JP3128781B2 - Manufacturing method of ultra-thin laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ultra-thin film laminate having a thickness of one layer at a molecular level and each layer having an independent structure.

[0002]

2. Description of the Related Art As a method for producing an organic thin film having a molecular level thickness, an LB method, a method using an inorganic layered compound, a vacuum deposition method, and the like are known. Such organic thin films have begun to be used in various fields, utilizing the characteristics of the organic compounds constituting them.

The LB method is described in, for example, “Surface / Thin Film Molecular Design Series 1 Molecular Design of LB Film” (Kiritsu Shuppan Co., Ltd., published on July 1, 1988) by Keiji Iriyama.
As described on page 2, a monomolecular film formed by developing a developing solution prepared by dissolving a predetermined compound in an organic solvent on a subphase such as water is applied to an appropriate substrate such as a glass substrate. It is made by transferring.

A method using an inorganic layered compound is described in, for example, "Chemical Review: Molecular Assemblies, Their Organization and Function, Structure and Function of Intercalation Compounds" (published May 25, 1983, written by Yamanaka Shoji), pages 65-79. As described in (1), a thin film is prepared by introducing a monomer between layers of a layered compound such as a clay mineral and polymerizing the monomer between the layers.

In the LB method, since the monomolecular film developed on the sub-phase is transferred one by one, it is necessary to repeat a number of steps to obtain a required film thickness, resulting in poor productivity. . Moreover, the apparatus itself is very expensive. Therefore, the LB method is not suitable for mass production of a thin film laminate.

On the other hand, in a method using an inorganic layered compound, it is very difficult to isolate a polymer from a composite film obtained by polymerizing a monomer between layers.
In this regard, a method using an inorganic layered compound has not been widely adopted. Further, when a thin film is manufactured by vacuum deposition or the like, it is difficult to control the thickness of the obtained thin film on a molecular level, and the apparatus itself is expensive.

Further, a method using an organic substance as a reaction field, for example, an inclusion polymerization in which a monomer is introduced into an inclusion compound such as urea or deoxycholic acid to carry out a polymerization reaction is also known. However, the polymer obtained by this method is linear, and it has not been possible to obtain a thin film having a sufficient area.

The present inventors have disclosed a method of using a molecular assembly formed by an amphiphilic compound as a reaction field as a method for producing an organic thin film which solves these problems.
No. 8885. In this method, a developing solution is prepared by adding a radical polymerizable monomer to a dispersion of an amphiphilic compound having a bilayer film forming ability. After evaporating the solvent from the liquid film formed by spreading this developing solution on the substrate, the monomers contained in the obtained thin film are polymerized, and then the amphiphilic compound is extracted to form an ultra-thin film stack. Manufacture the body. At this time, since the radical polymerization reaction proceeds between the layers of the multilayer bilayer formed by the amphiphilic compound, the obtained thin film becomes an ultrathin laminate having a molecular level thickness. Further, isolation of the polymerized polymer is easy, and operability is excellent.

[0009]

However, when a dispersion of an amphipathic compound to which a radical polymerizable monomer is added is used as a developing solution, a process in which the amphiphilic compound associates on a substrate to form a monomolecular film. In this case, the monomer is taken into the molecular assembly, so that the regularity of the monomolecular film structure is easily disturbed. Also,
The introduced monomer causes structural disturbance even in the process of evaporating the solvent from the developed liquid film to form a thin film. As a result, it has been difficult to obtain an ultra-thin film laminate in which each layer has an independent structure. In particular, when the compatibility between the amphiphilic compound and the monomer is poor, phase separation occurs between the two, and a laminated structure over the entire surface of the film may not be obtained.

Further, when a highly volatile monomer such as styrene is used as the radical polymerizable monomer, the monomer evaporates in the process of evaporating the solvent from the liquid film of the amphipathic compound formed on the substrate, and the desired monomer is evaporated. A polymer film cannot be obtained. In this regard, the present applicant has disclosed a method of preparing a multilayer bilayer thin film from an ionic amphiphilic compound and then introducing inorganic ions by an ion exchange method.
No. 310734. In the proposed method,
Since the ion exchange reaction of the counter ion of the amphiphilic compound is used, it is necessary that both the amphiphilic compound and the inorganic compound to be introduced are ionic. Therefore, this method cannot be applied to manufacture a polymer ultra-thin film laminate from a nonionic radically polymerizable monomer.

The present invention has been devised in order to solve such a problem. An amphiphilic compound is formed by forming a thin film in which an amphiphilic compound is molecularly oriented and then subjected to a contact treatment with a radical polymerizable monomer to thereby form an amphiphilic compound. It is an object of the present invention to obtain an ultra-thin laminate in which the structure is controlled at the molecular level and each layer has a structure independent of each other, without finding the excellent regularity inherent in the active compound.

[0012]

According to the present invention, there is provided a method for producing an ultra-thin film laminate, in which a dispersion of an amphipathic compound having a bilayer film forming ability is developed on a substrate, and After the solvent of the liquid is evaporated, the multilayer bilayer thin film of the amphipathic compound is brought into contact with a solution containing a radically polymerizable monomer to polymerize the monomer introduced into the thin film. It is characterized by extracting a solvent compound. As the amphiphilic compound, a compound having a fluorocarbon chain in the lyophobic portion can be used.

The amphiphilic compound used in the present invention includes a group having no affinity for a solvent (hereinafter referred to as a solvophobic group) and a group having an affinity for a solvent (hereinafter referred to as a lyophilic group). Group). When water is used as the solvent, sulfo groups, sulfate groups, ammonium groups, carboxylic acid groups, sulfonium salts, phosphonate salts,
There are phosphonium salts, polyethers, alcohols, polyols containing sugar residues, and combinations of these groups.
There are alicyclic groups, condensed polycyclic groups, those containing a fluorocarbon chain in these groups, and combinations of these groups.

In order to form a stable bilayer from this amphiphilic compound, for example, two or more alkyl long chains, an alkyl long chain containing a rigid segment such as azobenzene, biphenyl or the like, or a fluorocarbon chain is added to these groups. Are preferred. In this respect, the characteristics of the chemical structure of the amphiphilic compound having a bimolecular film structure, the reason why the thin film forming ability is high, typical examples of the compounds, and the like are described in detail in the specification of Japanese Patent Application No. 1-58889. , So that the description is omitted here.

As a solvent in which the amphiphilic compound is dispersed, an organic solvent other than water can be used. In this case, as the lyophobic group of the amphiphilic compound, a group partially having a fluorocarbon chain among the groups described above and combinations thereof are used. On the other hand, as the solvent-philic group, an alkyl group, an alicyclic group, a condensed polycyclic group, and a combination thereof can be used in addition to those described above. Examples of the amphiphilic compound containing a fluorocarbon chain include an amphiphilic compound in which a fluorocarbon chain and a hydrocarbon chain having higher molecular orientation are combined as disclosed in Japanese Patent Application No. 2-59019.

The dispersion of the amphiphilic compound is prepared by dissolving or dispersing a predetermined amount of the amphiphilic compound in a solvent. As a solvent, water is used in many cases, but when an amphiphilic compound containing a fluorocarbon chain is used, it is also possible to use an organic solvent. The organic solvents used at this time include alcohols, ethers, ketones, esters, halogenated alkanes,
Examples include nitriles, organic acids, organic bases, aromatic hydrocarbons, saturated and unsaturated hydrocarbons, and mixed solvents thereof. The type of the solvent is not particularly limited as long as the prepared dispersion is spread on a substrate and the solvent is evaporated to obtain a multilayer bilayer film.

The substrate on which the dispersion is spread includes a glass plate, a quartz plate, a graphite plate, a silicon plate, a Teflon plate, a dense polymer film, a porous polymer film, and the like. The surface of the substrate may be subjected to a hydrophilic treatment or a hydrophobic treatment depending on the type of the dispersion.

When the solvent is removed from the dispersion liquid spread on the substrate, a multilayer bilayer of an amphipathic compound is formed. In order to maintain the regularity of the molecular assembly of the amphiphilic compound in the process of removing the solvent, it is preferable to remove the solvent as slowly as possible. The conditions for removing the solvent depend on the solvent system of the developing solution, but in the case of an aqueous solution, for example, the removal is performed in a thermo-hygrostat set at a temperature of 25 ° C. and a relative humidity of 60% for about 3 days. . At this time, the thickness of the formed multilayer bilayer thin film is determined according to the surface area of the substrate on which the dispersion is spread, the concentration of the amphipathic compound in the dispersion, the amount of the dispersion, and the like. Then, the film thickness of the finally manufactured polymer ultra-thin film laminate is also determined.

The multilayer bilayer thin film obtained after the removal of the solvent is subjected to a contact treatment with a solution containing a radical polymerizable monomer (hereinafter simply referred to as a monomer) in a state of being attached to the substrate or being separated from the substrate. As contact processing,
A method of immersing a multilayer bilayer thin film in a monomer-containing solution,
There is a method of applying a monomer-containing solution to a multilayer bilayer thin film.

As the monomer, a monomer having a polymerization site such as an acryl group, a methacryl group, a vinyl ether group, a vinyl sulfone group, and a styrene group is used. Specifically, there are polyfunctional monomers represented by the following formulas (1) to (11). These monomers may be used alone or by copolymerizing several types. Note that R in Formulas (1) to (11) represents CH ₃ or H.

[0021]

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[0022]

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[0023]

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In addition to the polyfunctional monomers of the formulas (1) to (11), monofunctional monomers represented by the following formulas (12) to (23) may be used. Can also be used in coexistence.

[0025]

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[0026]

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When the contact treatment is performed by immersing the multilayer bilayer film in a monomer-containing liquid, the monomer which is in a liquid state under the immersion conditions can be used as it is as a contact treatment liquid. On the other hand, when the monomer is in a solid state or when the introduction rate of the monomer into the multilayer bilayer thin film is not sufficient, the monomer dissolved in the solvent is used. As the solvent used at this time, water can be used in many cases with respect to the water-soluble monomer. In the case of amphiphilic compounds containing a fluorocarbon chain, alcohols, ethers, ketones, esters, halogenated alkanes, nitriles, organic acids, organic salts, aromatic hydrocarbons, saturated and unsaturated carbon It is also possible to use hydrogens or a mixed solvent thereof.
Among these, a solvent that dissolves the monomer, does not dissolve the amphipathic compound and does not destroy the structure is selected as the solvent according to the types of the monomer and the amphiphilic compound. In addition. An appropriate polymerization initiator can be added to the solution containing the monomer.

Conditions for immersing the multilayer bilayer thin film in a solution containing a monomer include an amphipathic compound, a monomer,
Although it differs depending on the type of the solvent, there is no particular limitation as long as the monomer is sufficiently introduced into the multilayer bilayer thin film. For example, the monomer concentration in a monomer immersion bath is often 1/10 the molar ratio of monomer to solvent.
0-5 / 1 is used. The immersion time of the multilayer bilayer thin film is usually 5 hours to 10 days in order to sufficiently introduce the monomer while suppressing the gradual dissolution of the multilayer bilayer. The immersion treatment is usually performed at normal temperature and normal pressure. However, in order to promote the introduction of the monomer into the multilayer bilayer thin film, the immersion treatment may be performed at an increased temperature and / or pressure.

After the surface of the multilayer bilayer thin film that has been contact-treated with the monomer-containing solution is washed with water or a suitable organic solvent, a treatment such as photopolymerization, thermal polymerization, or radiation polymerization is performed.
As a result, the introduced monomer is polymerized using the multilayer bilayer thin film as a molecular template, and fixed as a polymer in a shape following the void structure of the multilayer bilayer thin film.

Subsequently, the amphiphilic compound is extracted and removed from the composite thin film of the multilayer bilayer film and the polymer using a solvent selected according to the type of the amphiphilic compound. By this processing, an ultra-thin film laminate having one layer at a molecular level and each layer having a structure independent of each other is obtained.

[0031]

[Action] Among amphiphilic compounds having both a lyophobic group and a lyophilic group in the same molecule, certain compounds form a molecular assembly having a bilayer structure similar to that of a biological membrane. The amphipathic compound that forms this bilayer is not only obtained as a solvent dispersion, but also after the solvent is gradually removed after the dispersion of the amphiphilic compound is spread on a solid substrate. It can be formed into a film-like multilayer bilayer thin film having self-supporting properties. It is known that the regular bilayer structure of the amphiphilic compound is maintained even in the obtained film-like multilayer bilayer thin film, and that it has a two-dimensional planar high lamellar structure. [Eg, Thin Solid Films, 121 , L
89 (1984)].

This lamellar structure is maintained even in a composite thin film obtained by developing a dispersion of an amphiphilic compound prepared by adding a different molecule such as a monomer on a solid substrate and then gradually removing the solvent. Have been. However, compared to the case of the amphipathic compound alone, the lowering of the regularity due to the mixing of foreign molecules is inevitable. For example, when observing the ultra-thin film laminate after polymerizing the monomer, there may be a case where each layer intersects with each other. That is, structural defects are induced by the introduction of the monomer, and it is difficult to obtain a uniform ultra-thin film laminate in which each layer is independent of each other.

In addition, in the method of adding a monomer to a dispersion of an amphipathic compound, when a monomer having low compatibility with the amphipathic compound or a highly volatile monomer is used, a laminated structure of an ultrathin film over the entire surface of the film is obtained. I can't get it.

Therefore, the present inventors have paid attention to the high regularity of the multilayer bilayer thin film made of the amphiphilic compound alone.
When a monomer is introduced into a multilayer bilayer thin film made of an amphiphilic compound alone, one layer has a molecular-level thickness without breaking the two-dimensionally planar lamella structure created by the amphiphilic compound. It was considered that a uniform ultra-thin film laminate in which each layer was independent of each other could be obtained. When using this method,
Even monomers with low compatibility or high volatility with amphiphilic compounds can be introduced into multilayer bilayer thin films, and it is expected that uniform ultra-thin film laminates following the lamellar structure will be obtained. Is done.

In the present invention, first, a multilayer bilayer thin film is prepared by using an amphiphilic compound alone. Since the thin film is obtained from a dispersion liquid containing no foreign molecules such as monomers, the amphiphilic compound in the thin film has a lamellar structure with high two-dimensional planarity. This lamellar structure changes depending on the solubility of the amphiphilic compound in the solvent, but is maintained even when the multilayer bilayer thin film is immersed in an appropriately selected solvent.

Then, when the multilayer bilayer thin film is subsequently immersed in the monomer-containing solution, the monomer is formed into layers between the stacked amphiphilic compounds and in a layered manner without destroying the bilayer structure. It is introduced into a space having a two-dimensional spread formed by the arrangement. Since the introduction of the monomer at this time is not based on the ion-exchange method proposed in Japanese Patent Application No. 23071034, both the amphiphilic compound and the monomer need not be ionic. Further, the monomer mainly penetrates from the side surface of the multilayer bilayer thin film and is introduced into the film along the bilayer layer.

The rate of introduction of the monomer varies depending on the combination of the amphiphilic compound and the monomer. However, generally speaking, when using an immersion bath consisting of only monomers,
Sufficient introduction speed cannot be obtained. Therefore, it is preferable to use a solution in which the monomer is dissolved in an appropriate solvent as the immersion bath. It is presumed that the solvent penetrates between the bilayer layers and spreads the layers to promote the introduction of the monomer.

Since the monomer is introduced between the layers of the multilayer bilayer thin film once formed as described above, a monomer having poor compatibility with the amphiphilic compound can be introduced without causing phase separation. . Further, when the solvent is evaporated from the dispersion of the amphipathic compound, the dispersion does not contain the monomer, so that the monomer is not left for a long time in the state of the monomer. Therefore, even a highly volatile monomer can be easily introduced into a multilayer bilayer thin film.

The amount of the monomer introduced into the multilayer bilayer thin film can be controlled by the monomer concentration in the immersion bath, the immersion time, and the like. If the amount is too small, a thin film over the entire surface of the bilayer thin film cannot be obtained after polymerization. Conversely, if the amount of introduction is extremely large, an ultra-thin laminate whose structure is controlled at the molecular level cannot be obtained. Therefore, although it depends on the molecular cross-sectional area of the amphipathic compound and the monomer, it is generally preferable to set conditions under which the monomer is introduced in an equivalent amount to the amphipathic compound.

The monomer incorporated in the multilayer bilayer thin film by the contact treatment is polymerized by photopolymerization, thermal polymerization, radiation polymerization or the like. At this time, the polymerization reaction of the monomer proceeds only in a plane in which the monomer is taken. Therefore, a laminate of a two-dimensionally crosslinked ultrathin polymer is formed inside the multilayer bilayer thin film. Therefore,
When the amphiphilic compound is extracted and removed with hot water or an organic solvent such as ethanol, a laminate of an ultra-thin polymer is obtained.

In the ultra-thin film laminate thus produced, a multilayer bilayer thin film is once formed from an amphipathic compound, and then a monomer is introduced thereinto to react a regular layered structure of the amphipathic compound. Since it is polymerized using as a field, one layer has a basic thickness of a molecular level and each layer has an ultrathin film laminated structure independent of each other. In addition, even for polymers that were difficult to make thin using conventional methods,
By this method, the film can be made thinner, and it is expected that the use thereof will be expanded and the functionality will be improved.

When the obtained ultra-thin film laminate is used as a selective separation membrane material by utilizing its characteristic layered structure,
Since the separation function is exhibited by the thin film layer at the molecular level, it exhibits extremely excellent high permeability. In addition, when used as a conductor, there is anisotropy between the film thickness direction and the film surface direction, so that the carrier mobility is greatly different. Further, as an organic layered compound, a functional molecule can be incorporated between layers to be used as a functional composite material having optical, electrical, and magnetic characteristics.

[0043]

【Example】

Example 1 A compound represented by the following formula (24) was used as an amphiphilic compound capable of forming a bilayer film.

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The amphiphilic compound (24) was ultrasonically dispersed in water to prepare a 30 mM dispersion. This dispersion was spread on a porous polytetrafluoroethylene film at a spread amount of 0.42 ml / cm ² , and dried for 3 days in a constant temperature and humidity atmosphere at a temperature of 25 ° C. and a relative humidity of 60%. The obtained multilayer bilayer thin film was a translucent film having self-supporting properties.

A monomer of the formula (1) (n = 14, R = H)
Was dissolved in pure water at a molar ratio of 1/25 to prepare a monomer solution. This monomer solution contains 4- (2-hydroxyethoxy) phenyl-, which corresponds to 2 mol% of the monomer (1).
(2-Hydroxy-2-propyl) ketone was added as a polymerization initiator.

After the multilayer bilayer thin film was immersed in the monomer solution and allowed to stand for 24 hours, the multilayer bilayer thin film was removed from the monomer solution. After the film surface was washed with pure water, the monomer was cross-linked and polymerized by irradiating the multilayer bilayer thin film with ultraviolet rays using a low-pressure mercury lamp. After the polymerization reaction, the multilayer bilayer thin film was immersed in ethanol to extract and remove the amphiphilic compound (24).

The obtained film was almost transparent and self-supporting, and had sufficient flexibility and strength. When the cross section of the film was observed with a scanning electron microscope (SEM), the film thickness was about 10 μm, and the thickness per layer was about 10 μm.
A multilayer structure of 00 ° was formed parallel to the film surface.

Example 2 A compound having a structure represented by the formula (25) was used as an amphiphilic compound capable of forming a bilayer film.

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The amphiphilic compound (25) was ultrasonically dispersed in cyclohexyl chloride to prepare a 120 mM dispersion. The dispersion was spread on a Teflon sheet surrounded by a Teflon O-ring at a spread amount of 0.13 ml / cm ² , and allowed to stand at normal temperature and normal pressure for 2 days to evaporate the solvent. The obtained multilayer bilayer thin film was a translucent film having self-supporting properties.

A monomer solution was prepared by dissolving the monomer of the formula (10) in cyclohexyl chloride at a molar ratio of 1/2. The monomer solution contained 50% by weight of 1-hydroxycyclohexyl phenyl ketone and 5 parts of benzophenone.
0% by weight of the mixture was added as polymerization initiator in an amount corresponding to 2 mol% of the monomer (10).

After the multilayer bilayer thin film was immersed in the monomer solution and left for 3 days, the multilayer bilayer thin film was taken out of the monomer solution. After the membrane surface was washed with methanol, the multilayer bilayer thin film was irradiated with ultraviolet rays using a low-pressure mercury lamp to crosslink and polymerize the monomer. After the polymerization reaction, the multilayer bilayer thin film was immersed in chloroform to extract and remove the amphiphilic compound (25).

The obtained film was almost transparent and self-supporting, and had sufficient flexibility and strength. FIG. 1 shows the result of SEM observation of the cross section of the film. The film thickness was about 20 μm, and a multilayer structure having a thickness of about 1000 ° per layer was formed parallel to the film surface. When this film was immersed in acetone and the swelling ratio was measured, the swelling ratio was significantly different from 16% in the film surface direction and 86% in the film thickness direction, indicating a large anisotropy reflecting the layered structure of the multilayer bilayer film. Was confirmed.

Comparative Example 1 A monomer solution containing the same polymerization initiator as in Example 2 in an amount of 2 mol% based on the monomer (10) was cast between quartz plates, and irradiated with ultraviolet light from a low-pressure mercury lamp to crosslink and polymerize the monomer. Was. The resulting polymer film is
It was self-supporting but brittle. SE section
M observation revealed a dense structure with a thickness of about 150 μm. When the swelling ratio was measured in the same manner as in Example 2, it was found that the thin film had no anisotropy of 9% in the film surface direction and 10% in the film thickness direction.

Comparative Example 2: The amphiphilic compound (25) was ultrasonically dispersed in cyclohexyl chloride to prepare a 40 mM dispersion. This dispersion is added to the amphiphilic compound (2
5) and an equimolar amount of the monomer (10) were added, and the same polymerization initiator as in Example 2 was used in an amount of 2 mol% based on the monomer (10).
added. The dispersion was spread on a Teflon sheet surrounded by a Teflon O-ring at a spread amount of 0.13 ml / cm ² , and allowed to stand at normal temperature and normal pressure for 2 days to evaporate the solvent. The resulting composite multilayer bilayer thin film was irradiated with ultraviolet light to crosslink and polymerize the monomer. After the polymerization reaction, the composite multilayer bilayer thin film was immersed in chloroform to extract and remove the amphiphilic compound (25).

The obtained film was almost transparent and self-supporting, and had sufficient flexibility and strength. When the cross section of the film was observed by SEM, the film thickness was about 30 μm.
Thus, a multilayer structure having a thickness of about 1000 ° per layer was formed in parallel with the film surface. However, intersecting portions were observed between the layers. The film was immersed in acetone and the swelling ratio was measured.
%, And anisotropy of 41% in the film thickness direction was confirmed, but the value was almost half that of Example 2.

Example 3 Monomer (8) in a molar ratio of 1: 9
And a mixture of the monomer and the monomer (20), and acetone was used as an extraction solvent for the amphipathic compound.
A polymer film was produced in the same manner as in Example 1. The resulting film was translucent and self-supporting.
When the cross section of the film was observed by SEM, the film thickness was about 5 μm.
Thus, a multilayer structure having a thickness per layer of about 100 ° was formed in parallel with the film surface.

Comparative Example 3: Monomer (8) in a molar ratio of 1: 9
A composite multilayer bilayer thin film was prepared in the same manner as in Comparative Example 2, except that a mixture containing the monomer and the monomer (20) was used. When this thin film was irradiated with ultraviolet rays and then immersed in acetone, the thin film was completely dissolved and no polymer film was obtained.

Example 4: A compound having a structure represented by the following formula (26) was used as an amphiphilic compound having a bilayer film forming ability.

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The amphiphilic compound (26) was dissolved in hexafluorobenzene to prepare a 150 mM dispersion. This dispersion was spread on a Teflon sheet surrounded by an O-ring made of Teflon at a spread amount of 0.20 ml / cm ² , and allowed to stand at normal temperature and normal pressure for one day to evaporate the solvent. The obtained multilayer bilayer thin film was a translucent film having self-supporting properties.

A monomer solution was prepared by dissolving the monomer of the formula (1) in pure water at a molar ratio of 1/10. This monomer solution contains 4- (2-hydroxyethoxy) phenyl-
(2-Hydroxy-2-propyl) ketone was added as a polymerization initiator in an amount corresponding to 2 mol% of the monomer (1).

After the multilayer bilayer thin film was immersed in the monomer solution and allowed to stand for 2 days, the multilayer bilayer thin film was removed from the monomer solution. After washing the film surface with pure water, the monomers were cross-linked and polymerized by irradiation with ultraviolet rays. After the polymerization reaction, the multilayer bilayer thin film was immersed in chloroform to extract and remove the amphiphilic compound (26). The obtained film was almost transparent and self-supporting, and had sufficient flexibility and strength. When the cross section of the film was observed by SEM, a multilayer structure having a thickness of about 40 μm and a thickness of about 1000 ° per layer was formed parallel to the film surface.

[0062]

As described above, in the present invention, a multilayer bilayer thin film is once prepared from an amphiphilic compound capable of forming a bilayer, and a monomer is introduced between the layers.
Monomers are two-dimensionally cross-linked and polymerized using a reaction field between the layers of the multilayer bilayer thin film. Therefore, the obtained thin film has a basic thickness on a molecular level, and each layer has a laminated structure of ultrathin films independent of each other. In this way, by separating the process of preparing a multilayer bilayer thin film and the process of introducing a monomer, it is possible to convert a monomer having poor compatibility with an amphiphilic compound or a monomer having a high volatility, which was difficult in the past, from a monomer having a high volatility. An ultra-thin film stack whose structure is controlled at the level is produced. The ultra-thin laminate obtained in this way utilizes its structural features to provide a material separation membrane, ion exchange membrane, solid electrolyte,
It is used as a highly functional material in a wide range of fields as an organic layered compound and the like.

[Brief description of the drawings]

FIG. 1 is an SEM photograph of an ultra-thin film laminate produced in Example 2.

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Claims (2)

(57) [Claims] 1. A multi-layer bilayer thin film of an amphiphilic compound obtained by spreading a dispersion of an amphiphilic compound capable of forming a bimolecular film on a substrate and evaporating a solvent of the dispersion. A method for producing an ultrathin film laminate, comprising contacting with a solution containing a radical polymerizable monomer, polymerizing the monomer introduced into the thin film, and extracting the amphiphilic compound. 2. The method for producing an ultra-thin film laminate according to claim 1, wherein the amphiphilic compound has a fluorocarbon chain in a lyophobic portion.