JPH03235958A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the electrophotographic sensitive body which is inexpensive and is highly durable by providing a photosensitive layer contg. specific aminophenyl silane compds. on a conductive base. CONSTITUTION:This photosensitive body has the photosensitive layer contg. at least one kind of the aminophenyl silane compds. expressed by formula I as an effective component on the conductive base. In the formula, R1 denotes an alkyl group, aryl group; n denotes 1 or 4 integer; m denotes integer of 4-n; R2 to R4 denote a hydrogen atom, amino group; h denotes 1 to 4 integer; k, ldenote 1 to 5 integer. The strength to heat and mechanical impact is upgraded and the inexpensive production is possible.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor containing a specific compound in its photosensitive layer.

[Prior art]

Conventionally, inorganic materials such as selenium, cadmium sulfide, and zinc oxide 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 by, for example, corona discharge, and then imagewise exposed to selectively dissipate the charge only in the exposed areas. An electrostatic latent image is obtained, and this latent image area is developed and visualized using electrostatic fine particles (toner) composed of a coloring material such as a dye or pigment and a binder such as a polymeric substance to form an image. This is one of the image forming methods.

The basic characteristics required of a photoreceptor in such an electrophotographic method are (1) ability to be charged to an appropriate potential in a dark place, (2) less dissipation of charge in a dark place,
(3) Examples include scales that quickly dissipate charge when irradiated with light.

Incidentally, the reality is that each of the above-mentioned inorganic substances has many advantages, but also has various disadvantages. For example, selenium, which is currently widely used, fully satisfies the conditions (1) to (3) above, but the manufacturing conditions are difficult, the manufacturing cost is high, it is not flexible, and it cannot be processed into a belt shape. It also has disadvantages, such as being difficult to handle and being sensitive to heat and mechanical shock, requiring careful handling.

Cadmium sulfide and zinc oxide are used as photoreceptors by being dispersed in a resin as a binder, but they cannot be used as is because of mechanical drawbacks such as smoothness, hardness, tensile strength, and abrasion resistance. cannot be used.

In recent years, electrophotographic photoreceptors using various organic materials have been proposed in order to eliminate the drawbacks of these inorganic materials, and some of them have been put into practical use. For example, poly-N-vinylcarbazole and 2.4.7-trinitrofluorene-
9-one (U.S. Pat. No. 3,484,237)
(described in the specification), a photoreceptor made by sensitizing poly-N-vinylcarbazole with a pyrylium salt dye (Japanese Patent Publication No. 1973-
25658), a photoreceptor whose main component is an organic pigment (described in JP-A-47-37543), a photoreceptor whose main component is a eutectic complex consisting of a dye and a resin (JP-A-47-37543) -10735), a photoreceptor made by dye-sensitizing a triphenylamine compound (U.S. Patent No. 3,18
0,730), a photoreceptor using an amine derivative as a charge transporting material (JP-A-57-195254), a photoreceptor using poly-N-vinylcarbazole and an amine derivative as a charge-transporting material (JP-A-Sho 58- Publication No. 1155)
, a photoreceptor using a benzidine compound among polyfunctional tertiary amino compounds as a photoconductive material (U.S. Pat. No. 3,265
, No. 496, Japanese Patent Publication No. 39-11546, Japanese Patent Application Publication No. 1973
3-27033). Although these photoreceptors have excellent properties and are considered to be of high practical value, considering the various requirements for photoreceptors in electrophotography,
The reality is that nothing that satisfactorily satisfies these requirements has yet been obtained.

[Problem to be solved by the invention]

SUMMARY OF THE INVENTION 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.

[Means to solve the problem]

According to the present invention, at least one aminophenylsilane compound represented by the following general formula (1) is disposed on a conductive support.
There is provided an electrophotographic photoreceptor characterized by having a photosensitive layer containing a seed as an active ingredient.

4- (wherein R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, n represents an integer of 1.2.3.4, m represents an integer of 4-n) .When m is 2 or more, R may be the same or different.R2, R3, R4
represents a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom, or a substituted or unsubstituted aryl group. In addition, h represents an integer of 1.2.3.4, k and Q represent an integer of 1.2.3.4.5, h,
When k and Q are 2 or more, R2, R3, and R4 may be the same or different. ) In the present invention, the aminophenylsilane compound represented by the general formula (1) contained in the photosensitive layer is, for example, the general formula (n) or the general formula (m) (wherein R2, R3, R,, h, k, Q are the same as before, X represents a halogen atom) and aminophenyllithium or aminophenylmagnesium halide represented by the general formula (m)
R1) m (IV) (wherein,
Hn, m are the same as before, and x represents a halogen atom. ) It is produced by reacting a haloylsilane compound represented by:

Specific examples of the aminophenylsilane compound represented by the general formula (1) obtained by the above synthesis method are illustrated below.

7- The photoreceptor of the present invention includes one or more of the above aminophenylsilane compounds in the photosensitive layer 2 (2', 27/,
2m or 2//II), but depending on the application of these aminophenylsilane compounds, as shown in Figure 1, Figure 2, Figure 3, Figure 4, or Figure 5. Can be used.

The photoreceptor in FIG. 1 consists of an aminophenylsilane compound, a sensitizing dye, and a binder (binder resin) on a conductive support 1.
A photosensitive layer 2 made of the following is provided. The aminophenylsilane compound here acts as a photoconductive material, and the generation and transfer of charge carriers necessary for light attenuation take place via the aminophenylsilane compound. However, since aminophenylsilane compounds have almost no absorption in the visible region of light, in order to form images with visible light, it is necessary to sensitize them by adding a sensitizing dye that absorbs in the visible region. There is.

The photoreceptor shown in FIG. 2 has a photosensitive layer 2' provided on a conductive support 1, in which a charge generating substance 3 is dispersed in a charge transport medium 4 made of an aminophenylsilane compound and a binder. be. The aminophenylsilane compound here forms the charge transport medium together with the binder (or binder and plasticizer), while the charge generating substance 3 (charge generating substance such as an inorganic or organic pigment) generates the charge carriers. do. In this case, the charge transport medium 4 is mainly responsible for receiving charge carriers generated by the charge generating substance 3 and transporting them. In this photoreceptor, the basic condition is that the absorption wavelength regions of the charge generating substance and the aminophenylsilane 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 generating substance 3, it is necessary to transmit light to the surface of the charge generating substance. The aminophenylsilane compound represented by the general formula (1) has almost no absorption in the visible region, generally absorbs light in the visible region, and when combined with a charge generating substance 3 that generates charge carriers, it is particularly effective at transporting charges. Its feature is that it works as a substance.

The photoreceptor in FIG. 3 is provided with a photosensitive material N2'' consisting of a laminated layer of a charge generation layer 5 mainly composed of a charge generation substance 3 and a charge transport layer 4 containing an aminophenylsilane compound on a conductive support 1. In this photoreceptor, light transmitted through the charge transport layer 4 reaches the charge generation layer 5, and charge carriers are generated in that region.On the other hand, the charge transport layer 4 does not allow injection of charge carriers. The generation of charge carriers necessary for optical attenuation is performed by a charge generation substance 3, and the transport of charge carriers is performed by a charge transport layer 4 (mainly acted by an aminophenylsilane compound). This mechanism is similar to the explanation given for the photoreceptor shown in FIG.

The photoreceptor in FIG. 4 is obtained by reversing the stacking order of the charge generation layer 5 and the charge transport layer 4 containing an aminophenylsilane compound in FIG. 3, and the mechanism of generation and transport of charge carriers is as described above. It can be done in the same way as explained. In this case, in consideration of mechanical strength, a protective layer 6 may be provided on the charge generation M5 as shown in FIG.

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

The thickness of the photosensitive layer is 3-50 ILm, preferably 5-20μ
m is appropriate. The amount of the aminophenylsilane compound in the photosensitive layer 2 is 30 to 70% by weight2, preferably about 50% by weight, and the amount of the sensitizing dye in the photosensitive layer 2 is 0.1 to 5% by weight, preferably It is 0.5 to 3% by weight. The sensitizers include triarylmethane dyes such as brilliant green, Victoria blue B, methyl violet, crystal violet, acid violet 6B, rhodamine B, rhodamine 6G, rhodamine G extra, eosin S, erythrosin, rose bengal, and fluorescein. xanthine dyes such as, thiazine dyes such as methylene blue, cyanine dyes such as cyanine, 2,6-diphenyl-4-(N,N-dimethylaminophenyl)thiapyrylium verchlorate,
Examples include pyrylium dyes such as benzopyrylium salts (described in Japanese Patent Publication No. 48-25658). In addition,
These sensitizing agents may be used alone or in combination of two or more.

In addition, in order to produce the photoreceptor shown in FIG. The photosensitive layer 2' may be formed by coating it on the support 1 and drying it.

The thickness of the photosensitive layer 2' is 3 to 50 μm, preferably 5 to 20 μm.
μl is appropriate. The amount of the aminophenylsilane compound in the photosensitive layer 2' is 10 to 95% by weight, preferably 30% by weight.
90% by weight, and the amount of the charge generating substance 3 in the photosensitive layer 2' is 0.1 to 50 da, preferably 1 to 2 da.
0 weight 2. Examples of the charge generating substance 3 include inorganic pigments such as selenium, selenium-tellurium, cadmium sulfide, cadmium-selenium sulfide, and α-silicon; examples of organic pigments include CI Pigment Blue 25 (Color Index CI 21180) and CI Pigment Red 41. (C121200), C.I. Acid Red 52 (CI 45100), C.I. Basic Red 3 (CI45210), an azo pigment having a carbazole skeleton (described in JP-A-53-95033), an azo pigment having a distyrylbenzene skeleton (described in JP-A-53-95033), Kaisho 53-1
33445), an azo pigment having a triphenylamine skeleton (described in JP-A-53-132347),
Azo pigments having a dibenzothiophene skeleton
-21728), azo pigments having an oxadiazole skeleton (described in JP-A-54-12742), azo pigments having a fluorenone skeleton (described in JP-A-54-12742),
22834 No. 15-), azo pigments having a bisstilbene skeleton (
(described in JP-A No. 54-17733), azo pigments having a distyryloxadiazole skeleton (described in JP-A-54-2
129), azo pigments having a distyrylcarbazole skeleton (described in JP-A-54-14967), such as C.I. Pigment Blue 1
Phthalocyanine pigments such as 6 (CI 74100),
For example, Sea Eye Butt Brown 5 (CI 73410)
, indigo pigments such as CI Bat Dye (CI 73030), Argo Scarlet B (manufactured by Bayer),
Examples include perylene pigments such as Indanthrene Scarlet R (manufactured by Bayer AG). Note that these charge generating substances may be used alone or in combination of two or more types.

Furthermore, in order to produce the photoreceptor shown in FIG. 3, a charge generating substance is vacuum-deposited on one or more conductive supports, or fine particles 3 of a charge generating substance are deposited in a suitable solvent in which a binder is dissolved if necessary. The dispersion is applied and dried, and if necessary, the surface is finished by puff polishing or other methods, and the film thickness is adjusted to form the charge generation layer 5. The charge transport layer 4 may be formed by applying a solution containing one or more aminophenylsilane compounds and a binder and drying. The charge generating material used to form the charge generating layer 5 is the same as that used in the description of the photosensitive layer 2'.

The thickness of the charge generation layer 5 is 5 μm or less, preferably 2 μm or less, and the thickness of the charge transport layer 4 is suitably 3 to 50 μm, preferably 5 to 20 μm. If the charge generation layer 5 is of a type in which fine particles 3 of the charge generation layer material are dispersed in a binder, the proportion of the fine particles 3 of the charge generation material in the charge generation layer 5 is preferably 10 to 95% by weight. is about 50 to 90% by weight. Further, the amount of the compound in the charge transport layer 4 is 10 to 95% by weight, preferably 30 to 90% by weight. To produce the photoreceptor shown in FIG. 4, a solution containing an aminophenylsilane compound and a binder is applied onto the conductive support 1 and dried to form the charge transport layer 4. Fine particles of charge generation layer material are placed on top of the charge transport layer.
If necessary, the charge generation layer 5 may be formed by applying a dispersion in a solvent containing a binder by a method such as spray coating and drying. The amount ratio of the charge generation layer or the charge transport layer is the same as that explained with reference to FIG. A protective layer 6 is further formed on the charge generation layer 5 of the photoreceptor thus obtained by spray coating or the like with a suitable resin solution, thereby producing the photoreceptor shown in FIG. 5. As the resin used here, the binder described later can be used.

In the production of any of these photoreceptors, the conductive support 1 is made of a metal plate or metal foil such as aluminum, a plastic film on which metal such as aluminum is vapor-deposited,
Alternatively, paper that has been subjected to conductive treatment may be used. Also,
As a binder, condensation resins such as polyamide, polyurethane, polyester, epoxy resin, polyketone, and polycarbonate, and vinyl polymers such as polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, and polyacrylamide are used. Any resin with adhesive properties can be used.

If necessary, a plasticizer is added to the binder, and examples of such plasticizers include halogenated paraffins, polychlorinated biphenyls, dimethylnaphthalene, and dibutyl phthalate.

Furthermore, in the photoreceptor obtained as described above, an adhesive layer or a barrier layer can be provided 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.

〔Example〕

The present invention will be explained below with reference to Examples. In addition, in the following examples, all parts are parts by weight.

[Synthesis of compound of general formula (1)] (Synthesis example of compound Nα1) ■Synthesis of 4-bromotriphenylamino 19- 36.80 g of triphenylamine and 26.70 g of N-bromosuccinimide were mixed with 750 g of carbon tetrachloride. Dissolved in 3
．． Heat to reflux for 5 hours. The reaction solution was cooled and insoluble materials were removed by filtration. When the tetraliquefied carbon is removed from this solution, a white powder is obtained. This was column purified with n-hexane, recrystallized several times with n-hexane and ethanol, and 4-bromotriphenylamine 21. ], Og (yield 43%) white needle crystals were obtained.

Melting point: 101° to 102.5° Elemental analysis values (%) were as follows for Cl8H4NBr.

CHN Actual value 66.66 4.26 4.04 Theoretical value 66.6g 4.35 4.32 ■Bis(N,N-diphenylamiphenyl)dimethylsilane (
Synthesis of Compound Nα1) Under an argon atmosphere, 6.48 g of 4-bromotriphenylamine synthesized in step ① above was dehydrated to produce 50% benzene.
A mixture of 12.6 ml of n-butyllithium and 25 ml of dehydrated diethyl ether was added dropwise over 30 minutes. Thereafter, after stirring at room temperature for 3 hours, a mixed solution of 1.13 mQ of dimethyldichlorosilane and 25 mQ of dehydrated diethyl ether was added dropwise over 40 minutes. Thereafter, the mixture was stirred at room temperature for 2 hours, and then heated under reflux for 2 hours to complete the reaction. This reaction solution was cooled, poured into ice water, and extracted with toluene. This extract was subjected to column treatment using silica gel with a developing solvent of cyclohexane. Add this further to ethanol/toluene = 2
The product was recrystallized twice with a mixed solvent of 71 to obtain 2.81 g (yield 55%) of bis(N,N-diphenylaminophenyl)dimethylsilane as colorless needles.

Melting point: 170.0-171.5°C Elemental analysis values (illustrated as C381 (34N2S1) were as follows.

CHN Actual value 83.49 6.32 4.99 Theoretical value 83.47 6.27 5.12 The infrared absorption spectrum of this compound is shown in FIG.

(Synthesis example of compound Nα24) 4-bromotriphenylamine and methyltrichlorosilane were reacted in the same manner as compound Nα1, and tris(
N,N-diphenylaminophenyl)methylsilane (compound Nα24) was obtained. Yield 1.46g (yield 31%)
white powder. Melting point: 236.5-238.0°C Elemental analysis values (%) for C5, H45N3Si were as follows.

CHN Actual value 84.93 6.05 5.26 Theoretical value 85.12 5.84 5.14 The infrared absorption spectrum of this compound is shown in FIG.

(Synthesis example of compound N (131)) 4-bromotriphenylamine and tetrachlorosilane were reacted in the same manner as compound N (11) to obtain tetrakis(N,N-diphenylaminophenyl)silane (compound &31). Yield: 2.64 g (yield 77%) white powder. Melting point: 318.0-320.0°C Elemental analysis values (%) for C7□H, GN4Si were as follows.

CHN Actual value 85,91 5,92 5.50 Theoretical value 86.02 5.61 5.57 The infrared absorption spectrum of this compound is shown in FIG.

Note that other aminophenyl compounds were synthesized in the same manner.

Example 1 76 parts of Diane Blue (CI Pigment Blue 25, CI 21180) as a charge generating substance, 1260 parts of a 2% tetrahydrofuran solution of polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) and 3700 parts of tetrahydrofuran were ground and mixed in a ball mill. The obtained dispersion was applied using a doctor blade onto the aluminum surface of a conductive support made of a polyester base coated with aluminum vapor, and air-dried to form a charge generation layer having a thickness of about 1 μm.

On the other hand, the charge transport materials were 2 parts of NQI's aminophenylsilane compound, 2 parts of polycarbonate resin (Painlight 1300, manufactured by Ondai), and 1 part of tetrahydrofuran.
After mixing and dissolving 6 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 120°C for 5 minutes to form a charge transport layer with a thickness of about 20 μm. A photoreceptor N1Ll was prepared by forming layers.

Examples 2 to 35 Photoreceptors Nα2 to 35 were prepared in exactly the same manner as in Example 1, except that the charge generating substance and the charge transporting substance (aminophenylsilane compound) were replaced with those shown in Table 1.

24- -27- -28-. Next, 2 parts of Nα1 aminophenylsilane compound,
3 parts of polyester resin (Polyester Adhesive 49000 manufactured by DuPont) and 45 parts of tetrahydrofuran were mixed and dissolved to prepare a charge transport layer forming liquid, and this was applied onto the above charge generation layer (selenium vapor deposition layer) using a doctor blade. The photoreceptor N036 of the present invention was obtained by coating the photoreceptor, air drying, and drying under reduced pressure to form a charge transport layer having a thickness of about 10 μm.

Example 37 Perylene pigment used instead of selenium Example 36 Selenium was vacuum-deposited to a thickness of about 1 μm on an aluminum plate with a thickness of about 300 μm to form a charge generation layer. A photoreceptor Nα37 was prepared in exactly the same manner as in Example 35, except that about 0.6 μl11) was formed and the aminophenylsilane compound Nα1 was used as the charge transport material.

Example 38 A mixture of 1 part of Diane Blue (same as that used in Example 1) and 158 parts of tetrahydrofuran was ground and mixed in a ball mill, and then 12 parts of an aminophenylsilane compound of Nα1 and a polyester resin ( A photosensitive layer forming solution obtained by adding 18 parts of DuPont Polyester Adhesive 49000) and further mixing was applied onto an aluminum-deposited polyester film using a doctor blade, and dried at 100°C for 30 minutes to form a thick film. Approximately 16μm
A photoreceptor Na38 of the present invention was prepared by forming a photoreceptor layer.

Example 39 On a polyester film substrate coated with aluminum,
The charge transport layer coating solution used in Example 1 was applied with a blade in the same manner as in Example 1, and then dried to form a charge transport layer with a thickness of about 20 μm. Bisazo pigment (P-2)13.
5 parts, polyvinyl butyral (product name: xY Union Carbide Plastic Co., Ltd.) 5.4 parts, T) IF 6
After pulverizing and mixing 80 parts of ethyl cellosolve and 1020 parts of ethyl cellosolve in a ball mill, 1700 parts of ethyl cellosolve was added and mixed with stirring to obtain a charge generation layer coating liquid. This coating solution was spray coated onto the above charge transport layer, and
After drying for 0 minutes, a charge generation layer having a thickness of about 0.2 μm was formed. Furthermore, a methanol/n-butanol solution of polyamide resin (trade name: CM-8000, manufactured by Toshi) was spray-coated on top of this charge generation layer and dried at 120°C for 30 minutes to a thickness of about 0.5 degrees. A protective layer is formed on the photoreceptor Nα3.
9 was created.

The photoreceptors Nα1 to Nα39 thus produced were tested using a commercially available electrostatic copying paper tester (SP'4 manufactured by KK Kawayo Denki Seisakusho).
After charging by corona discharge of 16 KV or +6 KV for 20 seconds using a 28 type, leave it in a dark place for 20 seconds, measure the surface potential Vpo (volt) at that time, and then expose it to tungsten lamp light. The illuminance of the body surface is 4.5
lux so that the surface potential is 1 of Vpo.
The time (seconds) until the temperature reached 72 was determined, and the exposure amount E1/2 (lux/second) was calculated. The results are shown in Table-2.

In addition, after each of the above-mentioned photoreceptors is charged using a commercially available electrophotographic copying machine, light is irradiated through the original image to form an electrostatic latent image, and the image is developed using a dry developer. When the image (toner image) was electrostatically transferred onto plain paper and fixed, a clear transferred image 31- was obtained. A similarly clear transferred image was obtained when a wet developer was used as the developer.

Table 2 2- [Effects] The photoreceptor of the present invention not only has excellent photosensitivity, but also has high strength against thermal and mechanical impact, and can be manufactured at low cost.

[Brief Description of the Drawings] Figures 1 to 5 are cross-sectional views enlarged in the thickness direction of an electrophotographic photoreceptor according to the present invention, and Figures 6, 7, and 8 are cross-sectional views of an electrophotographic photoreceptor according to the present invention. This is an infrared absorption spectrum of a phenylsilane compound.

Claims (1)

[Claims] (1) An electrophotographic photoreceptor comprising a photosensitive layer containing as an active ingredient at least one aminophenylsilane compound represented by the following general formula (I) on a conductive support. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. n represents an integer of 1, 2, 3, or 4. , m represents an integer of 4-n. If m is 2 or more, R_1 may be the same or different. R_2, R_
3. R_4 represents a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom, or a substituted or unsubstituted aryl group. Also, h is 1, 2, 3,
k and l represent integers of 1, 2, 3, 4, and 5, and when h, k, and l are 2 or more, R_2, R_3, R_4
may be the same or different. )