JP2000284515A - Electrophotographic photoreceptor and process cartridge and image forming device using that photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophotographic photoreceptor having high wear resistance and stable electrophotographic characteristics for repeated use at high temperature and high humidity and to obtain a good image even for repeated use by forming a specified resin layer as a surface layer and using a support consisting of a conductive support and an anodized film subjected to sealing treatment on the surface of the support. SOLUTION: The surface layer of the electrophotographic photoreceptor contains a curing siloxane resin having charge transfer ability. The conductive support has an anodized film which is subjected to sealing treatment. The curing siloxane resin layer may act as a charge transfer layer, however, the resin layer is preferably formed separately from the photosensitive layers such as a charge transfer layer and a charge generating layer or a single layer type charge generating and transfer layer. Moreover, an adhesive layer is preferably formed between the photosensitive layer and the resin layer. As for the material of the conductive support, a metal material such as aluminum, copper and brass, or a plastic material molded into a belt or drum can be used, and aluminum is preferable.

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), and a process cartridge and an image forming apparatus using the photosensitive member.

[0002]

2. Description of the Related Art In recent years, an organic photoconductor containing an organic photoconductive substance has been most widely used as an electrophotographic photoconductor. Organic photoreceptors are advantageous over other photoreceptors in that materials that can be used for various exposure light sources from visible light to infrared light can be easily developed, materials that do not pollute the environment can be selected, and manufacturing costs are low. However, the only disadvantage is that the mechanical strength is weak,
The problem is that the photoreceptor surface is deteriorated or scratched when copying or printing a large number of sheets.

[0003] Such a photoreceptor is generally formed by depositing an organic charge generating substance on a conductive support made of aluminum or an aluminum alloy, or forming an organic charge generating substance and an organic polymer resin as a binder. To form a charge generation layer by applying a coating liquid in which a solvent is mixed with a solvent, and then apply a coating liquid in which an organic charge transporting substance and an organic polymer resin as a binder are mixed with a solvent. To form a charge transport layer.

In recent years, demands for image quality of an electrophotographic image forming apparatus have become more and more severe. In particular, L
D, LED printers and other reversal development type printers are required to have high print quality. For example, it is also required to eliminate minute image black spots (so-called black spots) generated on a white background.

In general, in a Carlson method electrophotographic copying apparatus, after uniformly charging a photoreceptor, the charge is erased imagewise by exposure to form an electrostatic latent image, and the electrostatic latent image is formed. The toner is developed and visualized with a toner, and then the toner is transferred and fixed on paper or the like.

However, not all of the toner on the photoreceptor is transferred, and a part of the toner remains on the photoreceptor. When an image is repeatedly formed in this state, the formation of a latent image is disturbed by the effect of the residual toner. Therefore, it is not possible to obtain a high-quality copy without contamination. Therefore, it is necessary to remove the residual toner. The cleaning means is typically a fur brush, a magnetic brush, a blade, or the like, but a blade is mainly used in terms of performance, configuration, and the like. At this time, a plate-shaped rubber elastic body is generally used as the blade member.

As described above, since the surface of the electrophotographic photosensitive member is directly applied with an electric or mechanical external force by a charger, a developing device, a transfer means, a cleaning device, etc., the surface thereof is required to have durability. In particular, it is required to have mechanical durability against abrasion and scratches on the surface of the photoreceptor due to rubbing, film intrusion of foreign matter, and film peeling due to impact during paper jam processing. Above all, with respect to durability against scratches and film peeling due to impact, a strength as high as that of an inorganic photoreceptor is strongly required.

In order to satisfy the various characteristics required as described above, various things have been studied so far.

Regarding the image quality, there has been proposed a photoreceptor in which an alumite layer is formed on an aluminum substrate surface as a conductive substrate as an interface blocking layer for suppressing charge injection into the photosensitive layer. However, when such an alumite layer is used, the image quality such as black spots is improved, but the adhesion to the photosensitive layer is reduced, so that the resistance to a mechanical external force on the surface of the photosensitive layer is reduced. This causes problems such as scratches and film peeling.

On the other hand, with respect to mechanical durability, it has been reported that the use of BPZ polycarbonate as a binder (binder resin) on the surface of an organic photoreceptor improves the surface wear characteristics and toner filming characteristics. I have.
Japanese Patent Application Laid-Open No. Hei 6-118681 reports that a curable silicone resin containing colloidal silica is used as a surface protective layer of a photoreceptor.

However, a photoreceptor using a bisphenol Z-type polycarbonate binder still lacks abrasion resistance and does not have sufficient durability. On the other hand, in the surface layer of the curable silicone resin containing colloidal silica, the abrasion resistance is improved, but the electrophotographic properties after repeated use are insufficient, and fogging and image blur are liable to occur. Not enough.

As a method for improving such a defect, Japanese Patent Application Laid-Open No. 9-124943 and Japanese Patent Application Laid-Open No. 9-190004
In Japanese Patent Application Laid-Open No. H11-264, a photoreceptor having a resin layer in which an organosilicon-modified hole transporting compound is bound in a curable organosilicon polymer as a surface layer is proposed. However, this resin layer is liable to generate fog and image blur in a high humidity environment and does not have sufficient durability. Further, such a curable organosilicon compound film has high abrasion resistance, but is easily damaged or peeled off by an external impact, and has insufficient strength and adhesiveness.

[0013] With the recent development of digital technology, the image forming method using electrophotography has been predominantly performed by image exposure using a coherent light source such as a laser beam. It has been desired to develop an electrophotographic photoreceptor that does not generate, has high abrasion resistance, does not scratch or peel off due to external impact, and does not generate image blur.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems by providing a high surface hardness, a high abrasion resistance and a high scratch resistance, and an electrophotographic characteristic upon repeated use at high temperature and high humidity. The present invention is to provide an electrophotographic photoreceptor which is stable even under, and therefore, a good image is repeatedly obtained and does not generate moire even in the formation of a digital image by a laser beam or the like. An object of the present invention is to provide a process cartridge and an image forming apparatus.

[0015]

Means for Solving the Problems As a result of the present inventors' earnest efforts to solve the above problems, a specific resin layer was formed on the surface layer of the electrophotographic photosensitive member, and the surface of the support was formed on the conductive support. It has been found that the object of the present invention can be achieved by using a support on which an alumite membrane having been subjected to a sealing treatment is formed. That is, it has been found that the object of the present invention is achieved by adopting any one of the following constitutions.

1. In an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the surface layer of the electrophotographic photosensitive member is a layer containing a curable siloxane resin having a charge transporting ability, and the conductive support is provided on the surface thereof. An electrophotographic photoreceptor having a sealed alumite film formed thereon.

2. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photoreceptor is a layer containing a curable siloxane resin containing a partial structure having a charge transporting ability; Wherein an alumite film subjected to a sealing treatment is formed on the surface thereof.

3. 3. The electrophotographic photoreceptor according to the above item 2, wherein the partial structure having the charge transporting ability has the following structural formula.

[0019]

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(Wherein X is a charge-transporting group,
A group bonded to Y via a carbon atom constituting the imparting group,
Y is a divalent or higher valent atom or group excluding adjacent bonding atoms (Si and C). ) 4. 4. The electrophotographic photoreceptor according to the above item 2 or 3, wherein the partial structure having the charge transporting ability has the following structural formula.

[0021]

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(Wherein X is a charge-transporting group,
A group bonded to Y via a carbon atom constituting the imparting group,
Y is an oxygen atom, a sulfur atom, NR, R is a hydrogen atom,
Monovalent organic group. ) 5. In an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the surface layer of the electrophotographic photosensitive member is obtained by reacting an organic silicon compound having a hydroxyl group or a hydrolyzable group with a charge transporting compound having a hydroxyl group. An electrophotographic photoreceptor, comprising a resin layer containing a curable siloxane resin to be obtained, wherein the conductive support has a surface thereof on which an alumite film having been subjected to a sealing treatment is formed.

6. In an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the surface layer of the electrophotographic photosensitive member is reacted with an organosilicon compound having a hydroxyl group or a hydrolyzable group and a charge transporting compound having an amino group. An electrophotographic photoreceptor, which is a resin layer containing a curable siloxane resin to be obtained, wherein the conductive support has a surface thereof on which a sealed alumite film is formed.

[7] In an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the surface layer of the electrophotographic photosensitive member is obtained by reacting an organic silicon compound having a hydroxyl group or a hydrolyzable group with a charge transporting compound having a mercapto group. An electrophotographic photoreceptor, comprising a resin layer containing a curable siloxane resin to be obtained, wherein the conductive support has a surface thereof on which an alumite film having been subjected to a sealing treatment is formed.

8. 8. The electrophotographic photoreceptor according to any one of items 1 to 7, wherein the resin layer containing the curable siloxane resin is cured.

9. 9. The electrophotographic photoconductor according to any one of items 1 to 8, wherein the photosensitive layer has a charge generation layer and a charge transport layer.

10. 9. The electrophotographic photoconductor according to any one of the items 1 to 8, wherein the photosensitive layer has a charge generation / transport layer.

11. The electrophotographic photosensitive member according to any one of the above items 1 to 10, wherein an intermediate layer is provided between the conductive support and the photosensitive layer.

12. The thickness of the surface layer is 0.1 to 20 μm
m. The electrophotographic photosensitive member according to any one of 1 to 11 above, wherein

13. Any one of the above items 1 to 12, wherein an adhesive layer is provided between the surface layer and an adjacent layer.
13. The electrophotographic photoreceptor according to item 6.

14. Wherein the charge transport ability-imparting group is a triarylamine compound residue.
14. The electrophotographic photosensitive member according to any one of the above items 13.

15. 14. The electrophotographic photoreceptor according to any one of the items 3 to 13, wherein the charge transport ability-imparting group is a hydrazone compound residue.

16. 14. The electrophotographic photoreceptor according to any one of the items 3 to 13, wherein the charge transport ability-imparting group is a styryltriphenylamine compound residue.

17. 14. The electrophotographic photoreceptor according to any one of the items 3 to 13, wherein the charge transport ability-imparting group is a benzidine compound residue.

18. 14. The electrophotographic photoreceptor according to any one of the items 3 to 13, wherein the charge transport ability-imparting group is a butadiene compound residue.

19. Any one of the above items 11 to 18, wherein the intermediate layer is a resin layer
13. The electrophotographic photoreceptor according to item 6.

20. 20. The electrophotographic photosensitive member according to any one of items 11 to 19, wherein the intermediate layer is a resin layer formed by reacting an organic metal compound and an organic metal chelate compound.

21. 21. The electrophotographic photoconductor according to any one of the above items 1 to 20, wherein the electrophotographic photoconductor contains an antioxidant.

22. 22. The electrophotographic photoreceptor as described in 21 above, wherein the antioxidant is a compound having a partial structure of hindered phenol, hindered amine, thioether or phosphite.

23. 23. An image forming apparatus using the electrophotographic photosensitive member according to any one of 1 to 22 to form an image through charging, image exposure, development, transfer, separation, and cleaning.

24. A process cartridge used in an image forming apparatus that uses an electrophotographic photosensitive member and undergoes charging, image exposure, development, transfer / separation, and cleaning steps is the same as that of the above-described 1.
23. A process cartridge comprising a combination of the electrophotographic photoreceptor according to any one of Items 22 to 22, and at least one of a charger, an image exposure device, a developing device, and a cleaning device.

The present invention will be described in more detail.

In the present invention, the curable siloxane resin is produced by a known method, that is, using an organosilicon compound having a hydroxyl group or a hydrolyzable group. The organosilicon compound is represented by the following general formulas (A) to (D).

[0044]

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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 X represents a hydroxyl group or a hydrolyzable group.) In the case of a decomposable group, examples of the hydrolyzable group include a methoxy group, an ethoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group. 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, β- (3,4-epoxycyclohexyl) ethyl, γ-acryloxypropyl, γ
A (meth) acryloyl group of methacryloxypropyl, a hydrate group such as γ-hydroxypropyl and 2,3-dihydroxypropyloxypropyl, a vinyl group such as vinyl and propenyl, a mercapto group such as γ-mercaptopropyl, Amino-containing groups such as γ-aminopropyl, N-β (aminoethyl) -γ-aminopropyl, and γ-chloropropyl, 1,1,1-trifluorofluoropropyl, nonafluorohexyl, perfluorooctylethyl, etc. Examples include a halogen group, other nitro and cyano-substituted alkyl groups, and the like. Further, R _{1 to} R ₆ may have the same or different organic groups.

The organosilicon compound used as a raw material of the curable siloxane resin having a charge transporting ability or the curable siloxane resin having a partial structure having a charge transporting ability according to the present invention generally contains a hydrolyzable compound bonded to a silicon atom. When the number n of the decomposable groups is 1, the polymerization reaction of the organosilicon compound is suppressed. When n is 2, 3 or 4, a polymerization reaction is likely to occur, and especially when 3 or 4, the crosslinking reaction can be advanced 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 for the curable resin, a hydrolysis-condensation product obtained by hydrolyzing the organosilicon compound under acidic or basic conditions to oligomerize or polymerize can also be used.

As described above, the curable siloxane resin of the present invention is obtained by previously reacting a monomer, oligomer, or polymer having a siloxane bond in a chemical structural unit (hydrolysis reaction, reaction in which a catalyst or a crosslinking agent is added, etc.). Means a resin that has formed and cured a three-dimensional network structure. That is, it means a siloxane resin formed by promoting a siloxane bond by a hydrolysis reaction and subsequent dehydration condensation of an organosilicon compound having a siloxane bond to form a three-dimensional network structure.

Further, the surface layer may be a resin layer in which colloidal silica having a hydroxyl group or a hydrolyzable group is contained in a curable siloxane resin, and silica particles are incorporated in a part of a crosslinked structure.

In the present invention, the term "charge transport ability" is defined by a known method capable of detecting the charge transport ability of the ordinary Time-Of-Flight method, in which a detection current due to charge transport can be obtained. I can do it.

In the present invention, the partial structure having a charge transporting ability is one having a property that the partial structure itself has electron or hole drift mobility (= charge transporting ability imparting group).
It is. The curable siloxane resin in the present invention has a compound generally used as a charge transport material (hereinafter also referred to as a charge transport compound or CTM) as a partial structure in the curable siloxane resin.

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,
A chemical structure such as poly-9-vinylanthracene is contained as a partial structure of the curable siloxane resin.

On the other hand, electron transport type CTMs include succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, melitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, nitrobenzene, dinitrobenzene, trinitrobenzene, and the like. 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, A chemical structure such as 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid or melitic acid is contained as a partial structure of the curable siloxane resin.

In the present invention, preferred charge-transporting groups include the charge-transporting compounds which are generally used as described above, and have a partial structure in which the charge-transporting compound has a partial structure via a carbon atom constituting the charge-transporting compound. Is present in the curable siloxane resin via a linking atom or linking group of Y in the following formula via a carbon atom of the compound having:

[0055]

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Y is a divalent or higher valent atom or group excluding adjacent bonding atoms (Si and C).

However, when Y is a trivalent or higher atom, the bond of Y other than Si and C in the above formula is bonded to any of the constituent atoms in the curable resin capable of bonding, or It has a structure (group) linked to other atoms and molecular groups.

As shown by the following structural formula, an oxygen atom (O), a sulfur atom (S), and a nitrogen atom (N) are particularly preferable as the Y atom.

[0059]

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(Wherein X is a charge-transporting group,
A group bonded to Y in the formula via a carbon atom constituting the imparting group, Y is an oxygen atom (O), a sulfur atom (S), or NR, and R is a hydrogen atom or a monovalent organic group. Although the charge transport-imparting group X is shown as a monovalent group in the above formula, it is cured when the charge transport compound to be reacted with the siloxane curable resin has two or more reactive functional groups. It may be joined as a divalent or higher valent crosslink group in the conductive resin, or may be joined simply as a pendant group.

The above-mentioned atoms, ie, the atoms of O, S, and N, are formed by the reaction of a hydroxyl group, a mercapto group, or an amine group and an organic silicon compound having a hydroxyl group or a hydrolyzable group introduced into a compound having a charge transporting ability. It is a linking group that is formed and incorporates a charge transport compound into the curable siloxane resin as a partial structure.

Next, the charge transporting compound having a hydroxyl group, a mercapto group and an amine group in the present invention will be described.

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

X- (R ₇ -OH) mm ≧ 1 wherein X: a group for imparting charge transport ability, R ₇ : a single bond, a substituted or unsubstituted alkylene group, an arylene group, m: an integer of 1 to 5 It is.

Among them, the following are typical ones. For example, a triarylamine-based compound has a triarylamine structure such as triphenylamine as a charge transport ability-imparting group = X, and has an alkylene or arylene group extended through a carbon atom constituting X or extended from X. A compound having a hydroxyl group via is preferably used.

1. Triarylamine compounds

[0067]

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2. Hydrazine compounds

[0069]

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3. Stilbene compounds

[0071]

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4. Benzidine compound

[0073]

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5. Butadiene compound

[0075]

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6. Other compounds

[0077]

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

Synthesis of Exemplified Compound T-1

[0080]

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Step A In a four-headed kolben equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, 49 g of the compound (1) and phosphorus 184
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.

The precipitated crystals were filtered and dried, and then purified by adsorption of impurities using silica gel or the like and recrystallization with acetonitrile to obtain Compound (2). 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

[0085]

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Step A In a 300 ml Kolben equipped with a thermometer and a stirrer, add C
u, 30 g, K2CO3, 60 g, compound (1) 8 g,
100 g of the compound (2) was charged, the temperature was raised to about 180 ° C., and the mixture was 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 Kolben equipped with a thermometer, a dropping funnel, an argon gas introducing device and a stirrer was set to an argon gas atmosphere, and 7 g of the compound (3), 50 ml of toluene and 3 g of phosphoryl chloride were charged into the atmosphere. 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. To this, 15 ml of a hexane solution of n-BuLi (1.72 M) was added, 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).

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

The charge transporting compound having a mercapto group is a charge transporting substance having a commonly used structure and a compound having 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 a curable organosilicon compound can be exemplified, but is not limited to the following structure. Any compound may be used as long as it has a charge transporting ability and a mercapto group.

X- (R ₈ -SH) mm ≧ 1 wherein X is a charge transporting group, R _{8 is a} single bond, a substituted or unsubstituted alkylene or arylene group, and m is an integer of 1 to 5. is there.

[0093] Among them, the following are typical ones.

[0094]

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

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

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

Among them, the following are typical ones.

[0099]

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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.

Raw materials for forming the curable siloxane resin: From the general formulas (A) to (D) (hereinafter referred to as (A) to (D)), the composition ratio is: organosilicon compound: (A) + (B)
It is preferable to use 0.05 to 1 mol of the component (C) + (D) based on 1 mol of the component.

When the colloidal silica (E) is added, the total weight of the components (A) + (B) + C) + (D) is 1%.
It is preferable to use 1 to 30 parts by weight of (E) based on 00 parts.

When the reactive charge transporting compound (F) capable of forming a resin layer by reacting with the organosilicon compound or colloidal silica is added, the above (A) +
It is preferable to use 1 to 500 parts by weight of (F) based on 100 parts by total weight of the components (B) + C) + (D). When the component (A) + (B) is used beyond the above range, when the component (A) + (B) is small, the siloxane resin layer has a too low crosslinking density and insufficient hardness. Also, (A) +
If the component (B) is too large, the crosslink density is too high and the hardness is sufficient, but a brittle resin layer is formed. Excess or deficiency of the colloidal silica component of the component (E) has the same tendency as that of the component (A) + (B). On the other hand, when the amount of the component (F) is small, the charge transporting ability of the siloxane resin layer is small, causing a decrease in sensitivity and an increase in residual charge. When the amount of the component (F) is large, the film strength of the siloxane resin layer tends to be weak. Be looked at.

The curable siloxane resin of the present invention comprises a monomer or oligomer having a siloxane bond in a structural unit in advance.
Addition of a catalyst or a cross-linking agent to a polymer may form a new chemical bond to form a three-dimensional network structure. In addition, a hydrolysis reaction and subsequent dehydration condensation may promote a siloxane bond to form a three-dimensional network. A network structure can also be formed.

In general, a three-dimensional network structure can be formed by a condensation reaction of a composition containing alkoxysilane or a composition containing alkoxysilane and colloidal silica.

Examples of the catalyst for forming the above three-dimensional network structure include alkali metal salts of organic carboxylic acids, nitrous acid, sulfurous acid, aluminate, carbonic acid and thiocyanic acid, and organic amine salts (tetramethylammonium hydroxide, tetramethylammonium hydroxide). Ammonium acetate), tin organic acid salts (stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin malate), aluminum, zinc octenoic acid, naphthenate, An acetylacetone complex compound is exemplified.

Further, an antioxidant having a hindered phenol, hindered amine, thioether or phosphite partial structure can be added to the resin layer in the present invention.
This is effective in improving the potential stability and image quality when the environment changes.

Here, the hindered phenol refers to compounds having a branched alkyl group at the ortho position to the hydroxyl group of the phenol compound and derivatives thereof. (However, the hydroxyl group may be modified to alkoxy.) Examples of the hindered amine include compounds having an organic group represented by the following structural formula.

[0109]

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(In the formula, R ₁₁ represents a hydrogen atom or a monovalent organic group, R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ represent an alkyl group, and R ₁₆ represents a hydrogen atom, a hydroxyl group, or a monovalent organic group. Examples of the antioxidant having a hindered phenol partial structure include, for example, JP-A-1-118137 (P7 to P14).
The compounds described above are included, but the present invention is not limited thereto.

Examples of antioxidants having a hindered amine partial structure include, for example, JP-A-1-118138 (P7-
The compounds described in P9) may also be mentioned, but the present invention is not limited thereto.

The following are representative compounds.

[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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Examples of the antioxidants that have been commercialized include the following compounds, for example, “Irganox 107”.
6, Irganox 1010, Irganox 1098, Irganox 245, Irganox 1330, Irganox 3114, Irganox 1076, 3,5-di-t-butyl-4 -Hydroxybiphenyl '' or more hindered phenols,
"Sanol LS2626", "Sanol LS765"
"Sanol LS2626", "Sanol LS770",
“Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57”, “Mark LA”
67 "," Mark LA62 "," Mark LA68 ",
"Mark LA63" or higher, hindered amine type, "Sumilyzer-TPS", "Sumilyzer TP-D" or higher, thioether type, "Mark 2112", "Mark PEP?"
8 "," Mark PEP-24G "," Mark PEP-3 "
6 "," Mark 329K "," Mark HP-10 "or more phosphite type. Among these, hindered phenol and hindered amine antioxidants are particularly preferred.

The amount of the antioxidant to be added is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total resin layer composition.

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 of the present invention include phthalocyanine pigments, polycyclic quinone pigments, azo pigments, perylene pigments, indigo pigments,
Quinacridone pigments, azurenium pigments, squarylium dyes, cyanine dyes, pyrylium dyes, thiopyrylium dyes, xanthene dyes, triphenylmethane dyes, styryl dyes, and the like.
In M), a layer is formed alone or together with a suitable binder resin.

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.

The binder resin contained in the charge-generating layer (CGL) and the charge-transporting layer (CTL) in the case of the photosensitive layer having a single-layer structure and the laminate structure has a polycarbonate resin, a polyester resin, a polystyrene resin, a methacrylic resin, and the like.
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: 5 to 5: 1 by weight.
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 an appropriate solvent, and applying and drying the solution. The mixing ratio of the charge transport material and the binder resin is preferably from 3: 1 to 1: 3 by weight.

The thickness of the charge transport layer is usually from 5 to 50 μm, 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 curable siloxane resin layer of the present invention may also serve as the charge transport layer, but is preferably formed on a photosensitive layer such as a charge transport layer or a charge generation layer or a single-layer type charge generation / transport layer. In addition, it is preferable to provide a separate layer from these. In this case, it is more preferable to provide an adhesive layer between the photosensitive layer and the resin layer of the present invention.

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 electroconductive support of the electrophotographic photoreceptor of the present invention has a surface on which a sealed alumite film is formed. The alumite film treatment is usually carried out by using, for example, chromic acid, sulfuric acid, oxalic acid, phosphorous acid, and the like. The treatment is carried out in an acidic bath such as an acid, boric acid or sulfamic acid, but anodizing treatment in sulfuric acid gives the best results. In the case of the anodic oxidation treatment in sulfuric acid, the sulfuric acid concentration is preferably 100 to 200 g / l, the aluminum ion concentration is 1 to 10 g / l, the liquid temperature is about 20 ° C., and the electrolysis voltage is preferably about 20 V. It is not limited.

The average thickness of the anodic oxide film is usually 2
It is preferable that the film is formed to have a thickness of 0 μm or less, particularly 10 μm or less.

In the present invention, the anodic oxide film thus formed is used after being subjected to a sealing treatment in order to enhance the stability of the film. Examples of the method of the sealing treatment include a low-temperature sealing treatment immersed in an aqueous solution containing nickel fluoride as a main component, a high-temperature sealing treatment immersed in an aqueous solution containing nickel acetate as a main component, and other vapors. Sealing treatments such as sealing and boiling water sealing are mentioned, but not limited thereto. When using an aqueous nickel acetate solution, the concentration is 5 to 10 g / l, and the treatment temperature is 80.
It is preferable to use at a temperature of ９５95 ° C. and a pH of 5５〜6. The anodic oxide film thus formed may be dried after taking measures such as pure washing as necessary.

As a specific example of the processing method, see JP-A-2-7
No. 070, 3-212648 and 5-80565
And No. 9-15886.

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

The solvent or dispersion medium used for producing 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. Further, these solvents can be used alone or as a mixed solvent of two or more kinds.

The coating method for producing the electrophotographic photoreceptor of the present invention includes dip coating, spray coating,
Coating methods such as circular amount control type coating are used, but the coating process on the surface layer side of the photosensitive layer is 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 more, preferably 60 to 200 ° C., after the surface layer is formed by coating. 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, copolymerized nylon, alkoxymethyl And an intermediate layer using polyurethane, gelatin, and aluminum oxide, or a curable intermediate layer using a metal alkoxide, an organic metal chelate, or a silane coupling agent as disclosed 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 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.

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 applied 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. Around the periphery of the photoconductor drum 10, there are provided developing devices 14 each containing therein a developer having a toner and a carrier such as yellow (Y), magenta (M), cyan (C), black (K) and the like. The color development 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 which is brought into pressure contact with the transfer roller almost simultaneously, is separated by the peripheral surface of the photosensitive drum 10 and is conveyed to the fixing device 20 where it is heated. 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 unit 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 cartridge in which a photosensitive member, a charging device, a transfer device / separator, and a cleaning device are integrated.

An 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.

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 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.

[0158]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 A photoreceptor was produced as follows.

<Conductive Substrate> A diameter of 80 mm and a length of 360
The cylindrical aluminum drawn tube having a diameter of 2 mm was degreased and washed with an organic solvent and etched. Subsequently, after washing with water, it was immersed in 7% nitric acid at 25 ° C. for 1 minute, and further anodized at a current density of 1.0 A / dm ^{2 in} a 180 g / l sulfuric acid electrolytic solution after washing with water to form an alumite film having an average film thickness of 6 μm. Formed. Then, after washing with water, 10 g / l of a sealing agent containing nickel acetate as a main component is used.
Was immersed in an aqueous solution at 90 ° C. for 20 minutes to perform a sealing treatment.
Subsequently, after washing with pure water, drying was finally performed.

<Charge Generating Layer> Charge generating material: titanyl phthalocyanine (the maximum peak of the Bragg angle 2θ in Cu-Kα X-ray diffraction is 27.3 °) 60 g silicone resin solution (KR5240, 15% xylene-butanol solution, Shin-Etsu) 700 g of methyl ethyl ketone (2000 ml) were mixed and dispersed using a sand mill for 10 hours to prepare a charge generation layer coating solution. This coating solution was applied onto the conductive substrate by a dip coating method to form a 0.2 μm-thick charge generating layer.

<Charge Transport Layer> Charge transport material (D1) 200 g Bisphenol Z-type polycarbonate (Iupilon Z300, manufactured by Mitsubishi Gas Chemical Company) 300 g 1,2-Dichloroethane 2000 ml was mixed and dissolved, and the charge transport layer coating liquid was dissolved. Prepared. This coating solution is applied on the charge generation layer by a dip coating method,
A charge transport layer having a thickness of 25 μm was formed.

[0163]

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[0164] A commercially available primer PC-7J (manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted twice with toluene, and 100 μl after coating.
C. for 30 minutes to form an adhesive layer having a dry film thickness of 0.3 .mu.m.

Molecular sieve 4A was added to 10 parts by weight of a polysiloxane resin (containing 1% by weight of silanol group) having 80% by mole of methylsiloxane unit and 20% by mole of methyl-phenylsiloxane unit.
It was left to stand for 5 hours to perform a dehydration treatment. This resin was dissolved in 10 parts by weight of toluene, and 5 parts by weight of methyltrimethoxysilane and 0.2 parts by weight of dibutyltin acetate were added thereto to form a uniform solution.

6 parts by weight of dihydroxymethyltriphenylamine (Exemplified Compound T-1) was added thereto and mixed, and this solution was applied as a protective layer having a dry film thickness of 1 μm.
Drying was performed at 0 ° C. for 1 hour to prepare a photoconductor of Example 1.

For evaluation, the photoreceptor was tested for Konica 7050
(Konica laser digital copying machine: equipped with a cartridge in which the photosensitive member and the charger, the current organ, the cleaning device, and the static eliminator are integrated), and the initial charging potential was set to −650 V. .

In the environment of 20 ° C., 60% RH and 30 ° C., 80% RH, initial and 50,000 image evaluations were performed using A4 paper. In addition, the density of the solid black portion was 1.2 or more in reflection density, and an image having excellent uniformity was obtained. Further, the amount of wear of the photoconductor at the end of 100,000 sheets in both environments (50,000 sheets) was very small at 0.1 μm or less. Furthermore, scars on the photoreceptor surface were scarcely observed, and image defects due to scratches were found on the halftone image. Comparative Example-1 On the other hand, in Example-1, diphenylmethyltriphenylamine in the protective layer was replaced with triphenylamine. A photosensitive member of Comparative Example 1 was produced in exactly the same manner as in Example 1 except for the above.

Evaluation was performed in the same manner as in Example 1 above. As a result, good images were obtained in an environment of 20 ° C. and 60% RH, but fog occurred on 50,000 images at 30 ° C. and 80%.
In addition, image blurring occurred in a part of the image. In addition, the amount of wear of the photoconductor at the end of 100,000 sheets in a total of 50,000 sheets in both environments was 0.9 μm, which was larger than that of the present invention.

Comparative Example 2 On the other hand, a photoreceptor of Comparative Example 2 was produced in exactly the same manner as in Example 1 except that the conductive aluminum substrate in Example 1 was replaced with a mirror-finished one.

Evaluation was performed in the same manner as in Example 1 above. As a result, at 30,000 sheets at 20 ° C. and 60% RH, an image defect occurred due to peeling of the photosensitive layer.

Example 2 <Conductive Substrate> A mirror-finished cylindrical aluminum tube having a diameter of 80 mm and a length of 360 mm was degreased and washed with an organic solvent and etched. Subsequently, after washing with water, using a 150 g / l sulfuric acid, while maintaining the liquid temperature at 20 ° C., a DC voltage of 20 V
For 15 minutes to form an alumite film having an average film thickness of 7 μm. Next, after washing with water, the film was immersed in a 6 g / l aqueous solution of a sealing agent containing nickel acetate as a main component at 90 ° C. for 5 minutes to perform a sealing treatment. Subsequently, after washing with pure water, drying was finally performed.

The conductive aluminum substrate in Example 1 was replaced with the above-mentioned one, and the polysiloxane resin was replaced with a polysiloxane resin having 80 mol% of methylsiloxane units and 20 mol% of dimethylsiloxane units (2% by weight of silanol group). Example 2)
Was produced.

Example 3 The polysiloxane resin in Example 1 was prepared by adding 30 mol% of a methylsiloxane unit, 40 mol% of an ethylsiloxane unit,
The photoconductor of Example-3 was replaced with a photoconductor of Example-3 in exactly the same manner as in Example-1, except that the polysiloxane resin having 20 mol% of dimethylsiloxane units and 10 mol% of diethylsiloxane units (containing 2% by weight of silanol groups) was used. Produced.

Example-4 The polysiloxane resin used in Example 1 was a polysiloxane resin having 30 mol% of methylsiloxane units, 30 mol% of phenylsiloxane units, 20 mol% of dimethylsiloxane units, and 20 mol% of diethylsiloxane units. (2
Example 2 except that the composition of the Example
In the same manner as in Example 1, a photoconductor of Example 4 was produced.

Example-5 Except that dihydroxymethyltriphenylamine (Exemplified Compound T-1) in Example-1 was replaced with a hydrazone type (Exemplified Compound H-1), the procedure was the same as in Example-1. Thus, a photoreceptor of Example-5 was produced.

Example-6 Except that dihydroxymethyltriphenylamine (Exemplified Compound T-1) in Example-1 was replaced with a stilbene type (Exemplified Compound S-1), the procedure was the same as in Example-1. Thus, a photoreceptor of Example-6 was produced.

Example -7 The same procedure as in Example 1 was carried out except that dihydroxymethyltriphenylamine (Exemplified Compound T-1) in Example 1 was replaced with a benzidine-type (Exemplified Compound Be-1). Thus, a photoconductor of Example-7 was produced.

Example 8 The procedure of Example 1 was repeated except that the dihydroxymethyltriphenylamine (Exemplified Compound T-1) in Example 1 was replaced with a butadiene type (Exemplified Compound Bu-1). Thus, a photoreceptor of Example-8 was produced.

Example -9 The same procedures as in Example 1 were carried out except that dihydroxymethyltriphenylamine (Exemplified Compound T-1) in Example 1 was replaced with (Exemplified Compound So-1). -9 was prepared.

Example -10 Example 10 was carried out in the same manner as in Example 1 except that dihydroxymethyltriphenylamine (Exemplified Compound T-1) in Example 1 was replaced with (Exemplified Compound V-1). -10 was prepared.

Example-11 Example 11 was repeated except that dihydroxymethyltriphenylamine (Exemplified Compound T-1) in Example-1 was replaced with (Exemplified Compound W-1). -11 was prepared.

Example -12 Example -5 was performed in exactly the same manner as in Example -5 except that 5 parts by weight of colloidal silica was added to the protective layer.
Twelve photoreceptors were produced.

Example 13 In Example 6, colloidal silica was used for the protective layer.
A photoconductor of Example-13 was made in the same manner as Example-6, except that it was added by weight.

Example 14 In Example 7, colloidal silica was added to the protective layer.
A photoconductor of Example-14 was prepared in the same manner as Example-7, except that it was added by weight.

Example -15 In Example 8, colloidal silica was added to the protective layer.
A photoconductor of Example-15 was made in the same manner as Example-8, except that it was added by weight.

Example -16 In Example 9, colloidal silica was used for the protective layer.
A photosensitive member of Example 16 was prepared in the same manner as in Example 9 except that the weight part was added.

Example -17 An adhesive layer was produced in the same manner as in Example 1.

On top of this, commercially available curable siloxane resin K
Example 2-60 parts by weight of P-854 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 60 parts by weight of isopropanol were added and uniformly dissolved.
6 parts by weight of dihydroxymethyltriphenylamine (exemplified compound T-1) were added and mixed in the same manner as in Example 1, and this solution was applied so as to form a protective layer having a dry film thickness of 1 μm.
-Drying was performed for 1 hour to prepare a photoreceptor of Example-17.

Example-18 Example-18 was carried out in exactly the same manner as in Example-15 except that X-40-2239 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the siloxane resin KP-854 in Example-15. Was produced.

Example-19 Example-19 was carried out in the same manner as in Example-15 except that X-40-2269 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the siloxane resin KP-854 in Example-15. Was produced.

The photosensitive members of Examples 2 to 19 were evaluated in the same manner as the photosensitive member of Example 1.

No fogging occurred in the initial and 50,000 sheets under both environmental conditions of 20 ° C., 60% RH and 30 ° C., 80% RH, and the density of the solid black portion was 1.2 or more in reflection density. The density was obtained, and an image having excellent uniformity was obtained.
Further, the abrasion amount of the photoconductor at the end of 50,000 sheets was very small at 0.1 μm or less. Further, scars on the surface of the photoreceptor were scarcely observed, and no image defect due to scratches was observed on the halftone image.

Comparative Example 3 A photoreceptor of Comparative Example 3 was prepared in exactly the same manner as in Example 1 except that the conductive aluminum substrate in Example 1 was not subjected to the sealing treatment after the formation of the alumite film. did.

Evaluation was performed in the same manner as in Example 1 above. As a result, a good image was obtained in an environment of 20 ° C. and 60% RH. A defect has occurred.

Example-20 On the other hand, dihydroxymethyltriphenylamine in the protective layer in Example-1 was replaced with 4- [2- (triethoxysilyl)
Example 1 except that [ethyl] triphenylamine was used instead.
In the same manner as in Example 20, a photoconductor of Example -20 was produced.

Evaluation was performed in the same manner as in Example 1 above. As a result, a good image was obtained in an environment of 20 ° C. and 60% RH, but at 30 ° C. and 80% RH, a part of 50,000 images was blurred. There has occurred. The amount of abrasion of the photoconductor at the end of 100,000 sheets in 50,000 sheets in both environments was 0.6 μm, which was larger than that of the other examples.

Example 21 A photoconductor of Example 21 was prepared in the same manner as in Example 1, except that the following intermediate layer was provided between the conductive substrate and the charge generation layer. did.

<Intermediate layer> Zirconium chelate compound ZC-540 (Matsumoto Pharmaceutical Co., Ltd.) 200 g Silane coupling agent KBM-903 (Shin-Etsu Chemical Co., Ltd.) 100 g Methanol 700 ml Ethanol 300 ml After drying for an minute, an intermediate layer having a thickness of 1.0 μm was formed.

Example-22 The photoconductor of Example-22 was prepared in the same manner as in Example-1 except that 0.9 parts by weight of the hindered phenol compound (Exemplified Compound 1-10) was added. Was prepared.

Example 23 The photosensitive composition of Example 23 was prepared in the same manner as in Example 1 except that 0.6 parts by weight of a hindered phenolamine compound (Exemplified Compound 2-1) was added. The body was made.

The photosensitive members of Examples 21, 22, and 23 were evaluated in the same manner as the photosensitive member of Example 1.

No fogging occurs in the initial and 100,000 sheets under both environmental conditions of 20 ° C. 60% RH and 30 ° C. 80% RH, and the density of the solid black portion is 1.3 in reflection density.
The above density was obtained, and an image having excellent uniformity was obtained.
Further, the amount of wear of the photoconductor at the end of 100,000 sheets was very small at 0.1 μm or less. Further, scars on the surface of the photoreceptor were scarcely observed, and no image defect due to scratches was observed on the halftone image. No peeling of the photosensitive layer was observed.

[0204]

Industrial Applicability According to the present invention, an electron which has high abrasion resistance, has stable electrophotographic characteristics even under high temperature and high humidity, and can obtain a good image even when repeatedly used in digital image formation by laser light. A photoconductor can be provided, and a process cartridge and an image forming apparatus using the photoconductor can be provided.

[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.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 Photosensitive drum (or photoreceptor) 11 Exposure part using light emitting diode etc. 12 Charging device 13 Image exposing 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 Removable process cartridge in which photoconductor, charging device, transfer device / separator and cleaning device are integrated.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 5/14 101 G03G 5/14 101B 101D (72) Inventor Yoko Kitahara 2970-2, Ishikawacho, Hachioji-shi, Tokyo Konica Within the Company (72) Inventor Masahiko Kurachi 2970, Ishikawa-cho, Hachioji-shi, Tokyo Konica Corporation Inside the Company (72) Inventor Kazuhisa 2970, Ishikawa-cho, Hachioji-shi, Tokyo Konica Corporation F-term (reference) 2H068 AA03 AA16 AA20 AA38 AA42 AA50 BA12 BA13 BA21 BA57 BA58 BB33 BB57 CA33 FA03 FA07 FA27

Claims (24)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photosensitive member is a layer containing a curable siloxane resin having a charge transporting ability. An electrophotographic photoreceptor, wherein the body has a surface on which a sealed alumite film is formed. 2. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photosensitive member is a layer containing a curable siloxane resin containing a partial structure having a charge transporting ability, An electrophotographic photoreceptor, wherein the conductive support has a surface on which a sealed alumite film is formed. 3. The electrophotographic photosensitive member according to claim 2, wherein the partial structure having the charge transporting ability has the following structural formula. Embedded image (Wherein, X is a charge transporting ability-imparting group, which is a group that binds to Y via a carbon atom constituting the imparting group, and Y is a divalent or higher valent group excluding adjacent bonding atoms (Si and C)) Atom or group.) 4. The electrophotographic photosensitive member according to claim 2, wherein the partial structure having the charge transporting ability has the following structural formula. Embedded image (In the formula, X is a charge-transporting ability-imparting group, a group that binds to Y via a carbon atom constituting the imparting group, Y is an oxygen atom, a sulfur atom, NR, R is a hydrogen atom, 1 Valent organic groups.) 5. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photosensitive member has an organic silicon compound having a hydroxyl group or a hydrolyzable group, and a charge transporting compound having a hydroxyl group. A resin layer containing a curable siloxane resin obtained by reacting a conductive material, wherein the conductive support is provided with a sealed alumite film on the surface thereof. . 6. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photosensitive member has an organic silicon compound having a hydroxyl group or a hydrolyzable group, and a charge transporting property having an amino group. A resin layer containing a curable siloxane resin obtained by reacting a compound, wherein the conductive support has a surface on which a sealed alumite film is formed; body. 7. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the surface layer of the electrophotographic photosensitive member has an organosilicon compound having a hydroxyl group or a hydrolyzable group and a charge transporting compound having a mercapto group. A resin layer containing a curable siloxane resin obtained by reacting the conductive support, wherein the conductive support is provided with a sealed alumite film on the surface thereof. . 8. The electrophotographic photosensitive member according to claim 1, wherein the resin layer containing the curable siloxane resin is cured. 9. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a charge generation layer and a charge transport layer. 10. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a charge generating / transporting layer. 11. The electrophotographic photosensitive member according to claim 1, wherein an intermediate layer is provided between the conductive support and the photosensitive layer. 12. The surface layer has a thickness of 0.1 to 20 μm.
The electrophotographic photoreceptor according to claim 1, wherein: 13. The method according to claim 1, wherein an adhesive layer is provided between the surface layer and an adjacent layer.
13. The electrophotographic photoreceptor according to item 6. 14. The charge transporting ability-imparting group is a triarylamine compound residue.
14. The electrophotographic photosensitive member according to any one of the above items 13. 15. The electrophotographic photoreceptor according to claim 3, wherein the charge transporting ability-providing group is a hydrazone compound residue. 16. The electrophotographic photoreceptor according to claim 3, wherein the charge transporting group is a styryltriphenylamine compound residue. 17. The electrophotographic photoreceptor according to claim 3, wherein the charge transport ability-imparting group is a benzidine compound residue. 18. The electrophotographic photoreceptor according to claim 3, wherein the charge transport group is a butadiene compound residue. 19. The method according to claim 11, wherein said intermediate layer is a resin layer.
13. The electrophotographic photoreceptor according to item 6. 20. The electrophotographic photosensitive member according to claim 11, wherein the intermediate layer is a resin layer formed by reacting an organic metal compound and an organic metal chelate compound. . 21. The electrophotographic photoconductor according to claim 1, wherein the electrophotographic photoconductor contains an antioxidant. 22. The electrophotographic photoconductor according to claim 21, wherein the antioxidant is a compound having a partial structure of hindered phenol, hindered amine, thioether or phosphite. 23. An image forming apparatus using the electrophotographic photosensitive member according to claim 1 to form an image through charging, image exposure, development, transfer, separation, and cleaning. 24. The process cartridge according to any one of claims 1 to 22, wherein the process cartridge is used in an image forming apparatus that uses an electrophotographic photosensitive member and goes through steps of charging, image exposure, development, transfer / separation, and cleaning. A process cartridge comprising a combination of the electrophotographic photosensitive member described above and at least one of a charger, an image exposure device, a developing device, and a cleaning device.