as polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin, etc. , polycondensation type resins, and copolymer resins containing two or more of the repeating units of these resins, such as vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-maleic anhydride copolymer resins In addition to insulating resins such as composite resins, polymeric organic semiconductors such as poly-N-vinylcarbazole can be used. The proportion of this binder resin to CGM is in the range of 0 to 100% by weight, particularly 0 to 10% by weight.

An appropriate CTM may be added to the CGL2 as necessary.

Furthermore, this CGL can contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential or fatigue during repeated use, etc.

Examples of electron-accepting substances that can be used here include succinic anhydride, maleic anhydride, dibromaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride,
Tetrabromo phthalic anhydride, 3-nitro phthalic anhydride,
4-nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 11 3t 5) linitrobenzene, varanitrobenzonitrile, bicri chloride, quinone chlorimide, chloride, flumanil, dichlorodicyanobarabenzoquinone, anthraquinone, dinitroanthraquinone, 2,7-sinitrofluorenone, 2,4.7-
Dolinitrone fluorenone, 2.4,5.7-tetranitrofluorenone, 9-fluorenylidene [dicyanomethylene malonodinitrile], polynitro-9-fluorenylidene (dicyanomethylene malonodinitrile), hyfuric acid, 0-nitrobenzoic acid , p-nitrobenzoic acid, 3
, 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5
Examples include -nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds with high electron affinity. The addition ratio of the electron-accepting substance is CGM:electron-accepting substance=100 by weight.
: 0.01-200 preferably 100:0.1-1
It is 00.

The thickness of the CGL 2 formed as described above is preferably o.oos to 20 pm, particularly preferably 0.00 pm to 20 pm.
05-5 μm. If it is less than 0.005 μm, sufficient photosensitivity cannot be obtained, and if it exceeds 20 μm, sufficient charge retention cannot be obtained.

In addition, the above-mentioned CTL3 can be used to convert the above-mentioned compound into the above-mentioned CGL.
In the same manner as 2 (i.e., apply alone or dissolved and dispersed with the above-mentioned binder resin, and dry)
can be formed.

Further, other CTMs may be included.

In this case, the blending ratio of binder resin and total CTM is
100 parts by weight of binder resin, total CTM 10-50
It is preferable to set the amount to 0 parts by weight, and if a polycarbonate resin is used as the binder resin, 100 parts by weight of the polycarbonate resin is used.
It is preferred to use 0 to 200 parts by weight of total CTM as this provides excellent electrophotographic properties.

Furthermore, the above-mentioned electron-accepting substance can be added to the CTL for the purpose of improving sensitivity and further reducing residual potential or fatigue during repeated use. This electron-accepting substance is C
When added to both the GL and CT IVI layers, the electron-accepting substances added to each layer may be completely or partially the same, or may be completely different depending on the case.

Note that the electron-accepting substance may be added to either CGL or CTL.

The addition ratio of electron-accepting substances to CTL is the total CT in terms of weight ratio.
M: Electron accepting substance = ioo: o, oi~100
Preferably it is 100:0.1-50.

The thickness of CTL3 formed in this way is 2 to 100
μm Preferably 5 to 30 μm.

The present invention has been described above according to the specific configuration example shown in FIG. 1 or FIG. The mechanical structure of the electrophotographic photoreceptor can be arbitrarily selected.

For example, as shown in FIG. 3, a suitable intermediate layer 5 may be provided on the conductive support 1, the CGL 2 may be formed thereon, and the CTL 3 may be formed thereon.

This intermediate layer 5 has a function of preventing free carriers from being injected from the conductive support 1 into the photosensitive layer 4 when the photosensitive layer 4 is charged, and also has the function of preventing the photosensitive layer 4 from being injected into the photosensitive layer 4 integrally with the conductive support. It can have a function as an adhesive layer for adhering to. Materials for the intermediate layer 5 include metal oxides such as aluminum oxide and indium oxide, acrylic resins, methacrylic resins, vinyl chloride resins, vinyl acetate resins, epoxy resins, polyurethane resins, and Fe/-
Use polymeric substances such as polyester resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, medimine resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, etc. I can do it.

Further, as shown in FIG. 4, a CTL 3 is formed on the conductive support 1 with or without the intermediate layer 5 interposed therebetween, and a CGL 2 is formed thereon to constitute a photosensitive layer 4. Good too.

Further, FIG. 5 shows a single-layer photosensitive layer formed by dispersing the above CGM in a carrier transport phase containing the above CTM (that is, consisting of a mixed layer of a carrier generating substance phase and a carrier transport substance phase). An example of forming 4 is shown below.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

Example 1 A vinyl chloride-vinyl acetate-maleic anhydride copolymer [S-LEC M
F-104 (manufactured by Tsukimizu Kagaku Kogyo Co., Ltd.), thickness of approximately 0
．． Provide 1 μm intermediate layer, 2-3 X lo' To
4,10-dibromanthanthrone (Monolite Red 2 Y C,1,A 59
300) on the intermediate layer to a thickness of about 0.5 μm.
CGL was formed.

On the other hand, a coating solution for forming 9CTL was prepared according to the following procedure. Poly-N-vinylcarbazole "Rubican M170J" shown in (B-6) above as a polymeric organic semiconductor
(manufactured by BASF) 51F to monochlorobenzene 50-
dissolved in. Next, 6f of the amine derivative (A-9) and 3.5 tons of polycarbonate resin [2] (Nrite L-1250J (manufactured by Yondai Kasei Co., Ltd.) were mixed in 1°2-dichloroethane 40-
Add the obtained solution to the monochlorobenzene solution and mix thoroughly to complete the preparation. Apply the obtained solution on the CGL using a doctor blade and dry at 80 ° C for 1 hour. , thickness 13μm
A CTL was formed, thereby producing an electrophotographic photoreceptor (sample A1') of the present invention.

Example 2 In preparing the coating solution for CTL formation in Example 1, Exemplified Compound (A-15) was used as the amine derivative in place of Exemplified Compound (A-9), and 2. 4. 7-) Dinitro-9-fluorenone 0.0
The procedure was the same as in Example 1 except that 51F was added, and the thickness was about 0.
An electrophotographic photoreceptor (sample A 2 ) of the present invention was prepared by forming a CGL of 5 μm and a CTL of 13 μm.Run 3 Polycarbonate resin 2f and tetrabromophthalic anhydride 0.2t were mixed in 1,2-dichloroethane. 4.10-dibromanthanthrone 4t in a solution dissolved in 100-
was added and subjected to ultrasonic dispersion, and this dispersion was applied onto a conductive support having the same intermediate layer as in Example 1 to a thickness of 1 μm.
On the other hand, a coating solution for forming j9cTL was prepared by the following method. 5 tons of poly-N-vinylcarbazole was dissolved in 50 tons of monochlorobenzene. Next, the amine derivative (A-
33) 6F, picryl chloride 0.02f and polycarbonate resin 3.51% in 1,2-dichloroethane 40%
7! The resulting solution was added to the monochlorobenzene solution and thoroughly mixed to complete the preparation.

The resulting solution was applied onto the CGL using a doctor blade and dried at 80°C for 1 hour to form a layer with a thickness of 13 μm.
CTL was formed, and thereby an electrophotographic photoreceptor (sample plate 3) of the present invention was prepared.

Example 4 Instead of the polycyclic quinone dye in Example 2, N,N'-dimethylperylene-3,4,9, which is a perylene dye, was used.
, 10-tetracarboxylic acid diimide (Paliogen Maroon 3920 C91, A71130) tl- was used in the same manner as in Example 2 to form a CGL with a thickness of about 0.5 μm and a CTL with a thickness of 13 μm to form a CGL with a thickness of about 13 μm. An electrophotographic photoreceptor (sample A4) was prepared.

Example 5 On a conductive support made of 100 μm thick polyethylene terephthalate coated with aluminum, 2 to 3×1
Evaporation source temperature 300' in a vacuum atmosphere of 0-Torr
Selenium was evaporated at C for 1 minute to form a carrier generation layer consisting of amorphous selenium 9 with a thickness of 1 μm. Next, PVK (B-6) was replaced with (B-10) as the polymeric organic semiconductor.
The same CTL forming solution as used in Example 2 was applied except that a
Comparative Example 1 Amine derivative (A-9) x 5t and polycarbonate resin 15F were dissolved in 1,2-dichloroethane 100- A CTL forming solution containing no polymeric organic semiconductor was prepared.

This solution was applied onto the same CGL as in Example 1 to a thickness of 1
A CTL of 2 μm was formed, and an electrophotographic photoreceptor for comparison (Comparative Sample Shop 1) was prepared.

Comparative Example 2 Poly-N-vinyl carbacy, LL/10f'f: A solution dissolved in 100 g of monochlorobenzene and 1.5 l of polycarbonate resin in 1,2-dichloroethane 10-
A CTL-forming solution containing no amine derivative represented by the above general formula was prepared by mixing the solution dissolved in . This solution was applied onto the same CGL as in Example 1 to a thickness of 13 μm.
CTLi was formed to prepare a comparative electrophotographic photoreceptor (comparative sample A 2 ).

Comparison row 3 When preparing the CTL forming solution in Comparative Example 1,
．． 4. '7-Dolinitro 9-Fluorenone 0.31
A 12 μm thick C
TL was formed and a comparative electrophotographic photoreceptor (comparative sample A
3) was created.

Comparative Example 4 A 13 μm thick C
A comparative electrophotographic photoreceptor (comparative sample &4) was prepared.

Samples A1 to A5 obtained in the above examples and comparison rows and comparative sample A1-Ban 4 were measured using an electrometer SP-42.
8 type (newly manufactured by Kawaguchi Electric Co., Ltd.), a charging operation was performed for 5 seconds with an applied voltage of 6 KV to the discharge electrode of the charger, and the surface potential of the photosensitive layer surface immediately after this charging operation was determined. All V. , surface potential from -500M to -50(
V) -j is the amount of exposure required to attenuate E'::
(J-ux-sec) and ao (JALK・8e
C) The residual potential after exposure was defined as VR (V), and these were measured.Next, in order to examine the stability against ultraviolet light, each sample was exposed to an ultra-high pressure mercury lamp rSHL-100UVJ (manufactured by Toshiba Corporation).
Ultraviolet light was irradiated for 60 seconds with a light source-sample distance of 5 crn, and then the same measurements as above were performed again. The results are shown in the table below.

In the table above, the numbers in parentheses at the bottom indicate the characteristics after irradiation with ultraviolet light.

As is clear from the results, the photoreceptor of the present invention has good photosensitivity and exhibits extremely excellent stability against ultraviolet light.

[Brief explanation of the drawing]

The drawings show embodiments of the present invention, and FIGS. 1, 2, 3, 4, and 5 are sectional views of five examples of electrophotographic photoreceptors. In addition, in the symbols shown in the drawings, 1......Substrate 2......Carrier generation layer (CG
L) 3...Carrier transport layer (CTL) 4...--Photosensitive layer. Agent: Patent attorney Hiroshi Aisaka (and 1 other person) Book 4, Figure 5

Claims (1)

[Scope of Claims] 1. A photoreceptor having a photosensitive layer consisting of a carrier generation phase and a carrier transport phase, comprising an amine derivative represented by the following general formula CA) and a polymer having a fused aromatic ring or a heterocycle in the side chain. A photoreceptor characterized in that the carrier transport phase contains a molecular organic semiconductor. General formula [A]: [However, in this general formula, Ar", Ar": represents a substituted or unsubstituted phenyl group, and a halogen atom, an alkyl group, a nitro group, or an alkoxy group is used as a substituent. Ar”: Represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, fluorenyl group, or heterocyclic group, and substituents include an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, an aryloxy group, an aryl group, and an amino group. , nitro group, piperidino group, morpholino group, naphthyl group, anthryl group and substituted amino group. However,
An acyl group, an alkyl group, an aryl group, or an aralkyl group is used as a substituent for the substituted amino group. ]