JPH1063025A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophotographic photoreceptor having improved sensitivity by producing an electrophotographic photoreceptor with an electrode layer and a photoconductor layer and forming a thin self-organized polymer film on the photoreceptor layer side of the electrode layer. SOLUTION: The electrophotographic photoreceptor with an electrode layer and a photoconductor layer is produced and a thin self-organized polymer film is formed on the photoreceptor layer side of the electrode layer. The polymer film is formed, e.g. using a polymer having surface active groups such as alkoxysilyl, halosilyl, carboxyl, hydroxamic acid, phosphonic acid, sulfide, mercapto or disulfide groups. The self-organized polymer consists of a principal chain 2, optionally substd. alkylene groups 3 and surface active groups X which turn into residues Y in the groups X after bonding to the surface 4 of the electrode layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly, to an electrophotographic photoreceptor having improved sensitivity obtained by forming a photosensitive layer on an electrode layer coated with a self-assembled polymer thin film. Body, for example, photoreceptor for copy machine,
The present invention relates to a photoreceptor for a laser printer and the like.

[0002]

2. Description of the Related Art Conventionally, various inorganic and organic photoconductive materials have been used as photoconductive materials in electrophotographic photoreceptors (Toray Research Center, new development of electrophotographic photosensitive materials, 1994)). When an organic photoconductive material is used, in order to improve the sensitivity and durability of the photoconductor, a function-separated electrophotographic photoconductor in which a charge generation layer and a charge transport layer are laminated on an electrode layer is mainly used. I have. In addition, a photoconductor in which a single-layer photosensitive layer having both functions of charge generation and charge transport is formed on an electrode layer has been developed.

[0003] Such an electrophotographic photoreceptor basically comprises an electrode layer and a photosensitive layer. The electrode layer is formed of an aluminum tube in view of workability, surface properties, price, weight, and the like. Commonly used.

However, various defects such as non-uniform electrical characteristics, defects in the appearance of the coating film, or black spots, white spots, fog, etc. on printed images have been caused by defects on the aluminum surface (Aizawa). Masao, Journal of the Society of Electrophotography, Vol. 28, p. 186-195 (1989)). Various devices have been devised to suppress these defects. That is, the electrical characteristics of the photoconductor are improved, the adhesion between the electrode layer and the photosensitive layer is improved, the coating property of the photosensitive layer is improved, the electrode layer is covered with defects, the charge injection from the electrode layer is prevented, or interference fringes are generated. For the purpose of prevention and the like, an undercoat layer has been provided between the electrode layer and the photosensitive layer.

[0005] These devices include polymer coatings (JP-A-5-61232), coatings in which carbon is dispersed in a polymer (JP-A-51-65942), and tin or aluminum oxide as a polymer. Dispersed coating film (JP-A-58-55856) and coating film in which a silane coupling agent is dispersed in nylon (JP-A-5-107)
792), a coating film in which metal oxide particles treated with a silane coupling agent are dispersed in a polymer (Japanese Patent Laid-Open No.
JP-A-229872), a photoreceptor in which a zinc sulfide thin film is formed on a surface of an electrode coated with a silane coupling agent (JP-A-56-72448), and a silane coupling agent solution is applied on the electrode layer. A method of providing a charge injection blocking layer (Japanese Patent Application Laid-Open No. 61-109064), a method of preventing generation of an abnormal image by silylation of an electrode layer (Japanese Patent Application Laid-Open No. 62-287259), and treatment with a silane coupling agent. Is applied to an anodized aluminum substrate to form a hydrophilic layer, and a photosensitive layer is provided thereon (Japanese Patent Application Laid-Open No.
-50855), a method of treating an electrode layer with a chlorofluorocarbon solution of a silane coupling agent (JP-A-1-114856).
JP-A-4-247), a method of improving the wettability of an electrode layer by applying a silane coupling agent to the electrode layer.
461) and the like.

[0006]

However, in each of these disclosed examples, a coating film containing a silane coupling agent or the like is formed between the electrode layer and the photoreceptor layer, and the film thickness is 50 nm to 15 μm. Even if it was thick and did not lower the sensitivity, there was no effect of improving the sensitivity. In addition, some of them are intended only to remove the defects at the expense of sensitivity due to their thickness, and they are still unsatisfactory for constructing a high-sensitivity photoreceptor.

An object of the present invention is to provide an electrophotographic photosensitive member having improved sensitivity.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a self-assembled polymer thin film, preferably, a chemical film is formed directly on the photoconductor layer side of the electrode layer. Self-assembled polymer thin film bonded, for example, an alkoxysilyl group, a halosilyl group, a carboxyl group, a thin film composed of a polymer for forming a thin film having a functional group such as a mercapto group and organic alkoxysilanes, organic halosilanes, carboxylic acids, An electrophotographic photoreceptor in which a thin film formed by chemically bonding a polymer is formed on a self-assembled film made of a compound for forming a self-assembled film such as thiols is formed with the self-assembled polymer thin film. As a result, the above problems were solved, and the present invention was found to be an electrophotographic photosensitive member having improved sensitivity, and the present invention was completed.

That is, the present invention provides (1) an electrophotographic photosensitive member having an electrode layer and a photosensitive layer, wherein a self-assembled polymer thin film is formed on the photosensitive layer side of the electrode layer. (2) The electrophotographic photoreceptor according to the above (1), wherein the self-assembled polymer thin film is a film directly chemically bonded on the electrode layer, and (3) the self-assembled polymer thin film is (2) The electrophotographic photosensitive material according to the above (2), which is a thin film comprising a polymer for forming a self-assembled polymer thin film having at least one kind of surface active group selected from the group consisting of an alkoxysilyl group, a halosilyl group, a carboxyl group and a mercapto group. Body, (4) self-assembled polymer thin film
An alkoxysilyl group, a self-assembled polymer thin film made of a polymer for forming a self-assembled polymer thin film containing one or more surface active groups selected from the group consisting of a halosilyl group and a carboxyl group, and tin, indium, The electrophotographic photoreceptor according to the above (2), which is a thin film chemically bonded to an oxide of an electrode layer having an oxide of aluminum or copper, (5) a self-assembled polymer thin film,
The electrophotographic photoreceptor according to the above (2), (3) or (4), which is a film made of at least one polymer for forming a self-assembled polymer thin film selected from polymers containing a (meth) acrylic acid derivative unit. ,

(6) The self-assembled polymer thin film contacts the electrode layer with a solution of the polymer for forming a self-assembled polymer thin film to cause the polymer for forming the self-assembled polymer thin film to react with the electrode layer. The above (1) to (5), which are obtained by separating from the solution and washing with a solution in which the polymer for forming a self-assembled polymer thin film is dissolved to remove the unreacted polymer for forming a self-assembled polymer thin film. (7) The electrophotographic photoreceptor according to any one of (7), wherein the self-assembled polymer thin film forms an electrode layer with an alkoxysilyl group, and / or
Alternatively, the polymer for forming a self-assembled polymer thin film containing a halosilyl group is contacted with a solution of the polymer for forming a self-assembled polymer thin film, and the polymer for forming a self-assembled polymer thin film is reacted with the electrode layer. Any one of the above (1) to (5), which is obtained by washing with a solution in which the forming polymer is dissolved to remove the unreacted polymer for forming a self-assembled polymer thin film, followed by heat treatment. (8) The solution of the polymer for forming a self-assembled polymer thin film is composed of an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, an alcohol, an ether compound, a ketone compound and water. 1 selected from the group
The polymer for forming a self-assembled polymer thin film is added to at least one kind of solvent, and the concentration of surface active groups in the polymer for forming a self-assembled polymer thin film is 0.001 mmol / liter to 1 mo.
The electrophotographic photoreceptor according to the above (6) or (7), which is a solution dissolved in a range of 1 / liter.

(9) The self-assembled polymer thin film is composed of at least one compound for forming a self-assembled film selected from the group consisting of organic alkoxysilanes, organic halosilanes, carboxylic acids and thiols. The electrophotographic photoreceptor according to the above (2), which is a thin film obtained by chemically bonding a polymer, and (10) the self-assembled polymer thin film forms a self-assembled film having a functional group at a terminal on the electrode layer. The electrophotographic photoreceptor according to the above (9), which is a thin film formed by reacting a polymer having a functional group that reacts with the functional group, and (11) a self-assembled film formed of an organic alkoxysilane or an organic halosilane Self-assembled film composed of at least one compound for forming a self-assembled film selected from the group consisting of carboxylic acids and carboxylic acids, and has tin, indium, and aluminum on the surface. Or (9) is a self-assembled film that is oxide chemically bonded electrode layer having a copper oxide or (10) The electrophotographic photosensitive member according,

(12) The self-assembled film is at least one compound for forming a self-assembled film selected from the group consisting of organic alkoxysilanes, organic halosilanes and carboxylic acids, wherein the compound has 1 to 30 carbon atoms. A self-assembled film having an amino group at the terminal, comprising a self-assembled film having an amino group at the terminal, and a self-assembled film having an amino group at the terminal and a carboxyl group. (10) or (1) which is a thin film obtained by reacting a polymer having
(1) The electrophotographic photoreceptor according to (1), wherein the self-assembled polymer thin film is reacted with a polymer having maleic acid units and a self-assembled film having an amino group at a terminal to form an ammonium salt, and then heated. (14) The electrophotographic photoreceptor according to the above (12), which is a thin film obtained by forming an imide bond by treatment, wherein the self-assembled polymer thin film is an electrode having a self-assembled film having a functional group at a terminal After the layer is brought into contact with a solution of a polymer having a functional group that reacts with the functional group and reacted, the electrode layer is separated from the solution and washed with a solvent in which the polymer dissolves to remove unreacted polymer. The electrophotographic photoreceptor according to any one of the above (9) to (13), which is a thin film obtained by: (15) a terminal of the electrode layer on which a self-assembled film having a functional group at a terminal is formed; Has a functional group that reacts with the functional group A solution of the polymer is prepared by adding the polymer to one or more solvents selected from the group consisting of an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, an alcohol, an ether compound, a ketone compound and water. Concentration is 0.001 mmol / l to 1 mol
/ L is a solution dissolved within the range of (1)
4) the electrophotographic photoreceptor according to the above,

(16) The self-assembled film reacts the self-assembled film forming compound with the electrode layer by contacting the electrode layer with a solution of the self-assembled film forming compound, and then removes the electrode layer from the solution. The above-mentioned (9) to (15), which is a self-assembled film obtained by separating and washing with a solution in which the compound for forming a self-assembled film is dissolved to remove the unreacted compound for forming a self-assembled film. The electrophotographic photoreceptor according to any one of (17), wherein the self-assembled film uses an organic alkoxysilane and / or an organic halosilane as a compound for forming a self-assembled film,
And after the electrode layer is brought into contact with the solution of the compound for forming a self-assembled film to react the compound for forming a self-assembled film with the electrode layer, the electrode layer is separated from the solution, and the compound for forming a self-assembled film is formed. Any of the above (9) to (15), which is a self-assembled film obtained by washing with a dissolving solution to remove an unreacted compound for forming a self-assembled film, and then performing a heat treatment. (18) The solution of the compound for forming a self-assembled film is self-assembled in one or more solvents selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ether compounds and water. (16) above, which is a solution in which the compound for forming an organized film is dissolved in a concentration range of 0.001 mmol / L to 5 mol / L.
Or the electrophotographic photosensitive member according to (17),

(19) The electrophotographic photosensitive member according to any one of the above (1) to (18), wherein the thickness of the self-assembled polymer thin film is in the range of 1 to 10 nm, (20) the photosensitive member layer Wherein the phthalocyanine pigment is contained as a photosensitive substance, the electrophotographic photoreceptor according to any one of the above (1) to (19), and (21) the phthalocyanine pigment is oxotitanium phthalocyanine. 20) The electrophotographic photosensitive member according to the above.

[0015]

Next, the present invention will be described in detail.
In the electrophotographic photoreceptor of the present invention, the electrode layer may be any good conductor of electricity, for example, aluminum,
Metals such as copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, silver, platinum,
Alternatively, vapor deposition or sputtering of a metal on an electrode layer composed of an alloy containing one or more of these metals, a metal drum, a metal belt, or the like, a polymer film, a polymer tube, or the like, and application and heat treatment of a metal colloid. The electrode layer made of a metal containing at least one of the above-mentioned metals formed on the surface of a drum, a belt, etc., by a method such as coating, vapor deposition, pattering, etc. An electrode layer containing tin oxide (NESA), indium tin oxide (ITO), zinc oxide, titanium oxide, or the like formed on the surface may be used. Among these electrode layers, from the viewpoint of price, aluminum, tin oxide (NESA), or indium tin oxide (ITO) formed on the surface of an aluminum drum, a drum, a belt, or the like by a method such as evaporation, ion plating, or sputtering. Is preferred.

Further, tin oxide (NES) is used as an electrode layer.
A) When an electrode layer made of indium tin oxide (ITO) is used, vapor deposition, ion plating,
When an electrode layer formed by a method such as sputtering is subjected to a hydrophilic treatment such as an alkali solution treatment, an ozone treatment, irradiation of ultraviolet light in the presence of oxygen, irradiation of vacuum ultraviolet light, and hydrophilic treatment by plasma, It is effective and preferable for completely forming an organized polymer thin film. In the case of alkali solution treatment, for example, sodium hydroxide, lithium hydroxide, aqueous solution such as potassium hydroxide, alcohol solution,
What is necessary is just to immerse in a water / alcohol mixed solution, etc.
The alkali is usually 0.001 mmol / liter to 5 m
Although it is used at a concentration of ol / liter, a concentration of 0.01 mmol / liter to 1 mol / liter can be recommended. Although there is no particular limitation on the treatment time, usually, a range of 0.5 to 5 hours at room temperature can be recommended. Irradiation with ultraviolet light or vacuum ultraviolet light in the presence of oxygen can be performed by irradiating light having a wavelength of 150 nm to 380 nm in an oxygen-containing gas for a short time, for example, for about 1 minute to 1 hour. Hydrophilic treatment by plasma is achieved by performing treatment in the presence of oxygen using a dedicated plasma device or sputtering device.

As the electrophotographic photoreceptor of the present invention, a function-separated type photoreceptor layer in which a charge generation layer and a charge transport layer are laminated is mainly used, and a single layer having both functions of charge generation and charge transport is used. May be used.

The charge-generating material used in the photoreceptor layer may be an organic material or an inorganic material, but is preferably an organic photoconductive material, for example, an azo pigment, a quinone pigment, a perylene pigment, an indigo pigment. Pigments, thioindigo pigments, bisbenzimidazole pigments, phthalocyanine pigments, naphthalocyanine pigments, quinacridone pigments, quinoline pigments, anthraquinone pigments, oxazine pigments, triphenylmethane pigments, azurenium dyes, squarylium dyes And pyrylium dyes, cyanine dyes, pyrrolopyrrole pigments, and fullerene compounds such as C60 and C70. These are not limited to the exemplified compounds, and may be used as a mixture. Among these, phthalocyanine pigments are preferred, and oxotitanium phthalocyanine is particularly preferred.

These charge generation materials are applied, for example, by dispersing them in a binder resin via a self-assembled polymer thin film on an electrode, or by forming them by a method such as vacuum evaporation, sputtering, or CVD. Used.

The charge transporting material used in the function-separated type photoreceptor layer is generally classified into a substance for transporting electrons and a substance for transporting holes. it can. These materials are not particularly limited, and known material systems can be used. For example, new development of photosensitive materials for electrophotography (Toray Research Center, (199
The materials and the like described in 4)) can be used.
For example, chloranil compounds, tetracyanoquinodimethane compounds, trinitrofluorenone compounds, diphenoquinone compounds, condensed polycyclic aromatic compounds, hydrazone compounds, triphenylamine compounds, polyvinylcarbazole compounds, There are polysilane compounds and the like, and these may be used as a mixture of two or more. These materials are dispersed and applied in a binder resin, or are formed into a film by a method such as vacuum evaporation and used for a photosensitive layer. .

In the case of a single photoreceptor layer, the charge generating material is used by being dispersed and applied in a binder resin or formed into a film by a technique such as vacuum deposition. In this case, two or more kinds of charge generating materials may be used as a mixture, and further, a charge generation layer material and a charge transport layer material may be used as a mixture.

The binder resin used in the photoreceptor layer is not particularly limited, and for example, materials described in New Development of Electrophotographic Photosensitive Materials (Toray Research Center, (1994)) can be used. . For example, a polyvinyl resin, a polycarbonate resin, a polyester resin, a polyacrylic resin, a polymethacrylic resin, a styrene-butadiene copolymer, a vinylidene chloride-acrylonitrile copolymer, a vinyl chloride-vinyl acetate-maleic anhydride Examples thereof include an acid copolymer, a silicone resin, a phenol resin, an alkyd resin, polyvinyl butyral, polysulfone, and polyurethane, but are not limited thereto, and two or more kinds may be used in combination.

In addition to these binder resins, additives such as a plasticizer, a sensitizer, and a surface modifier may be added.

When a single photoreceptor layer is formed by coating, a coating material in which the above-mentioned charge generating material is dispersed or dissolved in a binder resin solution is usually used. In this case, the solvent is not particularly limited as long as the binder resin is dissolved. Further, a solvent that dissolves the charge generating material may be selected as needed.

Similarly, when the function-separated type photoreceptor layer is formed by coating, a coating material in which the above-mentioned charge generating material or charge transporting material is dispersed or dissolved in a binder resin solution is used. In this case, similarly, the solvent is not particularly limited, and an appropriate solvent that dissolves the binder resin for the charge generation material or the binder resin for the charge transport material can be used. Generally, the charge transport layer is formed on the charge generation layer. Therefore, when preparing the charge transport coating solution, it is preferable to use a solvent that does not dissolve the charge generation layer. Specific examples of solvents include alcohols such as methanol, ethanol, propanol and pentanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, dichloromethane, chloroform, carbon tetrachloride, 1,1,2-
Aliphatic halogenated hydrocarbons such as trichloroethane, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, ethers such as diglyme, ethyl acetate, esters such as propyl acetate, benzene, toluene, xylene, Chlorobenzene, 1,2-
It can be appropriately selected from aromatic hydrocarbons such as dichlorobenzene, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone. These can also be used as a mixture.

As a method of dispersing the charge generating material in the binder resin, a particularly commonly used method, for example, Masao Aizawa, Journal of the Electrographic Society of Japan, Vol. 28, p. 186-19
5 (1989) can be used. For example, a method of dispersing using a ball mill, a paint conditioner, a sand mill, a kneader, an attritor, a three-roll mill, a jet mill, or the like can be used.

As the coating method of the photoreceptor layer, a method generally used, for example, a coating method described in Masao Aizawa, Journal of the Institute of Electrophotography, Vol. 28, p. 186-195 (1989), etc. Can be used. To illustrate,
Coating methods such as dip coating, spray coating, ring coating, and blade coating are exemplified.

A feature of the electrophotographic photoreceptor of the present invention is that a self-assembled polymer thin film is formed on the photoreceptor layer side of the electrode layer. Compounds, for example, organic alkoxysilanes, organic halosilanes, carboxylic acids, hydroxamic acids, phosphonic acids, phosphate esters, thiols,
Self-assembled films composed of sulfides (including disulfides; the same applies hereinafter) and the like are already known.

When a substrate such as a metal is immersed in a solution of the above-mentioned specific compound (hereinafter, referred to as a "compound for forming a self-assembled film"), the compound for forming a self-assembled film is first adsorbed on the substrate surface, Then, special adsorption (chemisorption) occurs on the surface with chemical bonding or energy comparable to chemical bonding,
Finally, a dense monomolecular film (self-assembled film) is formed on the substrate surface while assembling itself (L. Wetzer,
R. Isokovich, J .; Sagiv,
Thin Solid Films, Vol. 99,
p235 (1983); P. Folker
s, C.I. B. Gorman, P.M. E. FIG. Lai
binis, S.P. Buchholz, G .; M.
Whitesides, R.A. G. FIG. Nuzzo,
Langmuir, Vol. 11, p813 (199
5)).

Here, for example, when a substrate having a metal oxide on the surface is used, as shown in the conceptual diagram of FIG.
Surfaces of alkoxysilyl groups, halosilyl groups, carboxyl groups, hydroxamic acid groups, phosphonic acid groups, phosphoric acid ester groups, etc. of organic alkoxysilanes, organic halosilanes, carboxylic acids, hydroxamic acids, phosphonic acids, phosphate esters, etc. When the active group is chemically bonded to the metal oxide on the surface and a substrate having no metal oxide on the surface is used, thiols,
The surface active groups such as mercapto group, sulfide group, disulfide group, etc. of the sulfides perform adsorption (chemisorption) comparable to the chemical bond with the surface to form a dense self-assembled film organized on the substrate surface. (IM Tidsw
ell et al. Chem. Phys. , Ninth
5, p2854 (1991), Toshiba Silicone,
Products Information, S-0
002). 1 and 2, 1 is an alkyl group which may be substituted, and M is a metal atom.

In the present invention, a self-assembled polymer thin film is a polymer thin film formed on a surface of an electrode layer in a self-organizing manner. Instead of a polymer having a surface active group similar to the compound for forming a self-assembled film (hereinafter, referred to as
A polymer thin film formed on a surface of an electrode layer in a self-organized manner, in the same manner as in the above-mentioned method for forming a self-assembled film, except that a "polymer for forming a self-assembled polymer thin film" A polymer thin film obtained by chemically bonding a polymer to the self-assembled film formed on the surface of the electrode layer in the same manner as the self-assembled film forming method is exemplified. Further, as the polymer thin film of the above 2), for example, a) a polymer thin film formed by forming a self-assembled film having a functional group at a terminal and then reacting a polymer having a functional group which reacts with the functional group; b) A polymer thin film formed by forming a self-assembled film having a polymerizable group at a terminal and then polymerizing the film.

The above-mentioned self-assembled polymer thin film of the present invention will be described in more detail. First, as the polymer thin film of the above 1), for example, an alkoxysilyl group, a halosilyl group, Formed on the electrode layer using a polymer having a surface active group such as a carboxyl group, a hydroxamic acid group, a phosphonic acid group, a phosphate group, a mercapto group, a sulfide group, and a disulfide group, as shown in the conceptual diagram of FIG. And self-assembled polymer thin films. In FIG. 3, 2 is a polymer main chain, 3 is an alkylene group which may be substituted, 4 is an electrode layer surface, X is a surface active group, and Y is a residue in X after bonding to the electrode layer surface. is there.

Next, as the polymer thin film of 2), a) As shown in the conceptual diagram of FIG. 4, a compound for forming a self-assembled film having a functional group at a terminal is used as a compound for forming a self-assembled film. A self-assembled polymer thin film formed by obtaining a self-assembled film having a functional group at the terminal, for example, an amino group, on an electrode layer and then reacting with a functional group that reacts with the self-assembled film, for example, a polymer having a carboxyl group. And b) FIG.
As shown in the conceptual diagram, a self-assembled film having a polymerizable group at the end is obtained on the electrode layer using a compound for forming a self-assembled film having a polymerizable group at the end as a compound for forming a self-assembled film. Then, a self-assembled polymer thin film formed by polymerizing the polymerizable group at the terminal of the obtained self-assembled film is exemplified. 4 and 5, 2 is a polymer main chain,
3 is an alkylene group which may be substituted, 4 is an electrode layer surface, X is a surface active group, Y is a residue in X after bonding to the electrode layer surface, A is a functional group, and A 'reacts with A Functional group, B is A
And a bonding unit formed by the reaction of A ′, C is a polymerizable group,
Is a polymer main chain formed by polymerization of C.

In the production method of the above 1), among the polymers for forming a self-assembled polymer thin film, an alkoxysilyl group, a halosilyl group, a carboxyl group,
A polymer having a hydroxamic acid group, a phosphonic acid group, a phosphate group, or the like, reacts with an electrode layer having a metal oxide on the surface to form a self-assembled polymer thin film, and has a mercapto group, a sulfide group, The polymer having a disulfide group or the like reacts with the electrode layer having no metal oxide to form a self-assembled polymer thin film on the surface of the electrode layer. In the methods 2) a) and b), among the compounds for forming a self-assembled film, organic alkoxysilanes, organic halosilanes, carboxylic acids, hydroxamic acids, phosphonic acids, phosphoric esters, etc. Reacts with an electrode layer having a metal oxide on the surface to form a self-assembled film, and thiols and sulfides react with an electrode layer having no metal oxide to form a self-assembled film on the electrode layer surface. Form a film.

As the electrode layer having a metal oxide on the surface, tin oxide (NES) originally composed of an oxide conductor is used.
A), in addition to electrode layers such as indium tin oxide (ITO), aluminum, copper, chromium, titanium, iron,
An electrode layer containing a natural oxide film generated on a metal such as nickel is suitable. It is known that a natural oxide film of these metals is formed on each surface of these metals [W. A. Nevin, G .; A. Ch
amberlain, IEEE Trans. Elec
tron Devices, Vol. 40, p. 75 (199
3), L. Wetzer, R.A. Isokovichi,
J. Sagiv, Thin Solid Films, Vol. 99, p235 (1983) and P. Folk
ers, C.I. B. Gorman, P.M. E. FIG. Laibin
is, S. Buchholz, G .; M. Whitesi
des, R.A. G. FIG. Nuzzo, Langmuir, 1st
1, p813 (1995) etc.]. Furthermore, these natural oxide films may be electrochemically subjected to anodic oxidation or the like, so that the metal oxide layer can be used thicker.

As the electrode layer having no metal oxide on the surface, an electrode layer having no oxide layer on the surface of gold, platinum, silver, copper or the like is preferable.

The combination of the polymer for forming a self-assembled polymer thin film or the compound for forming a self-assembled film with an electrode layer may be at least one selected from the group consisting of an alkoxysilyl group, a halosilyl group and a carboxyl group. A polymer for forming a self-assembled polymer thin film having a surface active group, or at least one compound for forming a self-assembled film selected from the group consisting of organic alkoxysilanes, organic halosilanes and carboxylic acids, and tin or indium on the surface. And an electrode layer having an oxide of aluminum or copper is preferred.

The main chain structure of the polymer for forming a self-assembled polymer thin film used in the production method 1) is not particularly limited, and may be a homopolymer or a copolymer.
Examples of the repeating unit include an ethylene structure, an oxyethylene structure, an iminoethylene structure, a peptide structure, and an inorganic polymer structure. However, the repeating unit is not limited to these examples. In particular, polymers containing (meth) acrylic acid derivative units are recommended.

The polymer for forming a self-assembled polymer thin film may have an alkoxysilyl group, halosilyl group, carboxyl group, hydroxamic acid group, phosphonic acid group, phosphate ester group, mercapto group, sulfide group, disulfide group or the like. An active group is usually provided at the terminal of the side chain. Among these surface active groups, an alkoxysilyl group, a halosilyl group, and a carboxyl group are preferable, and an alkoxysilyl group and a halosilyl group are particularly preferable.

Further, the structure of the spacer connecting these surface-active groups to the main chain of the polymer for forming a self-assembled polymer thin film is not particularly limited, but an alkylene group having 1 to 30 carbon atoms is preferable. Although the degree of polymerization of the polymer for forming a self-assembled polymer thin film is not particularly limited, it is 5 to 10,000.
Is particularly preferable, and a range of 20 to 5000 can be particularly recommended.

The polymer for forming a self-assembled polymer thin film is, for example, a compound for forming a self-assembled film having a polymerizable group, that is, an organic alkoxysilane, an organic halosilane, a carboxylic acid, a hydroxamic acid, a phosphonic acid,
Phosphate esters, thiols, sulfides, and the like having a polymerizable group can be obtained by homopolymerizing or copolymerizing with another polymerizable compound. Examples thereof include polyvinyl derivatives with vinyl groups such as (meth) acrylate and styryl groups, polyoxyethylene with epoxy groups, polyiminoethylene derivatives with oxazolyl groups, polypeptide derivatives with amino acid units, and inorganic compounds with boronic acid units. Examples thereof include polymers, but are not limited to these examples. The compound for forming a self-assembled film having a polymerizable group used herein is a commercially available compound (for example, methacrylic acid-3 described in a silicon compound reagent catalog of Shin-Etsu Chemical Co., Ltd.).
-Trimethoxysilylpropyl, etc.)
In addition, they can be appropriately synthesized and used (for example, methacrylic acid-11-triethoxysilylundecyl).

The terminal used in the production method of 2) a))
As a compound for forming a self-assembled film having a functional group,
Functional groups that can react with polymers having more than one kind of functional groups
What is necessary is just to have, for example, the following general formula (1)-
(6), AR₁SiR_TwoR_ThreeX ... (1) AR₁CO_TwoH (2) AR₁CONOHH (3) AR₁PO_ThreeH_Two ... (4) AR₁OPO_ThreeH_Two... (5)  AR₁SH (6) (where A represents a reaction with a polymer having one or more functional groups)
Possible functional groups, R₁Is an optionally substituted alkylene
Group or aromatic group, R_Two, R_ThreeAre the same or different
Good, lower alkyl, alkoxy or halogen source
And X represents an alkoxy group or a halogen atom. )
And the like, among which, among these, organic
Alkoxysilanes, organic halosilanes, carboxylic acids
Are preferable, and in particular, organic alkoxysilanes,
Orchids are preferred.

More specifically, the compounds having a functional group for forming a self-assembled film are described below.
Organic halosilanes, carboxylic acids, hydroxamic acids,
Phosphonic acids, phosphoric esters, thiols, sulfides, etc. having an amino group, a mercapto group, a cyano group, a carboxyl group or a halogen atom via an alkylene group having 1 to 30 carbon atoms, a carbon atom Number 1
Those having an aromatic group which may be substituted with an amino group, a mercapto group, a cyano group, a carboxyl group, a halogen atom, or the like via an alkylene group of from 30 to 30; and organic alkoxysilanes and organic halosilanes. And carboxylic acids having an amino group via an alkylene group having 1 to 30 carbon atoms are preferred. These may be commercially available compounds or may be appropriately synthesized. Further, the alkylene group having 1 to 30 carbon atoms may be substituted.

As the organic alkoxysilanes and the organic halosilanes, commercially available compounds, for example, compounds described in a silicon compound reagent catalog of Shin-Etsu Chemical Co., Ltd. or an organic silicon compound catalog of Toshiba Silicone Co., Ltd. can be used. Alternatively, they can be used after being appropriately synthesized.

Among these, an organic silane trialkoxide or an organic silane trihalide having a functional group at a terminal is preferable. Specific examples include chloromethyltrimethoxysilane, 2-cyanoethyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-cyanopropyltrichlorosilane, mercaptomethyltrimethoxysilane, 2-cyanoethyltrimethoxysilane, and 3-chloropropyltrimethoxysilane. Silane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane , Chloromethyltriethoxysilane, 4-
Chlorophenyltrimethoxysilane, 3-morpholinopropyltrimethoxysilane, 3-piperidinopropyltrimethoxysilane, 3-trimethoxysilylpropyl methacrylate, 11-triethoxysilylundecyl methacrylate, 6-cyanohexyltri Ethoxysilane, 11-cyanoundecyltriethoxysilane, 3-
(N, N-dipropylamino) propyltriethoxysilane, 3- (N, N-dihexylamino) propyltriethoxysilane, 3- (N, N-di-2-ethylhexylamino) propyltriethoxysilane, 11- Methyl triethoxysilylundecanoate, 11-bromoundecyltriethoxysilane, 10-bromodecyltriethoxysilane, 5-bromopentyltriethoxysilane,
10-cyanodecyltriethoxysilane, 5-cyanopentyltriethoxysilane, 10-mercaptodecyltriethoxysilane, 5-mercaptopentyltriethoxysilane, thioacetic acid-10-triethoxysilyldecyl, thioacetic acid-5-triethoxysilyl Pentyl, 5-
[5 '-(2'-methyl-2'-bora-1', 3'-dioxa) cyclohexyl] pentyltrichlorosilane and the like, but are not limited to the compounds exemplified herein. Among these, those having an amino group at the terminal are recommended.

Specific examples of the carboxylic acid having a functional group at its terminal include trimethylsilylacetic acid, 3-mercaptopropionic acid, 3-cyanopropionic acid, 3-chloropropionic acid, 3-bromopropionic acid, and 3-iodopropion. Acid, 4-chlorobutanoic acid, 4-bromobutanoic acid, 5-bromopentanoic acid, 6-bromohexanoic acid, 8
-Bromooctanoic acid, 11-bromoundecanoic acid, 12
-Bromododecanoic acid, 10-hydroxydecanoic acid, 12
-Hydroxydodecanoic acid, 16-hydroxyhexadecanoic acid, (+/-)-thioctic acid, b-alanine, 4-aminobutanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-amino Octanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 4-cyanobenzoic acid, 4-chlorophenylacetic acid, 4
-Bromophenylacetic acid, 4-hydroxyphenylacetic acid,
Examples thereof include 3- (4-hydroxyphenyl) propionic acid, 4-aminophenylacetic acid, 4-chlorocinnamic acid, 4-bromocinnamic acid, and 4-hydroxycinnamic acid, but are not limited to the compounds exemplified herein. Not something.

Further, specific examples of hydroxamic acids having a functional group at the terminal include 16, N-dihydroxyhexadecanamide, but are not limited to these exemplified compounds.

Specific examples of phosphonic acids or phosphoric esters having a functional group at a terminal include 2
-Aminoethylphosphonic acid, 3-aminopropylphosphonic acid, 2-aminoethyl dihydrophosphate, 6-aminohexyl dihydrophosphate, and the like, but are not limited to the compounds exemplified herein.

Thiols or sulfides,
Specific examples of the terminal having a functional group include 3-chloropropanethiol, 2-hydroxyethanethiol,
2-chloroethyl methyl sulfide, 2-chloroethyl ethyl sulfide, 2-hydroxyethyl methyl sulfide, 2-hydroxyethyl ethyl sulfide, 3-hydroxypropyl methyl sulfide, 4-hydroxybutyl methyl sulfide, 2-hydroxyethyl disulfide, 3- Hydroxypropyl sulfide, 3-mercaptopropionic acid, 4-chlorothiophenol, 4-bromothiophenol, 4-hydroxythiophenol,
Examples thereof include 2- (4-chlorophenyl) ethanethiol, but are not limited to the compounds exemplified herein. Aliphatic thiols synthesized by the reaction of alkyl halides with sodium hydrogen sulfide or thiourea,
Aromatic thiols synthesized by the reaction of an aryl Grignard reagent with sulfur can also be used.

Next, the polymer used in the method 2) a) may be any polymer having a functional group capable of reacting with the functional group of the self-assembled film. It is preferably in the middle. The reaction between the self-assembled membrane and the polymer can take various bonding forms such as ionic bonding and covalent bonding. The main chain structure of the polymer is not particularly limited and may be either a homopolymer or a copolymer. Examples of the repeating unit include an ethylene structure, an oxyethylene structure, an iminoethylene structure, a peptide structure, and an inorganic polymer structure. However, the present invention is not limited to this. Examples of the functional group of the polymer include an amino group, a mercapto group, a cyano group, a carboxyl group, and a halogen substituent.

Representative examples of the above polymers include allylamine-based polymers, ethyleneimine-based polymers, 4-vinylpyridine-based polymers, acrylonitrile-based polymers, (meth) acrylic-acid-based polymers, maleic-acid-based polymers, and vinyl chloride-based polymers. And the like, but are not limited to these exemplified polymers. Further, a polymer containing an ionic group, for example, an ammonium group as a cationic group, a polymer containing an onium group such as a phosphonium group or a pyridinium group, a sulfonic acid group as an anionic group, a polymer containing a carboxylic acid group, and the like. . Further, ionomers having an ionic group in the main chain can also be used.

The degree of polymerization of this polymer is not particularly limited, but is preferably in the range of 5 to 10,000, and particularly preferably in the range of 20 to 5
A range of 000 can be recommended.

Any of the above-mentioned polymers may be used. Among them, as a compound for forming a self-assembled film having a functional group at a terminal, the functional group is an amino group, and an alkylene group having 1 to 30 carbon atoms. Through an alkoxysilyl group,
When a compound having a halosilyl group or a carboxyl group is used, a polymer having a carboxyl group, particularly a polymer containing a (meth) acrylic acid unit, a maleic acid unit, a fumaric acid unit, or the like is preferable. Are most preferred.

The reaction between the self-assembled film having a functional group at the terminal formed on the electrode layer and the polymer having a functional group which reacts with the functional group usually involves the reaction of the polymer having a functional group which reacts with the functional group. Perform in solution. Reaction is at room temperature,
The reaction may be performed at normal pressure, or may be performed under heating, pressurizing, or light irradiation conditions as needed.

The compound for forming a self-assembled film having a polymerizable group used in the method 2) b) is a compound capable of forming a self-assembled film having a polymerizable group on an electrode layer, In addition, any material can be used as long as the formed self-assembled film having a polymerizable group can be polymerized. As a polymerizable group,
Examples thereof include a vinyl group such as a (meth) acrylate group and a styryl group, a cyclic ether group such as a glycidoxy group and an epoxy group, an oxazolyl group, an amino acid unit, a cyclic disulfide group, and a boronic ester group.

Specific examples of the compound for forming a self-assembled film having a polymerizable group at the terminal include 3-trimethoxysilylpropyl methacrylate, 3-trimethoxysilylpropyl acrylate, and 11-trimethoxymethacrylate. Ethoxysilylundecyl, 11-triethoxysilylundecyl acrylate, N, N-bis [3- (trimethoxysilyl) propyl] methacrylamide, 8-bis (2-
(Methacryloxyethyl) aminooctyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride, 3-glycidoxypropyltrimethoxysilane, 3- (N-allyl-N- Glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, N-glycidyl-N, N-bis [3-
(Trimethoxysilyl) propyl] amine, S- (8-
Triethoxysilyloctyl) -L-cysteine, 3-
Lipoyloxyaminopropyltriethoxysilane, 1
0- [2 '-(5'-dimethyl-2'-bora-1',
3'-oxa) cyclohexyl] decyltriethoxysilane and the like, but are not limited to the compounds exemplified herein.

The polymerization of the self-assembled film having a polymerizable group at the terminal formed on the electrode layer can be usually performed in a solid phase or a solution. . As the polymerization method, a self-assembled film having a vinyl group has radical polymerization by heat or light irradiation in the presence or absence of a polymerization initiator, and a self-assembled film having a cyclic ether group has an anion using a polymerization initiator. Polymerization, cationic polymerization using a polymerization initiator in a self-assembled film having an oxazolyl group, polycondensation using a condensing agent in a self-assembled film having an amino acid unit,
For a self-assembled film having a cyclic disulfide group, depolymerization using a reducing agent may be used, and for a self-assembled film having a boronic ester group, polymerization induced in a nonpolar solvent or under reduced pressure may be used. The degree of polymerization is not particularly limited, but is preferably in the range of 5 to 10000, and particularly preferably in the range of 20 to
A range of 5000 can be recommended.

A self-assembled polymer thin film of a polymer for forming a self-assembled polymer thin film having a surface active group, or a self-assembled compound for forming a self-assembled film having a functional group or a compound for forming a self-assembled film having a polymerizable group. As a method of forming an organized film on the electrode layer, for example, dissolving the polymer for forming a self-assembled polymer thin film or the compound for forming a self-assembled film in a solvent, immersing the electrode layer in the obtained solution, or the like. After the compound for forming a self-assembled film is reacted with the electrode layer by contacting with the method, the electrode layer is separated from the solution, and then the polymer for forming a self-assembled polymer thin film or the compound for forming a self-assembled film is formed. Washing with a solution in which is dissolved to remove unreacted polymer for forming a self-assembled polymer thin film or a compound for forming a self-assembled film. In addition, the reaction here is performed by a special adsorption (chemical adsorption) on the surface with a chemical bond generated between the polymer for forming the self-assembled polymer thin film or the compound for forming the self-assembled film and the electrode layer or an energy comparable to the chemical bond. Adsorption).

The solvent used here may be any solvent that dissolves the polymer for forming a self-assembled polymer thin film or the compound for forming a self-assembled film, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated It is appropriately selected from hydrocarbons, alcohols, ether compounds, ketone compounds, water and the like, and used alone or in combination.

Among these solvents, solvents suitable for the above-mentioned polymer for forming a self-assembled polymer thin film or a compound for forming a self-assembled film and having a halosilyl group are usually aliphatic hydrocarbons and aromatic hydrocarbons. Group hydrocarbons, halogenated hydrocarbons and ether compounds. Examples of these solvents include hexane, decane, hexadecane, benzene, toluene, xylene, carbon tetrachloride, chloroform, methylene chloride, 1,1,2-trichloroethane, diethyl ether, tetrahydrofuran, 1,4-
Examples thereof include dioxane and 1,2-dimethoxyethane, but are not limited to these solvents.
Any solvent having no hydroxyl group or carbonyl group can be used.

The solvent suitable for the polymer for forming a self-assembled polymer thin film or the compound for forming a self-assembled film, which has an alkoxysilyl group, includes:
Usually, water, alcohols, ketones, and solvents suitable for the above-mentioned polymer for forming a self-assembled polymer thin film or a compound for forming a self-assembled film having a halosilyl group can be used. To illustrate these solvents,
Examples include water, methanol, ethanol, propanol, 2-propanol, acetone, 2-butanone, and the solvents exemplified above.

Further, the above-mentioned polymer for forming a self-assembled polymer thin film or a compound for forming a self-assembled film comprises a carboxyl group, a hydroxamic acid group, a phosphonic acid group, a phosphate ester group, a mercapto group, a sulfide group, a sulfide group. Or as a solvent suitable for those having a disulfide group, usually, the above-mentioned polymer for forming a self-assembled polymer thin film or a compound for forming a self-assembled film, and a solvent or halosilyl group suitable for those having an alkoxysilyl group Solvents and the like suitable for those having the same can be mentioned.

The concentration of the above solution is not particularly limited, but if it is too low, it takes time for the reaction to proceed, and if it is too high, it becomes difficult to form a thin film, for example, a thin film having a thickness of 100 Å or less. Therefore, from the viewpoint of industrial productivity,
In the polymer for forming a self-assembled polymer thin film having a surface-active group, the concentration of the surface-active group is in the range of 0.001 mmol / L to 1 mol / L. For the compound for forming a self-assembled film having a group, a range in which the concentration of the compound is 0.001 mmol / L to 1 mol / L is recommended, but is not limited to this range.

When the above-described polymer for forming a self-assembled polymer thin film or a compound for forming a self-assembled film having a halosilyl group is used, an amine such as pyridine, triethylamine, dimethylaniline or the like is used for capturing hydrogen halide by-produced. May coexist. When using a polymer for forming a self-assembled polymer thin film or a compound for forming a self-assembled film having an alkoxysilyl group, formic acid,
It is also an effective method to add a carboxylic acid such as acetic acid as a catalyst.

A process for forming a self-assembled polymer thin film or a self-assembled film by bringing a solution of the polymer for forming a self-assembled polymer thin film or a compound for forming a self-assembled film into contact with an electrode layer by a method such as immersion. The temperature is not particularly limited, but in order to form a thin film, preferably a thin film having a thickness of 100 Å or less, the temperature is -10 to 150 ° C.
Is particularly preferable, and a range of 0 to 100 ° C. can be particularly recommended. The processing time is not particularly limited, but a long time is required when the temperature is low, and the processing is completed in a short time when the processing temperature is high. Generally, a range of 10 minutes to 2 days is preferred,
In particular, a range of 30 minutes to 1 day can be recommended. In addition, the treatment for a short time, for example, 1 hour is performed twice or more, preferably 2 to 3 times.
Repeating three times is also advantageous for forming a dense thin film and can be recommended. Furthermore, when using the polymer for forming a self-assembled polymer thin film or the compound for forming a self-assembled film, which has an alkoxysilyl group or a halosilyl group, heat treatment of the electrode layer after the treatment is performed by a self-assembly method. This is effective in completely forming the oxide film. The heat treatment temperature is not particularly limited, but may be 50
The range is preferably from 200 to 200 ° C, and particularly preferably from 50 to 150 ° C.

What is important for the formation of the self-assembled polymer thin film and the self-assembled film is to immerse the electrode layer in a predetermined concentration of the solution of the polymer for forming the self-assembled polymer thin film or the compound for forming the self-assembled film. After contacting for a predetermined time by the method described above, the solution is separated from the solution and washed with a solvent to remove the unreacted polymer for forming a self-assembled polymer thin film or the compound for forming a self-assembled film. At this time, as a solvent that can be used, a solvent used for producing a self-assembled polymer thin film or a self-assembled film can be used. At the time of this cleaning, use of an ultrasonic cleaner or the like is also an effective means.

In the manufacturing method according to the above 2) a), a self-assembled film having a functional group at a terminal formed on the electrode layer;
As a method of reacting a polymer having a functional group that reacts with the functional group, for example, a polymer having the functional group is dissolved in a solvent, and a self-assembled film having a functional group at a terminal is formed in the obtained solution. After the electrode layer is contacted by a method such as immersion to react with the polymer having a functional group, the electrode layer is separated from the solution, and then washed with a solution in which the polymer having the functional group is dissolved, and the unreacted polymer is washed. A method of removing a polymer having a functional group of

The solvent used here may be any solvent that dissolves the polymer having the above functional group, and may be used alone or in combination. Examples of these solvents include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ether compounds, ketone compounds, water, amide compounds, sulfoxide compounds, and the like. Hexane, decane, hexadecane, benzene, toluene, xylene, carbon tetrachloride, chloroform, methylene chloride, 1,1,2-trichloroethane, diethyl ether, tetrahydrofuran,
1,4-dioxane, 1,2-dimethoxyethane, methanol, ethanol, propanol, 2-propanol, acetone, 2-butanone, formamide, N-methylformamide, N, N-dimethylformamide, N,
N-dimethylacetylamide, dimethylsulfoxide,
Hexamethylphosphoric triamide, water and the like can be mentioned. Among these, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ether compounds, ketone compounds, and water are preferred, and ketone compounds are particularly preferred.

The concentration of the above solution is not particularly limited, but if it is too low, it takes time for the reaction to proceed, and if it is too high, it becomes difficult to form a thin film, for example, a thin film having a thickness of 100 Å or less. Therefore, from the viewpoint of industrial productivity,
Functional group concentration is 0.001 mmol / l to 1 mol
A range of / l is recommended, but is not limited to this range.

The treatment temperature for contacting the self-assembled film having a functional group at the terminal with a solution of a polymer having a functional group which reacts with the functional group is not particularly limited.
In order to form a thin film having a thickness of preferably 100 Å or less, the temperature is preferably in the range of −10 to 150 ° C.,
Particularly, a range of 0 to 100 ° C. can be recommended. The processing time is not particularly limited, but requires a long time when the temperature is low,
When the processing temperature is high, the processing is completed in a short time. Generally, a range of 10 minutes to 2 days is preferred, and a range of 30 minutes to 1 day is particularly recommended.

In the case where the bond between the self-assembled film having a functional group at the terminal on the electrode layer and the polymer having a functional group which reacts with the functional group is an ionic bond, a heat treatment is further performed after the formation of the self-assembled film. By performing the above, the film can be converted into a covalent bond, and a stronger and more stable thin film can be obtained. For example, when a self-assembled film having an amino group at the end is reacted with a polymer having a carboxyl group to form an ammonium salt, after forming the self-assembled film, heat treatment is further performed to form an amide bond or an imide bond. Convert,
A stronger and more stable thin film can be obtained. The self-assembled film having an amino group at the terminal used herein is at least one compound for forming a self-assembled film selected from the group consisting of organic alkoxysilanes, organic halosilanes and carboxylic acids, A self-assembled film having an amino group at the terminal, comprising an amino group via an alkylene group of Formulas 1 to 30, is preferred. As the polymer having a carboxyl group, a polymer having a maleic acid unit, particularly Polymers having ester units are preferred.

The temperature of the heat treatment for converting an ionic bond into a covalent bond is preferably in the range of 60 to 250 ° C., particularly preferably in the range of 100 to 200 ° C., and the treatment time is preferably in the range of 30 minutes to 48 hours. In particular, a range of 1 to 24 hours can be recommended. This heat treatment can be performed under reduced pressure.

Here, it is important to form a self-assembled polymer thin film by reacting a self-assembled film having a functional group at the terminal with a polymer having a functional group which reacts with the functional group. The electrode layer on which the self-assembled film having a group is formed is brought into contact with a solution of the polymer having the above-described functional group at a predetermined concentration by a method such as immersion for a predetermined time, then separated from the solution and unreacted by washing with a solvent. In removing the polymer having the above functional group. At this time,
As a solvent that can be used, a solvent that can dissolve the polymer having the above functional group can be used. At the time of this cleaning, use of an ultrasonic cleaner or the like is also an effective means.

In the method 2) b), the self-assembled film having a polymerizable group at the terminal formed on the electrode layer may be polymerized by, for example, dissolving a polymerization initiator in a solvent. After contacting the electrode layer formed with a self-assembled film having a polymerizable group at the terminal thereof by a method such as immersion and polymerizing the solution, the electrode layer is separated from the solution. Wash with a dissolving solution,
A method of removing the unreacted polymerization initiator can be used.

The solvent used here may be any solvent that dissolves the polymerization initiator. For example, the same solvent as that used for dissolving the polymer having a functional group in the production method of 2) a) is used. Solvents. These solvents can be used alone or in combination. The concentration of the polymerization initiator solution using these solvents is not particularly limited, but a range of 0.001 to 1 mmol / liter is recommended.

The processing temperature for polymerizing the electrode layer on which the self-assembled film having a polymerizable group at the terminal is formed is 30 to
A range of 200 ° C is preferred, and a range of 50 to 150 ° C can be particularly recommended. The processing time is not particularly limited, but may be 10
The range of minutes to 2 days is preferable, and the range of 30 minutes to 1 day can be particularly recommended.

In the case of polymerizing a self-assembled film having a vinyl group as a polymerizable group, a method of performing radical polymerization by irradiating light in a solid phase under degassing may be used. Examples of the light source used include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, and a metal halide lamp. The treatment temperature is not particularly limited, but is preferably in the range of 0 to 100 ° C, and particularly preferably in the range of 20 to 50 ° C. The processing time is not particularly limited, but is 10 seconds to 12 seconds.
A time range is preferable, and a range of 30 seconds to 1 hour can be particularly recommended.

However, when a self-assembled film having a boronic ester group as a polymerizable group is polymerized, usually, the self-assembled film is brought into contact with a hydrocarbon solvent to induce a polymerization reaction. Examples of the solvent used here include, but are not limited to, hexane, decane, hexadecane, isooctane, benzene, toluene, xylene, and the like. The treatment temperature is not particularly limited, but is preferably in the range of 0 to 150 ° C, and particularly preferably in the range of 20 to 60 ° C. The processing time is not particularly limited, but is preferably in the range of 30 minutes to 48 hours,
In particular, a range of 1 to 24 hours can be recommended.

The thickness of the self-assembled polymer thin film formed in this manner varies depending on the structure of the structural unit, but usually ranges from 0.3 to 10 nm. Especially 0.3-5n
A film thickness of m is recommended for the purpose of improving sensitivity.

[0080]

EXAMPLES The present invention will be described below in more detail with reference to Examples of the present invention, but the present invention is not limited to these Examples. The concentrations (%) of the solutions used in the examples are% by weight, and parts are parts by weight.

Example 1 5.0 n of an aluminum oxide layer formed on the surface by natural oxidation
1.0m, mirror-polished thickness formed with a thickness of m
m of an aluminum plate was added to a toluene solution of 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer (average molecular weight: 40,000, copolymerization ratio: 1 / 13.3) having a silyl group concentration of 0.5 mmol / liter at room temperature. After immersion for 6 hours, the substrate was taken out of the solution, washed sufficiently with toluene, and heated in an oven at 120 ° C. for 1 hour to obtain an aluminum plate having a self-assembled polymer thin film formed on the surface.

A thin film having a thickness of 2.0 nm was formed on the aluminum plate by ellipsometry analysis, and methacrylic acid-3- It was confirmed that a film composed of the trimethoxysilylpropyl / methyl methacrylate copolymer was formed. That is, it was confirmed that a self-assembled polymer thin film composed of 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer was formed on the aluminum plate.

Also, α-type oxotitanium phthalocyanine (α-OTiPc) was added to 15 g of a 0.52% butyral resin solution (the solvent was a mixed solvent having a weight ratio of dichloromethane / 1,1,2-trichloroethane of 4/6). .15g
And glass beads were added thereto, and the mixture was dispersed with a paint shaker for 3 hours to obtain a charge generating agent dispersion.

Further, 4.2 g of 1- (4'-diphenylaminobenzylidene) -amino-2-methylindole and 4.7 g of a polycarbonate resin (Iupilon PCZ-200 manufactured by Mitsubishi Gas Chemical Company) were mixed in a weight ratio of dichloromethane / chlorobenzene. The mixture was dissolved in 28.5 g of a 1/2 mixed solvent to obtain a charge transport agent solution.

Then, a self-assembled polymer thin film of an aluminum plate coated with a self-assembled polymer thin film comprising 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer obtained above was applied to the self-assembled polymer thin film using a spin coater. The dry thickness of the charge generator dispersion is 0.3 μm.
And dried at 120 ° C. for 30 minutes to form a charge generation layer. Further, a charge transporting agent solution is further applied thereon by using a spin coater so as to have a dry film thickness of 20 μm, and dried at 120 ° C. for 1 hour to prepare an electrophotographic photoreceptor (1) of the present invention. did.

The charge decay characteristics of the obtained electrophotographic photoreceptor (1) were measured using a paper analyzer (E Kawasaki Electric Co., Ltd.).
PA8100) as follows. That is, the electrophotographic photosensitive member (1) is corona-charged (−7K) in the dark.
V, static method), and the maximum surface potential (Vmax) at that time and the surface potential (Vlight) after corona charging and after holding for 5 seconds in the dark were measured, and the charge retention ratio (DD) during this period = (Vlight / Vmax × 100). Next, the electrophotographic photoreceptor (1) held in the dark for 5 seconds is irradiated with light having a wavelength of 790 nm and an intensity of 1 μW / cm ² for 10 seconds, the surface potential attenuation is measured during that time, and the residual potential after the light irradiation for 10 seconds is measured. Together with (Vr), the product (E _1/2 ) of the time (second) required for the surface potential to attenuate to 1/2 of Vlight and the irradiation light intensity, which is an index of the sensitivity of the electrophotographic photosensitive member, was determined. Table 1 shows the results.

Example 2 Instead of 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer (average molecular weight: 40,000, copolymerization ratio: 1 / 13.3), 3-trimethoxysilylpropyl methacrylate / methacrylic acid A self-assembled polymer thin film was formed on an aluminum plate in the same manner as in Example 1 except that an acid methyl copolymer (average molecular weight: 40,000, copolymerization ratio: 1 / 7.0) was used. Analysis and ellipsometry analysis revealed that a self-assembly of 2.0 nm thick self-consisting of 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer (average molecular weight 40,000, copolymerization ratio 1 / 7.0) was formed on an aluminum plate. It was confirmed that the polymerized polymer thin film was formed. Next, an electrophotographic photoreceptor (2) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used, and the charge light attenuation characteristics were determined. Table 1 shows the results.

Example 3 Instead of 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer (average molecular weight: 40,000, copolymerization ratio: 1 / 13.3), 3-trimethoxysilylpropyl methacrylate / methacrylic acid A self-assembled polymer thin film was formed on an aluminum plate in the same manner as in Example 1 except that an acid methyl copolymer (average molecular weight: 40,000, copolymerization ratio: 1 / 3.5) was used, and contact angle measurement and XPS analysis were performed. And ellipsometry analysis showed that a 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer (average molecular weight 40,000, copolymerization ratio 1
/3.5) was confirmed to form a self-assembled polymer thin film having a thickness of 2.0 nm. Then, in the same manner as in Example 1 except that this aluminum plate was used,
An electrophotographic photoreceptor (3) of the present invention was produced, and its charging light attenuation characteristics were determined. Table 1 shows the results.

Example 4 Instead of 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer (average molecular weight: 40,000, copolymerization ratio: 1 / 13.3), 11-triethoxysilylundecyl methacrylate / A self-assembled polymer thin film was formed on an aluminum plate in the same manner as in Example 1 except that a methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 49.6) was used, and the contact angle was measured. , XP
According to S analysis and ellipsometry analysis, a thickness consisting of methacrylic acid-11-triethoxysilylundecyl / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 49.6) on an aluminum plate 3. 0
It was confirmed that a self-assembled polymer thin film having a thickness of nm was formed. Next, the electrophotographic photoreceptor (4) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used.
Was prepared, and its charging light attenuation characteristics were determined. Table 1 shows the results.

Example 5 Instead of 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer (average molecular weight: 40,000, copolymerization ratio: 1 / 13.3), 11-triethoxysilylundecyl methacrylate / A self-assembled polymer thin film was formed on an aluminum plate in the same manner as in Example 1 except that a methyl methacrylate copolymer (average molecular weight: 75,000, copolymerization ratio: 1 / 22.0) was used, and the contact angle was measured. , XP
By S analysis and ellipsometry analysis, a thickness consisting of methacrylic acid-11-triethoxysilylundecyl / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 22.0) on an aluminum plate. 0
It was confirmed that a self-assembled polymer thin film having a thickness of nm was formed. Next, the electrophotographic photoreceptor (5) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used.
Was prepared, and its charging light attenuation characteristics were determined. Table 1 shows the results.

Example 6 Instead of 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer (average molecular weight: 40,000, copolymerization ratio: 1 / 13.3), 11-triethoxysilylundecyl methacrylate / A self-assembled polymer thin film was formed on an aluminum plate in the same manner as in Example 1 except that methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 11.6) was used, and the contact angle was measured. , XP
According to S analysis and ellipsometry analysis, a thickness consisting of methacrylic acid-11-triethoxysilylundecyl / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 11.6) on an aluminum plate. 0
It was confirmed that a self-assembled polymer thin film having a thickness of nm was formed. Next, the electrophotographic photoreceptor (6) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used.
Was prepared, and its charging light attenuation characteristics were determined. Table 1 shows the results.

Example 7 Instead of 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer (average molecular weight: 40,000, copolymerization ratio: 1 / 13.3), 11-triethoxysilylundecyl methacrylate was used. A self-assembled polymer thin film was formed on an aluminum plate in the same manner as in Example 1 except that a homopolymer (average molecular weight: 75,000) was used, and contact angle measurement, XPS analysis, and ellipsometry analysis were performed. On top, methacrylic acid-11-triethoxysilylundecyl homopolymer (average molecular weight 7.5
It was confirmed that a self-assembled polymer thin film having a thickness of 2.0 nm was formed. Next, an electrophotographic photoreceptor (7) of the present invention was produced in the same manner as in Example 1 except that this aluminum plate was used, and the charge-light decay characteristics thereof were determined. Table 1 shows the results.

Example 8 Instead of a toluene solution of 3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer (average molecular weight 40,000, copolymerization ratio 1 / 13.3) having a silyl group concentration of 0.5 mmol / liter, , A toluene solution having a silyl group concentration of 0.5 mmol / l (1.5 mmol concentration) of 11-trichlorosilylundecyl methacrylate / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 10.2) A self-assembled polymer thin film was formed on an aluminum plate in the same manner as in Example 1 except that triethylamine was used.
Analysis and ellipsometry analysis showed that 11-trichlorosilylundecyl methacrylate / methyl methacrylate copolymer (average molecular weight 7.5
It was confirmed that a self-assembled polymer thin film having a thickness of 3.0 nm and a copolymerization ratio of 1 / 10.2) was formed. Next, an electrophotographic photoreceptor (8) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used, and the charging light decay characteristics were determined. Table 1 shows the results.

Comparative Example 1 Electrophotography was carried out in the same manner as in Example 1 except that a mirror-polished aluminum plate was used without performing a treatment with a toluene solution of -3-trimethoxysilylpropyl methacrylate / methyl methacrylate copolymer. A photoreceptor (1 ') was prepared, and its charging light attenuation characteristics were determined. Table 1 shows the results.

Comparative Example 2 According to the description in JP-A-61-109064,
% Methanol solution of 3-trimethoxysilylpropyl methacrylate was applied to the same mirror-polished aluminum plate as that used in Example 1 using a spin coater, and then dried in a 100 ° C. oven. Heat for hours,
An aluminum plate having a coating film on the surface was obtained.

It was confirmed by ellipsometry that a 0.3 μm film was formed on the aluminum plate having a coating film on its surface. From this, it was confirmed that, in this film, 3-trimethoxysilylpropyl methacrylate molecules did not show an ordered molecular orientation and were stacked in random directions. Next, an electrophotographic photoreceptor (2 ') was prepared in the same manner as in Example 1 except that an aluminum plate having a coating film on its surface was used, and its charging light attenuation characteristics were determined. Table 1 shows the results.

Comparative Example 3 According to the description in JP-A-5-107792, a silicon additive (SH21PA manufactured by Toray Silicon) was added to a solution prepared by dissolving 5 parts of a polyamide resin (CM-8000 manufactured by Toray Industries, Inc.) in 65 parts of methanol. 0.05 part was added, and the dry film thickness was 1 μm on the same aluminum plate as used in Example 1.
m, to obtain an aluminum plate having a coating film on its surface, and then using the same electrophotographic photoreceptor (3 ') as in Example 1 except that an aluminum plate having a coating film on this surface was used. Was prepared, and its charging light attenuation characteristics were determined. Table 1 shows the results.

Comparative Example 4 A toluene solution of 10% concentration of 11-triethoxysilylundecyl methacrylate / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 11.6) was prepared in Example 1. Using a spin coater to apply the same mirror-polished aluminum plate as used in
By heating in an oven at a temperature of 1 ° C. for 1 hour, an aluminum plate having a coating film on the surface was obtained. On an aluminum plate having a coating film on this surface, 0.4 μm
m was formed. Next, an electrophotographic photoreceptor (4 ') was prepared in the same manner as in Example 1 except that an aluminum plate having a coating film on its surface was used, and its charging light attenuation characteristics were determined. Table 1 shows the results.

Comparative Example 5 A toluene solution of a 10% concentration of 11-trichlorosilylundecyl methacrylate / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 10.2) was prepared as follows:
The same mirror-polished aluminum plate as that used in Example 1 was applied using a spin coater and heated in an oven at 100 ° C. for 1 hour to obtain an aluminum plate having a coating film on the surface. Ellipsometric analysis confirmed that a 0.3 μm film was formed on the aluminum plate having a coating film on its surface. Next, an electrophotographic photoreceptor (5 ') was prepared in the same manner as in Example 1 except that an aluminum plate having a coating film on its surface was used, and its charging light attenuation characteristics were determined. Table 1 shows the results.

[0100]

[Table 1]

From the results shown in Table 1, the electrophotographic photosensitive members (1) to (8) of Examples 1 to 8 were compared with the electrophotographic photosensitive members (1 ') to (5') of Comparative Examples 1 to 5. In each case, the value of E _1/2 as an index of sensitivity was small, and the sensitivity was clearly high.

Example 9 5.0 n of an aluminum oxide layer formed on the surface by natural oxidation
1.0m, mirror-polished thickness formed with a thickness of m
m of an aluminum plate was treated with a methacrylic acid / methyl methacrylate copolymer (average molecular weight 40,000, copolymerization ratio 1/4.
5) After immersion in a methanol solution having a carboxyl group concentration of 0.5 mmol / l for 72 hours at room temperature, withdrawing from the solution, washing sufficiently with methanol, and heating in an oven at 120 ° C. for 1 hour to form a self- An aluminum plate on which an activated polymer thin film was formed was obtained.

A thin film having a thickness of 2.0 nm was formed on the aluminum plate by ellipsometry analysis, and a methacrylic acid / methyl methacrylate copolymer (average molecular weight: 4
It was confirmed that a self-assembled polymer thin film having a copolymerization ratio of 1 / 4.5) was formed. Next, an electrophotographic photoreceptor (9) of the present invention was prepared in the same manner as in Example 1 except that the aluminum plate was used, and the charge-light decay characteristics were determined. Table 2 shows the results.

Comparative Example 6 A 10% methanol solution of methacrylic acid / methyl methacrylate copolymer (average molecular weight: 40,000, copolymerization ratio: 1 / 4.5) was mirror-polished in the same manner as in Example 9. The resulting aluminum plate was coated with a spin coater and heated in an oven at 100 ° C. for 1 hour to obtain an aluminum plate having a coating film on the surface. Ellipsometry analysis confirmed that a 0.5 μm film was formed on the aluminum plate having a coating film on its surface. Next, an electrophotographic photoreceptor (6 ') was prepared in the same manner as in Example 1 except that an aluminum plate having a coating film on its surface was used, and its charging light attenuation characteristics were determined. Table 2 shows the results.

Example 10 A Pyrex glass substrate having a thickness of 1 mm (hereinafter abbreviated as an ITO substrate) on which an indium tin oxide electrode layer having a thickness of 40.0 nm was formed by sputtering, was treated with 11-triethoxysilyl methacrylate. After immersion in a toluene solution of decyl / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 11.6) having a silyl group concentration of 0.5 mmol / l for 6 hours at room temperature, the solution was taken out from the solution, and toluene was added. After sufficient washing, the substrate was heated in an oven at 120 ° C. for 1 hour to obtain an ITO substrate having a self-assembled polymer thin film formed on the indium tin oxide electrode layer.

On this ITO substrate, a 3.0-nm-thick methacrylic acid-11-triethoxysilylundecyl /
Methyl methacrylate copolymer (average molecular weight 75,000,
The formation of a self-assembled polymer thin film having a copolymerization ratio of 1 / 11.6) was confirmed by ellipsometry analysis and X-ray analysis.
Confirmed by PS analysis. Next, an electrophotographic photoreceptor (10) of the present invention was prepared in the same manner as in Example 1 except that the ITO substrate was used, and the charge-attenuation characteristic was obtained. Table 2 shows the results.

Comparative Example 7 An ITO substrate identical to that used in Example 10 was used without performing treatment with a toluene solution of methacrylic acid-11-triethoxysilylundecyl / methyl methacrylate copolymer. An electrophotographic photoreceptor (7 ') was prepared in the same manner as in No. 1, and the charging light decay characteristics were determined.
Table 2 shows the results.

Example 11 A copper plate having a copper oxide on its surface was treated with methacrylic acid-11
-Triethoxysilylundecyl / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1/11.
After immersion in a toluene solution having a silyl group concentration of 0.5 mmol / liter for 6 hours at room temperature for 6 hours, and then withdrawing from the solution,
After thoroughly washing with toluene, place in an oven at 120 ° C for 1
After heating for a time, a copper plate on which a self-assembled polymer thin film was formed was obtained.

On this copper plate, a self-made 3.0-nm-thick methacrylic acid-11-triethoxysilylundecyl / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 11.6) was used. The formation of an organized polymer thin film was confirmed by ellipsometry analysis and XPS analysis. Next, an electrophotographic photoreceptor (11) of the present invention was prepared in the same manner as in Example 1 except that this copper plate was used, and the charge-attenuation characteristics thereof were determined. Table 2 shows the results.

Comparative Example 8 A copper plate having a copper oxide on the same surface as that used in Example 11 was not treated with a toluene solution of methacrylic acid-11-triethoxysilylundecyl / methyl methacrylate copolymer. An electrophotographic photoreceptor (8 ') was prepared in the same manner as in Example 1 except that the above was used, and the charging light decay characteristics thereof were determined. Table 2 shows the results.

Example 12 A Pyrex glass substrate was immersed in a 5 mmol / liter methanol solution of 3-mercaptopropyltrimethoxysilane at room temperature for 24 hours to form a 3-mercaptopropylsiloxy group monomolecular film on the Pyrex glass substrate. After forming a self-assembled film, 100
A Pyrex glass substrate having a gold electrode layer on the self-assembled film was obtained by vacuum evaporation to a thickness of nm. Next, this Pyrex glass substrate was treated with toluene having a silyl group concentration of 0.5 mmol / liter of a 3,4-dithiopentyl methacrylate / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 11.0). 24 hours at room temperature
After soaking for a period of time, it was taken out of the solution and sufficiently washed with toluene to obtain a Pyrex glass substrate having a self-assembled polymer thin film formed on a gold electrode layer.

On the gold electrode layer of the Pyrex glass substrate, a 3.0 nm thick methacrylic acid-3,4-dithiopentyl / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1/11. The formation of the self-assembled polymer thin film composed of 0) was confirmed by ellipsometry analysis and XPS analysis. Next, in the same manner as in Example 1 except that this self-assembled polymer thin film used a Pyrex glass substrate formed on a gold electrode layer,
An electrophotographic photoreceptor (12) of the present invention was produced, and its charging light attenuation characteristics were determined. Table 2 shows the results.

Comparative Example 9 A Pyrex glass substrate having a gold electrode layer on a self-assembled film was obtained in the same manner as in Example 12. An electrophotographic photoreceptor (9 ') was prepared in the same manner as in Example 1 except that it was used without performing the treatment with the toluene solution, and the charging light attenuation characteristic was obtained. Table 2 shows the results.

Comparative Example 10-3,4-dithiopentyl methacrylate at a concentration of 10%
Methyl methacrylate copolymer (average molecular weight 75,000,
A toluene solution having a copolymerization ratio of 1 / 11.0) was prepared in Example 12
Was applied using a spin coater onto the gold electrode layer of a Pyrex glass substrate having the same gold electrode layer formed on the self-assembled film, and heated in an oven at 100 ° C. for 1 hour. On the gold electrode of this Pyrex glass substrate,
Ellipsometry analysis confirmed that a 0.4 μm film was formed. Next, an electrophotographic photoreceptor (10 ') was prepared in the same manner as in Example 1 except that this Pyrex glass substrate was used, and the charge light attenuation characteristics were determined.
Table 2 shows the results.

Example 13 A Pyrex substrate having a copper electrode having a thickness of 100 nm formed by vacuum evaporation was coated on a 3,4-dithiopentyl methacrylate / methyl methacrylate copolymer (average molecular weight 75,000, copolymerization ratio 1 / 11.0).
After being immersed in a 5 mmol / liter toluene solution for 24 hours at room temperature, pulled out of the solution, sufficiently washed with toluene, and heated in an oven at 120 ° C. for 1 hour, a self-assembled polymer thin film was formed on the copper electrode. A Pyrex substrate was obtained.

The Pyrex substrate has a thickness of 3.0
The formation of a self-assembled polymer thin film composed of a 3,4-dithiopentyl methacrylate / methyl methacrylate copolymer having an average molecular weight of 75,000 and a copolymerization ratio of 1 / 11.0 nm was determined by ellipsometry. Confirmed by analysis and XPS analysis. Next, an electrophotographic photoreceptor (13) of the present invention was prepared in the same manner as in Example 1 except that this Pyrex substrate was used, and the charge light attenuation characteristics were determined. Table 2 shows the results.

Comparative Example 11 A Pyrex glass substrate having the same copper electrode as that used in Example 13 was used without treatment with a toluene solution of methacrylic acid-3,4-dithiopentyl / methyl methacrylate copolymer. Except for the above, an electrophotographic photoreceptor (11 ') was prepared in the same manner as in Example 1, and the charging light decay characteristics were obtained. Table 2 shows the results.

[0118]

[Table 2]

From the results shown in Table 2, the electrophotographic photoreceptor (9) of Example 9 is different from the electrophotographic photoreceptor (6 ') of Comparative Example 6 and the electrophotographic photoreceptors of Comparative Examples 1 and 3 in Table 1. (1 '),
Compared with (3 ′), the value of E _1/2 as an index of sensitivity was small, and the sensitivity was clearly high.

Further, the electrophotographic photosensitive member of Example 10 (1
0) is compared with the electrophotographic photosensitive member (7 ′) of Comparative Example 7,
The electrophotographic photoreceptor (11) of Example 11 is different from the electrophotographic photoreceptor (8 ') of Comparative Example 8, and the electrophotographic photoreceptor (12) of Example 12 is different from the electrophotographic photoreceptor (12) of Comparative Example 9 and Comparative Example 10. Compared with the photoreceptors (9 ') and (10'), the value of E1 _{/ 2} , which is an index of the sensitivity, was small, and the sensitivity was clearly high.

Further, the electrophotographic photosensitive member of Example 13 (13)
In comparison with the electrophotographic photoreceptor (11 ') of Comparative Example 11, the value of E1 _{/ 2} as an index of sensitivity was small, and the sensitivity was clearly high.

Example 14 An aluminum oxide layer formed on the surface by natural oxidation was 5.0 n.
1.0m, mirror-polished thickness formed with a thickness of m
m aluminum plate was immersed in a 5 mmol / liter ethanol solution of 3-aminopropyltriethoxysilane at room temperature for 1 hour, pulled out of the solution, washed sufficiently with ethanol, and then heated in an oven at 120 ° C. for 1 hour. After cooling to room temperature, the same treatment was performed again to obtain an aluminum plate having a self-assembled film formed on the surface.
Next, it was confirmed by ellipsometry analysis and XPS analysis that a self-assembled film composed of a monomolecular film of a 3-aminopropylsiloxy group having a thickness of 1.0 nm was formed on the aluminum plate.

The aluminum plate having the 3-aminopropylsiloxy group monomolecular film formed thereon was treated with a maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight: 210,000) having a repeating unit concentration of 25 mm.
ol / liter of methyl ethyl ketone solution at room temperature for 20 minutes.
After immersion for a period of time, the substrate was taken out of the solution, washed sufficiently with methyl ethyl ketone, and dried under reduced pressure at 30 ° C. for 2 hours to obtain an aluminum plate having a self-assembled polymer thin film formed on the surface.

According to contact angle measurement, XPS analysis, FTIR analysis and ellipsometry analysis, a monomolecular film of 3-aminopropylsiloxy group was formed on this aluminum plate to form a salt with maleic acid monoethyl ester / methyl vinyl ether alternating copolymer. (Average molecular weight: 210,000) was confirmed to form a self-assembled polymer thin film bonded thereto. The thickness of the self-assembled polymer thin film is 4.0 n
m.

Next, the electrophotographic photosensitive member (1) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used.
4) was prepared, and its charging light attenuation characteristics were determined. Table 3 shows the results.

Example 15 The procedure of Example 14 was repeated except that the maleic acid / methyl vinyl ether alternating copolymer (average molecular weight: 100,000) was used instead of the maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight: 210,000). hand,
A self-assembled polymer thin film in which a maleic acid / methyl vinyl ether alternating copolymer (average molecular weight: 100,000) was bonded to a monomolecular film of 3-aminopropylsiloxy group on an aluminum plate to form a salt was prepared. Preparation of the self-assembled polymer thin film was confirmed by contact angle measurement, XPS analysis, FTIR analysis and ellipsometry analysis, and the film thickness was 4.0 n.
m. Next, the electrophotographic photosensitive member (1) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used.
5) was prepared, and its charging light decay characteristics were determined. Table 3 shows the results.

Example 16 An aluminum plate was prepared in the same manner as in Example 14 except that polymethacrylic acid (average molecular weight: 120,000) was used instead of the maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight: 210,000). A salt was formed with the above monolayer of 3-aminopropylsiloxy group to form a self-assembled polymer thin film to which polymethacrylic acid (average molecular weight: 120,000) was bonded. Preparation of self-assembled polymer thin film
It was confirmed by contact angle measurement, XPS analysis, FTIR analysis and ellipsometry analysis, and the film thickness was 5.0 nm. Next, an electrophotographic photoreceptor (16) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used, and the charge-attenuation characteristics were determined. Table 3 shows the results.

Example 17 Instead of maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight 210,000), methacrylic acid / methyl methacrylate copolymer (average molecular weight 40,000, copolymerization ratio 1 / 4.5) was used. Example 14 except for
In the same manner as described above, a salt is formed with a monomolecular film of 3-aminopropylsiloxy group on an aluminum plate to form a self-bonded methacrylic acid / methyl methacrylate copolymer (average molecular weight 40,000, copolymerization ratio 1 / 4.5). An organized polymer thin film was prepared. The creation of self-assembled polymer thin films involves contact angle measurement,
The thickness was confirmed by XPS analysis, FTIR analysis, and ellipsometry analysis, and the film thickness was 4.5 nm. Next, an electrophotographic photoreceptor (17) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used, and the charging light decay characteristics were determined. Table 3 shows the results.

Example 18 The procedure of Example 14 was repeated, except that poly-L-glutamic acid (average molecular weight: 50,000) was used instead of the maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight: 210,000). Poly-L by forming a salt with a monomolecular film of 3-aminopropylsiloxy group on an aluminum plate
-A self-assembled polymer thin film to which glutamic acid (average molecular weight: 50,000) was bound was prepared. Preparation of the self-assembled polymer thin film was confirmed by contact angle measurement, XPS analysis, FTIR analysis and ellipsometry analysis, and the film thickness was 4.0 nm.
Met. Next, the electrophotographic photoreceptor (18) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used.
Was prepared, and its charging light decay characteristics were determined. Table 3 shows the results.

Example 19 The same aluminum plate as used in Example 14 was used.
After being immersed in a 5 mmol / l methanol solution of 2-aminododecanoic acid for 72 hours at room temperature, pulled out of the solution, washed sufficiently with methanol, and then heated in an oven at 120 ° C. for 1 hour to form a self-assembled film on the surface. Was obtained. Next, it was confirmed by ellipsometry analysis and XPS analysis that a self-assembled film composed of a monomolecular film of 12-aminododecanoic acid having a thickness of 1.8 nm was formed on the aluminum plate.

The same procedure as in Example 14 was carried out except that the aluminum plate having a monomolecular film of 12-aminododecanoic acid was used instead of the aluminum plate having a monomolecular film of 3-aminopropylsiloxy group. Then, a self-assembled polymer thin film was formed, in which a monomolecular film of 12-aminododecanoic acid on an aluminum plate was salted and a monoethyl maleate / methyl vinyl ether alternating copolymer (average molecular weight 210,000) was bonded. Preparation of the self-assembled polymer thin film was confirmed by contact angle measurement, XPS analysis, FTIR analysis and ellipsometry analysis, and the film thickness was 5.0 n.
m. Next, the electrophotographic photosensitive member (1) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used.
9) was prepared, and its charging light decay characteristics were determined. Table 3 shows the results.

Comparative Example 12 A 10% ethanol solution of maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight: 210,000) was applied to the same aluminum plate as used in Example 14 by using a spin coater. Apply, 100
C. for 1 hour in an oven to obtain an aluminum plate having a coating film on the surface. The aluminum plate having a coating film on the surface was 0.4 μm thick by ellipsometry analysis.
It was confirmed that a film was formed. Next, an electrophotographic photoreceptor (12 ') was prepared in the same manner as in Example 1 except that an aluminum plate having a coating film on its surface was used, and its charging light attenuation characteristics were determined. Table 3 shows the results.

Comparative Example 13 A methanol solution of 10% polymethacrylic acid (average molecular weight: 120,000) was applied on the same aluminum plate as that used in Example 14 using a spin coater.
By heating in an oven at 0 ° C. for 1 hour, an aluminum plate having a coating film on the surface was obtained. On the aluminum plate having a coating film on the surface, 0.5 μm was obtained by ellipsometry analysis.
m was formed. Next, an electrophotographic photosensitive member (13 ') was prepared in the same manner as in Example 1 except that an aluminum plate having a coating film on its surface was used.
The charge light attenuation characteristics were determined. Table 3 shows the results.

[0134]

[Table 3]

From the results shown in Table 3, the electrophotographic photosensitive members (14) to (19) of Examples 14 to 19 were compared with Comparative Examples 12 and 1
3, the electrophotographic photoconductors (12 ') and (13'), the electrophotographic photoconductors (1 ') of Comparative Examples 1 and 3 in Table 1,
In comparison with (3 ′) and the electrophotographic photoreceptor (6 ′) of Comparative Example 6 in Table 2, E _1/2 which is an index of sensitivity is used.
Were small and clearly high sensitivity.

Example 20 An ITO substrate (a 1 mm-thick Pyrex glass substrate on which a 40.0 nm-thick indium tin oxide electrode layer was formed by sputtering) was used in place of the mirror-polished aluminum plate. In the same manner as in Example 14, a self-assembled polymer thin film formed into a salt with a monolayer of 3-aminopropylsiloxy group and bonded with a monoethyl maleate / methyl vinyl ether alternating copolymer (average molecular weight 210,000) was indium tin An ITO substrate on the oxide electrode layer was obtained. Preparation of the self-assembled polymer thin film was confirmed by contact angle measurement, XPS analysis, FTIR analysis and ellipsometry analysis, and the film thickness was 4.0 n.
m. Next, an electrophotographic photoreceptor (20) of the present invention was prepared in the same manner as in Example 1, and the charging light decay characteristics were determined. Table 4 shows the results.

COMPARATIVE EXAMPLE 14 A 10% ethanol solution of a maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight 210,000) was treated with the same IT as used in Example 20.
It is applied on an O substrate using a spin coater, and heated in an oven at 100 ° C. for 1 hour to form an IT having a coating film on the surface.
An O substrate was obtained. Ellipsometric analysis confirmed that a 0.4 μm film was formed on this ITO substrate. Then, Example 1 was repeated except that this ITO substrate was used.
An electrophotographic photoreceptor (14 ') was prepared in the same manner as described above, and the charging light decay characteristics thereof were determined. Table 4 shows the results.

Example 21 A 3-aminopropylsiloxy group monomolecular film and a salt were prepared in the same manner as in Example 14 except that a copper plate having a copper oxide on its surface was used instead of the mirror-polished aluminum plate. A copper plate having a self-assembled polymer thin film formed thereon and bonded with a maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight 210,000) on a copper oxide was obtained. Contact angle measurement, X
It was confirmed by PS analysis, FTIR analysis, and ellipsometry analysis, and the film thickness was 4.5 nm. Next, an electrophotographic photoreceptor (21) of the present invention was prepared in the same manner as in Example 1, and the charging light decay characteristics were determined. Table 4 shows the results.

Example 22 A Pyrex glass substrate having a gold electrode layer on a self-assembled film in the same manner as in Example 12 was immersed in a 5 mmol / liter ethanol solution of 16-mercaptohexadecanoic acid at room temperature for 24 hours. After that, the substrate was taken out of the solution and sufficiently washed with ethanol to obtain a Pyrex glass substrate having a self-assembled film formed on a gold electrode layer. Next, it was confirmed by ellipsometry analysis and XPS analysis that a self-assembled film made of 16-mercaptohexadecanoic acid having a thickness of 2.0 nm was formed on the gold electrode layer of the Pyrex glass substrate.

A pyrex glass substrate having a self-assembled film made of 16-mercaptohexadecanoic acid formed on a gold electrode layer was treated with polyallylamine (average molecular weight 10,000).
Was immersed in a methyl ethyl ketone solution having a repeating unit concentration of 25 mmol / liter at room temperature for 20 hours, pulled out of the solution, washed sufficiently with methyl ethyl ketone, and washed with
After drying under reduced pressure at 0 ° C. for 2 hours, a salt was formed with a monomolecular film of 16-mercaptohexadecanoic acid on the gold electrode layer to form a self-assembled polymer thin film in which polyallylamine (average molecular weight: 10,000) was bonded. . Preparation of the self-assembled polymer thin film was confirmed by contact angle measurement, XPS analysis, FTIR analysis, and ellipsometry analysis, and the film thickness was 4.0 nm.

Next, an electrophotographic photoreceptor (20) of the present invention was prepared in the same manner as in Example 1 except that a Pyrex glass substrate having the self-assembled polymer thin film formed on a gold electrode layer was used. Charging light attenuation characteristics were determined. Table 4 shows the results.

Comparative Example 15 A 10% concentration of an ethanol solution of polyallylamine (average molecular weight 10,000) was applied on a Pyrex substrate having the same gold electrode layer as used in Example 22 using a spin coater. Heat in an oven at 100 ° C for 1 hour,
A Pyrex glass substrate having a coating film on the gold electrode layer was obtained. From the ellipsometry analysis, it was confirmed that a 0.6 μm film was formed on the gold electrode layer of the Pyrex glass substrate. Next, an electrophotographic photoreceptor (15 ') was prepared in the same manner as in Example 1 except that this Pyrex glass substrate was used, and the charging light decay characteristics were determined. The results are shown in the table.

[0143]

[Table 4]

From the results shown in Table 4 above, the electrophotographic photosensitive member (20) of Example 20 is different from the electrophotographic photosensitive member (1) of Comparative Example 14.
4 ′) and the electrophotographic photoreceptor (7 ′) of Comparative Example 7 in Table 2, the value of E _1/2 as an index of sensitivity was small, and the sensitivity was clearly high.

Further, the electrophotographic photosensitive member of Example 21 (2
In 1), the value of E1 _{/ 2} as an index of sensitivity was smaller than that of the electrophotographic photoreceptor (8 ') of Comparative Example 8 in Table 2, and the sensitivity was clearly higher.

Further, the electrophotographic photosensitive member of Example 22 (2
2) shows that the value of E _1/2 as an index of sensitivity is smaller than that of the electrophotographic photosensitive member (15 ′) of Comparative Example 15 and the electrophotographic photosensitive member (9 ′) of Comparative Example 9 in Table 2. It was small and clearly sensitive.

Example 23 A monomolecular film of 3-aminopropylsiloxy group obtained in the same manner as in Example 14 was formed into a salt, and a maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight: 210,000) was bonded. Using an aluminum plate on which a self-assembled polymer thin film was formed,
For 6 hours to obtain an aluminum plate having a heat-treated self-assembled polymer thin film. Contact angle measurement,
According to XPS analysis, FTIR analysis, and ellipsometry analysis, the amino group of the monolayer of 3-aminopropylsiloxy group and the carboxyl group of maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight 210,000) were found on the surface of this aluminum plate. Reacted to form a self-assembled polymer thin film having a structure in which an imide bond was formed. The thickness of the self-assembled polymer thin film was 4.0 nm.

Next, the electrophotographic photosensitive member (2) of the present invention was prepared in the same manner as in Example 1 except that this aluminum plate was used.
3) was prepared, and its charging light decay characteristics were determined. Table 5 shows the results.

Example 24 A monomolecular film of 3-aminopropylsiloxy group, obtained in the same manner as in Example 19, was formed into a salt, and a maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight: 210,000) was bonded. Using an ITO substrate on which a self-assembled polymer thin film has been formed,
Heat treatment was performed for a time to obtain an ITO substrate having the heat-treated self-assembled polymer thin film. By contact angle measurement, XPS analysis, FTIR analysis and ellipsometry analysis,
On the surface of the ITO substrate, a 3-aminopropylsiloxy group monomolecular film amino group and maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight 21
It was confirmed that a self-assembled polymer thin film having a structure in which a carboxyl group of (10) reacted to form an imide bond was formed. The thickness of this self-assembled polymer thin film was 4.0.
nm.

Next, an electrophotographic photoreceptor (24) of the present invention was prepared in the same manner as in Example 1 except that the ITO substrate was used, and the charging light attenuation characteristics were determined. Table 5 shows the results.

Example 25 A Pyrex glass substrate having a gold electrode layer on a self-assembled film was used in the same manner as in Example 12, and this was placed in a 5 mmol / liter ethanol solution of 11-mercaptoundecanol for 24 hours at room temperature. After immersion, it was taken out of the solution and sufficiently washed with ethanol to obtain a Pyrex glass substrate having a self-assembled film formed on a gold electrode layer. Next, it was confirmed by ellipsometry analysis and XPS analysis that a self-assembled film made of 11-mercaptoundecanol having a thickness of 2.0 nm was formed on the gold electrode layer of the Pyrex glass substrate.

A pyrex glass substrate on which a self-assembled film made of 11-mercaptoundecanol was formed was used to prepare a polysiloxane oligomer (MKC silicate manufactured by Mitsubishi Chemical Corporation, average molecular weight: 550) having a repeating unit concentration of 10 mmol / liter. 12 at room temperature in methanol solution
After soaking for hours, withdraw from the solution, thoroughly wash with methyl ethyl ketone, and dry under reduced pressure at 30 ° C. for 2 hours.
A siloxane bond was formed with a monomolecular film of 11-mercaptoundecanol on the gold electrode layer to form a self-assembled polymer thin film in which a polysiloxane oligomer (average molecular weight: 550) was bonded. Preparation of the self-assembled polymer thin film was confirmed by contact angle measurement, XPS analysis, FTIR analysis, and ellipsometry analysis, and the film thickness was 4.0 nm.

Next, an electrophotographic photoreceptor (25) of the present invention was prepared in the same manner as in Example 1 except that the self-assembled polymer thin film used was a Pyrex glass substrate formed on a gold electrode layer. The charge light attenuation characteristics were determined. Table 5 shows the results.

Comparative Example 16 A methanol solution of a 10% polysiloxane oligomer (MKC silicate manufactured by Mitsubishi Chemical Corporation) was applied on a Pyrex substrate having the same gold electrode layer as that used in Example 25 using a spin coater. It was applied and heated in an oven at 100 ° C. for 1 hour to obtain a Pyrex glass substrate having a coating film on the electrode layer.
It was confirmed that a μm film was formed. Next, an electrophotographic photoreceptor (16 ') was prepared in the same manner as in Example 1 except that the Pyrex glass substrate was used, and the charging light attenuation characteristic was determined. Table 5 shows the results.

[0155]

[Table 5]

From the results shown in Table 5, the electrophotographic photoreceptor (23) of Example 23 was the same as the electrophotographic photoreceptors (1 ') and (3') of Comparative Example 1 and Comparative Example 3 in Table 1. As compared with the electrophotographic photoreceptor (12 ') of Comparative Example 12 in 3, the value of E1 _{/ 2} , which is an index of sensitivity, was small and clearly high.

Further, the electrophotographic photosensitive member of Example 24 (2
4) is compared with the electrophotographic photosensitive member (7 ') of Comparative Example 7 in Table 2 and the electrophotographic photosensitive member (14') of Comparative Example 14 in Table 4 to serve as an index of sensitivity E1 _//. The value of ₂ was small and clearly high sensitivity.

Further, the electrophotographic photosensitive member of Example 25 (2
5) shows that the value of E _1/2 as an index of sensitivity is smaller than that of the electrophotographic photosensitive member (16 ') of Comparative Example 16 and the electrophotographic photosensitive member (9') of Comparative Example 9 in Table 2. It was small and clearly sensitive.

Example 26 In the same manner as in Example 14, a monomolecular film of 3-aminopropylsiloxy group was formed into a salt, and a monoethyl maleate / methyl vinyl ether copolymer (average molecular weight: 210,000) was bonded. An aluminum plate having a self-assembled polymer thin film having a thickness of 4.0 nm was obtained.

Next, the x-type metal-free phthalocyanine (x-
H ₂ Pc) 0.35 g, dioxane 1.75 10% LEC M (manufactured by Sekisui Chemical Co., Ltd. vinyl chloride resin)
g, 11.0 g of a mixed solvent of methyl ethyl ketone / toluene (weight ratio: 3/1) and glass beads were charged into a mayonnaise bottle, and subjected to a dispersion treatment for 2 hours with a paint shaker to obtain a charge generating agent dispersion. Further, a charge transport agent solution was obtained in the same manner as in Example 1.

A charge generating layer was formed on the aluminum plate having the self-assembled polymer thin film obtained above in the same manner as in Example 1 except that the above-described charge generating agent dispersion was used. A charge transport layer was formed thereon, and an electrophotographic photoreceptor (26) was formed. Next, the corona charge was reduced to -6k.
V, the charging light decay characteristic was determined in the same manner as in Example 1 except that the static method was used. Table 6 shows the results.

Example 27 In the same manner as in Example 23, the amino group of the monomolecular film of 3-aminopropylsiloxy group reacted with the carboxyl group of maleic acid monoethyl ester / methyl vinyl ether alternating copolymer (average molecular weight 210,000). Thus, a self-assembled polymer thin film having a structure in which an imide bond was formed was prepared, and an aluminum plate having a 4.0 nm-thick self-assembled polymer thin film formed on the aluminum plate was obtained.

Next, a charge generating agent dispersion was obtained in the same manner as in Example 26, and a charge transporting agent solution was obtained in the same manner as in Example 1.

On the aluminum plate having the self-assembled polymer thin film obtained above, a charge generation layer was formed in the same manner as in Example 1 except that the above-described charge generation agent dispersion was used. A charge transport layer was formed thereon to form an electrophotographic photoreceptor (27). Next, the corona charge was reduced to -6k.
V, the charging light decay characteristic was determined in the same manner as in Example 1 except that the static method was used. Table 6 shows the results.

Comparative Example 17 An electrophotographic photosensitive member (17 ') was prepared in the same manner as in Example 26 except that a mirror-polished aluminum plate was used as it was without forming a self-assembled polymer thin film. Next, the charging light attenuation characteristic was obtained in the same manner as in Example 1 except that the corona charging was changed to -6 kV and a static method. Table 6 shows the results.

[0166]

[Table 6]

From the results shown in Table 6, the electrophotographic photosensitive members (26) and (27) of Examples 26 and 27 all had higher sensitivity than the electrophotographic photosensitive member (17 ') of Comparative Example 17. The value of E1 _{/ 2 as} an index was small, and the sensitivity was clearly high.

[0168]

The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having improved sensitivity.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram when a self-assembled film is formed on a substrate having a metal oxide on the surface.

FIG. 2 is a conceptual diagram when a self-assembled film is formed on a substrate having no metal oxide on the surface.

FIG. 3 is a conceptual diagram when a self-assembled polymer thin film is formed on an electrode layer using a polymer having a surface active group.

FIG. 4 is a conceptual diagram when a self-assembled polymer thin film is formed on an electrode layer using a compound for forming a self-assembled film having a functional group A at a terminal.

FIG. 5 is a conceptual diagram when a self-assembled polymer thin film is formed on an electrode layer using a compound for forming a self-assembled film having a polymerizable group C at a terminal.

[Explanation of symbols]

 Reference Signs List 1 optionally substituted alkyl group M metal atom 2 polymer main chain 3 optionally substituted alkylene group 4 electrode layer surface X surface-active group Y residue in X after bonding to electrode layer surface A functional group A 'Functional group which reacts with A' B Bonding unit formed by reaction between A and A 'C Polymerizable group 5 Polymer main chain formed by polymerization of C

Claims (21)

[Claims] 1. An electrophotographic photoconductor having an electrode layer and a photoconductor layer, wherein a self-assembled polymer thin film is formed on the photoconductor layer side of the electrode layer. 2. The electrophotographic photoreceptor according to claim 1, wherein the self-assembled polymer thin film is a film chemically bonded directly on the electrode layer. 3. A thin film comprising a polymer for forming a self-assembled polymer thin film having at least one surface active group selected from the group consisting of an alkoxysilyl group, a halosilyl group, a carboxyl group and a mercapto group. The electrophotographic photosensitive member according to claim 2, wherein 4. A self-assembled polymer comprising a polymer for forming a self-assembled polymer thin film, wherein the self-assembled polymer thin film contains at least one surface active group selected from the group consisting of an alkoxysilyl group, a halosilyl group and a carboxyl group. 3. The electrophotographic photoreceptor according to claim 2, wherein the electrophotographic photoreceptor is a thin film and is a thin film chemically bonded to an oxide of an electrode layer having an oxide of tin, indium, aluminum or copper on the surface. 5. The self-assembled polymer thin film is a film made of at least one polymer for forming a self-assembled polymer thin film selected from polymers containing a (meth) acrylic acid derivative unit. 4. The electrophotographic photosensitive member according to 4. 6. A self-assembled polymer thin film, the electrode layer being brought into contact with a solution of a polymer for forming a self-assembled polymer thin film to react the polymer for forming a self-assembled polymer thin film with the electrode layer. Separated from the solution, washed with a solution in which the polymer for forming a self-assembled polymer thin film is dissolved,
The electrophotographic photosensitive member according to any one of claims 1 to 5, which is obtained by removing an unreacted polymer for forming a self-assembled polymer thin film. 7. The self-assembled polymer thin film is formed by contacting the electrode layer with a solution of a polymer for forming a self-assembled polymer thin film containing an alkoxysilyl group and / or a halosilyl group. After reacting with the layer, the electrode layer is separated from the solution, washed with a solution in which the polymer for forming a self-assembled polymer thin film is dissolved, and the unreacted polymer for forming a self-assembled polymer thin film is removed. 6. It is obtained by processing.
The electrophotographic photosensitive member according to any one of the above. 8. The solution of a polymer for forming a self-assembled polymer thin film, wherein the solution is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ether compounds, ketone compounds and water. This is a solution in which a polymer for forming a self-assembled polymer thin film is dissolved in at least one kind of solvent so that the surface active group concentration in the polymer for forming a self-assembled polymer thin film is in a range of 0.001 mmol / L to 1 mol / L. The electrophotographic photosensitive member according to claim 6. 9. The self-assembled polymer thin film is formed on a self-assembled film comprising at least one compound for forming a self-assembled film selected from the group consisting of organic alkoxysilanes, organic halosilanes, carboxylic acids and thiols. 3. The electrophotographic photoreceptor according to claim 2, wherein the electrophotographic photoreceptor is a thin film formed by chemically bonding a polymer. 10. A self-assembled polymer thin film formed by forming a self-assembled film having a functional group at a terminal on an electrode layer and then reacting a polymer having a functional group which reacts with the functional group. The electrophotographic photosensitive member according to claim 9. 11. The self-assembled film is a self-assembled film made of at least one compound for forming a self-assembled film selected from the group consisting of organic alkoxysilanes, organic halosilanes and carboxylic acids, and The electrophotographic photoreceptor according to claim 9 or 10, wherein the electrophotographic photoreceptor is a self-assembled film chemically bonded to an oxide of an electrode layer having an oxide of tin, indium, aluminum or copper on the surface. 12. The self-assembled film is at least one compound for forming a self-assembled film selected from the group consisting of organic alkoxysilanes, organic halosilanes and carboxylic acids, and has 1 to 30 carbon atoms. It is a self-assembled film having an amino group at a terminal, comprising an amino group via an alkylene group, and a self-assembled polymer thin film,
The electrophotographic photoreceptor according to claim 10 or 11, wherein the electrophotographic photoreceptor is a thin film obtained by reacting a self-assembled film having an amino group at the terminal with a polymer having a carboxyl group to form an ammonium salt. 13. A self-assembled polymer thin film reacts a self-assembled film having an amino group at a terminal with a polymer having a maleic acid unit to form an ammonium salt, and then heat-treats to form an imide bond. The electrophotographic photoreceptor according to claim 12, which is a thin film obtained by the above method. 14. The self-assembled polymer thin film is reacted by bringing the electrode layer on which the self-assembled film having a functional group at the end is formed into contact with a solution of a polymer having a functional group that reacts with the functional group. The electrophotographic photosensitive material according to any one of claims 9 to 13, wherein the thin film is obtained by separating the electrode layer from the solution, washing the film with a solvent in which the polymer is dissolved, and removing unreacted polymer. body. 15. A solution of a polymer having a functional group which reacts with a functional group at a terminal of an electrode layer on which a self-assembled film having a functional group at a terminal is formed, comprises an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated 1 selected from the group consisting of hydrocarbons, alcohols, ether compounds, ketone compounds and water
The polymer is dissolved in at least one kind of solvent at a functional group concentration of 0.0
The electrophotographic photoreceptor according to claim 14, wherein the solution is a solution dissolved in a range of 01 mmol / liter to 1 mol / liter. 16. The self-assembled film, after the electrode layer is brought into contact with a solution of the compound for forming a self-assembled film to cause the compound for forming a self-assembled film to react with the electrode layer, the electrode layer is separated from the solution. 16. A self-assembled film obtained by washing with a solution in which the compound for forming a self-assembled film is dissolved to remove unreacted compounds for forming a self-assembled film. 2. The electrophotographic photoreceptor of claim 1. 17. The self-assembled film is formed by using an organic alkoxysilane and / or an organic halosilane as a compound for forming a self-assembled film, and contacting an electrode layer with a solution of the compound for forming a self-assembled film. After reacting the compound for forming an organized film with the electrode layer, the electrode layer is separated from the solution,
Washing with a solution in which the compound for forming a self-assembled film is dissolved,
The electrophotographic photosensitive member according to any one of claims 9 to 15, wherein the electrophotographic photosensitive member is a self-assembled film obtained by removing an unreacted compound for forming a self-assembled film and then performing a heat treatment. 18. A solution of the compound for forming a self-assembled film,
The concentration of the compound for forming a self-assembled film in one or more solvents selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, alcohols,
18. The electrophotographic photoreceptor according to claim 16, wherein the solution is a solution dissolved in a range of 01 mmol / liter to 5 mol / liter. 19. The film thickness of the self-assembled polymer thin film is 1
The electrophotographic photoreceptor according to any one of claims 1 to 18, which has a range of from 10 to 10 nm. 20. The electrophotographic photoreceptor according to claim 1, wherein the photoreceptor layer contains a phthalocyanine pigment as a photosensitive substance. 21. The electrophotographic photoconductor according to claim 20, wherein the phthalocyanine pigment is oxotitanium phthalocyanine.