JPH01107260A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve photosensitive characteristics and the strength resistant to heat and mechanical shock of an electrophotographic sensitive body by forming a photosensitive layer containing a specified amino compd. as an effective component on an electroconductive base body. CONSTITUTION:The title electrophotographic sensitive body has a photosensitive layer 2 contg. at least one kind of amino compd. expressed by the formula I on an electroconductive base body 1. In the formula I, R<1> is H, alkyl group, alkoxy group, aryloxy group, dialkylamino group, diarylamino group, or halogen; each R<2> and R<3> is a (un)substituted alkyl group or (un)substituted aryl group; Ar is an aromatic hydrocarbon group or a heterocyclic group; n is an integer 1 or 2. By this constitution, the photosensitive characteristics and resistance to heat and mechanical shock of an electrophotographic sensitive body are improved.

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 compound in a 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.

By the way, the reality is that each of the above-mentioned inorganic substances has many advantages, but at the same time it also has various disadvantages6.For example, selenium, which is currently widely used, has the above-mentioned (1) to (3). Although it fully satisfies the above conditions, the manufacturing conditions are difficult, the manufacturing cost is high, it is not flexible, it is difficult to process it into a belt shape, and it is sensitive to heat and mechanical shock, so it must be handled with care. There are also drawbacks such as the need for

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-dolinitrofluorene-9
-on (described in U.S. Pat. No. 3,484,237), a photoreceptor made by sensitizing poly-N-vinylcarbazole with a pyrylium salt dye (Japanese Patent Publication No. 48-2
5658, a photoreceptor whose main component is an organic pigment (described in JP-A-47-37543), and a photoreceptor whose main component is a eutectic complex consisting of a dye and a resin (described in JP-A-47-37543). 4
7-10735). Although these photoreceptors have excellent properties and are considered to be of high practical value, considering the various requirements for photoreceptors in electrophotography, it is still difficult to fully meet these requirements. The reality is that we have not been able to obtain anything that satisfies us.

〔the purpose〕

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.

〔composition〕

According to the present invention, there is provided a photoreceptor for electrophotography, which has a photosensitive layer containing as an active ingredient at least one kind of amino compound represented by the following general formula (1) on a conductive support. be done.

A photoreceptor for electrophotography, comprising a photosensitive layer containing as an active ingredient at least one kind of amino compound represented by the following general formula (1) on a conductive support.

(In the formula, R1 is a hydrogen atom, an alkyl group, an alkoxy group,
ali, -ruoxy group, dialkylamino group, diarylamino group, or halogen atom, R2 and R3 are substituted or unsubstituted alkyl groups, 'ei substituted or no iδ
Ar represents an aromatic hydrocarbon group or a heterocyclic group, and n represents an integer of 1 or 2. ) In the present invention, the amino compound represented by the general formula (1) to be contained in the photosensitive layer is, for example, the general formula (TI) (wherein RL, R2, R3, Ar, and n are the same as above)
It is produced by hydrogenating an unsaturated amino compound represented by

The amino compound represented by the general formula (1) obtained by the above synthesis method is illustrated below.

I H1+ -C turtle -C11゜2 H1-Q
--co, -Q-CH.

3 H1+ -C8゜4 H1-Q--C)1. -C-CH7-O)5
H1+ -C)'=-Q -C)6H1-O)--
Q-Q 16 H1-o-U-Rice U-Genus 19 H1-Q--0)-Q -Q-Q47 H,
2-G--Q -01-OCH348H2+ -0
)-CI(-+H- 49H2+ -0)-Kake Beshihoro 50 H2+-o-o-o-.

84 Parrot H92+-o-.

85 Parrot H, 2 I snore) ÷.

86 1l-QCIHs 2-Q--Q-lol ()lol8
7roI4H62+-o-o-o-o-o-.

88 Parrot H, 2 I) IΣ◎IΣ◎ 89 p-cm 2-C) - () Possible, () Crow 901
1iΣ()() 91 +a(Jl, 1-G--Q-false 924
-N(CH3), 1+-o-CI(3+u.

934-N(C*Hs)s 1-Q--Q-CHa-G
-CH3 The photoreceptor of the present invention is one in which the photosensitive layer 2 (2', 2'', 2'' or 21111) contains one or more of the above amino compounds. Figure 1, Figure 2, Figure 31 depending on how you apply it!
! i! -1 Can be used as shown in FIG. 44 or FIG.

The photoreceptor shown in FIG. 1 has a photosensitive layer 2 comprising an amino compound, a sensitizing dye, and a binder (binder resin) on a conductive support 1. The photoreceptor shown in FIG. The amino compound here acts as a photoconductive substance, and the generation and transfer of charge carriers necessary for light attenuation take place via the amino compound.

However, amino compounds have almost no absorption in the visible region of light, so 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. .

The photoreceptor shown in FIG. 2 has a photosensitive layer 2' in which a charge generator [3] is dispersed in a charge transport medium 4 made of an amino compound and a binder on a conductive support 1. . The amino compound here together with the binder (or binder and plasticizer) forms the charge transport medium, while the charge generating substance 3 (charge generating substance such as an inorganic or organic pigment) generates the charge carriers 1. 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 amino compound do not overlap each other, mainly in the visible region. This is the charge generating substance 3
This is because in order to efficiently generate charge carriers, it is necessary to transmit light to the surface of the charge generating substance. −
The amino compound represented by the maximum (I) has almost no absorption in the visible region, generally absorbs light in the visible region, and works particularly effectively as a charge transport material when combined with a charge generating material 3 that generates charge carriers. This is its feature.

In the photoreceptor shown in FIG. 3, a photosensitive layer 2' 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 amino compound is provided on a conductive support 1. It is something that In this photoreceptor, light transmitted through the charge transport layer 4 reaches the charge generation M5, and charge carriers are generated in that region, while the charge transport M4 receives charge carriers and transports them. The generation of charge carriers necessary for light attenuation is performed by the charge generation substance 3, and the transport of charge carriers is performed by the charge transport layer 4 (mainly an amino compound acts). 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 amino compound in FIG. 3, and the mechanism of generation and transport of charge carriers is as explained above. You can do the same thing. In this case, the fifth
A protection M6 can also be provided on the charge generation layer 5 as shown in the figure.

In order to actually produce the photoreceptor of the present invention, in the case of the photoreceptor shown in FIG. 1, one or more amino compounds are dissolved in a solution containing a binder, and then a sensitizing agent is added The photosensitive layer 2 may be formed by preparing a liquid containing the above ingredients, applying it onto the conductive support 1, and drying it.

The thickness of the photosensitive layer is 3 to 50 μm, preferably 5 to 20 μm
is appropriate. The amount of amino compound in photosensitive NI2 is 30-70% by weight2. Preferably about 50% by weight,
The amount of the sensitizing dye in the photosensitive layer 2 is 0.1 to 5% by weight, preferably 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
．． Examples include pyrylium dyes such as 6-diphenyl-4-(N,N-dimethylaminophenyl)thiapyrylium verchlorate and benzobyrylium salt (described in Japanese Patent Publication No. 48-25658). Note that these sensitizing agents may be used alone or in combination of two or more.

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 kinds of amino compounds and a binder, and the fine particles are dispersed on a conductive support. 1 and dried to form a photosensitive layer 2'.

The thickness of photosensitive NI2' is 3-50μ, preferably 5-2
0 μm is appropriate. The amount of the amino compound in the photosensitive layer 2' is 10 to 95% by weight, preferably 30 to 90% by weight.
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. As the charge generating substance 3, for example, selenium, selenium-
Tellurium, cadmium sulfide, cadmium-selenium sulfide, α
- Examples of inorganic pigments such as silicone and organic pigments include CI Pigment Blue 25 (Color Index CI
21180), CI Pigment Red 41 (C
I21200), Sea Acid Red 52 (CI
45100), CI Basic Red 3 (CI4
5210), azo pigments having a carbazole skeleton (described in JP-A-53-95033), azo pigments having a distyrylbenzene skeleton (JP-A-53-133445), azo pigments having a triphenylamine skeleton ( (described in JP-A No. 53-132347), an azo pigment having a dibenzothiophene skeleton (described in JP-A-54-21728)
(described in JP-A No. 54-22834), azo pigments having an oxadiazole skeleton (described in JP-A-54-12742), azo pigments having a fluorenone skeleton (described in JP-A-54-22834), bisstilbene skeletons. Azo pigment with (
(described in JP-A No. 54-17733), azo pigments having a distyryloxadiazole skeleton (described in JP-A-54-2
Azo pigments such as those described in Japanese Patent Laid-Open No. 129-129) and those having a distyrylcarbazole skeleton (described in Japanese Patent Application Laid-Open No. 14967-1983).

For example, CI Pigment Blue 16 (CI 7410
0), indigo pigments such as C.I. Butt Brown 5 (CI 73410), C.I. Butt Dye (CI73030), Argo Scarlet B (Bayer 11), Indanthrene Scarlet R (Bayer II), etc. Examples include perylene pigments. Note that these charge generating substances may be used alone or in combination of 28i or more.

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 dispersed in the inside is applied and dried, and if necessary, surface finishing and film thickness adjustment are performed by methods such as puff polishing to form a charge-generating Ji15. The charge transport layer 4 may be formed by coating a solution containing at least one amino compound and a binder and drying it. Note that the charge generation material used to form the charge generation layer 5 is the same as that of the photosensitive layer described above. This is the same as in the explanation of 2'.

The thickness of the charge generation layer 5 is 5 .mu.m or less, preferably 2 .mu.m or less, and the charge transport layer 4 has a thickness of 3 to 50 .mu.m, preferably 5 to 20 .mu.m. 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 charge generation layer 5 of the fine particles 3 of the charge generation material is
The proportion is 10 to 95% by weight, preferably 50-9
0. The weight is about 2. The amount of the compound in the charge transport layer 4 is 10 to 95% by weight, preferably 30 to 90% by weight. In order to produce the photoreceptor shown in FIG. 4, a solution containing an amino compound and a binder dissolved therein is coated on the conductive support 1 and dried to form a charge transport layer 4. The charge generation layer 5 may be formed by applying a dispersion of fine particles of the charge generation layer material on the layer by a method such as spray coating and drying a dispersion of the charge generation layer material in a solvent in which a binder is dissolved if necessary. The quantity ratio of the layer or charge transport layer is the third
The contents are the same as those explained in the figure. 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 the binder, condensation resins such as polyamide, polyurethane, polyester, epoxy resin, polyketone, and polycarbonate, and vinyl polymers such as polyvinyl ketone, polystyrene, and poly-N-vinylcarbazole are used. Any adhesive resin can be used.

If necessary, a plasticizer may be 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 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 maximum compound (1)] (Synthesis example of compound No. 13) -Phenyl-4-(4-N,N-bis(4-methylphenyl)amino)phenyl-1,3-butadiene 3.9
1 g was dissolved in dioxane 100+a Q, 0.20 g of Nishiki palladium-carbon was added thereto, and hydrogenation was carried out at 20° C. and a hydrogen pressure of 1 atm in a large shaking hydrogenation apparatus. After hydrogenation,
The mixture was filtered with Celite, and dioxane was distilled off under reduced pressure to obtain white crystals. This was recrystallized from ethanol to give white needle-like crystals of 1-phenyl-4-(4-N,N-bis(4-
2.60 g (yield 66.2%) of methylphenyl)aminophenylbutane was obtained. The melting point was 52.0-53.0°C.

Elemental analysis value (%) C-HN Actual value 89.00 7.64 The infrared absorption spectrum of the compound in 3.6 shows the C-H of the trans-olefin of 990a1-1 in the starting material butadiene compound.
Disappearance of absorption due to out-of-plane bending vibration was observed.

Example 1 76 parts of Diamble (CI Pigment Blue 25. CI 21180) as a charge generating substance, 1260 parts of a 2% tetrahydrofuran solution of polyester resin (Vylon 200. ■Toyobo Layer) and 3700 parts of tetrahydrofuran were pulverized and mixed in a ball mill. The resulting 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 with a thickness of about 1 μm.

On the other hand, as a charge transport substance, 2 parts of amino compound No. 13, 2 parts of polycarbonate resin (1300° to Panlite, manufactured by Ondai), and 16 parts of tetrahydrofuran were mixed and dissolved to form a solution, which was then used to generate the charge. Photoreceptor No. 1 was prepared by coating the layer using a doctor blade and drying at 80° C. for 2 minutes and then at 105° C. for 5 minutes to form a charge transport layer with a thickness of about 20 μm.

Examples 2 to 27 Photoreceptors N002 to 27 were prepared in exactly the same manner as in Example 1, except that the charge generating substance and the charge transport substance (amino compound) were replaced with those shown in Table 1.

Example 28 Selenium was vacuum-deposited to a thickness of about 1 μI on an aluminum plate with a thickness of about 300 μ to form a charge generation layer.
DuPont Polyester Adhesive 49000) 3
A charge transport layer forming liquid was prepared by mixing and dissolving 1 part and 45 parts of tetrahydrofuran, and this was applied onto the above charge generation layer (selenium vapor deposited layer) using a doctor blade, air dried, and then dried under reduced pressure. A charge transport layer having a thickness of about 10 μm was formed in this way to obtain photoreceptor No. 28 of the present invention.

Example 29 Except that a perylene pigment was used instead of selenium to form the charge generation layer (however, the thickness was about 0.6 μm), and Na6 was used instead of the amino compound Ma-13 as the charge transport material. Photoreceptor No. 29 was prepared in exactly the same manner as in Example 28.

Example 30 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 amino compound No. 13 and a polyester resin ( A photosensitive layer forming solution obtained by adding 18 parts of Polyester Adhesive 49000 (manufactured by DuPont) 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. A photoreceptor No. 30 of the present invention was prepared by forming a photoreceptor layer having a thickness of approximately 16 μm.

Example 31 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 having a thickness of about 20 μm. Bisazo pigment (P-2) 13
．． 5 parts, polyvinyl butyral (product name: XYHL Union Carbide Plastics Co., Ltd.) 5.4 parts, THF
After pulverizing and mixing 680 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 dried at 100° C. for 10 minutes to form a charge generation layer with a thickness of about 0.2 μm. Furthermore, a methanol-in-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 form a protective layer with a thickness of about 0.5 μm. to form a photoreceptor N
o, 31 was created.

Photoreceptors Nos. 1 to 31 thus produced were tested using a commercially available electrostatic copying paper tester (KK Kawahi Nichi Denki Seisakusho 5P).
-6KV or +6KV (7):10 using 428 type
After charging by discharging for 20 seconds, leave it in a dark place for 20 seconds, measure the surface potential Vpo (volts) at that time, and then apply tungsten lamp light until the illuminance on the photoreceptor surface is 4.5 lux. When irradiated in such a way, the surface potential becomes Vp.
Find the time (seconds) until it becomes 1/2 of o, and calculate the exposure amount E1/
2 (looks/seconds) was calculated. The results are shown in Table-2.

Further, after each of the one or more 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 resulting image (toner image) was electrostatically transferred onto plain paper and fixed, a clear transferred image was obtained. A similarly clear transferred image was obtained when a wet developer was used as the developer.

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

[Brief explanation of the drawing]

1 to 5 are cross-sectional views enlarged in the thickness direction of an electrophotographic photoreceptor according to the present invention. 1... Conductive support 2.21, 2#, 2#, l1llll... Photosensitive layer 3... Charge generating substance 4... Charge transporting medium or charge transporting layer 5... Charge generating layer 6 ...protective layer

Claims (1)

[Claims] (1) An electrophotographic photoreceptor comprising a photosensitive layer containing at least one amino compound represented by the following general formula (I) as an active ingredient on a conductive support. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 is a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, a dialkylamino group, a diarylamino group, or a halogen atom, and R^2 and R^3 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, Ar represents an aromatic hydrocarbon group or a heterocyclic group, and n represents an integer of 1 or 2.)