JPS60143349A - Photosensitive body - Google Patents

Abstract

PURPOSE:To improve sensitivity of a photosensitive body and its stability against UV rays by incorporating a specified carbazole 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 a carbazole deriv. represented by the formula in which R<1> is aryl; R<2> is H, halogen, alkyl, alkoxy, amino, or the like; and R<3> is aryl or heterocyclic. optionally substd. aryl. 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 carbazole deriv. as a carrier transfer material, light sensitization is effectively executed, a discharge curve has a sharply cut toe, especially, sensitivity in a low electric field is enhanced, and a fog-free good image can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. Prior Art 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 layer.

λ Prior Art According to a conventionally known electrophotographic photoreceptor, a carrier-generating substance (hereinafter referred to as -1"CGM) that absorbs visible light and generates charge carriers (hereinafter simply referred to as "carriers") is used.
There is a thing called J. ) (hereinafter sometimes referred to as "cGLJ") and this CG
Carrier transport material (hereinafter referred to as [CTMJ
That's what happens. ).
Hereinafter, it is sometimes referred to as "CTLJ".) The photosensitive layer is composed of the two basic functions of carrier generation and carrier transport. By assigning these functions to separate layers, the selection range of materials that can be used to construct the photosensitive layer is widened, and it is also possible to independently select materials or material systems that optimally perform each function. , this K has excellent 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 the following properties.

The types of CTM constituting the above photosensitive layer are as follows:
For example, styrylcarbazole derivatives (patent application 1986-35)
No. 069) has been proposed. Although this carbazole derivative has various advantages, it has been found that it still contains problems that need to be improved. That is, when a carbazole derivative is used alone as a CTM, the tail of the discharge curve is insufficiently cut, and the sensitivity in the low electric field region tends to be low. Therefore, the photoreceptor is likely to deteriorate due to ultraviolet light components when the copying machine is maintained under fluorescent light or sunlight.

1. Object of the Invention An object of the present invention is to improve the sensitivity and ultraviolet light stability of a photoreceptor.

↓ The 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 phase, in which a carbazole derivative represented by the following general formula [M] and a condensed aromatic compound in the side chain are used. The present invention relates to a photoreceptor characterized in that the carrier transport phase contains a polymeric organic semiconductor having a ring or a heterocycle.

General formula [M]: Tortoise 1 (However, R1 represents a substituted or unsubstituted aryl group, and R2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an amine group, a substituted amino group, or a hydroxyl group. (R3 represents a substituted or unsubstituted monocyclic group or a substituted or unsubstituted heterocyclic group.) Here, the above "phase" refers to each structure in addition to the case where it forms a so-called layer. It also includes cases where substances are in a phase where they come into contact with each other.

According to the present invention, since the above-mentioned polymeric organic semiconductor is used together with the above-mentioned carbazole derivative as CTM, this polymeric organic semiconductor has the property of generating photocarriers by absorbing ultraviolet light, and is capable of photosensitizing. contribute effectively to Therefore, the tail of the discharge curve becomes more sharp, and the sensitivity improves, especially in the low electric field region. As a result, conductive or insulating imaging can be obtained. - When a bias voltage is applied during the component development process, the sharpness of the edge of the image decreases and blur occurs due to the so-called fringe phenomenon, but 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 ultraviolet light, so it has the effect of preventing the deterioration of carbazole derivatives, and CTL UV light stability can be improved.

In addition, during 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 sensitizing effect can be further improved.

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

First, to illustrate the styrylcarbazole derivatives of '-(general formula CA) used as CTM in the present invention, for example, those having the following structural formula may be added.
It is not limited to these.

(A-9) OCH3 ci- H, CCli.

(A-20) CA-23) (A-24) (A-25) (A-26) CH3 (A-28) OCR.

(A-29) (A-30) (A-31) OCR.

In addition, examples of the polymeric organic semiconductor used in combination with the carbazole derivative as CTM in the present invention include, but are not limited to, those exemplified below.

(B-4) (-CH-CH,-)- (B-5) (-cH-cu, -)- (ns) CH2 (JI.

(B-13) (B-14) 02H.

(B-16) (B-17) (n-is) (B-19) (B-20) Among the polymeric organic semiconductors used in the CTL K of the present invention, poly-N-vinylcarno(sol or its derivatives) is effective. It is large and is preferably used.

Such poly-N-vinylcarbazole derivatives are those in which all or part of the cal/(sol ring in the repeating unit is substituted with various substituents, such as an alkyl group, a nitro group, an amino group, a hydroxy group, or a /10 gene atom). It is what was done.

Further, in the present invention, any inorganic pigment or organic pigment can be used as 10GM 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.

T1) Azo dyes such as monoazo dyes, polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbene dyes, and tyrosol dyes. (2) Perylene dyes such as helical anhydride and perylenic acid imide. Pigment (3) Anthraquinone derivative, anthorone derivative - dibenzpyrenequinone derivative, pyrantrone derivative -
Anthraquinone to polyquinone dyes such as violanthrone derivatives and inviolanthrone derivatives (4) In-kugoite + non-containing dyes such as indigo derivatives and thioindigo visiting conductors (5) Heptalocyanine-based pigments such as metallic heptalocyanine and metal-free phthalocyanine Dyes (61) Carbonium dyes such as diphenylmethane dyes, 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 dye member Nitro dye I Nitroso dye (6) Benzoquinone and naphthoquinone dye (2) Naphthalimide dye■ Perinone dye such as bisbenzimidazole derivatives (2) Quinacridone dye Next, according to the drawing The present invention will be specifically explained.

The photoreceptor of the present invention is constructed as shown in FIG. 1, for example. That is, CGL 2 containing the above-mentioned CGM as a main component is formed on the conductive support 1, and CTL 3 containing the above-mentioned bicizoline compound and polymeric organic semiconductor as main components is laminated on this carrier generation layer 2. , CGL2
and CTL3 constitute a 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 base IA is flexible such as paper or plastic sheet, and
It is appropriate that the material has sufficient strength against stress such as tension. The conductive layer IB can also be provided by laminating metal sheets, vacuum depositing metals, or by other methods.

CGL2 is made by the above-mentioned 00M alone, by adding an appropriate binder resin to it, or by adding a substance with high mobility for carriers of specific or non-specific polarity (i.e., a carrier transporting substance) from K. can be formed.

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. Can be done.

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:(O~1oo):(o~500) by weight.
), particularly preferably 1:(0-10):(0-50).

Examples of the solvent or dispersion medium used in the above method include n-butylamine, diethylamine, ethylenediamine-benzlovanolamine, monoethanolamine, triethanolamine, triethylenediamine, NlN-
Di,'thylformamide, acetone-methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol,
Ethanol, isopropanol, 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 copolymers In addition to insulating resins such as resins, polymeric organic semiconductors such as poly-N-vinylcarbazole can be used. The ratio of this binder resin to CGM is in the range of 0 to 100% by weight, and 0 to 10% by weight.

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

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

Examples of electron-accepting substances that can be used here include succinic anhydride, maleic anhydride, dibromaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride,
Tetrabromo 7-talic anhydride.

3-nitro-phthalic anhydride, 4-nitro-phthalic anhydride, pyromellitic anhydride-mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1.3.5-trinitrone Benzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, flumanil, dichlorodicyanobarabenzoquinone, anthraquinone, dinitroanthraquinone, 2,7-dinito c2 fluorenone, 2,4.7-)linitrofluorenone, 2. 4
, 5.7-tetranitrofluorenone, 9-fluorenylidene [dicyanomethylene malonodinitrile], polynitro-9-fluorenylidene [dicyanomethylene malonodinitrile], picric acid, 0-nitrobenzoic acid, p
-Nitrobenzoic acid, 3.5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3.5-dinitrosalicylic acid, phthalic acid, and other compounds with high electron affinity to mellitic acid can be mentioned. Further, the addition ratio of the electron-accepting substance is CGM:electron-accepting substance=too:o, ot to 200, preferably 10
0:・0.1-100.

The thickness of the CGL 2 formed by adding the above is preferably o, o o s to 20 μm, particularly preferably 0
．． 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.
Similarly to 2, it can be formed by applying and drying CTM (that is, dissolved and dispersed alone or together with the above-mentioned binder resin).Other CTMs may also be contained.

In this case, the blending ratio of binder resin and total CTM is
10-50 total CTM per 100 parts by weight of binder resin
It is preferably 0 parts by weight, and when using polycarbonate as the binder resin, 2 parts by weight per 100 parts by weight of polycarbonate.
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 C'TLK for the purpose of improving sensitivity and further reducing residual potential or fatigue during repeated use. When this electron-accepting substance is added to both the CGL and CTM 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 = too: 0.01-10
0 preferably 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. 2, but in the present invention, it is sufficient to contain the above-mentioned components as a CTL to be combined with a CGL. 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 KCTL 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. The materials of 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, duenol resins, polyester resins, alkyd resins, Polycarbonate resin, silicone resin, melamine resin-vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-
A polymeric material such as a maleic anhydride copolymer resin can be used.

Further, as shown in FIG. 4, the conductive support 1 is covered with K.

The photosensitive layer 4 may be constructed by forming the CTL 3 with or without the intermediate layer 5 and forming the CGL 2 thereon.

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

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

Example 1 On a conductive support made of polyethylene terephthalate with a thickness of 100 μm on which aluminum was vapor-deposited, vinyl chloride-vinyl acetate-maleic anhydride copolymer [Eslec M
Made of F-10J (manufactured by Sekisui Chemical Co., Ltd.) with a thickness of approximately 0.1
A CGL with a thickness of about 0.5 μm was formed by depositing an evaporation source temperature of 350° C. (Nn59300) on the intermediate layer in a vacuum atmosphere of 2 to 3×10 Torr.

On the other hand, a coating solution for CTL formation 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) was dissolved in monochlorobenzene 50. Next, Carbasol magazine conductor (A-14) 6.9
and polycarbonate resin “Panlite L-1250J (
(Manufactured by Yojin Kasei Co., Ltd.) 3.5 g and 1,2-dichloroethane 4
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 a thickness of 13μ.
m CTL is formed, and thus the electrophotographic photoreceptor of the present invention (
Sample Nn1) was created.

Example 2 Preparation of coating liquid for CTL formation in Example IK! ! On this occasion,
Exemplified compound (A-24) was used instead of exemplary compound (A-14) as a carbazole derivative, and 2,4.7-1J nitro-9-fluorenone 0.05. Same as Example 1 except that ji+ was added,
Thickness approximately 0.5μm 17) CG L and thickness 13μm
The electrophotographic photoreceptor of the present invention (sample hn
2) was created.

Example 3 4.10-dibromoanthanthrone 4I! 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 form a (F) CG L having a thickness of 1 μm.

On the other hand, a coating solution for CTL formation was prepared by the following method.

Poly-N-vinylcarbazole 5I! i+wo was dissolved in 50 g of monochlorobenzene. Next, carbazole derivative (A-3) 6.9 and picryl chloride 0.02
! ! and 3.5 g of polycarbonate resin were dissolved in 40 m of 1,2-dichloroethane, and the resulting solution was added to the monochlorobenzene solution and thoroughly mixed to complete the preparation.

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

11 In place of the polycyclic quinone dye in Example 2, perylene dye N,N-dimethylperylene-3,4,9,
A CGL with a thickness of about 0.5 μm and a CTL with a thickness of 13 μm were formed by pressing in the same manner as in Example 2 except that 10-tetracarboxylic acid di-fmide (Variogen Maroon 3920 C, 1, 71130) was used. The electrophotographic photoreceptor of the present invention (
Sample sample 4) was prepared.

Example 5 2 to 3
Evaporation source temperature 30 in a vacuum atmosphere of 10"" Torr
Selenium was vapor-deposited at 0° C. for 1 minute to form a carrier generation layer made of amorphous selenium with a thickness of 1 μm.

Next, the same CTL forming solution as used in Example 2 was applied, except that PVK-(B-10) was used instead of PVK-(B-6) as a monopolymer organic semiconductor, and vacuum was applied at 40°C for 24 hours. It was dried to form a CTL with a thickness of 13 μm, and an electrophotographic photoreceptor of the present invention (Sample No. 5) was prepared.

Comparative Example 1 Carbazole derivative (A-14) 15. ! A CTL forming solution containing no polymeric organic semiconductor was prepared by dissolving i+ and polycarbonate resin 15I9 in 100 ml K of 1,2-dichloroethane. This solution was applied onto the same CGL as in Example 1 to form a CTL with a thickness of 12 μm, thereby producing a comparative electrophotographic photoreceptor (comparative sample 1).

1L poly-N-vinylcarbazole 10.9 to monochlorobenzene 100mI! and a solution of polycarbonate resin 1.59 in 1.2-dichloroethane 10rR1.
A CTL-forming solution containing no carbazole derivative represented by the above general formula was prepared by mixing the solution containing 1C. This solution was applied onto the same CGL as in Example 1 to form a CTL with a thickness of 13 μm, and a comparative electrophotographic photoreceptor (
A comparative sample 2) was prepared.

Comparative Example 3 In preparing the CTL forming solution in Comparative Example 1 -TfL
K2,4.7-ToIJ Nitro9-Fluorenone 0,
3 II was added, but in the same manner as in Comparative Example 1, the thickness was 12
μm f) CT I, and a comparative electrophotographic photoreceptor (comparative sample No. 3) was prepared.

Comparative Example 4 A material with a thickness of 13 μm (D
A CTL was formed, and a comparative electrophotographic photoreceptor (comparative sample No. 4) was prepared.

Samples 1 ml to positive 5 obtained in the above Examples and Comparative Examples
and comparative samples M1 to 4 using an electrometer 5P-42.
8 type (Kawaguchi Electric Manufacturing Co., Ltd.), a charged image was created for 5 seconds with the voltage applied to the discharge electrode of the charger set to 16 KV, and the surface potential of the photosensitive layer surface immediately after this charging operation was determined by the VO1 surface. Change the potential from -500 (V) to -50 (V)
The amount of exposure necessary to attenuate up to 480 (lz*
sec ) and the residual potential after 30 (Jg-sec) exposure were defined as VR (V) and measured.

Next, in order to examine the stability against ultraviolet light, each sample was irradiated with ultraviolet light for 60 seconds using an ultra-high-pressure mercury lamp [8HL-100UvJ (manufactured by Toshiba Corporation) at a distance between the light source and the sample of 5cI11, and then the above-mentioned procedure was repeated. Similar measurements were made.

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 drawings]

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 reference numerals shown in 1 drawing, 1.........Substrate 2......Carrier generation layer (CGL)
3・・・・・・・・・Carrier transport layer (CTL)
4......It is a photosensitive layer. Agent: Patent attorney Hiroshi Aisaka (and 1 other person) Figure 2, Figure 31

Claims (1)

[Claims] 11. In a photoreceptor having a photosensitive layer consisting of a carrier generation phase and a carrier transport layer, a carbazole derivative represented by the following general formula (A) and a polymeric organic semiconductor having a fused aromatic ring or a heterocycle in a side chain are used as the carrier. A photoreceptor characterized in that it is contained in a transport layer. General formula [A]: 1 (However, R1 represents a substituted or unsubstituted aryl group, and R2 represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group-amino group, a substituted amino group, or a hydroxyl group. (R3 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.)