JPH02111962A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain a photosensitive body long in life by laminating an organic binder layer and a surface protective lubricant layer on the roughened surface layer of a photosensitive layer made of a specified material. CONSTITUTION:The surface layer of the photosensitive layer 101 is composed of an amorphous silicon hydride or amorphous carbon hydride type material and has a roughened surface, and it is coated with the organic polymer binder layer 21, and the surface protective lubricant layer 22 composed of perfluoropolyoxyalkyl groups or perfluoropolyoxyalkylene groups as a skeleton, thus permitting the obtained electrophotographic sensitive body to be enhanced in humidity resistance, cleanability, and abrasion resistance at the time of long repeated use, and prevented from peeling of the photosensitive layer, and extended in life.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an electrophotographic photoreceptor, and in particular to a hydrogenated amorphous silicon photoreceptor suitable for forming good images even when printed under high humidity. Regarding.

[Conventional technology]

Conventionally, Se and CdS have been used as electrophotographic photoreceptors.

Inorganic photoconductive materials such as As2S, etc. or organic photoconductive materials such as phthalocyanine-based gradients are used. Although these materials have excellent electrophotographic properties, their mechanical properties are low in hardness and 1Oi
It has drawbacks such as poor abrasion resistance.

In contrast, hydrogenated amorphous silicon (a-Si:
)() type photoreceptors have high hardness and excellent abrasion resistance, so they are expected to be long-life electrophotographic photoreceptors. However, the a-Si:H photoreceptor has the disadvantage of poor moisture resistance. For this reason, it has become common to provide a-SiC:H or the like as a surface protection base, but this is not sufficient.

In the electrophotographic printing process, there is a charging process due to corona discharge, so repeating the printing process oxidizes the surface protective layer and deteriorates the wettability. In order to prevent such moisture deterioration, for example, a-C:H:Fli as described in Japanese Patent Application No. 1982-22361, or
As described in No. 2 and Japanese Patent Application Laid-Open No. 55-70848, there is a method of providing a thermoplastic injection resin or resin model. but,
In the above method, there is a problem that 11 moisture properties and other 4 properties required for the surface protective layer of an electrophotographic photon, i.e., abrasion resistance and cleaning properties, are not necessarily compatible with each other. When the material is used for the surface protective layer, 1. Although the moisture resistance is greatly improved, there is a drawback that the ridge abrasion resistance and cleaning performance are significantly deteriorated.

[The problem that Teimei tries to solve]

In the above conventional technology, the electrophotographic photoreceptor's surface retention J't2 and 1- are required for 1, moisture resistance: f! jtIt is not possible to add each characteristic of abrasion resistance and cleaning property to γ,
There was a problem in that after turning over in the printing process, image deletion persisted due to high humidity, and the drawbacks of the a-3i:H:E light body could not be fully overcome.

The purpose of the present invention is to provide an electrophotographic J-8 optical body with a surface protective layer that has excellent moisture resistance and abrasion resistance and cleaning properties, thereby providing a long-life product that does not deteriorate even after repeated use. The purpose is to provide a photoreceptor.

[Failure to solve the problem]

As a result of intensive α research, the inventors of the Wooden Research Institute discovered that the above purpose was to create an a-3i:H system with unevenness on the surface of the photosensitive layer, an organic polymer binder layer and an organic fluorine-based surface on the outermost surface of the photoreceptor. The present invention has been completed based on the discovery that this can be achieved by forming the lubrication layer and the lubrication layer in one step.

That is, the present invention provides an electrophotographic photoreceptor having a two-light curve on the surface of a conductive substrate, in which the photosensitive layer is made of a bud of a hydrogenated amorphous silicon material or a hydrogenated amorphous carbon material having an uneven surface, An electrophotographic photoreceptor characterized in that a surface protective lubricant layer having a backbone of an organic polymer binder layer doperfluoropolyoxyalkylene group or perfluoropolyoxyalkylene group is formed on the surface of the photoreceptor. Regarding, also,
Irregularities are formed on the surface of the conductive substrate, and the surface of the j8 optical layer made of a hydrogenated amorphous silicon material or hydrogenated amorphous carbon material on the substrate is formed along the irregularities on the surface of the conductive substrate. A binder layer made of an organic polymer film is formed on the surface of the photosensitive screen, and the binder '4 contains a barf μ-olopolyoxyalkylene group or perfluoropolyoxyalkylene gel. The lubricant has a structure in which the non-fluorine-containing group is fixed in the binder layer, and the perfluoropolyoxyalkyl group or perfluoropolyoxyalkylene group is bonded to the binder layer. The present invention relates to an electrophotographic photosensitive material characterized in that a binder layer selectively precipitates on the surface to form a surface layer.

The fluorine-free group of the lubricant is embedded and fixed in the binder layer, thereby producing a four-child photoreceptor with excellent moisture resistance after corona irradiation, and excellent abrasion and cleaning properties. realizable.

The lubricant used in the present invention has the following structure (wherein Rf is perfluorinated polyoxyalkyl zy!,
Also, U perfluorinated polyoxyalkylene group, R1 is a direct bond or -CH, -Co-, -CON
H-.

R3 is a C2-C3 oxy--V7 group, R1 is a direct bond or 10-, -Coo-, -CONH-, -NH
CO-.

-0CxH1x- and -C(CHs)z- may be repeatedly different. a is an integer of 1 or 2, m is an integer of 0 or more, n is an integer of 1 or more, and X is an integer of 1 or 2).

When the above Rf is a perfluorinated polyoxyalkylene group, the following - formation % formula %).When the above Rf is a perfluorinated polyoxyalkylene group, the following - formation % formula %) (in the formula, t * 7 e z is An integer greater than or equal to 1, preferably t
is 5 or more, and y is 10 to 25.2 is 10 to 56). An example of these fluorine compounds is Krytx 143. commercially available from DuPont. Examples of S Rui include Hompurin Y1 and Hompurin 2 from Montefluos.

Specific examples of the lubricant include (in the formula, Rf barfluoropolyoxyalkyl group or perfluoropolyoxyalkylene group) The organic polymer binder used in the present invention is not particularly limited, but after curing It is necessary that at least a portion of the material be crosslinked. In the case of an a-Si:H photoreceptor, if the curing temperature is too high, hydrogen in the photosensitive layer will be desorbed and photoconductivity and other photographic properties will deteriorate. Those that harden in the following conditions are suitable.

Next, a typical example of a method for forming a binder opening, surface protection, and surface protection layer on the surface of an a-Si:H photoreceptor will be shown. A lubricant having a structure having a perfluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group and an appropriate known three-dimensional curing binder agent or plasticizing binder agent are mixed in an organic solvent in which they are well dissolved; For example, methyl ethyl ketone! = Dissolved in a mixture of vinegar, Butyl Cellsolve, and Freon Solvent. Thereafter, a layer of this bath liquid is exposed to light and formed on the surface of the layer. The forming method may be appropriately selected such as dipping method or spin coating method. After that, 8o-12
Swallow treatment is performed at 0°C for about 5 to 2 hours to evaporate the solvent. At this stage, since it has low affinity with the perfluorooxyalkyl J&H binder, it selectively precipitates on the surface of the binder layer to form a surface protective lubricating layer. The non-fluorine-containing groups are imbedded and fixed in the binder. Next, by performing heat treatment for 1 to 3 hours within a temperature range of 180 to 300"C, crosslinking of the binder 1 is promoted, and the fixation of the non-fluorine groups in the binder layer becomes stronger. The formation of the surface protection lubricant 1 is also completed.

If the thickness of the binder buds and the surface protection lubricant 1 are too thick, it is undesirable as it increases the residual potential in the electrophotographic properties, and the total thickness of both is usually 10 nm to 500 nm, and preferably 100 nm or less.

If the thickness is 100 nm or less, even if the organic polymer layer described above is formed, there will be no effect on the light guide tt4:, charging characteristics, etc.

Further, it is preferable that the lubricating layer for the surface body M has a total area ratio of 1 or more of the exposed portion of the surface body and the lubricating layer to the exposed portion of the surface body M that is photosensitive to 7 gJ.

In the present invention, a known hydrogenated amorphous silicon photoreceptor can be used as the photosensitive layer, but specifically, 1 of hydrogenated amorphous silicon thread material q is a-81:
H: B, a-SiC: H: B, a-3
iC:H,a-3iC)e:H,a-SiGe:H
:B.

a-SiN: Consists of one or more types of buds selected from the group consisting of H, and the layer of hydrogenated amorphous carbon material contains one or two types of a-C:H, a-C:H:F. and the photosensitive surface residue is a-SiC
: H, a-SiN: H, a-C: H.

From the group consisting of a-C:H:F, -j or two or more 1s are used.

By forming irregularities on the surface of the photoconductive substrate, similar irregularities can be formed on the 16-light beam 11, thereby improving the adhesion between the substrate surface and the photosensitive layer.

[Effect]

In the electrophotographic photoreceptor of the present invention, an inner tube is prepared by mixing a lubricant having a structure in which a perfluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group is combined with a non-fluorine-containing group. By surface protection,
- forms a perfluoropolyoxyalkyl group or a perfluoropolyoxyalkyl group -de, which selectively precipitates on the surface of the four layers to form a surface protective lubricating layer,
Non-fluorine groups are embedded and fixed in the binder layer.

The concentration of the fluoropolyoxyalkyl group precipitated on the surface varies depending on the binder concentration or lubricant concentration of the coating solution, but under the best conditions, the fluorine content on the surface of the protective lubricant layer is higher than that of Teflon. q, s
/1o, the fluorine surface strength (result of fluorine strength analysis by XPS (X-ray light', seed spectroscopic analysis)) is higher than that of Teflon, with an intensity ratio of 3/4.

Therefore, moisture resistance is greatly improved and the wear coefficient of one surface is reduced, so that wear resistance and cleaning properties are improved, and an electrophotographic photoreceptor with a long life can be obtained.

〔Example〕

Hereinafter, an example of the present invention will be explained using a broom 1 diagram, but the present invention is not limited to these embodiments.

Example 1 FIG. 1 shows a model of a-3L:
FIG. Outer diameter φ262X
Irregularities of 1 μm or less and a1 μm or more were formed on the surface of the At drum base 10 having a length of 4301 mm. The depth of the unevenness depends on the thickness of the gold film on the surface, and optimally the depth of the unevenness is [15
μm is good. Further, by making the surface of the substrate uneven, the adhesion of the photosensitive layer 1o1 is increased and film peeling is prevented.

On this substrate, as a representative example, a-3iC:H:B blocking, vll of 2 μm, a-3i:H:B 1t
The surface protection 1.13 of 30 pm% a-SiC:H was applied to the M generation conveyance 112 to a thickness of 0.5 μm. Here, the blocking layer also contains a-SiC: H, a-Si
N: H% A-SiGe: H for charge generation and transport to achieve high sensitivity at long wavelengths, a-S for surface body, a-S for capture
iN:H, a-C:H.

The product j may be one or more of a-C:H2F. a-Si: H1 Morimitsu, Tome 101 is made of glass.

High frequency power 500W, discharge pressure 6
7Pa, substrate temperature 250°C1 reaction gas total flow 6005
These are the manufacturing conditions for can.

Next, take out this photoreceptor from the plasma CVD equipment,
Organic surface protection according to the present invention i! I fabricated l11201. As a coating liquid, methyl ethyl ketone 13002, ethylene glycol acetate p7)-〇-butyl ether/l/13
0 t, a solvent mixed with 65 t of freon solvent, 4.4 t of epoxy resin, and 10 f of pheno-TV resin.
, ) Rie 1,000μ ammonium caulibol salt cL04t
are mixed, and the chemical structural formula is [where Rf is F (CF (C
Fs)-CF2O-)n-CF(CFs)-in
= average 14] was prepared by further mixing α4t with lubricant 23. Add the above a-Si-H to this solution.
The photoreceptor was immersed to form a film of organic binder 1 on the surface, and then preheated at 100°C for 1 hour and heat-cured at 200°C for 2 hours to complete organic surface body 514201. By heating after film formation, perfluoropolyoxyalkyl groups of the lubricant are oriented and precipitated on the surface of the organic binder W21, a surface protective lubricant 122 is formed, and non-fluorine-containing groups of the lubricant are embedded in the organic binder buds 21. An offer is made.

The thus obtained photoreceptor was mounted in a laser beam printer, and a printing test was conducted in a temperature and humidity room for 4 hours.

The temperature in the constant temperature and humidity chamber is within the range of 20°C to 25°C.
Additionally, the relative humidity was varied up to 80%. At this time,
No image deletion was observed and good printing performance was obtained.

Example 2 An a-si:H photoreceptor was produced in the same manner as in Example 1, and then the lubricant 7 shown in Table 1 was added to the coating solution of Example 1.
The seed term was replaced with an organic surface body M@. A printing test was conducted on the obtained photoreceptors under the same conditions as in Example 1, and it was found that no image deletion occurred and good printing performance was exhibited in all cases.

Table 1 [In the formula, Rf is F(CF(CFs)-CF2O-Kun-CF
(CFs)-, n = average 14] [Effects of all questions] According to the present invention, the organic binder and surface protection lubricant of Muki-Ki;
:H (fl) By sequentially forming on the photoreceptor, it has a long lifespan that is temperature resistant, easy to clean, prevents premature wear, and prevents the photoreceptor from peeling off during long-term repeated use. An electrophotographic photoreceptor can be realized.

[Brief explanation of the drawing]

Figure 1 shows the present invention, a painful case of a-Si:H system,
FIG. 3 is a vertical cross-sectional view of a light body. 10...At base 11...Blocking study 1
2...Charge generation electric transmission 113...Surface floor brightness 101-
a-Si: H photosensitive 21...Organic binder 22...Organic surface protection l National information 1 23...Lubrication 41 201...Organic surface body 1 Season 1 Figure 1

Claims (1)

[Scope of Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, wherein the photosensitive layer is made of a layer of a hydrogenated amorphous silicon material or a hydrogenated amorphous carbon material having an uneven surface, An electrophotographic photoreceptor characterized in that a surface protective lubricant layer having an organic binder layer and a perfluoropolyoxyalkyl group or a perfluoropolyoxyalkylene group as a skeleton is formed on the surface of the photosensitive layer. 2. Irregularities are formed on the surface of the conductive substrate, and the surface of the photosensitive layer made of a layer of hydrogenated amorphous silicon material or hydrogenated amorphous carbon material on the substrate is
Irregularities are formed along the irregularities on the surface of the conductive substrate, and a binder layer made of an organic polymer film is formed on the surface of the photosensitive layer. The lubricant contains a structure in which a fluoropolyoxyalkylene group and a non-fluorine-containing group are combined, and the non-fluorine-containing group is fixed in a binder layer, and a perfluoropolyoxyalkyl group or a perfluoropolyoxy An electrophotographic photoreceptor characterized in that alkylene groups are selectively precipitated on the surface of a binder layer to form a surface protective lubricant layer. 3. The photosensitive layer includes a layer of hydrogenated amorphous silicon material such as a-Si:H:B, a-SiC:H:B, a-S
iC:H, a-SiGe:H, a-SiGe:H:B,
Consisting of one or more layers selected from the group consisting of a-SIN:H, and the layer of hydrogenated amorphous carbon material is one selected from a-C:H and a-C:H:F. The surface layer of the photosensitive layer is a-SiC:
The electron according to claim 1 or 2, characterized in that it is composed of one or more layers selected from the group consisting of H, a-SIN:H, a-C:H, and a-C:H:F. Photographic photoreceptor. 4. The electrophotographic photoreceptor according to claim 1 or 2, wherein a total area ratio of the exposed portion of the surface protective lubricant layer to the exposed portion of the photosensitive layer is 1 or more. 5. Claims 1 and 2, characterized in that the surface protective lubricating layer and the binder layer have a total thickness of 10 to 300 nm.
or 4. The electrophotographic photoreceptor according to 4. 6. After forming an organic polymer binder layer containing a lubricant having a structure in which a perfluoropolyoxyalkyl group or a perfluoropolyoxyalkylene group and a non-fluorine-containing group are combined on the surface of the photosensitive layer having irregularities, 3. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is subjected to heat treatment.