JPS59191057A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain a photosensitive body which satisfies thoroughly the conditions required as a photosensitive body and can form a sharp image by using a specific stilbene compd. as a photoconductive material. CONSTITUTION:The compd. expressed by the general formula ( I ), for example, alpha-methyl-4-N,N-diphenylamino stilbene, is used as a photoconductive material in a photosensitive body. A photosensitive layer consisting of the stilbene compd. as well as a sensitizing dye and a binder (binder resin) is provided on a conductive base. A photoconductive layer dispersed with an electric charge generating material (inorg. or org. pigment) in an electric charge conveying medium consisting of the stilbene compd. and the binder is provided on the conductive base. A photosensitive layer consisting of a laminate of an electric charge generating layer consisting essentially of an electric charge generating material and an electric charge conveying layer contg. the stilbene compd. may otherwise be provided on the conductive base.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor containing a specific stilbene compound in its photosensitive layer.

BACKGROUND OF THE INVENTION Conventionally, inorganic materials such as selenium, cadmium sulfide, and acid have been used as photoconductive materials for photoreceptors used in electrophotography. The "electrophotographic method" referred to here generally means that a photoconductive photoreceptor is first charged in a dark place using, for example, an electric current, and then imagewise exposed to selectively remove the charge only in the exposed areas. An electrostatic latent image is obtained by dissipating the latent image into an electrostatic latent image, and this latent image is developed using electrostatic fine particles (1 to 1) consisting of a binder consisting of a colored material such as a dye or pigment and a binder such as a polymeric substance. This is one of the image forming methods that visualizes and forms images.

The basic characteristics required of a photoreceptor in such electrophotography are (1) ability to be charged to an appropriate potential in a dark place, low dissipation of charge at the 21R8 location, ( 3) It is possible to quickly dissipate the charge by light irradiation.

By the way, although each of the above-mentioned inorganic materials has many advantages, it is also true that they also have various disadvantages. For example, selenium, which is currently widely used, satisfies the above (]) to (3) (although 4 is fully satisfied,
Due to difficult manufacturing conditions, go to "Manufacturing"1'/J11
It hurts, 7iJ + 孭VI considerably, ＼ le 1 - 1
It has disadvantages such as it is difficult to remove and is sensitive to heat and mechanical damage, so it requires cleaning.Cadmium sulfide and zinc oxide - (Resin (dispersion) C is used as a photosensitive material, but it is smooth 4'+=) Because it has mechanical drawbacks such as hardness e, tensile strength +-g, and abrasion resistance, it is left as is. I can't stand it (I can't put it in a pot and use it for 1 history).

In recent years, in order to eliminate the drawbacks of these inorganic materials, electrophotographic photoreceptors using various organic materials have been developed and put into practical use.

For example, poly-N-vinylcarbazole and 2°4.7-
A photoreceptor made from 1-linyl-1-lonol-A-9-Δn is described in U.S. Pat. (Iej Publication No. 48-25658 (this description), a photoreceptor whose main component is an organic pigment (described in Publication No. 47-37543), whose main component is a eutectic complex consisting of a dye and a resin. Photoconductor Japanese Patent Publication No. 47-107
3', described in Publication No. 3). These photoreceptors (having excellent characteristics 1-F, 331 are practically 1L)
In electrophotography, considering the requirements for the photoreceptor, the The reality is that we are not getting what we are satisfied with.

However, all of the photosensitive materials listed so far differ depending on the purpose or manufacturing method.In general, good characteristics can be obtained by using an excellent photoconductive material. It is.

Purpose An object of the present invention is to provide a photoreceptor that can overcome the various drawbacks of the conventional photoreceptors mentioned above and fully satisfy the conditions required in electrophotography. Another object of the present invention is to provide an electrophotographic photoreceptor that is easy to manufacture, relatively inexpensive, and has excellent durability.

Construction The inventor has conducted research at 171 on many photoconductive materials,
As a result of the inspection, the following general formula (1) (wherein R1 represents an argyl group or an aralkyl group, and △r is a substituted or unsubstituted naphshima alkyl group or a substituted or unsubstituted)
3 is a hydrogen atom, an alkyl group, an alkoxy group, an alkylene diΔxy group, a halogen atom, or a substituted amino group represented by R,i-N/\5 (wherein R4 and R5 are an alkyl group, a substituted or unsubstituted aralkyl group or substituted or unsubstituted IQ aryl group), nl is an integer of 1.2 or 3, and when m is 2 or 3, R3 may be the same group or a different group 1 1) It has been found that a stilbene compound represented by (represents an integer of 0 or 1) works effectively as a photoconductive substance for an electrophotographic photoreceptor. Here, the substituents on the naphthyl group of Δr include an alkyl group, an alkoxy group, a halogen atom, a substituted amino group, etc.
Substituents on the aralgyl group or aryl group of RA or R5 include alkyl groups, alkoxy groups, thioalkoxy groups, thiophenoxy groups, halogen atoms, dialkylamino groups, hydroxy groups, carboxy groups or esters thereof, acyl groups, and aryl groups. , lyloxy group, aralkyloxy group, trihenomethyl group, cyan group, etc. Furthermore, it has been discovered that this stilbene compound can be combined with various materials to create photoreceptors with unexpected effects, as will be apparent from the description below. The present invention was completed based on these findings.

That is, the present defense provides that a photosensitive layer is provided on a conductive support (in an electrophotographic photoreceptor, the photosensitive layer contains a stilbene compound represented by the general formula <I) in 11x. It is characterized by the following.

The present invention will now be described in more detail with reference to the accompanying drawings. FIGS. 1 to 3 are three representative cross-sectional views of the photoreceptor according to the present invention, and in the numbers indicated therein, 1 is the conductive support, and 2.2'-, 2" is the conductive support. Photosensitive layer, 3
is a charge-generating material; 4 is a charge-transporting medium or layer; 5 is a charge-transporting material;
represents a charge generation layer.

The stilbene compound represented by the general formula (I) used in the present invention has the following general formula (1[) (wherein, R1 represents an alkyl group or an aralkyl group, and R represents a lower alkyl group). A phenyl derivative represented by the following general formula (■Ar-(
CH═CH)nCHO--(I[)F In the formula, Ar and n are the same as in the general formula <I>] It can be obtained by reacting with an aldehyde compound represented by the following formula.

Specific examples of the stilbene compound represented by the general formula (I) thus obtained are shown in Table 1.

Compound R11] 8r27C21
-150 Now N-(◎-・2803 H7(r,)O Yato(@C229C3H7(
i) o +N-(〈=di)230C4+-15(
η)0 N-40)3I Cl-12<EEE> O
Gold NK@232 Cl-130 tatami-N combination CH mountain 33C21-1s O-4 eyes == giant) -N-kuku; 〈== giant ε) c+-+ mountain 34 C1-12◇〉
OXφXNbe@-CI-(mountain 35 Cl-130+N
() OC old) z36 CH30 (c I ◎ C2 shi 2 A concrete example of the structure is as follows.

Production Example 1 Reethyl α-methylbenzylphosboxylate 242 Q
<0.01 mol) and 2.73 tJ (0.01 mol) of 4-N,N-diphenylaminobenzaldehyde were dissolved in N,N-dimethylformamyl'15111λ, and potassium l\-tort-butoxide was dissolved in this. 1.
35 (] was added at 22-35 °C/after adding c0, la
After stirring for 7 hours at
It's diluted. The produced oil was extracted with toluene, the toluene layer was washed with water, dried, and the toluene was distilled off to give yellow crystals.
04a g (yield 84.0%) was obtained. Melting point is 96.
The temperature ranged from 5 to 99.5°C.

Next, recrystallize from ethanol to obtain α of yellow needle-like crystals.
-Methyl-4--N,N-diphenylaminostilbene was obtained in pure form. (Exemplary Compound No. 2Ci in Table 1) The melting point was 100.5 to 1015°C.

The photoreceptor of the present invention contains one or more of the above-mentioned stilbene compounds in the photosensitive layer.
It can be used as shown in FIG.

The photoconductor shown in FIG. acts as a photoconductive substance, and the generation and transfer of charge carriers necessary for light attenuation are carried out through stilbene compounds.However, since stilbene compounds have almost no absorption in the visible region of light, they do not absorb visible light. In order to form an image, it is necessary to sensitize by adding a sensitizing dye that absorbs in the visible region.

The photoreceptor shown in FIG. 2 has a photosensitive layer 2-, in which a charge-generating substance 3 is dispersed in a charge-carrying medium 4 made of a stilchen compound and a binder, provided on a conductive support 1. . The stilbene compound here together with the binder (or binder and plastic mesh) forms the charge transport medium 4, while the charge generating substance 3 (a charge generating substance such as an inorganic or organic pigment) generates the charge carriers. In this case, the charge transport medium 4 is primarily responsible for receiving charge carriers generated by the charge generating substance 3 and transporting them. The basic condition for this photoreceptor is that the absorption wavelength regions of the charge generating substance and the stilbene compound do not overlap with each other, mainly in the visible region. This is because in order to efficiently generate charge carriers in the charge generation material 3, it is necessary to transmit light to the surface of the charge generation material. The stilhen compound represented by the general formula (1) has almost no absorption in the visible region, generally absorbs light in the visible region, and when mixed with silk and the charge generating material 3 that kills charge carriers, it becomes a particularly effective charge transporting material. As 1lIj < is a characteristic of Nobiso.

The photoreceptor in FIG. 3 has a photosensitive layer 2'' consisting of a conductive support 1, a charge generation layer 5 mainly composed of a charge generation substance 3, and a charge transport layer 4 containing a stilbene compound. In this photoreceptor, charge transport @
The 9 that passed through 4 reaches the Denyu I Bongyu layer 5, and the light accumulation of charge carriers occurs in that area, while the charge carrier 4t receives an injection of charge carrier 4\ (pu, its The R generation of charge carriers necessary for optical attenuation is carried out by a charge generating substance 3C, and the transport of charge carriers is carried out by a stilhen compound acting as a charge transport layer 4. ().The HM li is connected to the photoreceptor shown in FIG.
The explanation is the same as that given above.

To actually produce the photoreceptor of the present invention, in the case of the photoreceptor shown in Figure 1, one or more stilhen compounds are dissolved in a solution containing a binder, and then added to The photosensitive layer 2 may be formed by preparing a liquid containing an infectious agent, coating the liquid on the conductive support 1, and drying it.

Thickness f of photosensitive layer 2, 13 to 50 μm, preferably 5 to 2
0 μm is appropriate. The proportion of the stilthen compound in the photosensitive layer 2 is 30 to 70% by weight, preferably about 50% by weight, and the lfi of the sensitizing dye in the photosensitive layer 2 is 01 to 70% by weight.
5% by weight, preferably 0.5-3% by weight C1,
As an infection charge (Yo, Brillian I~Green, Billa 1
~Rear Blue [3, Methyl Violet, Crystal Violet 1~, Acid Violet 1 to 6 1゛ Reallylmethane dye like B, Rhodamine 13, []-
Damin 6G, Rhodamine G Extra, KoA Shin S, Eri 1 Herosine, Loin Bengal, Xanthine dyes such as fluorescein, Deasin dyes such as medilene blue, Cyanine dyes such as cyanine, 2,6-diphenyl -4-(N,N-dimethylaminophenyl) diabilylium verchloride-1, biryllium dyes such as henzopyrylium salt (described in Japanese Patent Publication No. 25658/1973), and the like.

Incidentally, these sensitizing agents may be used alone, or two or more (jf) may be used.

Further, in order to produce the photoreceptor shown in FIG. 2, fine particles of the charge generating substance 3 are dispersed in a solution containing one or more stilchen compounds and a binder, and the fine particles are dispersed in a conductive support. The photosensitive layer 2- may be formed by coating and drying the photosensitive layer 2- on the photosensitive layer 1.

The thickness of the photosensitive layer 2- is 3 to 50 μnl, preferably 5 to 50 μnl.
20 μm is appropriate. The maximum weight of the stilhen compound in the photosensitive layer 2- is 10 to 95%, preferably 30 to 90%.
The amount of the charge generating substance 3 in the photosensitive layer 2 is 0.1 to 50% by weight, preferably 1 to 20% by weight.

Examples of the charge generating substance 3 include inorganic pigments such as selenium, tellurium sulfide, cadmium sulfide, cadmium selenium sulfide, and α-silicon; examples of the pigment include CI Pigment Blue 25 (Color Index CI);
21180), CI Pigment Red 41 (
CI 21200), Sea Eye Acid Red 52
(C[45100), C.I. Basic Red 3
(CI 45210), an azo pigment having a carbazole skeleton (described in JP-A-53-95033),
Azo pigment with a disdyryl-Hensen skeleton (Unexamined Japanese Patent Publication No. 5
No. 3-133445), azo pigments with a 1 to rifenylamine skeleton (described in JP-A-53-32347), azo pigments with a dibenzodiofene skeleton (JP-A-54-21728) (described in the official publication), azo face oni 4 having an oxylydiazole skeleton (Japanese Patent Application Laid-open No. 5412
742), an azo pigment having a fluorenone skeleton (described in Japanese Patent Application Laid-open No. 54-22834), and an azo pigment having a histochemical structure (described in Japanese Patent Application Laid-open No. 54-177).
No. 33 Publication) Disdyryloki 4 Nacyazole bone A with each right side Azo face (Described in Japanese Patent Application Laid-open No. 54-2129), Disburylcarbazole bone) Azo I with each right side
! Azo pigments such as C.I. Pigment Blue 16 (C
174100), e.g. C.I. Butt Brown 5 (Cl 73410),
Indigo pigments such as CI Battie (CI 73030), Argo Scarlet B (manufactured by Bayerne 1)
, Interlene Scarlet 1-R (manufactured by Bayer H) and other perylene-based faces "A'l', +".

Note that these charge generating substances may be used alone or 62 or more types may be used in combination.

Furthermore, to fabricate the photoreceptor shown in Fig. 3, conductivity ↑1
Vacuum vaporizing the charge generating material 3 on the support 1 or
A dispersion of fine particles of the charge generating substance 3 (in which a binder is dissolved if necessary) is applied and dried, and if necessary, the surface is finished and the film is polished by a method such as buffing. The charge generation layer 5 is formed by adjusting the thickness, and a solution containing one or more stilbene compounds and a binder is applied thereon and dried to form the charge transport layer 4. good. Here, the charge generation layer 5 is formed (the charge generation material 3 used here is the same as that used in the description of the photosensitive layer 2-).

The thickness of the H charge generation layer 5 is 5 μm or less, preferably 2 μm or less, and the thickness of the charge transport layer 4 is within the range of 3 to 50 μm, preferably 5 to 20 μm.

If the charge generation layer 5 is of a type in which fine particles of the charge generation substance 3 are dispersed in a binder, the proportion of the fine particles of the charge generation substance 3 in the charge generation layer 5 is 10 to 95% by weight,
Preferably it is about 50 to 90% by weight. The stilbene compound content in the charge transport layer 4 is 10 to 95% by weight, preferably 30 to 90% by weight.

In order to manufacture these photosensitive materials, the conductive support 1 is coated with a metal plate or metal foil such as aluminum, a plastic film coated with a metal such as aluminum, or a conductive treatment. Il+I!i paper, etc. are used.Also, the binder is a condensation resin such as polyamide, polyurethane, polyester, epoxy resin, polycarbonate, polycarbonate, polyhinylcarbonate, etc.
Vinyl polymers such as polystyrene, polystyrene, poly-N-vinylcarbazole, and polyacrylamide are used, but any insulating and adhesive resin can be used. If necessary, a plasticizer is added to the binder, and examples of such plasticizers include halogenated paraffins, polychlorinated biphenyls, dimedylnaphthalene, and dibutyl phthalate.
I can give an example.

Furthermore, the photoreceptor obtained as described above may be provided with an adhesive layer or a barrier layer between the conductive support and the photosensitive layer, if necessary. Materials used for these layers include polyamide, nitrocellulose, aluminum oxide, etc., and the film thickness is preferably 1 μm or less.

To make a copy using the photoreceptor of the present invention, the photoreceptor surface is charged and exposed, then developed and, if necessary, transferred to paper or the like. The photoreceptor of the present invention has excellent advantages such as high sensitivity and flexibility.

Examples are shown below. In the following examples, all parts are parts by weight.

Example 1 76 parts of Diane Blue (CI Pigment Blue 25, CI 21180) and 2 parts of polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) were used as charge generating substances.
1260 parts of % tetrahydrone furan solution and 3700 parts of tetrahydrofuran were ground and mixed in a ball mill, and the resulting dispersion was coated onto the aluminum surface of a conductive support made of aluminum vapor-deposited polyester base J using a doctor blade. Then, dry naturally to a thickness of about 1μ.
A telegraph generating layer of m was formed.

On the other hand, as a charge transport substance, 2 parts of stilbene compound No. 26, polycarbonate resin (Panlite K 130
0, manufactured by Teijin Ltd.) 2 parts and 7 trahydrofuran 16
After mixing and dissolving the parts to form a solution, this was applied onto the charge generation layer using a doctor blade, and dried at 80'C for 2 minutes and then at 105°C for 5 minutes to a thickness of about 20mm! 1
A photoreceptor N091 was prepared by forming a charge transport layer of m.

Examples 2 to 33 Charge generating substance and charge transporting substance (stilbene compound)
Photosensitive Iho Nos. 0.2 to 33 were prepared in exactly the same manner as in Example 1, except that the materials were replaced with those shown in Table 2.

Table 2 Example 34 Selenium was vacuum-deposited to a thickness of approximately 1 μm on an aluminum plate approximately 300 μm thick to form an electrical conductor Fi.
C, then No. 26, 2 parts of Sudirbene compound, 3 parts of polynisder resin (Decobon Co., Ltd. %'l Boriesder Adhesive 49000), J, Bide 1-Rahydrofuran, 4 parts.
Mix 5 parts and 18VH to prepare a charge transport layer forming liquid.
This was applied to one layer of two lightning bolts (relen vapor deposited layer) using doctor spray 1~, air dried, and then dried under reduced pressure to a thickness of about 10μ] 11. ) to form a 3/l photoreceptor according to the present invention.

Example 35 Electricity using perylene face o'mi 1 instead of relene! ``I generation 1fi (however, j''-7-za is approximately 0.3μ01), and the sudirbene compound is
Photoreceptor No. 35 was prepared in exactly the same manner as in Example 34, except for the claws, in which photoreceptor No. 32 was used in place of photoreceptor No. o, 26.

Example 36 Diample - (same as used in Example 1r knee) 1
158 parts of tetrahydrofuran were added to 158 parts of tetrahydrofuran in a ball mill, and then 12 parts of stilbene compound No. 32 and 18 parts of polyester resin (Polyester Adhesive 49000 manufactured by DuPont) were added to C1. The photosensitive layer forming liquid obtained by mixing was applied onto an aluminum-deposited polyester film using a doctor blade, and dried at 100°C for 30 minutes to a thickness of about 16 μm.
A photoreceptor No. 36 of the present invention was prepared by forming a photoreceptor layer.

Regarding the photoreceptors N011-36 thus produced, commercially available electrostatic copying paper test equipment E! 'l(K K II [ZI
-6KV or + using Denki Seisakusho 5P428 type)
After charging with 6 KV corona discharge for 20 seconds, it was left in a dark place for 20 seconds, and the surface potential Vpo at that time was
(volt), then irradiate the photoreceptor surface with tungsten lamp light so that the illumination intensity is 4.5 lux, and the time (seconds) until the surface potential becomes 1/2 of vl)0.
was determined, and the exposure ff1E1/2 (lux/second) was calculated. The results are shown in Table-3.

Further, each of the photoreceptors described above is charged with a commercially available electrophotographic copying machine, and then light is irradiated through the original image to form an electrostatic latent image, which is developed using a dry developer. When the obtained images (images 1 to 1) were electrostatically transferred onto plain paper and fixed, a clear transferred image was obtained. When a wet type developer was used as the developer, a similarly clear transferred image was obtained.

Table 3 Photoreceptor Vpo F 1/2N
O1 (volts) (lux seconds) 1 ~ 1
240 2.7 2 -1120 2.53 -1
300 1.44 -1320
4.25 -1205 1.36
-1310 1.67 -980
4.1 8 -1030 2.3 9 -950 2.2 10, -1180 1.011
-890 0.812 -1360
1.213 -1280 1.4
14 -1600 1.415
-1190 1.71e -1430
1,2 1-7-12201,4 18-15801,2 19-14203,2 20-12601,1 21-12001,4 22-13501,2 23-12401,3 24-1150,1,2 25-11001 ,1 26~1200 1.3 27 -1050 1.228
-1110 1.029
-620 0.730 -1
210 1.131 -69
0 0.732 -1450
1.633 -1060
1.834, -1410 4
．． 135 -1300 5.23
6 +12.10 2.9 Effects As mentioned above, the photoreceptor of the present invention has the general formula (I)
By using a dirubene compound shown in 1 to 11 minutes, forming two clear images.

4. f in the drawing! If! , 154i rJ2 light Fig. 1,
Figure 21 115C. Figure 3 shows the electrons related to the present invention.
FIG. 2 is an enlarged cross-sectional view of the LJ′ true photoreceptor in the photoreceptor 1j direction.

1... Lead t(1・1!1 Support A book 2.2
', 2'' ・Photosensitive layer 3...Electric transport material list 4...Electric transport medium or charge 1 General transport layer 5... Electron I'I:J light (to layer edge δ' [application Person stock company?L Rico - Agent Patent attorney Hide Komatsu

Claims (1)

[Claims] 1. For electrophotography, comprising a photosensitive layer containing at least one stilbene compound represented by the following general formula (I) as an active ingredient on a conductive support. Photoreceptor. Be 1 (wherein R1 represents an alkyl group or an aralkyl group,
Ar is a substituted or unsubstituted naphthyl group;
: l is a hydrogen atom, an argyl group, an alkoxy group, an argylene dioxy group, a substituted amino group represented by halogen\5 (wherein RA and R5 are an alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group), and the river is 1.2
, or an integer of 3, and when m is 2 or 3, R3
may be the same base or different bases] n' indicates an integer of O or 1. )