JPS60143347A - Photosensitive body - Google Patents

Abstract

PURPOSE:To improve sensitivity of photosensitive body and its stability against UV rays by incorporating a specified hydrazone 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 hydrazone deriv. represented by the formula in which X and Y are each H or halogen; R<1>, R<2> are each optionally substd. aryl; and Ar is arylene. Here, the phase means a so-called layer and also the phase in which each constituent material contacts with each other. Since said org. polymer semiconductor is used together with said hydrazone deriv. as a carrier transfer material, light sensitization is effectively executed. As a result, a discharge curve has a sharply cut toe, and especially, sensitivity in a low electric field is enhanced, and a fog-free good image can be obtained. Since said semiconductor has high UV absorptivity, it can prevent deterioration of the hydrazone derivs., and enhance the UV stability of the CTL.

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 =1-yari7 generation phase and a carrier transport layer.

2. Conventional technology Conventionally known electrophotographic photoreceptor 1: According to.

A carrier-generating substance (hereinafter referred to as "c") that absorbs visible light and generates charge carriers (hereinafter referred to as "carrier" for S)
There is something called GMJ. ) (hereinafter sometimes referred to as "cGLJ"), and a carrier transport substance C that transports either or both of the positive and negative carriers generated in the CGL of
It is sometimes called cTMJ. ) and a carrier transport layer (hereinafter sometimes referred to as "cTLJ") to constitute a photosensitive layer.

In this way, two necessary factors are carrier generation and transport.
By distributing the two basic functions to the separate layers that form the photosensitive layer, the range of materials that can be used in the construction of the photosensitive layer is widened, and the materials or material systems that optimally fulfill each function can be selected. It becomes possible to make independent selections. In addition, this also enables the initial characteristics 1 required in electrophotographic process.
For example, it is possible to obtain an electrophotographic photoreceptor having excellent properties such as high surface potential when charged, high charge retention ability, high photosensitivity, and high stability in repeated use.

The types of CTM constituting the above photosensitive layer are 1.
For example, the following have been proposed:

(1) Hydrazone derivative (% Application No. 55-147544).

(2) Combination use of hydrazone derivatives and bisazo pigments (Japanese Patent Application No. 57-208518).

Although these hydrazone derivatives have various advantages, it has been found that they still contain problems that need to be improved.

That is, when a hydrazone 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. Since the sensitivity tends to decrease, the photoreceptor is likely to deteriorate due to 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, namely 1. The present invention provides a photoreceptor having a photosensitive layer comprising a carrier generation phase and a carrier transport phase, which has the following general formula (A
) and a polymeric organic semiconductor having a fused aromatic ring or a heterocycle in a side chain are contained in the carrier transport phase.

General formula [A]: N = -CHAr NN t (wherein, (This is a ren group.) Here, the above-mentioned "phase" includes not only a so-called layered structure but also a case in which the constituent substances form a layer 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 hydrazone derivative 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 in the 1% low electric field region is improved.

As a result, conductive or insulating imaging can be obtained. - When a bias voltage is applied during the development process, the sharpness of the edges of the image decreases due to the so-called fringe phenomenon, resulting in #shading, 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 hydrazone derivatives, and CTL UV light stability can be improved.

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 hydrazone derivative 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.

(The following margin continues on the next page) (A-1) (A-2) (A-a) (A-4) (A-5) (A-6) (A-7) (A-8) ( A-9) (A-H)) (A-11) (A-12) (A-13) (A-14) In addition, in the present invention, the above-mentioned high Examples of molecular organic semiconductors include the following:
It is not limited to these.

(B-1) (B-2) (B-3) (B-4) (B-5) (B-6) (B-”7) (B-8) 10CH-CH, ÷.

CH.

(B-9) CH.

CH.

10) (B-11) (B-12) -(-cH-Cut÷ (B-13) ÷CH-CHI+□ -0 (B-14) (B-15) C,H.

(B-16) (B-17) 10-CH-CH, 10 shade CM.

Yin (B-18) CB-19) (B-20) ÷CH-cH, 100 copies Among the polymeric organic semiconductors used in BACTL, poly-N-vinylcarbazole or its derivatives are highly effective, Preferably used. What is such a poly-N-vinylcarbazole derivative?

All or part of the carbazole ring in the repeating unit is substituted with a substituent such as an alkyl group, a nido-p group, a 7-mino group, a hytoxy group, or a halogen 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 carriers. In addition to inorganic pigments such as amorphous selenium, trigonal 7-2-arsenic alloy, 7-tellurium alloy, cadmium sulfide, cadmium selenide, cadmium sulfide, mercury sulfide, lead oxide, etc. 5 organic dyes may be used.

(1) 7zo dyes such as mono 7zo dyes, polyazo dyes, metal complex azo dyes, virazonazo dyes, stilbene 7zo dyes and thiazole 7zo dyes (2) Perineic anhydride and berineimide, etc. Perinone pigments (3) 7-anthraquinone derivatives, anthofuntone derivatives, dibenzpinequinone derivatives, pyrantone derivatives,
Violant conductor and isobitol 7) Anthraquinone or polycyclic quinone dyes such as R7 derivatives (4) Indigoid dyes such as indigo derivatives and thioindigo derivatives (5) Metal phthalcyanine and metal-free p-cyanine Phthalcyanine dyes (6) Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthine dyes and acridine dyes (7) Quinoneimine dyes such as 7zine dyes, oxazine dyes and thiazine dyes (8) Cyanine dyes and 7 Methine dyes such as dimethine dyes (9) Quinoline dyes (lO) Nido dyes (11) Nido pso 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 hydrazone derivative 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 l, for example, a sheet of metal such as aluminum, nickel, copper, zinc, aluminum, silver, indium, tin, platinum, gold, stainless steel, brass, etc. can be used. However, the invention is not limited to these examples.For example, as shown in FIG.
A conductive layer IB can also be provided on A to constitute the conductive support l. In this case, the substrate IA is paper.

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

CGL 2 can be prepared by the CGM described above alone or with the addition of a suitable binder resin.

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 &C, a binder resin or a carrier transport substance may be added, in which case the ratio of binder resin to carrier transport substance is 1:1 by weight: (0-100): (0-5
00), particularly 1: (θ~10):(0~50).

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

For example, n-butylamine, diethylamine, ethylenediamine, isopropanolamine, monoethanolamine, triethanolamine, triethylenediamine, N
, N-dimethylform 7mide.

Acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, l:I roform, l,
2-diku exa ethane, diku ρρ methane.

Tetrahydrofuran, dioxane, methanol.

Ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, and others can be used.

In addition, as the binder resin, 1, for example, polyethylene,
Polyppi V7. Acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polywanthanum resin, phenolic resin.

Addition polymerization type resins such as polyester resins, liquid resins, polycarbonate resins, silicone resins, melamine resins Single polycondensation type resins, and copolymers containing two or more of the repeating units of these resins Combined Resin 1 Other than insulating resins such as vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, etc.

Examples include polymeric organic semiconductors such as poly-N-vinylcarbazole. And the ratio of this binder resin to CGM is 0~! 00% by weight, especially 0-1
It is in the range of 0 weight.

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

CGLK 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 and maleic anhydride.

Dibpm maleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetraphum phthalic anhydride.

3-2) a Phthalic anhydride, 4-nido-phthalic anhydride, beemellitic anhydride, mellitic anhydride, tetracyanoquinodimethane, tetracyanoquinodimethane.

O-dinito-ty benzene, m-dinito-p benzene.

1.3.5-) Linitone benzene, paranide ρ benzonitrile, picrylic ρ ride, quinone chloride,
Coolanil, pullmanil, diku RR dicyanobara benzoquinone 77 nthraquinone, dinito 1177 nthraquinone, 2,7-dinitrofluorenone, 2,4.7-) linitrho fluoronone.

2.4,5.7-titranito p-fluoronone, 9-fluoronylidene [dicyanomethylenemalonodinitrile],
Polynide ty-9-fluoronylidene [dicyanomethinma rho-nodinitrile], picric acid-0-di)benzoic acid, p-nide G7 benzoic acid, 3.5-dini) G7 benzoic acid, pentafluorobenzoic acid, 5 Examples include -nitrosalicylic acid, 3,5-dinitosalicyl cR, phthalic acid, mellitic acid, and other compounds with high electron affinity. Further, the addition ratio of the electron-accepting substance is CGM:electron-accepting substance-100:0.01 to 2 at a weight ratio of 1.
9O is preferably 100:0.1 to 100.

The thickness of the CGL 2 formed by the above 5K process is preferably 0.005 to 20 μm, particularly preferably 0.0 μm.
It is 5 to 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.
It can be formed in the same manner as in 2 (that is, by coating and drying a dissolved and dispersed product alone or together with the above-mentioned binder resin). and.

Other CTMs may also 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.

The above-mentioned electron-accepting substance can also be added to the bearing pressure and this 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 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 either one of CGL and CTL may be added as the electron-accepting substance.

The addition ratio of electron-accepting substances to CTL is the total CT in terms of weight ratio.
M: electron-accepting substance=100:0.01-100, 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 2, but one aspect of 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 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 carrier IJ from being injected from the conductive support l into the photosensitive layer 4 when the photosensitive layer 4 is charged, and also has the function of integrally integrating the photosensitive layer 4 with the conductive support. It can be made to function as an adhesive layer for adhesion. The material of the intermediate layer 5 is as follows:
Aluminum oxide.

Metal oxides such as indium oxide, acrylic resins.

Metac IJ resin, vinyl chloride resin, vinyl acetate resin,
Epoxy resin, polywanthane resin, phenolic resin-polyester resin, alkyd resin 2 polycarbonate resin, silicone resin, melamine resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maninic anhydride copolymer resin, etc. Polymeric substances can be used.

Also, as shown in FIG. 4, on the conductive support 1.

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

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 On a conductive support made of 100 μm thick polyethylene terephthalate with aluminum vapor deposited.

An intermediate layer with a thickness of about 0.1 μm made of vinyl chloride-vinyl acetate-mannic anhydride copolymer "Eslec MF-10J (manufactured by Omizu Kagaku Kogyo Co., Ltd.) is provided, and 2 to 3 x 10-'
3 at a vacuum pressure of Torr and an evaporation source temperature of 350°C.
The polycyclic quinone dye 4, 1O-dibenzentamine (Monolite Red 2YC) was used.

I, N1159300) was deposited on the intermediate layer to form a CGL with a thickness of about 0.5 μm.

On the other hand, a coating solution for CTL formation was prepared in the first step.

Poly-N-vinylcarbazole represented by (B-6) above as a polymeric organic semiconductor [Rubican M170J
(manufactured by BASF) 5 & 7 rubenzene 50ml
dissolved in. Next, hydrazone derivative (A-2)6.
? and polycarbonate resin "Panrai" L-1250J
3.5I (manufactured by Yondai Kasei Co., Ltd.) was dissolved in 40 ml of 1,2-dichloroethane, and the resulting solution was added to the 7-dichlorobenzene 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.

A CTL having a thickness of 13 μm was formed, thereby producing an electrophotographic photoreceptor (sample 1 kl) of the present invention.

Example 2 In preparing the coating solution for CTL formation in Example IK, Exemplified Compound (A-5) was used instead of Exemplified Compound (A-2) as a hydrazone derivative, and 2,4.7 was further used as an electron-accepting substance. -) II 2) +y-9-Fluonone 0.
The procedure was the same as in Example 1 except that 05# was added, and the thickness was about 0.
An electrophotographic photoreceptor (sample tooth 2) of the present invention was prepared by forming a 5 μm CGL and a 13 μm thick CTL.

Example 3 Into a solution in which polycarbonate resin 2I and tetraphthalic anhydride 0.2II were dissolved in 100d of 1,2-dichloroethane, 4.10-dibupm7ton)Gl was added.
41I was added to 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.

Bo1+-N-vinylcarbazole 5I was dissolved in 50ml of 7-chlorbenzene. next.

6Ii of hydrazone derivative (A-5), 0.02Ii of picrylic pride and 3.5g of polycarbonate resin
．． 2-dichloroethane 40! The solution obtained by dissolving in ILt was added to the above-mentioned 7-mer benzene solution and thoroughly mixed to complete the preparation.

The obtained solution was applied using the CGL upper button doctor's pump and dried at SO 0 C for 1 hour.

A CTL having a thickness of 13 μm was formed, thereby producing an electrophotographic photoreceptor (sample rlh3) of the present invention.

Example 4 Instead of the polycyclic quinone dye in Example 2 /<I
J-type dye-t-N,N-dimethylberine-3
, 4,9,10-tetracarboxylic acid diimide (Variogun Maroon 3920 C0I, Qi 71130) was used in the same manner as in Example 2 to form a CG with a thickness of about 0.5 μm.
An electrophotographic photoreceptor (sample t4) of the present invention was prepared by forming a CTL with a thickness of 13 μm and a thickness of 13 μm.

Example 5 On an electrically conductive support made of 100 μm thick polyethine terephthalate on which aluminum was vapor deposited.

Selenium was evaporated for 1 minute at an evaporation source temperature of 300°C in a vacuum atmosphere of 2 x 3 x 10-' Torr to a thickness of I.
A carrier generation layer made of amorphous selenium of Itm was formed. Next, PVK (B-6
) was applied with the same CTL forming solution as used in Example 2, except that CB-10) was used instead of CB-10), and vacuum-dried at 40°C for 24 hours to form a CTL with a thickness of 13 μm. An electrophotographic photoreceptor (sample N15) was prepared.

Comparative Example Ehydrazone Derivative (A-5) 15. A CTL forming solution containing no polymeric organic semiconductor was prepared by dissolving P and polycarbonate resin 15y in 100d of 1,2-dichloroethane. Apply this solution on the same CGL as in Example 1,
A CTL having a thickness of 12/Am was formed, and a comparative electrophotographic photoreceptor (comparative sample No. 1) was prepared.

Comparative Example 2 A solution obtained by dissolving poly-N-vinylcarbazole 11 in 100 ml of 7-p-benzene and a solution obtained by dissolving 1.51 polycarbonate resin in 10 ml of 1,2-dichloroethane were mixed to form a solution represented by the general formula above. A CTL forming solution was created that did not contain a hydrazone-conductor. This solution was applied onto the same CTL as in Example 1, and the CTL with a thickness of 13 μm was coated.
form.

A comparative electrophotographic photoreceptor (comparative sample IVkL2) was prepared.

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

Furthermore, 2,4.7-) linito-9-fluoronone 0.3
A CTL having a thickness of 12 μm was formed in the same manner as in Comparative Example 1 except that g was added, and a comparative electrophotographic photoreceptor (comparative sample No. 3) was prepared.

Comparative Example 4 A comparative electrophotographic photoreceptor (comparative sample Interval 4
)It was created.

Obtained in the above Examples and Comparative Examples. Sample 11&&1~
Ik5 and comparison samples N11 to 4 were installed using ρ meter S.
P-4zsmcC (manufactured by Kawaguchi Electric Seisakusho)), the voltage applied to the discharge electrode of the charger was -6 kV, and charging was performed for 5 seconds. Immediately after this charging operation, the surface potential Vo and surface potential of the photosensitive layer surface were measured. -500 (vl to -5
The exposure amount required to attenuate to 0 (v) is E (ix-aea) and 30 C1x-t.
rec )0 The residual potential after exposure was defined as VB (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 [5HL-100UVJ (manufactured by Toshiba Corporation)].
UV light was irradiated for 60 seconds with a distance between the light source and the sample of 5 mm, and then the same measurements as above were performed again.

The results are shown in the table below.

Margins below C continue on the first page) In the table above, the numbers in parentheses at the bottom indicate the characteristics after irradiation with ultraviolet light.

As is clear from these results, it can be seen that the photoreceptor of the present invention 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. In addition, the reference numerals shown in one drawing. l・・・・・・・・・・・・・・・・・・・・・Substrate 2・・・・・・・・・・・・・・・・・・Carrier generation layer ( CGL')3・・・・・・・・・・・・・・・
・・・・・・Carrier transport layer (CTL) 4・・・・・・
...Self...Self...Photosensitive layer.

Claims (1)

[Claims] 1. A photoreceptor having a photosensitive layer consisting of a carrier generation phase and a carrier transport layer, comprising a hydrazone derivative represented by the following general formula (A) and a fused aromatic ring or a heterocycle in the side chain. A photoreceptor characterized in that the carrier transport layer contains a polymeric organic semiconductor. General formula [A] Ni- (However, X and Y are hydrogen atoms or /SP hydrogen atoms, H+ and Ut are substituted or unsubstituted aryl groups, and Ar is a substituted or unsubstituted 7-line group.)