JPH10180933A - Inorganic and organic layer polymer single layer film and its multilayer laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a self-organizing monomolecular film (SAM) having high uniformity by using an inorganic and organic hybrid layer polymer and its laminated multilayer film. SOLUTION: This polymer single layer film or multilayer laminated film comprises a metal substrate, a crystalline laminated structure having a tetrahedron surface structure having at least one type atom selected from Si and Ge as a center and an octahedron surface structure having at least one type metal selected from Mg, Al, Ni, Co, Cu, Mn, Fe, Li, V, Zr, Ti, Pb, Sn, Sb, Ga, In, Zn, Tl and Ce as a central atom, an organic side chain bonded by a covalent bond to the central atom of the tetrahedron surface structure, a functional group blended with a metal or covalent bonded to an end of the side chain, and bonded to the metal via the functional group, thereby forming a SAM.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layered film formed by covalent bonding together with a monolayer film of an inorganic-organic layered polymer or a metal film on a metal surface substrate capable of protecting a metal surface. About.

[0002]

2. Description of the Related Art A self-assembled monolayer (hereinafter abbreviated as ASM) is formed by allowing an organic molecule having a functional group capable of reacting with a metal on one or both sides to act on the metal surface. There are known ways to do this.
Japanese Unexamined Patent Publication No. 7-502479 discloses that a single-layer film is formed on gold by using hexanedithiol and octanedithiol. However, in the bifunctional compound in which the organic group is an alkyl group as described above, the mobility of the functional groups at both ends is high, and both functional groups in the molecule react with the substrate at the same time. It is difficult to form a single layer film having high regularity and uniformity in the inside. Further, it is difficult to form a multilayer film in which a single-layer film and a metal film are multilayered using functional groups at both ends in one molecule.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a self-assembled monolayer having uniform and high regularity utilizing an inorganic-organic silicon-based polymer filed by the present applicant (Japanese Patent Application Laid-Open No. Hei 7-126396). It is an object to obtain a molecular film (SAM) and a laminated multilayer film thereof.

[0004]

Means for Solving the Problems The present inventors have introduced a functional group capable of coordinating with a metal instead of a polymerizable functional group on the surface of the inorganic-organic silicon-based polymer filed previously. Have found that a SAM can be formed on a metal surface substrate, and have completed the present invention. The first inorganic-organic polymer monolayer film of the present invention comprises a metal surface substrate, at least one kind of atom selected from Si and Ge, or a part of the atom being Al,
A tetrahedral surface structure having a central atom of an atom substituted by at least one atom selected from Fe and P, and Mg, Al,
Ni, Co, Cu, Mn, Fe, Li, V, Zr, T
i, Pb, Sn, Sb, Ga, In, Zn, Tl, Ce
With at least one metal selected from the group consisting of:
A crystalline laminated structure having a tetrahedral structure, and silicon, G, which is a central atom of a tetrahedral structure forming the laminated structure.
e, at least a part of at least one kind of atom selected from e is bonded to an organic layer by a covalent bond, and a functional group capable of coordinating or covalent bonding to a metal is provided at a terminal of a side chain of the organic layer. The inorganic-organic layered polymer having a bond with the metal of the metal surface substrate via the functional group of the organic side chain of the inorganic-organic layered polymer on the metal surface substrate to form a single layer film. It is characterized by having.

[0005] The second laminated inorganic-organic layered polymer multilayer film of the present invention is characterized in that at least one kind of atom selected from Si and Ge, or at least one kind of atom selected from Al, Fe and P is used. Tetrahedral surface structure with the atom replaced by the atom as the central atom and Mg, Al, Ni, Co, Cu, M
n, Fe, Li, V, Zr, Ti, Pb, Sn, Sb,
A crystalline laminated structure composed of an octahedral structure having at least one metal selected from Ga, In, Zn, Tl, and Ce as a central atom, and a center of a tetrahedral structure forming the laminated structure. At least a part of at least one kind of atom selected from atoms of Si and Ge is bonded to an organic layer by a covalent bond, and a coordination bond or a covalent bond to a metal is provided at a terminal of a side chain of the organic layer. An inorganic-organic layered polymer having a possible functional group is formed on a metal substrate by forming a single layer film of the inorganic-organic layered polymer and a metal film on the organic side chain of the inorganic-organic layered polymer. And at least one layer is laminated.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The first aspect of the present invention is a structure in which a single-layer film (monomolecular film) of an inorganic-organic layered polymer is formed on a metal surface substrate. The inorganic layer of the inorganic-organic layered polymer has 4
At least one atom selected from Si and Ge forming the central atom of the octahedral surface structure, and Mg, Al, Ni, Co, Cu, Mn, F constituting the central atom of the octahedral surface structure
e, Li, V, Zr, Ti, Pb, Sn, Sb, Ga,
At least one metal atom selected from In, Zn, Tl, and Ce forms a crystalline laminated structure. This laminated structure has a so-called 2: 1 type structure in which tetrahedral surfaces are formed on both sides of an octahedral surface, and a so-called 1: 1 type structure in which a tetrahedral surface is formed on one side of an octahedral surface. There is. When it is desired to include a large amount of organic groups or to improve the bonding strength between organic groups, a 2: 1 type structure is more preferable.

The 2: 1 type or 1: 1 type structure can be formed by adjusting the ratio of the atoms forming the tetrahedral surface to the atoms forming the octahedral surface. 4
A part of at least one of Si and Ge, which are central atoms of the facet, can be replaced by one or more atoms selected from Al, Fe and P. These A
l, Fe, and P can be easily introduced by central atom substitution with Si or Ge.

The organic layer is formed by covalently bonding to an organic group having a functional group that reacts with a metal on some or all of atoms forming a tetrahedral plane structure. The maximum possible amount of the organic group to be introduced is 1 to 3 per central atom of the tetrahedron.
More than enough can be introduced. Si that is covalently bonded to an organic side chain is composed of a layer having a structure in which oxygen is tetrahedral coordinated with the Si as a center and, for example, Mg having a octahedral surface forming atom as a central atom, and an oxygen is octahedral around the Mg. The layer having the coordinated structure forms a crystalline laminated structure which is laminated. This organic group has a functional group that reacts with a metal to form a covalent bond at a terminal, and forms an organic layer of an inorganic-organic layered polymer.

The raw material for forming the tetrahedral surface structure may be a mercapto group, a cyano group, a pyridine, or the like, as a part or all of R of inexpensive organoalkoxysilane R _X Si (OH) _4-X used as a silane coupling agent. By using a compound having a functional group such as a nitrogen-containing heterocyclic compound, a desired functional group can be introduced into the terminal of the organic side chain of the inorganic-organic layered polymer. Any of such organoalkoxysilanes may be used. Particularly known are (mercaptomethyl) dimethoxyethoxysilane,
(Mercaptomethyl) methyldiethoxysilane, (mercaptomethyl) methyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2- Cyanoethylethoxysilane, (cyanomethylphenethyl) triethoxysilane, 3-cyanopropyldimethylmethoxysilane, 3-cyanopropyltriethoxysilane, 2- (trimethoxysilyl) ethyl-2-
Pyridine and the like.

Examples of the compound having an atom constituting the tetrahedral surface include an organic silicon compound such as an organoalkoxysilane having an alkoxy group and a functional group capable of binding to a metal, and an organic germanium compound such as an organogermanium. Available. Compounds having atoms constituting the octahedral plane include Mg, Al, Ni, C
o, Cu, Mn, Fe, Li, V, Zr, Ti, Pb,
An inorganic salt, an organic salt, an alkoxide, or the like of at least one metal atom selected from Sn, Sb, Ga, In, Zn, Tl, and Ce is used. Of these, Al and Fe are atoms constituting the octahedral plane, and a part thereof is an atom which replaces a part of Si and Ge of the atoms constituting the tetrahedral plane.

The production of the inorganic-organic layered polymer is based on the inorganic part 4
The solution can be synthesized by mixing solutions in which the organometallic compound constituting the icosahedral surface and the metal compound constituting the octahedral surface are dissolved, and adding an alkaline solution for adjusting the pH to the mixed solution. The mixing of the solution of the metal compound forming the tetrahedral surface with the solution of the metal compound forming the octahedral surface is performed by mixing a compound having atoms forming the tetrahedral surface, a compound having atoms forming the octahedral surface, Accordingly, a polar solution in which a compound having P or a silicon alkoxide, a germanium alkoxide, or a germanium halide is dissolved is used as a mixed solution. As the polar solvent, one, or a mixed polar solution of two or more of water, alcohol, acetone, organic acid, inorganic acid and the like can be used. The above-mentioned compounds do not necessarily need to be completely dissolved, and the object can be achieved even in a certain dispersed state.

Preparation of Inorganic-Organic Layered Polymer Monolayer Film As shown in the conceptual diagram of the mechanism of the formation of the monolayer film in FIG. 5, the inorganic-organic layered polymer 1 dispersed in a solvent on the gold surface of the substrate was subjected to ASM. The single-layer film a is formed utilizing the properties. That is, the inorganic-organic layered polymer produced by the above method is dispersed in a solvent. Desirable types of solvents vary depending on the length of the organic side chain of the inorganic-organic layered polymer and the type of the introduced functional group, but require an inorganic solvent such as water, or an organic solvent, or a mixed solvent thereof. Prepare accordingly. It is considered that the inorganic-organic layered polymer particles in the suspension are sufficiently swelled and dispersed to have high mobility and easily act on the metal surface, but such particles are sufficiently prepared. If it is a system, it is not necessary that all of the inorganic-organic layered polymer particles in the liquid be well swollen.

A substrate having a metal surface is immersed in the suspension prepared above. This substrate is made of gold, silver, platinum, mercury, copper, iron, nickel, cadmium, osmium, or contains these metals, which reacts and bonds with the functional group at the terminal of the organic side chain of the inorganic-organic layered polymer. It must be made of an alloy or covered with these metals by means such as vapor deposition. The time required for forming a monolayer film depends on conditions such as the type of functional group at the terminal of the organic side chain of the inorganic-organic layered polymer, the concentration of the suspension, the type of metal element on the substrate surface, and the temperature. However, it generally takes several hours to several days. After immersion, if necessary, washing and drying are performed, whereby a single-layer film of an inorganic-organic layered polymer is obtained on the substrate.

[0014] The second invention of the present application is directed to a monolayer film of an inorganic-organic layered polymer, wherein a metal film bonded to a terminal functional group of an organic side chain is further interposed on the monolayer film of the inorganic-organic layered polymer. It is configured by lamination. In this multi-layer structure, a metal is vapor-deposited or a metal ion is bonded to the upper surface of the inorganic-organic layered polymer monomolecular film formed on the metal surface substrate, and the inorganic-organic layered polymer monolayer is again formed on the metal film upper surface. The layer film is formed by immersing the inorganic-organic layered polymer in a solution. By repeating these operations, a multilayer laminated film of an inorganic-organic layered polymer and a metal film can be formed.

Preparation of Inorganic-Organic Layered Polymer Multilayer Film As shown in the conceptual diagram of the mechanism of the formation of the single-layer film in FIG. 5, the functional groups existing on the surface of the single-layer film a formed on the gold surface of the substrate By bonding metal ions or atoms, the inorganic-organic layered polymer multilayer film is sandwiched with the metal b. By further acting an inorganic-organic layered polymer on b, a laminated multilayer film can be formed.

The upper surface of the single-layer film obtained as described above is plated with gold, vapor-deposited or coated with a colloidal metal.
After coating with a metal such as silver, platinum, mercury, copper, iron, nickel, cadmium, osmium or an alloy containing these metals, the obtained laminated film is immersed in a liquid in which an inorganic-organic layered polymer is dissolved. Then, by performing the film forming process of the inorganic-organic layered polymer, one layer of the inorganic-organic layered polymer film can be further laminated on the upper surface of the single layer film. By repeating this operation, a desired number of laminated inorganic-organic layered polymer multilayer films can be produced.

[0017]

As described above, the inorganic-organic layered polymer of the present invention has a structure in which the crystalline inorganic structural portion is formed by laminating tetrahedral surfaces and octahedral surfaces. An organic group is bonded to the central atom by a covalent bond, and the organic group has a functional group capable of bonding to a metal at the terminal. Therefore, since the inorganic-organic layered polymer has a functional group regularly arranged at the terminal of the organic group, that is, at the outer surface, the functional group can contact and react with the metal and easily form a covalent bond. A single layer film of an inorganic-organic layered polymer can be obtained as a uniform film.

Therefore, if a monolayer film of an inorganic-organic layer polymer is formed on a metal surface substrate, a functional group which reacts with a metal is present on the upper surface of the inorganic-organic layer polymer single layer film. A bonded metal film can be formed by vapor deposition or the like. Further, it is also possible to stack a plurality of layers regularly by repeating a single layer film of an inorganic-organic layered polymer and a metal film. The inorganic-organic layered polymer can be used for protection of metal surfaces, rust prevention, layered diffraction gratings, capacitors, and the like. Furthermore, utilizing the reactivity with metals, not only as a membrane but also for the adsorption of harmful metals,
It can be used for collection.

[0019]

The present invention will be described below in detail with reference to examples. (Example 1) 50 ml of 1 g of magnesium chloride hexahydrate
And dissolved in methanol. To this, 3.1 g of 3-mercaptopropyltrimethoxysilane was added and stirred. Further, 200 ml of deionized water and 10 ml of a 1N aqueous solution of sodium hydroxide were added, followed by stirring at room temperature for 72 hours.
The deposited precipitate was separated by filtration, washed with water, and vacuum dried to obtain a white laminated structure. This laminated structure has a crystalline laminated structure in which a tetrahedral surface structure centered on silicon atoms and an octahedral surface structure centered on magnesium atoms are stacked, and the tetrahedral surface silicon is centered on silicon, Elemental analysis and X-ray diffraction confirmed that the propyl group having a terminal mercapto group was a mercapto-magnesium layered polymer forming a covalent bond to silicon to form an organic layer.

Elemental analysis results: H (4.9%), C (2
3.4%), a S (20.9%), its composition formula _{[(C 36 H 24 O 12 Si} 12 S 12) Mg 2 (OH 3) ] - 2
It is believed to be 1H ₂ O. The calculated component ratios from this composition formula are H (3.7%), C (23.4%), and S (2
0.8%). Confirmation of layered structure by X-ray diffraction The obtained sample was subjected to powder X-ray diffraction measurement. The measurement conditions were 40 kV, 30 mA, Cukα (λ = 0.154).
nm). The result is shown in FIG. From the chart of FIG. 1, the formation of the layered structure was confirmed by the presence of the (001) peak. The d value = interlayer distance (1.47 nm) indicates the presence of organic side chains between the layers. Also, (02
From the d value (0.42 nm) of (0), the length of the b-axis of the unit cell of the tetrahedral sheet is estimated to be 0.84 nm. This value is in good agreement with the value (0.86-0.92 nm) for the 2: 1 type clay mineral having a smectite structure.

Preparation of Mercapto-Magnesium Layered Polymer Monolayer Film and Its Confirmation by Quartz Microbalance A mercapto-magnesium layered polymer / chloroform solution (3.33 × 10 ⁻³ g / l) was prepared, and 1 Quartz on which gold deposition was performed was immersed in an area of 0.4 square centimeters, and the weight of a film formed in the gold deposition area was measured at a vibration frequency of 5 MHz by a quartz crystal microbalance method. FIG. 2 shows how the resonance frequency of the quartz resonator changes over time at this time. Resonance frequency is 1 after 21 hours
Reduced to 90 hertz. The following relationship exists between the total weight change (Δm (ng)) and the frequency change (Δf (Hz)).

Δm = Δf × S S = −17.7 ng / Hz · cm ² The weight of the film formed therefrom is estimated to be 3.3 × 10 ³ nanograms per square centimeter. Molecular weight M _W mercapto unit cell - theoretical value of the weight increase during monolayer formation when the area per unit cell of the tetrahedral sheet of magnesium layered polymer and s is however _{Δm = M W / N A ×} S N _A is Avogadro's number According to the composition formula, M _W = 1845 and s = 0.50 × 0.84
It is a square name, and when this is substituted, Δm = 1.0 ×
The 10 ³ nanograms / sq cm. The measured value (3.3 × 10 ³ nanograms) was the theoretical value (1.0 × 10 3
³ nanograms), but considering the overlapping around the particles of the mercapto-magnesium layered polymer in the film, there is almost one layer of the mercapto-magnesium layered polymer (schematic structure shown in FIG. 5a) on the gold surface. It is considered that a film consisting of

(Example 2) Nickel chloride hexahydrate 0.6
70 g was dissolved in 50 ml of methanol. This is followed by 3-mercaptopropyltrimethoxysilane 3.0
g was added and stirred. Add 200 ml of deionized water and 1
10 ml of an aqueous solution of sodium hydroxide N
Stir for 2 hours. The deposited precipitate was separated by filtration, washed with water, and vacuum dried to obtain a white laminated structure. This laminated structure is
It has a crystalline laminated structure in which a tetrahedral surface structure centered on silicon atoms and an octahedral surface structure centered on nickel atoms are stacked, and has a mercapto group at the terminal with silicon as the central atom on the tetrahedral surface. Elemental analysis and X-ray diffraction confirmed that the propyl group was a mercapto-nickel layered polymer forming a covalent bond to silicon to form an organic layer.

Elemental analysis results: H (5.44%), C
(19.5%), S (15.3%), and its composition formula
Is [(C₃₆H_{twenty four}O₁₂Si₁₂S₁₂) Ni_Two(OH_Three)] ・
55H _TwoO is considered. Ingredients from this formula
The calculated ratios are H (5.4%), C (17.1%), S (1
5.2%). Confirmation of layered structure by X-ray diffraction The obtained sample was subjected to powder X-ray diffraction measurement. Measurement
Conditions are 40 kV, 30 mA, Cukα (λ = 0.154)
nm). The result is shown in FIG. Chart of FIG.
Formation of a layered structure due to the presence of a peak from (001) to
confirmed. The d value = interlayer distance (1.43 nanometers)
) Indicates the presence of organic side chains between layers. Also, (02
Tetrahedral sheet from d value (0.43 nanometer) of 0)
The length of the b-axis of the unit cell is assumed to be 0.86 nm.
Piled up. This value is a 2: 1 type clay with smectite structure
Well with mineral values (0.86-0.92 nanometers)
Matches.

Preparation of Mercapto-Nickel Layered Polymer Monolayer Film and Its Confirmation by Quartz Microbalance A mercapto-nickel layered polymer / chloroform solution (1.67 × 10 ⁻² g / l) was prepared and contained therein 0%. A gold-deposited crystal was immersed in an area of .43 square centimeters, and the weight of a film formed in the gold deposition area was measured at a vibration frequency of 5 MHz by a quartz crystal microbalance method. FIG. 4 shows how the resonance frequency of the quartz resonator changes over time at this time. The resonance frequency becomes 6 after 520 minutes.
Reduced to 8 hertz. The following relationship exists between the total weight change (Δm (ng)) and the frequency change (Δf (Hz)).

Δm = Δf × S where S = −17.7 ng / Hz · cm ² The weight of the film formed therefrom is estimated to be 1.2 × 10 ³ nanograms per square centimeter. Molecular weight M _W mercapto unit cell - theoretical value of the weight increase during monolayer formation when the area per unit cell of the tetrahedral sheet of nickel layered polymer and s is however _{Δm = M W / N A ×} S N _A is Avogadro's number. From the composition formula, M _W = 2526 and s = 0.51 × 0.86.
It is a square name, and when this is substituted, Δm = 1.3 ×
The 10 ³ nanograms / sq cm. The measured value (1.2 × 10 ³ nanograms) is the theoretical value (1.3 × 10 ³ nanograms).
³ nanograms), and mercapto-
It is considered that a nickel monolayer film (schematic structure shown in FIG. 5A) was obtained.

Example 3 A gold crystal was immersed in a mercapto-nickel layered polymer / chloroform solution for 48 hours.
Thereafter, this was washed with chloroform and further immersed in a colloidal gold solution (2.4 × 10 ⁶ / ml) for 3 hours. Excessive gold colloid adhered to the surface was removed by washing with water. B shown in the conceptual diagram of the mechanism in FIG. 5 was obtained.
After drying in air, the film was further immersed in a mercapto-nickel layered polymer / chloroform solution for 48 hours. C shown in the conceptual diagram of the mechanism in FIG. 5 was obtained. By repeating this operation, a multilayer film composed of two to six layered mercapto-nickel layered polymer and gold colloid was formed.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction pattern of a mercapto-magnesium layered polymer.

FIG. 2 is a chart showing the change over time of the resonance frequency of a quartz resonator immersed in a mercapto-magnesium layered polymer chloroform solution by a quartz crystal microbalance method.

FIG. 3 is an X-ray diffraction pattern of a mercapto-nickel layered polymer.

FIG. 4 is a chart showing a change over time of a resonance frequency of a quartz oscillator immersed in a mercapto-nickel layered polymer chloroform solution by a quartz crystal microbalance method.

FIG. 5 is a conceptual diagram showing a mechanism of forming a multilayer film using a mercapto-metal layer polymer. In the reaction steps in the conceptual diagram, a is a schematic diagram of a single-layer film, b is a laminated film of a mercapto-metal layer polymer and a metal film, c is a laminated multilayer film, and 1 is a schematic diagram of a mercapto-metal layer polymer.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazuhisa Yano 41-Cho, Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture Inside Toyota Central Research Institute, Inc. (72) Inventor Kohiko Yamagishi 40 (72) Inventor Yuji Hotta Kita-ku, Kita-ku, Sapporo-shi

Claims (2)

[Claims] 1. A metal surface substrate and at least one kind of atom selected from Si and Ge, or a part of the atom
e, a tetrahedral plane structure having a central atom substituted by at least one atom selected from P and Mg, Al, N
i, Co, Cu, Mn, Fe, Li, V, Zr, Ti,
A crystalline laminated structure having an octahedral structure having at least one metal selected from Pb, Sn, Sb, Ga, In, Zn, Tl, and Ce as a central atom, and forming the laminated structure At least a part of at least one kind of atom selected from Si and Ge which is a central atom of the tetrahedral surface structure is bonded to an organic layer by a covalent bond, and a terminal of a side chain of the organic layer is located on a metal. An inorganic-organic layered polymer having a functional group capable of coordination or covalent bonding, and a metal on a metal surface substrate via the organic side chain functional group of the inorganic-organic layered polymer on the metal surface substrate. An inorganic-organic layered polymer single-layer film, wherein a bond is formed to form a single-layer film. 2. A tetrahedral surface structure having, as a central atom, at least one kind of atom selected from Si and Ge, or an atom obtained by substituting a part of the atom with at least one kind of atom selected from Al, Fe, and P. And Mg, Al, Ni, Co, C
u, Mn, Fe, Li, V, Zr, Ti, Pb, Sn,
A crystalline laminated structure having an octahedral surface structure having at least one metal selected from Sb, Ga, In, Zn, Tl, and Ce as a central atom, and 4 forming the laminated structure.
At least a part of at least one atom selected from the group consisting of Si and Ge, which is a central atom of the planar surface structure, is bonded to an organic layer by a covalent bond, and is coordinated to a metal at a terminal of a side chain of the organic layer. An inorganic-organic layered polymer having a functional group capable of bonding or covalent bond, a single-layer film of the inorganic-organic layered polymer and a metal film on a metal surface substrate, and an organic layer of the inorganic-organic layered polymer. An inorganic-organic layered polymer multilayer film characterized in that at least one layer is bonded by bonding through a side chain functional group.