JP2001013707A - Electrophotographic photoreceptor and electrophotographic image forming device using the photoreceptor and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having stable repetitive potential characteristics, giving a clear copied image in any environment and having good scuffing and filming resistances by incorporating a specified siloxane resin into the resin layer of an electrophotographic photoreceptor. SOLUTION: The electrophotographic photoreceptor has a resin layer containing a siloxane resin having a crosslinked structure obtained by allowing one or more compounds of formula I or II to react with one or more organosilicon compounds of formula III or one or more products obtained by hydrolyzing and condensing the organosilicon compounds. In the formulae I and II, A is a mono- or polyvalent compound group having antioxidant function, R1 and R3 are each a single bond or a divalent group, R2 is an optionally substituted hydrocarbon group, Z1 is hydroxyl or a hydrolyzable group, (m) is an integer of 0-2 and (n) and (l) are each an integer of 1-4. In the formula III, R4 is an organic group with C bonding directly to Si, Z2 is hydroxyl or a hydrolyzable group and (r) is an integer of 0-3.

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 (hereinafter, also simply referred to as a photosensitive member), an electrophotographic image forming apparatus using the photosensitive member, and a process cartridge used in the apparatus.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic photosensitive member, an inorganic photosensitive member having a photosensitive layer mainly composed of an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide, and silicon has been widely used. However, these are not always satisfactory in sensitivity, thermal stability, moisture resistance, durability, and the like. In addition, some inorganic photoreceptors contain substances that are harmful to the human body in the photoreceptor, and thus pose a problem in disposal. There is.

In order to overcome the disadvantages of these inorganic photoconductors, research and development of organic photoconductors having a photosensitive layer containing various organic photoconductive compounds as main components have been actively conducted in recent years. In particular, a function-separated type photoreceptor in which the charge generation function and the charge transport function are respectively assigned to different substances allows each material to be selected from a wide range, and a photoreceptor having any performance can be relatively easily formed. Much research has been done because it can be produced, and it is widely used in practice.

[0004] Such an organic photoreceptor is subjected to various electrical and mechanical external forces such as corona charging, toner development, transfer to paper, and cleaning, so that various performance degradation phenomena inside and on the surface of the photoreceptor. Appears.

More specifically, potential characteristics such as image blur, charging potential, reduction in sensitivity, and increase in residual potential are caused by discharge products such as ozone and nitrogen oxide (NOx) generated at the band electrode and ultraviolet rays during exposure. The image quality is deteriorated due to the change, the occurrence of wear and tear due to friction at the time of development and cleaning, and the adhesion (filming) of paper powder and toner from the transfer paper.

As one of the technical measures against the above-mentioned problems, a surface protective layer is provided on the surface of the photoreceptor to improve mechanical durability, suppress the depletion of the photoreceptor, generate scratches and paper. It has been studied to suppress adhesion of powder and toner.
For example, it is possible to provide a curable siloxane resin layer as a protective layer on a surface layer of a photoreceptor.
No.-51155, JP-A-1-217364, 1-2
No. 0036, No. 3-129360, No. 3-1555
No. 58, No. 3-139655, and No. 5-40359.

However, in such a method of providing a curable siloxane resin layer, the mechanical strength and abrasion resistance of the surface are sufficiently larger than those of the conventional photoreceptor, but the chargeability, sensitivity and residual potential of the photoreceptor are increased. The problem is that the image may be easily deteriorated under conditions such as high temperature and high humidity, and the resolution is reduced particularly under conditions such as low temperature and low humidity, The problem is that the image becomes blurred and a clear image cannot be obtained. The image blurring at low temperature and low humidity was particularly remarkable immediately after the use of the device under low temperature and low humidity, and immediately after a predetermined period of time (for example, after use, at the time of first copy on the next day).

[0008]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to stabilize repetitive potential characteristics, give clear copied images in all environments, have good scratch and filming resistance, and It is an object of the present invention to provide an electrophotographic photoreceptor which is excellent in durability with little wear even when copying or printing, an image forming apparatus equipped with the photoreceptor, and a process cartridge.

[0009]

The object of the present invention is attained by adopting one of the following constitutions.

[0010] 1. In an electrophotographic photosensitive member having a photosensitive layer and a resin layer on a conductive support, a crosslinked structure obtained by reacting at least the following two components (a) and (b) with the resin layer of the electrophotographic photosensitive member An electrophotographic photoreceptor comprising a layer containing a siloxane-based resin having the formula:

Component (a): The following general formula (1) or (2)
(B) component: at least one kind of an organosilicon compound represented by the following general formula (3) or a hydrolytic condensate thereof:

[0012]

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(In the general formulas (1) and (2), A represents a monovalent or polyvalent compound group having an antioxidant function, and R ₁ , R ₃
Represents a single bond or a divalent group, and R ₂ represents a substituted or unsubstituted 1
Represents a monovalent hydrocarbon group. Z ₁ represents a hydroxyl group or a hydrolyzable group. m represents an integer of 0 to 2, and n and l represent integers of 1 to 4.

In the general formula (3), R ₄ represents an organic group in which carbon is directly bonded to a silicon atom in the formula, Z ₂ represents a hydroxyl group or a hydrolyzable group, and r is an integer of 0-3. Represents ) 2. In an electrophotographic photosensitive member having a photosensitive layer and a resin layer on a conductive support, the resin layer of the electrophotographic photosensitive member includes the two components (a) and (b) and the component (a) or (b). An electrophotographic photosensitive member comprising a layer containing a siloxane-based resin having a crosslinked structure obtained by reacting a charge transporting compound having a reactive group capable of forming a resin by bonding.

3. 3. The electrophotographic photosensitive material according to the above item 1 or 2, wherein A in the general formula (1) or (2) is a monovalent or polyvalent compound group having a hindered phenol or hindered amine chemical structure. body.

4. 4. The electrophotographic photoreceptor as described in the above item 2 or 3, wherein the charge transporting compound having a reactive group is a charge transporting compound having a hydroxyl group.

5. 5. The electrophotographic photosensitive member according to any one of items 1 to 4, wherein the resin layer is a surface layer.

6. An electrophotographic photoreceptor, at least charged,
An electrophotographic image forming apparatus having image exposure, development, and cleaning means, wherein the electrophotographic photosensitive member according to any one of the above items 1 to 5 is used as the electrophotographic photosensitive member. Image forming device.

[7] An electrophotographic photoreceptor, at least charged,
The process cartridge used in the electrophotographic image forming apparatus having image exposure, development, and cleaning means is the aforementioned 1
An electrophotographic photoreceptor and a charger according to any one of claims 1 to 5,
A process cartridge having one of an image exposing unit, a developing unit, and a cleaning unit integrally, and being designed to be freely inserted into and removed from the electrophotographic image forming apparatus.

Hereinafter, the present invention will be described in detail.

The present inventors have made intensive efforts to solve the above problems, and as a result, modified the conventional siloxane resin to add an antioxidant function and a charge transport function to the siloxane resin structure, thereby converting the conventional siloxane resin. It has been found that various problems of the used electrophotographic photosensitive member can be solved. Hereinafter, the present invention will be described in detail.

The siloxane-based resin in the present invention can be obtained by incorporating a compound having an antioxidant function into a part of the siloxane resin structure and modifying the siloxane resin structure.

The siloxane resin of the present invention has the general formula (3)
Can be produced using an organosilicon compound represented by the formula: That is, the organosilicon compound represented by the general formula (3) is represented by the following general formulas (h) to (k).

[0024]

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(In the formula, R _{1 to} R ₆ represent an organic group in which carbon is directly bonded to silicon in the formula, and Z _{3 to} Z ₆ represent a hydroxyl group or a hydrolyzable group.) When Z _{3 to} Z ₆ are a hydrolyzable group, the hydrolyzable group includes a methoxy group, an ethoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group, a butoxy group, a methoxyethoxy group and the like. No. Examples of the organic group in which carbon is directly bonded to silicon represented by R _{1 to} R ₆ include alkyl groups such as methyl, ethyl, propyl and butyl, aryl groups such as phenyl, tolyl, naphthyl and biphenyl, and γ-glycidyl. Epoxy-containing groups such as xypropyl and β- (3,4-epoxycyclohexyl) ethyl, (meth) acryloyl-containing γ-acryloxypropyl and γ-methacryloxypropyl, γ-hydroxypropyl, 2,3-dihydroxy A hydroxyl group such as propyloxypropyl, a vinyl group such as vinyl and propenyl, a mercapto group such as γ-mercaptopropyl, an amino group such as γ-aminopropyl and N-β (aminoethyl) -γ-aminopropyl; γ-chloropropyl, 1,1,1-trifluoropropyl, nonafluorohexyl, perfluorooctylethyl And nitro and cyano-substituted alkyl groups. Further, R _{1 to} R ₆ may have the same or different organic groups.

In general, when the number n of hydrolyzable groups bonded to silicon atoms of the organosilicon compound used as a raw material of the siloxane resin is 1, the polymerization reaction of the organosilicon compound is suppressed. You. n is 2, 3 or 4
In the case of (3), the polymerization reaction is likely to occur.
It is possible to advance the crosslinking reaction to a high degree. Therefore, by controlling these, it is possible to control the preservability of the obtained coating layer liquid, the hardness of the coating layer, and the like.

As a raw material of the siloxane-based resin, a hydrolysis-condensation product obtained by hydrolyzing the organosilicon compound under an acidic condition or a basic condition and oligomerizing or polymerizing the compound can also be used.

As described above, the siloxane-based resin having a crosslinked structure of the present invention is obtained by reacting a monomer, oligomer, polymer or the like having a siloxane bond in a chemical structural unit in advance (hydrolysis reaction, catalyst or crosslinking agent). (Including added reactions, etc.) means a resin that has formed and cured a three-dimensional network structure. That is, it means a resin formed as a result of forming a three-dimensional network structure by promoting a siloxane bond by a hydrolysis reaction and subsequent dehydration condensation of an organosilicon compound having a siloxane bond.

The component (a) of the present invention, that is, the compound represented by the general formula (1) or (2) will be described.

The monovalent or polyvalent compound group having an antioxidant function represented by A has a chemical structure having a function of inhibiting a radical chain for capturing radicals generated by heat, light or the like. Examples include a compound group having a chemical structure of hindered phenol or hindered amine or a compound group having a chemical structure capable of decomposing peroxides, for example, a compound group having a chemical structure such as thioether or phosphite. In particular, A is preferably a monovalent or polyvalent compound group having a hindered phenol or hindered amine chemical structure.

R represents a single bond or a divalent group represented by R ₁ or R ₃ , and is particularly preferably an alkylene group such as methylene, ethylene and propylene, and an arylene group such as phenylene. R
_The substituted or unsubstituted monovalent hydrocarbon group represented by _{2 includes} a substituted or unsubstituted monovalent hydrocarbon group such as methyl, ethyl, propyl, butyl, chloromethyl, and γ-hydroxypropyl.
Valent hydrocarbon groups. Examples of the hydrolyzable group for Z ₁ include an alkoxy group such as methoxy and ethoxy, a halogen group, and an acyloxy group. Particularly, an alkoxy group having 6 or less carbon atoms is preferable. m represents an integer of 0 to 2,
n and l represent an integer of 1 to 4.

Here, the compound group having a hindered phenol chemical structure means a compound group having a branched alkyl group at a position ortho to the hydroxyl group of phenol (however, the hydroxyl group may be modified to alkoxy).

The compound group having a hindered amine chemical structure means a compound group represented by the following structural formula.

[0034]

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(Wherein R ₂₁ is a hydrogen atom, a monovalent or polyvalent organic group, R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ are an alkyl group, and R ₂₆ is a hydrogen atom, a hydroxyl group, a monovalent or polyvalent. The following are specific examples of the compound having an antioxidant function represented by the general formula (1) or (2) of the present invention, but the compound of the present invention is not limited thereto. Not something.

[0036]

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[0037]

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[0039]

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[0040]

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[0041]

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The compound of the component (a) reacts with the organosilicon compound of the component (b) to form a siloxane-based resin having a crosslinked structure having an antioxidant function. Component (a) is preferably 0.001 to 20% by weight based on the siloxane-based resin. If it is less than 0.001% by weight, the effect of preventing the resin layer from deteriorating is small, and if it exceeds 20% by weight, the film strength is reduced.

Another siloxane resin of the present invention is:
Further, a chemical structure having a charge transporting function is incorporated in the resin. This is incorporated into the siloxane-based resin by a reaction between the organosilicon compound and a charge transporting compound having a reactive group described below.

Examples of the charge transporting compound having a reactive group that reacts with the organic silicon compound include a charge transporting compound having a hydroxyl group, a mercapto group, an amine group, and an organic silicon-containing group.

The charge transporting compound having a hydroxyl group is as follows:
It is a commonly used charge transport material and a compound having a hydroxyl group. For example, a charge transporting compound represented by the following general formula can be mentioned, but it is not limited to the following structure, and any compound having a charge transporting ability and having a hydroxyl group may be used.

X- (R ₇ -OH) _m wherein X: a compound group having charge transporting ability, R ₇ : a single bond, a substituted or unsubstituted alkylene group, an arylene group, m: an integer of 1 to 5 is there.

Next, specific examples of the charge transporting compound having a reactive group having a mercapto group are shown below.

The charge transporting compound having a mercapto group is a compound which is a commonly used charge transporting substance and has a mercapto group. That is, typically, a charge transporting compound represented by the following general formula that can form a resin layer by bonding to the organosilicon compound can be exemplified, but is not limited to the following structure. Any compound having charge transporting ability and having a mercapto group may be used.

X- (R ₈ -SH) _m wherein X: a compound group having charge transporting ability, R ₈ : a single bond, a substituted or unsubstituted alkylene, arylene group, m: an integer of 1 to 5 .

Further, the charge transporting compound having an amino group will be described.

The charge transporting compound having an amino group is a commonly used charge transporting substance and a compound having an amino group. That is, typically, there can be mentioned a charge transporting compound represented by the following general formula that can form a resin layer by reacting with the organosilicon compound, but is not limited to the following structure, Any compound having charge transporting ability and having an amino group may be used.

X- (R ₉ -NR ₁₀ H) _m wherein X: a compound group having charge transporting ability, R ₉ : a single bond, a substituted or unsubstituted alkylene, a substituted or unsubstituted arylene group, R ₁₀ : A hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, m: an integer of 1 to 5.

Among the charge transporting compounds having an amino group, in the case of a primary amine compound (—NH ₂ ), two hydrogen atoms may react with an organosilicon compound and be linked to a siloxane structure. In the case of a secondary amine compound (—NHR ₁₀ ), one hydrogen atom reacts with the organosilicon compound, and R ₁₀ may be a group that remains as a branch or a group that causes a cross-linking reaction, and includes a charge transport material. It may be a compound residue.

Further, the charge transporting compound having a silicon atom-containing group will be described.

The charge transporting compound having a silicon atom-containing group is a charge transporting substance having the following structure. This compound can also combine with the organosilicon compound to form a resin layer.

X-(— Y—Si (R ₁₁ ) _3-a (R ₁₂ ) _a ) _n (wherein X is a compound group having charge transport performance,
₁₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, R ₁₂ represents a hydrolyzable group or a hydroxyl group,
Y represents a substituted or unsubstituted alkylene group or an arylene group. a represents an integer of 1 to 3, and n represents an integer. Specific examples of the charge-transporting compound having a reactive group represented by the general formula are shown below. For example, a triarylamine-based compound has a triarylamine structure such as triphenylamine as a compound group having a charge transporting property = X, and an alkylene extended through a carbon atom constituting X or from X, A compound having a hydroxyl group via an arylene group.

[0057]

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[0058]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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Next, a synthesis example of the charge transporting compound having a hydroxyl group will be described.

Synthesis of Exemplified Compound T-1

[0069]

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Step A In a four-headed kolben equipped with a thermometer, a cooling tube, a stirrer, and a dropping funnel, 49 g of the compound (1) and phosphorus 184 chloride were added.
g was added and dissolved by heating. 117 g of dimethylformamide was gradually added dropwise from the dropping funnel.
The mixture was kept at ９５95 ° C. and stirred for about 15 hours. Next, the reaction solution was gradually poured into a large excess of warm water, and then slowly cooled with stirring.

After the precipitated crystals were filtered and dried, compound (2) was obtained by purification by adsorption of impurities with silica gel or the like and recrystallization with acetonitrile. Yield 30
g.

Step B 30 g of compound (2) and 100 ml of ethanol were charged into a kolben and stirred. After gradually adding 1.9 g of sodium borohydride, the solution was kept at 40 to 60 ° C. and stirred for about 2 hours. Next, the reaction solution was gradually poured into about 300 ml of water and stirred to precipitate crystals. After filtration, the resultant was sufficiently washed with water and dried to obtain a compound (3). The yield was 30 g.

Synthesis of Exemplified Compound S-1

[0074]

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Step A In a 300 ml kolben equipped with a thermometer and a stirrer, add C
Then, 30 g of u, 60 g of K ₂ CO ₃ , 8 g of compound (1) and 100 g of compound (2) were added, and the mixture was heated to about 180 ° C. and stirred for 20 hours. After cooling, the mixture was filtered and purified by column to obtain 7 g of compound (3).

Step B A 100-ml corben equipped with a thermometer, a dropping funnel, an argon gas introducing device and a stirrer was placed in an argon gas atmosphere, and 7 g of the compound (3), 50 ml of toluene, and 3 g of phosphoryl chloride were added thereto. While stirring at room temperature, D
2 g of MF was slowly added dropwise, and then the temperature was raised to about 80 ° C. and the mixture was stirred for 16 hours. The mixture was poured into warm water of about 70 ° C. and cooled. This was extracted with toluene, and the extract was washed with water until the pH of the water reached 7. After drying over sodium sulfate, the mixture was concentrated and purified by column to obtain 5 g of compound (4).

Step C 100 ml with an argon gas introducing device and a stirring device
1.0 g of t-BuOK and 60 ml of DMF were charged into the Kolben, and the atmosphere was changed to an argon gas atmosphere. Compound (4)
2.0 g and 2.2 g of the compound (5) were added, and the mixture was stirred at room temperature for 1 hour. This was poured into a large excess of water, extracted with toluene, the extract was washed with water, dried over sodium sulfate,
After concentration, column purification was performed, and 2.44 g of compound (6) was obtained.
I got

Step D Toluene was charged into a 100 ml kolben equipped with a thermometer, a dropping funnel, an argon gas introducing device and a stirrer to make an argon gas atmosphere. 15 ml of a hexane solution of n-BuLi (1.72 M) was added thereto, and the mixture was heated to 50 ° C. To this, 2.44 g of compound (6) was added in 30 ml of toluene.
The dissolved liquid was added dropwise, and the mixture was stirred at 50 ° C. for 3 hours. After cooling to −40 ° C., 8 ml of ethylene oxide was added, the temperature was raised to −15 ° C., and the mixture was stirred for 1 hour.
Thereafter, the temperature was raised to room temperature, 5 ml of water was added, and ether 2 was added.
After extraction with 00 ml, the extract was washed with saturated saline.
After washing the washing solution to pH, it was dried over sodium sulfate, concentrated and purified by column to obtain 1.0 g of compound (7).

It is presumed that the compound (a) or the charge transporting compound having a reactive group reacts with the organosilicon compound (b) and is incorporated into a siloxane-based resin having a crosslinked structure. As a result, the photoreceptor having a resin layer containing the siloxane-based resin may cause image blur and change in potential characteristics due to discharge products such as ozone and nitrogen oxide (NOx) generated at the band electrode, and friction during development and cleaning. Image quality degradation caused by wear, scratches, toner adhesion (filming)
A remarkable effect is exhibited, and the durability of the electrophotographic photosensitive member can be improved.

The charge transporting compound having a reactive group in the present invention has a reactive group capable of forming a siloxane-based resin by reacting with the above-mentioned organosilicon compound and the like, and has a low electron or hole drift mobility. As long as it has a compound, it can be used as the charge transporting compound having a reactive group of the present invention. Another definition is Time-Of-
Any charge-transporting compound having the above-mentioned reactive group that can obtain a detection current due to charge-transport by a known method such as the Flight method that can detect charge-transport performance may be used.

For example, hole transport type CTM: xazole, oxadiazole, thiazole, triazole, imidazole, imidazolone, imidazoline, bisimidazolidin, styryl, hydrazone, benzidine, pyrazoline,
Stilbene compound, amine, oxazolone, benzothiazole, benzimidazole, quinazoline, benzofuran, acridine, phenazine, aminostilbene, poly-N-vinylcarbazole, poly-1-vinylpyrene,
Any material having a chemical structure such as poly-9-vinylanthracene and a reactive group such as the above-mentioned hydroxyl group, amine, mercapto or alkoxysilyl may be used.

On the other hand, succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, melitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, nitrobenzene, dinitrobenzene, trinitrobenzene, etc. Tetranitrobenzene, nitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bromanyl, benzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,4'-dinitrobenzophenone, 4-nitrobenzalmalonedinitrile, α-cyano-β- (p-cyanophenyl) -2-
(P-chlorophenyl) ethylene, 2,7-dinitrofluorene, 2,4,7-trinitrofluorenone, 2,
4,5,7-tetranitrofluorenone, 9-fluorenylidenedicyanomethylenemalononitrile, polynitro-9-fluoronylidenedicyanomethylenemalonodinitrile, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3, Charge transporting compounds having a reactive group having a chemical structure such as 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, and melitic acid are used.

As the organosilicon compound (b), which is a raw material for forming the siloxane-based resin having a crosslinked structure, the above-mentioned general formulas (h), (i), (j) and (k) (hereinafter referred to as (h) to (h))
(Referred to as (k)), and the composition ratio thereof is [(j) +
(K)] It is preferable to use 0.05 to 1 mol. In particular, when a high-density crosslinked structure is formed in a siloxane-based resin, it is necessary that the components (h) and (i) be sufficient.

The compound (a) is preferably used in an amount of 0.001 to 20 parts by weight based on 100 parts by weight of the component (b).

The addition amount of the charge transporting compound (d) having a reactive group capable of forming a resin layer by reacting with the organosilicon compound depends on the amount of the components (a) + (b) + (d). It is preferable to use 1 to 500 parts by weight of (d) based on 100 parts by weight in total. When the amount of the component (a) is less than the above range, the effect of preventing the photoreceptor of the present invention from deteriorating against ozone and NOx is not sufficient. On the other hand, if the amount of the component (a) is too large, the film properties of the siloxane-based resin layer are not sufficient, resulting in a resin layer with large abrasion. On the other hand, when the amount of the component (d) is small, the charge transporting ability of the siloxane-based resin layer is small, causing a decrease in sensitivity and an increase in residual charge. When the amount of the component (d) is large, the film strength of the siloxane-based resin layer is reduced. There is a tendency.

Further, colloidal silica:
The component (e) may be added when the siloxane-based resin is formed. In the case of colloidal silica, the hydroxyl groups present on the surface of the colloidal silica also react with the siloxane-based resin to enhance the film strength of the resin layer. The amount of the colloidal silica (e) added is preferably 0.01 to 15% by weight of the entire resin layer.

The siloxane-based resin having a crosslinked structure according to the present invention is formed by adding a catalyst or a crosslinker to a monomer, oligomer or polymer having a siloxane bond in advance to form a new chemical bond in order to promote the crosslinked structure. It is also possible to form a three-dimensional network structure. Further, a three-dimensional network structure can be formed from an oligomer or polymer in which a siloxane bond has been promoted by a hydrolysis reaction of an organosilicon compound and subsequent dehydration condensation.

As the catalyst for forming the three-dimensional network structure, organic carboxylic acid, nitrous acid, sulfurous acid, aluminate,
Each alkali metal salt of carbonic acid and thiocyanic acid, organic amine salt (tetramethylammonium hydroxide, tetramethylammonium acetate), tin organic acid salt (stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyl) And octenoic acid, naphthenate, and acetylacetone complex of aluminum and zinc.

Further, an antioxidant having a chemical structure of hindered phenol, hindered amine, thioether or phosphite can be added to the photosensitive layer other than the resin layer in the present invention, so that the potential stability and image quality at the time of environmental change can be improved. It is effective for improvement.

The layer structure of the electrophotographic photoreceptor of the present invention is not particularly limited, but may be a charge generation layer, a charge transport layer, or a charge generation / charge transport layer (a single layer having both functions of charge generation and charge transport). It is preferable to adopt a structure in which a photosensitive layer such as a photosensitive layer) and a resin layer of the present invention are provided thereon. Further, each of the charge generation layer, the charge transport layer, or the charge generation / charge transport layer may be composed of a plurality of layers.

Examples of the charge generating substance (CGM) contained in the photosensitive layer according to the present invention include phthalocyanine pigments, polycyclic quinone pigments, azo pigments, perylene pigments, indigo pigments, quinacridone pigments, azurenium pigments, squalilium dyes, Examples include cyanine dyes, pyrylium dyes, thiopyrylium dyes, xanthene dyes, triphenylmethane dyes, styryl dyes, and the like. These charge generating substances (CGM) are used alone or together with a suitable binder resin to form a layer.

The charge transport material (C) contained in the photosensitive layer
TM) include, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazoline derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, benzidine compounds, pyrazoline derivatives, stilbenes Compound,
Amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, etc. These charge transport materials (CTM) are usually used to form a layer together with a binder.

As the binder resin contained in the charge generating layer (CGL) and the charge transport layer (CTL) in the case of the photosensitive layer having a single layer structure and the laminated structure, a polycarbonate resin, a polyester resin, a polystyrene resin, a methacryl resin,
Acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl butyral resin, polyvinyl acetate resin, styrene-butadiene resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-maleic anhydride copolymer resin, urethane resin, silicon resin,
Epoxy resin, silicon-alkyd resin, phenol resin, polysilane resin, polyvinyl carbazole and the like can be mentioned.

In the present invention, the ratio between the charge generating substance and the binder resin in the charge generating layer is from 1:10 to 1 by weight.
0: 1 is preferred. The thickness of the charge generation layer is preferably 5 μm or less, and particularly preferably 0.05 to 2 μm.

The charge transport layer is formed by dissolving the charge transport material and the binder resin in a suitable solvent, and applying and drying the solution. The mixing ratio of the charge transport material and the binder resin is preferably from 10: 1 to 1:10 by weight.

The thickness of the charge transport layer is usually from 5 to 50 μm, particularly preferably from 10 to 40 μm. When a plurality of charge transport layers are provided, the thickness of the upper layer of the charge transport layer is 10
μm or less, and preferably smaller than the total thickness of the charge transport layer provided below the charge transport layer.

The siloxane-based resin layer of the present invention may serve also as the charge transport layer when the resin layer is a charge transport layer, and the photosensitive layer itself may be used as the resin layer when the resin layer is a single layer type. Is preferably provided as a separate resin layer on a photosensitive layer such as a charge transport layer, a charge generation layer, or a single-layer charge generation / transport layer. In this case, an adhesive layer may be provided between the photosensitive layer and the resin layer of the present invention. Further, a thinner surface layer may be provided on the resin layer for the purpose of improving the surface characteristics of the electrophotographic photosensitive member.

Next, the electroconductive support of the electrophotographic photoreceptor of the present invention includes: 1) a metal plate such as an aluminum plate or a stainless steel plate; 2) a support such as paper or a plastic film;
A thin metal layer such as aluminum, palladium, or gold provided by lamination or vapor deposition. 3) On a support such as paper or plastic film,
Examples thereof include those in which a layer of a conductive compound such as a conductive polymer, indium oxide, or tin oxide is provided by coating or vapor deposition.

The material of the conductive support used in the present invention is mainly aluminum, copper, brass, steel,
A belt-shaped or drum-shaped metal material such as stainless steel or another plastic material is used. Among them, aluminum excellent in cost, workability and the like is preferably used, and a thin-walled cylindrical aluminum tube usually formed by extrusion or drawing is often used.

The conductive support used in the present invention preferably has a roughened surface having a ten-point average surface roughness Rz of more than 0.3 μm and not more than 2.5 μm. More preferably, it is 0.6 μm or more and 2.0 μm or less.

When the ten-point average surface roughness Rz is 0.3 μm or less, the adhesiveness is insufficient, and when a laser light source is used as an exposure light source, moire is generated in an image, which is not practical. When Rz is larger than 2.5 μm, there is a problem that a processed line appears in an image.

As a method for roughening the conductive support, in the case of a metal tube made of aluminum or the like, a metal surface is mirror-polished and then finely grooved with a diamond tool or the like, or the metal tube is blasted by sand blasting. A method of roughening the surface is preferable, but the present invention is not limited to these methods.

The shape of the support may be a drum shape, a sheet shape, or a belt shape, and is preferably a shape most suitable for the applied electrophotographic apparatus.

The solvent or dispersion medium used in the production of the photoreceptor of the present invention includes n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, methylethylketone,
Methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, Tetrahydrofuran, dioxolan, dioxane,
Methanol, ethanol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide,
Methyl cellosolve and the like. Although the present invention is not limited to these, dichloromethane, 1,2-dichloroethane, methyl ethyl ketone and the like are preferably used. In addition, these solvents can be used alone or as a mixed solvent of two or more kinds.

The coating method for producing the electrophotographic photosensitive member of the present invention includes dip coating, spray coating,
A coating method such as circular amount control type coating is used, but the coating process on the resin layer side of the photosensitive layer is performed by spray coating or circular amount control type in order to minimize dissolution of the lower layer film and to achieve uniform coating processing. (A typical example is the circular slide hopper type.)
It is preferable to use a coating method such as coating. The spray coating is described in detail in, for example, JP-A-3-90250 and JP-A-3-269238,
The circular amount control type coating is described in, for example, JP-A-58-1.
It is described in detail in JP-A-89061.

The photoreceptor of the present invention is preferably heated and dried at a temperature of 50 ° C. or higher, preferably 60 to 200 ° C., after the resin layer is formed. By this heating and drying, the remaining coating solvent can be reduced, and the curable resin layer can be sufficiently cured.

In the present invention, it is preferable to provide an intermediate layer having a barrier function between the conductive support and the photosensitive layer.

Materials for the intermediate layer include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, and phenol resin polyamides (nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethyl And an intermediate layer using polyurethane, gelatin, and aluminum oxide, or a hardening intermediate layer using a metal alkoxide, an organic metal chelate, or a silane coupling agent as described in JP-A-9-68870. The thickness of the intermediate layer is preferably from 0.1 to 10 μm, particularly preferably from 0.1 to 10 μm.
5 μm is preferred.

In the present invention, a coating for compensating for surface defects of the support is provided between the support and the intermediate layer, and interference fringes, which is a problem particularly when image input is performed by a laser beam, are performed. A conductive layer for the purpose of preventing generation and the like can be provided. This conductive layer is made of carbon black,
It can be formed by applying and drying a solution in which conductive powder such as metal particles or metal oxide particles is dispersed in a suitable binder resin. The thickness of the conductive layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

The electrophotographic photoreceptor of the present invention is applicable to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers. It can be widely applied to devices such as light printing, plate making, and facsimile.

FIG. 1 is a sectional view showing an example of an image forming apparatus having the electrophotographic photosensitive member of the present invention.

In FIG. 1, reference numeral 10 denotes a photosensitive drum (photosensitive member) serving as an image carrier, and an organic photosensitive layer is coated on the drum.
A photoreceptor coated with the resin layer of the present invention thereon is grounded and driven to rotate clockwise. Reference numeral 12 denotes a scorotron charger, which applies uniform charging to the peripheral surface of the photosensitive drum 10 by corona discharge. Prior to the charging by the charger 12, in order to eliminate the history of the photoconductor in the previous image formation, exposure by the exposure unit 11 using a light emitting diode or the like may be performed to remove electricity from the peripheral surface of the photoconductor.

After the photosensitive member is uniformly charged, the image exposing unit 13 performs image exposure based on the image signal. The image exposure device 13 in this figure uses a laser diode (not shown) as an exposure light source. The light on the photosensitive drum is scanned by the light whose optical path is bent by the reflection mirror 132 through the rotating polygon mirror 131, the fθ lens, and the like, and an electrostatic latent image is formed.

Next, the electrostatic latent image is developed by the developing device 14. Developing devices 14 each having a built-in developer composed of toner and carrier such as yellow (Y), magenta (M), cyan (C), black (K), etc., at the periphery of the photosensitive drum 10.
First, development of the first color is performed by a developing sleeve 141 which rotates with a built-in magnet and holding a developer. The developer comprises, for example, a carrier in which an insulating resin is coated around a ferrite core, and a toner in which a pigment corresponding to a color and a charge control agent, silica, titanium oxide, etc. are added using polyester as a main material. The developer is regulated to a layer thickness of 100 to 600 μm on the developing sleeve 141 by a layer forming means (not shown), and is conveyed to a developing area to be developed. At this time, normally, a DC and / or AC bias voltage is applied between the photosensitive drum 10 and the developing sleeve 141 to perform the development.

In the color image formation, after the visualization of the first color is completed, the image forming process of the second color is started, and the uniform charging is performed again by the scorotron charger 12 to form the latent image of the second color. It is formed by the exposure device 13. An image forming process similar to that for the second color is performed for the third color and the fourth color, and a visible image of four colors is formed on the peripheral surface of the photosensitive drum 10.

On the other hand, in a monochrome electrophotographic apparatus, the developing device 1
Reference numeral 4 is composed of one kind of black toner and can form an image by one development.

After the image is formed, the recording paper P is fed to the transfer area by the rotation of the paper feed roller 17 at the time when the transfer timing is adjusted.

In the transfer area, a transfer roller (transfer device) 1 is mounted on the peripheral surface of the photosensitive drum 10 in synchronization with the transfer timing.
8, the multicolor image is transferred collectively by sandwiching the fed recording paper P.

Next, the recording paper P is neutralized by a separation brush (separator) 19 brought into pressure contact with the transfer roller almost at the same time, and separated by the peripheral surface of the photosensitive drum 10 to be conveyed to the fixing device 20, where the heat roller 201 and pressure roller 2
After the toner is welded by heating and pressurizing 02, the toner is discharged to the outside of the apparatus via the discharge roller 21. The transfer roller 18 and the separation brush 19 are retracted and separated from the peripheral surface of the photosensitive drum 10 after the recording paper P has passed to prepare for the formation of the next toner image.

On the other hand, the photosensitive drum 10 from which the recording paper P has been separated removes and cleans the residual toner by pressing the blade 221 of the cleaning device 22 and receives the charge removal by the exposure unit 11 and the charge by the charger 12 again. The next image forming process is started. When a color image is formed on the photoconductor by superimposition, the blade 221 moves immediately after the cleaning of the photoconductor surface and retreats from the peripheral surface of the photoconductor drum 10.

Reference numeral 30 denotes a detachable process cartridge in which a photosensitive member, a charging device, a transfer device / separator, and a cleaning device are integrated.

The electrophotographic image forming apparatus is constructed by integrally combining the above-described photoreceptor, a developing device, a cleaning device, and other components as a process cartridge, and this unit is configured to be detachable from the apparatus main body. You may.
Also, a process cartridge is formed by integrally supporting at least one of a charger, an image exposing unit, a developing unit, a transfer or separating unit, and a cleaning unit together with a photoreceptor. It may be configured to be detachable using a guide means such as a rail of the apparatus body.

The process cartridge generally includes an integral type cartridge and a separate type cartridge described below. The integral type cartridge is configured such that at least one of a charger, an image exposing unit, a developing unit, a transfer or separating unit, and a cleaning unit is integrally formed with a photoconductor, and is detachable from an apparatus main body. Are a charging device, an image exposure device, a developing device, a transfer or separation device, and a cleaning device which are configured separately from the photoreceptor, but have a configuration detachable from the apparatus main body and are incorporated in the apparatus main body. When integrated, it is integrated with the photoconductor. The process cartridge in the present invention includes both types of cartridges.

When the image forming apparatus is used as a copying machine or a printer, the image exposure is performed by irradiating the photosensitive member with reflected light or transmitted light from the original, or by reading the original with a sensor and converting it into a signal. Scanning of a laser beam, driving of an LED array, or driving of a liquid crystal shutter array is performed by irradiating the photosensitive member with light.

When used as a facsimile printer, the image exposure unit 13 performs exposure for printing received data.

The electrophotographic photoreceptor of the present invention can be applied to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers. It can be widely applied to devices such as light printing, plate making, and facsimile.

[0127]

Example 1 To prepare a coating solution, methyltrimethoxysilane 60 was used.
Parts, 10 parts of dimethyldimethoxysilane, 3 parts of the exemplary compound (A-1) of the present invention, 40 parts of a charge transporting compound having a reactive group (HCT-3), colloidal silica (methanol dispersion, solid content 30% by weight) ) 8% 5% acetic acid aqueous solution 4
0 parts / 800 parts of isopropanol, 65-70 ° C
For 5 hours. Thereafter, 0.4 parts of tetramethylammonium acetate as a curing catalyst was added and dissolved to prepare a resin layer composition.

Next, in order to produce a photoreceptor, a titanium chelate compound “TC-750” was placed on a cylindrical aluminum drum.
(Matsumoto Pharmaceutical Co., Ltd.) 20 parts, silane coupling agent "KB
M-503 "(manufactured by Shin-Etsu Chemical Co., Ltd.), 13 parts of which was dissolved in 100 parts of a mixed solvent of isopropanol / water = 100: 3, dip-coated and heated and cured at 150 ° C. for 30 minutes to a thickness of 1.0 μm. Was provided.

In addition, Cu-Kα is used as a charge generating material.
The maximum peak of Bragg angle 2θ in characteristic X-ray diffraction is 2
A coating liquid in which 6 parts of titanyl phthalocyanine having 7.2 degrees, 7 parts of a silicone resin “KR-5240” (manufactured by Shin-Etsu Chemical Co., Ltd.) and 200 parts of t-butyl acetate are dispersed using a sand grinder is applied by dip coating to obtain a film. A charge generation layer having a thickness of 0.3 μm was formed.

Next, 200 parts of the following charge transport material (CT-1) and antioxidant (AO-1) 5 were used as the charge transport material.
Coating solution prepared by dissolving 300 parts of bisphenol Z-type polycarbonate "Iupilon Z300" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in 2000 parts of 1,2-dichloroethane was applied on the charge generation layer with a circular slide hopper to obtain a film thickness. 25μ
m of the charge transport layer was formed.

Next, the above-mentioned composition for a resin layer was applied by a circular slide hopper and cured by heating at 110 ° C. for 90 minutes.
Photosensitive member 1 was prepared by forming a resin layer having a thickness of 2.0 μm and having an antioxidant functional group and a charge transport functional group of the present invention.

[0132]

Embedded image

Example 2 60 parts of methyltrimethoxysilane, 30 parts of phenyltrimethoxysilane, 3 parts of Exemplified Compound (A-3) of the present invention, and charge transport having a reactive group were prepared. Photoconductor 2 was prepared in the same manner as in Example 1, except that 30 parts of the neutral compound (HCT-4) and 10 parts of colloidal silica (methanol dispersion, solid content: 30% by weight) were used.

Example 3 50 parts of methyltrimethoxysilane, 25 parts of γ-glycidoxypropyltrimethoxysilane, 5 parts of Exemplified Compound (A-9) of the present invention, -Transporting Compound Having a Group (HCT-13) 50
Parts, colloidal silica (methanol dispersion, solid content 30
Photosensitive member 3 was prepared in the same manner as in Example 1 except that the amount was changed to 10 parts by weight.

Example 4 30 parts of methyltrimethoxysilane, 25 parts of phenyltrimethoxysilane, 10 parts of dimethyldimethoxysilane, 5 parts of Exemplified Compound (A-5) of the present invention, and 30 parts of the composition for a resin layer in Example 1 were reacted. Except that the charge-transporting compound (HCT-6) having a functional group was changed to 40 parts, colloidal silica (methanol dispersion, solid content 30% by weight) was changed to 10 parts, and the curing catalyst was changed to dibutyltin dilaurate 0.4 parts. Then, a photoreceptor 4 was produced in the same manner as in Example 1.

Example 5 30 parts of methyltrimethoxysilane, 25 parts of phenyltrimethoxysilane, 10 parts of dimethyldimethoxysilane, 5 parts of Exemplified Compound (A-13) of the present invention, Photoconductor 5 was prepared in the same manner as in Example 4, except that the charge transporting compound having a functional group (HCT-29) was changed to 40 parts and colloidal silica (methanol dispersion, solid content: 30% by weight) was changed to 10 parts. .

Example 6 30 parts of methyltrimethoxysilane, 25 parts of phenyltrimethoxysilane, 10 parts of perfluorooctylethyltrimethoxysilane were prepared using the resin layer composition of Example 4
Photoconductor 6 was prepared in the same manner as in Example 4, except that 5 parts of the exemplary compound (A-9) of the present invention and 12 parts of colloidal silica (methanol dispersion, solid content: 30% by weight) were used.

Example 7 The composition for a resin layer in Example 1 was prepared using 60 parts of methyltrimethoxysilane, 20 parts of phenyltrimethoxysilane, 3 parts of the exemplary compound (A-16) of the present invention, and charge transport having a reactive group. Same as Example 1 except that 40 parts of the reactive compound (HCT-3) and 8 parts of colloidal silica (methanol dispersion, solid content 30% by weight) were used and the curing catalyst was changed to 0.4 parts of zinc octenoate. Thus, a photoreceptor 7 was prepared.

Example 8 The composition for a resin layer in Example 7 was prepared by adding 50 parts of methyltrimethoxysilane, 10 parts of dimethyldimethoxysilane,
10 parts of methacryloxypropyltrimethoxysilane,
5 parts of the exemplified compound (A-20) of the present invention, 30 parts of the charge transporting compound having a reactive group (HCT-18), and colloidal silica (methanol dispersion, solid content 30% by weight) 10
A photoreceptor 8 was prepared in the same manner as in Example 7, except that the parts were changed.

Example 9 The composition for a resin layer in Example 7 was prepared by adding 70 parts of methyltrimethoxysilane, 10 parts of γ-aminopropyltrimethoxysilane, 5 parts of the exemplary compound (A-22) of the present invention, and a reactive group. Photoconductor 9 was prepared in the same manner as in Example 7, except that the charge transporting compound (HCT-7) was changed to 40 parts and colloidal silica (methanol dispersion, solid content: 30% by weight) was changed to 10 parts.

Comparative Example 1 A photoreceptor 10 was prepared in the same manner as in Example 1, except that the exemplary compound (A-1) of the present invention was omitted.

Comparative Example 2 Photosensitive member 11 was prepared in the same manner as in Example 6, except that Exemplified Compound (A-9) of the present invention was omitted.

Comparative Example 3 A photoconductor 12 was prepared in the same manner as in Example 7, except that the exemplary compound (A-16) of the present invention was omitted.

Comparative Example 4 A photoconductor 13 was produced in the same manner as in Example 1, except that the resin layer was not provided.

Evaluation 1 The photoconductors obtained in each of the examples and comparative examples were modified with a digital copying machine “Konica 7050” manufactured by Konica Corporation and adjusted to adjust the exposure to the photoconductor sensitivity (reversal development, laser exposure). ), Set the initial charge potential to -650 V, and after 30,000 times continuous copy actual shooting test (image output of A4) under high temperature and high humidity (HH) environment (33 ° C; 80%) 1
After resting for a period of time, under a low temperature and low humidity (LL) environment (15 ° C; 30 ° C)
%), A 30,000-time continuous copy actual copying test (image output of A4) was performed 60,000 times in total, and the copied image and the scratches on the surface of the photoreceptor in the actual copying test were observed and evaluated every 1000 sheets. In addition, the thickness loss of the photoconductor before and after the actual photographing test was measured.
Table 1 shows the results.

The film thickness of the photosensitive layer is measured at random at 10 locations of uniform thickness, and the average value is taken as the film thickness of the photosensitive layer. The EDDY560C eddy current film thickness measuring device
(Made by HELMUT FISCHER GMBTE CO), and the difference between the thicknesses of the photosensitive layers before and after the actual photographing test is defined as the thickness loss.

[0147]

[Table 1]

From the results shown in Table 1, the electrophotographic photosensitive member having a resin layer containing the antioxidant function of the present invention in a siloxane resin is a comparative electrophotographic photosensitive member not having the antioxidant function in the siloxane resin. On the other hand, it can be seen that a remarkable improvement effect was obtained in a continuous copy actual test under severe environmental conditions of high temperature, high humidity and low temperature and low humidity.

Example 10 To prepare a coating solution, methyltrimethoxysilane 60 was used.
Parts, 10 parts of dimethyldimethoxysilane, 5 parts of the exemplary compound (A-21) of the present invention, 40 parts of the charge transporting compound having a reactive group (HCT-24), colloidal silica (methanol dispersion, solid content of 30% by weight) ) 40 parts of 5% acetic acid aqueous solution / 800 parts of isopropanol were added to 10 parts,
A hydrolysis reaction was performed at 70 ° C. for 5 hours. Thereafter, 0.4 parts of tetramethylammonium acetate as a curing catalyst was added and dissolved to prepare a resin layer composition.

Next, in order to prepare a photoreceptor, 6 parts of polyamide resin “X1874M” (manufactured by Daicel Huls) were placed on a cylindrical aluminum drum using methanol: n-butanol =
An intermediate layer solution dissolved in 200 parts of a 4: 1 mixed solvent was applied by dip coating to form an intermediate layer having a thickness of 0.5 μm.

Further, as a charge-generating substance, the compound represented by the chemical formula (C)
G-1) 10 parts, 4 parts of butyral resin "BM-S" (manufactured by Sekisui Chemical Co., Ltd.) and 200 parts of methyl isobutyl ketone were dispersed and applied by a sand grinder by dip coating to form a film having a thickness of 0.5 μm. A charge generation layer was formed.

Next, as a charge transporting substance, the compound represented by the chemical formula (CT-
2) 200 parts, hindered amine compound "Sanol LS
2626 "(manufactured by Sankyo Chemical Co., Ltd.) and 5 parts of bisphenol Z-type polycarbonate" Iupilon Z300 "(manufactured by Mitsubishi Gas Chemical Co., Ltd.) dissolved in 2000 parts of 1,2-dichloroethane. It was applied by a hopper to form a charge transport layer having a thickness of 20 μm.

Next, the above-mentioned composition for a resin layer was applied by a circular slide hopper, and cured by heating at 110 ° C. for 90 minutes.
A surface protection generating layer having a thickness of 2.0 μm is formed to
Was prepared.

[0154]

Embedded image

Example 11 The composition for a resin layer in Example 10 was prepared by adding 30 parts of methyltrimethoxysilane, 25 parts of phenyltrimethoxysilane,
10 parts of dimethyldimethoxysilane, 5 parts of the exemplary compound (A-17) of the present invention, 40 parts of a charge transporting compound having a reactive group (HCT-12), colloidal silica (methanol dispersion, solid content 30% by weight) 8 A photoreceptor 15 was produced in the same manner as in Example 10 except that the parts were changed.

Example 12 The composition for a resin layer in Example 10 was prepared by adding 30 parts of methyltrimethoxysilane, 25 parts of phenyltrimethoxysilane,
Perfluorooctylethyltrimethoxysilane 10
Parts, Exemplified Compound (A-23) of the present invention, 5 parts, charge transporting compound having a reactive group (HCT-30), 40 parts, colloidal silica (methanol dispersion, solid content: 30% by weight)
Except that the photosensitive member 1 was changed to 12 parts,
No. 6 was produced.

Comparative Example 5 A photoreceptor 17 was prepared in the same manner as in Example 10, except that the exemplified compound (A-21) of the present invention was omitted.

Comparative Example 6 Example 1 was repeated except that no resin layer was provided.
In the same manner as in Example No. 0, a photoreceptor 18 was produced.

The obtained photoreceptor was evaluated as follows.

Evaluation 2 The photoreceptors obtained in the respective Examples and Comparative Examples were mounted on an evaluation machine in which an analog copy machine “U-Bix3340” manufactured by Konica Corporation was modified and the exposure amount was adjusted, and the initial charge position was measured. To -750
V, and was suspended for 1 hour after 30,000 actual shooting tests in a high-temperature and high-humidity (HH) environment (33 ° C .; 80%), and then in a low-temperature and low-humidity (LL) environment (15 ° C; 30%)
A total of 60,000 actual-photographing tests were carried out at, and a copy image and scratches on the surface of the photoreceptor were observed in the actual-photographing test. Table 2 shows the results.

[0161]

[Table 2]

As can be seen from the results shown in Table 2, the electrophotographic photoreceptor having a resin layer containing the antioxidant function of the present invention in a siloxane resin does not have the antioxidant function in the siloxane resin. On the other hand, it can be seen that a remarkable improvement effect was obtained in a continuous copy actual test under severe environmental conditions of high temperature, high humidity and low temperature and low humidity.

[0163]

According to the present invention, there is no problem in chargeability, sensitivity and residual potential, and the potential stability by repeated use is good.
It is possible to provide an electrophotographic photoreceptor that gives a clear copy image under all environments, has good scratch resistance and filming resistance, has little wear due to repeated use, and has excellent durability.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of an image forming apparatus having an electrophotographic photosensitive member according to the present invention.

DESCRIPTION OF SYMBOLS 10 Photoconductor drum (or photoconductor) 11 Exposure unit using light emitting diode or the like 12 Charger 13 Image exposure device 14 Developing device 17 Paper feed roller 18 Transfer roller (transfer device) 19 Separation brush (separator) 20) Fixing device 21 Discharge roller 22 Cleaning device 30 Process cartridge

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor ▲ Saki ▼ Tomoko Mura 1 Konica Co., Ltd., Sakuracho, Hino-shi, Tokyo In-house F-term (reference) 2H068 AA02 AA13 AA16 AA20 BA58 BB33 BB49 FA27

Claims (7)

[Claims] In an electrophotographic photosensitive member having a photosensitive layer and a resin layer on a conductive support, the resin layer of the electrophotographic photosensitive member reacts at least the following two components (a) and (b). An electrophotographic photoreceptor comprising a layer containing a siloxane-based resin having a crosslinked structure obtained by the above method. (A) Component: at least one compound represented by the following general formula (1) or (2) (b) Component: 1 of an organosilicon compound represented by the following general formula (3) or a hydrolytic condensate thereof More than species (In the general formulas (1) and (2), A represents a monovalent or polyvalent compound group having an antioxidant function, R ₁ and R ₃ represent a single bond or a divalent group, and R ₂ represents a substituent. , Represents an unsubstituted monovalent hydrocarbon group, Z ₁ represents a hydroxyl group or a hydrolyzable group, m represents an integer of 0 to 2, n and l represent integers of 1 to 4. The general formula ( In 3), R ₄ represents an organic group in which carbon is directly bonded to a silicon atom in the formula, Z ₂ represents a hydroxyl group or a hydrolyzable group, and r represents an integer of 0 to _3. ) 2. An electrophotographic photosensitive member having a photosensitive layer and a resin layer on a conductive support, wherein the resin layer of the electrophotographic photosensitive member comprises the two components (a) and (b) and the component (a) or (b). (B)
An electrophotographic photoreceptor, which is a layer containing a siloxane-based resin having a crosslinked structure obtained by reacting a charge transporting compound having a reactive group capable of forming a resin when combined with a component. . 3. The method according to claim 1, wherein A in the general formula (1) or (2) is a monovalent or polyvalent compound group having a hindered phenol or hindered amine chemical structure. Item 3. The electrophotographic photosensitive member according to Item 2. 4. The electrophotographic photoreceptor according to claim 2, wherein the charge transporting compound having a reactive group is a charge transporting compound having a hydroxyl group. 5. The electrophotographic photosensitive member according to claim 1, wherein the resin layer is a surface layer. 6. An electrophotographic image forming apparatus having an electrophotographic photosensitive member and at least means for charging, image exposure, development and cleaning, wherein the electrophotographic photosensitive member is An electrophotographic image forming apparatus using the electrophotographic photoreceptor according to any one of the preceding claims. 7. A process cartridge used in an electrophotographic image forming apparatus having an electrophotographic photosensitive member and at least means for charging, image exposure, development, and cleaning.
An electrophotographic photoreceptor and a charger according to any one of claims 1 to 5,
A process cartridge having one of an image exposing unit, a developing unit, and a cleaning unit integrally, and being designed to be freely inserted into and removed from the electrophotographic image forming apparatus.