JPS62153859A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the titled body having excellent properties of sensitivity, repeating property and durability by incorporating a polycyclic quinone compd. and a hydrazone derivatives having specific structure to the titled body. CONSTITUTION:The titled body contains at least one kind of the polycyclic quinone compd. shown by formula I-III, as an electrostatic charge generating material, and the specific hydrazone compd. shown by formula IV or V as an electrostatic charge transfer material. In formulas I-III, R is a halogen atom, nitro group, cyano group or an alkyl, an alkoxy, an aryloxy or an amino group which may be substd., (n) is an integer of 0-4. In formulas IV and V, R1 or R3 is an alkyl, an aralkyl or an aryl group which may be substd, R2 is hydrogen atom, a halogen atom, an alkyl or an alkoxy group.

Description

Detailed Description of the Invention (Objective of the Invention) (Industrial Application!F) The present invention relates to an electrophotographic photoreceptor, and more specifically, it relates to an electrophotographic photoreceptor in which a polycyclic resin is applied as a charge generating material on a conductive support. By containing a non-compound and a hydrazone compound as a charge transporting material.

The present invention provides an electrophotographic photoreceptor having poor photosensitivity and durability.

(Prior Art) The electrophotographic method has already been published by Carlson in US Patent No. 2.297.
As disclosed in No. 691, this photographic method is an ingenious combination of electrostatic and photoconductive phenomena, in which a photoconductive photoreceptor is exposed in the dark by corona discharge or the like.

After uniformly charging the surface, photoconductivity is used to transform the image into an electrostatic latent image, which is then colored with charged powder (toner).
It is one of the image forming methods that attaches a substance and converts it into a visible image.

The basic electrical and photoelectric properties required of a photoreceptor in such electrophotography are that it can be charged to an appropriate potential in a dark place, that this potential can be maintained for an appropriate amount of time, and that it can be charged quickly by light irradiation. For example, the electric charge can be dissipated.

In such photoreceptors, amorphous selenium,
Inorganic photoconductive materials such as cadmium sulfide and zinc oxide have been widely used. Although these inorganic materials satisfy the above conditions, they also have some drawbacks. For example, cadmium sulfide and zinc oxide It is used as a photoreceptor by dispersing it in a resin as an agent.

Since it has mechanical defects such as smoothness, flexibility, hardness, tensile strength, and abrasion resistance, it cannot withstand repeated use as it is. Furthermore, when using cadmium sulfide, consideration must also be given to hygiene issues.

In addition, amorphous selenium must be manufactured by vapor deposition, which not only increases manufacturing costs but also has no flexibility and is difficult to process into a belt shape.
It has drawbacks such as the toxicity of selenium and its sensitivity to heat and mechanical shock, so care must be taken when handling it.

In recent years, in order to eliminate the drawbacks of these inorganic photoreceptors,
Research on organic photoreceptors is progressing, and organic photoreceptors.

Ease of film formation! ! Two types of organic photoreceptors have been proposed, and some are in practical use because they have many advantages such as ease of manufacture, light weight, flexibility, and variable spectral sensitivity.

For example, poly-N-vinylcarbazole and 2.4.7-
Photoreceptor consisting of dolinitrofluoren-9-one (US Pat. No. 3,484,237), poly-N-vinylcarbazole sensitized with pyrylium salt dye (Japanese Patent Publication No. 48-25658), Photoreceptor whose main component is a eutectic complex consisting of a dye and a resin
Publication No.) etc.

Additionally, an electrophotographic photoreceptor has been proposed that combines a substance that generates electric charge when exposed to light (called a charge-generating substance) and a substance that can transport the generated electric charge (called a charge-transporting substance). . For example, U.S. Patent No. 3.791.
No. 826 discloses a photoreceptor in which a charge transport layer is provided on a charge generation layer, and U.S. Pat. A photoreceptor having a photosensitive layer is described. This kind of charge generation and charge transport.

By sharing the functions with different substances,
In other words, by the combination of a charge generating substance and a charge transporting substance,
Its properties are better and a useful photoreceptor is provided.

Until now, many charge-generating substances useful in this type of photoreceptor have been known. On the other hand, various materials have been proposed as charge transport materials.

The current situation is that it is difficult to say that the situation is necessarily satisfactory.

The basic properties of an excellent charge transport material are:

It must be able to maintain a sufficient potential when charged, and it must be able to sufficiently transmit light of an effective wavelength to generate charges from the charge-generating substance, and furthermore, It has the ability to rapidly transport charged charges.In addition, the required properties for practical use are as follows:
It can be used alone or dissolved in a binder to form a uniform film, and its electrostatic properties do not deteriorate or change under harsh environmental conditions such as temperature, humidity, and ozone and NOx generated during corona discharge. It is necessary not to bring So far, as this type of charge transport material, polyphenyl compounds such as triphenyl, classified by chemical structural formula,
U.S. Patent No. 3.717.462, U.S. Patent No. 4.15
0.987, hydrazone compounds described in JP-A-55-52064, US Pat. No. 3.820.
989, 2,5-bis(P-diethylaminophenyl) as described in U.S. Pat. No. 3,189,477.
-1,3,4-oxadiazole, U.S. Pat. No. 3.83
Pyrazoline compounds described in No. 7.851 are relatively excellent charge transport materials that have been proposed in recent years. However, at present, these charge transport materials cannot be said to satisfy all of the above conditions.

(Problems to be Solved by the Invention) The present invention provides an electrophotographic photoreceptor having excellent sensitivity, repeatability, durability, and the like.

[Structure of the invention]

(Means for Solving the Problem) As a result of intensive research, the present inventors have found that when a polycyclic quinone compound is used as a charge-generating material, a hydrazone compound with a specific structure has a charge that is useful for electrophotographic photoreceptors. They discovered that it is a charge transport material, and further discovered that an electrophotographic photoreceptor using this charge transport material has excellent properties.1 The present invention has been completed. A photographic photoreceptor is provided using a polycyclic quinone compound and a hydrazone derivative having a specific structure.

The purpose of the present invention is to contain a polycyclic bovine non-compound as a charge-generating material and a specific charge-transporting material to achieve high sensitivity and low residual potential. An object of the present invention is to provide a high-speed electrophotographic photoreceptor. Another object of the invention is charging exposure,
When used as a photoreceptor for repetitive transfer type electrophotography where the development and transfer steps are repeated, there is little fatigue deterioration due to repeated use, and it can also be used in various harsh environments such as high temperatures rather than low temperatures, and high humidity rather than low humidity. An object of the present invention is to provide an electrophotographic photoreceptor that maintains stable characteristics and has excellent durability and ring-filling properties.

Such an object of the present invention is to contain at least one polycyclic bovine compound represented by the following general formula (1), (2) or (3) as a charge generating material, and to contain at least one polycyclic bovine compound represented by the following general formula (4) as a charge transporting material. Alternatively, it can be achieved by containing a specific hydrazone compound shown in (5).

(In the formula, R is a halogen atom, a nitro group, or a cyano group.

An alkyl group or an alkoxy group that may have a substituent.

represents an aryloxy group or an amine group, n is 0 to 4
represents an integer. ) (In the formula, R5 or Rj represents an alkyl group, an aralkyl group, or an aryl group that may have a substituent, and Rx represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.) To further explain the substituents: , R is a halogen atom such as a hydrogen atom, a bromine atom, a chlorine atom; a nitro group; a cyano group; a methyl group, an ethyl group, a phthalimidomethyl group, etc.
Alkyl groups which may have substituents; alkoxy groups such as methoxy and ethoxy groups; aryloxy groups such as phenokine and tolyloxy groups; and amino groups. R1 and R3 are a methyl group and an ethyl group.

Alkyl group that may have a direct substituent such as chloromethyl group, trichloromethyl group, trifluoromethyl group; Aralkyl group that may have a substituent such as hensyl group, naphthylmethyl group, methylbenzyl group, chlorohensyl group, etc. Group: An aryl group which may have a substituent such as a phenyl group, a naphthyl group, a chlorophenyl group, or a methylphenyl group. R
λ is a hydrogen atom; a halogen atom such as a bromine atom or a chlorine atom;
Alkyl groups such as methyl group and ethyl group; alkoxy groups such as methoxy group and ethoxy group.

The polycyclic non-compounds which are charge generating materials represented by the general formulas (1), (2) and (3) are as follows.

(+-3) (1-4) (1-di)
(1-f:) (+-q) (λ-1) (, z-3) (+-1) (2-J) (λ-4) (No. 2-) (3-1) (J- 2) (J-3) Further, specific hydrazone compounds which are charge transport materials represented by general formulas (4) and (5) are as follows, for example.

(Dou-1) Ki (+-2) (S''-ship (Sir 5) (Dar 6) These compounds can be used alone or in combination of two or more.

The photoreceptor of the present invention contains a polycyclic quinone compound as a charge generating material as described above, and a specific hydrazone compound as a charge transporting material. A photoreceptor with the following characteristics can be obtained. For example, 3) a structure in which a hydrazone compound as a charge transporting material is provided on a conductive support substrate in the same layer as a charge generating material; 1) a structure usually referred to as a single-layer photoreceptor, or a 1st layer mainly containing a charge generating material; It can be used in a configuration commonly referred to as a laminated type photoreceptor, which is made by laminating two second layers mainly containing a charge transporting material on a conductive support substrate. These configurations are appropriately selected depending on the polarity of the photoreceptor used.

Since the hydrazone compound in the present invention does not have film-forming ability by itself, a binder resin is used to form it as a photosensitive layer. Further, since the charge generating material does not form a film by itself except for a polymeric resin such as citemo polyvinyl carbazole, a binder may be used if necessary.

The binder preferably used in the present invention is a highly electrically insulating film-forming polymer or copolymer. These high molecular weight polymers and copolymers are 1
Binders preferably used in the present invention include phenolic resin, polyester resin, vinyl acetate resin, polycarbonate resin, polypeptide resin, cellulose resin, polyurethane resin, polyvinylpyrrolidone, polyethylene oxide, polyvinyl chloride resin, starch, and polyvinyl alcohol. , acrylic copolymer resin, methacrylic copolymer resin, silicone resin, polyacrylonitrile copolymer resin, polyacrylamide, polyvinyl butyral, polyvinyl carbazole, polyvinylidene chloride resin, and the like.

These polymer binders can be used alone or in a mixture of 2M or more, but the binders that can be used in the present invention are not limited to these. Furthermore, in the photoreceptor of the present invention, a charge generation layer containing a charge generation material as a main component is provided on the conductive support via an intermediate layer if necessary, and adjacent to the charge generation layer the charge generation layer containing a charge transporting material as a main component is provided. Product F with charge transport material
It may be an i configuration. In addition, in the case of such a laminated structure, which of the charge generation layer and the charge transport layer is to be used as the upper layer is determined depending on whether the chargeability is positive or negative.

Generally, when negatively charged, it is advantageous in terms of characteristics to have a charge transport layer as an upper layer. In addition, when the photoreceptor of the present invention has a laminated structure consisting of separate layers of a charge generation layer and a charge transport layer, the charge generation layer is placed directly on the conductive support or optionally with an adhesive or a barrier. After providing an intermediate layer such as a single layer, ■ Vacuum deposition, ■ Applying a solution of the charge generating substance dissolved in an appropriate solvent, or ■ Dispersing the charge generating substance finely in a solvent using a ball mill, attritor, etc. It can be provided by a method such as coating a dispersion obtained by mixing and dispersing with a polymeric binder as necessary. The polymer binder used at this time may be the same as that used for the charge transport layer.

Alternatively, it may be a single photosensitive layer comprising a specific hydrazone compound according to the present invention and a binder.

Further, in the specific hydrazone compound according to the present invention, the amount of the charge transport material is preferably 10 to 300 parts by weight per 100 parts by weight of the binder. However, the present invention is not limited only to this range. The thickness of the photosensitive layer is determined by the required photosensitivity and durability, as well as the mixing ratio of the charge generating material and the charge transporting material to the binder. The thickness of the photosensitive layer on the supporting conductive substrate is preferably 50 .mu. or less, preferably about 7 to 30 .mu. from the viewpoint of film flexibility.

The photosensitive layer can also be coated with a layer that serves as a protective layer, if necessary.

As the support for use in the electrophotographic photoreceptor of the present invention, any support may be used as long as it is imparted with electrical conductivity.

Any type of conductive layer conventionally used may be used. Specifically, aluminum.

Metals such as copper, stainless steel, brass, and aluminum.

Examples include plastics in which indium oxide, tin oxide, etc. are vapor-deposited or laminated, and conductive particles 2 such as carbon blanks, plastics in which tin particles, and aluminum particles are dispersed. Further, its shape may be sheet-like, cylindrical, or other shapes.

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples. Hereinafter, in the examples, the compound number in the example indicates the compound number added in the above example, and "part" indicates part by weight.

Example 1 Compound (1-1) 0.4 parts Polyester resin (Vylon 200) 0.5 parts 1,2-dichloroethane 9.5 parts or more of the composition was dispersed in a vibrating mill for 2 hours to obtain a The photoconductive composition was coated on an 80μ aluminum plate with a wire bar so that the dry film thickness was 0.5μ.
A charge generation layer is formed by drying for 1 hour in an oven uniformly heated to .degree. Next, a solution having the following composition was prepared so that it was coated on the charge generation layer to a thickness of 15 μm.

Compound (4-3) 0.3 parts Polyester resin (Vylon 200) 0.4
The film was coated with 2.6 parts dichloroethane using a wire bar, and dried for 30 minutes in an oven uniformly heated to 80° C. to prepare a laminated photoreceptor.

-5, OKV for the sample thus obtained.

Corona discharge was applied with a corona gap of 10 m and a charging speed of 10 m/mtn, and 10 seconds after the discharge stopped, exposure was performed using a 2854 tungsten light source at an illuminance of 5.0 Lux. The amount of light irradiation required for the potential immediately before exposure to decrease by 50% at this time was defined as the sensitivity. The sample measured in this way had a maximum surface charge of -650V.

The dark decay rate was 3.0%, the sensitivity was 2.2 Lux·Sec, and the residual potential was -98 V.

Example 2 Compound (1-2) 0.4 parts Acrylic resin (Dianal HR1130, 2 parts Vinyl chloride-vinyl acetate 41 fat (VMCH) 0.21 Ethyl acetate 14 parts or more of the composition was mixed in a vibrating mill with 2 parts After time dispersion, the resulting photoconductive composition was applied onto a laminate film of 5 μm thick aluminum foil and 75 μm polyester film to a dry film thickness of 0.5 μm.
It was coated with a wire bar to a thickness of 5 μm and left in an oven uniformly heated to 130° C. for 1 hour to form a charge generation layer. Then, in Example 1, compound (4-3
) instead of (4-4), a laminated photoreceptor was prepared and tested in the same manner as in Example 1, and the maximum surface charge amount -
1,080V, dark decay rate 9.8%, sensitivity 1.6 Lu
x-sec + residual potential -78V.

Example 3 Compound (3-1) 1 part Compound (5-2) 2.5 parts Acrylic polyol (Takelac A-702) 3.6 parts Epoxy resin (Epon 1007) 0.5 parts Methyl ethyl ketone 1.2 parts Cellosolve acetate A photoconductive composition is obtained by milling 1.2 parts or more of the composition in a magnetic ball mill for 48 hours.

Next, this composition was placed on an 80μ aluminum plate to a dry film thickness of 8μ.
The photoreceptor was coated with a wire bar so that the photoreceptor was coated with a wire bar, and placed in an oven uniformly heated to 110° C. for 1 hour to obtain a single-layer photoreceptor. According to Example 1, the sample thus obtained was measured as corona discharge +5.7 KV, and the maximum surface charge amount was 520 V, the dark decay rate was 12.4%,
Sensitivity 3.9 Lux-sec, residual potential -112■
Met.

Example 4 In Example 1, compound (2-1) was substituted for compound (1-1).
), and instead of polyester (sealing (Byron 200), polycarbonate resin (Panlite L-1250
), a laminated photoreceptor was produced in the same manner as in Example 1. When the sample thus obtained was measured in the same manner as in Example 1, the maximum surface charge amount was -720V, and the dark decay rate was 13.
, 2%, sensitivity 2. I Lux-seC9 residual potential-7
It was 2V.

Examples 5 to 16 Tests were conducted in the same manner except that the charge generating material and charge transporting material in Example 4 were replaced with the materials shown in the table below.

(The following is a blank space) [Effects of the invention] The present invention has the above structure, and when using it,
High sensitivity even for positive and negative charges. There is little deterioration of the photoreceptor due to repeated use, and from a practical standpoint, it has excellent charge retention ability from low to high temperatures and from low humidity to high humidity, environmental friendliness with respect to sensitivity changes, and durability.

Claims (1)

[Scope of Claims] 1. Contains at least one polycyclic quinone compound selected from the following general formula (1), (2) or (3) as a charge-generating material, and contains at least one polycyclic quinone compound selected from the following general formula (4) as a charge-transporting material. )
An electrophotographic photoreceptor comprising at least one hydrazone compound selected from (5) or (5). General formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents a halogen atom, a nitro group, a cyano group, an alkyl group that may have a substituent, an alkoxy group, an aryloxy group, or an amino group, and n represents an integer of 0 to 4.) General formula (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 or R_3 represents an alkyl group, an aralkyl group, or an aryl group that may have a substituent, R_
2 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. )