JPH0643667A - Image retaining member and device using the member - Google Patents

Abstract

PURPOSE:To obtain an image retaining member with rapidly enhanced durability and having a stabilized potential characteristic by providing a surface layer contg. a high-m.p. polyester resin, a curing resin and a silicone-base interdigital graft polymer. CONSTITUTION:A protective layer 1 as the surface layer is formed at the outermost part of an image retaining member and is used to protect the inner layer. A photoconductive layer 2 is provided in the image retaining member or not. Since the protective layer 1 has excellent wear resistance and a small frictional resistance, the layer is useful as the surface protective layer for the image retaining member. Mixture of the high-m.p. polyester resin, curing resin and silicone-base interdigital graft polymer makes the surface layer more effective than ever, and the high-m.p. polymer resin has high crystallinity because of its high m.p. Consequently, the curing resin chain is uniformly and densely entangled with the high-m.p. polymer chain, and a highly durable surface layer is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image holding member for holding an electrostatic image and / or a toner image, and more particularly to an image holding member having excellent durability and an apparatus using the same.

[0002]

2. Description of the Related Art Generally, an image holding member includes an electrophotographic photosensitive member and other image holding members such as an electrostatic image and / or an electrostatic image forming member such as an intermediate transfer member and an electrostatic recording member of a color copying machine requiring a large number of transfers. Alternatively, there is a member that holds the toner image.

The electrophotographic photosensitive member has various configurations in order to obtain predetermined characteristics or according to the type of electrophotographic process applied. Typical electrophotographic photoreceptors are a photoreceptor having a photoconductive layer formed on a support and a photoreceptor having a protective layer on the surface thereof, which are widely used. The photoreceptor composed of a support and a photoconductive layer is used for image formation by the most common electrophotographic process, that is, charging, image exposure and development, and optionally transfer. Further, regarding the photoreceptor provided with a protective layer, this protective layer is for the purpose of protecting the photoconductive layer, improving the mechanical strength of the photoreceptor, improving the dark decay characteristics, or applying to a specific electrophotographic process. It is provided for. A typical example of such a specific electrophotographic process is
There is a method that uses the method of injecting electric charge from the support side at the time of charging and moving the electric charge between the protective layer and the photoconductive layer. As a typical example of such a method, as disclosed in Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, primary charging, secondary charging having a polarity opposite to that of primary charging, or This is a method of forming an electrostatic image by AC neutralization, simultaneous image exposure and overall exposure. Also,
In the above method, image exposure may be carried out before or after secondary charging or AC neutralization. The whole surface exposure may be omitted.

Another method is US Pat. No. 304.
The one disclosed in Japanese Patent No. 1167 is cited.

The electrophotographic photosensitive member is applied to a predetermined electrophotographic process to form an electrostatic image, and the electrostatic image is developed and visualized.

Some representative examples of other image bearing members are described next.

(1) For the purpose of improving the reusability of the electrophotographic photosensitive member, the electrostatic image formed on the electrophotographic photosensitive member is transferred to another image holding member for development, and then the toner image is recorded on the recording member. Is transcribed to. (2) Further, as another electrophotographic process for forming an electrostatic image on another image holding member in correspondence with the electrostatic image formed on the electrophotographic photosensitive member, a screen-shaped electron having a large number of fine openings. An electrostatic image is formed on the photographic photosensitive member by a predetermined electrophotographic process, and the corona charging process is performed on another image holding member via this electrostatic image to modulate the ion current of the corona to form an electrostatic image. A process for forming a final image by forming the image on another image holding member, developing the toner with the toner, and transferring the toner to a recording medium is exemplified.
(3) According to another electrophotographic process, the toner image formed on the electrophotographic photosensitive member or other image holding member is not directly transferred to the recording body but is transferred to another image holding member and then The toner and the image are transferred and fixed from the image holding member to the recording medium. This process is particularly useful for color image formation or high speed copying. Usually, many recording materials are highly flexible, such as paper and film,
Therefore, rather than transferring the three-color image to the recording medium while accurately aligning the three-color image, the three-color image is transferred to an image holding member that can be formed of a material that hardly causes deformation,
Transferring this to the recording medium at one time forms a more accurately aligned color image. In addition, it is effective to transfer the toner image to the recording medium through the image holding member for the speeding up of copying. (4) As another process, an electric signal can be applied to the multi-needle electrode to form an electrostatic image according to the electric signal on the surface of the image holding member, and this can be developed into an image.

The image holding member used in the electrostatic image forming process as described in (1) to (4) does not require a photoconductive layer.

As described above, as an image holding member on which an electrostatic image or a toner image is formed, various kinds of surface layers are generally insulating layers, including electrophotographic photoreceptors whose surface layers are protective layers or photoconductive layers. Members are used.

The image holding member is required to have electric characteristics according to the recording process to be applied, but the durability of the image holding member is an important property. Durability is a property required when the image holding member is repeatedly used.

That is, as a matter of course, the image holding member has a predetermined sensitivity according to the electrophotographic process to be applied,
It is required to have electrical characteristics and also optical characteristics. Particularly in the case of a photoconductor that can be used repeatedly, the surface layer of the photoconductor is directly subjected to electrical and mechanical external forces such as corona charging, toner development, transfer to paper, and cleaning treatment. Sex is required.
Specifically, due to deterioration caused by ozone and NO _x generated during corona charging, sensitivity decrease, potential decrease, residual potential increase,
Also, durability against abrasion and scratches on the surface due to rubbing is required.

Further, the cleaning property is an important factor, and it is essential to reduce the frictional resistance in order to improve the cleaning property.

Since the surface of the image holding member is mainly composed of a resin and a photoconductive material, the performance of the resin is particularly important, and an excellent resin satisfying the above-mentioned various characteristics has been demanded. Recently, as a resin satisfying these requirements, a polycarbonate resin has come to be used as a binder (binder) for the surface layer.

However, the durability is about 50,000 to 100,000 sheets, although the durability of several thousand to 10,000 sheets at the time when the acrylic resin was used was extended to 50,000 to 100,000 sheets by using the polycarbonate resin. Se or a that is an inorganic photoconductor
The durability when using -Si (amorphous Si) could not reach 300,000 to 1,000,000 sheets.

Therefore, many studies have been made to provide a protective layer by adding a conventional resin or a fluorinated resin, but due to the provision of a layer in which charge does not move due to the constitution of the photosensitive layer, it is inevitably used for durability. As a result, the residual potential (Vr) was increased and the sensitivity was lowered. This problem can be improved by making the thickness of the protective layer thin, for example, 2 to 3 μm or less, but the result is that the conventionally used resin still has large wear due to durable use-the durability is not improved. Has ended.

Further, when a resin containing polytetrafluoroethylene (hereinafter sometimes abbreviated as "PTFE") is used for the protective layer, a soft resin must be used in order to bring out good cleaning characteristics of PTFE. There is. This is because the surface of the photoconductor is gradually scraped as it is used for a long time, so that a fresh PTFE is exposed on the surface, and the effect of PTFE is not well expressed with a hard binder. However, with a soft binder,
The effect of PTFE increases the durability of the protective layer, but since the film is soft, scratches due to rubbing with a cleaning blade and cracks (peeling of the film) due to impact are likely to occur. Further, when the transfer paper comes into contact with the image holding member such as the front end or the rear end of the transfer paper, the contact portion of the image holding member becomes scratched, resulting in image defects such as black stripes. Further, with respect to the problems of increase in residual potential and decrease in sensitivity due to durable use, the same problems as those of the ordinary protective layer remain.

It is also possible to use a resin having a high hardness to improve the wear resistance, but the coefficient of frictional resistance becomes several steps higher than that when polycarbonate or the like is used on the surface,
There is room for improvement in that it is difficult to obtain good cleaning characteristics.

[0018]

(1) To provide an image holding member which is further extended in durability characteristics and has stable potential characteristics. (2) To provide a method for manufacturing the image holding member. (3) To provide various devices using the image holding member.

[0019]

SUMMARY OF THE INVENTION The present invention relates to an image holding member having a surface layer containing a high melting point polyester resin and a cured resin, and a silicone type comb-type graft polymer, and a method for producing the same.

By providing the surface layer of the present invention on the image holding member, there is almost no abrasion due to the durability test and stable potential characteristics are exhibited, and even after the durable use, streak image generation due to scratches and density gradient due to partial abrasion are exhibited. It is possible to obtain an image holding member free from defects, and as a result, it is possible to obtain a good copy image.

The image holding member of the present invention will be described below with reference to the drawings. Here, FIGS. 1 to 3 are schematic cross-sectional views showing various aspects of the image holding member of the present invention in which the surface layer is a protective layer. In each figure, the same reference numeral represents the same layer.

In the figure, reference numeral 1 denotes a protective layer, which is located at the outermost portion of the image holding member and protects the inner layer thereof. Reference numeral 2 is a photoconductive layer, but it may not be present in the image holding member of the present invention as described above. 3 is a support. Reference numeral 4 is a charge transport layer, and 5 is a charge generation layer. The upper and lower positions of these two layers may be in any positional relationship.

The protective layer 1 is extremely useful as a surface protective layer of an image holding member because it has a small frictional resistance despite its markedly excellent abrasion resistance. This is different from the conventional single resin or copolymer resin, as a result of the mixture of the high melting point polyester resin, the cured resin and the silicone type comb-type graft polymer, which causes the characteristics of each resin component to act synergistically. , I think that it has brought about an effect that has never been seen before.

Since the protective layer 1 of the present invention is extremely tough, it can be made thin, and the thickness of the protective layer is set to 3 μm or less, preferably 0.1 to 2 μm. Further, as the image holding member, the photoconductive layer 2 can be provided if necessary.

Examples of the photoconductive layer include Se and aS
A substance having an inorganic photoconductivity such as i, ZnO, CdS or a substance having an organic photoconductivity such as an organic dye, an organic pigment or a polysilane compound is used. Further, the photoconductive layer has a structure in which the charge generation layer 6 and the charge transport layer 5 are laminated in this order on the support 4, or the support 4 depending on the layer structure.
There is a layer in which the charge transport layer 5 and then the charge generation layer 6 are laminated in this order, or a layer having one or more layers in which a charge generation substance and a charge transport substance are mixed. Further, these layer configurations are the minimum, and an intermediate layer may be provided if necessary. Other components can be added to each layer (including the protective layer) used in the present invention, if necessary. It does not matter whether the component is a low molecular weight substance or a high molecular weight substance.

4 to 6 are schematic cross-sectional views showing various aspects of the image holding member of the present invention in which the surface layer is a photoconductive layer. In each figure, the same reference numeral represents the same layer.

In the figure, 6 is a photoconductive layer, which is formed of a high melting point polyester resin, a cured resin, a silicone-type comb-type graft polymer, a charge generating substance and a charge transporting substance. 3 is a support. Reference numeral 7 denotes a charge transport layer, which is mainly formed of a charge transport material, a high melting point polyester resin and a cured resin, and a silicone-type comb-type graft polymer. Reference numeral 8 denotes a charge generation layer, which is mainly formed of a charge generation substance. Reference numeral 9 denotes a charge generation layer, which is mainly formed of a charge generation substance, a high melting point polyester resin and a cured resin, and a silicone-type comb-type graft polymer. Reference numeral 10 denotes a charge transport layer, which is mainly composed of a charge transport material.

Examples of the photoconductive layer include Se and a-Si.
(Amorphous Si) An inorganic photoconductive substance such as ZnO or CdS or an organic photoconductive substance such as an organic dye, an organic pigment or a polysilane compound is used. Further, the photoconductive layer is, depending on its layer structure, first a charge generation layer on the support,
Then, a layer in which a charge transport layer is laminated in this order, a layer in which a charge transport layer is formed first on a support, then a layer in which a charge generation layer is formed in this order, or one or more layers in which a charge generation material and a charge transport material are mixed There are things that you have. Further, these layer configurations are the minimum, and an intermediate layer may be provided if necessary.

The surface layer of the image holding member of the present invention, for example, the resin component used for forming the protective layer 1, the photoconductive layer 6, the charge transport layer 7 and the charge generation layer 9 as described above will be described.

The polyester is a condensation polymer of an acid component and an alcohol component, and is a polymer obtained by condensation of dicarboxylic acid and glycol or condensation of a compound having a hydroxy group and a carboxy group such as hydroxybenzoic acid.

Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid as acid components,
Aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, and oxycarboxylic acids such as hydroxyethoxybenzoic acid can be used.

As the glycol component, ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexanedimethylol, polyethylene glycol, polypropylene glycol or the like can be used.

Polyfunctional compounds such as pentaerythritol, trimethylolpropane, pyromellitic acid and their ester-forming derivatives may be copolymerized within the range where the polyester resin is substantially linear.

As the polyester resin used in the present invention, a high melting point polyester resin is used.

The high melting point polyester resin has an intrinsic viscosity of 0.4 measured at 36 ° C. in orthochlorophenol.
dl / g or more, preferably 0.5 dl / g or more, and more preferably 0.65 dl / g or more are used.

Preferred high melting point polyester resins include polyalkylene terephthalate resins. The polyalkylene terephthalate resin is mainly composed of terephthalic acid as an acid component and alkylene glycol as a glycol component.

Specific examples thereof include polyethylene terephthalate (PET) mainly composed of a terephthalic acid component and an ethylene glycol component, a terephthalic acid component and 1,
Examples include polybutylene terephthalate (PBT) mainly composed of 4-tetramethylene glycol (1,4-butylene glycol) component, polycyclohexyl dimethylene terephthalate (PCT) mainly composed of terephthalic acid component and cyclohexane dimethylol component. it can. Examples of other preferable high molecular weight polyester resins include polyalkylene naphthalate resins. The polyalkylene naphthalate-based resin is mainly composed of a naphthalenedicarboxylic acid component as an acid component and an alkylene glycol component as a glycol component, and specific examples thereof include polyethylene naphthalene dicarboxylic acid component and an ethylene glycol component. Examples thereof include phthalate (PEN).

The high melting point polyester resin has a melting point of preferably 160 ° C. or higher, particularly preferably 200 ° C.
That is all.

The high melting point polyester resin has high crystallinity because it has a high melting point. As a result, it is considered that the entanglement between the cured resin polymer chain and the high melting point polymer chain becomes uniform and dense, and a highly durable surface layer can be formed. In the case of a low-melting point polyester resin, since the crystallinity is low, there are places where the degree of entanglement with the cured resin polymer chain is large and places where the degree of entanglement is small, resulting in poor durability.

Other thermoplastic resins, such as polycarbonate, polyamide, polyarylate, polyoxymethylene, polyphenylene oxide, polyphenylene sulfide, polyethylene, polypropylene, ethylene-propylene copolymer, as long as they do not impair the properties of the high melting point polyester resin. In addition to polystyrene, styrene-butadiene copolymer, at least one kind of saturated polyester resin oligomer and the like can be blended.

The curable resin component forming the curable resin component used in the present invention is a resin which is polymerized or crosslinked by heat or preferably a photopolymerization initiator or a crosslinking agent and irradiation with light such as ultraviolet rays. As the curable resin component, an ionic polymerizable or crosslinkable one is particularly preferable.

Ion-polymerizable or cross-linkable ones do not prevent polymerization or cross-linking by oxygen in the air, so that curing proceeds in the same manner in the thickness direction of the surface layer, and the surface layer having more excellent durability. Is thought to form. Examples of such photoion-curable resin include epoxy resin, urethane resin, phenol resin, melamine resin, acrylic resin and silicone resin. More preferably,
A cationically polymerizable resin component can be mentioned.

As the cation-polymerizable resin, one or a mixture of two or more cation-polymerizable resins whose main component is an epoxy resin having two or more oxirane rings in one molecule is preferable. As this type of epoxy resin, an aromatic epoxy resin, a novolac epoxy resin, an alicyclic epoxy resin, or the like is used.

As such an aromatic epoxy resin,
For example, Epicoat 828, Epicoat 834, Epicoat 836, Epicoat 1001, Epicoat 100
4, Epicoat 1007, Epicoat 190P, Epicoat 191P (above, trade name of products of Yuka Shell Epoxy Co., Ltd.), DER331, DER332, DER661, D
ER664, DER667 (trade names of Dow Chemical Company products), Araldite 260, Araldite 28
0, Araldite 6071, Araldite 6084, Araldite 6097 (these are trade names of products manufactured by Ciba-Geigy Co., Ltd.) and the like, and these may be used alone or in combination.

As the novolac type epoxy resin,
For example, Epicoat 152, Epicoat 154 (these are trade names of oil-based shell epoxy products), Araldite EP
N1138, Araldite EPN1139, Araldite ECN1235, Araldite ECN1273, Araldite ECN1280, Araldite ECN1299
(These are the product names of Ciba-Geigy products)
They are used alone or as a mixture.

Examples of the alicyclic epoxy resin include Araldite CY175, Araldite CY177, Araldite CY179, Araldite CY192 (above,
Ciba-Geigy product name), ERL4221, ER
L4229, ERL4234 (these are trade names of products manufactured by Union Carbide Co., Ltd.) and the like can be used alone or in combination.

It is also possible to use other butadiene type epoxy resins and the like, and it is also possible to use a mixture of the above various epoxy resins.

For the cationically polymerizable compound used in the present invention, a monofunctional epoxy diluent may be used within a range that does not deteriorate the curing characteristics. Examples of such monofunctional epoxy diluents include phenyl glycidyl ether and t-
Butyl glycidyl ether and the like can be mentioned.

Furthermore, it is also possible to use a cationically polymerizable vinyl compound mixed with the epoxy resin, and examples of such cationically polymerizable vinyl compound include styrene, allylbenzene, triallyl isocyanate,
Examples thereof include triallyl cyanate, vinyl ether, N-vinylcarbazole, N-vinylpyrrolidone and the like.

The curing treatment of the cured resin used in the present invention can be carried out by heat curing, but it is desirable to perform photocuring by irradiation of ultraviolet rays.

When photocuring, a photopolymerization initiator is added. Examples of the photopolymerization initiator that releases a Lewis acid that initiates the polymerization of the cationically polymerizable compound by irradiation with ultraviolet rays include aromatic diazonium salts, aromatic halonium salts, and Vth groups.
Examples thereof include photosensitive aromatic onium salts of Group Ib or Group Vb elements.

The aromatic diazonium salt is a compound represented by the following general formula (1):

[0053]

[Outside 16] [Wherein R ¹ and R ² are a hydrogen atom, an alkyl group or an alkoxy group, R ³ is a hydrogen atom, an aromatic group, an amide group or an aromatic group linked by a sulfur atom, M is a metal or a semimetal, and Q is
Each represents a halogen atom. a is a number from 1 to 6, and a = (bc) is established, and b is c <b ≦ 8.
Is a number satisfying the above relation, c is a number of 2 to 7, and is equal to the valence of M. ] For example, the following compounds can be mentioned.

[0054]

[Outside 17] Etc.

The aromatic halonium salt is represented by the general formula [(R ⁴ ) _d (R ⁵ ) _e X] ⁺ _f [MQ _g ] ^-(gn) (2) [wherein R ⁴ is a monovalent aromatic organic compound]. A group, R ⁵ is a divalent aromatic organic group, X is a halogen atom such as I, Br and Cl, M is a metal or metalloid, Q is a halogen atom,
d is 0 or 2, e is 0 or 1, g is a number satisfying the relationship of h <g ≦ 8, and (d + e) is equal to 2 or X. ] The compound shown by these, for example,

[0056]

[Outside 18] Etc.

Further, the group VIb element or the photosensitive aromatic onium salt of the group Vb element is a compound represented by the general formula (3): [(R ⁶ ) _i (R ⁷ ) _j (R _{^{8) k Y] + 1 [}} MQ m] - (mn) (3) [ wherein, R ⁶ is a monovalent aromatic organic radical, R ⁷ is an alkyl group,
A monovalent aliphatic organic group selected from a cycloalkyl group and a substituted alkyl group, R ⁸ is a polyvalent organic group constituting a heterocyclic structure selected from an aliphatic organic group and an aromatic organic group, Y is S,
A Group VIb element of Se or Te or a Group Vb element selected from N, P, As, Sb and Bi, M represents a metal or a semimetal, and Q represents a halogen atom. i is an integer from 0 to 4, j
Is an integer of 0 to 2, k is an integer of 0 to 2, and (i
+ J + k) is equal to the valence of Y, is equal to 3 when Y is a VIb group, and is equal to 4 when Y is a Vb group, and i = (m-
n) holds, m represents a number satisfying the relationship of n <m ≦ 8, and n is an integer of 2 to 7 and is equal to the valence of M. Examples of the onium salt of the Group VIb element include, for example,

[0058]

[Outside 19] Etc.

The onium salt of the Vb group element is, for example,

[0060]

[Outside 20] Etc.

The resin composition used in the present invention is preferably dissolved in a solvent and applied to a substrate.

As the lubricating material used in the present invention, organic polymer powder such as Teflon, vinyl fluoride, vinylidene fluoride, polyethylene, polyethylene terephthalate, polybutylene terephthalate, vinyl chloride, nylon, polypropylene, polyoxymethylene, etc., Solid lubricants such as graphite, molybdenum disulfide, BN, SiN, Sb ₂ O ₃ , mica, CdCl ₂ , phthalocyanine, fluorinated graphite, ZnS, ZnO, liquid paraffin, micro wax (paraffin), low molecular weight polyethylene wax, etc. Hydrocarbon lubricants, fatty acid lubricants such as stearic acid and lauric acid,
Fatty acid amide lubricants such as stearic acid amide, palmitic acid amide, methylene bis stearoamide, ethylene glycol monostearate, butyl stearate, ester lubricants such as hydrogenated castor oil, cetyl alcohol,
Synthesis of alcohol-based lubricants such as stearyl alcohol, metal soaps such as zinc stearate and lead stearate, silicones, chlorinated biphenyls, fluoroesters, polychlorotrifluoroethylene, phosphoric acid esters, polyphenyl ethers, polyglycols, etc. Lubricants and the like can be mentioned.

These lubricants may be used alone or in combination of two or more.

The silicone-type comb-type graft polymer according to the present invention is polymerizable with a modified silicone which is a condensation reaction product of a silicone selected from the following general formulas (1) and (2) and a silicone of the following general formula (3). It can be obtained by copolymerizing with a compound having a functional group.

[0065]

[Outside 21] R _{1 to} R ₅ are groups selected from alkyl groups and aryl groups. n is a positive integer.

[0066]

[Outside 22] R ₆ and R ₇ are groups selected from alkyl groups and aryl groups. n is a positive integer.

[0067]

[Outside 23] R ₈ , R ₉ and R ₁₀ are groups selected from a hydrogen atom, a halogen atom, an alkyl group and an aryl group, R ₁₁ is a group selected from an alkyl group and an aryl group, X is a group selected from a halogen atom and an alkoxy group, n is an integer of 1 to 3.

The silicone-type comb-type graft polymer used in the present invention has a structure in which a silicone-containing side chain is technically dangling from the main chain.

R represented by the above general formulas (1) and (2)
₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are alkyl groups or aryl groups, which may have a substituent. For example, the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group or the like, which may be substituted with a halogen atom or the like. Further, the aryl group is a phenyl group, a naphthyl group or the like, and may have a substituent. Preferred are a methyl group and a phenyl group. n shows an average degree of polymerization, and is preferably 1 or more and 1000 or less, and particularly preferably 10 or more and 500 or less. R represented by the general formula (3)
₈ , R ₉ and R ₁₀ are hydrogen atoms, fluorine is a halogen atom,
Chlorine, bromine and iodine. Both the alkyl group and the aryl group may have a substituent, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the aryl group include a phenyl group and a naphthyl group. It is preferably a hydrogen atom.

R ₁₁ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, which may be substituted with a halogen atom or the like. The aryl group is a phenyl group, a naphthyl group or the like and may have a substituent. Preferred are a methyl group and a phenyl group.

X is a halogen atom such as fluorine, chlorine, bromine or iodine, preferably a chlorine atom.

The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a pudoxy group and the like, which may have a substituent.

Preferably, methoxy group, ethoxy group, 2
A methoxy-ethoxy group. n is an integer of 1 to 3.

Specific examples of the general formulas (1) to (3) are shown below.

[0075]

[Outside 24]

[0076]

[Outside 25]

[0077]

[Outside 26]

[0078]

[Outside 27]

[0079]

[Outside 28]

[0080]

[Outside 29]

[0081]

[Outside 30]

[0082]

[Outside 31]

[0083]

[Outside 32]

[0084]

[Outside 33]

[0085]

[Outside 34]

[0086]

[Outside 35]

[0087]

[Outside 36]

General formula (1) and / or general formula (2)
The silicone represented by may react both of (1) and (2) with the silicone of the general formula (3) to form a modified silicone. The condensation reaction between the general formulas (1) and (2) and the general formula (3) usually proceeds extremely smoothly in accordance with the organic chemical reaction operation, and is described in, for example, JP-A-58-167606.
As disclosed in JP-A-59-126478 and JP-A-59-126478, stable modified silicone can be obtained by controlling the reaction molar ratio and reaction conditions.

The compound having a polymerizable functional group is a macromolecule composed of a polymerizable monomer having no silicon atom or a polymer having a polymerizable functional group at the terminal and having a relatively low molecular weight of about 1,000 to 10,000. Examples thereof include monomers. As the polymerizable monomer, examples of olefin compounds include low molecular weight linear unsaturated hydrocarbons such as eletin, propylene and butylene, vinyl chloride, vinyl halides such as vinyl fluoride, and organic acids such as vinyl acetate. Vinyl esters, styrenes, styrene substitutes and other vinyl aromatic compounds such as vinyl pyridine and vinyl naphthylene, acrylic acid, methacrylic acid, and their acrylic acid, including amide and acrylonitrile, derivatives of methacrylic acid, N-vinyl There are N-vinyl compounds such as carbazole, N-vinylpyrrolidone and N-vinylcaprolactam, and vinylsilicon compounds such as vinyltriethoxysilane. Di-substituted ethylene can also be used, examples of which include vinylidene fluoride and vinylidene chloride. Further, maleic anhydride, maleic acid and fumaric acid esters can also be used.

The polymerizable monomer may be used alone or in combination of two or more kinds.

As a method for polymerizing the silicone-type comb-type graft polymer, radical polymerization such as solution polymerization method, suspension polymerization method, bulk polymerization method and the like can be applied, but the radical polymerization method by the solution polymerization method is simple and preferable. .

The copolymerization ratio of the modified silicone is preferably 5 to 90% by weight, more preferably 10 to 70% by weight. The polymer obtained has a number average molecular weight of 500 to 100,000, particularly 1,000 to 50,000.
Is preferred.

As the solvent for dissolving the resin composition of the present invention, those used as a solvent for dissolving the high melting point polyester resin can be used, but generally, cresols,
Chloroform, dichloroethane, tetrachloroethane,
One or a mixture of two or more kinds of halogenated hydrocarbons such as trichloropropane and tetrachlorobenzene and fluorine-containing alcohols such as tetrafluoroethanol and hexafluoroisopropanol is preferable.

A particularly preferred solvent is a fluorine-containing alcohol such as tetrafluoroethanol or hexafluoroisopropanol, or a mixed solvent containing one or more of these. The advantage of these fluorine-containing alcohols over the conventional chlorine-based solvents is that they have little effect on electrophotographic production and can withstand long-term use even in high temperature and high humidity environments. .

The mixing ratio of the curable resin to 100 parts by weight of the high melting point polyester resin is 3 to 50 parts by weight, preferably 8 to 45 parts by weight, more preferably 10 to 40 parts by weight. The mixing ratio of the Lewis acid free type photopolymerization initiator is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight with respect to 100 parts by weight of the cured resin. The content of the silicone-type comb-type graft polymer is 0.01 to 10%, preferably 0.01 to 5% by weight of the surface layer of the image holding member.

As a coating method, an arbitrary method such as a dipping method, a roll coater, a bar coater, a spray or a brush coating can be used. In particular, the dipping method (dipping method) is preferable because the resulting coating film is excellent in uniformity.

The irradiation conditions of the ultraviolet rays are from room temperature to the decomposition temperature of the high molecular weight polyester resin, preferably the glass transition temperature or higher and the melting start temperature or lower, particularly preferably 20 ° C. or higher higher than the glass transition temperature. The temperature is lower than the melting start temperature by 20 ° C. or lower. Irradiation time is 60
Seconds or less, preferably 30 seconds or less, more preferably 5 to 1
5 seconds.

Irradiation conditions are appropriately selected depending on the amount of the solvent-insoluble matter of the obtained crosslinked product. The ultraviolet ray generally has a wavelength of 200 to 500 nm, preferably 300 to 400 n.
m is used.

The surface layer of the present invention consisting of a specific resin component was prepared by dissolving 100 mg of the cured product in 10 ml of a solvent with heating and stirring for 1 hour at 100 ° C., and then removing the undissolved portion remaining after filtering and washing with a 3G glass filter. Curing is performed by irradiating ultraviolet rays to an amount such that the insoluble matter (gel) when dried to reach a constant temperature at 0 ° C becomes 10% by weight or more, preferably 15% by weight or more, particularly preferably 20% by weight or more. Be done.

Examples of the support of the image support member according to the present invention include those having the forms shown below.

(1) Aluminum, aluminum alloys,
Corrosion-resistant steel (stainless steel), copper or other metal formed into a plate or drum shape.

(2) A thin film formed by vapor-depositing or laminating a metal such as aluminum, palladium, rhodium, gold or platinum on a non-conductive support such as glass, resin or paper or the conductive support described in (1) above. Formed.

(3) A layer of a conductive compound such as a conductive polymer, tin oxide or indium oxide is vapor-deposited on a non-conductive support such as glass, resin or paper or the conductive support described in (1) above. Or, it is formed by applying it as a dispersion paint with a conductive or non-conductive polymer.

An undercoat layer having a barrier function or an adhesive function may be provided between the support and the photoconductive layer.
The thickness of the undercoat layer is 5 μm or less, preferably 0.1 to 3 μm
m is suitable. The undercoat layer can be formed of, for example, casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66, nylon 610, copolymer nylon, N-alkoxymethylated nylon, etc.), polyurethane, aluminum oxide, or the like.

Examples of effective charge generating substances used in the present invention include the following substances. These charge generating substances may be used alone or in combination of two or more.

(1) Azo pigments: monoazo, bisazo,
(2) Phthalocyanine-based pigment: metal-phthalocyanine,
(3) Indigo pigments: indigo, thioindigo, etc. (4) Perylene pigments: perylene anhydride, perylene imide, etc. (5) Polycyclic quinone pigments: condensed rings of anthraquinone, pyrenequinone, etc. Compounds: (6) squarylium dyes; (7) pyrylium salts, thiopyrylium salts; (8) triphenylmethane dyes; (9) inorganic substances such as selenium and amorphous silicon.

The layer containing the charge-generating substance, that is, the charge-generating layer 6 is formed by dispersing the above-mentioned charge-generating substance in, for example, a suitable binder, and coating this on a support. be able to. It can also be manufactured by forming a thin film on the support 4 by a dry method such as vapor deposition, sputtering or CVD.

The binder can be selected from a wide range of binder resins, for example, polycarbonate resin, polyester resin, polyarylate resin, butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, acrylic resin. , Methacrylic resin, vinyl acetate resin, phenol resin, silicone resin, polysulfone resin, styrene-butadiene copolymer resin, alkyd resin, epoxy resin, urea resin, vinyl chloride-vinyl acetate copolymer resin, and the like. It is not limited to.

These may be used alone or as a copolymer, and may be used alone or in combination of two or more. The amount of resin contained in the charge generation layer is selected to be 80% by weight or less, preferably 0 to 40% by weight. The thickness of the charge generation layer is 5 μm or less, and preferably a thin film layer having a thickness of 0.01 μm to 1 μm.

Various sensitizers may be added to the charge generation layer.

The charge transport layer is provided above or below the charge generation layer and has a function of receiving charge carriers from the charge generation layer in the presence of an electric field and transporting them. Charge transport layer 5
Is formed by dissolving a charge-transporting substance in a solvent together with a suitable binder as necessary and applying it, and its film thickness is generally 5 to 40 μm, but 15 to 30 μm.
m is preferred.

The charge transport material includes an electron transport material and a hole transport material, and the electron transport material is, for example, 2, 4,
Examples thereof include electron-withdrawing substances such as 7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, chloranil and tetracyanoquinodimethane, and polymers obtained by polymerizing these electron-withdrawing substances.

As the hole-transporting substance, polycyclic aromatic compounds such as pyrene and anthracene; heterocyclic compounds such as carbazole, indole, imidazole, oxazole, thiazole, oxadiazole, pyrazole, pyrazoline, thiadiazole and triazole; p- Diethylaminobenzaldehyde-N, N-diphenylhydrazone,
N, N-diphenylhydrazino-3-methylidene-9-
Hydrazone compounds such as ethylcarbazole; α-phenyl-4′-N, N-diphenylaminostilbene, 5
-[4- (di-p-tolylamino) benzylidene] -5
A styryl compound such as H-dibenzo [a, d] cycloheptene; a benzidine compound; a triarylmethane compound; triphenylamine or a polymer having a group composed of these compounds in its main chain or side chain (for example, poly-N). -Vinylcarbazole, polyvinylanthracene, etc.).

In addition to these organic charge transport materials, selenium,
Selenium-tellurium, amorphous silicon (α-Si),
Inorganic materials such as cadmium sulfide can also be used.

These charge transport materials may be used alone or in combination.
A combination of two or more species can be used.

When the charge transport material has no film-forming property, a suitable binder (binding resin) can be used. Specifically as the binder, acrylic resin, polyarylate, polyester, polycarbonate, polystyrene, acrylonitrile-styrene copolymer resin, polysulfone, polyacrylamide, polyamide,
Insulating resin or elastomer such as chlorinated rubber, Poly N
Examples include organic photoconductive polymers such as vinylcarbazole and polyvinylanthracene.

Another specific example of the present invention is an image holding member containing the above-mentioned azo pigment and charge transporting substance in the same layer. At this time, a charge transfer complex composed of poly-N-vinylcarbazole and trinitrofluorenone can be used as the above-mentioned charge transport material.

The image-holding member of this example can be formed by applying a liquid prepared by dispersing the above-mentioned azo pigment and charge-transporting substance in a suitable resin solution onto a support and drying it.

The image holding member having the photoconductive layer according to the present invention is used not only for electrophotographic copying machines as electrophotographic photoreceptors but also for laser beam printers, CRT printers, LED printers, liquid crystal printers, laser plate making and facsimiles. It can be widely used in electrophotographic application fields such as printers.

Among the image holding members of the present invention, examples of the image holding member having no photoconductive layer include a surface layer on the support for the purpose of holding an electrostatic latent image or a toner image. ,
Alternatively, a surface layer is provided on a support through a dielectric layer, and the surface layer contains a high melting point polyester resin and a curable resin, especially a photoion curable resin, and a layer containing a silicone-based comb-type graft polymer. The thing formed is mentioned.

Application examples of the image holding member having no photoconductive layer include a toner layer, an intermediate transfer member for an electrostatic latent image, an electrostatic recording member and the like.

FIG. 7 shows a schematic structure of a general transfer type electrophotographic apparatus using a drum type photoconductor on which the image holding member of the present invention is mounted.

In FIG. 7, reference numeral 41 is a drum type photosensitive member as an image bearing member, which is rotationally driven around the shaft 41a in the direction of the arrow at a predetermined peripheral speed. During the rotation of the photoconductor 41, the peripheral surface of the photoconductor 41 is uniformly charged with a positive or negative predetermined potential by the charging means 42. Then, in the exposure section 43, the light image exposure L ( Slit exposure, laser beam scanning exposure, etc.). As a result, electrostatic latent images corresponding to the exposed images are sequentially formed on the peripheral surface of the photoconductor.

The electrostatic latent image is then developed with toner by the developing means 44, and the toner developed image is transferred by the transfer means 45.
A transfer material P fed from a sheet feeding unit (not shown) between the photoconductor 41 and the transfer means 45 in synchronization with the rotation of the photoconductor 41.
Are sequentially transferred to the surface.

The transfer material P that has received the image transfer is separated from the surface of the photoconductor and is introduced into the image fixing means 48 to undergo the image fixing, and is printed out as a copy.

The surface of the photoconductor 41 after the image transfer is cleaned by the cleaning means 46 to remove the residual toner after transfer, and is repeatedly used for image formation.

As the uniform charging means 42 for the photoconductor 41, a corona charging device is generally widely used. Also, as the transfer device 45, corona transfer means is widely and generally used. In the electrophotographic apparatus, a plurality of constituent elements such as the photoconductor 41, the developing unit 44, and the cleaning unit 46 described above are integrally combined as an apparatus unit, and the unit is attached to and detached from the apparatus main body. It may be configured freely. For example, the photoconductor 41 and the cleaning unit 4
6 and 6 may be integrated into a single device unit, and may be detachably configured by using guide means such as a rail of the device body. At this time, the charging means 42 is attached to the device unit.
And / or the developing unit 44 may be included.

When the electrophotographic apparatus is used as a copying machine or a printer, the light image exposure L is reflected light from a manuscript, transmitted light or a manuscript is read out and converted into a signal, and scanning of a laser beam and a light emitting diode are performed by this signal. This is performed by driving the array, driving the liquid crystal shutter array, or the like.

When used as a facsimile printer, the optical image exposure L becomes an exposure for printing the received data. FIG. 5 is a block diagram showing an example of this case.

In FIG. 5, the controller 51 controls the image reading section 50 and the printer 59. The entire controller 51 is controlled by the CPU 57.
The read data from the image reading unit is transmitted to the partner station through the transmission circuit 53.

The data received from the partner station is sent to the printer 59 through the receiving circuit 52. The image memory 56 stores predetermined image data. The printer controller 58 controls the printer 59. 54 is a telephone.

The image received from the line 55 (image information from the remote terminal connected via the line) is demodulated by the receiving circuit 52, and then the CPU 57 decodes the image information to successively process the image memory 56. Stored in. When an image for at least one page is stored in the image memory 56, the image of that page is recorded. The CPU 57 reads out the image information for one page from the image memory 56 and sends the decoded image information for one page to the printer controller 58. When the printer controller 58 receives the image information for one page from the CPU 57, the printer controller 58 controls the printer 59 to record the image information of the page. In addition,
The CPU 57 is receiving the next page during recording by the printer 59.

As described above, an electrophotographic apparatus equipped with the image holding member of the present invention can be used as a printer to receive and record images.

[0134]

【Example】

Example 1-1 An aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm was used as a base, on which an alkoxymethylated nylon 5 was added.
% Methanol solution was applied by a dipping method to form an undercoat layer (intermediate layer) having a film thickness of 1 μm.

Next, 10 parts by weight of a pigment having the following structural formula (parts by weight,
The same applies hereinafter), 8 parts of polyvinyl butyral

[0136]

[Outside 37] And 50 parts of cyclohexanone were mixed and dispersed in a sand mill apparatus using 100 parts of glass beads having a diameter of 1 mm for 20 hours. Methyl ethyl ketone 70-120 was added to this dispersion.
(Appropriately) parts are added and coated on the undercoat layer, and the mixture is applied at 100 ° C for 5
It was dried for a minute to form a 0.2 μm charge generation layer.

Next, on the charge generation layer, 10 parts of the following styryl compound represented by the structural formula:

[0138]

[Outside 38] 10 parts of bisphenol Z-type polycarbonate was dissolved in 65 parts of monochlorobenzene. This solution was applied onto a substrate by a dipping method and dried with hot air at 120 ° C. for 60 minutes to form a 20 μm thick charge transport layer.

Next, a protective layer having a thickness of 1.0 μm was formed on the charge transport layer by the following method.

A high melting point polyethylene terephthalate (A) obtained by using terephthalic acid as an acid component and ethylene glycol as a glycol component (intrinsic viscosity of 0.
70 dl / g, melting point 258 ° C (1 using a differential calorimeter)
It measured at the temperature rising rate of 0 degree-C / min. Also, the measurement sample is 5 mg, and the polyester resin to be measured is 280 ° C.
It was prepared by melting after melting at 0.degree. C. and quenching with ice water at 0.degree. The same in the following examples), glass transition temperature 70 ° C.) 100 parts, and epoxy resin (B) [epoxy equivalent 160; aromatic ester type; trade name: Epicoat 190P (produced by Yuka Shell Epoxy Co.)] 30 parts Was dissolved in 100 ml of a mixed solution of phenol and tetrachloroethane (1: 1). Then, 3 parts of triphenylsulfonium hexafluoroantimonate (C) was added as a photopolymerization initiator, and then 30 parts of modified silicones of general formulas (1) -1: n average 30 and (3) -48 were used. A resin composition solution was prepared by adding 2 parts of a silicone-based comb type graft polymer synthesized by using 70 parts of methyl methacrylate as a comonomer.

As the light irradiation conditions, a 2 kw high-pressure mercury lamp (30 w / cm) was irradiated at 130 ° C. for 8 seconds from a position 20 cm apart to cure the light.

The photoconductor drum thus manufactured was mounted on a copying machine [trade name: NP-3525 (manufactured by Canon Inc.)], and a durability test was conducted on 600,000 sheets of paper at a temperature of 24 ° C. and a relative humidity of 55%. went. The results are shown in Table 1-1.

Comparative Example 1-1 A photoreceptor was prepared in the same manner as in Example 1-1, except that the protective layer used in Example 1-1 was not used, and a durability test was conducted in the same manner as in Example 1-1. It was The results are shown in Table 1-1.

Comparative Example 1-2 Instead of the protective layer used in Example 1-1, a charge transport layer (C
As a binder used in TL), 4 parts of bisphenol Z type polycarbonate, 70 parts of monochlorobenzene, and 1 part of PTFE fine powder were mixed and dispersed in a sand mill for 10 hours to prepare a coating liquid. This coating solution was applied onto the CTL by spraying so as to have a film thickness of 1.0 μm to form a protective layer, and a durability test was conducted in the same manner as in Example 1-1. The results are shown in Table 1-1.

Comparative Example 1-3 A coating solution was re-prepared so that the protective layer used in Comparative Example 1-2 had a thickness of 12.0 μm, and spray-applied to a thickness of 1
A protective layer having a thickness of 2.0 μm was provided, and a durability test was conducted as in Example 1-1. The results are shown in Table 1-1.

The photoconductor drum thus prepared was mounted on a copying machine [trade name: NP-3525 (manufactured by Canon Inc.)], and a durability test of 600,000 sheets of paper was conducted in the same manner as in Example 1-1. It was The results are shown in Table 1-1.

Example 1-2 High melting point polyester resin obtained by using terephthalic acid as an acid component and 80 mol% of ethylene glycol and 20 mol% of polyethylene glycol [molecular weight 1000] as a glycol component (intrinsic viscosity 0.68 dl / g, melting point 2
10 ° C., glass transition temperature 68 ° C.), the silicone-type comb-type graft polymer is used as a modified silicone, and the general formulas (1) -2: n average 30 and (3) -47 are used, and 30 parts of the modified silicone is used. An experiment similar to that of Example 1-1 was performed, except that 3 parts of a silicone-type comb-type graft polymer synthesized by using 80 parts of methyl methacrylate as a monomer was added. The results are shown in Table 1-1.

Example 1-3 High melting point polyester resin obtained by using terephthalic acid as an acid component and a mixture of 63 mol% of ethylene glycol and 37 mol% of polyethylene glycol as a glycol component (intrinsic viscosity 0.67 dl / g, Melting point 195 ° C,
The same experiment as in Example 1-1 was performed except that the glass transition temperature of 65 ° C. was used. The results are shown in Table 1-1.

Example 1-4 High melting point polyester resin (intrinsic viscosity 0.66 dl / g, obtained by using terephthalic acid as an acid component and a mixture of 50 mol% of ethylene glycol and 50 mol% of polyethylene glycol as a glycol component) Melting point 180 ° C,
The same experiment as in Example 1-2 was performed except that the glass transition temperature of 64 ° C. was used. The results are shown in Table 1-1.

Example 1-5 High melting point polyester resin (intrinsic viscosity 0.64 dl / g, obtained by using terephthalic acid as an acid component and a mixture of 40 mol% of ethylene glycol and 60 mol% of polyethylene glycol as a glycol component) Melting point 161 ° C.,
Glass transition temperature of 60 ° C.), the silicone-type comb-type graft polymer is used as a modified silicone, and general formulas (2) -26: n average 300, and (3) -58, and 20 parts of modified silicone are used, and a copolymerization monomer is used. The same experiment as in Example 1-1 was carried out except that 3 parts of the silicone-type comb-type graft polymer synthesized by using styrene / methyl methacrylate = 30 parts / 50 parts as a body was added. The results are shown in Table 1-1.

Examples 1-6 Epoxy resin [epoxy equivalent 184-
194; Bisphenol type; Trade name: Epikote 828
(Oilized Shell Epoxy Co., Ltd.)] was used, and the same experiment as in Example 1-5 was performed. The results are shown in Table 1-1.

Example 1-7 A photoreceptor was prepared in the same manner as in Example 1-1, except that the amount of the epoxy resin used in Example 1-1 was changed to 10 parts. went. The results are shown in Table 1-1. The protective layer used had a thickness of 0.8 μm.

Example 1-8 Except for irradiating the high pressure mercury lamp light used in Example 1-1 for 5 seconds, a photosensitive member exactly the same as in Example 1-5 was prepared and a durability test was conducted in the same manner as in the same example. went. The results are shown in Table 1-1.
The protective layer used had a thickness of 0.9 μm.

Example 1-9 An aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm was used as a base. A 5% methanol solution of the alkoxymethylated nylon used in Example 1-1 was applied thereto by a dipping method to form an undercoat layer (intermediate layer) having a film thickness of 1 μm. Next, 3 parts of ε-type Cu-PC which is a charge generating substance and 6 parts of a hydrazone compound of the following structural formula which is a charge transporting substance,

[0155]

[Outside 39] 6 parts of the bisphenol Z-type polycarbonate used in Example 1-1 and 50 parts of monochlorobenzene were mixed and dispersed in a sand mill for 30 hours to prepare a coating liquid. This coating solution was applied onto a substrate by a spray method to form a photosensitive layer having a film thickness of 20 μm.

Then, a protective layer having a thickness of 1.0 μm was formed on this photosensitive layer in the same manner as in Example 1-1, and the durability test was conducted in the same manner. The results are shown in Table 1-1.

Example 1-10 A photoconductor similar to that of Example 1-1 was prepared except that the order of the layer constitution of the charge generation layer and the charge transport layer of Example 1-1 was reversed. The durability test was performed in the same manner as in. The results are shown in Table 1-1. The protective layer used had a thickness of 0.9 μm.

Example 1-11 An aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm was used as a substrate, and a 5% methanol solution of the alkoxymethylated nylon used in Example 1-1 was applied thereto by a dipping method to give a film thickness. An undercoat layer (intermediate layer) of 1 μm was provided.

Next, the black angles 2θ ± 0.2 ° in the X-ray diffraction of Cu-Kα rays are 9.0 °, 14.2 °, and 2
Crystalline oxotitanium phthalocyanine pigment having strong peaks at 3.9 ° and 27.1 ° 10 parts polyvinyl butyral 8 parts and cyclohexanone 50 parts diameter 1
The mixture was mixed and dispersed for 20 hours by a sand mill device using 100 parts of glass beads of mm.

70 to 1 of methyl ethyl ketone was added to this dispersion.
20 (appropriate) parts are added and coated on the undercoat layer at 100 ° C.
And dried for 5 minutes to form a 0.2 μm charge generation layer.

Next, on the charge generation layer, 10 parts of a styryl compound having the following structural formula was added.

[0162]

[Outside 40] 10 parts of the bisphenol Z type polycarbonate used in Example 1-1 was dissolved in 65 parts of monochlorobenzene. This solution is applied onto a substrate by a dipping method,
It was dried with hot air at 0 ° C. for 60 minutes to form a 20 μm thick charge transport layer.

Next, a protective layer having a thickness of 1.0 μm was provided on the charge transport layer by the following method. High melting point polybutylene terephthalate (PBT) (A) obtained by using terephthalic acid as an acid component and 1,4-tetramethylene glycol as a glycol component (intrinsic viscosity 0.72 dl
/ G, melting point 22.4 ° C, glass transition temperature 35 ° C) 10
0 part and 30 parts of the epoxy resin (B) used in Example 1-1 were dissolved in 100 ml of a mixed solution of phenol and tetrachloroethane (1: 1). Then, 3 parts of triphenylsulfonium hexafluoroantimonate (C) was added as a photopolymerization initiator, and as a silicone-based comb-type graft polymer, a modified silicone of the general formula (1) -7: n average 30, (3) was used. A resin composition solution was prepared by adding 2 parts of what was synthesized using −63, modified silicone 15 parts, and comonomer styrene 85 parts.

As the light irradiation conditions, a 2 kw high-pressure mercury lamp (30 w / cm) was irradiated at 130 ° C. for 8 seconds from a position 20 cm away to cure the light.

The photoconductor drum thus manufactured was mounted on a copying machine [trade name: NP-3525 (manufactured by Canon Inc.)], and a durability test of 600,000 sheets of paper was carried out in the same manner as in Example 1-1. It was The results are shown in Table 1-2.

Comparative Example 1-4 A photoreceptor was prepared in the same manner as in Example 1-11 except that the protective layer in Example 1-11 was not used.
A durability test was conducted in the same manner as in. The results are shown in Table 1-2.

Comparative Example 1-5 Instead of the protective layer used in Example 1-11, the same binder as used in the charge transport layer (CTL) was used, and bisphenol Z type polycarbonate 4 used in Example 1-1 was used. Part, 70 parts of monochlorobenzene, and 1 part of PTFE fine powder were mixed and dispersed in a sand mill for 10 hours to prepare a coating liquid. This coating solution is sprayed onto the CTL to give a film thickness of 1.0μ.
Then, a durability test was conducted in the same manner as in Example 1-11 by applying the coating solution so that the coating film had a thickness of m to form a protective layer. The results are shown in Table 1-2.

Comparative Example 1-6 The coating solution was re-prepared so that the protective layer used in Comparative Example 1-5 had a thickness of 12.0 μm, and spray-applied to a thickness of 1
A 2.0 μm protective layer was provided.

The photoconductor drum thus manufactured was mounted on a copying machine [trade name: NP-3525 (manufactured by Canon Inc.)], and a durability test of 600,000 sheets of paper was conducted in the same manner as in Example 1-11. It was The results are shown in Table 1-2.

Comparative Example 1-7 Instead of the high melting point polyethylene terephthalate used in Example 1-1, a polyester resin having a softening point of 163 ° C. (which has no melting point because it is amorphous) (Vylon 200: Toyobo Co., Ltd.) A photosensitive drum similar to that of Example 1-1 was manufactured except for using the same), and the characteristics were evaluated. The results are shown in Table 1-1.

Example 1-12 High-melting point polycyclohexanedimethylene terephthalate (PCT) resin obtained by using terephthalic acid as an acid component and cyclohexanedimethylol as a glycol component (intrinsic viscosity 0.66 dl / g, melting point 290 ° C., The same experiment as in Example 1-11 was performed except that a glass transition temperature of 80 ° C. was used. The results are shown in Table 1-2.

Example 1-13 High melting point polyethylene naphthalate resin (PEN) obtained by using 1,10-naphthalenedicarboxylic acid as an acid component and ethylene glycol as a glycol component.
The same experiment as in Example 1-11 was carried out except that (intrinsic viscosity 0.69 dl / g, melting point 280 ° C., glass transition temperature 85 ° C.) was used. The results are shown in Table 1-2.

Example 1-14 High melting point polyester resin obtained by using a mixture of terephthalic acid as an acid component and 63 mol% of 1,4-tetramethylene glycol as a glycol component and 37 mol% of polyethylene glycol (having an intrinsic viscosity of 0). .67 dl /
g, melting point 190 [deg.] C., glass transition temperature 15 [deg.] C.) The same experiment as in Example 1-11 was carried out. The results are shown in Table 1-2.

Example 1-15 An experiment similar to that of Example 1-11 was conducted, except that the epoxy resin used in Example 1-6 was used as the cured resin.
The results are shown in Table 1-2.

Example 1-16 A photoreceptor was prepared in the same manner as in Example 1-11 except that the amount of the epoxy resin used in Example 1-11 was changed to 10 parts, and a durability test was conducted. The results are shown in Table 1-2. The protective layer used had a thickness of 0.9 μm.

Example 1-17 A photoreceptor was prepared in the same manner as in Example 1-11 except that the high pressure mercury lamp used in Example 1-11 was irradiated for 5 seconds, and a durability test was conducted. The results are shown in Table 1-2. The protective layer used had a thickness of 1.0 μm.

Example 1-18 An aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm was used as a base. A 5% methanol solution of the alkoxymethylated nylon used in Examples 1-11 was applied to this by a dipping method to form an undercoat layer (intermediate layer) having a film thickness of 1 μm. Next, 3 parts of the pigment used in Example 1-11, which is a charge generating substance, 6 parts of the styryl compound used in Example 1-1, which is a charge transporting substance, and 6 parts of the bisphenol Z-type polycarbonate used in Examples 1-11. Parts and 50 parts of monochlorobenzene were mixed and dispersed in a sand mill for 30 hours to prepare a coating liquid.
This coating solution is applied on the substrate by a spray method to give a film thickness of 20 μm.
m photosensitive layer was formed.

Then, a protective layer having a thickness of 1.0 μm was formed on the photosensitive layer in the same manner as in Example 1-11, and the durability test was conducted in the same manner. The results are shown in Table 1-2.

Example 1-19 A photoreceptor was prepared in the same manner as in Example 1-11 except that the order of the layer structure of the charge generation layer and the charge transport layer in Example 1-11 was reversed, and the durability was evaluated. I did a test. The results are shown in the table.
The protective layer used had a thickness of 0.8 μm.

Example 1-20 Same as Example 1-11 except that 100 ml of hexafluoroisopropanol was used instead of 100 ml of the mixed solution of phenol and tetrachloroethane (1: 1) used in Example 1-11. A photoconductor was produced in this manner, and the same durability test as in the same example was conducted. The results are shown in Table 1-2.

Examples 1-21 and 1-22 The photoconductor of Example 1-11 and the photoconductor of Example 1-20 were placed in a copying machine [trade name: NP under the environment of temperature 30 ° C. and relative humidity 85%]. -3525 (manufactured by Canon Inc.)] was used to perform a durability test on 100,000 sheets of paper passing in the same manner as in Example 1-11. The results are shown in Table 1-2.

[0182]

[Table 1]

[0183]

[Table 2]

Example 2-1 An aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm was used as a base, on which 5 parts of an alkoxymethylated nylon was used.
% Methanol solution was applied by a dipping method to form an undercoat layer (intermediate layer) having a film thickness of 1 μm.

Next, 10 parts by weight of a pigment having the following structural formula (parts by weight,
The same shall apply hereinafter) and polyvinyl butyrers

[0186]

[Outside 41] 8 parts and 50 parts of cyclohexanone were mixed and dispersed in a sand mill apparatus containing 100 parts of glass beads having a diameter of 1 mm for 20 hours. Methyl ethyl ketone 70-12
0 (appropriate) part is added and coated on the undercoat layer, dried at 100 ° C. for 5 minutes to form a 0.2 μm charge generation layer (CGL).
Was formed. Next, using 130 parts of hydrazone having the following structural formula on this charge generation layer,

[0187]

[Outside 42] By the following method, the prepared resin liquid was mixed and dissolved (the mixing ratio of hydrazone and the resin component was 1: 1) to obtain a coating liquid. This coating solution is applied onto the charge generation layer by a dipping method and irradiated with light to form a charge transport layer (CT having a thickness of 20 μm).
L) was prepared.

The resin liquid is a high melting point polyethylene terephthalate (A) obtained by using terephthalic acid as an acid component and ethylene glycol as a glycol component (intrinsic viscosity 0.70 dl / g, melting point 258 ° C., glass transition temperature 7
0 ° C.) 100 parts and epoxy resin (B) [epoxy equivalent 1
60; Aromatic ester type; Trade name: Epicoat 19
30 parts of 0P (produced by Yuka Shell Epoxy Co., Ltd.) were dissolved in 100 ml of a mixed solution of phenol and tetrachloroethane (1: 1).

Then, 3 parts of triphenylsulfonium hexafluoroantimonate (C) was added as a photopolymerization initiator, and further 2 parts of the silicone type comb-type graft polymer used in Example 1-1 was added to the resin composition. A product solution was prepared.

The coating liquid thus prepared was applied onto the charge generation layer by dipping and irradiated with light,
A charge transport layer (CTL) having a film thickness of 20 μm was created.

As the light irradiation conditions, a 2 kw high-pressure mercury lamp (30 w / cm) was irradiated at 130 ° C. for 8 seconds from a position 20 cm away to cure the light.

The photoconductor drum thus manufactured was mounted on a copying machine [trade name: NP-3525 (manufactured by Canon Inc.)], and a paper feed of 600,000 was applied in an environment of a temperature of 24 ° C. and a relative humidity of 55%. The durability test of the sheet was performed. The results are shown in Table 2-1.

Example 2-2 High melting point polyester resin obtained by using terephthalic acid as an acid component and 80 mol% of ethylene glycol and 20 mol% of polyethylene glycol [molecular weight 1000] as a glycol component (intrinsic viscosity 0.68 dl / g, melting point 2
10 ° C., glass transition temperature 68 ° C.), and the silicone-based comb-type graft polymer 3 used in Example 1-2.
The same experiment as in Example 2-1 was performed except that the parts were added. The results are shown in Table 2-1.

Example 2-3 High melting point polyester resin obtained by using a mixture of terephthalic acid as an acid component and 63 mol% of ethylene glycol and 37 mol% of polyethylene glycol [molecular weight 1000] as a glycol component (intrinsic viscosity: 0. 67 dl /
g, melting point 195 ° C., glass transition temperature 65 ° C.), but the same experiment as in Example 2-1 was performed. The results are shown in Table 2.
-1.

Example 2-4 High melting point polyester resin obtained by using a mixture of terephthalic acid as an acid component and 50 mol% of ethylene glycol as a glycol component and 50 mol% of polyethylene glycol [molecular weight 1000] (intrinsic viscosity: 0. 66 dl /
g, melting point 180 ° C., glass transition temperature 64 ° C.), except that the same experiment as in Example 2-2 was performed. The results are shown in Table 2.
-1.

Example 2-5 High melting point polyester resin obtained by using a mixture of terephthalic acid as an acid component and 40 mol% of ethylene glycol and 60 mol% of polyethylene glycol [molecular weight 1000] as a glycol component (intrinsic viscosity: 64 dl /
g, melting point 161 ° C., glass transition temperature 60 ° C.), and the same experiment as in Example 2-1 was performed except that 3 parts of the silicone-based comb-type graft polymer used in Example 1-5 was further added. It was The results are shown in Table 2-1.

Example 2-6 Epoxy resin [epoxy equivalent 184-
194; Bisphenol type; Trade name: Epikote 828
(Oilized Shell Epoxy Co., Ltd.)] was used, and the same experiment as in Example 2-5 was performed. The results are shown in Table 2-1.

Comparative Example 2-1 A charge transport layer was prepared by using 130 parts of bisphenol type polycarbonate and 900 parts of monochlorobenzene instead of the resin liquid of the charge transport layer used in Example 2-1, and Example 2-1. A durability test was conducted in the same manner as in. The results are shown in Table 2-1.

Comparative Example 2-2 In order to improve the durability characteristics of the photoconductor used in Comparative Example 2-1, a protective layer using a conventionally known PTFE fine powder was provided as follows, and a durability test was conducted. I went. The results are shown in Table 2.
-1.

The protective layer used here was 4 parts of the above-mentioned bisphenol Z type polycarbonate and monochlorobenzene 70.
Parts and 1 part of PTFE powder were mixed and dispersed in a sand mill for 10 hours to prepare a coating liquid. CT this coating solution by spraying
A protective layer was formed by coating L so as to have a film thickness of 1.0 μm.

Comparative Example 2-3 A coating solution was re-prepared so that the protective layer used in Comparative Example 2-2 had a film thickness of 12.0 μm, and spray-applied to give a film thickness of 1
A 2.0 μm protective layer was provided and a durability test was conducted. The results are shown in Table 2-1.

Comparative Example 2-4 Instead of the high melting point polyethylene terephthalate used in Example 2-1, a polyester resin having a softening point of 163 ° C. (has no melting point because it is amorphous) (Byron 200: Toyobo Co., Ltd.) A photoconductor drum similar to that of Example 2-1 except that the same was used, and the characteristics were evaluated. The results are shown in Table 2-1.

Example 2-7 An aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm was used as a base. A 5% methanol solution of the alkoxymethylated nylon used in Example 2-1 was applied to this by a dipping method to form an undercoat layer (intermediate layer) having a film thickness of 1 μm. Next, a styryl compound 10 having the following structural formula was formed on the intermediate layer.
Department and

[0204]

[Outside 43] 10 parts of polymethylmethacrylate was dissolved in 65 parts of THF. This solution was applied by a dipping method and dried with hot air at 125 ° C. for 70 minutes to form a charge transport layer having a film thickness of 15 μm.

Next, 10 parts of the pigment having the following structural formula and a resin solution corresponding to 7 parts of the resin component of the charge transport layer used in Example 2-1 were added to the charge transport layer and mixed in a sand mill for 20 hours. It was dispersed and used as a coating liquid. Using this coating solution, a film thickness of 0.
An 8 μm charge generation layer was formed and a durability test was conducted. The results are shown in Table 2-1.

[0206]

[Outside 44]

Example 2-8 An aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm was used as a substrate, and a 5% methanol solution of the alkoxymethylated nylon used in Example 2-1 was applied to the substrate by a dipping method to give a film thickness. An undercoat layer (intermediate layer) of 1 μm was provided.

Next, ε-type Cu-PC3 which is a charge generating substance
Parts and 6 parts of the hydrazone compound used in Example 2-1 which is a charge transport material and a resin solution corresponding to 10 parts of the resin component of the charge transport layer used in Example 2-1 are added and mixed and dispersed in a sand mill for 30 hours. A coating liquid was prepared. Using this coating solution, a photosensitive layer having a film thickness of 18 μm was formed and a durability test was conducted. The results are shown in Table 2-1.

Example 2-9 A photoreceptor was prepared in the same manner as in Example 2-1 except that the amount of the epoxy resin used in Example 2-1 was changed to 10 parts, and a durability test was conducted. The results are shown in Table 2-1.

Example 2-10 Except for irradiating the high pressure mercury lamp light used in Example 2-1, for 6 seconds, a photoconductor identical to that of Example 2-1 was prepared and a durability test was conducted. The results are shown in Table 2-1.

Example 2-11 An aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm was used as a substrate, and a 5% methanol solution of the alkoxymethylated nylon of Example 2-1 was applied thereto by a dipping method to form a film having a thickness of 1 μm. An undercoat layer (intermediate layer) was provided.

Next, 10 parts (parts by weight, the same applies hereinafter) of the pigment of Structural Formula 2- (1), 8 parts of polyvinyl butyral and 50 parts of cyclohexanone were added to glass beads 10 having a diameter of 1 mm.
The mixture was mixed and dispersed for 20 hours by a sand mill device containing 0 part. 70 to 120 (appropriate) parts of methyl ethyl ketone was added to this dispersion and applied on the undercoat layer, and dried at 100 ° C. for 5 minutes to form a charge generation layer (CGL) having a thickness of 0.2 μm. Next, 130 parts of hydrazone used in Example 2-1 was mixed and dissolved in the prepared resin liquid on the charge generation layer by the following method to obtain a coating liquid. This coating solution was applied onto the charge generation layer by a dipping method and irradiated with light to form a charge generation layer (CTL) having a film thickness of 20 μm.

The resin liquid is a high melting point polybutylene terephthalate (PBT) (A) obtained by using terephthalic acid as an acid component and 1,4-tetramethylene glycol (1,4-butanediol) as a glycol component. 0.72 dl / g, melting point 224 ° C, glass transition temperature 3
100 parts of 5 ° C.) and 30 parts of the epoxy resin (B) used in Example 2-1 were dissolved in 100 ml of a mixed solution of phenol and tetrachloroethane (1: 1).

Then, 3 parts of triphenylsulfonium hexafluoroantimonate (C) as a photopolymerization initiator was added, and further 3 parts of the silicone-type comb-type graft polymer used in Examples 1-11 was added to give a resin composition. A product solution was prepared.

The coating solution thus prepared was applied onto the charge generation layer by a dipping method and irradiated with light,
A charge transport layer (CTL) having a film thickness of 20 μm was created.

As the light irradiation conditions, a 2 kw high-pressure mercury lamp (30 w / cm) was irradiated for 20 seconds at 130 ° C. from a position 20 cm away to cure.

The photoconductor drum thus manufactured was mounted on a copying machine [NP-3525 (manufactured by Canon Inc.)], and the durability of 600,000 sheets of paper was passed in an environment of a temperature of 24 ° C. and a relative humidity of 55%. I did a test. The results are shown in Table 2-2.

Example 2-12 High-melting point polycyclohexanedimethylene terephthalate [(PC obtained by using terephthalic acid as an acid component and cyclohexanedimethylol as a glycol component)
T); intrinsic viscosity 0.66 dl / g; melting point 290 ° C, glass transition temperature 80 ° C], but the same experiment as in Example 2-11 was performed. The results are shown in Table 2-2.

Example 2-13 High melting point polyethylene naphthalate (PEN) obtained by using 1,10-naphthalenedicarbobonic acid as an acid component and ethylene glycol as a glycol component (intrinsic viscosity 0.69 dl / g, melting point) 280 ° C, glass transition temperature 8
The same experiment as in Example 2-11 was performed except that (5 ° C.) was used. The results are shown in Table 2-2.

Example 2-14 High melting point polyester resin obtained by using terephthalic acid as an acid component, 63 mol% of 1,4-tetramethylene glycol as a glycol component and 27 mol% of polyethylene glycol (molecular weight 1000) (intrinsic viscosity 0.67
dl / g, melting point 190 ° C., glass transition temperature 15 ° C.) was used, and the same experiment as in Example 2-11 was performed. The results are shown in Table 2-2.

Example 2-15 An experiment similar to that of Example 2-11 was conducted, except that the epoxy resin used in Example 2-6 was used as the cured resin. The results are shown in Table 2-2.

Example 2-16 An aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm was used as a base. A 5% methanol solution of the alkoxymethylated nylon of Example 2-11 was applied thereto by a dipping method to form an undercoat layer (intermediate layer) having a film thickness of 1 μm. next,
On this intermediate layer, 10 parts of the styryl compound used in Example 2-7 and 10 parts of polymethylmethacrylate used in Example 2-7 were dissolved in 65 parts of THF. This solution is applied by a dipping method and dried with hot air at 125 ° C. for 70 minutes to give a film thickness of 1
A 5 μm charge transport layer was created.

Then, Example 2-7 was formed on the charge transport layer.
10 parts of the pigment used in Example 2 and a resin solution corresponding to 7 parts of the resin component of the charge transport layer used in Example 2-11 were added, and mixed and dispersed in a sand mill for 20 hours to obtain a coating solution. A charge generation layer having a film thickness of 0.8 μm was formed using this coating solution, and a durability test was conducted. The results are shown in Table 2-2.

Example 2-17 An aluminum cylinder having an outer diameter of 80 mm and a length of 360 mm was used as a substrate, and a 5% methanol solution of the alkoxymethylated nylon used in Example 2-11 was applied thereto by a dipping method to form a film thickness. An undercoat layer (intermediate layer) of 1 μm was provided.

Next, ε-type Cu-PC3 which is a charge generating substance
Parts and 6 parts of the hydrazone compound used in Example 2-1 which is a charge-transporting substance, and a resin solution corresponding to 10 parts of the resin component of the charge-transporting layer used in Examples 2-11 were added, and the mixture was mixed with a sand mill to obtain
A coating solution was prepared by mixing and dispersing for 0 hours. Using this coating solution, a photosensitive layer having a film thickness of 18 μm was formed and a durability test was conducted. The results are shown in Table 2-2.

Example 2-18 A photoreceptor was prepared in the same manner as in Example 2-11 except that the amount of the epoxy resin used in Example 2-11 was changed to 10 parts, and a durability test was conducted. The results are shown in Table 2-2.

Example 2-19 A photoreceptor was prepared in the same manner as in Example 2-11 except that the high pressure mercury lamp light used in Example 2-11 was irradiated for 6 seconds, and a durability test was conducted. The results are shown in Table 2-2.

Example 2-20 The same as Example 2-11 except that 100 ml of hexafluoroisopropanol was used instead of 100 ml of the phenol / terolachloroethane (1: 1) mixture used in Example 2-11. A photoconductor was prepared and a durability test was conducted in the same manner as in the same example. The results are shown in Table 2-2.

Examples 2-21 and 2-22 The photoconductor of Example 2-11 and the photoconductor of Example 2-20 were mounted on a copying machine [trade name: NP-3525 (manufactured by Canon Inc.)], An endurance test of 100,000 sheets of paper was conducted in an environment of a temperature of 30 ° C. and a relative humidity of 85%. The results are shown in Table 2-
2 shows.

[0230]

[Table 3]

[0231]

[Table 4]

[0232]

The image-holding member according to the present invention has a surface layer containing a high melting point polyester resin and a cured resin and a silicone-type comb-type graft polymer, so that the image holding member has almost no abrasion due to a durability test and has stable potential characteristics. As shown in the figure, it is possible to obtain an image holding member which is free from streak images due to scratches and has no density gradient due to partial abrasion even after durable use, and as a result, it is possible to obtain good copied images.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of an image holding member having a configuration of the present invention.

FIG. 2 is a schematic cross-sectional view of another image holding member having the configuration of the present invention.

FIG. 3 is a schematic cross-sectional view of still another image holding member having the configuration of the present invention.

FIG. 4 is a schematic cross-sectional view of still another image holding member having the configuration of the present invention.

FIG. 5 is a schematic sectional view of still another image holding member having the configuration of the present invention.

FIG. 6 is a schematic cross-sectional view of still another image holding member having the configuration of the present invention.

FIG. 7 is a schematic configuration diagram of a transfer type electrophotographic apparatus equipped with a general drum type electrophotographic photosensitive member.

FIG. 8 is a block diagram of a facsimile system using the electrophotographic apparatus as a printer.

Claims (38)

[Claims] 1. An image holding member containing a high melting point polyester resin, a cured resin and a lubricant. 2. The image holding member according to claim 1, wherein the lubricant is silicon-based. 3. A compound having a polymerizable silicone and a modified silicone, which is a condensation reaction product of a silicone selected from the following general formulas (1) and (2) and a silicone of the following general formula (3). An image holding member comprising a silicone-type comb-type graft polymer obtained by copolymerizing with. [Outer 1] (R _{1 to} R ₅ are groups selected from an alkyl group and an aryl group, and n is a positive integer.) (R ₆ and R ₇ are groups selected from an alkyl group and an aryl group, and n is a positive integer.) (R ₈ , R ₉ and R ₁₀ are groups selected from a hydrogen atom, a halogen atom, an alkyl group and an aryl group, R ₁₁ is a group selected from an alkyl group and an aryl group, and X is a group selected from a halogen atom and an alkoxy group. , N is an integer of 1 to 3.) 4. The image holding member according to claim 1, wherein the high melting point polyester resin has a melting point of 160 ° C. or higher. 5. The high melting point polyester resin 10 as the cured resin.
The image holding member according to claim 1, wherein the image holding member is contained in an amount of 3 to 50 parts by weight with respect to 0 parts by weight. 6. The image holding member according to claim 1, wherein the high melting point polyester resin is a polyethylene terephthalate resin. 7. The image holding member according to claim 1, wherein the high melting point polyester resin is a polybutylene terephthalate resin. 8. The image holding member according to claim 1, wherein the high melting point polyester resin is a polycyclohexanedimethylene terephthalate resin. 9. The image holding member according to claim 1, wherein the high melting point polyester resin is a polyethylene naphthalate resin. 10. The image holding member according to claim 1, wherein the curable resin is a photoion-cured epoxy resin. 11. The image holding member according to claim 2, wherein the curable resin is a photoion-cured epoxy resin. 12. The image-holding member according to claim 1, wherein the content of the graft polymer is 0.01 to 10% by weight of the surface layer of the image-holding member. 13. The image holding member according to claim 1, wherein the surface layer is a protective layer. 14. The image holding member according to claim 11, wherein the protective layer has a thickness of 3.0 μm or less. 15. The image holding member according to claim 11, wherein the image holding member has at least the protective layer and a photoconductive layer. 16. The image holding member according to claim 13, further comprising an organic photoconductive layer as the photosensitive layer. 17. The image holding member according to claim 14, wherein the organic photoconductive layer is a laminate of a charge generation layer and a charge transport layer. 18. The image holding member according to claim 2, wherein the surface layer is a protective layer and has an organic photoconductive layer. 19. The image holding member according to claim 1, wherein the surface layer is an organic photoconductive layer. 20. The image holding member according to claim 17, wherein the organic photoconductive layer is a charge transport layer. 21. The image holding member according to claim 17, wherein the organic photoconductive layer is a charge generation layer. 22. The image holding member according to claim 2, wherein the surface layer is an organic photoconductive layer. 23. A method for producing an image holding member having a surface layer, wherein the surface layer comprises a high melting point polyester resin and a photocurable resin in a solvent, and a silicone selected from the following general formulas (1) and (2). A silicone-type comb-type graft polymer obtained by copolymerizing a modified silicone, which is a condensation reaction product of silicone of the following general formula (3), with a compound having a polymerizable functional group. [Outside 4] (R _{1 to} R ₅ are groups selected from an alkyl group and an aryl group, and n is a positive integer.) (R ₆ and R ₇ are groups selected from an alkyl group and an aryl group, and n is a positive integer.) (R ₈ , R ₉ and R ₁₀ are groups selected from a hydrogen atom, a halogen atom, an alkyl group and an aryl group, R ₁₁ is a group selected from an alkyl group and an aryl group, and X is a group selected from a halogen atom and an alkoxy group. , N is an integer of 1 to 3) is applied to form a uniform coating solution and then photocured to form the image holding member. 24. The method for producing an image holding member according to claim 21, wherein the high melting point polyester resin has a melting point of 160 ° C. or higher. 25. The method of manufacturing an image holding member according to claim 21, wherein the photocurable resin is an epoxy resin. 26. The method for producing an image holding member according to claim 21, wherein the content of the graft polymer is 0.01 to 10% by weight of the surface layer of the image holding member. 27. The method for producing an image holding member according to claim 21, wherein a photopolymerization initiator that liberates a Lewis acid upon irradiation with light is present in the coating liquid. 28. The method of manufacturing an image holding member according to claim 21, wherein the solvent used in the coating liquid contains a fluorine-containing alcohol. 29. A high melting point polyester resin and a photocurable resin, and a silicone selected from the following general formulas (1) and (2) and at least one of the following general formula (3): A silicone-type comb-type graft polymer obtained by copolymerizing a modified silicone, which is a condensation reaction product with silicone, with a compound having a polymerizable functional group. [Outside 7] (R _{1 to} R ₅ are groups selected from alkyl groups and aryl groups, and n is a positive integer.) [Ex. 8] (R ₆ and R ₇ are groups selected from alkyl groups and aryl groups, and n is a positive integer.) (R ₈ , R ₉ and R ₁₀ are groups selected from a hydrogen atom, a halogen atom, an alkyl group and an aryl group, R ₁₁ is a group selected from an alkyl group and an aryl group, and X is a group selected from a halogen atom and an alkoxy group. , N is an integer of 1 to 3) together with an image holding member having a surface layer to form a unit, which is a single unit that is detachably attached to the apparatus main body. 30. The apparatus unit according to claim 27, wherein the high melting point polyester resin has a melting point of 160 ° C. or higher. 31. The device unit according to claim 28, wherein the surface layer is a layer selected from a protective layer and an organic photoconductive layer. 32. The apparatus unit according to claim 28, wherein the content of the graft polymer is 0.01 to 10% by weight of the surface layer of the image holding member. 33. A high-melting-point polyester resin, a photocurable resin, and a modified silicone which is a condensation reaction product of a silicone selected from the following general formulas (1) and (2) and a silicone of the following general formula (3): A silicone-type comb-type graft polymer obtained by copolymerizing with a compound having a functional group. [Outside 10] (R _{1 to} R ₅ are groups selected from an alkyl group and an aryl group, and n is a positive integer.) [Ex. 11] (R ₆ and R ₇ are groups selected from an alkyl group and an aryl group, and n is a positive integer.) (R ₈ , R ₉ and R ₁₀ are groups selected from a hydrogen atom, a halogen atom, an alkyl group and an aryl group, R ₁₁ is a group selected from an alkyl group and an aryl group, and X is a group selected from a halogen atom and an alkoxy group. , N is an integer of 1 to 3), a latent image forming member, a latent image forming means, a means for developing the formed latent image, and a means for transferring the developed image to a transfer material. Electrophotographic device. 34. The electrophotographic apparatus according to claim 31, wherein the high melting point polyester resin has a melting point of 160 ° C. or higher. 35. The electrophotographic apparatus according to claim 31, wherein the content of the graft polymer is 0.01 to 10% by weight of the surface layer of the image holding member. 36. A high-melting-point polyester resin, a photocurable resin, and a modified silicone which is a condensation reaction product of a silicone selected from the following general formulas (1) and (2) and a silicone of the following general formula (3): A silicone-type comb-type graft polymer obtained by copolymerizing with a compound having a functional group. [Outside 13] (R _{1 to} R ₅ are groups selected from an alkyl group and an aryl group, and n is a positive integer.) (R ₆ and R ₇ are groups selected from alkyl groups and aryl groups, and n is a positive integer.) (R ₈ , R ₉ and R ₁₀ are groups selected from a hydrogen atom, a halogen atom, an alkyl group and an aryl group, R ₁₁ is a group selected from an alkyl group and an aryl group, and X is a group selected from a halogen atom and an alkoxy group. , N is an integer of 1 to 3), an electrophotographic apparatus provided with an image holding member having a surface layer having a surface layer having an integer of 1 to 3, latent image forming means, means for developing the formed latent image and means for transferring the developed image to a transfer material. And a facsimile having a receiving means for receiving image information from a remote terminal. 37. The facsimile machine according to claim 34, wherein the high melting point polyester resin has a melting point of 160 ° C. or higher. 38. The facsimile machine according to claim 34, wherein the content of the graft polymer is 0.01 to 10% by weight of the surface layer of the image holding member.