JP2003005410A - Electrophotographic photosensitive member, process cartridge having the electrophotographic photosensitive member, and electrophotographic apparatus - Google Patents

Abstract

(57) [Problem] To provide an injection-charging type electrophotographic photosensitive member that does not cause image defects such as fog images due to charging failure. SOLUTION: The charged particles having a particle size of 10 μm to 10 nm, and an elastic charged particle carrier that carries the charged particles, and the resistance of the particles carried on the carrier is 10 ^12.
〜１０10 ^-1 Ω · cm, and the loading amount of the particles is 0.1 mg.
/ Cm ² ５０50 mg / cm ^{2 In} an electrophotographic photoreceptor used in an electrophotographic apparatus having a charging device of an injection charging method, the difference between H and the indentation depth of an indenter in a surface film physical property test on a surface layer of the photoreceptor is obtained. The curve showing the relationship has no inflection point, HU is 200 or more, (1) E is 6.0 to 9.0, (2) H plast is 1.2 times or more to HU, (3) An electrophotographic photosensitive member that satisfies any one of 30% or more of Wt with respect to Wt, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used in an injection charging process, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art Conventionally, as a charging means of an electrophotographic apparatus,
Corona chargers were widely used. The corona charger is a non-contact type charging device, and is provided with, for example, a discharge electrode such as a wire electrode and a shield electrode surrounding the discharge electrode, and the discharge opening is opposed to the image carrier, which is the body to be charged, to make non-contact. And exposing the image carrier to a discharge current generated by applying a high voltage to the discharge electrode and the shield electrode, the surface of the image carrier is charged to a predetermined potential.

On the other hand, in recent years, since it has advantages such as low ozone and low electric power as compared with a corona charger, a contact system in which a charging member to which a voltage is applied is brought into contact with the charged member to charge the charged member. The charging device (contact charging device) has been put into practical use.

In the contact charging device, an electrically conductive charging member such as a roller type (charging roller), a fur brush type, a magnetic brush type, or a blade type is brought into contact with a member to be charged which is an image bearing member, and the charging member is brought into contact with the charged member. A predetermined charging bias is applied to charge the body to be charged to a predetermined potential.

Further, the contact charging mechanism includes two types of charging mechanisms, (1) discharge charging mechanism and (2) direct injection charging mechanism.

For example, a roller charging method using a conductive roller (charging roller) as a contact charging member is preferable from the viewpoint of stability of charging and is widely used. In this roller charging, the charging mechanism is a discharge charging mechanism. Dominate.

Since the discharge charging system has a constant discharge threshold value between the contact charging member and the member to be charged, it is necessary to apply a voltage higher than the charging potential to the contact charging member. Further, although the generated amount is remarkably smaller than that of the corona charger, it is unavoidable that discharge products are generated, so that the harmful effect of active ions such as ozone is unavoidable.

Therefore, a direct injection charging method in which charges are directly injected from the contact charging member to the charged body to charge the surface of the charged body is disclosed in Japanese Patent Application No. 04-158128 and Japanese Patent Application Laid-Open No. 06-003921. Has been proposed by.

According to this method, the contact charging member having a medium resistance comes into contact with the surface of the body to be charged, and the charge is directly injected onto the surface of the body to be charged without going through the discharge phenomenon, that is, basically without using the discharge mechanism. It is something to do. Therefore, even if the voltage applied to the contact charging member is equal to or lower than the discharge threshold value, the member to be charged can be charged to a potential corresponding to the applied voltage. This direct injection charging mechanism does not cause the generation of ions, so that no harm is caused by the generation of discharge.

Among the injection charging methods, the following charging means are provided as means for realizing stable charging for a long period of time with excellent charging uniformity by using a simple and low-cost charging member such as a charging roller or a fur brush. A device is mentioned. The charged particles are mainly composed of conductive particles having a particle size of 10 μm to 10 nm, and a charged particle carrier that carries the charged particles and has a surface having conductivity and elasticity, and the charged particles are electrophotographic. A charging means for contacting a photoreceptor and charging the surface of the electrophotographic photoreceptor, wherein the resistance of the particles carried on the carrier is 10 ¹² -10 ^-1 Ω · cm,
The supported amount of the particles is 0.1 mg / cm ^{2 to} 50 mg / cm ^2.
Is. As a result, sufficient contact property can be obtained in direct charging, and uniform charging is possible.

[0011]

However, in the injection charging system in which the conductive particles are present on the contact surface between the charging member and the photoreceptor as described above, the photoreceptor is rubbed by the conductive particles and the photoreceptor. There is a problem in that scratches occur, charging defects occur in that portion, and image defects such as a fog image occur from there.

An object of the present invention is to provide an electrophotographic photoconductor which does not cause image defects such as a fog image due to charging failure by suppressing scratches on the photoconductor caused by conductive particles when the injection charging method is used. Another object of the present invention is to provide a process cartridge having the electrophotographic photosensitive member and an electrophotographic apparatus.

[0013]

Means for Solving the Problems That is, the present invention comprises charged particles containing conductive particles having a particle diameter of 10 μm to 10 nm as a main component and a surface having conductivity and elasticity, and carrying the charged particles. Is a charging means for charging the surface of the electrophotographic photosensitive member by contacting the electrophotographic photosensitive member, and the resistance of the particles carried on the supporting member is 10 ¹² to 10 10. a ^{-1 Ω} · cm, an electrophotographic photosensitive member used in an electrophotographic apparatus supporting amount of said particles have a charging device which is ^{0.1mg / cm 2 ~50mg / cm 2} , to the surface layer of the photosensitive member Constant environment (22.
The curve showing the relationship between the hardness H and the indentation depth in the surface film physical property test at 5 ° C., 50% RH) has no inflection point, and the universal hardness value HU is 200 or more, and (1), (2), (3) are all satisfied.

(1) A constant environment of the electrophotographic photosensitive member (2
Young's modulus E in the surface film physical property test at 2.5 ° C., 50% RH) is 6.0 [GPa] or more, 9.0 [GP]
a] or less.

(2) A constant environment of the electrophotographic photosensitive member (2
The hardness value H plast of plastic deformation in the surface film physical property test at 2.5 ° C. and 50% RH) is 1.2 times or more that of HU.

(3) A certain environment (2
The work amount We of elastic deformation in the surface coating physical property test at 2.5 ° C., 50% RH) is 30% with respect to the total work amount Wt.
That is all.

Further, the present invention is a curve showing the relationship between the hardness H and the indentation depth of the surface layer of the electrophotographic photosensitive member in the physical property test of the surface film in a constant environment (22.5 ° C., 50% RH). Has no inflection point, the universal hardness value HU is 200 or more, and (1) above,
An electrophotographic photosensitive member characterized by satisfying all of (2) and (3).

The present invention also provides a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The physical property test of the surface coating of the present invention is carried out by a hardness meter Fischerscope H manufactured by Fischer GmbH, Germany.
100 was used (see FIG. 5). This test is for thin film,
It is possible to analyze the hardness of a cured film or an organic film, and at the time of preparation of the sample, the film was formed to a film thickness of about 10 μm so as not to be affected by the base. Therefore, the base is not particularly limited to a glass plate, an aluminum plate, an aluminum cylinder, or the like. The curing conditions and the like were exactly the same as in the production of the photoreceptor. In the measurement, a diamond indenter 7 having a shape of a quadrangular pyramid and a facing angle of 136 ° is used, and when the set load is gradually pushed into the film, the indentation depth under the load is applied. The hardness value H is displayed by the ratio of the test load divided by the surface area of the indentation generated by the test load. The universal hardness value HU is represented by the hardness value at the set maximum indentation depth. In FIG. 5, 5 is an aluminum cylinder on which only the surface layer is formed, 6 is a photosensitive member stand, 8 is a movable table, and 9 is a microscope position.

FIG. 1 is a graph showing an example of the result of the physical property test of the surface film using the above hardness tester. The unit of each physical property in the present invention is also shown.

(1) HU ... Universal hardness [N / mm ² ] 224.9 (2) Wt ... Total work [nJ] 48.73 (3) We ... Work of elastic deformation [nJ] 20.43 41 .92% (4) Wr ... Work of plastic deformation [nJ] 28.30 58.08% (5) E / (1-ν ² ) ≈E ... Young's modulus [GPa] ν (<< 1) ... Poisson Ratio 5.87 ± 0.15 (6) H plast ... Hardness value of plastic deformation [N / mm ² ] 370 ± 5 (7) hr ′ ... Intersection point [μm] of tangent to curve BC and x-axis 2. 262 ± 0.015

Point A is the measurement start point. A → B is a curve corresponding to the pushing of the indenter. Point B is the point when the maximum set indentation depth is reached, and the value obtained by dividing the load at point B by the surface area of the indentation generated at that time is the universal hardness value HU. The curve B → C is a curve corresponding to “return” after the indenter is pushed. That is, this curve corresponds to the elastic content of the measurement sample. When a straight line passing through two points corresponding to 95% and 60% of the maximum load is drawn on the curve BC, the inclination is empirically the Young's modulus E. Further, when the intersection of the straight line and the x-axis is hr ', the hardness value H plast of plastic deformation is obtained by the hardness value at the indentation depth hr'. In addition, the work amount We of elastic deformation in the measurement is C
-Represented by the area enclosed by B-D-C, the work W of plastic deformation
r is represented by the area surrounded by ABCA. Total work W
t is We + Wr and is represented by the area surrounded by A-B-D-A.

If the universal hardness value HU is less than 200 in the surface layer of the electrophotographic photosensitive member, the photosensitive member is likely to be scratched by the charge promoting particles.

If the elasticity of the resin is insufficient, a phenomenon occurs such that the surface of the photoconductor is cracked when the charge promoting particles are pressed against the photoconductor. This means that the curve showing the relationship between the hardness value H and the indentation depth h in the surface film physical property test shows a rapid change in hardness at the indentation depth h when the surface is cracked, as shown in FIG. It means having an inflection point P shown. It is considered that such surface cracking leads to deep scratches.

In the surface layer of the photoreceptor, Young's modulus E
If the value is less than 6.0, scratches are likely to occur due to the pressing of the electrification-promoting particles, and if a resin having a Young's modulus E significantly higher than 9.0 is used, the surface of the surface is similar to the above due to insufficient elasticity of the resin. Cracks and deep scratches occur.

The plastic deformation, that is, the hardness value with scratches, H p
As described above, last correlates with the value of HU, and the larger the ratio of H plast to HU, the larger the elastic component. Then, similarly to the above, the H plast value is 1.2 of HU.
If less than twice the amount of resin is used, the elasticity of the resin will be insufficient.

The work amount We of elastic deformation is the total work amount Wt.
Even when it is less than 30% with respect to (= We + Wr), that is, when We / (We + Wr) × 100 <30%, deep scratches develop due to insufficient elasticity of the resin.

Next, the photosensitive layer will be described.

The photosensitive layer of the electrophotographic photosensitive member of the present invention has a single layer or a laminated structure. In the case of a laminated structure, a charge generation layer that generates photocarriers and a charge transport layer that moves carriers are laminated. The surface layer may be formed by either the charge generation layer or the charge transport layer. However, in the injection charging process of the present invention, it is preferable to provide an injection layer on the outermost surface in order to establish the charging property.

The thickness of the single-layer photosensitive layer is preferably 5 to 100 μm, more preferably 10 to 60 μm. The content of the charge generation material and the charge transport material is 20 to
It is preferably 80% by mass, and more preferably 30 to 70% by mass. In the laminated photoreceptor, the film thickness of the charge generation layer is preferably 0.001 to 6 μm, more preferably 0.01 to 2 μm. The content of the charge generation material is preferably 10 to 100% by mass, and more preferably 40 to 100% by mass. The thickness of the charge transport layer is preferably 5 to 100 μm, more preferably 10 to 60 μm. The content of the charge transport material is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.

The charge generating material used in the present invention includes phthalocyanine pigments, polycyclic quinone pigments, azo pigments,
Perylene pigment, indigo pigment, quinacridone pigment, azurenium salt dye, squarylium dye, cyanine dye,
Examples thereof include pyrylium dyes, thiopyrylium dyes, xanthene dyes, quinoneimine dyes, triphenylmethane dyes, styryl dyes, selenium, selenium-tellurium, amorphous silicon, cadmium sulfide and zinc oxide.

The solvent used for the charge generation layer coating material is selected from the solubility and dispersion stability of the resin and charge generation material used, but as the organic solvent, alcohols, sulfoxides, ketones, ethers and esters are used. , Aliphatic halogenated hydrocarbons, aromatic compounds and the like can be used.

The charge generation layer contains the above charge generation material together with 0.3 to 4 times the amount of the binder resin and the solvent on a mass basis.
A homogenizer, an ultrasonic wave, a ball mill, a sand mill, an attritor, a roll mill, or the like is used to disperse well, coat and dry to form.

Examples of the charge transport material used in the present invention include pyrene compounds, carbazole compounds, hydrazone compounds, N, N-dialkylaniline compounds, diphenylamine compounds, triphenylamine compounds, triphenylmethane compounds, pyrazoline compounds, styryl compounds and Examples thereof include stilbene compounds.

The charge transport layer is generally formed by dissolving the above charge transport material and the binder resin in a solvent and applying the solution. The mixing ratio of the charge transport material and the binder resin is 2: on a mass basis.
It is preferably about 1 to 1: 2. Chlorinated hydrocarbons such as chlorobenzene, chloroform and carbon tetrachloride are used as the solvent. When applying this solution, a coating method such as a dip coating method and a spray coating method can be used, and drying is performed at a temperature in the range of 10 ° C to 200 ° C, preferably 20 ° C to 150 ° C for 5 minutes. It can be carried out for 5 to 5 hours, preferably 10 minutes to 2 hours under blast drying or static drying.

As the binder resin used for forming the charge transport layer, acrylic resin, styrene resin, polyester, polycarbonate resin, polyarylate, polysulfone, polyphenylene oxide, epoxy resin,
A resin selected from polyurethane resin, alkyd resin, unsaturated resin and the like is preferable. The thickness of the charge transport layer is 5 to
The thickness is preferably 40 μm, more preferably 10 to 30 μm.

As described above, in the present invention, it is preferable to provide the injection layer (protective layer) on the outermost surface in both the single layer and laminated layers. That time,
A surface film physical property test is performed on the protective layer (surface layer). The thickness of the protective layer is preferably 1 to 20 μm,
More preferably, it is 10 μm. The protective layer may contain the above-mentioned charge generating material, charge transporting material, metal and oxides thereof, nitrides, salts, alloys, and conductive materials such as carbon. Examples of the binder resin used in the protective layer include acrylic resin, xylene resin, silicone resin, epoxy resin, urea resin, alkyd resin and butyral resin.

The conductive support used in the electrophotographic photosensitive member of the present invention is a metal or alloy such as iron, copper, nickel, aluminum, titanium, tin, antimony, indium, lead, zinc, gold and silver, or those. It is possible to use the oxides, carbon, conductive resins and the like. The shape is cylindrical,
There are belts and sheets. The conductive material may be molded and processed, but may be applied as a paint or vapor-deposited.

Further, between the conductive support and the charge generation layer,
A binding layer and an undercoat layer for the purpose of preventing interference fringes may be provided.

The binder layer is used for improving the adhesiveness of the photosensitive layer, improving coatability, protecting the support, covering defects on the support, improving charge injection from the support, and protecting the photosensitive layer against electrical damage. Formed for. The binder layer may be formed of casein, polyvinyl alcohol, ethyl cellulose, ethylene-acrylic acid copolymer, polyamide, modified polyamide, polyurethane, gelatin and the like. The thickness of the binder layer is preferably 5 μm or less, and 0.2 to 3
More preferably, it is μm.

In the present invention, the charging member, which is made of an elastic material and is placed in contact with the photosensitive member, has a peripheral speed difference with respect to the surface of the photosensitive member, and at least the conductive particles are present in the contact portion between the charging member and the photosensitive member. The photosensitive member is carried and charged by applying a voltage to the charging member.

3 and 4 show the means for supplying the conductive particles to the contact portion between the charging member and the photosensitive member, the method is not limited to these. In FIGS. 3 and 4, 1 is a photoconductor, 2 is a contact charging member arranged in contact with the photoconductor,
Reference numeral 3 is a conductive particle, and 4 is a conductive particle supply means. S1 is a power source. The charging roller 2 is manufactured by forming a medium resistance layer 2b of rubber or foam on the core metal 2a.
The medium resistance layer 2b is formulated with a resin (for example, urethane), conductive particles (for example, carbon black), a sulfiding agent and a foaming agent, and is formed in a roller shape on the cored bar 2a. After that, the surface may be polished if necessary. When an electrophotographic photosensitive member is used as the member to be charged, a resistance of 10 ⁴ to 10 ⁷ Ω is desirable in order to obtain sufficient chargeability and leak resistance. The material of the charging roller is not limited to the elastic foam, and the material of the elastic body may be EPDM, urethane, NB.
Examples thereof include rubber materials in which a conductive material such as carbon black or metal oxide is dispersed in R, silicone rubber, IR, etc. for resistance adjustment, and those obtained by foaming these materials. It is also possible to adjust the resistance by using an ion conductive material without particularly dispersing the conductive substance.

The conductive particles intervening in the nip portion between the charging member and the photosensitive member in the examples described later are charge promoting particles for the purpose of assisting charging. Hereinafter, the particles are charge-accelerating particles. In the present invention, the specific resistance of the charge promoting particles is 10 ⁶ Ω · c.
m, and the conductive zinc oxide particles 3 having an average particle diameter of 3 μm were used.
As the material for the particles, various conductive particles such as conductive inorganic particles such as other metal oxides or a mixture with organic substances can be used. Here, the particle resistance is preferably 10 ¹⁰ Ω · cm or less in order to transfer charges through the particles.
Further, the particle size is preferably 50 μm or less in order to obtain good charging uniformity, and is preferably the constituent pixel size or less in order to prevent light scattering by particles during image exposure. The lower limit of the particle size is 10 nm as a limit for stably obtaining the particles. Further, when used for charging the photoconductor, colorless or nearly white particles are suitable so as not to interfere with the latent image exposure. Furthermore,
In the case of color recording, in consideration of the case where the charging promoting particles are transferred from the photosensitive member to the recording paper, colorless or nearly white one is preferable.

[0044]

EXAMPLES Next, specific examples of the present invention will be shown below.

Example 1 10 parts by mass of conductive titanium oxide (tin oxide coating, average primary particle size 0.4 μm), 10 parts by mass of phenol resin precursor (resole type), 1 part of methanol
After 0 parts by mass and 10 parts by mass of butanol were dispersed in a sand mill, they were applied to an aluminum cylinder having an outer diameter of 29.92 mm and a length of 357.5 mm by a dip coating method and cured at 140 ° C., and then the volume resistance was 5 × 10 ^9. Ω ・
A conductive layer having a thickness of 20 cm and a thickness of 20 μm was provided. Next, the following methoxymethylated nylon (degree of methoxymethylation of about 30
%) 10 parts by mass

[0046]

[Chemical 1] And 150 parts by mass of isopropanol were mixed and dissolved, and then coated on the conductive layer by a dip coating method to provide an undercoat layer (binder layer) having a film thickness of 1 μm.

Next, the Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction is 9.0 °, 14.2 °, 23.
4 parts by mass of oxytitanium phthalocyanine (TiOPc) having strong peaks at 9 ° and 27.1 °, 2 parts by mass of polyvinyl butyral (trade name: S-REC BM2, manufactured by Sekisui Chemical Co., Ltd.) and 60 parts by mass of cyclohexanone are glass with a diameter of 1 mm. After being dispersed for 4 hours with a sand mill using beads, 100 parts by mass of ethyl acetate was added to prepare a dispersion liquid for a charge generation layer. This was applied by a dip coating method to form a charge generation layer having a thickness of 0.3 μm.

Next, 10 parts by mass of the following triphenylamine,

[0049]

[Chemical 2] Polycarbonate resin (bisphenol Z, molecular weight 40
000) 10 parts by mass, 50 parts by mass of monochlorobenzene and 15 parts by mass of dichloromethane were stirred and mixed, and then applied on the charge generation layer by a dip coating method to provide a charge transport layer having a thickness of 17 μm.

Next, the following 6-functional acrylic monomer 2
0 parts by mass,

[0051]

[Chemical 3] And 5 parts by mass of the following bifunctional acrylic monomer,

[0052]

[Chemical 4] 50 parts by mass of tin oxide fine particles having an average particle size of 400 L before dispersion, 20 parts by mass of polytetrafluoroethylene resin fine powder (average particle size 0.18 μm), 18 parts by mass of 2-methylthioxanthone as a photopolymerization initiator, and ethanol Dispersion of 150 parts by mass with a sand mill for 66 hours.

Here, the functional number means the number of functional groups represented by the following structural formulas, which each binder has.

[0054]

[Chemical 5] Using this prepared solution, a film was formed on the above charge transport layer by a dip coating method by a coating method, and photocured with a high pressure mercury lamp at a light intensity of 800 mW / cm ² for 30 seconds, and then at 120 ° C. The surface layer was provided by drying with hot air for 100 minutes. At this time, the film thickness of the obtained surface layer was 4 μm. In this way, the photoconductor A was manufactured. Separately from this, a cylinder A ′ having a surface layer of 12 μm provided on an aluminum cylinder having an outer diameter of 29.92 mm and a length of 357.5 mm was produced. By providing a layer having a thickness 10 times or more the indenter indentation depth of 1 μm in the surface film physical property test, the influence of the base during measurement can be excluded.

With respect to the cylinder A'prepared in this way, a surface coating physical property test (manufactured by Fisher Instruments, Fisher Scope H100V) was conducted, and the surface layer had a universal hardness HU, a Young's modulus E, and a plastic deformation hardness. H plast, elastic deformation work We and total work Wt were respectively obtained.

The measurement conditions at this time were a maximum indentation depth of 1 μm and 60 measurement points in the depth direction, and measurement was carried out in a constant environment (room temperature 22.5 ° C., humidity 50% RH).

As a result, the universal hardness HU is 250.
[N / mm ² ], Young's modulus E was 8.3, plastic deformation hardness value H plast was 350, and elastic deformation work We was 35% of Wt.

Image evaluation is carried out by a copier GP manufactured by Canon Inc.
-55 was used after being modified for injection charging as follows. In order to perform the injection charging, an elastic charging roller as shown in FIG. 4 and conductive particles 3 shown in the figure are used, and this charging roller has a rubber middle resistance layer formed on a core metal. It was produced by. The medium resistance layer is formulated with urethane resin, conductive particles (carbon black), a sulfiding agent, a foaming agent, etc., and is molded into a roller shape on a cored bar, and then the surface is polished to a diameter of 12 mm and a length of 250 mm. The elastic conductive roller of was produced. When the resistance of this roller was measured, it was 10
It was 0 kΩ. Total pressure of roller core metal 9.8N (1k
The measurement was performed by applying 100 V to the core metal and the conductive support in a state of being pressure-bonded to the photoreceptor so that the load of g) is applied. In this example, the charging contact width of the charging roller 2 is 3 mm.
Met. This charging roller was rotationally driven in the clockwise direction of the arrow at about 80 rpm so that the surface of the charging roller and the surface of the photoconductor moved in opposite directions at the charging contact portion. That is, the surface of the charging roller 2 as the contact charging member has a speed difference with respect to the surface of the photoconductor 1 as the member to be charged.

The conductive particles 3 are charge accelerating particles for the purpose of accelerating charging. In this example, conductive zinc oxide particles having a specific resistance of 10 ⁶ Ω · cm and an average particle diameter of 3 μm including secondary agglomerates are used. Using.

Example 2 15 parts by mass of the 6-functional acrylic monomer represented by the above formula (4) and 2 represented by the formula (5).
Photoreceptor B and cylinder B ′ were prepared and images were evaluated in the same manner as in Example 1 except that the amount of the functional acrylic monomer was changed to 5 parts by mass. The results of the surface film physical property test are HU.
Is 230, E is 8.0, H plast is 385, We is Wt
Was 42%.

[Example 3] Photosensitive member C and cylinder C'were prepared and image-evaluated in the same manner as in Example 1 except that the fine powder of polytetrafluoroethylene resin was changed to 15 parts by mass. The result of surface film physical property test shows that HU is 27.
5, E is 8.3, H plast is 400, We is 35 Wt.
%Met.

[Embodiment 4] The photoconductor D and the cylinder D ′ were prepared in the same manner as in Embodiment 1, except that the light curing condition with the above-mentioned high-pressure mercury lamp was set to 700 mW / cm ² for a light amount and 25 seconds for a time. It was produced and image-evaluated. The results of the physical property test on the surface film indicate that HU is 230, E is 8.2, and Hplast is 31.
0 and We were 34% of Wt.

[Example 5] The hot air drying temperature was set to 100 ° C.
Photosensitive member E and cylinder E ′ were prepared and images were evaluated in the same manner as in Example 1 except that the above was used. The test results by the physical property test of the surface film are 245 for HU, 8.3 for E, and H plast.
Was 348 and We was 36% of Wt.

Example 6 The image evaluation was carried out in the same manner as in Example 1 using the photoconductor A with the zinc oxide fine particles having a particle size of 10 μm.

Example 7 22.5 parts by mass of the hexafunctional acrylic monomer represented by the above formula (4) and 2 represented by the formula (5).
A photoreceptor F and a cylinder F ′ were prepared and image evaluation was performed in the same manner as in Example 1 except that the amount of the functional acrylic monomer was 2.5 parts by mass. As a result of surface film physical property test,
HU was 283, E was 9.1, H plast was 335, and We was 31% of Wt.

[Example 8] A photoconductor G and a cylinder G'were prepared in the same manner as in Example 1 except that the polytetrafluoroethylene resin fine powder was used in an amount of 10 parts by mass, and images were evaluated. The result of surface film physical property test shows that HU is 27.
5, E is 9.1, H plast is 400, We is Wt 29
%Met.

[Example 9] A photoconductor H and a cylinder H'were prepared and image-evaluated in the same manner as in Example 1 except that the hot air drying temperature was changed to 90 ° C. As a result of the surface film physical property test, HU was 245, E was 8.3, H plast was 293, and We was 29% of Wt.

[Comparative Example 1] The above-mentioned injection charger was changed to a corona charger, and the copier was modified so that a printing durability test could be carried out. A printing test and image evaluation were performed.

[Comparative Example 2] The procedure of Example 1 was repeated except that 25 parts by mass of the 6-functional acrylic monomer represented by the above formula (4) and 0 of the bifunctional acrylic monomer represented by the formula (5) were used. A photoconductor I and a cylinder I ′ were prepared and image evaluation was performed. As a result of the surface film physical property test, the curve showing the relationship between the hardness H and the indentation depth h of the indenter has an inflection point, and
U is 295, E is 9.6, H plast is 328, We is W
It was 28% of t.

[Comparative Example 3] Except that the amount of the hexafunctional acrylic monomer represented by the formula (4) was 22.5 parts by mass and the amount of the bifunctional acrylic monomer represented by the formula (5) was 2.5 parts by mass.
In the same manner as in Example 1, a photoreceptor J and a cylinder J ′ were prepared and image evaluation was performed. As a result of surface film physical property test, HU is 283, E is 9.1, H plast is 335, W
e was 28% of Wt.

[Comparative Example 4] The procedure of Example 1 was repeated except that the amount of the hexafunctional acrylic monomer represented by the above formula (4) was 0 and the amount of the bifunctional acrylic monomer represented by the formula (5) was 25 parts by mass. Then, a photoconductor K and a cylinder K ′ were produced and image evaluation was performed. HU was 19 as a result of the surface film physical property test.
0, E is 7.1, H plast is 520, We is Wt 51
%Met.

[Comparative Example 5] Photoreceptors L and L'were prepared in the same manner as in Example 1 except that the conditions for photocuring with the high-pressure mercury lamp were such that the light amount was 100 mW / cm ² and the time was 10 seconds. It was produced and image evaluation was performed. As a result of the surface film physical property test, HU was 150 due to poor photocuring of the surface layer.

[Comparative Example 6] The same image evaluation as in Example 1 was carried out by using the photoconductor A without using the zinc oxide fine particles as the charge accelerating particles present in the contact portion between the charging member and the photoconductor.

[Comparative Example 7] In Example 1, the rotation of the charging member was set to be free so as to be driven by the rotation of the photoconductor, and the image evaluation was similarly performed using the photoconductor A.

These photoconductors A to L were incorporated into a copying machine GP-55 manufactured by Canon Inc., which was modified for injection charging, as described in Example 1, and they were placed at 22.5 ° C. and 50% RH.
Under a constant environment of 10K, a copy durability test of 10K sheets was performed, and scratches on the photoconductor and images after the durability test were examined and evaluated. The results of the copy durability test are shown in Table 1. The criteria for the results of the surface film physical property test in Table 1 are as follows.

◯: HU ≧ 2 in the surface film physical property test
00 and hardness H-indentation depth h curve does not have an inflection point, and 6.0 ≦ E ≦ 9.0, H plast ≧ 1.2 × H
U, We / Wt ≧ 0.3 are all achieved.

Δ: HU ≧ 2 in the surface film physical property test
00 and hardness H-indentation depth h curve does not have an inflection point, and 6.0 ≦ E ≦ 9.0 or H plast ≧ 1.2
Achieve either × HU or We / Wt ≧ 0.3.

X: The above condition is not achieved.

[0079]

[Table 1]

[0080]

As described above, according to the present invention,
An electrophotographic photosensitive member that does not cause image defects such as a fog image due to poor charging by suppressing scratches generated on the photosensitive member by conductive particles when using an injection charging method, and a process having the electrophotographic photosensitive member Enables cartridges and electrophotographic devices.

[Brief description of drawings]

FIG. 1 is a graph showing the results of a surface film physical property test.

FIG. 2 is a graph showing a relationship between an indentation depth h and a hardness H in a surface film physical property test, in the case where an inflection point P occurs.

FIG. 3 is a configuration diagram of a contact charging member used in the present invention.

FIG. 4 is a configuration diagram of a contact charging member used in the present invention.

FIG. 5 is a diagram showing a measuring method of a surface film physical property test.

[Explanation of symbols]

1 Photoconductor (image bearing member, charged body) 2 Charging roller (contact charging member) 3 Charge promoting particles (conductive particles) 4 Regulation blade (Particle supply means) 5 Aluminum cylinder with only the surface layer deposited 6 Photoconductor stand 7 indenter 8 mobile tables 9 Microscope position

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Haruyuki Tsuji             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F term (reference) 2H068 AA08                 2H200 GA23 GA44 HA02 HB12 HB17                       LA12

Claims (8)

[Claims] 1. A charged particle containing conductive particles having a particle size of 10 μm to 10 nm as a main component and a surface having conductivity and elasticity, and a charged particle carrier for supporting the charged particles, The charged particles are a charging unit that contacts the electrophotographic photosensitive member and charges the surface of the electrophotographic photosensitive member, and the resistance of the particles carried on the carrier is 10 ¹² to 10 ⁻¹ Ω · cm. Carried amount of 0.1 mg / cm ^{2 to} 50 mg /
In an electrophotographic photosensitive member used in an electrophotographic apparatus having a charging device having a charging device of cm ² , the hardness H in the surface film physical property test in a constant environment (22.5 ° C., 50% RH) for the surface layer of the photosensitive member The curve showing the relationship with the indentation depth has no inflection point, the universal hardness value HU is 200 or more, and the following (1),
An electrophotographic photosensitive member characterized by satisfying any one of (2) and (3). (1) A constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
Young's modulus E in the surface film physical property test at 0% RH)
Is 6.0 [GPa] or more and 9.0 [GPa] or less. (2) Constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
The hardness value H plast of plastic deformation in the surface film physical property test at 0% RH) is 1.2 times or more that of HU. (3) Constant environment of the electrophotographic photosensitive member (22.5 ° C., 5
The work amount We of elastic deformation in the surface film physical property test at 0% RH) is 30% or more with respect to the total work amount Wt. 2. A curve showing the relationship between the hardness H and the indentation depth of the indenter in a physical property test for the surface film in a constant environment (22.5 ° C., 50% RH) with respect to the surface layer of the electrophotographic photosensitive member. And has a universal hardness value HU of 20
An electrophotographic photoreceptor, which is 0 or more and satisfies all of the following (1), (2), and (3). (1) A constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
Young's modulus E in the surface film physical property test at 0% RH)
Is 6.0 [GPa] or more and 9.0 [GPa] or less. (2) Constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
The hardness value H plast of plastic deformation in the surface film physical property test at 0% RH) is 1.2 times or more that of HU. (3) Constant environment of the electrophotographic photosensitive member (22.5 ° C., 5
The work amount We of elastic deformation in the surface film physical property test at 0% RH) is 30% or more with respect to the total work amount Wt. 3. An electrophotographic apparatus main body integrally supporting an electrophotographic photosensitive member, an elastic member, a charging member disposed in contact with the photosensitive member, and at least one unit selected from a developing unit and a cleaning unit. A process cartridge that can be freely attached to and detached from the charging member, wherein the charging member has a particle diameter of 10 μ
The charging particle is mainly composed of conductive particles having a particle size of m to 10 nm, and a charged particle carrier that has a surface having conductivity and elasticity and that supports the charged particle. It is a charging means that contacts and charges the surface of the electrophotographic photosensitive member, the resistance of the particles carried on the carrier is 10 ¹² to 10 ⁻¹ Ω · cm, and the carried amount of the particles is 0.
In the process cartridge is ^{1mg / cm 2 ~50mg / cm 2} , a constant environment (22.5 ℃, RH 50%) for the surface layer of the photosensitive member and the indentation depth of hardness H and indenter of the surface film physical property test with The curve showing the relationship has no inflection point and the universal hardness value HU is 200
A process cartridge characterized by using a photoreceptor satisfying any one of the above (1), (2), and (3). (1) A constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
Young's modulus E in the surface film physical property test at 0% RH)
Is 6.0 [GPa] or more and 9.0 [GPa] or less. (2) Constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
The hardness value H plast of plastic deformation in the surface film physical property test at 0% RH) is 1.2 times or more that of HU. (3) Constant environment of the electrophotographic photosensitive member (22.5 ° C., 5
The work amount We of elastic deformation in the surface film physical property test at 0% RH) is 30% or more with respect to the total work amount Wt. 4. A curve showing the relationship between the hardness H and the indentation depth of the indenter in the physical property test of the surface coating in a constant environment (22.5 ° C., 50% RH) for the surface layer of the electrophotographic photosensitive member. And has a universal hardness value HU of 20
A process cartridge comprising an electrophotographic photosensitive member which is 0 or more and satisfies all of the following (1), (2), and (3). (1) A constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
Young's modulus E in the surface film physical property test at 0% RH)
Is 6.0 [GPa] or more and 9.0 [GPa] or less. (2) Constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
The hardness value H plast of plastic deformation in the surface film physical property test at 0% RH) is 1.2 times or more that of HU. (3) Constant environment of the electrophotographic photosensitive member (22.5 ° C., 5
The work amount We of elastic deformation in the surface film physical property test at 0% RH) is 30% or more with respect to the total work amount Wt. 5. The charged particle supplying means used for the primary charging means, when charged particles are stored in a developing means together with a developer, transferred to the photoreceptor, and transferred to a recording medium,
5. The process cartridge according to claim 3, wherein a part of the process cartridge is not transferred and remains on the photoconductor and is supplied to the charging unit. 6. An electrophotographic apparatus comprising an electrophotographic photosensitive member, an elastic member, and a charging member, an image exposing unit, a developing unit, and a transferring unit, which are arranged in contact with the photosensitive member, the charging member comprising: The charged particles are mainly composed of conductive particles having a particle size of 10 μm to 10 nm, and a charged particle carrier that carries the charged particles and has a surface having conductivity and elasticity, and the charged particles are electrophotographic. The charging means is for charging the surface of the electrophotographic photoreceptor by contacting the photoreceptor, the resistance of the particles carried on the carrier is 10 ¹² to 10 ⁻¹ Ω · cm, and the carried amount of the particles is 0. 1 mg / cm ^{2 to} 50 mg / cm ² in the electrophotographic apparatus, the hardness H and the indentation of the indenter in the surface film physical property test with respect to the surface layer of the photoreceptor in a constant environment (22.5 ° C., 50% RH) The curve showing the relationship with depth shows the inflection point It was not, and the universal hardness value HU
Is 200 or more and the following (1), (2),
An electrophotographic apparatus satisfying any one of (3). (1) A constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
Young's modulus E in the surface film physical property test at 0% RH)
Is 6.0 [GPa] or more and 9.0 [GPa] or less. (2) Constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
The hardness value H plast of plastic deformation in the surface film physical property test at 0% RH) is 1.2 times or more that of HU. (3) Constant environment of the electrophotographic photosensitive member (22.5 ° C., 5
The work amount We of elastic deformation in the surface film physical property test at 0% RH) is 30% or more with respect to the total work amount Wt. 7. A curve showing the relationship between the hardness H and the indentation depth of a surface film in a constant environment (22.5 ° C., 50% RH) with respect to the surface layer of an electrophotographic photosensitive member is an inflection point. And has a universal hardness value HU of 20
An electrophotographic apparatus which is 0 or more and satisfies all of the following (1), (2) and (3). (1) A constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
Young's modulus E in the surface film physical property test at 0% RH)
Is 6.0 [GPa] or more and 9.0 [GPa] or less. (2) Constant environment of the electrophotographic photoreceptor (22.5 ° C., 5
The hardness value H plast of plastic deformation in the surface film physical property test at 0% RH) is 1.2 times or more that of HU. (3) Constant environment of the electrophotographic photosensitive member (22.5 ° C., 5
The work amount We of elastic deformation in the surface film physical property test at 0% RH) is 30% or more with respect to the total work amount Wt. 8. A charged particle supplying means used for the primary charging means, when charged particles are stored in a developing means together with a developer, transferred onto the photoreceptor, and transferred to a recording medium,
8. The electrophotographic apparatus according to claim 6, wherein a part of the electrophotographic apparatus is not transferred and remains on the photoconductor and is supplied to the charging unit.