JP5445886B2 - Method for forming a modified solid surface and modified solid surface - Google Patents

Description

The present invention relates to a method for forming a modified solid surface ( solid surface modification method ) and a solid surface modified thereby.

A method of modifying a solid surface by fixing a molecular layer having a predetermined function on the solid surface has been conventionally performed. Recently, as a technique for realizing a dense and highly oriented film structure, a self-assembled monolayer (SAM) has attracted attention.
Self-assembled monolayer film is an adsorptive compound having an adsorptive group (eg, mercapto group) having adsorptivity to a solid surface (eg, noble metal) and a chain hydrophobic group (eg, long-chain alkyl group) (Eg, long chain alkanethiol). In other words, the adsorptive compound has a molecular structure in which an adsorptive group is provided at one end of a chain hydrophobic group.
When the solid surface is immersed in the solution of the adsorptive compound, the molecule of the adsorbing compound is adsorbed on the solid surface, and then the molecule of the adsorbing compound is caused by the intermolecular interaction (van der Waals force) of the chain hydrophobic group. Self-assembled, molecules rise at a certain angle with respect to the solid surface, and a monomolecular film oriented in a certain direction is formed.

The other end of the chain hydrophobic group is usually substituted with a functional group. Depending on the type of the functional group, the solid surface can be arbitrarily modified. As types of functional groups, reactive groups, hydrophilic / hydrophobic groups, electrochemically active groups, photochemically active groups, catalytically active groups, fluorescently active groups and sensor active groups have been proposed.
Patent Document 1 discloses that two types of adsorptive compounds having different functional groups are used in combination (Claim 7). As examples of the two kinds of adsorbing compounds, a long-chain alkanethiol having a terminal carboxyl group and a long-chain alkanethiol having a terminal amino group are described (page 6).
Patent Documents 2 and 3 describe an energy donor (adsorptive) compound having an organic residue that absorbs light as a functional group, and an energy acceptor (adsorptive) that absorbs light having an absorption wavelength region overlapping with excitation light of the compound. ) Discloses an invention using a compound in combination (claims 1 and 3 of claim 1). In the inventions described in Patent Documents 2 and 3, an energy donor compound and an energy acceptor compound are allowed to coexist in a self-assembled monolayer film so as to collect and move light energy like an antenna. (Paragraph numbers 0013 and 0018 of Patent Document 2 and FIG. 1 of Patent Document 3).

Japanese National Patent Publication No. 10-507126 (claims 7 and 6) JP 2001-303022 (Claim 1 and paragraph numbers 0013 and 0018) JP 2002-025635 A (Claim 1 and FIG. 1)

An object of the present invention is to form a self-assembled monolayer film having a functional group from a compound that is chemically stable and easy to store.
Another object of the present invention is to provide a self-assembled monolayer film in which the types and ratios of the adsorptive group and the functional group can be arbitrarily determined as necessary.
Furthermore, the object of the present invention is also to produce a self-assembled monolayer film having a stable film structure.

The present invention relates to an adsorbent compound having an adsorptive group having an adsorptivity to a solid surface and a chain hydrophobic group having 8 to 100 carbon atoms, a functional group and 8 to 8 carbon atoms in a solvent. The adsorbent compound is obtained by immersing the solid surface in a solution in which a non-adsorbable compound having 100 chain hydrophobic groups and having substantially no adsorptivity to the solid surface is dissolved . A self-assembled monolayer consisting of an adsorbing compound and a non-adsorbing compound is formed on the solid surface by an intermolecular interaction between the chain hydrophobic group of the non-adsorbing compound and the chain hydrophobic group of the non-adsorbing compound, A method of forming a solid surface modified by a functional group of a non-adsorbing compound is provided.

The present invention can be implemented in the following aspects 2 to 6.
2. The solid surface is made of metal.
3. The adsorptive group to the solid surface contains a sulfur atom.
4). The chain hydrophobic groups of the adsorptive compound and the non-adsorptive compound are both chain alkyl groups.
5. The non-adsorbing compound has a plurality of chain hydrophobic groups.
6). The functional group is a hydrophilic group.

The present invention also relates to a solid surface modified by a self-assembled monolayer film, wherein the self-assembled monolayer film has an adsorptive group having adsorptivity to the solid surface and the number of carbon atoms of 8 to 100. Non-adsorptive compound having a linear hydrophobic group and a functional group and a linear hydrophobic group having 8 to 100 carbon atoms and having substantially no adsorptivity to a solid surface The self-assembled monolayer is formed by the intermolecular interaction between the chain hydrophobic group of the adsorptive compound and the chain hydrophobic group of the non-adsorptive compound, and the functional group of the non-adsorptive compound. Also provided is a modified solid surface characterized in that the solid surface is modified.

As a result of the inventor's research, it is advantageous to use a self-assembled monolayer film by using an adsorbing compound and a non-adsorbing compound in combination, rather than using the two types of adsorbing compounds proposed previously. It was found that can be formed.
According to the present invention, when an adsorbing compound having the above-described definition and a non-adsorbing compound are used in combination, the chain hydrophobic group of the adsorbing compound and the non-adsorbing compound have no adsorbing group. A self-assembled monolayer film can be formed by intermolecular interaction (van der Waals force) with the chain hydrophobic group of the non-adsorbing compound.

The adsorptive compound used in the conventional self-assembled monolayer film usually has two types of reactive groups, ie, an adsorptive group and a functional group. In this case, the adsorptive group and the functional group may react, and the adsorbent compound is chemically unstable and often difficult to store.
According to the present invention, it is possible to impart only an adsorptive group as a reactive group to an adsorbent compound and impart only a functional group as a reactive group to a non-adsorbable compound. In this case, if the adsorptive compound and the non-adsorptive compound are stored separately, there is no possibility that the adsorptive group reacts with the functional group. Therefore, according to the present invention, a self-assembled monolayer film having a functional group can be formed from a chemically stable and easy-to-store compound.

In the present invention, the adsorptive compound having an adsorptive group and the non-adsorptive compound having a functional group are used in combination. Therefore, the type and ratio of the adsorptive group and the functional group are required in the self-assembled monolayer film. It can be arbitrarily determined according to.
Furthermore, in the method of the present invention, before the self-assembled monolayer film is formed on the solid surface, a step of dissolving the adsorbing compound and the non-adsorbing compound in a solvent is performed in advance. According to the inventor's research, a self-assembled monolayer film having a stable film structure can be produced by previously mixing an adsorbing compound and a non-adsorbing compound.

FIG. 1 is a conceptual diagram for explaining a normal self-assembled monolayer film.
As shown in FIG. 1, a normal self-assembled monolayer film is composed of an adsorptive compound having an adsorptive group (2), a chain-like hydrophobic group (3), and a functional group (5), and has a solid surface (1 ). The self-assembled monolayer film is self-assembled by intermolecular interaction (van der Waals force) of the chain-like hydrophobic group (3), and is oriented in a certain direction.

FIG. 2 is a conceptual diagram for explaining a conventional self-assembled monolayer film using two types of adsorptive compounds in combination.
As shown in FIG. 2, the conventional self-assembled monolayer film using two kinds of adsorbing compounds has a first group having an adsorbing group (2), a chain-like hydrophobic group (3), and a functional group (5). 1 adsorbing compound and a second adsorbing compound having an adsorbing group (2), a chain-like hydrophobic group (3) and another functional group (6), adsorbed on the solid surface (1) Yes. In the conventional self-assembled monolayer film, two types of adsorptive compounds are used in combination for the purpose of using two types of functional groups (5, 6) in combination.

FIG. 3 is a conceptual diagram for explaining a self-assembled monolayer film according to the present invention.
As shown in FIG. 3, the self-assembled monolayer film according to the present invention comprises an adsorptive compound having an adsorptive group (2) and a chain hydrophobic group (3), a chain hydrophobic group (4) and a functional group. It consists of a non-adsorbing compound having a group (5) and is adsorbed on the solid surface (1). By adopting such a configuration, the above-described effects of the present invention can be obtained.

FIG. 4 is a schematic diagram showing a basic aspect of the present invention.
The self-assembled monolayer film shown in FIG. 4 is composed of an adsorptive compound (octadecanethiol) having an adsorptive group (2) composed of a mercapto group and a chain hydrophobic group (3) composed of an octadecyl group, and a heptadecyl group. It is made of a non-adsorbing compound (stearic acid) having a functional group (5) composed of a chain hydrophobic group (4) and a carboxyl group, and is adsorbed on a solid surface (1) composed of gold (Au).

FIG. 5 is a schematic diagram showing a preferred embodiment of the present invention.
Although the orientation is omitted in the embodiment shown in FIG. 5, the actual self-assembled monolayer film is oriented in a certain direction as in FIGS. 3 and 4.
The self-assembled monolayer film shown in FIG. 5 is composed of an adsorptive compound (octadecanethiol) having an adsorptive group (2) composed of a mercapto group and a chain hydrophobic group (3) composed of an octadecyl group, and a heptadecyl group. Non-adsorbing compound (stearic acid 2,3,5) having a linear hydrophobic group (4) and a functional group (5) comprising 2,3,5,6-tetra (pentaoxyethylene) -1,4-sorbitan , 6-tetra (pentaoxyethylene) -1,4-sorbitan) and adsorbed on the solid surface (1) made of gold (Au).
As in the embodiment shown in FIG. 5, the non-adsorbing compound preferably has a plurality of chain hydrophobic groups (4). When the non-adsorbing compound has a plurality of chain hydrophobic groups, some of the chain hydrophobic groups may not participate in the formation of the self-assembled monolayer film.

[Adsorbent compound]
The adsorptive compound has an adsorptive group and a linear hydrophobic group having 8 to 100 carbon atoms. The adsorptive compound can be defined by the following formula (I).
(I) (Ad-) _m (-LR) _n
In the formula (I), Ad is an adsorptive group, L is a chain hydrophobic group having 8 to 100 carbon atoms, R is a hydrogen atom or a functional group, and m and n are each independently It is an integer of 1 or more.

The adsorptive group is determined according to the type of substance constituting the solid surface. The bond between the adsorptive group and the substance constituting the solid surface is preferably an ionic bond or a coordinate bond.
That the adsorptive group has adsorptivity is a relative definition in relation to a non-adsorbing compound. Depending on the use of the solid surface, it is often sufficient that a small amount of the adsorptive compound can be adsorbed on the solid surface. The adsorbing compound only needs to be adsorbed on the solid surface more than the non-adsorbing compound when only one compound is treated under the same conditions. When treated under the same conditions, the adsorptive compound can preferably be adsorbed on the solid surface in an amount (molar ratio) that is twice or more that of the non-adsorbable compound, and more preferably 5 times or more can be adsorbed on the solid surface. Preferably, it is most preferable that 10 times or more amount can be adsorbed on the solid surface.

When the solid surface is made of a metal or a semiconductor compound, the adsorptive group is preferably a group containing a sulfur atom, a selenium atom or a tellurium atom, a cyano group (NC-) or a silyl group (H ₃ Si-). Examples of the group containing a sulfur atom include a mercapto group (HS-), an alkylthio group (R-S-, R is an alkyl group), an alkylpolythio group (R (-S-) _p , R is an alkyl group, p is An integer of 2 or more) and a thioisocyanato group (NCS-). Examples of the group containing selenium atom or tellurium atom are those in which the sulfur atom (S) in the example of group containing sulfur atom is replaced with selenium atom (Se) or tellurium atom (Te).

When the solid surface is made of an oxide, the adsorptive group includes a carboxyl group (HOOC-), a phosphono group ((HO) ₂ (O =) P-), and a phosphonooxy group ((HO) ₂ (O =) PO. -) And a substituted silyl group (X ₃ Si—, X is a halogen atom, an amino group or an alkoxy group) are preferred.
When the solid surface is made of silicone, the adsorptive group is preferably an alkenyl group, alkynyl group, hydroxy group or formyl group.
When the solid surface is made of silicon nitride, the adsorptive group is preferably a halogenated alkyl group (eg, alkyl bromide group).
When the solid surface is made of carbon (eg, diamond), the adsorptive group is preferably an alkenyl group, alkynyl group, diazo group, or halogenated alkyl group (eg, alkyl iodide group).
The adsorptive compound preferably has one adsorptive group per molecule.
Particularly preferred combinations of adsorbing groups and solid surfaces are shown in Table 1 below.

Table 1 ─────────────────────────────────────────
Adsorbable group Solid surface ─────────────────────────────────────────
Base metals containing sulfur atoms (eg, Au, Ag, Cu, Pt, Pd, Hg, Fe), semiconductors
Compound (eg, GaAs, InP)
────────────────────────────────────────
Selenium atom or metal (eg, Au, Ag)
Groups containing tellurium atoms─────────────────────────────────────────
Cyano group Metal (eg, Pt, Pd, Au, Ag)
────────────────────────────────────────
Silyl group metal (eg, Au)
────────────────────────────────────────
Carboxyl group oxide (eg, Al ₂ O ₃ , AgO, CuO, Zr / Al ₂ O ₃ ,
Oxide _-NH 2)
────────────────────────────────────────
Phosphono group, phosphine oxide (eg, ZrO ₂ , TiO ₂ , Al ₂ O ₃ , Ta ₂ O ₅ ,
Phonoxy group Zr / Al ₂ O ₃ )
────────────────────────────────────────

Table 1 (continued)
────────────────────────────────────────
Adsorbable group Solid surface ─────────────────────────────────────────
Substituted silyl group oxide (eg, glass, mica, SiO ₂ , SnO ₂ , GeO ₂ ,
_{ZrO 2, TiO 2, Al 2} O 3, ITO, SUS, PZT)
────────────────────────────────────────
Alkenyl groups, hydrogen-terminated silicones, halogenated silicone rukinyl groups, hydroxy groups, formyl groups ────────────────────────────── ───────────
Alkyl bromide group Silicon nitride ────────────────────────────────────────
Alkenyl group, a hydrogen-terminated diamond rukinyl group, diazo group, alkyl iodide group ─────────────────────────────── ─────────

The chain hydrophobic group has a chain structure having 8 to 100 carbon atoms. More preferably, the chain structure has 10 to 50 carbon atoms.
In addition to the chain structure, it may have a branch or a substituent (eg, halogen atom, aryl group). Further, an arylene group or a hetero atom (eg, oxygen atom, sulfur atom) may intervene in the chain structure. Even when an arylene group or a hetero atom is present in the chain structure, it is preferable that a region consisting of only a chain structure having 8 or more carbon atoms exists.
The chain structure portion preferably has no substituent. The chain structure is preferably a saturated hydrocarbon group (alkylene group).
The adsorptive compound preferably has one chain hydrophobic group per molecule.

  The adsorptive compound may have a functional group. Details of the functional group are the same as those of the non-adsorbing compound (described later). The functional group of the adsorptive compound may be different from the functional group of the non-adsorbing compound. It is preferable that the adsorptive compound does not have a functional group.

A particularly preferred adsorptive compound can be defined by the following formula (II).
_{(II) Ad- (CH 2)} q -H
In the formula (II), Ad is an adsorptive group, and q is an integer of 8 to 100.

[Non-adsorbing compounds]
The non-adsorbing compound has a functional group and a chain hydrophobic group having 8 to 100 carbon atoms.
Further, the non-adsorbing compound has substantially no adsorptivity to the solid surface. Non-adsorbing is a relative definition in relation to adsorbing compounds. The non-adsorbing compound should be less adsorbed on the solid surface than the adsorbing compound when only one compound is treated under the same conditions. When the non-adsorbing compound is treated under the same conditions, the amount adsorbed on the solid surface (molar ratio) is preferably 1/2 or less, more preferably 1/5 or less of the adsorbing compound, Most preferably, it is 1/10 or less.

The non-adsorbing compound can be defined by the following formula (III).
(III) (HL) _r (-Fu) _s
In the formula (III), L is a chain hydrophobic group having 8 to 100 carbon atoms, Fu is a functional group, and r and s are each independently an integer of 1 or more.

The chain hydrophobic group has a chain structure having 8 to 100 carbon atoms. The definition of the chain-like hydrophobic group of the non-adsorbing compound is the same as the definition of the hydrophobic group of the adsorbing compound.
The non-adsorbing compound preferably has a plurality of chain hydrophobic groups per molecule.

The functional group can be determined depending on the application of the self-assembled monolayer film. Functional groups similar to those of the conventionally known self-assembled monolayer films can be employed in the present invention.
Examples of functional groups are reactive groups (eg, carboxyl groups, amino groups, phosphoric acid groups, sulfonic acid groups, phosphonic acid groups, mercapto groups), hydrophilic groups (eg, carboxyl groups, hydroxyl groups, polyoxyalkylene groups). ), Hydrophobic group (eg, alkyl group), electrochemically active group (eg, ferrocene, quinone, Ru (NH ₄ ) ₃ ²⁺ ), photochemically active group (eg, porphyrin, Ru (bipyridine) ₃ ²⁺ ), Catalytically active groups (eg, metalloporphyrins), fluorescently active groups (eg, ferricenylnitrophenylethylene), sensor active groups (eg, cyclodextrins), structural isomerization groups (eg, azobenzene, spiropyran) and mediator groups (eg, , Ferrocene, pyridine).
The non-adsorbing compound preferably has one functional group per molecule.

A particularly preferred non-adsorbing compound can be defined by the following formula (IV).
_{(IV) (H- (CH 2} ) t -) u Fu
In the formula (IV), t is an integer of 8 to 100, u is an integer of 2 or more, and Fu is a functional group.

[Solid surface]
The present invention can be used to modify various solid surfaces in the same manner as conventional self-assembled monolayers.
Examples of solid surfaces are metals (eg, Au, Ag, Cu, Pt, Pd, Hg, Fe), semiconductor compounds (eg, GaAs, InP), oxides (eg, Al ₂ O ₃ , AgO, CuO, Zr). / _Al 2 _{O 3,} oxides _{-NH 2, ZrO 2, TiO 2} , Ta 2 O 5, glass, _{mica, SiO 2, SnO 2, GeO} 2, ITO, SUS, PZT), silicone, silicon nitride (e.g., Si ₃ N ₄ , SiN _x ) and carbon (eg, diamond).
The metal is not particularly limited, but the present invention can be applied particularly advantageously to noble metals that are difficult to modify. The terminal of silicone may be a hydrogen atom or a halogen atom.
There is no particular limitation on the shape of the product provided with the solid surface. For example, a layer (eg, a metal layer) made of a material (solid) different from the substrate is provided on a substrate (eg, a glass plate), and the present invention can be carried out on the solid layer.

[Production by solution method]
(Preparation of solution)
In the method of the present invention, a solution is prepared by dissolving an adsorbing compound and a non-adsorbing compound in a solvent.
As the solvent, water or an organic solvent is used. The solvent is preferably an organic solvent, more preferably an alcohol, ester, ketone or ether, and most preferably an alcohol. More preferably, the alcohol is a monohydric alcohol having 1 to 6 carbon atoms.
The concentration of the adsorbing compound and the non-adsorbing compound in the solution is preferably 0.002 to 20 mM, more preferably 0.005 to 10 mM, most preferably 0.01 to 5 mM. preferable.

(Immersion treatment)
In the method of the present invention, a solid surface is immersed in the obtained solution, whereby a self-assembled monolayer film composed of an adsorbing compound and a non-adsorbing compound is formed on the solid surface.
The immersion time is preferably 1 minute to 1 week, more preferably 10 minutes to 1 day, and most preferably 30 minutes to 10 hours.
The immersion temperature is preferably 0 to 100 ° C, more preferably 5 to 50 ° C, and most preferably 10 to 30 ° C.

[Production by vapor phase method]
The present invention can also be carried out by a gas phase method.
In the combination of a highly volatile adsorbing compound and a non-adsorbing compound, a self-assembled monolayer film can be formed simply by placing a solid surface under the vapor of each compound. Specifically, a gas phase method can be carried out by using a mixed vapor obtained by vaporizing a mixed solution of an adsorbing compound and a non-adsorbing compound mixed in a solvent. Alternatively, the vapor phase method may be carried out by mixing the vapor of the adsorbing compound and the vapor of the non-adsorbing compound prepared separately.
When the vapor phase method is performed in a vacuum chamber, the self-assembled monolayer film can be easily controlled to the conditions required depending on the application.

[Example 1]
A solution was prepared by dissolving 1.5 mM octadecanethiol (adsorbing compound) and 1.5 mM poly (about 20) oxyethylene sorbitan (non-adsorbing compound) in ethanol at room temperature.
A glass plate having a gold surface (water contact angle: 25 °) was immersed in the solution obtained at room temperature for 1 hour. The contact angle of water with the gold surface after immersion was measured and found to be 88 °.
Furthermore, after the gold surface was washed with ethanol, the contact angle of water with the gold surface after immersion was measured and found to be 88 °.

[Example 2]
At room temperature, a solution was prepared by dissolving 2.7 mM octadecanthiol (adsorbing compound) and 0.3 mM poly (about 20) oxyethylene sorbitan (non-adsorbing compound) in ethanol.
A glass plate having a gold surface (water contact angle: 25 °) was immersed in the solution obtained at room temperature for 1 hour. When the contact angle of water with the gold surface after immersion was measured, it was 112 °.
Furthermore, after the gold surface was washed with ethanol, the contact angle of water on the gold surface after immersion was measured and found to be 108 °.

[Comparative Example 1]
A solution was prepared by dissolving 3 mM octadecanethiol (adsorbing compound) in ethanol at room temperature.
A glass plate having a gold surface (water contact angle: 25 °) was immersed in the solution obtained at room temperature for 1 hour. It was 132 degrees when the contact angle of water with respect to the gold | metal | money surface after immersion was measured.
Furthermore, after the gold surface was washed with ethanol, the contact angle of water with the gold surface after immersion was measured and found to be 134 °.

[Comparative Example 2]
A solution was prepared by dissolving 1.5 mM octadecanethiol (adsorbing compound) and 1.5 mM octanoic acid (non-adsorbing compound) in ethanol at room temperature.
A glass plate having a gold surface (water contact angle: 25 °) was immersed in the solution obtained at room temperature for 93 hours. When the contact angle of water with the gold surface after immersion was measured, it was 118 °.

[Example 3]
A solution was prepared by dissolving 1.5 mM octadecanethiol (adsorbing compound) and 1.5 mM stearic acid (non-adsorbing compound) in ethanol at room temperature.
A glass plate having a gold surface (water contact angle: 25 °) was immersed in the solution obtained at room temperature for 15 hours. The contact angle of water with the gold surface after immersion was measured and found to be 92 °.

[Example 4]
A solution was prepared by dissolving 1.5 mM octadecanethiol (adsorbing compound) and 1.5 mM 1-octadecanol (non-adsorbing compound) in ethanol at room temperature.
A glass plate having a gold surface (water contact angle: 25 °) was immersed in the solution obtained at room temperature for 15 hours. The contact angle of water with the gold surface after immersion was measured and found to be 94 °.

According to the present invention, it is possible to arbitrarily determine the kind and ratio of the adsorptive group and the functional group from a chemically stable and easy-to-store compound, and by producing a self-assembled monolayer film having a stable film structure, The solid surface can be modified arbitrarily according to the usage situation.
The present invention can also be applied to the formation of a two-layer film or a multilayer film. That is, another layer can be laminated using a functional group present on the surface of the monolayer film (surface opposite to the solid surface). If the relationship between the lowermost layer (the layer on the most solid surface side) and the solid surface satisfies the definition of the present invention, an embodiment in which a double film or a multiple film is formed is also included in the present invention. In addition, in the case where the lower layer in the two adjacent layers of the two-layer film or multilayer film is regarded as a solid surface, and the relationship between the upper layer and the lower layer (solid surface) satisfies the definition of the present invention, This corresponds to an aspect of the present invention.

It is a conceptual diagram for demonstrating a normal self-assembled monolayer film. It is a conceptual diagram for demonstrating the conventional self-assembled monolayer film which used together two types of adsorbent compounds. It is a conceptual diagram for demonstrating the self-assembled monolayer film according to this invention. It is a schematic diagram which shows the basic aspect of this invention. It is a schematic diagram which shows the preferable aspect of this invention.

Explanation of symbols

1 Solid surface 2 Adsorbable group 3, 4 Chain hydrophobic group 5, 6 Functional group

Claims (10)

An adsorbent compound having an adsorptive group having an adsorptivity to a solid surface and a linear hydrophobic group having 8 to 100 carbon atoms, and a functional group and a chain having 8 to 100 carbon atoms in a solvent; By adsorbing the solid surface in a solution in which a non-adsorbing compound having a hydrophobic group and having substantially no adsorptivity to the solid surface is dissolved , the above-described adsorptive compound has a chain hydrophobic property. A self-assembled monolayer film composed of an adsorbing compound and a non-adsorbing compound is formed on the solid surface by an intermolecular interaction between the adsorbing group and the chain hydrophobic group of the non-adsorbing compound. A method of forming a solid surface modified with functional groups of The method of forming a modified solid surface according to claim 1, wherein the solid surface comprises a metal. The method of forming a modified solid surface according to claim 1, wherein the adsorptive group on the solid surface contains a sulfur atom. The method for forming a modified solid surface according to claim 1, wherein the chain hydrophobic groups of the adsorptive compound and the non-adsorptive compound are both chain alkyl groups. The method of forming a modified solid surface according to claim 1, wherein the non-adsorbing compound has a plurality of chain hydrophobic groups. The method for forming a modified solid surface according to claim 1, wherein the functional group is a hydrophilic group. The method for forming a modified solid surface according to any one of claims 1 to 6, wherein the adsorbing compound and the non-adsorbing compound are dissolved in the solution at a concentration of 0.002 to 20 mM, respectively. .   A solid surface modified by a self-assembled monolayer film, wherein the self-assembled monolayer film has an adsorptive group having an adsorptivity to the solid surface and a chain hydrophobic group having 8 to 100 carbon atoms And a non-adsorbing compound having a functional group and a chain-like hydrophobic group having 8 to 100 carbon atoms and having substantially no adsorptivity to a solid surface, A self-assembled monolayer is formed by the intermolecular interaction between the chain hydrophobic group of the adsorptive compound and the chain hydrophobic group of the non-adsorptive compound, and the solid surface is modified by the functional group of the non-adsorptive compound. A modified solid surface, characterized in that   The modified solid surface according to claim 8, wherein both of the chain hydrophobic groups of the adsorptive compound and the non-adsorptive compound are chain alkyl groups.   The modified solid surface according to claim 8, wherein the functional group is a hydrophilic group.

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