JP4177340B2 - Self-assembled polymer thin film - Google Patents

Description

  The present invention relates to a self-assembled polymer thin film adsorbed on a metal oxide layer.

  Accordingly, it is possible to provide a novel self-assembled polymer thin film useful for surface treatment of electrodes used in electrophotographic photoreceptors such as photoconductors for copy machines and photoreceptors for laser printers.

  Conventionally, when an organic photoconductive material is used in an electrophotographic photosensitive member, a function-separated electrophotographic photosensitive member in which a charge generation layer and a charge transport layer are laminated on an electrode layer in order to improve the sensitivity and durability of the photosensitive member. The body is mainly used. In addition, a photoreceptor in which a single photosensitive layer having both charge generation and charge transport functions is formed on an electrode layer has been developed.

  Such an electrophotographic photoreceptor is basically composed of an electrode layer and a photosensitive layer, and an aluminum tube is generally used as the electrode layer in terms of processability, surface properties, price, weight, and the like. ing.

  However, due to defects on the surface of the aluminum, various defects such as non-uniform electrical characteristics, defects on the appearance of the coating film, black spots on the image in printing, whitening, and fogging have occurred (Non-patent Document 1). reference). Various devices have been devised to suppress these defects. That is, improvement in electrical characteristics of the photoreceptor, improvement in adhesion between the electrode layer and the photosensitive layer, improvement in coating property of the photosensitive layer, defect coating of the electrode layer, prevention of charge injection from the electrode layer, or interference fringes For the purpose of prevention, an undercoat layer has been provided between the electrode layer and the photosensitive layer.

  As the undercoat layer, a coating film coated with a silane coupling agent solution (see Patent Document 1), a coating film in which a silane coupling agent is dispersed in nylon (see Patent Document 2), and a chlorofluorocarbon solution of a silane coupling agent. There is an example in which a coating film using a silane coupling agent is used as disclosed in a treated coating film (see Patent Document 3) and the like. As the silane coupling agent used here, 3-glycidoxypropyltrimethoxysilane, -3-trimethoxysilylpropyl methacrylate, heptadecafluorodecyltrimethoxysilane, and Shin-Etsu Chemical Co., Ltd. silicon compound reagent catalog The silane coupling agents described in 1) are known.

JP 61-109064 A JP-A-5-107792 JP-A-1-114856 Masao Aizawa, Journal of Electrophotographic Society, 28, p186-195 (1989)

  However, these are all applied by brush coating, dip coating, flow coating, dip coating, roll coating, spin coating, spray coating, flow coating or bar coating with a solution or dispersion of a silane coupling agent. The film thickness obtained was as thick as 50 nm to 15 μm, and even if the sensitivity of the photoreceptor was not lowered, there was no effect of improving the sensitivity. In addition, some of them sacrifice the sensitivity in order to eliminate the above-mentioned defects, and none of them is satisfactory in order to obtain a highly sensitive photoreceptor.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a dense thin film that can improve the sensitivity of a photoreceptor and is uniform, strong, and controlled in film thickness.

  As a result of intensive studies to solve the above problems, the present inventors have found that an alkylene ammonium monoalkyl maleate / alkyl vinyl ether alternating copolymer, an alkylene maleimide / alkyl vinyl ether alternating copolymer, or an alkylene (meth) acrylate polymer is bonded via a siloxane bond. The self-assembled polymer thin film adsorbed on the metal oxide layer on the substrate is a homogeneous, strong, easy-to-control film thickness, dense thin film, and the effect of improving the sensitivity of electrophotographic and other photoreceptors As a result, the present invention has been completed.

That is, the present invention provides the following general formula (1) or (2)

(In the formulas (1) and (2), M is a metal atom, R ₁ and R ₂ are alkyl groups, R ₃ and R ₄ are methyl groups or hydrogen atoms, n is an integer of 1 to 12, and x is 10 or more. An integer, y is an integer of 2 or more, and z is an integer of 0 or more.) And a self-assembled polymer thin film layer adsorbed on the metal oxide layer. Is to provide.

  The self-assembled polymer thin film adsorbed on the metal oxide layer of the present invention is a dense thin film that is homogeneous, strong and easy to control the film thickness, and has a high effect of improving the sensitivity of the electrophotographic photoreceptor.

  A compound having an active group on the surface of the substrate (hereinafter, an active group on the surface of the substrate is referred to as a “surface active group”, and a compound having an active group on the surface of the substrate is referred to as a “surface active compound”) When immersed in the solution, the surface active groups in the surface active compound chemically react with the substrate surface in parallel with the spontaneous assembly of the surface active compound, and finally a dense chemisorbed single molecule on the substrate surface. Form a membrane layer (A. Ulman, “An Introduction to Ultrathin Organic Films from Langmuir-Blodgett to Self-Assembly”, Chapter 3, Academic Press, Inc., 19). For example, in the case of a substrate having a metal oxide layer on the surface, it is added to a solution of a surface active compound having an alkoxysilyl group, a halosilyl group, a carboxyl group, a hydroxamic acid group, a phosphonic acid group, a phosphate ester group, etc. as surface active groups. When immersed, a dense chemisorbed monolayer is formed on the substrate surface. The self-assembled film refers to a dense chemisorbed monomolecular film formed on the substrate surface in this way.

  Here, as the substrate having a metal oxide layer on the surface, for example, an oxide-based transparent substrate such as NESA (tin oxide), ITO (indium tin oxide), zinc oxide thin film, glass, tin, indium, aluminum, Examples thereof include a substrate made of a metal such as copper, chromium, titanium, iron, nickel, silicon, etc., and having a natural oxide film of these metals on the surface. In substrates made of these metals, it is known that natural oxide films of these metals are formed on the respective surfaces [W. A. Nevin, G.M. A. Chamberlain, IEEE Trans. Electron Devices, Vol. 40, p75 (1993), L.L. Wetzer, R.A. Isocovici, J. et al. Sagiv, Thin Solid Films, Vol. 99, p235 (1983) and J. Am. P. Folkers, C.I. B. Gorman, P.M. E. Laibinis, S.M. Buchholz, G.M. M.M. Whitesides, R.A. G. Nuzzo, Langmuir, Vol. 11, p813 (1995), etc.]. Further, these natural oxide films can be electrochemically anodized and the like to thicken the oxide layer. Among these substrates, a substrate made of ITO (indium tin oxide) and an aluminum substrate having an aluminum natural oxide film on the surface are preferable, and an aluminum substrate having an aluminum natural oxide film on the surface is particularly preferable.

  The self-assembled polymer thin film is, for example, 1) a polymer formed by forming a self-assembled film using a surface active compound having a functional group at the terminal and then reacting the functional group with one or more kinds of polymers. Thin film, 2) Polymer thin film formed in a self-organized manner using a polymer having a surface active group at the end of a side chain, 3) After forming a self-assembled film using a surface active compound having a polymerizable group at the end It is a polymer thin film formed by polymerizing a terminal polymerizable group.

  The self-assembled polymer thin film of the present invention comprises an alkylene ammonium monoalkyl maleate / alkyl vinyl ether alternating copolymer, an alkylene maleimide / alkyl vinyl ether alternating copolymer, or an alkylene (meth) acrylate polymer that is a metal oxide on a substrate via a siloxane bond. Is a self-assembled polymer thin film having a structure bonded to the following general formula (1), (2) or (3)

(In the formulas (1) to (3), M is a metal atom, R ₁ and R ₂ are alkyl groups, R ₃ and R ₄ are methyl groups or hydrogen atoms, n is an integer of 1 to 12, and x is 10 or more. An integer, y is an integer of 2 or more, and z is an integer of 0 or more.) A self-assembled polymer thin film having a structure represented by: Here, x is preferably an integer of 100 to 2000, y is preferably an integer of 5 to 50, and z is preferably an integer of 0 to 200. Among these, the self-assembled polymer thin film represented by the general formula (1) or (2) is preferable because the effect of improving the sensitivity of the electrophotographic photosensitive member is high.

  Self-assembled polymer thin film comprising a structure in which an alternating copolymer of alkylene ammonium monoalkyl maleate / alkyl vinyl ether is bonded to a metal oxide on a substrate through a siloxane bond [hereinafter referred to as “self-assembled polymer thin film (1) and For example, after a self-assembled film having an amino group as a functional group is formed on a substrate, a monoalkyl maleate / alkyl vinyl ether alternating copolymer is formed on the self-assembled film by salt formation in a solution. Can be formed.

  A self-assembled polymer thin film (hereinafter referred to as “self-assembled polymer thin film (2)”) having a structure in which an alkylene maleimide / alkyl vinyl ether alternating copolymer is bonded to a metal oxide on a substrate through a siloxane bond is: For example, after forming the self-assembled polymer thin film (1) in the same manner as described above, it can be formed by heat treatment and generating an imide bond by a cyclization reaction.

  On the other hand, a self-assembled polymer thin film having a structure in which an alkylene (meth) acrylate polymer is bonded to a metal oxide on a substrate via a siloxane bond [hereinafter referred to as “self-assembled polymer thin film (3)” is For example, the following general formula (4)

(Wherein R ₁ is an alkyl group, R ₃ and R ₄ are a methyl group or a hydrogen atom, Y ₁ , Y ₂ and Y ₃ are at least one halogen atom or an alkoxy group, and the other are a halogen atom, an alkoxy group or An alkyl group, n is an integer of 1 to 12, y is an integer of 2 or more, and z is an integer of 0 or more.) An alkylene having a silicon atom bonded to a halogen atom or an alkoxy group in the side chain (meta ) Self-organized using acrylate polymer. Here, y is preferably an integer of 5 to 50, and z is preferably an integer of 0 to 200.

  The alkylene (meth) acrylate polymer having a silicon atom bonded to a halogen atom or an alkoxy group in the side chain used here, for example, polymerizes an alkylene (meth) acrylate having a silicon atom bonded to a halogen atom or an alkoxy group alone. Alternatively, it can be obtained by copolymerizing this with an alkyl (meth) acrylate. Polymerization can be performed by irradiating the solution containing the monomer with light or heating using various light sources in the presence of a polymerization initiator. Polymerization by light irradiation is also performed in the absence of a photoinitiator. be able to. After termination of the polymerization reaction, the polymer is preferably isolated by reprecipitation. As the alkylene (meth) acrylate having a silicon atom bonded to a halogen atom or an alkoxy group, a commercially available compound such as 3-trimethoxysilylpropyl methacrylate described in the silicon compound reagent catalog of Shin-Etsu Chemical Co., Ltd. is used. It can also be used by appropriately synthesizing. For example, 11-triethoxysilylundecyl methacrylate is obtained by condensing 10-undecen-1-ol with methacrylate to convert it to methacrylate having a double bond at the terminal, and then in the presence of a transition metal catalyst, trichlorosilane and It can be obtained by reacting and then adding ethanol.

  When forming the self-assembled polymer thin film (1), for example, first, a self-assembled film having an amino group at the terminal is formed on the substrate by using a surface active silicon compound having an amino group at the terminal as a functional group. As the surface active silicon compound having an amino group at the end used at this time, a compound having an amino group at the end and having a silicon atom bonded to a halogen atom or an alkoxy group is preferable. For example, 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 6-aminohexyltrichlorosilane, 6-aminohexyltrimethoxysilane, 6-aminohexyltriethoxysilane, 11-aminoundecyltrichlorosilane, 11-amino Examples include, but are not limited to, undecyltrimethoxysilane and 11-aminoundecyltriethoxysilane.

  In order to form a self-assembled film having an amino group at the terminal using a surface active silicon compound having an amino group at the terminal, for example, the compound is dissolved in a solvent and the substrate is brought into contact with the solution. Then, the substrate is pulled up and washed with a solvent in which this compound is dissolved. Examples of the solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ether compounds, and the like.

  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-dioxane, 1,2 -Dimethoxyethane and the like, and a mixture thereof may be mentioned, but are not limited to these solvents, and any solvent having no hydroxyl group or carbonyl group can be used. However, in the case of using a surface active silicon compound having an amino group having a silicon atom bonded to an alkoxy group as a terminal, an alcohol compound such as methanol, ethanol or 2-propanol, a ketone compound such as acetone or 2-butanone, And a mixed solvent containing these can be used.

  The concentration is not particularly limited, but if the concentration is too low, it takes time for the reaction to proceed. If the concentration is too high, it is difficult to form a monomolecular film. Therefore, the range of 0.001 mmol / liter to 5 mol / liter is preferable. Moreover, when using the compound which has the silicon atom couple | bonded with the halogen atom, it is preferable to coexist amines, such as a pyridine, a triethylamine, a dimethylaniline, in order to capture | acquire the hydrogen halide byproduced.

  The treatment temperature for forming a self-assembled film by bringing the substrate into contact with the surface active silicon compound solution having an amino group at the end is not particularly limited, but in order to form a monomolecular film, it is −10 to 60 ° C. The range of 0-30 degreeC can be recommended especially. The processing time is not particularly limited, but a long time is required when the processing temperature is low, and the processing is completed in a short time when the processing temperature is high. In general, a range of 1 minute to 12 hours is preferable, and a range of 30 minutes to 6 hours is particularly recommended. It is also advantageous for forming a dense monomolecular film that a treatment for a short time, for example, 1 hour, is repeated twice or more, preferably 2 to 3 times.

  Furthermore, what is important for the formation of a monomolecular film is that the substrate is brought into contact with a solution of a surface active silicon compound having a terminal amino group at a predetermined concentration for a predetermined time, and then the substrate is separated from the solution and washed with a solvent. It is to remove the surface active silicon compound having an unreacted amino group at the terminal. At this time, as the solvent, the above-mentioned solvent capable of dissolving the surface active silicon compound having an amino group at the terminal can be used. Moreover, heat-treating the substrate after the treatment is effective for complete formation of the self-assembled film. Although this heat processing temperature does not have a restriction | limiting in particular, The range of 50-200 degreeC is preferable, and the range of 50-150 degreeC is especially preferable.

  After forming a self-assembled film having an amino group at the terminal as described above on the substrate, the substrate is immersed in a solution of alternating monoalkyl maleate / alkyl vinyl ether copolymer to form a salt. A maleate / alkyl vinyl ether alternating copolymer is organized on a self-assembled film to form a self-assembled polymer film (1).

  In this case, the monoalkyl maleate / alkyl vinyl ether alternating copolymer may be, for example, monoethyl maleate / methyl vinyl ether alternating copolymer, monohexyl maleate / methyl vinyl ether alternating copolymer, monoethyl maleate / hexyl vinyl ether alternating copolymer, monohexyl male copolymer. Examples include, but are not limited to, ate / hexyl vinyl ether alternating copolymers.

  Any solvent may be used as long as it dissolves the monoalkyl maleate / alkyl vinyl ether alternating copolymer. For example, methanol, ethanol, propanol, 2-propanol, acetone, 2-butanone, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, formamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide, hexamethylphosphoric triamide, etc. are mentioned, but a strong salt is formed. Therefore, a less polar solvent is preferred. The concentration is not particularly limited but is preferably in the range of 0.001 mmol (monomer unit) / liter to 5 mol (monomer unit) / liter. The treatment temperature is not particularly limited, but a range of 0 to 100 ° C is preferable, and a range of 0 to 60 ° C is particularly recommended. The treatment time is not particularly limited, but is preferably in the range of 30 minutes to 72 hours, and particularly preferably in the range of 2 hours to 24 hours in order to effect salt formation effectively.

  After the immersion in the solution, the substrate is separated from the solution, and the copolymer that is not salt-formed with the self-assembled film is sufficiently washed and removed with a solvent, followed by drying. The ultrathin film comprising the self-assembled polymer thin film (1) Is important for the formation of At this time, the solvent may be any solvent that dissolves the copolymer.

  Moreover, when the substrate on which the self-assembled polymer thin film (1) is formed is heat-treated, an imide bond is generated by a cyclization reaction, and the self-assembled polymer thin film (2) can be obtained. The temperature of the heat treatment is preferably in the range of 100 to 200 ° C., and the time is preferably 2 to 24 hours. The heat treatment can also be performed in a reduced pressure.

  The formation of the self-assembled polymer thin film (3) on the substrate using the alkylene (meth) acrylate polymer having a silicon atom bonded to the halogen atom or the alkoxy group represented by the general formula (4) is basically performed. Solvent to be used, concentration of solution, treatment time, treatment temperature, cleaning of substrate after treatment, heat treatment, etc., etc., according to the method for forming a self-assembled film with a surface active silicon compound having an amino group at its terminal Can do. That is, it can be formed by dissolving an alkylene (meth) acrylate polymer having a silicon atom bonded to a halogen atom or an alkoxy group represented by the general formula (4) in a solvent, and contacting the substrate with the solution. These are the same as in the case of forming a self-assembled film having an amino group at the end. The concentration is not particularly limited, but a range of 0.001 mmol (monomer unit) / liter to 5 mol (monomer unit) / liter is preferable. When using an alkylene (meth) acrylate polymer having a silicon atom bonded to a halogen atom, it is preferable to coexist an amine such as pyridine, triethylamine or dimethylaniline for the purpose of capturing by-produced hydrogen halide.

  The treatment temperature is not particularly limited, but is preferably in the range of −10 to 150 ° C., and in particular, the range of 0 to 100 ° C. can be recommended. The processing time is not particularly limited, but a long time is required when the processing temperature is low, and the processing is completed in a short time when the processing temperature is high. In general, the range of 30 minutes to 48 hours is preferable, and the range of 1 to 24 hours is particularly recommended. It is also advantageous for forming an ultrathin film that a treatment for a short time, for example, 3 hours, is repeated twice or more, preferably 2 to 3 times. Furthermore, what is important for the formation of a self-assembled polymer thin film is to remove the unreacted polymer by contacting the substrate with a polymer solution of a predetermined concentration for a predetermined time, then separating the substrate from the solution and washing with a solvent. There is to do. At this time, as the solvent, the same solvent as in the formation of the self-assembled film (1) can be used. Moreover, heat-treating the substrate after the treatment is effective for complete formation of the self-assembled polymer thin film. Although this heat processing temperature does not have a restriction | limiting in particular, The range of 50-200 degreeC is preferable, and the range of 50-150 degreeC is especially preferable.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

(Example 1)
A 5 mmol / liter ethanol solution of 3-aminopropyltriethoxysilane was prepared, and the aluminum substrate was immersed in this solution at room temperature for 1 hour, then taken out, thoroughly washed with ethanol, and placed in a constant temperature bath at 120 ° C. Heated for 1 hour. After cooling to room temperature, the self-assembled film formed on the aluminum substrate is obtained again by repeating immersion, washing and heating in a 5 mmol / liter ethanol solution of 3-aminopropyltriethoxysilane under the same conditions. This was analyzed by contact angle measurement, X-ray photoelectron spectroscopy (XPS) and ellipsometry analysis, and a film thickness of 1.4 nm in which a propyleneamino group was bonded to an aluminum oxide layer on an aluminum substrate via a siloxane bond. It was confirmed that a self-assembled film was formed.

  Next, the aluminum substrate on which the self-assembled film was formed was immersed in a 25 mmol (repeat unit) / liter 2-butanone solution of a monoethyl maleate / methyl vinyl ether alternating copolymer (molecular weight 210,000) at room temperature for 20 hours. Then, it was taken out, sufficiently washed with 2-butanone, and dried under reduced pressure at 25 to 30 ° C. for 2 hours to obtain a self-assembled polymer thin film formed on an aluminum substrate.

The obtained self-assembled polymer thin film was analyzed by contact angle measurement, FTIR measurement (Fourier transform infrared absorption spectrum measurement), XPS analysis and ellipsometry analysis.
(A) Contact angle with contact water (2 μl) (average of 6 points): 61 ± 3 °
(B) FTIR measurement (ATR method) Characteristic absorption: 1560 cm −1 (νC═O, carboxylate)
(C) XPS analysis content ratio (takeoff angle: 90 °): C1s, 45.8%; N1s, 1.3%; O1s, 37.0%; Si2p, 1.5%; Al2p, 14.4% (D) Ellipsometry analysis film thickness (average of 36 locations): 3.0 ± 0.1 nm

  From these results, a thin film of monoethyl maleate / methyl vinyl ether alternating copolymer (molecular weight 210,000) formed by salt formation with a self-assembled film in which propyleneamino groups are bonded to an aluminum oxide layer on an aluminum substrate via a siloxane bond. It was confirmed that a self-assembled polymer thin film was laminated.

(Example 2)
The aluminum substrate on which the self-assembled polymer thin film obtained in the same manner as in Example 1 was formed was heated under reduced pressure at 150 ° C. for 6 hours, so that the propylene maleimide / alkyl vinyl ether alternating copolymer was formed on the substrate via the siloxane bond. A self-assembled polymer thin film having a structure bonded to a metal oxide was obtained.

The resulting self-assembled polymer thin film was analyzed by contact angle measurement, FTIR measurement, XPS analysis and ellipsometry analysis.
(A) Contact angle measurement Contact angle with water (2 μl) (average of 6 points): 67 ± 2 ° (B) FTIR measurement (ATR method)
Characteristic absorption: 1704 cm −1 (νC═O, imide bond)
(C) XPS analysis-containing element ratio (takeoff angle: 90 °): C1s, 52.5%; N1s, 1.2%; O1s, 34.4%; Si2p, 1.2%; Al2p, 10.6% Bond energy: 403.6 eV (N1s, imide bond)
(D) Ellipsometry analysis film thickness (average of 36 locations): 3.2 ± 0.2 nm

  From these results, the amino group of the self-assembled film in which the propyleneamino group is bonded to the aluminum oxide layer on the aluminum substrate via the siloxane bond, and the carboxy of the monoethyl maleate / methyl vinyl ether alternating copolymer (molecular weight 210,000). It was confirmed that a self-assembled polymer thin film having a structure in which an imide bond was formed by the reaction of the group was formed.

(Reference Example 1)
A thin film of monoethyl maleate / methyl vinyl ether alternating copolymer (molecular weight 210,000) formed by salt formation with a self-assembled film in which propyleneamino groups are bonded via a siloxane bond formed on the aluminum substrate in Example 1 is laminated. An electrophotographic photosensitive member (1) was obtained on the self-assembled polymer thin film, and its charged light attenuation characteristics were obtained. The results are shown in Table 1 .

(Reference Example 2)
The amino group of the self-assembled film formed on the aluminum substrate in Example 2 in which the propylene amino group is bonded via a siloxane bond reacts with the carboxy group of the monoethyl maleate / methyl vinyl ether alternating copolymer (molecular weight 210,000). Then, an electrophotographic photoreceptor (2) was obtained in the same manner as in Reference Example 1 on a self-assembled polymer thin film having a structure in which an imide bond was formed, and the charged light attenuation characteristics were obtained. The results are shown in Table 1 .

(Comparative Example 1)
An aluminum substrate having a self-assembled polymer thin film in which a propyleneamino group and a monoethyl maleate / methyl vinyl ether alternating copolymer (molecular weight 210,000) thin film are laminated with a self-assembled film in which propyleneamino groups are bonded via a siloxane bond Instead, an electrophotographic photoreceptor (1 ′) was obtained in the same manner as in Reference Example 1 except that the mirror-polished aluminum substrate was used as it was, and the charged light attenuation characteristics were obtained. The results are shown in Table 1 .

From the results of Table 1 above, the electrophotographic photoreceptors (1) to ( 2 ) of Reference Examples 1 and 2 are E1 / 2 as an index of sensitivity as compared to the electrophotographic photoreceptor (1 ′) of Comparative Example 1. The values of all were small and clearly high sensitivity.

Claims (3)

The following general formula (1) or (2) composed of a metal oxide layer and a self-assembled polymer thin film layer adsorbed on the metal oxide layer

(In the formulas (1) and (2), M is a metal atom, R ₁ and R ₂ are alkyl groups, R ₃ and R ₄ are methyl groups or hydrogen atoms, n is an integer of 1 to 12, and x is 10 or more. An integer, y is an integer of 2 or more, and z is an integer of 0 or more) . An electrophotographic photoreceptor using the laminate according to claim 1 . (I) A substrate having a metal oxide layer on the surface is chemically adsorbed with a surface active silicon compound having a surface active group and an amino group that can be adsorbed on the metal oxide layer on the surface of the substrate, and has an amino group at the end. Adsorbing the self-assembled film on the metal oxide layer;
(Ii) contacting the metal oxide layer adsorbed by the self-assembled film having an amino group at its end with an alternating copolymer composed of a monoalkyl maleate and an alkyl vinyl ether, thereby bringing the amino group in the self-assembled film into contact; And the carboxy group in the alternating copolymer is formed, and then the self-assembled film and the non-salt-formed copolymer are washed away with a solvent, thereby self-assembled adsorbed on the metal oxide layer. Forming a film as a self-assembled polymer thin film,
The method for manufacturing a laminate according to claim 1, wherein the performed in this order.