JPS60143350A - Photosensitive body - Google Patents

Abstract

PURPOSE:To improve sensitivity of a photosensitive body and its stability against UV rays by incorporating a specified styryl compd. 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 styryl compd. represented by the formula in which R<1>, R<2> are each alkyl, phenyl, or the like; R<3> is phenyl, naphthyl, or the like; and R<4>-R<7> are each H, halogen, alkyl, 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 styryl compd. 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 1, such as an electrophotographic photoreceptor, having a photoreceptor layer comprising a carrier generation phase and a carrier transport layer.

2. Conventional technology According to conventionally known electrophotographic photoreceptors.

A carrier-generating substance (hereinafter referred to as [c
There is something called GMJ. ) and a carrier transporting layer (hereinafter referred to as
In this way, the two basic functions of generating carriers and transporting them can be performed in the photosensitive layer. By assigning these functions to separate layers, the selection range of materials that can be used to form the sensory layer is widened, and it becomes possible to independently select materials or material systems that optimally perform each function.

In addition, this also provides the characteristics required in the VL photographic process, such as a high surface potential when charged.
Large charge retention capacity and high photosensitivity.

Furthermore, it is possible to obtain an electrophotographic photoreceptor having excellent properties such as high stability during repeated use.

There are two types of CTM constituting the above photosensitive layer.
For example, styryl compounds (Japanese Patent Application No. 148346/1982)
is proposed.

It has been found that although this styryl compound has various advantages - it still contains problems that should be improved. In other words, when a styryl compound is used alone as a CTM, the tail of the discharge curve is insufficiently cut, the voice tends to be low in the low electric field region, and the stability against ultraviolet light is insufficient. Sensitivity tends to decrease due to irradiation, so when copying machines are maintained under fluorescent lights or sunlight, their purple color.

The photoreceptor is easily deteriorated by external light components.

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: 1. The present invention provides a photoreceptor having a photoreceptor layer comprising a carrier generation phase and a carrier transport layer.

A styryl compound represented by the following general formula (A).

The present invention relates to a photoconductor characterized in that the carrier transport layer contains a polymeric organic semiconductor having a fused aromatic ring or a heterocycle in a side chain.

General formula [A]: [However, in this general formula, R1 and R1 represent a substituted or unsubstituted furkyl group or phenyl group, and a furkyl group, an alkoxy group, or a phenyl group is used as the substituent.

Rs: substituted or unsubstituted phenyl group.

It represents a naphthyl group, a hepthryl group, a fluoronyl group, or a heterocyclic group, and an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, or a phenyl group is used as a substituent.

R', R', R', R': Hydrogen atom -/Xl:
Table br. ] 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 seven layers in contact with each other.

According to the present invention, since the above-mentioned polymeric organic semiconductor is used together with the above-mentioned styryl compound as the CTM, this polymeric organic semiconductor has the property of generating photocarriers by absorbing ultraviolet light.

Effectively contributes to photosensitization. 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 images can be obtained. - When a bias 1 section pressure is applied in the component development process, the sharpness of the edge of the image decreases due to the so-called fringe phenomenon, causing blurring, 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 the ultraviolet light, so it has the effect of preventing the deterioration of styryl compounds. The ultraviolet light stability of CTL can be improved.

In addition, 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.

The sensitizing effect can be further improved.

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

First, the styryl compound of the above general formula (A) used as the CTM in the present invention will be exemplified.

For example, those having the following structural formula can be mentioned, but are not limited thereto.

Specific examples of the styryl compound represented by the general formula (A) include those having the following structural formula, but are not limited thereto.

(A-1) (A-2) (A-a) (A-4) (A-5) (A-6) (A-7) (A-8) (A-9) (A-10) (A-11) (A-12) (A-13) (A-14) (A-15) (A-16) 4C (A-17) 5C (A-18) (A-19) H,C (A-20) (A-zt) H2CO (A-22) (A-23) H,CO (A-24) (A-26) (A-27) (A-zs) (A-29) ( A-30) (A-31) (A-32) (A-33) (A-34) In addition, in the present invention, as the CTM, the polymeric organic semiconductor used in combination with the styryl compound described above includes: Examples include, but are not limited to, the following examples.

(B-1) (B-2) (B-3) (B-4) (B-5) (B-a) (B-7) (B-8) CH.

(B-9) CH.

CH.

(B-10) (B-11) (B-13) +CHCHt + n (B-14) (B-15) (B-16) (33-17) CH.

(B-18) (B-19) (B-20) (-CH”-C)It÷ Among the polymeric organic semiconductors used in the CTL of the present invention, bo1l-N-vinylcarbazole or its derivatives are effective. It is large and is preferably used.

Such poly-N-vinylcarbazole derivatives are those in which all or part of the carbazole ring in the repeating unit is substituted with various substituents 1, such as a furkyl group, a nido ρ group, an amino group, a hydroxy group, or a hepgen atom. Furthermore, in the present invention, any inorganic pigment or organic dye can be used as the CGM as long as it absorbs visible light and generates free carrier I77. Inorganic pigments such as amorphous, trigonal, selenium-arsenic alloy, selenium-tellurium alloy, cadmium sulfide, cadmium selenide, cadmium sulfur nitride, mercury sulfide, lead oxide, lead sulfide, and other primary representative examples Organic dyes such as those shown in may also be used.

(1) 7zo dyes such as 7zo dyes, poly 7zo dyes, metal complex 7zo dyes, pilaf 9fufu dyes, stilbene 7zo dyes, and thiazole 7zo dyes) Perylenic anhydride and perylenic anhydride Perylene dyes such as substances (3) 7-anthraquinone derivatives, 1-tonthraquinone derivatives, dibenzpyrenequinone derivatives, pyranthrone derivatives,
77 traquinone or polycyclic quinone dyes such as violant ty7 conductor and inviolanthrone derivatives (4) Indigoid dyes such as indigo conductor and thioindigo derivatives (5) Metal phthalcyanine and thermometal lid psi 7 Phthocyanine dyes (6) such as diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, and acridine dyes (7) Quinoneimine dyes (8 ) Methine dyes such as cyanine dyes and azomethine dyes (9) Quinoline dyes (lO) Nitro dyes (11) Nido-ρso dyes' (12) Benzoquinone and naphthoquinone dyes (13)
Naphthalimide dyes (14) Perinone dyes such as bisbenzimidazole derivatives (15) Quinacridone dyes Next, the present invention will be specifically explained with reference to one drawing.

The photoreceptor of the present invention is constructed as shown in FIG. 1, for example. That is, CGL2 containing the above-mentioned CGM as a main component is formed on the conductive support l, and CTL3 containing the above-mentioned styryl 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 weight, for example, metal sheets such as aluminum, nickel, copper, zinc, varactor A, silver, indium, tin, platinum, gold, stainless steel, and brass can be used. For example, as shown in FIG.
It is also possible to provide a conductive layer IB on A to constitute a tetraelectric support l. . In this case, the substrate IA is paper.

A material that is flexible, such as a plastic sheet, and has sufficient strength against stress such as bending and tension is suitable. The conductive layer IB can also be provided by laminating metal sheets, vacuum depositing metals, or by other methods.

CGL2 is made of the above-mentioned CGM alone or by adding a suitable binder resin thereto.

Alternatively, it can be formed by adding a substance having high mobility for carriers of specific or non-specific polarity (ie, a carrier transporting substance).

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, a binder (phantom resin or a carrier transport substance may be added, and in that case, the ratio of the carrier transport substance: the binder resin: the carrier transport substance is 1:(θ) by weight). ~100): (0~5
00), particularly l:(0-10)=(0-50).

As the solvent or dispersion medium used in the above method.

For example, n-butyrylamine, diethylamine, ethylenediamine, isopropanolamine, monoethanolamine, triethanolamine, triethylamine,
N,N-dimethylformamide, 7setone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, apform, 1,2-dichlorop-etha/+dikuG7R methane, tetrahyto-furan, dioxane, methanol, ethanol, isopropanol, fIF -Ethyl acid.

Butyl acetate, dimethyl sulfoxide, and others can be used.

In addition, as the binder resin, 1, for example, polyethylene,
Polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polylanthanum resin, phenolic resin.

Addition polymer resins such as polyester resins, alkyd resins, polycarbonate resins, silylon resins, melamine resins, 1-poly addition type resins, 9-poly condensation type resins, and copolymer resins containing two or more of the repeating units of these resins. 1 Insulating resins such as vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-mannic anhydride copolymer resin, and the like.

Examples include polymeric organic semiconductors such as poly-N-vinylcarbazole. The ratio of this binder resin to CGM is 0 to 100% by weight, and 0 to 1% by weight.
It is in the range of 0% 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.

Electron-accepting substances that can be used here include 1
For example, succinic anhydride, maninic anhydride.

Dibum maninic anhydride, phthalic anhydride, tetraflulphthalic anhydride, tetraphthalic anhydride.

3-nido-ρ phthalic anhydride, 4-nido-ρ-7thalic anhydride, peamelitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane.

O-dinitrobenzene, m-dinitrobenzene.

1.3.5-) Linito p-benzene, paranide p-benzonitrile, vicrylic chloride, quinone coolimide,
riρ ranyl, pullmanil, diku pρ dithi 7 novala penzoquinone, 7 nthraquinone, dini) ty 7 nthraquinone, 2,7-dini) a fluorenone, 2,4,7-dolinitrofluoronone.

2.4,5.7-tetranitoρ fluorenone, 9-fluorenylidene [dicyanomethylenemalonodinitrile],
Polynide--9-fluorenylidene [di-7nomethinemalonodinitrile], picric acid, 0-2)9benzoic acid, p-nitrobenzoic acid (li, 3,5-cyni) t
Examples include benzoic acid, pentafluorobenzoic acid, 5-di)a salicylic acid, 3.5-dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds with high electron affinity. In addition, the shielding ratio of the child-receptive substance is 1
Weight ratio: CGM:IE electron-accepting substance: 100:0.0
1 to 200, preferably loo: o, s to 100.

The thickness of the CGL2 formed as described above is preferably 0.005 to 20 μm, particularly preferably 0.0 μm.
It is 5 to 5 μm. If it is less than 0,00 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.
It can be formed in the same manner as in 2 (that is, by coating alone or dissolving and dispersing the above-mentioned binder resin together and drying). Further, other CTMs may be included.

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 this CTL' 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 alpha bone-bearing substance to CTL is the total CT in terms of weight ratio.
M: Electron accepting substance = 100: 0.01 to 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 in accordance with the specific configuration example shown in FIG. 1 or 2, but the present invention is as follows.

It is sufficient to contain the above-mentioned components as a CTL to be combined with a CGL, and the mechanical structure of the electrophotographic photoreceptor can be arbitrarily selected.

For example, as shown in Figure 3, a suitable intermediate layer 5 is provided on the conductive support l, and CG L2 is formed through this.
Additionally, KCTL3 may be formed.

This intermediate layer 5 has a function of preventing 7 leak carriers from being injected into the photosensitive layer 4 from the conductive support l when the photosensitive layer 4 is charged, and also has the function of integrating the photosensitive layer 4 with the conductive support. It can be made to function as a adhesive layer for adhesive bonding. The material for the intermediate layer 5 is aluminum oxide.

Metal oxides such as indium oxide, acrylic resins.

Methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, polyester resin, phenol resin, alkyd resin 2 polycarbonate resin, silicone resin, melamine resin, vinyl chloride-vinyl acetate copolymer fat, vinyl chloride- A polymeric material such as vinyl acetate-maleic anhydride copolymer resin can be used.

Also, as shown in FIG. 4, on a conductive support l.

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

Further, FIG. 5 shows a photosensitive layer formed by dispersing the above CGM in a carrier-transporting phase containing the above CTM (that is, a single-layer photosensitive layer consisting of a mixed layer of a carrier-generating substance phase and a carrier-transporting 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 On an electrically conductive support made of 100 μm thick polyethylene terephthanate with vapor deposited aluminum.

An intermediate layer with a thickness of about 0.1 μm made of vinyl chloride-vinyl acetate-mannic anhydride copolymer "Essuntsu MF-10J (manufactured by Block Chemical Industry Co., Ltd.)" was provided, and 2 to 3X 10-
3 at an evaporation source temperature of 350°C in a vacuum atmosphere of 4 Torr.
4,10-dism, which is a polycyclic quinone dye (Monolite Red 2YC, I, I&
59300) on the intermediate layer to a thickness of about 0.5
A CGL of μm was formed.

On the other hand, a blood fluid for CTL formation was prepared according to the first procedure.

Poly-N-vinylcarbazole "Rubican M170J" shown in (B-6) above as a polymeric organic semiconductor
(manufactured by BASF) 5 g was dissolved in 50 d of chlorbenzene. Next, 3.51 styryl compound (A-1s) 6y and polycarbonate resin "Panrai" L-1250J (manufactured by Yondai Kasei Co., Ltd.) were added to 40 m
The obtained solution was added to the above-mentioned 7-p-benzene solution and thoroughly mixed to complete the production of G4.

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 1kl). Created.

Example 2 When manufacturing the coating liquid for CTL formation in Example 1 using FA,
Exemplified Compound (A-21) was used instead of Exemplified Compound (A-18) as the styryl compound, and 2,4,7-dorini)rho-9-fluorenone 0.
The procedure was the same as in Example 1 except that 05# was added, and the thickness was about 0.
A 5 μm CTL was formed to prepare a Naruko photographic photoreceptor (sample ff12) of the present invention.

Example 3 4 g of 4.10-dibudimanthofunthrone was added to a solution of 2 g of polycarbonate resin and 0.21 g of tetrapumephthalic anhydride dissolved in 100 d of 1,2-dichloroethane.
and perform ultrasonic dispersion.

This dispersion was applied onto a conductive support having the same intermediate layer as in Example 1 to form a CGL with a thickness of 1 μm.

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

Polymer)-N-vinylcarbazole 59 was dissolved in 50 mgK of tribenzene. next.

1. Styryl compound (A-az) 6F, picryl chloride 0.02II and polycarbonate resin 3.5I.
Dissolve 4Qm/lc of 2-dicoolethane, add the resulting solution to the monocumylbenzene solution, mix thoroughly, and add 1.
Finished making s.

The obtained solution was applied onto the CGL using a doctor blade and dried at 80° C. for 1 hour.

A CTL having a thickness of 13 μm was formed, thereby producing an electrophotographic photoreceptor (sample size 3) of the present invention.

In place of the polycyclic quinone dye in Example 2, N,N-dimethylvericin-3,4,9, which is a basic J dye, was used.
A CGL with a thickness of about 0.5 μm was prepared in the same manner as in Example 2 except that 10-tetracarboxylic acid diimide (Variogua FF 73920 C91, RL & T71130) was used.
Then, a CTL having a thickness of 13 μm was formed to prepare an electrophotographic photoreceptor (sample ff14) of the present invention.

Example 5 On an electrically conductive support made of 100 μm thick polyethene phthalate on which aluminum was vapor-deposited.

At an evaporation source temperature of 300°C in a vacuum atmosphere of 2 to 3 X 10 Torr! A thin film was deposited for 1 minute to form a 1 μm thick amorphous selenium forming layer. Next, we replaced PVK (B-6) with (
The same CT as used in Example 2 except that B-10) was used.
Vacuum-dry the L-formed melody at 40"C for 24 hours to a thickness of 1.
An electrophotographic photoreceptor (sample r!15) of the present invention was prepared by forming a CTL of 3 μm.

Comparative Example 1 Styryl compound (A-1s) lsy and 15 g of polycarbonate resin were dissolved in 100 m of 1,2-dichloroethane to prepare a CTI forming solution containing no polymeric organic semiconductor. 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 N11).

Comparative Example 2 10 g of polyJ-N-vinylcarbazole was added to monochlorobenzene 1QQm7! and polycarbonate resin 1.5.9 in 1.2-dichloroethane 10-
A CTL-forming solution containing no styryl compound represented by the above general formula was prepared by mixing the solutions dissolved in the following. This solution was applied onto the same CGL as in Example 1 to a thickness of 13 μm.
A comparative electrophotographic photoreceptor (comparative sample 2) was prepared by forming a CTL of nl.

Comparative example 3 In preparing the CTL forming solution in Comparative Example 1.

Furthermore, the same procedure as in Comparative Example 1 was carried out except that 0.3.9 of 2,4.7-)linitrho-9-fluontsuno□□j was added, and the thickness was 1.
A CTL of 2 μm was formed, and a comparative electrophotographic photoreceptor (comparative sample No. 3) was prepared.

Comparative Example 4 Same as Example 2 except that a compound represented by the following structural formula was used as a polymeric organic semiconductor, 1 Ct-, thickness 13 μm.
A comparative electrophotographic photoreceptor (comparative sample 1'!14) was prepared.

Obtained in the above Examples and Comparative Examples. Sample 1'&1~I
V&L5 and comparative samples Arashi 1 to 4 with Electmeter 5
P-428 (manufactured by Kawaguchi Electric Seisakusho Co., Ltd.) was attached to the charger, and the voltage applied to the discharge electrode of the charger was 16 kV, and the charging operation was performed for 5 seconds. The surface potential was Vo + the surface potential was -500 (00 to attenuate from vl to -50M, the exposure amount required was EC1x, trec), the residual potential after exposure was VB (vl), and these were measured.

Next, in order to investigate the stability against ultraviolet light, each sample was heated using an ultra-high pressure mercury lamp "5HL-10OUV" (Toshiba Corporation).
Ultraviolet light was irradiated for 60 seconds with a distance between the light source and the sample of 5 cm, and then the same measurements as described above were performed again.

The results are shown in the table below.

(The following margin continues on the first page) In the table above, the numbers in parentheses at the bottom indicate the characteristics after irradiation with ultraviolet light.

Akira I-1 or trr&Irk&aFJH from this MI nest
trzw12. It can be seen that -h-1+ has good photosensitivity and exhibits extremely excellent stability against ultraviolet light.

[Brief explanation of drawings]

The drawings illustrate embodiments of the invention. FIG. 1, FIG. 2, FIG. 3, FIG. 4, and FIG. 5 are sectional views of five examples of electrophotographic photoreceptors. Note that the code pressure shown in the first drawing is as follows. 1・・・・・・・・・・・・・・・・・・・・・Substrate 2・・・・・・・・・・・・・・・・・・Carrier generation layer ( CGL)3・・・・・・・・・・・・・・・
・・・・・・Carrier transport layer (CTL) 4・・・・・・
・・・・・・・・・・・・・・・Photosensitive layer. Agent: Patent attorney Hiroshi Aisaka (1 other person) Figure 1 Figure 2 Figure 3

Claims (1)

[Claims] 1. A photoreceptor having a photoreceptor layer consisting of a carrier generation phase and a carrier transport layer, which has a styryl compound represented by the following general formula (A) and a side chain Kifi-fused aromatic ring or heterocycle. A photoreceptor comprising a polymeric organic semiconductor for carrier transport. General formula [A]: [However, in this general formula, R1 and R2 represent a substituted or unsubstituted alkyl group or phenyl group, and an alkyl group, an alkoxy group, or a phenyl group is used as the substituent. Rs: substituted or unsubstituted phenyl group. It represents a naphthyl group, a hepthryl group, a fluoronyl group, or a heterocyclic group, and a furkyl group, an alkoxy group, a halogen atom, a hydroxyl group, or a phenyl group is used as a substituent. R4, 几fi, Ha, R? :Hydrogen atom, hydrogen atom, furkyl group, alkoxy group or furkyl7ξ
) represents a group. ]