JP2010235651A - Water-repellent supramolecular organization and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-repellent supramolecular organization which is excellent in strength and resistance to environmental characteristics. <P>SOLUTION: This water-repellent supramolecular organization is such that fullerene structural bodies are organized into the stratified form, wherein the fullerene structural body is composed of a bimolecular film structure in which fullerene derivatives have been organized, and has a particulate shape with a flake structure and the fullerene derivatives are each mutually polymerized. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a water-repellent supramolecular tissue and a method for producing the same, and more particularly to a water-repellent supramolecular tissue and a method for producing the same that are excellent in strength and environmental resistance.

  Nanocarbons typified by fullerenes, carbon nanotubes, and carbon nanohorns are expected to be applied to electronic materials, catalysts, and biomaterials, and are attracting attention.

  In recent years, the inventor of the present application has reported that structures of various dimensions (0 to 3 dimensions) can be arbitrarily produced using fullerene derivatives as a unit among such nanocarbons (see, for example, Patent Document 1). .)

  According to Patent Document 1, the fullerene derivative is composed of a spherical fullerene moiety, an alkyl chain moiety, and a binding moiety that binds them, and the alkyl chain moiety can maintain flatness. By utilizing the balance between the collective force due to the π-π interaction at the fullerene site and the hydrophobic force at the alkyl chain site and the collective force due to van der Waals force, A structure can be constructed.

  Furthermore, the inventor of the present application has developed a supramolecular structure that imitates the surface structure of a lotus leaf using the fullerene derivative described in Patent Document 1 (see, for example, Patent Document 2). According to Patent Document 2, the inventor of the present application pays attention to a fullerene structure in which the bilayer structure formed by the fullerene derivative described in Patent Document 1 is organized, and by organizing the fullerene structure in layers. It has been found that the resulting supramolecular organization has a fractal structure similar to the surface structure of the lotus leaf and exhibits super water repellency.

  Further, according to Patent Document 2, it is known that the supramolecular structure has heat resistance up to about 100 ° C., chemical resistance (organic solvent) resistance to ethanol or acetone, and acid / alkali resistance. . However, the structure of such a supramolecular organization is only maintained by the fullerene π-π interaction in the fullerene derivative and the hydrophobic interaction and van der Waals force of the alkyl chain in the fullerene derivative. Therefore, such a supramolecular organization is relatively brittle and does not have sufficient strength for practical use.

  On the other hand, techniques for improving the strength of organic materials are known (see, for example, Patent Documents 3 and 4). Although patent document 3 is related with an organic gelling agent, the technique which improves the intensity | strength of an organic gelling agent is disclosed by photopolymerizing the diacetylene group contained in the molecule | numerator by ultraviolet irradiation. Patent Document 4 shows a fullerene polymer obtained by polymerizing fullerene by applying polymerization energy such as light. Such fullerene polymers are known to have the full properties of fullerene, high electrical conductivity, and high mechanical strength.

  However, the improvement in strength due to the introduction of a diacetylene group as shown in Patent Document 3 may not be assured since the original structure of the substance may be impaired (see, for example, Non-Patent Documents 1 and 2). .

  Non-Patent Document 1 relates to a molecular assembly of polymerizable amphiphilic molecules having a diacetylene group, and discloses that a diacetylene group is polymerized by ultraviolet irradiation. In addition, according to Non-Patent Document 1, it is shown that the regularity of the structure of the molecular assembly after ultraviolet irradiation changes depending on the length of the spacer composed of the alkyl chain of the polysynthetic amphiphilic molecule, It can be seen that the structure of the molecular assembly is not always maintained before and after UV irradiation.

  Non-Patent Document 2 relates to a helical tube or ribbon formed of a hybrid of a diacetylene group-containing chiral lipid having a twisted lamella structure and silica. It has been shown that when such a tube body and ribbon body are irradiated with ultraviolet rays, the original structure changes (for example, FIG. 4d of Non-Patent Document 2). From these Non-Patent Documents 1 and 2, it can be seen that it is difficult to specify whether or not to maintain the original structure by polymerization and further to maintain the original characteristics in a complicated material system.

  There is no example of applying the technique described in Patent Document 3 or 4 to a fullerene derivative, and it is a matter of course that a supramolecular structure using the above-mentioned fullerene derivative is polymerized to improve strength and environmental resistance characteristics. Absent.

JP 2007-137809 A JP 2008-303148 A JP 2000-248257 A JP-A-8-59220

Shouchun Yin et al., Langmuir 2007, 23, 5936-5941 Annela M.M. Seddon et al., Angew. Chem. Int. Ed. 2002, 41, no. 16, 2998-2991 S. B. Lee et al., Nano Lett. 2005, 5, 2202-2206 G. Wenz et al. Macromolecules 1984, 17, 837-850. A. Fery et al., Polymer 2007, 48, 7221-7235 J. et al. E. Sader, J .; Appl. Phys. 1998, 84, 64-76

  An object of the present invention is to provide a water-repellent supramolecular structure excellent in strength and environmental resistance and a method for producing the same.

  Invention 1 is a water-repellent supramolecular structure in which fullerene structures are organized in layers, wherein the fullerene structure has a bilayer structure in which fullerene derivatives are organized, and has a flake-structured particulate form. And the fullerene derivatives are polymerized with each other.

  Invention 2 is that in the water-repellent supramolecular organization described in Invention 1, the fullerene moieties of the fullerene derivatives are polymerized with each other, and the alkyl chains of the fullerene derivatives are polymerized with each other. Features.

  Invention 3 is the water-repellent supramolecular organization according to Invention 1, wherein the fullerene derivative is represented by the formula (1), the fullerene moiety A represented by the formula (2), and a benzene ring bonded to the fullerene moiety. And an alkyl chain R bonded to each of the 3, 4, and 5 positions of the benzene ring,

  Here, in the formula (1), each of the alkyl chains R includes at least 20 carbon atoms and a polymerizable functional group, and each of the alkyl chains R is polymerized via the polymerizable functional group. In the formula (2), (Fu) represents a fullerene, X represents a hydrogen atom or a methyl group, the benzene ring is bonded to a nitrogen-containing 5-membered ring of the fullerene moiety A, and the fullerene moiety Are polymerized to each other via the fullerene.

  Invention 4 is characterized in that, in the water-repellent supramolecular structure according to Invention 3, the polymerizable functional group is a diacetylene group.

Invention 5 is that in the water-repellent supramolecular structure according to Invention 3, each of the alkyl chains R is —O (CH ₂ ) ₉ C≡C—C≡C (CH ₂ ) ₁₃ CH _3. Features.

  Invention 6 is a method for producing a water-repellent supramolecular structure according to any one of Inventions 1 to 5, wherein a mixture of a fullerene derivative, tetrahydrofuran and methanol is heated to precipitate a fullerene structure. The fullerene derivative is represented by the formula (1), the fullerene moiety A represented by the formula (2), the benzene ring bonded to the fullerene moiety, and the 3, 4, and 5 positions of the benzene ring, respectively. A bonded alkyl chain R;

  Here, in the formula (1), each of the alkyl chains R includes at least 20 carbon atoms and a polymerizable functional group, and cools, holds, and stabilizes the fullerene structure. And a step of stratifying the fullerene structure and irradiating the fullerene structure with light.

  Invention 7 is characterized in that, in the method described in Invention 6, the heating and precipitating step is performed in a temperature range of 40 ° C to 60 ° C.

  Invention 8 is characterized in that, in the method according to Invention 6, the step of cooling, holding and stabilizing is performed in a temperature range of −10 ° C. to −90 ° C. for 12 hours to 24 hours.

  A ninth aspect of the invention is characterized in that, in the method of the sixth aspect, the step of irradiating the light is performed in a deoxygenated atmosphere.

Invention 10 is characterized in that, in the method described in Invention 6, each of the alkyl chains R is —O (CH ₂ ) ₉ C≡C—C≡C (CH ₂ ) ₁₃ CH ₃ .

  Invention 11 is the method according to Invention 6, wherein a poor solvent for the fullerene derivative is added to the mixture after the heating and precipitating steps and before the layering step and the light irradiation step. The method further includes a step.

  In the water-repellent supramolecular structure according to the present invention, fullerene derivatives are organized to form a bilayer structure, and the fullerene structure having a flake-like particle shape is organized in layers. Such a structure exhibits water repellency. In the water-repellent supramolecular organization, each of the fullerene derivatives is polymerized with each other. As a result, the strength increases and the environmental resistance characteristics such as temperature, various organic solvents, and pH can be remarkably improved.

Schematic diagram of water-repellent supramolecular organization (A), fullerene structure (B), and bilayer structure (C) according to the present invention The flowchart which shows the manufacturing step of the water-repellent supramolecular organization body 100 of this invention. Schematic diagram showing changes due to light irradiation of the present invention The flowchart which shows another manufacturing step of the water-repellent supramolecular structure | tissue 100 of this invention. The figure which shows the HR-cryo-TEM image of the fullerene structure which consists of the fullerene derivative 1 before the light irradiation of the reference example 1. The figure which shows the XRD pattern of the fullerene structure which consists of the fullerene derivative 1 before the light irradiation of the reference example 1. The figure which shows the FT-IR spectrum of the fullerene structure which consists of the fullerene derivative 1 before the light irradiation of the reference example 1. The figure which shows the SEM image of the supramolecular organization body which layered the fullerene structure before the light irradiation of the reference example 1 The figure which shows the UV-vis spectrum of the supramolecular organization body which layered the fullerene structure before the light irradiation of the reference example 1 The figure which shows the state of the contact angle with the water of the supramolecular organization body which made the fullerene structure layered before the light irradiation of the reference example 1, and the thin film which made the fullerene derivative 1 layered The figure which shows the HR-cryo-TEM image of the fullerene structure which consists of fullerene derivative 1 after the light irradiation (9 hours) of Example 1. The figure which shows the FT-IR spectrum of the fullerene structure which consists of fullerene derivative 1 accompanying the light irradiation of Example 1. The figure which shows the FT-IR spectrum of the product E shown to the scheme 1 accompanying light irradiation The figure which shows the SEM image of the water-repellent supramolecular organization body after the light irradiation (9 hours) of Example 2. The figure which shows the UV-vis spectrum of the water-repellent supramolecular organization body after the light irradiation of Example 2. The figure which shows the UV-vis spectrum of the product E shown to the scheme 1 accompanying light irradiation The figure which shows the Raman spectrum of the water-repellent supramolecular structure | tissue accompanying light irradiation of Example 2. The figure which shows the DSC differential scanning calorie | heat amount change of the water-repellent supramolecular organization body after light irradiation of Example 3 The figure which shows the relationship between the distortion of a water-repellent supramolecular organization body after light irradiation of Example 3, and force. The figure which shows distribution of the hardness of the water-repellent supramolecular structure | tissue after light irradiation of Example 3 The figure which shows distribution of the adhesive force of the water-repellent supramolecular organization body after light irradiation of Example 3 The figure which shows the SEM image of the water-repellent supramolecular organization body before and behind the heating of Example 4 The figure which shows the state of the contact angle with the water of the water-repellent supramolecular organization body before and behind the heating of Example 4 The figure which shows the heating temperature dependence of the contact angle with respect to the water of the water-repellent supramolecular structure | tissue of Example 4. The figure which shows the state of the contact angle with the water of the supramolecular organization body before and behind the heating of the comparative example 1 The figure which shows the SEM image of the water-repellent supramolecular organization body before and behind being immersed in chloroform of Example 5. The figure which shows the various organic solvent dependence of the contact angle with water of the water-repellent supramolecular structure | tissue of Example 5 The figure which shows the SEM image of the supramolecular structure | tissue by the prior art before and behind being immersed in chloroform of the comparative example 2.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, the same number is attached | subjected to the same element and the description is abbreviate | omitted.

  FIG. 1 shows a schematic diagram of a water-repellent supramolecular structure (A), a fullerene structure (B), and a bilayer structure (C) according to the present invention.

  FIG. 1A shows a state in which the water-repellent supramolecular structure 100 of the present invention is positioned on a substrate 110, and the water-repellent supramolecular structure 100 is in a layered form. The base material 110 may be any base material such as a semiconductor substrate such as Si or GaAs, a quartz substrate, a glass substrate, or a metal substrate. The base material 110 does not need to be a flat plate, and may have a curvature or unevenness on the surface. Thus, if the water-repellent supramolecular organization 100 of the present invention is located on the substrate 110, the handling is simple.

  In the water-repellent supramolecular tissue body 100 of the present invention, the fullerene structure 120 schematically shown in FIG. 1B is organized in a layered manner. Furthermore, the fullerene structure 120 has a particulate shape, and its surface has a flake structure. Due to the surface flake structure, the water-repellent supramolecular tissue body 100 of the present invention exhibits water repellency.

  The fullerene structure 120 has a bilayer structure 140 in which fullerene derivatives 130 schematically shown in FIG. 1C are organized. Note that “the fullerene derivative 130 is composed of the bilayer structure 140” means that the fullerene structure 120 is configured with the bilayer structure 140 as a basic structure. The fullerene derivatives 130 in the bimolecular film structure 140 are polymerized (150, 160) with each other. Thereby, the water-repellent supramolecular structure 100 of the present invention is excellent in strength. In detail, the water-repellent supramolecular structure 100 of the present invention has a collective force due to the π-π interaction of the fullerene site of the fullerene derivative 130 and a collective force due to the hydrophobic interaction and van der Waals force of the alkyl chain. In addition, since the fullerene derivative 130 has bonding strength due to polymerization (150, 160), the fullerene derivative 130 has strength higher than that of the supramolecular structure described in Patent Document 2, for example.

  Specifically, in the polymerization of the fullerene derivative 130 described above, the fullerene sites of the fullerene derivative 130 are polymerized with each other (150), and the alkyl chains of the fullerene derivative 130 are polymerized with each other (160). ). In the present specification, “polymerized” means addition polymerization represented by polymerization or dimerization by radical polymerization or polymerization by cationic polymerization, but the degree of polymerization is not necessarily high. , It may not be partially polymerized / dimerized.

  Next, the water-repellent supramolecular structure 100 of the present invention will be described in more detail using a general formula.

  The water-repellent supramolecular organization 100 of the present invention is composed of a fullerene derivative 130. The fullerene derivative 130 is represented by the following formula (1), the fullerene site A represented by the following formula (2), and the alkyl chain R bonded to each of the 3, 4 and 5 positions of the benzene ring bonded to the fullerene site A: including. In formula (2), (Fu) represents fullerene, X represents a hydrogen atom or a methyl group, and a benzene ring is bonded to the nitrogen-containing 5-membered ring of the fullerene moiety A.

  In formula (1), each of the alkyl chains R is an alkyl chain containing at least 20 carbon atoms from the viewpoint of polymerization efficiency and water repellency. Further, each alkyl chain R is polymerized via a polymerizable functional group. From the viewpoint of polymerization efficiency and maintaining the structure of the bilayer structure 140 after polymerization, the polymerizable functional group is located at the same position of each alkyl chain R, and the alkyl chain R having such a polymerizable functional group is It is desirable that each be the same.

  Examples of the polymerizable functional group include, but are not limited to, a diacetylene group, an epoxy group, and an olefin group. Preferably, the alkyl chain R has a diacetylene group as the polymerizable functional group. This is because if the position of the diacetylene group in each of the alkyl chains R is the same position, the structure of the fullerene derivative 130 and the bilayer structure 140 may be impaired, whether in the middle or at the end of the alkyl chain R. This is because the polymerization can be achieved. FIG. 1C shows a state in which the alkyl chain R has a diacetylene group in the middle as a polymerizable functional group and is polymerized between the alkyl chains R.

Specifically, each of the alkyl chains R having such a diacetylene group is represented by —O (CH ₂ ) ₉ C≡C—C≡C (CH ₂ ) ₁₃ CH ₃ , — (CH ₂ ) ₉ C≡C —C≡C (CH ₂ ) ₁₃ CH ₃ or —S (CH ₂ ) ₉ C≡C—C≡C (CH ₂ ) ₁₃ CH ₃ . These contain a sufficient number of carbon atoms from the viewpoint of polymerization efficiency and water repellency, and have similar characteristics. Further, with these alkyl chains R, polymerization can be achieved without impairing the structures of the fullerene derivative 130 and the bilayer structure 140. In the present invention, for example, polymerization of a diacetylene group is achieved by conjugation between alkyl chains R as schematically shown in FIG. In addition, the unsaturated bond (triple-triple bond) of the diacetylene group does not necessarily become a saturated bond, but includes, for example, a change from a triple-triple bond to a double-triple bond, and necessarily has a high degree of polymerization. Note that it does not have

  On the other hand, when the alkyl chain R has an epoxy group or an olefin group as the polymerizable functional group, the position of the epoxy group or the olefin group is preferably used in order to maintain the structures of the fullerene derivative 130 and the bilayer structure 140. Is the end of the alkyl chain R.

  Although the polymerizable functional group contained in the alkyl chain R has been described as one, it is not limited to this. As long as the above conditions are satisfied, each of the alkyl chains R may have a plurality of polymerizable functional groups or a combined polymerizable functional group. However, since the degree of unsaturation of the alkyl chain R is increased, it becomes difficult to maintain the fullerene derivative 130 and the bilayer structure 140 and the polymerization efficiency may be reduced. It is sufficient to have one polymerizable functional group.

The fullerene in the fullerene part A of the fullerene derivative 130 is selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ , and C ₈₄ . These fullerenes have similar properties and are produced industrially and are readily available. Of these C ₆₀ is advantageous for handling as well as a low cost is simple. As described above, fullerenes at fullerene site A are polymerized to each other (150). Specifically, fullerenes in adjacent fullerene sites A in the bilayer structure 140 are polymerized with each other. FIG. 1C shows a state in which fullerenes are polymerized with each other although fullerenes that are not partially polymerized are included.

  Thus, in the water-repellent supramolecular structure 100 of the present invention, the fullerene sites A of the fullerene derivatives 130 are polymerized with each other, and the alkyl chains R of the fullerene derivatives 130 are polymerized with each other (also referred to as a double crosslink). Call). By adopting such a structure, it is possible to achieve higher strength than the existing supramolecular organization while maintaining the water repellency of the existing supramolecular organization. Furthermore, it was found that the water-repellent supramolecular structure 100 of the present invention has significantly improved temperature resistance, various organic solvents, and environmental resistance characteristics such as pH. Thereby, there is no restriction on the use environment of the water-repellent supramolecular tissue body 100 of the present invention, the practical application can be promoted, and the use expansion can be greatly expected.

  As described above, the fullerene site A and the alkyl chain R in the water-repellent supramolecular tissue body 100 of the present invention do not necessarily need to be completely polymerized, but naturally, the higher the degree of polymerization, the higher the strength. Get higher. Moreover, environmental resistance characteristics, such as temperature tolerance, can also improve, so that a polymerization degree is high. Accordingly, it is desirable to appropriately select a water-repellent supramolecular tissue having a different degree of polymerization depending on the application. In the present specification, “completely polymerized” means a stable state in which polymerization does not proceed any further, and it should be noted that the degree of polymerization is not necessarily high.

  Next, an exemplary method for producing the water-repellent supramolecular tissue body 100 of the present invention will be described.

  FIG. 2 is a flowchart showing manufacturing steps of the water-repellent supramolecular organization 100 of the present invention.

  FIG. 3 is a schematic diagram showing changes due to light irradiation of the present invention.

  Step S210: A mixture of fullerene derivative 130 (FIG. 1) and a predetermined solvent is heated. As a result, a fullerene structure (not shown) composed of the bilayer structure 310 in which the fullerene derivative 130 is organized is deposited. The fullerene derivative 130 is the same as the fullerene derivative described with reference to FIG. It should be noted here that the fullerene derivative 130 is not polymerized. The given solvent is tetrahydrofuran (THF) and methanol. Preferably, the mixing ratio of THF and methanol is 3: 2 (volume% ratio). With this mixing ratio, a fullerene structure can be produced with good yield.

  The mixture is heated in a temperature range of 40 ° C to 60 ° C. The heating time is preferably 15 minutes to 30 minutes considering the composition variation due to evaporation of the solvent. By such heating, a fullerene structure composed of the bilayer structure 310 is generated as a precipitate in the mixture. Such precipitates can be visually confirmed.

  Step S220: The mixture containing the fullerene structure obtained in Step S210 is cooled and held. As a result, the fullerene structure composed of the bilayer structure 310 is stabilized. Cooling and holding are performed in a temperature range of −10 ° C. to −90 ° C. for 12 hours to 24 hours. Considering the freezing point of THF and methanol (-98 ° C to -108 ° C), a temperature range of -10 ° C to -20 ° C is sufficient.

  Step S230: The fullerene structure obtained in step S220 is layered. As a result, a water-repellent supramolecular organization comprising a fullerene structure is obtained. However, again, the fullerene derivative 130 constituting the water-repellent supramolecular organization is not polymerized.

  The stratification is performed by, for example, an LB method in which a fullerene structure is developed on the water surface, a layer made of the fullerene structure is formed at the interface between air and water, and the formed layer is transferred to the substrate 110 (FIG. 1). (Langmuir-Blodgett method). The LB method is preferable because a uniform and high-quality layer can be obtained, but is not limited to this method. For example, a dipping method in which the substrate 110 is immersed in a solution containing the fullerene structure, a dropping method in which a solution containing the fullerene structure is dropped on the substrate 110, and a fullerene structure is contained on the rotating substrate 110. You may employ | adopt the spin coat method which dripping a solution. Further, step S240 may be performed a plurality of times depending on the required thickness.

  Such layering is usually performed on the base material 110. As the base material 110, any base material such as a semiconductor substrate, a quartz substrate, a glass substrate, and a metal substrate can be applied. It does not need to be a flat plate, and may have a curvature or unevenness on the surface. Since the water-repellent supramolecular tissue body 100 of the present invention can be formed on the substrate 110 having a shape corresponding to the application, it is advantageous for practical use.

  Step S240: Light is applied to the water-repellent supramolecular tissue obtained in Step S230. Thereby, the water-repellent supramolecular organization has the fullerene structure 120 (FIG. 1) composed of the bilayer structure 140 (FIGS. 1 and 3) in which the bilayer structure 310 is polymerized. That is, each of the fullerene sites A of the fullerene derivative 130 constituting the bimolecular film structure 310 and each of the alkyl chains R are polymerized with each other.

  Although the light irradiation depends on the type of the polymerizable functional group described with reference to FIG. 1, for example, if the polymerizable functional group is a diacetylene group, ultraviolet rays are preferable, and if it is an epoxy group, visible light is preferable. .

  The light irradiation is preferably performed in a deoxygenated atmosphere. When light irradiation is performed in an atmosphere containing oxygen, epoxidation may occur on the surface of the fullerene site A of the fullerene derivative 130 constituting the bilayer structure, and epoxide may be generated. Such generation of epoxide may reduce the water repellency of the finally obtained water-repellent supramolecular structure 100. Examples of the deoxygenated atmosphere include a vacuum or an inert gas atmosphere such as nitrogen or argon.

  As described above with reference to FIG. 1, the fullerene site A and the alkyl chain R of the water-repellent supramolecular tissue body 100 of the present invention do not necessarily need to be completely polymerized. It is desirable to be able to control. For example, light irradiation can be performed, for example, at room temperature using a 150 W Hg lamp, but the degree of polymerization can be controlled by changing the time of light irradiation. Under the above-mentioned conditions of light irradiation, when it is irradiated for 9 hours, it is completely polymerized, and the degree of polymerization does not change even if light irradiation is further performed.

  Whether or not a fullerene structure having a desired degree of polymerization has been obtained can be determined by, for example, spectra of Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-vis), and Raman spectroscopy. For example, when the alkyl chain R of the fullerene derivative 130 has a diacetylene group, the FT-IR spectrum shows whether the polymer is completely polymerized from the appearance of a band showing C≡C bond in polydiacetylene and the change in its intensity. I understand. Further, from the UV-vis spectrum or Raman spectrum, the degree of polymerization can be determined from the decrease in the intensity of the band indicating fullerene.

  As described above, the water-repellent supramolecular tissue body 100 of the present invention is obtained through steps S210 to S240.

  FIG. 4 is a flowchart showing another manufacturing step of the water-repellent supramolecular organization 100 of the present invention.

  FIG. 4 is the same as the manufacturing method of FIG. 2 except that steps S230 and S240 are reversed.

  Step S410: A mixture of the fullerene derivative 130 (FIG. 1) and a predetermined solvent is heated to precipitate a fullerene structure.

  Step S420: The fullerene structure obtained in Step S410 is cooled, held, and stabilized.

  Step S430: Light is irradiated to the fullerene structure obtained in Step S420. In this case, the fullerene structure obtained in step S420 may be filtered and handled as a solid powder.

  Step S440: The fullerene structure obtained in step S430 is layered.

  Steps S410 and S420 are the same as steps S210 and S220, respectively, step S430 is the same as step S240 except that the fullerene structure is not layered, and step S440 is a polymerization of the fullerene structure. Except for this point, it is the same as step S230, and thus the description thereof is omitted.

  Thus, according to the production method of the present invention, the light irradiation to the fullerene structure, that is, the polymerization of the fullerene derivative 130 in the fullerene structure may be before layering or after layering. It does not matter the order. The production method of the present invention includes a heating step for a specific mixture and a precipitation step for a fullerene structure, a cooling / holding / stabilization step for the fullerene structure, a layering step for the fullerene structure, and a light irradiation step for the fullerene structure. Need only be included.

  In addition, after step S220 in FIG. 2 and before step S230, and after step S420 in FIG. 4 and before step S430, a step of adding a poor solvent for fullerene derivative 130 to the mixture containing the fullerene structure is further added. It may be included. As a result, the fullerene structure composed of the bimolecular film structure 310 (FIG. 3) can be effectively stabilized even at room temperature. The poor solvent is, for example, methanol.

  The present invention will now be described in detail using specific examples, but it should be noted that the present invention is not limited to these examples.

<Reference Example 1>
In Reference Example 1, a fullerene derivative (i) used in the present invention, a fullerene structure (ii) obtained by organizing the fullerene derivative, and a water-repellent supermolecular structure (iii) obtained by layering the fullerene derivative (i) were synthesized. Various characteristics before polymerization were investigated.

As the fullerene derivative of the present invention, the alkyl chain R in the above formula (1) is —O (CH ₂ ) ₉ C≡C—C≡C (CH ₂ ) ₁₃ CH ₃ , and in the above formula (2) (Fu ) Was C ₆₀ and X was CH ₃ to synthesize fullerene derivative 1. Subsequently, the synthesized fullerene derivative 1 was organized into a bilayer structure, and a fullerene structure having this as a basic structure and a water-repellent supramolecular organization composed of the fullerene structure were synthesized. First, the synthesis procedure of the fullerene derivative 1 used in the present invention will be described in detail.
(I) Synthesis of fullerene derivative 1

  A synthesis procedure of fullerene derivative 1 is shown in Scheme 1.

  Fullerene derivative 1 is obtained starting from 1-hexadecin A and via B, C, D and E. These will be described in detail.

Step a: N-bromosuccinimide (8.9 g, 50.0 mmol), 1-hexadecin A (8.88 g, 20.0 mmol), AgNO ₃ (800 mg, 4.7 mmol), and acetone (80 mL) Were mixed and stirred at room temperature for 2 hours, and the white suspension was filtered. The filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography using n-hexane as an eluent to obtain a colorless oily product B. Product B was identified using nuclear magnetic resonance (NMR spectroscopy). The equipment used was a Bruker DMX400. An identification result is shown. The identification result showed that product B was bromoalkyne.

¹ H NMR (400 MHz, CDCl ₃ ): δ 2.20 (t, 2H, J = 7.2 Hz), 1.62-1.15 (m, 24H), 0.90 (t, 3H)
Step b: Hydroxylamine hydrochloride (0.5 g) and cuprous chloride (0.25 g) in an argon atmosphere with 10-undecin-1-ol (10.0 mmol) and 70% aqueous ethylamine solution (5.0 mL) And methanol (20.0 mL) and tetrahydrofuran (THF) (80.0 mL) were added, and the mixture was stirred for 10 minutes to perform Cadiot-Chodkiewicz coupling. Next, the product B (3.01 g, 10.0 mmol) obtained in step a was added and stirred for 30 minutes. When the color of these mixed solutions changed to blue, a trace amount of hydroxylamine chloride was further added. The reaction was allowed to stir at room temperature for 3 hours.

Next, the mixed solution was diluted with 300 mL of water and extracted with CH ₂ Cl ₂ . Since the extracted product was combined with the organic phase, it was washed with saturated Na ₂ CO ₃ and water and dried with sodium sulfate. The solvent was distilled off under reduced pressure, and recrystallization was performed several times from acetone and ethanol to obtain a product C (1.98 g, 5.1 mmol, 71%) as a colorless solid. Product C was identified using NMR spectroscopy. An identification result is shown. The identification result showed that the product C was a diacetylene compound terminated with a hydroxyl group.

¹ H NMR (400 MHz, CDCl ₃ ): δ 3.60-3.66 (m, 2H, —O—CH ₂ ), 2.23 (t, 4H, J = 7.2 Hz, —CH ₂ -t-t _{-CH 2 -), 1.59-1.46 (m} , 6H), 1.41-1.22 (m, 34H), 0.89 (t, 3H, J = 6.1Hz, -CH 3)
Step c: PPh ₃ (8.9 g, 50.0 mmol) and CBr ₄ (800 mg, 2.2 mmol) were added between product C (2.0 g, 20.0 mmol) and dehydrated THF (40 mL) in an argon atmosphere. In addition to the mixed solution, the reaction was allowed to stir at room temperature for 30 minutes. The mixed solution was then concentrated under reduced pressure. The residue was purified by silica gel column chromatography using n-hexane as an eluent to obtain a colorless oily product D (11.04 g, 90%). The product D was identified using NMR spectroscopy. An identification result is shown. The identification result showed that product D was a derivative of product C terminated with bromine.

¹ H NMR (400 MHz, CDCl ₃ ): δ 3.40 (t, 2H, J = 6.8 Hz, —CH ₂ —Br), 2.23 (t, 4H, J = 6.8 Hz, —CH ₂ —t) _{-t-CH 2 -), 1.80-1.88} (m, 2H, CH 2 CH 2 Br), 1.51-1.27 (m, 36H, CH 2), 0.88 (t, 3H , J = 6.8 Hz, CH ₃ —CH ₂ )
Step _{d: K 2 CO 3 (1.04g} , 7.5mmol) and, and KI (25 mg), and 3,4,5-hydroxybenzaldehyde (430 mg, 2.5 mmol), the product D (4.52 g, 10 mmol) and dehydrated dimethylformamide (DMF) (60 mL) were stirred in an argon atmosphere for 16 hours at 70 ° C. to perform Williamson ether synthesis. The reacted mixture was cooled to room temperature, poured into water (200 mL), and extracted twice with dichloromethane (200 mL). The extracted organic phase was dried using sodium sulfate. The solvent was concentrated under reduced pressure and the residue was purified by silica gel column chromatography using dichloromethane / methanol (50/1) as eluent to give white solid product E (2.1 g, 1.6 mmol, 64%). Obtained. Product E was identified using NMR spectroscopy. An identification result is shown. The identification result showed that product E was a precursor benzaldehyde.

¹ H NMR (400 MHz, CDCl ₃ ): δ 9.83 (s, 1H), 7.08 (s, 2H), 4.06 (t, 2H, J = 6.6 Hz), 4.03 (t, 4H) _{, J = 6.4Hz), 2.20 (} t, 12H, J = 6.4Hz, -CH 2 -t-t-CH 2 -), 1.87-1.70 (m, 6H), 1. 47-1.26 (m, 108H), 0.88 (t, 9H, J = 6.8 Hz)
Step e: Adopting the Prato method, product E (600 mg, 0.47 mmol), N-methylglycine (445 mg, 5.0 mmol), C ₆₀ (504 mg, 0.7 mmol) and dehydrated chlorobenzene (500 mL) The mixture was heated and reacted at 130 ° C. for 20 hours in an argon atmosphere. After cooling, the solvent was distilled off under reduced pressure. The residue was roughly purified by silica gel column chromatography using chloroform as an eluent. The crude product was purified by gel permeation chromatography (Bio-beads S-X3, toluene) and recrystallized from chloroform / methanol to synthesize a brown solid product (398 mg, 0.18 mmol, 38%).

  In addition to NMR spectroscopy, products were identified by Fourier transform infrared spectroscopy (FT-IR), matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and UV-visible spectroscopy . The FT-IR spectrum was measured with a Bruker EQINOX 55 / S spectrophotometer using KBr pellets. The MALDI-TOF-MS spectrum was measured in a reflection mode using Bruker Reflex II (matrix: 2- (4-hydroxyphenylazo) benzoic acid). The UV-vis spectrum was measured using a Varian Cary 50 Conc spectrophotometer. An identification result is shown. From the identification result, it was found that the product was the target fullerene derivative 1.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.26-6.68 (br, 2H), 4.97 (d, 1H, J = 9.6 Hz), 4.81 (s, 1H), 4.25 (D, 1H, J = 9.6 Hz), 4.02-3.92 (m, 6H), 2.85 (s, 3H), 2.27-2.18 (m, 12H), 1.75 -1.65 (m, 6H), 1.55-1.20 (m, 108H), 0.88 (t, 9H, J = 6.8 Hz)
¹³ C NMR (100 MHz, CDCl ₃ ): δ 156.0, 154.0, 153.8, 153.4, 153.1, 147.2, 147.0, 146.4, 146.1, 146.0, 145.9, 145.7, 154.4, 145.2, 144.6, 144.3, 143.1, 143.0, 142.5, 142.1, 142.1, 142.0, 141. 8, 141.6, 141.5, 140.1, 140.0, 139.6, 138.3, 136.5, 136.1, 135.7, 131.8, 83.6, 73.1, 70.0, 69.2, 68.9, 65.3, 40.0, 31.9, 30.2, 29.6, 29.4, 29.3, 29.1, 28.8, 28. 3, 25.9, 22.6, 19.2, 14.1
FT-IR (cm < ^-1 >): 2924.0, 2852.4, 2776.7, 2256.3, 1587.4, 116.4
MALDI-TOF-MS: Calculated value 2013.75 of C ₁₅₀ H ₁₄₉ NO ₃ , measured value 2013.45 [M ⁻ ]
UV-vis (n-hexane, 0.5 × 10 ⁻⁵ M): λ _max (ε, M ⁻¹ cm ⁻¹ ) = 210 (178820), 254 (129676), 313 (43120), 430 (4254)
(Ii) Synthesis of Fullerene Structure Composed of Bilayer Structure Organizing Fullerene Derivative 1 A mixture of fullerene derivative 1 (2.0 mg, 1 μmol), tetrahydrofuran THF, and methanol was heated at 50 ° C. for 15 minutes ( Step S210 in FIG. 2 and Step S410 in FIG. 4). Here, the mixing ratio of THF and methanol was 3: 2 by volume%, and the total was 1 mL.

  The mixture was cooled to 20 ° C. and kept at −14 ° C. for 24 hours to precipitate a dark yellow precipitate (step S220 in FIG. 2 and step S420 in FIG. 4). Furthermore, methanol (3 mL) which is a poor solvent for the fullerene derivative 1 was added to the mixture containing the precipitate, and the precipitate was stabilized at room temperature.

  Observation by high-resolution cryo-transmission electron microscope (HR-cry-TEM) that the precipitate is a fullerene structure (not polymerized) having a bilayer structure of fullerene derivative 1 as a basic structure, powder Identification by X-ray diffraction (XRD) and FT-IR was performed.

  Observation with HR-cryo-TEM was performed with a JEOL transmission electron microscope JEM-4000SFX at an acceleration voltage of 400 kV. Observation results were recorded on photographic film using a low-dose system that minimizes radiation damage to the sample by the electron beam. A sample for HR-cryo-TEM was prepared as follows.

  A mixture containing precipitates was dropped onto a carbon-coated copper grid, and excess solution on the grid was removed with filter paper. The grid was then frozen in liquid propane maintained at a temperature of 100K or less in an osmosis cryofixation apparatus. The frozen grid was used as a sample for HR-cryo-TEM. In addition, in order to observe the structure of the sample as it is, no staining or the like is performed.

  The sample was placed in a partition of a custom cryotransfer system attached to an HR-cryo-TEM. The cryotransfer system includes a liquid helium stage and can maintain the sample at about 4K.

  Powder XRD diffraction was performed at 25 ° C. using a RIGAKU RINT Ultimate III X-ray diffractometer using Cu Kα rays (λ = 0.15405 nm) monochromatized with a monochromator. Identification by UV-vis and FT-IR is as described above. The results of these HR-cryo-TEM, XRD and FT-IR are shown in FIGS.

  FIG. 5 is a diagram showing an HR-cryo-TEM image of the fullerene structure composed of the fullerene derivative 1 before light irradiation in Reference Example 1.

  The inset in FIG. 5 is a fast Fourier transform image of a striped image. FIG. 5 shows the end of the fullerene structure. FIG. 5 shows that the fullerene structure has a multilayer structure (multilamella structure). As shown in the inset of FIG. 5, according to the fast Fourier transform (FFT) analysis, the interlayer distance was found to be 5.7 ± 0.1 nm. Furthermore, it can be seen from the fact that the bright spot of the third spot appears in the FFT, the multilayer structure has extremely high regularity. Considering the size of fullerene derivative 1 (about 4.5 nm), it is suggested that the fullerene structure has a bilayer structure 310 (FIG. 3).

  FIG. 6 is a diagram showing an XRD pattern of the fullerene structure composed of the fullerene derivative 1 before light irradiation in Reference Example 1.

According to FIG. 6, the fullerene structure exhibits reflections of (001), (002), (003), (004), (005), (006), (007), (008) and (009). It was. This indicates a regular multilayer structure over a long distance, and agrees well with the results of FIG. The interlayer distance obtained from FIG. 6 is 6.0 nm, which is slightly larger than the result of FIG. This slight difference is due to differences in experimental conditions such as temperature and pressure. In addition, FIG. 6 showed two broad halos at about 10.3 ° and about 19.4 °. These halos correspond to the in-plane average distance between adjacent C ₆₀ (about 8.7 nm) and the in-plane average distance between alkyl chains (about 0.46 nm), respectively.

  FIG. 7 is a diagram showing an FT-IR spectrum of the fullerene structure composed of the fullerene derivative 1 before light irradiation in Reference Example 1.

FT-IR spectra of Figure 7, the asymmetric stretch mode of the methylene groups in the wave number 2924 cm ^-1, and showed the symmetric stretching mode of the methylene groups in the wavenumber 2852cm ^-1. This indicates that in the fullerene structure, the alkyl chain of the fullerene derivative 1 constituting the fullerene structure is not in a crystalline state. Furthermore, according to the orthorhombic sublattice structure oligomethylene group, as shown in the insert of FIG. 7, a broad peak splitting around a wave number of about 1463cm ^-1 (postmitotic wavenumber 1467cm ^-1 and 1460 cm ^{- 1} ). This peak splitting corresponds to the scissor mode of the methylene group, and suggests that in the fullerene structure, the alkyl chains of the fullerene derivative 1 are in mesh with each other as shown in the bilayer structure 301 (FIG. 3).

  As described above, the bilayer structure in which fullerene derivative 1 is organized by performing steps S210 (S410) and S220 (S420) shown in FIG. 2 (or FIG. 4) on fullerene derivative 1 according to FIGS. It was confirmed that a fullerene structure composed of 310 (FIG. 3) was formed.

(Iii) A layered LB method of a fullerene structure having a bilayer structure in which the fullerene derivative 1 is organized as a basic structure was employed for layering. The fullerene structure, which is the precipitate obtained in (ii) above, is developed on the water surface, a layer composed of the fullerene structure is formed at the interface between air and water, and the formed layer is formed into a Si substrate, quartz glass, and Each was transferred to glass (slide glass cover) to produce a thin film in which the fullerene structure was organized in layers (step S230 in FIG. 2). The thin film thus obtained was examined to be composed of a fullerene structure and to have water repellency.

  The surface of the thin film layered on the Si substrate was observed with a scanning electron microscope (SEM). Observation by SEM was performed with a Philips XL30 electron microscope at an acceleration voltage of 3 kV. As a sample for SEM, a sample obtained by sputtering Au on a thin film on a Si substrate with a JFC-1300 JEOL automatic sputter coater equipped with an MTM-20 film thickness controller was used. Similar to (i) above, the UV-vis spectrum of the thin film layered on the quartz substrate was measured. These results are shown in FIGS.

  FIG. 8 is a view showing an SEM image of a supramolecular structure obtained by layering the fullerene structure before irradiation with light in Reference Example 1.

  From FIG. 8, it was confirmed that the thin film obtained on the Si substrate was a supramolecular structure composed of a fullerene structure having a particulate shape. Further, as shown in the inset (scale bar = 500 nm), it was confirmed that the surface of the fullerene structure had a flake structure. The size of the particulate shape was about 1 μm, and the thickness of each flake of the flake structure was about 100 nm.

  FIG. 9 is a diagram showing a UV-vis spectrum of a supramolecular structure obtained by layering the fullerene structure before irradiation with light in Reference Example 1.

FIG. 9 also shows the UV-vis spectrum of fullerene derivative 1 obtained in (i) above. The UV-vis spectrum of the supramolecular organization showed three peaks with absorption maxima at 329 nm, 271 nm and 212 nm. On the other hand, as described above, the UV-vis spectrum of the fullerene derivative 1 (uniform dispersion state in the solution) showed three peaks having absorption maximum values at 313 nm, 254 nm, and 210 nm. By layering the fullerene structure in which the fullerene derivative 1 is organized, the three peaks shift to 16 nm, 17 nm, and 2 nm (red shift) on the longer wavelength side, respectively, and the absorption in the visible region increases. This suggests that a π-π interaction is acting between adjacent C ₆₀ in the fullerene structure in the layered thin film.

  As described above, in addition to FIGS. 5 to 7, FIG. 8 and FIG. 9 also show a fullerene structure having a particle shape of flake structure, which consists of a bilayer structure 310 (FIG. 3) in which the fullerene derivative 1 is organized. It was confirmed that a body was formed and that a supramolecular structure in which the shape of the fullerene structure was maintained even when the fullerene structure was layered was formed.

  Next, the surface wettability was examined from the contact angle of the supramolecular structure on the Si substrate with water. The contact angle with water was measured at room temperature using a contact angle measuring system G10 apparatus (Kruss (but u is umlaut), Germany). The results are shown in FIG.

  FIG. 10 is a diagram illustrating a contact angle state of water with a supramolecular structure layered with a fullerene structure and a thin film layered with a fullerene derivative 1 before light irradiation in Reference Example 1.

  FIG. 10A shows the state of the contact angle between the supramolecular organization and water. FIG. 10B also shows the contact angle state of the layered thin film directly with water without organizing the fullerene derivative 1 synthesized in (i) above. Specifically, a chloroform solution containing the fullerene derivative 1 was applied onto a Si substrate by spin coating, and layered to obtain a thin film.

  From FIG. 10 (A), the supramolecular structure exhibited a high water repellency having a contact angle of about 146.2 ° by organizing the fullerene derivative 1 and layering the fullerene structure. On the other hand, FIG. 10B shows that when the fullerene derivative 1 is directly layered to form a thin film, the contact angle is 102.1 ° and the water repellency is extremely low. Therefore, in order to fully develop the water repellency, it is effective to organize the fullerene derivative 1 into a bilayer structure 310 (FIG. 3) and to layer the fullerene structure based on this structure. I found out.

  The fullerene structure synthesized in (ii) of Reference Example 1 was irradiated with light (step S430 in FIG. 4), the fullerene derivative 1 constituting the fullerene structure was polymerized, and the characteristics were examined. Light irradiation was performed for up to 11 hours using a low-pressure Hg lamp of 150 W at 25 ° C. Specifically, the time of light irradiation is 4 minutes, 30 minutes (0.5 hours), 43 minutes, 108 minutes, 180 minutes (3 hours), 198 minutes, 312 minutes, 426 minutes, 540 minutes (9 hours) 666 minutes (11 hours).

  The state of the front end portion of the fullerene structure after the light irradiation was observed with HR-cryo-TEM. The preparation of the sample for HR-cryo-TEM was the same as (ii). The observation result of the fullerene structure subjected to light irradiation for 9 hours is shown in FIG.

  FIG. 11 is a diagram showing an HR-cryo-TEM image of the fullerene structure composed of the fullerene derivative 1 after light irradiation (9 hours) in Example 1.

  The inset in FIG. 11 is a fast Fourier transform image of a striped image. FIG. 11 shows that the fullerene structure maintains a multilayer structure (multilamella structure) even after light irradiation, as in FIG. 5. As shown in the inset of FIG. 11, according to the FFT analysis, the interlayer distance was found to be 5.7 ± 0.1 nm as in FIG. Furthermore, from the fact that the bright spot of the tertiary spot appeared in the FFT, it can be seen that the multilayer structure maintains extremely high regularity even after light irradiation.

  The FT-IR spectrum was measured about the fullerene structure after light irradiation. The FT-IR spectrum was measured in the same manner as (i) and (ii) at 25 ° C. in an argon atmosphere. The results are shown in FIG.

  Reference experiments were performed to interpret the results. As a reference experiment, the product E (precursor benzaldehyde shown in Scheme 1) obtained in step d of (i) above is irradiated with light, and the product E, specifically, the diacetylene group of the product E has An alkyl chain equipped with was polymerized. A low pressure Hg lamp of 150 W at 20 ° C. was used for light irradiation. The time of light irradiation was changed to 0 minutes, 1 minute, 3 minutes, 5 minutes, 6 minutes, 10 minutes, 15 minutes, 25 minutes, 35 minutes, 75 minutes and 180 minutes. The FT-IR spectrum was measured for the product E irradiated with light at 0 minutes, 5 minutes, 35 minutes, 75 minutes and 180 minutes. These results are shown in FIG.

  12 is a diagram showing an FT-IR spectrum of the fullerene structure composed of the fullerene derivative 1 after light irradiation in Example 1. FIG.

  FIG. 12 shows each FT-IR spectrum of the fullerene structure irradiated with light for 4 minutes, 43 minutes, 108 minutes, 198 minutes, 312 minutes, 426 minutes, and 666 minutes, and the light shown in FIG. 7 for reference. The FT-IR spectrum (light irradiation time 0 minutes) of the fullerene structure which consists of the fullerene derivative 1 before irradiation is also shown.

According to FIG. 12, as the light exposure time is increased, the intensity of the absorption band centered at 2256cm ^-1 and 2191cm ^-1 corresponding to the asymmetric oscillation mode of the diacetylene group was lower. On the other hand, as the light irradiation time increased, an absorption band centered at 2212 cm ⁻¹ corresponding to the asymmetric vibration mode of the C≡C triple bond of polydiacetylene appeared and its intensity increased. The FT-IR spectrum of FIG. 12 has no isosbestic point. This suggests that two or more types are included in the polymerization reaction by light irradiation.

  Although not shown, the FT-IR spectrum of the fullerene structure irradiated with light for 540 minutes (9 hours) coincided with that of the fullerene structure irradiated with light for 666 minutes. From this, it is considered that the fullerene structure was completely polymerized and stabilized when irradiated for 9 hours under the above-mentioned light irradiation conditions.

  FIG. 13 is a diagram showing an FT-IR spectrum of the product E shown in Scheme 1 after light irradiation.

According to FIG. 13, similar to the behavior of 12, as the light exposure time is increased, the intensity of the absorption band centered at 2256cm ^-1 and 2179cm ^-1 was low. Similarly to the behavior of FIG. 12, as the light irradiation time increased, an absorption band centered at 2215 cm ⁻¹ appeared and its intensity increased.

  12 and 13 suggest that polymerization was performed between the alkyl chains of fullerene derivative 1 constituting the fullerene structure. Thereafter, the polymerized fullerene structure is layered (step S440 in FIG. 4), and a supramolecular structure can be synthesized. As described above, the effectiveness of the method shown in FIG. 4 of the present invention was demonstrated from Example 1.

  The water-repellent supramolecular organization on the various substrates synthesized in (iii) of Reference Example 1 is irradiated with light (Step S240 in FIG. 2), and the fullerene derivative 1 constituting the water-repellent supramolecular organization is polymerized. The characteristics were investigated. The light irradiation was performed for up to 11 hours using a low-pressure Hg lamp of 150 W at 25 ° C. as in Example 1. Specifically, the time of light irradiation is 4 minutes, 30 minutes (0.5 hours), 43 minutes, 108 minutes, 180 minutes (3 hours), 198 minutes, 312 minutes, 426 minutes, 540 minutes (9 hours) 666 minutes (11 hours).

  The state of the surface of the water-repellent supramolecular organization after light irradiation was observed by SEM. FIG. 14 shows the observation results of the water-repellent supramolecular organization subjected to light irradiation for 9 hours.

  FIG. 14 is a view showing an SEM image of the water-repellent supramolecular organization after light irradiation (9 hours) in Example 2.

  FIG. 14 shows the same morphology as in FIG. 8, and even after light irradiation, the fullerene structure maintained a particulate shape, and it was confirmed that the entire surface had a flake structure. The size of the particulate shape was about 1 μm, and the thickness of each flake of the flake structure was about 100 nm.

  Combined with the result of FIG. 11 of Example 1, the morphology of the fullerene structure before light irradiation is the fullerene structure before layering and after light irradiation, and the supramolecular structure after layering and after light irradiation. Was also maintained well.

The UV-vis spectrum and the Raman spectrum were measured for the water-repellent supramolecular organization after light irradiation. These results are shown in FIGS. 15 and 17, respectively. The measurement of the UV-vis spectrum was performed in the same manner as (i) at 25 ° C. in an argon atmosphere. The Raman spectrum was measured using a HAL100 Witec spectrophotometer at a laser wave number of 785 cm ^{−1 in} an argon atmosphere at 25 ° C. The laser intensity was kept as low as possible to prevent C ₆₀ from polymerizing during the measurement. In addition, the water-repellent supramolecular organization on the quartz substrate after light irradiation was used for the measurement of UV-vis spectrum and Raman spectrum.

  As in Example 1, a reference experiment was performed to interpret the results. UV-vis spectrum was measured for product E used in Example 1, which was irradiated with light for 0 minutes, 1 minute, 3 minutes, 6 minutes, 10 minutes, 15 minutes and 25 minutes. The results are shown in FIG.

  FIG. 15 is a diagram showing a UV-vis spectrum of a water-repellent supramolecular organization associated with light irradiation in Example 2.

  FIG. 15 shows the UV-vis spectrum of the water-repellent supramolecular structure after 666 minutes (11 hours) of light irradiation, and for reference, the UV-vis of the water-repellent supramolecular structure before light irradiation shown in FIG. A vis spectrum (light irradiation time 0 minutes) is also shown.

According to FIG. 15, the intensity of the C ₆₀ absorption band was reduced and broadened by light irradiation. This suggests that polymerization occurred between adjacent C ₆₀ in the fullerene structure constituting the water-repellent supramolecular organization. Although not shown, the UV-vis spectrum of the water-repellent supramolecular structure irradiated with light for 540 minutes (9 hours) coincided with that of the water-repellent supramolecular structure irradiated with light for 666 minutes. As in FIG. 12 of Example 1, it is considered that the fullerene structure in the water-repellent supramolecular structure was completely polymerized and stabilized when irradiated for 9 hours under the above-described light irradiation conditions.

  FIG. 16 is a diagram showing a UV-vis spectrum of the product E shown in Scheme 1 after light irradiation.

  According to FIG. 16, as the light irradiation time increased, an absorption band near 550 nm appeared and its intensity increased. This is in good agreement with the finding shown in Non-Patent Document 3 that when a polydiacetylene having a long conjugate length is produced, an absorption band is generated at about 550 nm.

  The result of FIG. 15 is different from that of FIG. With reference to the knowledge shown in Non-Patent Document 4 that polydiacetylene having a conjugated length and a structure changed by polymerization is generated, in the water-repellent supramolecular organization according to the present invention, The diacetylene group in the chain suggests that it is difficult to become a polydiacetylene having a long conjugated length (trans-type double-triple-double bond) (for example, a bilayer structure 140 in FIG. 3). Specifically, the triple-triple bond of the diacetylene group in the alkyl chain of the fullerene derivative 1 is partially changed to a non-linear cis double-triple-double bond.

  The fullerene structure after polymerization as schematically shown in the bilayer membrane structure 140 (FIG. 3) is caused by the arrangement of diacetylene groups in the alkyl chain in the fullerene derivative 1. The arrangement of the diacetylene groups in the alkyl chain in the fullerene derivative 1 used in the present invention is somewhat incomplete compared to that of the product E in Scheme 1, and as a result, polymerization by light irradiation is hindered and stretched. Formation of polydiacetylene having type conjugation is suppressed.

  FIG. 17 is a diagram showing a Raman spectrum of the water-repellent supramolecular organization after light irradiation in Example 2.

FIG. 17 shows Raman spectra of water-repellent supramolecular structures irradiated with light for 30 minutes (0.5 hours), 180 minutes (3 hours), and 540 minutes (9 hours), respectively. 2 shows the Raman spectrum of the water-repellent supramolecular organization (light irradiation time 0 minutes) and the Raman spectrum of fullerene C ₆₀ used in step e of (i) above.

According to FIG. 17, as the light irradiation time increased, the intensity of the band centered at 1467 cm ⁻¹ corresponding to the C ₆₀ pentagonal pinch mode decreased. In addition to FIG. 15, this also suggests that polymerization occurred between adjacent C ₆₀ in the fullerene structure.

  As mentioned above, it is suggested from FIGS. 15-17 that it polymerized between the fullerene site | parts of the fullerene derivative 1 which comprises a water-repellent supramolecular structure | tissue, and between alkyl chains. Further, from Example 2, the effectiveness of the method shown in FIG. 2 of the present invention was shown.

  According to Examples 1 and 2, in a fullerene structure in which fullerene derivative 1 is organized and a molecular assembly such as a water-repellent supramolecular organization in which the fullerene derivative 1 is layered, after polymerization by light irradiation, However, it was confirmed for the first time that the morphology of the fullerene structure before polymerization shown in FIGS. 5 and 8 was well maintained.

  In Example 2, using a water-repellent supramolecular structure that was completely polymerized and stabilized and irradiated with light for 9 hours, the change in calorific value and strength characteristics were examined. The calorie change was measured using DSC 204 at a scanning speed of 5 ° C./min in an argon atmosphere, and a differential scanning calorie change diagram was obtained. For the measurement of change in calorific value, a water-repellent supramolecular structure on the Si substrate after light irradiation for 9 hours was peeled off from the Si substrate and used as a powder. The results are shown in FIG.

  The intensity characteristics were measured in the atmosphere by the colloid probe method shown in Non-Patent Document 5 using an atomic force microscope AFM (MFP 1D, Asylum research). For measurement of strength characteristics, a water-repellent supramolecular organization on a glass substrate after light irradiation for 9 hours was used. A glass bead (Polyscience Inc.) having a diameter of about 50 μm was attached with two epoxy adhesives (UHU Plus endfest 300, UHU GmbH & Co. KG, Germany) using a micromanipulator (Suttner Instruments Co.). Rescantilever (MicroMash) was used. The spring constant of the cantilever was determined by the Sader method shown in Non-Patent Document 6. Four different areas were measured for each sample. These results are shown in FIGS.

  FIG. 18 is a diagram showing a DSC differential scanning calorific value change of the water-repellent supramolecular organization after light irradiation in Example 3.

For reference, FIG. 18 also shows the DSC differential scanning calorimetric change (before UV irradiation) of the water-repellent supramolecular tissue before light irradiation. According to the DSC differential scanning calorimetric change of the water-repellent supramolecular structure before light irradiation, a broad peak around 15 ° C. (indicated by a black circle in the figure) and a clear peak centered at 29.1 ° C. Indicated. Each of these peaks is an endothermic peak resulting from a phase transition of the alkyl chain in the fullerene derivative 1 constituting the water-repellent supramolecular organization from a solid phase to a solid-liquid intermediate phase. The enthalpy ΔH and entropy ΔS determined from these peaks were 55.4 kJmol ⁻¹ and 180 Jmol ⁻¹ K ⁻¹ , respectively. Furthermore, the DSC differential scanning calorimetric change of the water-repellent supramolecular texture before light irradiation showed a clear peak centered at 140.3 ° C. (melting point of fullerene derivative 1). This peak is an endothermic peak resulting from the phase transition from the solid-liquid intermediate phase to the isotropic phase.

  On the other hand, the DSC differential scanning calorimetric change of the water-repellent supramolecular structure after light irradiation shows endothermic peaks at 15 ° C., 29.1 ° C., and 104.3 ° C., but the intensity is repellent before light irradiation. It was less than 5% of that of the aqueous supramolecular organization. This slightly detected endothermic peak is considered to be an unreacted monomer in the fullerene derivative 1 in the water-repellent supramolecular organization after light irradiation. This also indicates that, as described above, even when the fullerene derivative 1 is completely polymerized, the degree of polymerization is not necessarily high.

  Furthermore, the DSC differential scanning calorimetric change of the water-repellent supramolecular organization after light irradiation showed a broad peak at 51.2 ° C. This is considered to be a glass transition point of alkyl chains polymerized with each other in the water-repellent supramolecular organization after light irradiation.

  As described above, by polymerizing a water-repellent supramolecular structure composed of a fullerene structure in which fullerene derivative 1 is organized by light irradiation, the structure is stable without phase transition even when the melting point of fullerene derivative 1 is exceeded. I understood it. That is, it was shown that the water-repellent supramolecular organization after light irradiation has high thermal stability.

  FIG. 19 is a diagram showing the relationship between strain and force of the water-repellent supramolecular tissue body after light irradiation in Example 3.

  For reference, FIG. 19 also shows the relationship between the strain and force of the water-repellent supramolecular organization before light irradiation. The solid line indicates the forward path, and the dotted line indicates the return path. According to the behavior of the water-repellent supramolecular organization after light irradiation, it can be seen that a large force is applied as the strain increases. This indicates that the water-repellent supramolecular organization after light irradiation has higher strength than that before light irradiation. From FIG. 19, the hardness of the water-repellent supramolecular organization before and after the light irradiation was calculated to be 0.64 N / m and 14.4 N / m, respectively.

  FIG. 20 is a view showing the hardness distribution of the water-repellent supramolecular organization after light irradiation in Example 3.

  For reference, FIG. 20 also shows the hardness distribution of the water-repellent supramolecular organization before light irradiation. From FIG. 20, it was found that the water-repellent supramolecular structure after light irradiation has a higher strength than that before light irradiation over the entire sample. Specifically, the hardness of the water-repellent supramolecular structure before light irradiation was 0.54 ± 0.48 N / m, but the hardness of the water-repellent supramolecular structure after light irradiation was 14.5 ±. 1.7 N / m, an increase of about 25 times that before light irradiation.

  FIG. 21 is a diagram showing the distribution of adhesive strength of the water-repellent supramolecular tissue body after light irradiation in Example 3.

  For reference, FIG. 21 also shows the distribution of adhesive strength of the water-repellent supramolecular tissue before light irradiation. From FIG. 21, it was found that the water-repellent supramolecular organization after light irradiation has a lower adhesive force over the entire sample than that before light irradiation. Specifically, the adhesive strength of the water-repellent supramolecular tissue before light irradiation was 425 ± 90 nN, but the adhesive strength of the water-repellent supramolecular tissue after light irradiation was 140 ± 28 nN. This is because, for example, the adhesive force of the water-repellent supermolecular structure after light irradiation is lower than that before light irradiation. Shows excellent cleaning function.

  The relationship between heat resistance and water repellency of the water-repellent supramolecular structure of the present invention was examined. As the sample, the water-repellent supramolecular structure on the Si substrate that was completely polymerized and stabilized in Example 2 and irradiated with light for 9 hours was used.

  The surface of the supramolecular structure heated at 150 ° C. (temperature setting not lower than the melting point (140.3 ° C.) of fullerene derivative 1) for 12 hours was observed by SEM. The results are shown in FIG. The contact angle with water of the supramolecular organization heated at 200 ° C. for 20 hours was measured. The results are shown in FIG. Furthermore, about the supramolecular organization body which heated up to each temperature of 150 degreeC, 50 degreeC, 75 degreeC, 100 degreeC, 125 degreeC, 150 degreeC, 200 degreeC, 250 degreeC, and 300 degreeC and hold | maintained at each temperature for 3 minutes, The heating temperature dependence of the contact angle was investigated. The measurement was performed at room temperature after heating at each heating temperature. The results are shown in FIG.

  22 is a SEM image of the water-repellent supramolecular organization before and after heating in Example 4. FIG.

  22A is an SEM image of the water-repellent supramolecular structure before heating, and FIG. 22B is an SEM image of the water-repellent supramolecular structure after heating. FIG. 22 shows that there is no change in the morphology of the supramolecular organization even before and after heating. This result agrees with the result of FIG. 18, and the water-repellent supermolecular structure of the present invention is stable even when the melting point (140.3 ° C.) of the fullerene derivative 1 constituting the water-repellent supermolecular structure is exceeded. It shows that. This shows the high thermal stability of the structure of the water-repellent supramolecular organization of the present invention.

  FIG. 23 is a diagram showing the contact angle state of the water-repellent supramolecular tissue body with water before and after heating in Example 4.

  FIG. 23A shows the state of contact angle of water with the water-repellent supramolecular structure before heating, and FIG. 23B shows the state of contact angle with water of the water-repellent supramolecular structure after heating. Indicates the state. FIG. 23A shows that the supramolecular structure before light irradiation through steps S210 to S240 shown in FIG. 2 has high water repellency (contact angle 145.3 °). This indicates that even when the fullerene derivative 1 is polymerized by light irradiation, the water repellency exhibited by the water-repellent supramolecular structure before light irradiation is maintained well (for example, FIG. 10A). . FIG. 23 (B) shows that the water-repellent supramolecular structure after heating also has high water repellency (contact angle 144.1 °). From this, it was found that heating the supramolecular structure at a temperature exceeding the melting point of the fullerene derivative 1 has no effect on the water repellency (contact angle 144.1 °).

  FIG. 24 is a view showing the heating temperature dependence of the contact angle of water-repellent supramolecular tissue body of Example 4 with respect to water.

  FIG. 24 also shows the values of the contact angle of the supramolecular tissue body obtained in FIG. Up to a heating temperature of 200 ° C., the contact angle value was not dependent on the heating temperature. That is, it can be seen that the supramolecular organization of the present invention has extremely high heat resistance and high water repellency up to a heating temperature of 200 ° C. When the heating temperature exceeded 250 ° C., although the water repellency was exhibited, a decrease in the contact angle value was observed. At a temperature of 250 ° C. or higher, the water-repellent supramolecular structure of the present invention can be applied depending on the required degree of water repellency.

<Comparative Example 1>
The relationship between the heat resistance and water repellency of the supramolecular structure of the fullerene derivative 1 that was not irradiated with light, ie, that was not polymerized, was examined. As the sample, the supramolecular structure on the Si substrate obtained in (iii) of Reference Example 1 was used. The contact angle of water with a supramolecular structure heated at 150 ° C. for 5 seconds was measured. The results are shown in FIG.

  FIG. 25 is a diagram illustrating a state of a contact angle with water of the supramolecular organization before and after heating in Comparative Example 1.

  FIG. 25 (A) shows the contact angle of the supramolecular tissue body with water before light irradiation and before heating, and is the same as FIG. 10 (A). FIG. 25 (B) shows the state of the contact angle of the supramolecular organization with water before light irradiation and after heating. As described with reference to FIG. 10 (A), even before light irradiation, the flake structure of the fullerene structure constituting the supramolecular organization exhibits good water repellency (contact angle 146.2 °). . However, as shown in FIG. 25 (B), when the supramolecular tissue that was not irradiated with light was heated, the water repellency (contact angle 100.8 °) was significantly reduced. As described with reference to FIG. 18, when heated at a temperature exceeding the melting point (140.3 ° C.) of the fullerene derivative 1 constituting the supramolecular organization, the fullerene structure cannot be maintained. This is because the flake structure is broken.

  From Example 4 and Comparative Example 1, it was shown that the polymerization of the fullerene derivative 1 constituting the supramolecular organization contributed to maintaining high heat resistance.

  The chemical resistance of the water-repellent supramolecular structure of the present invention and the relationship between acid / alkali resistance and surface wettability were investigated. As the sample, the water-repellent supramolecular structure on the Si substrate that was completely polymerized and stabilized in Example 2 and irradiated with light for 9 hours was used.

The water-repellent supramolecular tissue after light irradiation was immersed in various organic solvents, and the relationship between chemical resistance and acid / alkali resistance and surface wettability was investigated. The surface of the water-repellent supramolecular tissue immersed in chloroform (CHCl ₃ ) for 12 hours was observed with an SEM. The results are shown in FIG. Ethanol, acetone, tetrahydrofuran (THF), acetonitrile (CH ₃ CN), ethyl acetate (AcOEt), chloroform (CHCl ₃ ), toluene and n-hexane as various organic solvents, pH = 1 strong acid aqueous solution and pH as acid / alkali The water-repellent supramolecular structure after irradiation with light was immersed in each of the 11 strong alkaline aqueous solutions for 3 minutes, washed with acetone, dried, and then contacted with water. The results are shown in FIG.

  FIG. 26 shows SEM images of the water-repellent supramolecular organization before and after immersion in chloroform in Example 5.

  FIG. 26A shows an SEM image of the water-repellent supramolecular structure before immersion in chloroform, and FIG. 26B shows an SEM image of the water-repellent supramolecular structure after immersion in chloroform. Further, from FIG. 26B, it was found that the morphology of the supramolecular tissue body of the present invention was not affected even when the fullerene derivative 1 was immersed in chloroform as a good solvent for a long time.

  FIG. 27 is a diagram showing various organic solvent dependences of the contact angle of water-repellent supramolecular tissue body of Example 5 with water.

  According to FIG. 27, even when the water-repellent supramolecular tissue of the present invention is immersed in a strong acidic and strong alkaline aqueous solution, a good solvent for the fullerene derivative 1 such as chloroform, THF and toluene, and other typical organic solvents. The contact angles were all maintained at 144 ° or more, and it was found that there was no effect on the high water repellency.

<Comparative example 2>
As the supramolecular organization according to the prior art, the chemical resistance of the supramolecular organization described in Patent Document 2 was examined. The fullerene derivative 2 in which the alkyl chain R in the above formula (1) is —O (CH ₂ ) ₁₉ CH ₃ , (Fu) is C ₆₀ in the above formula (2), and X is CH ₃ is used. Thus, the supramolecular organization described in Patent Document 2 was synthesized.

  Fullerene derivative 2 was dissolved in 1,4-dioxane solution (1 mL), heated at 70 ° C. for 2 hours, and cooled to room temperature. This produced a black-brown precipitate at the bottom of the solution. In the same procedure as in (iii) of Example 1, the precipitate was layered on the Si substrate to synthesize a supramolecular organization.

  Subsequently, the supramolecular organization according to the prior art was irradiated with light in the same manner as in Examples 3 and 4. Light irradiation was performed for 9 hours using a low-pressure Hg lamp of 150 W at 25 ° C. The state of the surface of the supramolecular organization according to the prior art after light irradiation was observed by SEM. Thereafter, the supramolecular structure according to the prior art after the light irradiation was immersed in chloroform, which is a good solvent for the fullerene derivative 2, for 5 seconds, and then the surface state of the supramolecular structure was observed again by SEM. The observation results are shown in FIG.

  FIG. 28 is a diagram showing SEM images of supramolecular structures according to the prior art before and after immersion in chloroform of Comparative Example 2.

  FIG. 28 (A) shows the state of the surface of the supramolecular structure after irradiation with light and before immersion in chloroform, and FIG. 28 (B) shows the prior art after irradiation with light and after immersion in chloroform. Shows the surface of the supramolecular organization. From FIG. 28 (A), it was confirmed that even when the supramolecular structure according to the prior art was irradiated with light, the same morphology as that of the water-repellent supramolecular structure of the present invention shown in FIG. 26 (A) was exhibited. On the other hand, FIG. 28B shows that most of the supramolecular structures are dissolved in chloroform, and only a small part of the supramolecular structures remain on the Si substrate.

  The alkyl chain of the fullerene derivative 2 constituting the supramolecular organization according to the prior art does not have a polymerizable functional group. Therefore, in the supramolecular organization according to the prior art after the light irradiation, the fullerene sites of the fullerene derivative 2 constituting the supramolecular organization are polymerized with each other, but the alkyl chains are not polymerized with each other. It is considered that due to the polymerization of the fullerene site, only a part of the supramolecular organization remained on the Si substrate.

  From Example 5 and Comparative Example 2, the high environmental resistance of the water-repellent supramolecular structure is that the fullerene sites of the fullerene derivative 1 constituting the water-repellent supramolecular structure are polymerized with each other and the alkyl chains are polymerized with each other. It has been shown that this is achieved.

  As described above, in the water-repellent supramolecular structure according to the present invention, the fullerene derivative is organized to form a bilayer structure, and the fullerene structure having a flake-like particle shape is organized in layers. . Such a structure exhibits water repellency. In the water-repellent supramolecular organization, each fullerene derivative is polymerized. Thereby, the water-repellent supramolecular structure according to the present invention has high strength and high environmental resistance such as high chemical resistance, acid / alkali resistance, and heat resistance. Such a water-repellent supramolecular structure can be used for various members and products that are required to have environmental resistance, such as waterproof, anti-fogging, moisture-proof, and anti-icing and snow-proofing properties. The water-repellent supramolecular organization according to the present invention can also be used as a high mechanical durability material and an optoelectronic material. Furthermore, the water-repellent supramolecular organization of the present invention may be applied to MEMS / NEMS, microchannels, etc. that require low friction and non-wetting.

DESCRIPTION OF SYMBOLS 100 Water-repellent supramolecular organization 110 Base material 120 Fullerene structure 130,310 Fullerene derivative 140 Bimolecular film structure 150,160 Polymerization

Claims (11)

The fullerene structure is a water-repellent supramolecular structure organized in layers, and the fullerene structure has a bilayer structure in which fullerene derivatives are organized, and has a particle shape of flake structure,
A water-repellent supramolecular organization, wherein the fullerene derivatives are polymerized with each other. In the water-repellent supramolecular organization according to claim 1,
The fullerene moieties of the fullerene derivatives are polymerized with each other,
The water-repellent supramolecular organization, wherein the alkyl chains of the fullerene derivatives are polymerized with each other. The water-repellent supramolecular organization according to claim 1, wherein the fullerene derivative is represented by the formula (1), the fullerene site A represented by the formula (2), a benzene ring bonded to the fullerene site, and the An alkyl chain R bonded to each of the 3, 4 and 5 positions of the benzene ring,
Here, in the formula (1), each of the alkyl chains R includes at least 20 carbon atoms and a polymerizable functional group, and each of the alkyl chains R is polymerized via the polymerizable functional group. And
In the formula (2), (Fu) represents a fullerene, X represents a hydrogen atom or a methyl group, the benzene ring is bonded to a nitrogen-containing 5-membered ring of the fullerene moiety A, and the fullerene moiety is the fullerene. A water-repellent supramolecular structure characterized in that they are polymerized with each other.   The water-repellent supramolecular organization according to claim 3, wherein the polymerizable functional group is a diacetylene group. 4. The water-repellent supramolecular organization according to claim 3, wherein each of the alkyl chains R is —O (CH ₂ ) ₉ C≡C—C≡C (CH ₂ ) ₁₃ CH _3. Water repellent supramolecular organization. It is a manufacturing method of the water repellent supramolecular organization according to any one of claims 1 to 5,
A step of heating a mixture of a fullerene derivative, tetrahydrofuran and methanol to precipitate a fullerene structure, wherein the fullerene derivative is represented by the formula (1), and the fullerene site A represented by the formula (2): A benzene ring bonded to the fullerene moiety, and an alkyl chain R bonded to each of the 3, 4, and 5 positions of the benzene ring,
Here, in the formula (1), each of the alkyl chains R includes at least 20 carbon atoms and a polymerizable functional group; and
Cooling, holding and stabilizing the fullerene structure;
Layering the fullerene structure;
Irradiating the fullerene structure with light. A manufacturing method comprising:   The method according to claim 6, wherein the heating and precipitating step is performed in a temperature range of 40 ° C. to 60 ° C.   The method according to claim 6, wherein the step of cooling, holding and stabilizing is performed at a temperature range of -10 ° C to -90 ° C for 12 hours to 24 hours.   The method according to claim 6, wherein the irradiating step is performed in a deoxygenated atmosphere. The method of claim 6, wherein each of the alkyl chain R, characterized in that it is a _{-O (CH 2) 9 C≡C-} C≡C (CH 2) 13 CH 3, method.   The method according to claim 6, further comprising adding a poor solvent for the fullerene derivative to the mixture after the heating and precipitating step and before the layering step and the light irradiation step. A method characterized by comprising.