JPH03245154A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance durability and adhesiveness of a photosensitive layer by forming a coating film containing a polysilane and conductive particles on a metallic substrate and backing it into a ceramic state to form a conductive layer. CONSTITUTION:The coat film containing the conductive particles and the polysilane is formed on a metallic substrate and backed to >= 300 deg.C into a ceramic state to form the conductive layer. The polysilane is allowed to form Si-C bonds to convert it into the ceramic superior in strength, hardness, abrasion resistance, heat resistance, and corrosion resistance but low in conductivity, therefore, it is preferred to add the fine conductive particles in order to use it for the conductive layer of the phtosensitive body. The fine conductive particles can be embodied by particles of SnO2, In2O3, TiO2 treated to enhance conductivity, and carbon, and the like or powders of Al, Cu, Fe, and the like, thus permitting high image-quality to be maintained at the time of repeated uses, high in resistance to cracking and peeling, and enhanced in adhesiveness.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor that has excellent mechanical and electrophotographic durability, box quality, and production stability. Regarding.

Explanation of the prior art] Since it was discovered that certain organic compounds exhibit photoconductivity, many organic photo-conductors have been developed2. organic photoconductive polymer, kalhagul,
Low-molecular organic photoconductors such as anthracene, bilagrins, oxadiazoles, hydrazones, polyarylalkanes, phthalocyanine pigments, azo pigments, aninine 12114, polycyclic quinone pigments, perylene pigments, indigo dyes, thioindigo Dyes, or IIIfi materials and dyes such as methine squaric acid dyes are known.

In particular, photoconductive pigments and dyes are easier to synthesize than inorganic materials, and the variety of compounds that exhibit photoconductivity in an appropriate wavelength range has expanded, making it possible to use a large number of photoconductive compounds. IL'gi-based organic dyes have been proposed, e.g., U.S. Patent No. 4.123.
．． No. 270, No. 4.247.614, No. 4.25
], No. 613, No. 4.251.614, No. 4,2
No. 56,821, No. 4,260,672, No. 4,
No. 268.596, No. 4.278,747, No. 4
, 293.628, etc.! 1 in the photosensitive layer which is functionally separated into a load generation layer and a 1i transport layer.
Electrophotographic photoreceptors using disazo pigments that exhibit photoconductivity are known as an example of IFI.

An electrophotographic photoreceptor using such an organic photoconductor is
By appropriately selecting the binder, it is possible to form a coating, making it possible to provide a photoreceptor with extremely high productivity and low cost.Moreover, it has the advantage that the sensitive wavelength range can be freely controlled by selecting the mR material. .

Among them, a laminated photoreceptor is obtained by laminating a charge transport layer and a charge generation layer mainly composed of a charge generation material.
It has better residual potential, memory, repeatability, etc. than other single-layer photoreceptors, and is especially advantageous in improving sensitivity. However, in recent years, a-5e series, CdS series, a-3
It has the same or higher sensitivity, memory, repeatability, and durability as high-sensitivity IL-free photoreceptors such as the i-series! Development of photoreceptors is desired. However, the current situation is that there are still many unresolved problems in the development of such high-performance It-containing photoreceptors.

In other words, there is #! The photoconductor has weak mechanical strength, and is used in copying machines,
When used in printers, etc., pinholes, minute cracks, friction at the edges, peeling, etc. occur on the photoreceptor, causing image defects.

In addition, the organic photoreceptor is placed on a conductive support with a thickness of 10 to 40 μm.
It is customary to use a thin M2 cloth to remove impurities, scratches, etc. on the support.
Defects such as dents and bubbles easily cause disturbances in the coating film, causing image defects.

In particular, in the case of so-called functionally separated organic photoreceptors, which emit i+ by laminating a charge transport layer (CTL) on top of an IIT charge generation layer (CGL), they have extremely high sensitivity and low residual potential. However, on the other hand, it has the disadvantage of increasing dark decay and optical memory, and to counter this, it is necessary to make the charge generation layer even thinner (generally 0.01 to 6 μm). Therefore, the protrusions on the support At present, it is more susceptible to defects such as dents, scratches, and dents, causing various image defects and making it impossible to obtain high-quality images.

In order to solve this problem, attempts have been made in recent years to provide a conductive layer containing an organic polymer as a main component between the support and the charge generation layer. According to this method, image defects,
ii due to repeated use! j It is possible to reduce the deterioration in quality.

However, since the thickness of the conductive layer is usually 10 to 50 μm, it is necessary to make the electrical resistance considerably low. Generally speaking, 101 ohms, preferably IQ1! A specific resistance value of Ω·■ or less is required, and techniques for blending organic or inorganic conductive substances, ionic substances, etc. into organic polymers are also known in order to achieve this goal. Such conductive layers often have tty injection properties.

Furthermore, the surface properties of the conductive layer have a large effect on image characteristics and durability characteristics. In particular, if sufficient adhesive strength cannot be obtained between the conductive layer and the photosensitive layer, pinholes, cracks from the edges of the photosensitive layer, peeling, cracking, etc. may occur when the photoreceptor is used for a long time. This causes a significant decrease in properties and durability.

For example, by using a thermosetting resin as the organic polymer of the conductive layer, g-friction, peeling, etc., especially at the end of the photoconductor, should be further improved, but if the surface is smooth, The adhesive strength between the photosensitive layer and the photosensitive layer is rather lower than when a thermoplastic resin is used.

As described above, at present, a conductive layer on a photoreceptor support that is resistant to mW due to durability, peeling, etc., and has high adhesive strength with the photosensitive layer has not been obtained.

In addition, in the case of a photoconductor with exposed metal at the end of the photoconductor,
There is also the problem that the metal support is subject to wear and tear due to durability.

[Purpose of the invention]

An object of the present invention is to provide an electrophotographic photoreceptor that maintains high image quality even during long-term use, is resistant to cracking and rolling of the photosensitive layer, and has excellent adhesive properties, that is, has high image quality and high durability. There is a particular thing.

Another object of the present invention is to provide an electrophotographic photoreceptor free from image defects caused by protrusions, dents, scratches, and dents on the support.

[Structure and effects of the invention]

The electrophotographic photoreceptor of the present invention is characterized in that a coating film containing conductive particles and borinelan is formed on a metal support, and a conductive layer is formed by firing at 300° C. or higher to form a ceramic.

Hereinafter, the structure of the electrophotographic photoreceptor of the present invention will be explained in detail.

In the present invention, a coating film containing conductive particles and one or more polysilanes is formed on a metal support. Examples of polysilanes include the following.

1sopropyl Me Borinlan produces Si-C bonds by firing and becomes a ceramic. Although the 5i-C sintered body has excellent strength, hardness, abrasion resistance, heat resistance, and corrosion resistance, it has low conductivity, so when it is used as a conductive layer of a photoreceptor, it is necessary to add conductive fine particles.

As conductive fine particles, S n Ch, I nzO
s, conductive treatment T i○2. Particles such as carbon, A
N powder.

Examples include Cu powder and Fe powder. The amount of conductive fine particles added is preferably 0.5 to 50% by weight based on the total weight of the conductive layer.

The electrophotographic photoreceptor of the present invention basically consists of a support, a conductive layer, an adhesive layer, and a photosensitive layer in order from the bottom layer, and the photosensitive layer is a charge generation layer (CGL) and a charge transport layer. (
In the so-called functionally separated photoreceptor consisting of CGL and CTL, in the structure when CGL and CTL are laminated in this order,
The most significant effect. However, even when the photosensitive layers are laminated in the order of CTL and CGL, the present invention can be an effective technique even when the adhesion between the CTL and the adhesive layer is particularly poor.

Supports used in the present invention include metal, sheet-like,
Although various shapes such as a belt shape and a cylindrical shape are possible, the conductive supports shown below are common.

For example, aluminum, aluminum alloy, copper, zinc,
Stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold, platinum, etc. can be used.

Next, in most cases, the layers after the contact layer are coated with a solution dissolved or dispersed in a solvent. When forming a layer by coating, use coating methods such as dip coating, spray coating, spinner coating, bead coating, Meyer bar coating, blade coating, roller coating, and curtain coating. It can be carried out.

The Wi4 thickness of the conductive layer used in the present invention should be set to an optimal value depending on the surface condition of the support (scratches to unevenness, dents, etc.), and can be set widely from about 0.5 to 100 μm. Usually it is about 10 to 50 μm.

In the present invention, as a method for forming a conductive layer, the above-mentioned polysilane is dissolved in Hensen, toluene, hexene, tetrahydrofuran, dioxane, etc., and a solution to which conductive powder is added is coated on a metal support, Heat to 300°C or higher. At this time, after drying at low temperature to form a coating film,
It is preferable to heat and bake by raising the temperature to 00° C. or higher.

The adhesive layer is required to be able to prevent carrier injection from the support or conductive layer to the photosensitive layer, and to have an electrical resistance of 150 or less compared to the photosensitive layer. In general, many have high electrical resistance, and therefore the proper WIJ thickness is 5 μm or less, preferably 0.1 to 2 μm.

Examples of materials used as the adhesive layer include casein, gelatin, polyamide (nylon 6, nylon 66, etc.).
, nylon 6]0, copolymerized nylon, alkoxymethylated nylon), polyurethane, polyvinyl alcohol,
Nitrocellulose resin, ethylene-acrylic acid copolymer resin, phenolic resin, acrylic resin, polyester,
Examples include polyether.

The charge generation layer is formed by applying and drying a coating liquid in which a charge generation substance as described below is dispersed in a suitable binder resin.

The charge generating substance used in the present invention is a pigment, but even a dye soluble in a solvent can be used by selecting a solvent and forming particles.

Examples of charge-generating substances include phthalocyanine pigments, anthanthrone pigments, dihenzbilene pigments, vilanthrone pigments, azo pigments, indigo pigments, quinacridone pigments, cyanine dyes, scuvialylium dyes, azulenium salt compounds, pyrylium, thiopyrylium dyes, and xanthine dyes. Examples include dyes, quinoneimine dyes, triphenylmethane dyes, and styryl dyes.

The charge transport layer includes chloranil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2.4.7
-Dolinitro-9-fluoreno, 2.4,5.7-tetranitro-9-fluorenone, 2.4.71linitro-
9-dicyanomethylenefluorenone, 2,4.5.7-
Electron-withdrawing substances such as titranitroxanthone, 2,4.8-)linitrothioxanthone, molecularized substances of these electron-withdrawing substances, or pyrene, N-ethylcarbazole, N-isobrobylcarbadul, N-methyl -N
-Phenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino 3-methylidene-10-ethylphenothiazine, N,N -diphenylhydrazino-3-methylidene]
1.3 .1) Hydrazones such as trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone, p-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazine, 2,5-bis(p -diethylaminophenyl)-
1,3,4-oxadiazole, 1-phenyl-3-(
p-diethylaminostyryl)-5-(p-diethylaminophenyl) birapurine, 1- [quinolyl + 21)
-3-(p-diethylaminostyryl)-5-(p-
diethylaminophenyl)pyrazoline, ■-[pyridyl(213-3-<p-diethylaminostyryl)-5-
(p-diethylaminophenyl)pyrazoline, 1-[6-
Medkin-pyridyl f21) -3-(p-diethylaminostyryl)-5-(p-diethylaminophenyl)
Birapurine, 1-(pyridyl f31)-3(p-diethylaminostyryl)-5-(p-diethylaminophenyl)pyrazoline, 1-[Levidyl+211-3-(p-
diethylaminostyryl)-s-(p-diethylaminophenyl) birapurine, 1- [pyridyl (2)]-3
~(p-diethylaminostyryl)-4-methyl-5-
(p-diethylaminophenyl) birapurine, 1-(pyridyl(21)-3-(α-methyl-p-stylaminostyryl)-5-<p-diethylaminophenyl)pyrazoline, 1-phenyl-3-(p~ diethylaminostyryl)-4-methyl-5-(p-diethylaminophenyl>pyrazoline, 1-phenyl 3-(α-benzyl-
p-diethylaminostyryl) -5-(p-diethylaminophenyl) birapurines such as spirovirapurine, 2-(p-stylaminostyryl) -6
-Oxazole compounds such as dinithylaminobenzoxazole, 2-(p-diethylaminophenyl)-4-(p-dimethylaminophenyl)-5-(2-chlorophenyl)oxazole, 2-(p-diethylaminostyryl)-6- Thiazole compounds such as diethylaminobenzothiazole, triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)phenylmethane, 1,1-bis(4-N,N-diethylamino-
2-methylphenyl)hebutane, l, 1.2.Poly7lylalkanes such as 2-tetrakis(4-N,N-dimethylamino-2methylphenyl)ethane, α-phenyl-4-N,N'- Diphenylaminostilbene, N-
Ethyl-3<α-phenylstyryl)carbazole 4-N
, styryl compounds such as N'-dibenzylamino-9-fluorenylidene, triphenylamine, poly-N-
Vinyl carbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9 vinylphenylanthracene, pyrene-formaldehyde resin,
Applying a coating liquid in which a hole-transporting substance such as ethylcarbazole formaldehyde resin is dissolved in a film-forming resin,
Formed by drying.

Furthermore, these ':L transport substances can be used in combinations of 211 or more.

As a binder, polyarylate resin, polysulfone resin, polyamide resin, acrylic resin, acrylonitrile #d! iIa, methacrylic resin, vinyl chloride resin, vinyl acetate resin, phenolic resin, epoxy resin, polyester resin, alkyd resin, polycarbonate, polyurethane, or copolymer resin containing two or more repeating units of these resins, such as styrene. Butadiene copolymer styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, etc. can be used.

The thickness of the photosensitive layer is 5 to 50 μm, preferably 10 to 30 μm.
m, but in the case of a functionally separated type in which CGL and CTL are laminated in this order, CGL is 0.01 to 5 um, preferably 0.
．． 05-3pm, CTL is 5-50μm, preferably 1
0 to 30 μm is appropriate.

If necessary, a protective layer containing an organic binder as a main component may be added.
It may be provided as the top layer with a film thickness of 5 to 10 μm.

Further, a lubricating substance, an ultraviolet absorber, and an antioxidant may be included in the uppermost layer.

The electrophotographic photoreceptor of the present invention can be applied to electrophotographic devices W-1Q such as copying machines, LBPs (laser beam printers), LED printers, LCD printers (liquid crystal shutter printers), and microreader printers.
Furthermore, it can be widely applied to devices that apply electrophotographic technology, such as display, recording, light printing, plate making, and facsimile.

By using the electrophotographic photoreceptor of the present invention, strength,
A photoreceptor having an a1'gj layer with excellent hardness and abrasion resistance could be obtained. The conductive layer formed by the polysilane pit bottom is resistant to abrasion and peeling due to durability, and has high adhesive strength with the adhesive layer, resulting in a highly durable electrophotographic photoreceptor.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these in any way.

23 parts by weight of raw electrically conductive titanium oxide and 1 part by weight of 7 parts of polysilane shown by the structural formula below were mixed with 100 parts by weight of toluene, and the dissolved liquid was poured into an 80φ stainless steel cylinder. The film was coated by dipping and dried at 120°C for 20 minutes.Furthermore, it was burnished at 500°C for 30 minutes to bond the polysilane with 5i-C to form a ceramic conductive layer. The film thickness at this time was 20 μm.

Next, copolymerized nylon resin (product name: Amilan CM800)
0, made by Toshi) (parts by weight, the same applies hereinafter) and 8 parts of a copolymerized nylon resin (trade name: Niresin EF30T made by Teikoku Kagaku) were dissolved in a mixed solution of 60 parts of methanol and 40 parts of phthanol, and then melted on the above conductive layer. An adhesive layer with a thickness of 1 μm was provided by dip coating.

Next, 10 parts of a disazo pigment having the following structural formula, 6 parts of vinegar #cellulose butyrate #J resin (II product name: CAB-381; manufactured by Eastman Chemical) and 60 parts of cyclohexanone were mixed in a sand mill apparatus using 1φ glass beads for 20 hours. Dispersed. Add 100 parts of methyl ethyl ketone to this dispersion,
The adhesive layer was coated by dip coating on the adhesive layer and dried by heating at 100° C. for 10 minutes to provide a single charge generation layer with a coating weight of 1 g/m'.

Next, 10 parts of a hydrazone compound having the following structural formula and a polycarbonate resin (trade name: Panlite L-
1250; Teijin Chemical Co., Ltd. (15 parts) was dissolved in 80 parts of dichloromethane. Apply this liquid on the charge generation layer ii above and
Hot air drying was performed at 00° C. for 1 hour to form a 20 μm thick T cargo transport layer.

Copy II (NP352) of photoreceptor 1 thus formed.
5 (manufactured by Canon) to produce images. W after initial and 50,000 image durability! Table 1 shows if. Note that the exposure amount was 3 lux·sec.

Otsuki Group A photoreceptor was produced in the same manner as in Example 1, except that the polysilane of the conductive layer in Example 1 had the following structural formula.

Evaluation of the photoreceptor was also conducted in the same manner as in Example 1, and is shown in Table 1.

The polysolane in the conductive layer of Example 1 has the following structural formula 1soP
A photoreceptor was produced in the same manner as in Example 1, except that ropyl Me was used, 17 parts of carbon powder was used as the conductive particles, and 83 parts of polysilane were used.

Evaluation of the photoreceptor was also conducted in the same manner as in Example 1, and is shown in Table 1.

A photoreceptor was produced in the same manner as in Example 1, except that the polysilane in the conductive layer of Example 1 had the following structural formula, the conductive particles were 17 parts of AI powder, and 83 parts of porinlan.

Evaluation of the photoreceptor was also conducted in the same manner as in Example 1, and is shown in Table I.

Otoyo Mawari The polysolane in the conductive layer of Example 1 is expressed by the following structural formula: (Si)x,.

A photoconductor was prepared in the same manner as in Example 1, except that the conductive particles were SnO, 23 parts of powder, and 77 parts of porinlan, and the firing conditions were 550° C. for 30 minutes. The results are shown in Table 1.

A conductive layer was dip-coated on the scanning panel in the same manner as in Example 1, and the coating was applied at 120°C and 20°C.
After drying under pressure for several minutes, it was fired at 250° C. for 30 minutes. The conductive layer was laminated in the same manner as in Example 1 to form a photoreceptor.

The evaluation method was performed in the same manner as in Example 1, and the results are shown in Table 1.

(100 parts by weight of U-grown conductive titanium oxide powder, 1 part by weight of titanium oxide powder)
200 parts by weight of the phenol resin were mixed with a solvent of 50 parts by weight of methanol and 50 parts by weight of methylcellosolve, and then dispersed in a Sun 1' mill for 6 hours. This dispersion was applied by dipping onto an 80φ aluminum cylinder, heated and dried at 150°C for 20 minutes, and 20μ
m conductive layers were provided.

On the obtained conductive layer, an adhesive layer is formed in the same manner as in Example 1, and 1 is a charge generation layer. A photoreceptor was produced by sequentially laminating the material and the cargo transport layer.

The evaluation method was performed in the same manner as in Example 1, and the results are shown in Table 1.

(The following is a blank space) [Summary of the effects of the invention] The present invention provides an electronic device in which a coating film containing polysilane and conductive particles is formed on a metal support, and a conductive layer is formed by firing at 300°C or higher to form a ceramic. By using a photographic photoreceptor, it is possible to obtain a photoreceptor with excellent adhesiveness that is durable for long-term use, maintains high image quality, and resists cracking and peeling of the photosensitive layer. Further, by using the electrophotographic photoreceptor of the present invention, it is possible to obtain an electrophotographic photoreceptor free from image defects caused by protrusions, dents, scratches, and dents on the support. Further, by using the electrophotographic photoreceptor of the present invention, it is possible to prevent the ends of the photoreceptor from being worn out.

Claims (1)

[Claims] An electrophotographic photoreceptor using a metal support, characterized in that a coating film containing conductive particles and polysilane is formed on the metal support, and a conductive layer is formed by firing at 300°C or higher to form a ceramic. A photoreceptor for electrophotography.