JP2014218548A - Molecular film and built-up film formed by laminating molecular film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ultra-highly densified organic molecular film.SOLUTION: A molecular film includes amphiphilic molecules represented by general formula (1), which are oriented vertical to the surface direction in the molecular film, and a cross-sectional area occupied by one amphiphilic molecule is not more than 20 sqÅ (in general formula (1), X represents a 1-10C alkylene group in which one carbon atom, or two or more carbon atoms not adjacent to each other may optionally be substituted with oxygen or sulfur atom; Y represents a polar group or a group of atoms having a polar group; p1 represents an integer of 1-20; each of p2 and p3 represents an integer of 0-8; p4 represents an integer of 0 or 1; q represents an integer of 0-30; n represents an integer of 1-10; and s represents an integer of 1-30).

Description

  The present invention relates to a molecular film and a cumulative film in which molecular films are laminated. Specifically, the present invention relates to a molecular film containing amphiphilic molecules, an ultra-high-density molecular film, and a cumulative film formed by stacking the molecular films.

  A Langmuir-Blodgett film (hereinafter referred to as “LB film”) is known as a thin film made of an organic compound. The LB film is a molecular film composed of amphiphilic molecules having a hydrophobic group and a hydrophilic group. The amphiphilic molecule is developed on the surface of the water, and the developed liquid is condensed and highly packed. It is an agglomerated film.

  Like an LB film, a molecular film (organic material) composed of carbon as a main element has a skeleton formed by a bond type called a covalent bond and various other bond modes. Furthermore, the organic compounds that make up the molecular film are composed of various intermolecular interactions between carbon chains (cohesive forces due to various electrostatic forces and dispersive forces (van der Waals forces) consisting of groups, and the bonding electrons that make up the carbon chains. The molecular film is formed by a thermodynamically stable anisotropic structure that depends on the excluded volume effect due to the carbon chain and molecular structure. It is formed from a very wide variety of organic structures, but typical intermolecular distances or carbon chain distances in organic materials are 3-4 mm, and there are no exceptions to this distance (e.g., Non-patent documents 1 and 2).

  On the other hand, inorganic materials also form aggregate structures on the same principle, but metals have a strong and high-density aggregate structure due to metal bonds (characteristic electrostatic force of free electrons and Coulomb force). Many inorganic compounds such as metal oxides also have a strong agglomerated structure based on strong chemical bonds such as ionic metal bonds. Also, as is clear from the periodic table, general organic compounds are mainly composed of so-called light elements up to the third period, and inorganic compounds such as metals are conversely formed by heavy elements after the third period. Many are composed. For this reason, it can be roughly distinguished that the organic compound is loosely aggregated by the light element and the inorganic compound is densely aggregated by the heavy element. Therefore, since the inorganic compound has a denser element aggregation state, the gas permeability is extremely small and the density is high. An inorganic compound has a high refractive index because it has a high electron density per unit volume.

Despite being a carbon-based compound, a material having physical properties similar to those of an inorganic compound is diamond composed only of carbon covalent bonds. Diamond has extremely high hardness, high density (3.513 g / cm ³ ), and high refractive index (2.42). Although these physical property values are far from general organic compounds, diamond is composed of only carbon without any hydrogen and all elements are covalently bound together. Is very close and can take a high density and high refractive index like metal. Therefore, in terms of the agglomeration structure, diamond does not have any agglomeration element contributed by van der Waals force, which is a weak physical bonding force, which is a general characteristic of organic compounds. At the same time, it can be seen that being a carbon compound is not a direct cause of low density, low density, and low refractive index.

  However, while special organic compounds such as diamond have high density and high refractive index, in general organic compounds, elements do not approach each other more than a certain distance, and low density, low density, low refraction Have a rate. As described above, one of the distances between the intermolecular distances or the carbon chain distances of organic compounds is the concept of van der Waals radii. This is derived from current chemistry common sense that the equilibrium value of electron repulsion by the electron cloud and van der Waals attraction is about 3%.

  Factors that cause a gap of about 3 mm in the intermolecular distance or intercarbon chain distance of hydrocarbon-based organic compounds are (1) thermal fluctuation of molecular chains, (2) rigidity of molecular chains, and (3) molecular chains. Of van der Waals attraction, and its time integration is presumed to maintain / require this constant volume. That is, (1) As the thermal fluctuation of the molecular chain, the molecule vibrates or rotates on a time scale longer than femtoseconds, and gathers with a certain degree of randomness according to the second law of thermodynamics. In addition, (2) as the rigidity of the molecular chain, the atoms are usually connected by a strong covalent bond between two different points in the molecule and can be easily cut by human power. Cannot be folded or folded. Therefore, it is not easy to gather the messy state so as to squeeze the wet towel. Further, (3) as the van der Waals attraction between molecular chains, the different two points are fixed by the intermolecular interaction with each other adjacent molecules or functional groups on the time scale of the fluctuation of the electron cloud, that is, the electron wave packet motion. Because it is attosecond order (Non-patent Document 3) and the orientation state of all molecules is fixed in that state, even if a single rod-like molecule is an entity, it is more We think that we recognize or illusion that the volume of a large cylinder is an entity. Since this space is generated in the order of attoseconds to femtoseconds, it cannot be reduced by real-time actions such as compression. This does not depend on the shape or size of the molecule, but the space of molecular aggregates is formed in the order of attoseconds to femtoseconds. For many organic compounds, these factors are statistically similar. Therefore, the hypothesis that organic compounds may have almost the same gap can be considered.

  In order to verify such a hypothesis, it is conceivable to calculate the ab-initio calculation with the contribution of van der Waals force. However, in order to accurately reflect the contribution of van der Waals force, It is necessary to use a simple basis function, and the calculation of the size of the molecular model necessary for the determination requires a time that is almost impossible even with current computers, and is not considered to be a realistic method (non- Patent Document 4).

Mitsuhiro FUKUDA, Yoshinori TAMAI and Satoru KUWAJIMA, J. Comput. Chem. Jpn., Vol. 3, No. 1, pp. 13.20 (2004) Atsuhiro Fujimori, 47, 10 pages, 1-24 pages 2009 Waseda Univ. News & Press release 2011/08/29 Seiji Tsuzuki, Kazuaki Honda, Journal of the Crystallographic Society of Japan, Vol. 46, No. 2, pp. 165-171 2004

  As described above, in general carbon-based organic compounds, no examples have been found in which the intermolecular distance is made closer than the van der Waals radius concept. No examples have been found that show values comparable to or exceeding those of inorganic compounds.

  In addition, due to the concept of van der Waals radii, there is a fixed chemistry philosophy that the intermolecular distance of carbon-based organic compounds cannot be approached beyond a certain distance. It is difficult to find a methodology that can That is, it has been considered that it is impossible to form an ultra-high-density molecular film (organic material) from the conventional technology and fixed wisdom.

  As mentioned above, it has been thought that it is impossible to obtain a highly dense molecular film (organic material). However, if a highly dense molecular film (organic material) is obtained, its chemical theory In addition to progress, there will be innovative advances in industry. Specifically, when the carbon-based organic compounds are so close to each other that the electron clouds of adjacent molecules or adjacent carbon chains affect each other like metal, the molecular film becomes extremely dense, and only the molecular film is a gas. And the permeation and shielding of substances can be controlled with extremely high accuracy. Moreover, being dense means that a dense hole can be formed at the same time. Furthermore, in terms of density, it is possible to form a molecular film having a density exceeding that of diamond. Thus, when a highly densified molecular film is obtained, it is considered that the engineering function of the molecular film is remarkably evolved.

  Moreover, when a highly densified molecular film is obtained, it is possible to approach the electronically active elements so as to affect each other's electron cloud, suggesting the possibility of the electronic interaction. . That is, almost all current organic compound semiconductors require the contribution of π electrons, but there are new semiconductors in which the active element σ electrons exchange electrons via p-orbitals and d-orbitals. That is, it may suggest a revolutionary evolution of electronic functions. More realistically, the electron density per unit volume increases dramatically, and it becomes possible to form a dielectric, that is, a high electron density dielectric having no free electrons, thereby dramatically increasing the refractive index. Is also possible. In this way, when an ultra-highly dense molecular film is obtained, the optical element industry will also make dramatic progress, and there is a possibility that it will have a great influence on the display and the like.

Therefore, the present inventors proceeded with a study for the purpose of obtaining an ultra-high-density organic molecular film in order to break the conventional theoretical common sense and bring about technical innovation. That is, an object of the present invention is to provide an ultra-highly densified organic molecular film having a close intermolecular distance that goes beyond the concept of van der Waals radii.

As a result of intensive studies to solve the above problems, the present inventors have found that an amphiphilic organic compound in which a hydrogen element is replaced with a fluorine element, the amphiphile having a specific structure and a carbon chain length. It has been found that an ultra-high-density molecular film can be obtained by forming a molecular film using an organic compound. Furthermore, the present inventors have found that an ultra-high-density molecular film has very high density and refractive index, and has completely different physical properties from conventional molecular films, leading to the completion of the present invention. It was.
Specifically, the present invention has the following configuration.

[1] A molecular film containing an amphiphilic molecule represented by the following general formula (1), wherein the amphiphilic molecule is oriented perpendicular to a plane direction in the molecular film, A molecular film characterized in that the occupied cross-sectional area of one amphiphilic molecule is 10 sqｓ or less.
(In General Formula (1), X represents an alkylene group having 1 to 10 carbon atoms, and one carbon atom or two or more carbon atoms not adjacent to each other may be substituted with oxygen or sulfur atoms. Y represents a polar group or an atomic group having a polar group, p1 represents an integer of 1 to 20, p2 and p3 each represents an integer of 0 to 8, and p4 represents an integer of 0 or 1. Q represents an integer of 0 to 30, n represents an integer of 1 to 10, and s represents an integer of 1 to 30, provided that-[(CF ₂ ) _p1 ( CF (CF ₃ )) _{p 2} (C (CF ₃ ) ₂ ) _{p 3} (O) _{p 4} } _—p1 (CF ₂ ), p2 (CF (CF ₃ )) and p3 (C ( CF _{3) 2} bond order) is not limited Incidentally, when q is 2 or more, a plurality of _{-. [(CF 2) p1} (CF (CF 3)) p2 (C (C _{3) 2) p3 (O)} p4} -. , Respectively may be the same or different from each other hand, when s is 2 or more, the plurality of n and q, each be the same or different from each other May be.)
[2] The molecular film according to [1], wherein an occupied cross-sectional area of one amphiphilic molecule is 5 sqÅ or less.
[3] The molecular film according to [1], wherein an occupied cross-sectional area of one of the amphiphilic molecules is 1 sqÅ or less.
[4] The molecular film according to any one of [1] to [3], wherein a film density of the molecular film is 3.5 g / cm ² or more.
[5] The molecular film according to any one of [1] to [4], wherein a refractive index of the molecular film is 3.0 or more.
[6] The molecular film according to any one of [1] to [5], wherein a surface pressure of the molecular film is 5 mN / m or more.
[7] The molecular film according to any one of [1] to [6], wherein an average film thickness of the molecular film is 0.5 to 20 nm.
[8] The occupying cross-sectional area of one amphiphilic molecule is 1/3 or less of the occupying cross-sectional area calculated from the van der Waals radius, according to any one of [1] to [7] Molecular film.
[9] The molecular film according to any one of [1] to [8], wherein in the general formula (1), p2 and p3 are each an integer of 0.
[10] In any one of [1] to [9], in the general formula (1), when Y represents an atomic group having a polar group, Y has an optionally substituted cyclic group. A molecular film according to 1.
[11] The molecular film according to any one of [1] to [10], wherein in the general formula (1), when Y represents a polar group, Y is a hydroxyl group.
[12] An amphiphilic molecule (a) in which Y is an atomic group having a polar group in the general formula (1), and an amphiphilic molecule (b) in which Y is a polar group in the general formula (1); The molecular film according to any one of [1] to [11], wherein
[13] The molecular film as described in [12], wherein in the amphiphilic molecule (a), Y is a cyclic structure-containing atomic group having a polar group.
[14] The molecular film according to [12] or [13], wherein the amphiphilic molecule (a) and the amphiphilic molecule (b) have a molar ratio of 1: 6 to 400: 1. .
[15] The molecular film according to any one of [1] to [14], wherein the amphiphilic molecule has a molecular weight of 200 to 5000.
[16] The molecular film according to any one of [1] to [15], wherein the molecular film is a single layer film.
[17] The molecular film as described in any one of [1] to [16], wherein the amphiphilic molecule is fixed in the molecular film.
[18] A laminated molecular film comprising the molecular film according to any one of [1] to [17] and a substrate.
[19] The laminated molecular film according to [18], wherein the substrate is a gold substrate.
[20] The laminated molecular film according to [18], wherein the substrate is a resin substrate.
[21] A cumulative film formed by laminating two or more molecular films according to any one of [1] to [17].
[22] A laminated cumulative film comprising the cumulative film according to [21] and a substrate.

According to the production method of the present invention, it is possible to obtain a molecular film in an ultra-highly dense state in which the intermolecular distance is reduced beyond the concept of van der Waals radii.
In addition, according to the present invention, engineering properties, optical properties, and electronic properties that are not on the extension of conventional technical common sense and theoretical common sense can be exhibited by reducing the intermolecular distance of the carbon-based organic compound to the limit. New materials can be provided.

FIG. 1 is a schematic cross-sectional view of a molecular film of the present invention. FIG. 2 is a graph showing a π-A curve in the compression process. FIG. 3 is a schematic cross-sectional view of the cumulative film of the present invention. FIG. 4 is a diagram schematically showing a process of forming a molecular film. FIG. 5 is a diagram schematically showing the collapse phenomenon of the molecular film. FIG. 6 is a diagram schematically showing a process of collecting a molecular film by the vertical immersion method. FIG. 7 is a diagram schematically showing a process of collecting a molecular film by the horizontal adhesion method. FIG. 8 is a graph showing a π-A curve in the compression process. FIG. 9 is a graph showing a π-A curve in the compression process, and compares the example and the comparative example. FIG. 10 is a graph showing a π-A curve and an occupied cross-sectional area when an amphiphilic molecule having no cyclic group is included. FIG. 11 is a graph showing a π-A curve in the compression process of another example. FIG. 12 is a schematic diagram illustrating the FT-IR RAS method. FIG. 13 is a graph showing the peak wave number of C-CF ₃ stretching vibration. FIG. 14 is a diagram showing an ultra-high resolution non-contact three-dimensional surface shape of a molecular film. FIG. 15 shows the results of an analysis in which a molecular chain model was calculated using WINN TAR. FIG. 16 is a diagram comparing rotation barrier energies of molecular chain models. FIG. 17 is a diagram illustrating an incident angle dependency profile of X-ray reflectivity. FIG. 18 is a diagram for explaining the outline of the measurement method by the surface plasmon resonance (SPR) method. FIG. 19 is a graph showing the relationship between the compressibility and the surface pressure of the molecular chain. FIG. 20 is a graph showing the relationship between the number of repeated compressions and the surface pressure.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

(Amphiphilic molecules)
The present invention relates to a molecular film formed from amphiphilic molecules, which is a highly dense molecular film. Here, the amphiphilic molecule refers to a molecule having both a hydrophilic group and a hydrophobic group in one molecule. Among them, molecules that have both stronger hydrophilic groups and stronger hydrophobic groups express better amphiphilic functions, and when deployed on the water surface, the hydrophilic group is directed to the water surface, and the hydrophobic group is air. A Langmuir film (monomolecular film) that is stably oriented toward the interface side is formed. In the case of a perfluoro group, it has strong hydrophobicity and water repellency, and has a strong tendency toward the air interface side. Therefore, the hydrophilic group is a benzene ring that is not very strong in hydrophilicity or a triphenylene ring that is a condensed ring. Even Langmuir film (monomolecular film) is formed. That is, the property of the amphiphilic molecule used in the present invention is the ability to form a Langmuir film stably and depends on the relative strength of the hydrophilic / hydrophobic group in the molecule.

  The amphiphilic molecule used in the present invention is selected from those capable of forming a molecular film on the water surface and accumulating on a solid substrate. Specifically, the amphiphilic molecule that can be used in the method for producing a molecular film of the present invention is represented by the following general formula (1). In this molecular film containing amphiphilic molecules, the distance between the amphipathic molecular chains (intermolecular distance) can be approached to the limit, exceeding the concept of van der Waals radii. It becomes a highly densified state.

In general formula (1), X represents an alkylene group having 1 to 10 carbon atoms, and one carbon atom or two or more carbon atoms that are not adjacent to each other may be substituted with oxygen or sulfur atoms. Y represents a polar group or an atomic group having a polar group. p1 represents an integer of 1 to 20, p2 and p3 each represents an integer of 0 to 8, and p4 represents an integer of 0 or 1. q represents an integer of 0 to 30, n represents an integer of 1 to 10, and s represents an integer of 1 to 30. However, the general formula (1) in the _{- [(CF 2) p1 (} CF (CF 3)) p2 (C (CF 3) 2) p3 (O) p4} - constituting the p1 amino (CF _2), p2 amino (CF (CF ₃₎₎ and p3 amino (C (CF _{3) 2)} binding of the order of is not limited. When q is 2 or more, a plurality of-[(CF ₂ ) _{p 1} (CF (CF ₃ )) _{p 2} (C (CF ₃ ) ₂ ) _{p 3} (O) _{p 4} } _-may be the same as each other. May be different. When s is 2 or more, the plurality of n and q may be the same as or different from each other.

  In general formula (1), X represents an alkylene group having 1 to 10 carbon atoms. The alkylene group represented by X may have a substituent, but is preferably an alkylene group having no substituent. Moreover, the carbon number of an alkylene group should just be 1-10, it is preferable that it is 1-6, it is more preferable that it is 1-4, and it is more preferable that it is 1 or 2.

In general formula (1), Y represents a polar group or an atomic group having a polar group. In the present invention, the polar group portion of Y acts as an adsorbing group that adsorbs to the substrate. Polar group moiety, protective film formed from a substrate and carbon formed from gold or glass, SiO ₂ and ZrO ₂ or the like oxide film, adsorbed to nitride film, a boride film and the resin film or the like .

In the general formula (1), when Y is a polar group, Y represents, for example, a hydroxyl group (—OH), an amino group (—NH ₂ ), a mercapto group (—SH), a carboxyl group (—COOH), an alkoxycarbonyl group. Group (—COOR; where R is an alkyl group), carbamoyl (—CONH ₂ ), ureido group (—NHCONH ₂ ), sulfonamide group (—SO ₂ NH ₂ ), phosphoric acid group (—OP (═O) (OH ₂ ), a sulfonic acid group (—SO ₃ H), and a sulfino group (—S (═O) OH). Among these, a hydroxyl group is particularly preferable.

In addition, in the general formula (1), when Y is an atomic group having a polar group, the polar group that Y has is a monovalent group located at the end, but it is divalent or higher than the end. It may be a group. As an example in case the polar group which Y has is a monovalent | monohydric polar group located in the terminal, the thing similar to the polar group mentioned above can be mentioned. Moreover, as an example in case the polar group which Y has is bivalent or more groups located other than a terminal, a carbonyl group (-CO-), a carbonyloxy group (-COO-), an amino group (-NH- or -NR-; where R is an alkyl group), disulfide group (-S-S-), sulfinyl group (-S (= O)-), aminocarbonyl group (-NHCO-), ureylene group (-NHCONH-), Imino group (C═NH or C═NR (R: is a substituent)), imide group (—C (═O) NHC (═O—)), sulfonimide group (—S (═O) ₂ NHS (= O) ₂ -) and aminosulfonyl group (-NHSO ₂ -) can be increased. In addition, when Y is a divalent group, a group obtained by removing one hydrogen atom from a group listed as a monovalent group can be raised. When Y is a trivalent group, an amino group (—NR -; Where R is an alkyl group).

When Y is an atomic group having a polar group, Y preferably has an optionally substituted cyclic group. Examples of cyclic groups include aromatic ring residues (aromatic cyclic groups) and non-aromatic ring residues (eg, 12-azacrown-4 and 15,18,21,24-azacrown, etc. Both azacrown rings and non-aromatic cyclic groups such as cyclohexane rings) are included. Further, it may be a residue of a ligand coordinated to a metal, or may originally be a chain group that forms a cyclic structure only when coordinated to a central metal. In other words, in the present specification, the “cyclic group” is originally a chain-like non-cyclic group, but a plurality of molecules aggregate to form a cyclic structure type aggregate, supramolecule or complex. In the meaning of a cyclic group.
The atoms constituting the cyclic group are not particularly limited, but preferably contain at least carbon atoms as ring constituting atoms. The cyclic group may be selected from cyclic groups having only carbon atoms as ring-constituting atoms, and from cyclic groups having hetero atoms such as nitrogen atoms, oxygen atoms and sulfur atoms as ring-constituting atoms together with carbon atoms. It may be selected. From the standpoint of substrate adsorptivity, it is preferably selected from a cyclic group having a hetero atom as a ring constituent atom, and particularly selected from a cyclic group containing a nitrogen atom such as a residue of a triazine ring. Further, the cyclic group may be a polycyclic cyclic group formed by cyclically connecting a plurality of heterocyclic residues (for example, phthalocyanine, porphyrin, corrole and the like). Note that these cyclic groups may be coordinated to the central metal. As for the cyclic group which Y has, the description of paragraph [0032]-[0039] of Unexamined-Japanese-Patent No. 2012-184339 can be referred, for example.

  The cyclic group which Y may have may include various substituents including a polar group such as a hydroxyl group. A polar group such as a hydroxyl group may be directly bonded to the ring constituting atom of the cyclic group, or a polar group may be bonded via a linking group. Examples of the linking group include an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms and the like (provided that one carbon atom in the linking chain, Alternatively, two or more carbon atoms that are not adjacent to each other may be substituted with an atom such as oxygen, nitrogen, or sulfur, and a hydrogen atom may be substituted with a fluorine atom). Examples of the substituent that can be substituted with the cyclic group that Y may have may include, for example, those described in paragraphs [0040] and [0041] of JP2012-184339A. .

  The compound represented by the general formula (1) is an amphiphilic molecule. Since the perfluoro group is hydrophobic and water repellent, Y automatically represents a group containing a polar group. Depends on the magnitude of the relative difference between the hydrophilicity and hydrophobicity of Y and the perfluoro group. Since the perfluoro group is very hydrophobic, if s is 3 or more, even if Y has a benzene ring or a condensed ring thereof, the molecule behaves in an amphiphilic manner.

In the said General formula (1), p1 represents the integer of 1-20. p1 is preferably an integer of 1 to 15, more preferably an integer of 1 to 12, still more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.
Moreover, in the said General formula (1), p2 and p3 represent the integer of 0-8, respectively. p2 and p3 are each preferably an integer of 0 to 5, more preferably an integer of 0 to 3, further preferably an integer of 0 to 1, and particularly preferably an integer of 0.
In the general formula (1), p4 represents an integer of 0 or 1. p4 is preferably an integer of 1.
In the said General formula (1), q represents the integer of 0-30. q is preferably an integer of 0 to 20, more preferably an integer of 0 to 10, and further preferably an integer of 0 to 6.
In the said General formula (1), n represents the integer of 1-10. n is preferably an integer of 1 to 8, and more preferably an integer of 1 to 6.
Moreover, in the said General formula (1), s represents the integer of 1-30. s is preferably an integer of 1 or 2, and more preferably an integer of 1.

  As the amphiphilic molecule used in the present invention, only one kind of the amphiphilic molecule represented by the general formula (1) may be used as described above. In addition, when forming a molecular film using only the amphiphilic molecule represented by the general formula (1) and Y is a polar group, the dropping rate and the like to be described later are adjusted. Thus, a homogeneous molecular film can be formed.

In the present invention, the amphiphilic molecule (a) in which Y is an atomic group having a polar group in the general formula (1), and the amphiphilic molecule (b) in which Y is a polar group in the general formula (1). May be used in combination. That is, an amphiphilic molecule (a) in which Y is an atomic group having a polar group and an amphiphilic molecule (b) in which Y is a polar group are introduced on the surface of the aqueous phase to form a molecular film. Also good.
In the present invention, when only the amphiphilic molecule (b) is used, the surface activity is increased, and there is a concern that a part thereof becomes micelle and is dispersed in the aqueous phase, but by adding a small amount of the amphiphilic molecule (a), The micellization of the amphiphilic molecule (b) can be effectively suppressed. It is considered that the amphiphilic molecule (a) is insoluble in water, and the orientation as a film by the interaction of molecular chains having perfluoro groups is more stable than micelle formation.
Among them, in the amphiphilic molecule (a), Y is preferably a cyclic structure-containing atomic group having a polar group, and the amphiphilic molecule (a) having a cyclic group and the amphiphilic molecule having no cyclic group. It is preferable to use (b) in combination. In this way, by adding even a small amount of the amphiphilic molecule (a) having a cyclic group, the amphiphilic molecule (a) having a cyclic group is compressed to fill each other's irregularities like gears so that the film itself It is thought that a little hardened contributes to the stability of the monolayer. Thus, by using the amphiphilic molecule (a) and the amphiphilic molecule (b) in combination, the molecular film formed by the amphiphilic molecule can have a higher density structure.

  The molar ratio of the amphiphilic molecule (a) and the amphiphilic molecule (b) contained in the molecular film of the present invention is preferably 1: 6 to 400: 1. The molar ratio of the amphiphilic molecule (a) to the amphiphilic molecule (b) is preferably 1: 1 to 400: 1, more preferably 6: 1 to 200: 1, and 10: 1 to More preferably, it is 150: 1. By setting the molar ratio of the amphiphilic molecule (a) to the amphiphilic molecule (b) within the above range, a more dense molecular film can be obtained.

As described above, the amphiphilic molecule represented by the general formula (1) contains a molecular chain having a perfluoro group. In the present specification, when Y is a cyclic structure-containing atomic group having a polar group in the general formula (1), a molecular chain having a perfluoro group may be referred to as a side chain. . Here, the side chain _means- [X-[(CF ₂ ) _{p 1} (CF (CF ₃ )) _{p 2} (C (CF ₃ ) ₂ ) _{p 3} (O) _{p 4} } -C _{n in} the general formula (1). F _{2n + 1} ].

  In the present invention, the molecular chain having a perfluoro group is preferably a perfluoroethyleneoxy chain (PFPE chain). This is because the rotation barrier energy of the perfluoroethyleneoxy chain is small and the molecule is excellent in flexibility. In addition, the perfluoroethyleneoxy chain is electronically unaffected by the surrounding environment and does not affect the surroundings. In this way, the perfluoroethyleneoxy chain can be adapted by changing its structure flexibly along with the surroundings. In the present invention, by using a perfluoroethyleneoxy chain as an amphiphilic molecule, the distance between the amphiphilic molecular chains can be shortened to the limit, and an ultra-highly dense molecular film can be formed.

  Specific examples of the amphiphilic molecule represented by the general formula (1) are illustrated, but the amphiphilic molecule used in the present invention is not limited thereto.

  Further, specific examples of the amphiphilic molecule represented by the general formula (1) include compounds described in paragraphs [0074] to [0080] of JP 2012-184339 A in addition to the above exemplary compounds. Can be mentioned.

  The molecular weight of the amphiphilic molecule used in the present invention is preferably 200 to 5,000, more preferably 250 to 2,000, and further preferably 300 to 800. By setting the molecular weight of the amphiphilic molecule within the above range, it is possible to suppress the entanglement of the amphiphilic molecular chains. Thereby, it is possible to eliminate the interaction between molecular chains that hinders densification, and it is possible to more effectively reduce the intermolecular chain distance.

  A major feature of the π-A curve of the amphiphilic molecule represented by the general formula (1) is that the surface pressure hardly changes (Plateau property) until the compressibility becomes considerably high. However, the principle of film collection in the LB film production system is that “the decrease in the film area due to the adsorption of the film onto the substrate causes a decrease in the surface pressure, which is detected by the pressure sensor and compressed until the original surface pressure is reached. Because it is assumed that the surface pressure due to compression changes, the amphiphilic molecule represented by the general formula (1) cannot be used for accurate measurement and membrane sampling in principle. is there. Therefore, in the present invention, a material having no Plateau property may coexist in the π-A curve. The material having no plateau property is preferably an amphiphilic molecule represented by the general formula (1), and Y is an atomic group having a polar group and a structure similar to that having a cyclic group. In addition, it is preferable to add about 20: 1-200: 1 the raw material which does not have Plateau property with respect to the amphiphilic part represented by General formula (1).

  Moreover, when the amphiphilic molecule represented by the general formula (1) is a rod-like molecule, it is preferable that the free volume of the molecule is small, that is, it is rigid. This is because the molecular chain having the perfluoro group to be substituted is stably vertically aligned. Comparing HD-15 and HD-18, the molecular chain of HD-15 has a large degree of freedom of rotation, and the skeleton of HD-18 is rigid, so that it is more densely oriented. As for the side chains, HD-11 and HD-12 having compact side chains are more densely oriented than HD-18 and HD-13. Further, HD-12 and HD-13 in which molecular chains having perfluoro groups are more densely oriented, that is, densely substituted in the 3,4,5-position on the benzene ring, are 3,4- A dense Langmuir film is formed as a result of being more densely oriented than the substitutes HD-11 and HD-18.

(Molecular membrane (Langmuir membrane))
The molecular film of the present invention includes the above-described amphiphilic molecule, and the amphiphilic molecule is oriented perpendicular to the plane direction in the molecular film. FIG. 1 shows a schematic sectional view of a molecular film 5 of the present invention. As shown in FIG. 1A, the molecular film 5 is composed of amphiphilic molecules 1. The amphiphilic molecule 1 has a hydrophobic group 2 and a hydrophilic group 4, and is arranged so that the hydrophobic groups 2 are adjacent to each other, and the hydrophilic groups 4 are arranged to be adjacent to each other, thereby forming the molecular film 5. Form.

  Within the molecular film, the distance between the amphiphilic molecular chains (intermolecular distance) is close to the limit, exceeding the concept of van der Waals radii, and is in a highly densified state where the intermolecular distance is close. . This is because the amphiphilic molecules recognize each other's concavo-convex structure, and each amphiphilic molecule flexibly corresponds to the concavo-convex structure, thereby reducing the occupied cross-sectional area per single chain. Conceivable.

The molecular film obtained by the production method of the present invention is a single-layer film, and the molecular film does not have an overlapping portion that is partially overlapped. In addition, since the molecular film obtained by the present invention is formed by regularly compressing and compressing amphiphilic molecules, the film thickness is the molecular length of the amphiphilic molecules. That is, the molecular film of the present invention is an ultrathin film, and its surface is extremely smooth.
Such an orientation state of the functional group of the molecular film can be measured by an FT-IR RAS spectrum. In the FT-IR RAS spectrum, only the IR absorption in the direction perpendicular to the substrate is detected, so that the orientation state of the amphiphilic molecules can be known. That is, when the side chain having a perfluoro group is oriented perpendicularly to the planar direction of the substrate, only the absorption of the terminal trifluoromethyl (C—CF ₃ ) group near 1260 cm ⁻¹ can be seen. Although only the absorption of the difluoromethylene (CF ₂₎ group leaving the vicinity of 1295 ^-1 when being horizontally oriented visible, the LB film of the compound of the general formula (1) without exception 1260 cm ^-1 near end trifluoromethyl (C Only the absorption of the —CF ₃ ) group can be seen, and it can be seen that the side chain having a perfluoro group is oriented vertically and the discotic nucleus is oriented horizontally with respect to the substrate.

The wave number of the C-CF ₃ stretching peak is shifted to a high wave number by compression. This is considered to be because the C—C—O bond, which was originally bent in the side chain that is most affected by compression, is gradually extended by the pressure of the adjacent group to increase the binding energy. That is, it is considered that a continuous change called high wave number shift occurs. Even in this case, the compression state is gradually changing, and the possibility that multi-layering such as superposition occurs in the compression process is substantially denied.
The presence or absence of superposition of the film can be examined by an optical interference film thickness measuring device or an X-ray reflectivity measuring method that can detect a change in film thickness on the order of angstroms in a non-contact manner. There is no superposition of.

  In the present invention, the occupied cross-sectional area of one amphiphilic molecule is 10 sqÅ or less, preferably 5 sqÅ or less, and particularly preferably 1 sqÅ or less. Thus, in the molecular film obtained by the present invention, the occupied cross-sectional area of one amphiphilic molecule is narrowed to the limit, and the intermolecular distance approaches beyond the concept of van der Waals radius. The occupied cross-sectional area of one amphiphilic molecule is the area of the cross section perpendicular to the long axis of one amphiphilic molecule, and is within the area parallel to the interface occupied by only the amphiphilic molecule (AsqÅ). When N amphiphilic molecules are present in A, it can be calculated by A / N (sqÅ / book).

  In the present invention, the occupied sectional area of one amphiphilic molecule calculated as described above is preferably 1/3 or less of the occupied sectional area calculated from the van der Waals radius, and is 1/5 or less. More preferably, it is 1/10 or less. Thus, in the present invention, the distance between molecules can be made far beyond the concept of van der Waals radii.

  The surface pressure of the molecular film is preferably 5 mN / m or more, more preferably 10 mN / m or more, and further preferably 15 mN / m or more. Thus, by setting the surface pressure of the molecular film within the above range, the molecular film obtained in the present invention can maintain its strength and durability while being an ultrathin film. The surface pressure of the molecular film can be measured using a Wilhelmi plate.

  The relationship between the developed area A (occupied cross-sectional area) that changes in the compression process and the surface pressure π of the molecular film at that time can be represented by a π-A curve. With this π-A curve, the state of interaction between amphiphilic molecules can be seen. The π-A curve shows the total area of the Langmuir film with respect to the surface pressure, the occupancy area of the molecule obtained by subtracting the total area by the total number of molecules, and the orientation perpendicular to the fluorine chain. In some cases, it represents the cross-sectional area of a single carbon chain.

  The structure, composition, and development amount of the fluorine compound mixture constituting the Langmuir film for explaining the π-A curve are shown below.

FIG. 2A shows a π-A curve in the compression process, where the vertical axis represents the surface pressure and the horizontal axis represents the occupied cross-section of one molecular chain having a perfluoro group (perfluoropolyether chain). Represents. The state where 7 mg of a fluorine compound is expanded on a 926 cm ² trough is started, and finally it is compressed about 10 times by 92 cm ² . It shows that. The occupied cross-sectional area of one perfluoropolyether chain at this point is approximately 0.5 sqÅ as indicated by the dotted line.
Further, it can be seen that the development of the THF solution of the fluorine compound has already developed a very high concentration fluorine compound before compression. The solution concentration is 10 mg / mL THF, which is added 0.7 mL or 7 mg on about 926 cm ² of water surface. Nevertheless, the phenomenon that the Langmuir film collapses is completely observed in the subsequent compression process, the π-A curve, and the FT-IR RAS spectrum of the Langmuir film collected on the Au substrate described later. Absent.

The π-A curve in FIG. 2A is not described from the surface pressure of 0 mN / m. This is because the process of developing the fluorine compound solution in the 926 cm ² trough is omitted.
FIG. 2B shows a π-A curve at the time of development. The horizontal axis represents the time required for expansion, but the amount of fluorine compound expanded in the trough increases with time, and the occupied sectional area of one perfluoropolyether chain decreases. This is also a kind of π-A curve.

  The refractive index of the molecular film of the present invention is preferably 3.0 or more, more preferably 3.5 or more, and further preferably 4.0 or more. Although it is most necessary to be able to control the refractive index to exhibit an optical function, it is very important to obtain a large refractive index. This is because, even with inorganic compounds and organic dielectric films, at most about 1.8 is called an ultrahigh refractive index, and it is of great significance that the above-described refractive index can be realized by the technique of the present invention. It can be said. Such a refractive index is higher than that of diamond. In the present invention, the refractive index can be increased to the above range by densifying the amphiphilic molecules.

The refractive index of the molecular film is usually measured by ellipsometry, but the Langmuir film, which is the molecular film of the present invention, has a thickness of about 1 nm, and an accurate value cannot be measured by ellipsometry. In addition, since a model calculation formula that conforms to main information about the structure is necessary, there is a concern about reliability when applied to an unknown film.
On the other hand, in the surface plasmon (SPR) method, the resonance angle of the reflected light of the light changes depending on the dielectric constant only by adsorbing a sample (dielectric thin film) of about 1 nm on the metal surface. The sample can be measured, and the dielectric constant, that is, the refractive index can be measured with higher sensitivity. This is because light does not generally couple with an electron wave (plasmon), but on the metal surface, an electron wave mode that causes coupling with light occurs due to its special characteristics. This is a surface plasmon, and is totally reflected. An evanescent wave is generated on the surface, and only the evanescent wave is coupled with the surface plasmon. This method is an established method (Surface Plasmon Spectroscopy of Organic monolayer Assemblies I. Pockrand, JDSwalen, JGGordon IIand mRPhilpott, Surface Science 74,
237-244 (1977)), and it is useful as a high-sensitivity sensor for enzymes in biological systems, and its application is being developed widely.

The film density of the molecular film is preferably 3.5 g / cm ² or more, more preferably 4.0 g / cm ² or more, and further preferably 4.5 g / cm ² or more. Thus, in the present invention, the film density of the molecular film can be increased to the above range by densifying the amphiphilic molecule to an ultrahigh density. The film density of the molecular film is w / A (g / g) where w (g) is the weight of the amphiphilic molecule present in the area parallel to the interface occupied by only the amphiphilic molecule (AsqÅ). cm ² ).

The film thickness of the monolayer molecular film obtained in the present invention is preferably 0.5 to 20 nm. The thickness of the molecular film is preferably 0.5 nm or more, more preferably 0.8 nm or more, and more preferably 1.2 nm or more. Further, the film thickness of the molecular film is preferably 20 nm or less, more preferably 10 nm or less, further preferably 5 nm or less, and particularly preferably 2 nm or less.
Thus, in the present invention, the thickness of the molecular film can be reduced to a single molecular length level, and even such an ultra-thin film has a high refractive index and a high density. Further, when these Langmuir films are accumulated, a film thickness for expressing a necessary function at a thickness of 10 nm, 50 nm, or 100 nm is a preferable film thickness. In the method of the present invention, since the film thickness is also controlled by the accumulation method, the film thickness can be realized and controlled with extremely high accuracy.

  In the present invention, the density and film thickness can be directly measured simultaneously by X-ray reflection measurement of the molecular film formed on the silicon wafer. Since the refractive index of a substance with respect to X-rays is slightly larger than 1, when a X-ray is incident near the surface of a substance having a flat surface, total reflection occurs. For this reason, by measuring the incident angle dependency on the surface of the thin film to the total reflection X-ray intensity (reflectance) with respect to the incident X-ray intensity, each incident dependency profile of the X-ray reflectance (see FIG. 17 described later) is obtained. The structural parameters (density, film thickness, roughness) of the thin film can be evaluated in a non-destructive system. In addition, since such a X-ray reflectivity method requires a substrate that is as smooth as possible, it is preferable to use a silicon wafer as the substrate.

  In the present invention, a molecular film can be formed on a substrate to form a laminated molecular film. FIG. 1B shows a schematic cross-sectional view of the laminated molecular film. As shown in FIG. 1B, the molecular film 5 may be laminated on the substrate 20 to form a laminated molecular film. The molecular film 5 can maintain its ultra-high density on the substrate 20, and such a laminated molecular film can also be used for various applications.

As a substrate that can be used for the laminated molecular film, a glass substrate, a silicon substrate, a polyimide, a triacetyl cellulose, a resin substrate such as polyethylene terephthalate or zeonoor, a gold substrate, or the like can be used. Among these, it is preferable to use a gold substrate. This is because the gold substrate has a smooth surface and a surface lined up smoothly at the atomic level.
A gold substrate whose surface is covered with a gold thin film can be used. For example, a glass substrate on which a 50 nm gold thin film is coated may be used. An example of such a gold substrate is an infrared RAS mirror (Au 15 mm × 25 mm × 45 mm thickness on 26 mm × 77 mm × 1 mm thickness glass, manufactured by JASCO Engineering Co., Ltd.).

In the molecular film of the present invention, the amphiphilic molecules are arranged in an ultra-highly densified state as described above, and the amphiphilic molecules are preferably fixed so that this state is maintained. .
The Langmuir film of the present invention is characterized in that the fluorine chain has a small intermolecular interaction, and does not contribute to immobilization. Therefore, the rate of accumulation of the monolayer molecular film (cumulative rate) is usually 50%. Degree. However, mutual embedding is promoted by recognizing the unevenness of neighboring molecules, that is, the content of the disk-shaped compound is increased, it is left at low temperature, accumulated in that state, and between hydrophilic groups (for example, very close hydroxyl groups) Improving the viscosity of the Langmuir film due to the interaction of hydrogen bonds and the like promotes immobilization, and at the same time, can increase the accumulation rate to about 80 to 98%.
In general, a polymerizable amphiphilic molecule obtained by partially incorporating a polymerizable vinyloxy group, an acrylate group, or an epoxy group is 1/20 to 1/1 / of the amphiphilic molecule of the general formula (1). Coexistence of about 100 moles, compression and standing for several degrees, or irradiation with ultraviolet light enables immobilization, and an LB film with a cumulative rate of almost 100% can be obtained.

(Cumulative film)
Furthermore, the present invention relates to a cumulative film formed by laminating two or more single-layer molecular films. FIG. 3 shows a schematic cross-sectional view of the cumulative film 6 of the present invention. As shown in FIG. 3, at least two layers, preferably three or more layers, are stacked on the molecular film 5 to form the cumulative film 6. In the cumulative film 6, 2 to 10 molecular layers 5 are preferably laminated, more preferably 2 to 6 layers, and more preferably 2 to 4 layers.

  The orientation of the molecular film 5 that forms the cumulative film 6 is not particularly limited. For example, a cumulative film may be formed on the substrate 20 side so that the hydrophobic group 2 is oriented as shown in FIG. 3A, or as shown in FIG. A cumulative film may be formed so that the hydrophilic groups 4 are oriented on the substrate 20 side. Further, as shown in FIG. 3C, in the first molecular film closest to the substrate side, the hydrophilic group 4 is oriented on the substrate side and laminated on the first molecular film. In the second-layer molecular film, a cumulative film is formed so that the hydrophobic group 2 is oriented toward the substrate side, and in the third-layer molecular film, the hydrophilic group 4 is oriented toward the substrate side. May be. Note that FIG. 3C illustrates a preferable cumulative film configuration because the layers are laminated so that the hydrophilic groups and the hydrophobic groups are adjacent to each other, so that the stability is high.

  Note that the cumulative film 6 may also be formed so as to be stacked on the substrate 20 in the same manner as the molecular film 5. In this specification, a structure in which a cumulative film is stacked on a substrate as described above may be referred to as a cumulative stacked film.

(Method of manufacturing molecular film (Langmuir film))
In the production of a molecular film, it is necessary that the water level of the trough surface where the film is prepared is always constant. Moreover, it is preferable to cover the entire trough with a transparent vinyl sheet so that condensation and water evaporation do not occur. Such a vinyl sheet functions to keep humidity constant and prevent dust from entering the water surface. Furthermore, it is preferable to introduce | transduce 1-2 L / min nitrogen in a vinyl sheet, and nitrogen is introduce | transduced so that it may not hit a water surface.
In order to avoid the vibration of the water surface due to the vibration of the trough itself, the trough is preferably installed on an active drive vibration isolation table. In the present invention, for example, a vibration isolation table active minute vibration control system (TS-150 (desktop type), manufactured by HERZ Co., Ltd.) can be used.

The method for producing a molecular film (Langmuir film) of the present invention generally includes the following steps (1) to (4).
(1) Step of developing a developing solution containing amphiphilic molecules on the surface of the aqueous phase (2) Step of volatilizing the developing solvent (3) Step of reducing the area of the surface of the aqueous phase and compressing the amphiphilic molecules (4) Step of Collecting Molecular Film on Substrate In addition, in the production method of the present invention, it is sufficient to include at least the developing step (1) and the step (3) compressing the amphiphilic molecule, and if necessary, (2) Steps (4) and (4) may be provided, and steps other than the above steps may be further provided.

FIG. 4 is a diagram schematically showing a process of forming a Langmuir film, and shows an outline of the manufacturing processes (1) to (4) described above.
As shown in the step (1) in FIG. 4, first, the developing solution S containing the amphiphilic molecule 1 is introduced onto the surface of the aqueous phase W. Thereby, the amphiphilic molecule 1 is developed on the surface of the aqueous phase W. Next, the developing solvent contained in the developing solution S is volatilized. The state where all the developing solvent is volatilized is shown in the step (2) in FIG. As shown in the step (2) of FIG. 4, in a state where the developing solvent is volatilized, the hydrophilic group 4 is oriented so as to face the surface side of the aqueous phase W and the hydrophobic group 2 faces the air side. To do.

After volatilizing the developing solvent, a step of narrowing the surface area of the aqueous phase and compressing the amphiphilic molecules is provided. As shown in the step (3) of FIG. 4, in the compression step, the development area of the amphiphilic molecules is narrowed by the barrier (frame) 10. In (3) of FIG. 4, the traveling direction of the barrier (frame) 10 is indicated by an arrow.
When the development area is further narrowed through the step (3) in FIG. 4, the hydrophilic groups 4 approach the surface side of the aqueous phase W and the hydrophobic groups 2 face the air side, respectively, and are arranged in a regular array. A film having a thickness of one molecule, that is, a single-layer monomolecular film 5 (molecular film 5) is formed.
In the present invention, the step of (3 ′) in FIG. 4 includes a step of further compressing so that the occupied cross-sectional area of one amphiphilic molecule is not more than a predetermined area. By providing such a compression step, in the present invention, it is possible to obtain an ultra-highly dense molecular film 5 having a close intermolecular distance that exceeds the concept of van der Waals radii.

  In the step (3 ′) of FIG. 4, after the compression is performed until the occupied cross-sectional area of one amphiphilic molecule becomes a predetermined area or less, the step of collecting the obtained molecular film 5 on the substrate 20 is performed. Provided. 4, the molecular film 5 is collected on the substrate 20 with the hydrophilic group 4 side of the molecular film 5 oriented on the surface of the substrate 20. The molecular film 5 may be collected in a state where the hydrophobic group 2 side of the molecular film 5 is oriented on the surface of the substrate 20. Thus, the process of collecting the molecular film is also referred to as a transfer process.

  Below, each process of (1)-(4) is demonstrated in detail.

(1) Step of developing a developing solution containing amphiphilic molecules on the liquid (aqueous phase) surface In the developing step, a developing solution in which the amphiphilic molecules are dispersed in a solvent is introduced onto the surface of the aqueous phase. As a result, the amphiphilic molecules are developed on the surface of the aqueous phase. When introducing the developing solution onto the surface of the aqueous phase, it is preferable to drop the developing solution onto the surface of the aqueous phase. In this way, by gradually introducing the developing solution to the surface of the aqueous phase, the amphiphilic molecules are uniformly developed on the surface of the aqueous phase.

  As a solvent for dispersing the amphiphilic molecule, it is preferable to use a chloroform solvent, a tetrahydrofuran solvent, or a fluorine-based solvent. ∨ertrel XF-UP (Mitsui / Dupont Fluoro Chemical Co., Ltd.), HFE-7100DL (Sumitomo 3M Co.), HFE-7200 (Sumitomo 3M Co., Ltd.) and the like can be mentioned. Of these, a tetrahydrofuran solution (THF solution) is preferably used.

  When the amphiphilic molecule is dissolved in the developing solvent, the amphiphilic molecule is preferably dispersed as much as possible in the developing solvent. This is because the orientation state of the amphiphilic molecules remaining at a high concentration on the water surface is greatly affected by the orientation state in the developing solvent as the solvent volatilizes when deployed on the water surface. For this reason, it is preferable to use a developing solvent that can disperse the amphiphilic molecules. In the case of a fluorinated solvent, it is more stable that the amphiphilic molecule aggregates with the fluorine chain facing outward and the polar group facing inward, and tends to remain on the water surface in the aggregated state. There is a concern that it will be difficult. Chloroform tends to be preferable in terms of the above points. However, since the specific gravity is large, droplets that sink to the bottom of the trough and do not contribute to film formation may remain. In consideration of the above, the tetrahydrofuran solvent is preferable as the developing solvent of the present invention, including volatility, solubility, operability during dropping, and reproducibility. However, fresh tetrahydrofuran solvent without stabilizers is required.

  The concentration of the amphiphilic molecule in the developing solution in which the amphiphilic molecule is dispersed is preferably 0.1 to 10 mg / mL, more preferably 0.5 to 5 mg / mL, and 1 to 3 mg. More preferably, it is / mL. In order to avoid association and aggregation on the liquid surface even in the developing solution, the concentration of the amphiphilic molecule in the developing solution is preferably not more than the above upper limit value.

  The dropping speed of the developing solution in which the amphiphilic molecules are dispersed is preferably 1 to 200 μL / min, more preferably 5 to 100 μL / min, and further preferably 10 to 50 μL / min. In the present invention, the concentration of the amphiphilic molecules in the developing solution is within the above range, and the dropping rate of the developing solution is within the above range, thereby effectively suppressing aggregation of the amphiphilic molecules. And a more uniform molecular film can be formed.

The method of dropping the developing solution is not particularly limited as long as it can achieve the above-described dropping rate, but it is preferable to drop it using a microsyringe. The dropping speed is preferably adjusted according to the type of the developing solvent used, and the dropping speed is preferably controlled by the size of the dropped grains.
When dropping and developing, the distance between the water surface and the needle tip of the microsyringe is preferably 5 mm to 1 cm. Usually, about 25 μL is added per minute, but the surface tension differs greatly between tetrahydrofuran and the fluorine solvent, and the volume of one drop of the fluorine solvent is relatively small, so the interval of the addition time is naturally narrow.

The addition amount of development solution is dispersed amphiphilic molecules is dependent on the area of the trough, when the order of 900 cm ^2, is preferably 100～1000MyuL, more preferably 200~750μL, 300~500μL More preferably. That is, the concentration of the amphiphilic molecule is preferably introduced to the surface of the aqueous phase so as to be 0.5 to 20 mg / mL, more preferably 2 to 15 mg / mL. More preferably, it is introduced so as to be 10 mg / mL. Therefore, the amount of deployment solution is preferably introduced such that the 0.25~10μg / cm ^2, and more preferably to be introduced so that 1~7.5μg / cm ^{2, 2.} More preferably, it is introduced so as to be 5 to 5 μg / cm ² .
By setting the addition amount of the developing solvent within the above range, it is possible to efficiently form an ultra-highly dense molecular film.

  The aqueous phase in which the developing solution in which the amphiphilic molecules are dispersed is dropped is not particularly limited as long as it is an aqueous phase used in general LB film production. For example, the solution is preferably water, more preferably pure water, and most preferably ultrapure water. For example, ultrapure water (18.2 MΩ) can be prepared using an ultrapure water production apparatus: Lab [manufactured by MILLIPORE Co., Ltd.], and the water temperature is preferably 25 ± 0.1 ° C. However, in some cases, a trace amount of metal salts, a pH adjusting reagent, or the like may be added.

The temperature of the aqueous phase to which the developing solution in which the amphiphilic molecules are dispersed is dropped is preferably 10 to 40 ° C, more preferably 15 to 30 ° C, and further preferably 20 to 25 ° C. . By setting the temperature of the aqueous phase within the above range, aggregation of amphiphilic molecules can be suppressed, and a homogeneous molecular film can be formed. Furthermore, the stability of the amphiphilic molecule can be enhanced by setting the temperature of the aqueous phase within the above range.
The temperature of the aqueous phase is preferably substantially constant during the molecular film production process. In particular, in the compression step, it is preferable that the temperature of the aqueous phase has little fluctuation. Specifically, the temperature fluctuation of the aqueous phase in the compression step is preferably ± 1 ° C., more preferably ± 0.5 ° C., and further preferably ± 0.1 ° C. By setting the temperature variation of the aqueous phase within the above range, it is possible to prevent the viscosity of the film, the intermolecular interaction, and hence the π value, which is the surface pressure, from being greatly affected by the temperature variation. By setting the temperature fluctuation of the aqueous phase in the compression step within the above range, a highly dense molecular film can be formed.

(2) Step of volatilizing developing solvent In the present invention, it is preferable to provide a step of volatilizing the developing solvent to volatilize the solvent used in the solution of amphiphilic molecules. This volatilization step is performed over steps (1) to (2) in FIG. In the present invention, the volatilization of the solvent is performed by putting time after dropping the amphiphilic molecule. Specifically, the solvent can be volatilized by allowing to stand for 1 minute to 60 minutes under normal conditions (25 ° C., relative humidity 40%). The standing time is preferably 1 minute or more, more preferably 5 minutes or more, further preferably 10 minutes or more, and particularly preferably 20 minutes or more. Thus, the solvent is volatilized under the above conditions, whereby the amphiphilic molecules can be regularly oriented.

  The amphiphilic molecules are aligned with the hydrophilic group (polar part) directed to the surface of the aqueous phase and the hydrophobic group directed to the air surface side by volatilizing the developing solvent. At this time, since the van der Waals force is small in the fluorine group, it is considered that the fluorine group is arranged almost only by the excluded volume effect. However, as far as judging from the FT-IR RAS spectrum, the fluorine group is perpendicular to the water surface in a highly ordered manner. Oriented. In addition, since the molecules in the upper layer on the air surface side are relatively energetically unstable, the amphiphilic molecules are aligned in a single layer. Thus, in the present invention, a single molecular layer can be obtained with good reproducibility.

(3) The process of narrowing the area of the aqueous phase surface and compressing the amphiphilic molecule The compression process is a process of narrowing the area of the aqueous phase surface where the amphiphilic molecule is developed and further compressing the amphiphilic molecule. In the compression step, the area of the surface of the aqueous phase where the amphiphilic molecules are developed is narrowed to a certain extent, and then the amphiphilic molecules are compressed. That is, the compression step includes a step of narrowing the development area where the amphiphilic molecule is expanded ((3) in FIG. 4) and a step of compressing the amphiphilic molecule ((3 ′) in FIG. 4). Will be.

Examples of the compression method used in the compression step include compression methods such as constant velocity compression, equal strain (equal compression ratio) compression, and equilibrium relaxation compression. Constant speed compression is a method of narrowing the surface area of the aqueous phase by moving the barrier at a constant speed. The specific compression speed is preferably 1 to 20 mm / min, and more preferably 2 to 10 mm / min. Equal strain (equal compression ratio) compression is a method of compressing by moving the barrier so that the surface area of the aqueous phase is narrowed at a constant rate. The specific compression speed is preferably 1 to 20% / min, and more preferably 2 to 10% / min.
The equilibrium relaxation compression is a compression method in which compression is performed intermittently. Specifically, constant velocity compression (15 mm / min) is performed for 10 seconds, and then is stopped for 30 seconds. During that time, the reduction due to the relaxation of the surface pressure is repeated for 30 seconds until the decrease is 0.2 mN / m or less. Compression method.

The amphiphilic compounds used in this evaluation are known to undergo a compression process with their side chains oriented perpendicular to the water surface, but the compression process involves plastic deformation and molecularization when the main skeleton is mainly densified. It is considered that the contact between fluorine chains inside and between molecules proceeds with elastic deformation due to thermal fluctuation. As for elastic deformation, it is considered that when compression is stopped, the elastic deformation relaxes with time.
The constant velocity compression method and the constant strain compression method in which the compression does not stop in the middle are expressed as a surface pressure like a plastic deformation without canceling the elastic deformation, but the equilibrium relaxation compression method is stopped after compression for about 10 seconds. However, since the surface pressure increased by the previous compression is reduced and the compression is started when the reduction is subsided, the next compression is started. It can be regarded as only the contribution of the surface pressure due to the intermolecular interaction of side chains. Therefore, by comparing the equal strain method and the equilibrium relaxation method, it is possible to estimate and compare the contribution of elastic deformation of side chains such as fluorine chains.
As described above, the equilibrium relaxation compression method can reduce the contribution of elastic deformation interaction as much as possible to estimate the compressibility dependence of the surface pressure due to plastic deformation alone, but at the same time requires a very long measurement time. Evaluation is performed by the iso-distortion compression method.

  Such a compression process can be accurately recorded by measuring the surface tension of the aqueous phase using a surface tension sensor. By performing the compression, the surface area (film thickness) is increased at the same time as the area of the molecular film is narrowed. Therefore, the process of the compression process can be traced by recording the change in the surface tension.

The molecular film formed by compression is characterized by the surface tension (membrane pressure, mN / m unit) and the area of the molecular film (area parallel to the interface occupied only by amphiphilic molecules). There is a relationship. This relationship can be represented by a π-A curve.
In addition, from the π-A curve, the occupied cross-sectional area per amphiphilic molecule can be calculated. The occupied cross-sectional area per amphiphilic molecule can be calculated by (surface area of the aqueous phase in which the amphiphilic molecule is developed) / (number of molecules of the developed amphiphilic molecule).

  The amphiphilic molecule represented by the general formula (1) is developed on the water surface, and when the compression proceeds, the surface pressure starts to increase from the initial value of 0 mN / m. At this time, the expanded amphiphilic molecule means that for the first time, all the molecules have started to make some contact. As the compression proceeds further, the degree of contact increases and the surface pressure increases accordingly. In the present invention, the amphiphilic molecule is oriented in a compressed state in which the gap between the adjacent side chains gradually disappears because the fluorine chain, which is the side chain, is oriented perpendicularly from the water surface. However, since the existence of a plurality of side chains that replace the molecule itself forms the unevenness of the molecule after that, it comes closer to fill the gap between the unevennesses of the molecules adjacent to each other. At this time, the π-A curve changes from a monotonic increase until then to a so-called plateau straight line in which the surface pressure does not increase or decrease, and the change point becomes an inflection point. This inflection point corresponds to the degree of compression in a state where molecules are closely packed in a general amphiphilic compound compression process.

  In addition, when the compression is further performed beyond the close-packed state, the surface pressure may be drastically decreased with a general amphiphilic compound. This is because the Langmuir film, which is a single-layer molecular film formed on the surface of the aqueous phase, is destroyed by pressure, and as shown in FIG. 5, a part of the molecular film rides on the adjacent molecular film and overlaps. This is because of This is an irreversible Langmuir film collapse phenomenon and is not repaired.

  In the Langmuir film of amphiphilic compounds with fluorine side chains, an example of overlapping rather than decay as shown in Fig. 5 has been reported (J. Paczeny, P. Niton, A. Zywocinski, K. Sozanski, R. Holyyst, M. Fiaikowski, R. Kieffer, B. Glettner, C. Tschierske, D. Pociecha and E. Gorecka, Soft Matter, 2012, 8, 5262-5272.). However, this amphiphilic compound having a fluorine chain is a tetraol formed by hydration of glycidyl groups substituted at both ends of the rod-like skeleton, and they form a Langmuir film to form an adjacent tetraol. Are linked by hydrogen bonds to form a giant supramolecular film, and it is said that superposition occurs such that it is folded and stacked as a sheet, not a simple Langmuir film collapse phenomenon, It is a special phenomenon caused by the structure.

On the other hand, in the Langmuir film formation process of the amphiphilic compound having a fluorine chain of the present invention, the surface pressure increases according to the development as described above, and an inflection point is reached in the vicinity of the most closely packed state, Thereafter, densification proceeds so that the irregularities of the main chain skeleton portions of adjacent molecules are filled with each other. In this process, the interaction between adjacent molecules enters the gap even when compressed only by the fluorine side chain, so that there is almost no change in the intermolecular interaction, and there is a region where the surface pressure does not change with compression (plateau). it is conceivable that.
However, similarly to the normal compression process, when the gap is filled, the surface pressure rapidly increases.
Even in a region where the compression exceeds the limit and the π-A curve vibrates slightly and complicatedly, the above-mentioned “abrupt decrease in surface pressure” suggesting the collapse of the Langmuir film does not occur. In many cases, the Wilhelmi plate for measuring the surface pressure is inclined by being pushed by the Langmuir film.

(4) Step of collecting molecular film on substrate After the molecular film reaches a desired surface pressure, the molecular film can be collected (transferred) onto the substrate by bringing the molecular film into contact with the substrate. That is, in the present invention, the molecular film can be collected (transferred) on the substrate after the occupation cross-sectional area per one amphiphilic molecule forming the molecular film becomes not more than a predetermined value.

  As a method for collecting the molecular film on the substrate, a known method can be used, and is not particularly limited, but in the present invention, the molecular film is collected on the substrate by the vertical dipping method and the horizontal adhesion method. Is preferred. In particular, it is preferable to collect the molecular film on the substrate by a vertical immersion method.

  FIG. 6 is a diagram schematically illustrating how a molecular film is collected by the vertical immersion method, and FIG. 6A is a diagram schematically illustrating a process of collecting the molecular film on the surface of the substrate 20. . In FIG. 6A, the molecular film is collected on the surface of the substrate 20 by moving the substrate 20 in the direction of the arrow. The substrate 20 may proceed from the hydrophobic group 2 side of the molecular film, or may proceed from the hydrophilic group 4 side. When the substrate 20 is advanced from the hydrophilic group 4 side, it is necessary to immerse the substrate 20 in the aqueous phase in advance.

  The moving speed of the substrate 20 is preferably a speed at which the molecular film can be collected on the substrate 20, preferably a speed of 0.5 to 5 mm / min, and a speed of 0.5 to 3 mm / min. Is more preferable, and it is still more preferable that it is about 1-2 mm / min. By setting the moving speed of the substrate 20 within the above range, the molecular film can be collected on the substrate without breaking the ultra-high density state.

  FIG. 6B is a diagram showing a process of further accumulating a single-layer molecular film. A film in which a plurality of single-layer molecular films are stacked is called a cumulative film. As shown in FIG. 6B, the present invention may be a method for manufacturing a cumulative film including a step of laminating molecular films. In FIG. 6B, after collecting one molecular layer as shown in FIG. 6A, the substrate is further brought into contact with the molecular film. In this case, a new molecular film comes into contact with the molecular film collected in advance, and a cumulative film in which a plurality of molecular films are stacked can be formed.

The cumulative film is a laminate of a plurality of single-layer molecular films, and it is preferable that a required film thickness is accumulated. That is, the step of contacting and collecting the substrate and the molecular film is repeated by the number of stacked layers. The number of stacked layers can be adjusted as appropriate according to the application. In this way, by laminating a plurality of highly densified single-layer molecular films, a dense polymer molecular film having lower gas permeability can be obtained.
In this cumulative film, not only the cumulative film of the same Langmuir film but also the stacking of different kinds of cumulative films may greatly expand its function. For example, an optical reflection film can obtain good characteristics only by stacking films having different refractive indexes.

  FIG. 7 is a diagram schematically showing how a molecular film is collected by the horizontal adhesion method. In FIG. 7A, the molecular film 5 is collected (transferred) on the substrate 20 by bringing the substrate 20 into contact with the hydrophilic base side. On the other hand, in FIG. 7B, the molecular film 5 is collected (transferred) by bringing the substrate 20 into contact with the hydrophobic group side. When the affinity between the substrate 20 and the hydrophilic group is high, the hydrophilic group and the hydrophobic group of the molecular film 5 are inverted as shown in FIG. 7B, and the molecular film 5 is collected (transferred) on the substrate 20. Is done. Many substrates are generally highly polar until reaching the metal, inorganic compound, or resin, so the film sampling method with the hydrophilic surface of the Langmuir film facing the substrate is the most thermodynamically stable. Therefore, it is preferable.

<Board>
As the substrate used in the step of collecting the molecular film on the substrate, a substrate having a smooth surface and no undulation is generally preferable. For example, in a gas permeation control film, the resin substrate is preferably as smooth as possible.
However, it is indispensable in the field of MEMS and the like, for example, by providing the film of the present invention on a surface having complicated unevenness of the order of 10 nm, for example, to protect fine unevenness, to provide another function, and to provide releasability. Since the Langmuir film of the present invention can sufficiently handle the film thickness of about 1 nm, smoothness is not required in all cases.

In the present invention, the substrate may be a water surface or another liquid surface as long as it is a flat surface present on the substrate. Since the molecular film is a highly dense film containing fluorine, for example, the volatilization of the liquid can be suppressed, or the contact with oxygen can be completely blocked. However, generally, a glass substrate, a silicon substrate, a resin substrate, a gold substrate, or the like can be used. Among these, it is preferable to use a gold substrate. This is because the gold substrate has a smooth surface, a high adsorptivity, and a surface arranged smoothly at the atomic level.
A gold substrate whose surface is covered with a gold thin film can be used. For example, a glass substrate on which a 50 nm gold thin film is coated may be used. An example of such a gold substrate is an infrared RAS mirror (Au 15 mm × 25 mm × 45 mm thickness on 26 mm × 77 mm × 1 mm thickness glass, manufactured by JASCO Engineering Co., Ltd.). In general, the surface treatment technique for adsorption / immobilization of the Langmuir membrane of the present invention is important.

<Pretreatment of substrate>
As pretreatment of the gold substrate, ultrasonic cleaning is preferably performed. Specifically, the gold substrate is ultrasonically cleaned in acetone. The ultrasonic cleaning is preferably performed for 1 to 30 minutes. After the cleaning, it is preferable to take out the gold substrate, then further wash with acetone, and then dry with a nitrogen gun. Furthermore, as a pretreatment of the gold substrate, it is preferable to perform cleaning with UV ozone. The UV ozone cleaning treatment is preferably performed for 1 to 30 minutes each on the front and back sides. As the UV ozone cleaner, for example, UVO-CREANER Model No. 42 Jelight Company, Inc. The thing made from can be used. The gold substrate washed as described above is preferably immersed in ultrapure and held until use.

  Further, a glass or silicon substrate is subjected to UV-ozone treatment after cleaning for general degreasing purposes in the same manner as a gold substrate. The resin substrate can also be promoted to adsorbability by performing UV-ozone treatment after cleaning the surface under conditions that do not significantly invade the substance.

(Fixing process)
In this invention, it is preferable to include the process of fixing between the amphiphilic molecules which passed through the compression process. In particular, when a single-layer molecular film is laminated to form a polymer film, it is preferable to fix the compressed molecular film before accumulation. Examples of the immobilization method include increasing the viscosity and immobilization.

  The Langmuir film of the present invention is characterized in that the fluorine chain has a small intermolecular interaction, and does not contribute to immobilization. Therefore, the rate of accumulation of the monolayer molecular film (cumulative rate) is usually 50%. Degree. However, mutual embedding is promoted by recognizing adjacent molecular irregularities, that is, increasing the content of discotic compounds, standing at low temperature and accumulating in that state, and between hydrophilic groups (eg, very close hydroxyl groups) Improving the viscosity of the Langmuir film due to the interaction of hydrogen bonds and the like promotes immobilization, and at the same time, can increase the accumulation rate to about 80 to 98%. Most basically, it is highly compressed and left for a long time. This is because the degree of order increases to increase the intermolecular interaction, and the polar sites approach each other and stabilize by interacting with each other. In this respect, cooling at the same time promotes this increase in viscosity and fixation. In this way, a new immobilization method is possible in which the molecular skeleton itself is densified, the irregularities thereof are filled, and the viscosity is irreversibly increased.

Moreover, even if it has a simple hydrogen bonding group such as a hydroxyl group such as HD-10, it can be expected to crystallize the hydroxyl group when it is present in an unprecedented state.
Furthermore, the Langmuir film itself can be expected to be fixed by irradiating with ultraviolet rays. This is what is actually done with lubricants for hard disks, but it is because the molecular chains with perfluoro groups are irradiated with UV light and immobilized, and it is super dense. This is because an unexpected polymerization reaction can be expected.
In general, a polymerizable amphiphilic molecule obtained by partially incorporating a polymerizable vinyloxy group, acrylate group or epoxy group is 1/20 to 1/100 of the amphiphilic molecule of the general formula (1). It can be immobilized by allowing it to coexist to about a mole, compressing it, and leaving it for several degrees, or irradiating it with ultraviolet rays, and an LB film with a cumulative rate of almost 100% can be obtained. In this case, it is also preferable that polymerizable groups exist at both ends of the fluorine chain.

  Thus, by providing the fixing step, the molecular film can be peeled from the substrate, and an ultra-thin film having a one-dimensional or two-dimensional structure having abnormal characteristics can be obtained.

(Application of molecular film)
In the molecular membrane obtained by the present invention, the radius calculated from the occupied cross-section of one amphiphilic molecule becomes smaller than the covalent bond radius. Shielding performance that is not comparable to the polymer layer can be obtained.
Thus, since the molecular film obtained by the present invention can acquire high shielding properties, it can further have functions such as chemical resistance, weather resistance, heat resistance, and insulation. Specifically, it can be applied to an optical film, a shielding film, a high sensitivity sensor, and a biological functional film.

  Furthermore, the molecular film obtained by the present invention has a high refractive index. Therefore, a transparent dielectric thin film can be formed, and application to a lens or a reflection control film is also possible.

  The molecular film obtained in the present invention can also function as a lubricating film. By using the molecular film of the present invention, it is possible to suppress film breakage during compression and an increase in surface pressure. In particular, as a hard disk lubricant, an ultra-dense filled film containing a discotic compound is expected to exhibit durability, antifouling properties, and lubricity that cannot be compared with conventional lubricating films.

  Moreover, ultimate durability and releasability are exhibited as a release agent film. In short, it is a highly durable film and is expected as a new organic plating protective film.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Specific examples of compounds used in the present invention are shown below, but are not limited thereto.

(Synthesis Example 1 Synthesis of HD-10)
HD-10, which is a PFPE chain used in the present invention, was synthesized from commercially available triethylene glycol monoethyl ether by the following route.

The above triethylene glycol monoethyl ether acetate was perfluorinated by Exfluor, USA. Since the form that can be purchased from Exfluor is the ester, it was reduced with NaBH ₄ to give HD-10. In addition, HD-16 is also used in the present invention.

(Synthesis Example 2 Synthesis of HD-16)
HD-16, which is a PFPE chain used in the present invention, was synthesized by the following route.

<Methanesulfonylation>
In a 10 L three-necked flask, 873.65 mL of triethylene glycol monoethyl ether (Tokyo Kasei), 5 L of acetonitrile, and 693.1 mL of triethylamine were added, and 387 mL of methanesulfonyl chloride was added by ice cooling. Subsequently, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight. The next morning, the mixture was filtered through Celite and the solvent was distilled off under reduced pressure to obtain 1249.53 g of ethoxytriethyleneoxy methanesulfonate.

<Extension and acetylation of oxyethylene chain>
Next, 12.6.28 g of triethylene glycol and 168.32 g of tert-butoxy potassium were mixed in a 5 L three-necked flask, and 384.48 g of ethoxytriethyleneoxy methanesulfonate was added at 100 to 130 ° C. over 2 hours with increasing temperature. Thereafter, stirring was continued at 140 ° C. for 3 hours. After cooling to room temperature, 4 L of ethyl acetate and 2 L of hexane were added, stirred well, allowed to stand, and left overnight. The next morning, the reaction solution was filtered, and the solvent was distilled off under reduced pressure. The obtained residue was distilled under reduced pressure to distill off excess triethylene glycol at 138 ° C./230 Pa. In this residual viscous liquid, 200 mL of acetic anhydride was added, heated at 140 ° C. for 2 hours, and then distilled under reduced pressure to obtain 384.48 g of hexaethylene glycol monoethyl ether at 193-4 ° C./190 Pa.

<Perfluorination>
The obtained hexaethylene glycol monoethyl ether was perfluorinated by Exfluor, USA.

<Ester reduction>
Since the form that can be purchased from Exfluor is the ester, it was reduced with NaBH ₄ to give HD-16. Into a 3 L three-necked flask, 50 g of sodium borohydride (Aldrich), 0.48 L of tetrahydrofuran and 0.16 L of distilled water were added, and methyl perfluoro-3,6,9,12,15,18-hexaoxaeicosanoate (Exfluor Corporation) ) 260 g was added on ice. Subsequently, after stirring at room temperature for 2 hours, 0.36 L of 4N aqueous hydrochloric acid was added under ice cooling, the organic layer was extracted, and the solvent was distilled off under reduced pressure to remove 1H, 1H-perfluoro-3,6. , 9, 12, 15, 18-hexaoxaeicosanol 275 g was obtained.

(Synthesis Example 3 Synthesis of HD-1)
A discotic compound HD-1 was synthesized using HD-10 obtained as described above as a side chain.

<Ester reduction>
Into a 1 L three-necked flask, 11.88 g of sodium borohydride (Aldrich), 200 mL of tetrahydrofuran and 66 mL of distilled water were added, and 89.49 g of methyl perfluoro-3,6,9-trioxaundecanoate (Exfluor) was added to methanol-ice. It added at -3 to 1 degreeC by cooling. Subsequently, after stirring at room temperature for 3 hours, 0.36 L of 4N hydrochloric acid was gradually added under ice-cooling, and then the organic layer was extracted and the solvent was distilled off under normal pressure. To obtain 71.91 g. This was distilled under normal pressure at 138-9 ° C. to obtain 63.11 g of 1H, 1H-perfluoro-3,6,9-trioxaundecanol.

<Trifurylation>
Next, 30 g of 1H, 1H-perfluoro-3,6,9-trioxaundecanol is dissolved in a mixed solvent of 25 methylene chloride and 25 mL of AK-225 in a 500 mL three-necked flask, and trifluoromethanesulfonic anhydride (Tokyo Kasei) is dissolved. 24.56 g was added to methanol by ice cooling (-10 to -1 ° C). Next, 8.66 mL of pyridine was gradually added, followed by stirring at the same temperature for 10 minutes, 100 mL of 1N hydrochloric acid was added, the organic layer was extracted, and the solvent was distilled off under reduced pressure. The obtained residue was purified by vacuum distillation at 99 to 100 ° C./35 torr to obtain 25.14 g of 1H, 1H perfluoro-3,6,9-trioxaundecanyl trifluoromethanesulfonate.

<Alkylation>
In a 300 mL three-necked flask, 25.14 g of 1H, 1H perfluoro-3,6,9-trioxaundecanyl trifluoromethanesulfonate, 3.49 g of 4-nitrocatechol, 25 mL of N, N-dimethylacetamide and 15 mL of AK-225 And 6.53 g of potassium carbonate was added at room temperature. Subsequently, after stirring at 80 ° C. for 5 hours, potassium carbonate was removed by filtration, washed with 30 ml of 1N aqueous hydrochloric acid and extracted with a total of 300 mL of AK-225, and the solvent was distilled off under reduced pressure. Low boiling components were removed as much as possible at 130 mbar. The obtained residue was subjected to column chromatography with a developing solvent (AK-225: hexane: ethyl acetate = 1: 2: 0.2) to obtain 3,4-bis (1H, 1H perfluoro-3,6,9). -Trioxaundecanyloxy) nitrobenzene 15.22g was obtained.

<Reduction of nitro group>
Into a 100 mL three-necked flask, put 3.45 g of reduced iron, 60 mL of isopropyl alcohol, 6 mL of distilled water, and 1.24 g of ammonium chloride and heat to reflux. When the iron turns grayish black, 3,4-bis (1H, 1H 10.15 g of perfluoro-3,6,9-trioxaundecanyloxy) nitrobenzene was slowly added over 50 minutes. The mixture was further refluxed for 2 hours, and after cooling, the reaction solution was filtered through Celite. After concentrating the filtrate, the obtained residue was subjected to column chromatography with a developing solvent (AK-225: hexane: ethyl acetate = 1: 2: 0.1) to obtain 3,4-bis (1H, 1H perfluoro). 9.26 g of -3,6,9-trioxaundecanyloxy) aniline was obtained.

<Triarylmelamineization>
Into a 100 mL three-necked flask, 9.26 g of 3,4-bis (1H, 1H perfluoro-3,6,9-trioxaundecanyloxy) aniline, 23 mL of 2-butanone, and 8 mL of AK-225 were placed. 0.501 g of cyanuric chloride (Tokyo Kasei) was gradually added. After 1 hour, 0.666 g of sodium acetate and 1 ml of water were added under ice-cooling, and after 1 hour at room temperature and reflux for 1 hour, 0.747 g of potassium carbonate was added. At room temperature, 56 mg of succinic anhydride was added, and heating under reflux was continued for 5 hours. The reaction solution was filtered through Celite, and the filtrate was washed and extracted with 1N aqueous hydrochloric acid, and the solvent was evaporated under reduced pressure. The obtained residue was subjected to column chromatography using a developing solvent (hexane: ethyl acetate = 3: 1) to obtain 6.31 g of NLO-7778.

  Since the following raw material aniline and the product NLO-7784 appear in similar positions by TLC, they are highly polarized with succinic anhydride to facilitate separation by column chromatography.

(Synthesis Example 4 Synthesis of HD-4)
The discotic compound HD-4 was synthesized by the following procedure.

  223 mg (0.75 mmol) of compound (1) and 1.97 g (2.48 mmol) of compound (2) were placed in a glass reaction vessel, and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) was taken. 13.7 mg (0.09 mmol) was added. After reacting at 100 ° C. for 2 hours, purification by silica gel column chromatography gave 706 mg (0.263 mmol, yield 35.1%) of HD-4.

The identification data of HD-4 was as follows.
¹ H-NMR [CDCl ₃ ]: δ [ppm] = 3.50 (3H, m), 3.67 (3H, t, J = 8.7 Hz), 3.83 (6H, d, J = 4. 2Hz), 3.94 (6H, m), 4.78 (3H, m), 5.03 (3H, s).
¹⁹ F-NMR [CDCl ₃ ]: δ [ppm] -88.8 (66F, m), -86.9 (9F, s), -77.9 (6F, m).

(Synthesis Example 5 Synthesis of HD-5)
The discotic compound HD-5 was synthesized by the following procedure.

  400 mg (1.36 mmol) of the compound (4), 1 mL of N, N-dimethylformamide (DMF) and 3.57 g (4.49 mmol) of the compound (2) are placed in a glass reaction vessel, and 1,8-diazabicyclo [5 4.0] undec-7-ene (DBU) 24.8 mg (0.163 mmol) was added and allowed to react at 100 ° C. for 10 hours. After cooling, liquid separation was performed with ethyl acetate-15 wt% saline-FC-72 (trade name, manufactured by Sumitomo 3M), and the FC-72 layer was dried over sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 274 mg (0.102 mmol, yield 7.5%) of HD-5.

The identification data of HD-5 was as follows.
¹ H-NMR [CDCl ₃ ]: δ [ppm] = 2.38 (3H, d, J = 3.6 Hz), 3.78 (6H, m), 3.90 (6H, t, J = 7. 5 Hz), 3.98 (6H, d, J = 4.2 Hz), 4.15 (3H, m), 6.11 (3H, s).
¹⁹ F-NMR [CDCl ₃ ]: δ [ppm] -88.9 (66F, m), -87.0 (9F, s), -78.0 (6F, m).
MALDI / TOF-MS: m / z = 2704.2 [M ⁺ + Na].

(Synthesis Example 6 Synthesis of HD-6)
The discotic compound HD-6 was synthesized by the following procedure.

  59 mg (0.343 mmol) of compound (6), 1.29 g (1.51 mmol) of compound (7) and 1 mL of N, N-dimethylformamide (DMF) were placed in a glass reaction vessel and reacted at 100 ° C. for 8 hours. . After standing to cool, the solution was separated with ethyl acetate-15 wt% brine-FC-72, and the FC-72 layer was dried over sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 794 mg (0.222 mmol, yield 64.6%) of HD-6.

The identification data of HD-6 was as follows.
¹ H-NMR [CDCl ₃ ]: δ [ppm] = 2.00-2.99 (24H, m), 3.59 (8H, m), 3.88 (12H, m).
¹⁹ F-NMR [CDCl ₃ ]: δ [ppm] -90.1 to -87.1 (100F), -79.0 to -78.4 (8F).
MALDI / TOF-MS: m / z = 3580.3 [M ⁺ ].

(Synthesis Example 7 Synthesis of HD-17)
The discotic compound HD-17 was synthesized by the following procedure.

  1.50 g (6.09 mmol) of compound (1) was placed in a glass reaction vessel and dissolved in 6 mL of tetrahydrofuran (THF) and 6 mL of N, N-dimethylacetamide (DMAc). 1.70 g (12.2 mmol) of potassium carbonate and 8.72 g (9.39 mmol) of the compound (2) were added and reacted at 80 ° C. for 1 hour. After standing to cool, the mixture was separated with ethyl acetate-water. The organic layer was washed with 10 wt% saline and 25 wt% saline and dried over sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1.18 g (1.17 mmol, yield 19.3%) of compound (3).

The identification data of the compound (3) were as follows.
¹ H-NMR [CDCl ₃ ]: δ [ppm] = 1.79 (1H, t, J = 5.4 Hz), 3.61 (2H, t, J = 5.1 Hz), 3.77 (2H, m), 4.16 (2H, t, 10.2 Hz), 7.73 (3H, m), 8.13 (1H, m).
¹⁹ F-NMR [CDCl ₃ ]: δ [ppm] -88.7 (22F, m), -86.9 (3F, s), -73.3 (2F, m).
MALDI / TOF-MS: m / z = 1046.9 [M ⁺ + Na].

  Next, 1.52 g (1.51 mmol) of compound (3) was taken in a glass reaction vessel and dissolved in 10 mL of acetonitrile. 626 mg (4.53 mmol) of potassium carbonate and 375 mg (3.02 mmol) of m-toluenethiol were added and reacted at room temperature for 2 hours. Liquid separation was performed with ethyl acetate-water-FC-72, and the FC-72 layer was dried over sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1.12 g (1.34 mmol, yield 88.6%) of compound (4).

The identification data of the compound (4) was as follows.
¹ H-NMR [CDCl ₃ ]: δ [ppm] = 1.49 (1H, s), 2.12 (1H, s), 2.90 (2H, t, J = 5.0 Hz), 3.23 (2H, t, 10.5 Hz), 3.64 (2H, m).
¹⁹ F-NMR [CDCl ₃ ]: δ [ppm] -88.8 (22F, m), -86.9 (3F, s), -75.7 (2F, m).

  Furthermore, 1.12 g (1.34 mmol) of the compound (4) was placed in a glass reaction vessel and dissolved in 3 mL of tetrahydrofuran (THF). Under ice cooling, 41.2 mg (0.223 mmol) of compound (5) was added and stirred for 1 hour. After reacting for 4 hours under reflux with heating, THF was distilled off under reduced pressure. 1,4-Dioxane (3 mL) was added, and the reaction was performed under reflux with heating for 4 hours. 1,4-Dioxane was distilled off under reduced pressure. 2 mL of halocarbon 1.8 oil (trade name, manufactured by Halocarbon) was added and reacted at 120 ° C. for 5 hours. After standing to cool, the solution was separated with FC-72-water, and the FC-72 layer was dried over sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 170 mg (0.0656 mmol, yield 29.4%) of HD-17.

The identification data of HD-17 was as follows.
¹ H-NMR [CDCl ₃ ]: δ [ppm] = 3.72-3.90 (12H), 4.30 (6H).
¹⁹ F-NMR [CDCl ₃ ]: δ [ppm] -73.2 to -74.9 (6F), -87.2 to -91.1 (75F).
MALDI / TOF-MS: m / z = 2592.3 [M ⁺ ].

(Examples 1 and 2)
<LB film production equipment>
NL-LB400-MWC and LB FILM DEPOSITATION SYSTEM-controller (manufactured by Philgen Co., Ltd.) was used as the LB film manufacturing apparatus main body. For compression, a clean barrier method using the entire trough was used.
Peripheral groups of the LB film manufacturing apparatus include a PC controller (manufactured by NEC), an active micro vibration control system TS-150 (desktop type) (manufactured by HERZ) as an anti-vibration table, and a trough water temperature controller CTR42WS and CTE42WS (manufactured by Yamato-Komatsu Co., Ltd.) were used.
The entire LB film production apparatus was covered with vinyl, and nitrogen gas was introduced at 2 L / min to prevent dust from entering. Moreover, the ultrapure water introduced into the trough was prepared using an ultrapure water production apparatus Lab (manufactured by MILLIPORE).

<Preparation of developing solution>
HD-1 was mixed with AK-225 (Asahi Glass Co., Ltd.) to prepare a developing solution. The concentration of the developing solution was 407.48 μmol / L. Here, AK-225 is a mixture of CF ₃ CF ₂ CHCl ₂ and CF ₂ ClCF ₂ CF ₂ Cl.

<Development process>
2 L of the above-mentioned ultrapure water (18.2 MΩ) was introduced into the trough of the LB film production apparatus, and the water temperature was set to 25.0 ° C. by the trough water temperature controller. After 2 hours, it was confirmed that the surface pressure π value of the LB film production apparatus was stable, the surface pressure value was reset to zero, and then the HD-1 solution was gradually removed with a microsyringe (1 drop [1 to 3 μL]). / 30 seconds). The dripping amount was as shown in Table 1.

<Compression process>
Forty minutes after the start of the dropping of the developing solution, compression of the area where HD-1 was developed was started in the isostrictive compression mode and the compression rate (5% / min). Compressed from the maximum area (926.4 cm ² ) to the minimum area (95.2 cm ² ). The π-A curve of HD-1 during the compression process is shown in FIG. In FIG. 8, the diameter corresponding to the occupied area of one molecule is converted into the diameter of the discotic molecule corresponding to the occupied area. The diameter of the disk-shaped nucleus of HD-1 is 13 to 15 mm, and in FIG. 8, it increases monotonously to near the occupied area similar to the diameter of triphenylmelamine (13 to 15 mm) of the disk-shaped molecular skeleton, but it is sharp there It had an inflection point, and the surface pressure hardly changed during the subsequent compression process.

  The value of the rising portion of the π-A curve in the most compressed state in FIG. 8 is clearly less than 10 sqÅ, which is an LB monolayer film in which the occupied cross-sectional area of the molecular chain having a perfluoro group is less than 10 sqÅ. Even if the cross-sectional area (document value) of the perfluoroalkyl group, which is also a partial structure of a molecular chain having a perfluoro group, is 35 sqÅ, this data is in an abnormally high compression state. Suggests.

  In the compression process, an equilibrium relaxation mode may be used. The compression time for each time was set to 15 seconds, the compression speed at that time was defined as 15 mm / min, moved by 15/4 mm, and stopped. Here, the surface pressure rises by the amount of compression, but if the surface pressure changes below the relaxation surface pressure of 0.04 mN / m during the resting relaxation time of 90 sec, further compression starts and 0.04 mN / m or more. If the surface pressure was changed, the sample was kept still for 90 seconds. The change was continued for 90 seconds until the change in surface pressure became 0.04 mN / m or less. In this mode, when elastic deformation is included due to compression, by waiting until it is relaxed, the π-A of only plastic deformation is accurately detected so that the unrecoverable amount of elastic deformation is not regarded as plastic deformation. It is a more accurate compression mode for capturing changes in the image, but it is a very time-consuming measurement method. However, if the π-A curve in this equilibrium relaxation mode vibrates, it indicates that the compression region is a compression process in which elastic deformation occurs together with plastic deformation.

<Collection process>
The monolayer film obtained as described above was collected on a gold substrate. The gold substrate used in the sampling process was an infrared RAS mirror (Au 15 mm × 25 mm × 45 nm thick on 26 mm × 77 mm × 1 mm thick glass manufactured by JASCO Engineering Co., Ltd.). The gold substrate was washed with 10 minutes of ultrasonic waves in acetone, taken out, further washed with acetone, and dried under a nitrogen stream. Next, set the UV ozone cleaner (UVO-CRENER Model No. 42 Jelite Company, Inc.) at a depth of 5 mm and perform cleaning treatment with UV light and ozone for 10 minutes each on the front and back for a total of 20 minutes. went.

  A pre-treated gold substrate (infrared RAS mirror) was installed in the dipper of the LB film manufacturing apparatus, and immersed to 5 mm above the uppermost part of the Au sputtered film. After that, when the surface thickness of the formed LB monolayer film became a predetermined condition, the gold substrate was pulled up and collected. The gold substrate ascending speed was 1.0 mm / min. The molecular chain occupation cross-sectional area of the molecular film thus obtained is shown in Table 1.

(Examples 3 to 15)
In Examples 3 to 15, a molecular film including an amphiphilic molecule having a cyclic group and an amphiphilic molecule having no cyclic group was prepared. HD-1 and HD-10 were mixed at a molar ratio shown in Table 1 to prepare a tetrahydrofuran solution of the mixture. The tetrahydrofuran solution was compressed at an isostrictive mode of 3% / min to form an LB monolayer film. Here, the apparatus of Example 1 was used, and expansion and compression were performed under the conditions shown in Table 1. The molecular chain occupation cross-sectional area of the molecular film thus obtained is shown in Table 1.

(Examples 16 and 17)
In Examples 16 and 17, a Langmuir film was prepared from an amphiphilic molecule (PFPE chain compound) having no cyclic group. A tetrahydrofuran solution of HD-10 was compressed at 3% / min in an isosteric mode to form an LB monolayer film. Here, the apparatus of Example 1 was used, and expansion and compression were performed under the conditions shown in Table 1. The molecular chain occupation cross-sectional area of the molecular film thus obtained is shown in Table 1.

(Comparative Examples 1 and 2)
In the comparative example, a Langmuir film was prepared using the following compounds.

HD-8 is a compound in which the PFPE side chain of HD-1 is replaced with an alkyl group. The chloroform solution of C-1 [concentration: 438.2266 μmol / L CHCl ₃ 140 μL at 25.0 ° C.] was developed and compressed under the conditions shown in Table 1 using the apparatus of Example 1. The molecular chain occupation cross-sectional area of the molecular film thus obtained is shown in Table 1. The π-A curve is shown in FIG. The molecular occupation area in the limit compression state of HD-8 was 70 sqÅ.
HD-9 is also an amphiphile, and it was confirmed by FT-IR RAS spectrum that the side chain was oriented vertically to the air surface on the iron surface, and the triarylmelamine ring was oriented horizontally on the iron surface. Especially on the water surface, when the degree of compression increased, a stable Langmuir film was not formed, so the cross-sectional area occupied by molecular chains could not be measured.

These π-A curves shown in FIGS. 9A to 9C are HD-8 (FIG. 9A), HD-7 (FIG. 9B), HD-1 (FIG. 9C). )), The π-A curve is the result of evaluation by the iso-strain method, and the π-A curve is the result of evaluation by the equilibrium relaxation method. For each discoidal compound, three differences which are considered to be derived from side chains are clearly seen.
The first is that the molecular occupation area where the surface pressure begins to increase, that is, where the discotic compound begins to contact, is HD-8 <HD-7 << HD-1. This can be interpreted that, in general, the larger the intermolecular interaction, the more the aggregation cannot be solved, and the apparent area occupied by the molecule is small because it exists as a lump from the beginning.
The second is the relative value of the surface pressure, but it represents the difference in surface pressure due to contact between the side chains, and the fact that it corresponds to the magnitude of the rotational barrier energy is very interesting for understanding the surface pressure of the membrane. It is a result.
The third is exactly the difference in the contribution of elastic deformation. The contribution of the alkyl chain of HD-8 is extremely large from the beginning, and it can be seen that the interaction derived from van der Waals attraction works remarkably. HD-7 is considerably smaller than HD-8, but it appears that the time for relaxation of the entanglement of the side chain due to thermal fluctuation is probably increased due to the rigidity of the perfluoroalkyl group in the highly compressed state and the dense state. Inferred. On the other hand, in HD-1, almost the same π-A curve is obtained by the equal strain method and the equilibrium relaxation method, and it can be seen that the elastic deformation is immediately eliminated even by the continuous compression operation. This is considered to be a synergistic effect that the intermolecular interaction of the perfluoroethyleneoxy chain is small and the flexibility is extremely high.
These results strongly support that the alkyl chains are actually much easier to interact than the PFPE chains, and conversely, the PFPE chains can be densified without affecting each other.

Further, as can be seen from FIG. 9 (d), the following relationship is observed in the occupied sectional area.
PFPE chain 6.8 sqÅ <PFA chain 9.1 sqÅ <Alkyl chain 11.7 sqÅ
Kato Sadaji; Surface Science Vol.21, No.10, pp.608-614, (2000). PFA chain is reported to be 35 sqÅ and alkyl chain is 19 sq 、. In addition, HERies, Sci. Amer., 244, No. 3 152 (1961) reports a value similar to 20 sqÅ for both stearyl and hexatriacontyl chains. On the other hand, regarding the PFA chain, JP-A-5-7747 reports the limit occupancy area of the LB film as 43 sqÅ.
Thus, the measured values of the examples of the present invention are measured under similar conditions, and are much clearer for PFA chains that are much smaller than any of the reported literature values and have a larger van der Waals radius than alkyl chains. It is a small value.
However, these orders are not the substantial occupied cross-sectional area of each side chain, and the elastic deformation at the time of compression due to the interaction between the side chains, which has been clarified in FIGS. 9A to 9C, is not eliminated. The rest should be considered as the value estimated as the integral of plastic deformation. Therefore, this order is an order of magnitude of influence or contribution of side chain interactions.
Also, from the viewpoint of the occupied cross-sectional area of the side chain, since fluorine is larger than hydrogen, PFPE chain to PFA chain> Alkyl chain is clear, and Alkyl chain is probably substantially smaller than 6.8 sqÅ indicated by PFPE chain. It is guessed.

  In Examples 1 and 2, the limit compression occupation area of HD-1 alone was determined, and 1/6 of the area was defined as the limit occupation cross-sectional area of one side chain PFPE. Furthermore, in Examples 2 to 15, HD-10 was added to HD-1 and the critical compression cross-sectional area thereof was determined. The ratio of HD-10: HD-1 was gradually increased, and the value of the ratio approaching 1 was defined as the limit occupation cross-sectional area of HD-10, that is, one PFPE chain. Further, in Examples 16 and 17, the limit compression occupation cross-sectional area at the depth of HD-10 single shot was obtained. The limit compression occupation cross-sectional area of each Example and Comparative Example is shown in Table 1 below.

Table 1 shows the composition of each example and comparative example and the limit occupation cross section of one molecular chain having a perfluoro group read from each π-A curve. As can be seen from Table 1, in Examples 1 to 17, the limit occupation cross-sectional area of one molecular chain having a perfluoro group is 10 sqÅ or less, and it can be seen that an ultra-highly dense molecular film is obtained. . Among them, in Examples 2 to 17, the limit occupation cross-sectional area of one molecular chain having a perfluoro group is 5 sqÅ or less. Surprisingly, in Examples 16 and 17, one molecular chain having a perfluoro group is single The limit occupation cross-sectional area was 1 sqÅ or less.
By this verification method, in Examples 16 and 17 of Table 1, a slight increase in surface pressure was observed in the most compressed state. It was found that only a part of HD-10 was dissolved in water. Conversely, when HD-1 coexists, it was suggested that HD-10 exists in a stable mixed film on the water surface.
On the other hand, in Comparative Example 1, the limit occupation cross-sectional area of one molecular chain is 70 sqÅ, indicating that the degree of densification is extremely inferior. In Comparative Example 2, since a stable Langmuir film was not formed on the water surface, the occupied cross-sectional area of the molecular chain could not be measured.

In Table 1, the weights of HD-1 and HD-10 of Examples 2 to 15 are the respective weights [mg] to be put into a 10 mL volumetric flask. In practice, however, a THF solution of HD-1 and HD-10 is prepared in advance for more accurate weighing, and the volume corresponding to the required mg is weighed into a 10 mL volumetric flask, and then becomes 10.0 mL. Diluted with THF.
In each experiment, a π-A curve (actually almost a straight line) before development of the HD-1 / HD-10 mixed film was measured, and after the π-A curve was measured, HD- on the water surface was measured. The 1 / HD-10 mixed film is sucked and removed by suction until the surface pressure becomes a negative value, and then the π-A curve is measured again before the development of the HD-1 / HD-10 mixed film. It was confirmed that it was not different from the π-A curve.
Because HD-10 is a fluorine-based water-repellent alcohol, it is also a surfactant and partly dissolves during the formation of a mixed film of HD-1 / HD-10 to form micelles and exists in water There are concerns. However, if the HD-1 / HD-10 mixed film on the water surface is removed, HD-10 will come on the water surface as a surfactant, so if its π-A curve is measured, This is because it is possible to confirm the presence or absence of high sensitivity.

A graph showing the relationship between the composition of the mixed developing solution of HD-1 and HD-10 and the limit occupation cross-sectional area is shown in FIG. The critical compression cross-sectional area of one PFPE chain obtained from each π-A curve in FIG. 10A was obtained as follows. An example of HD-1: HD-10 = 1: 99 of Example 12 in Table 1 is shown.
In this case, the molecules having the area occupied by the molecule in FIG. 10A are calculated by regarding “one molecule for HD-1 and 99 molecules for HD-10” as “one molecule”. Therefore, the molecular weight is HD-1 3030.82 + HD-10 448.008 × 99 = 47390.74, which is 6.66 mg / mL ÷ 47390.74 = 140.34 μmol / L in terms of concentration. 600 μL of this was developed. From the obtained π-A curve (FIG. 10B), first, the molecular occupation area [65.7 sqÅ] of “one molecule” was obtained, and this was determined as the PFPE chain 6 of HD-1 constituting the “one molecule”. The (average) cross-sectional area [0.626 sqÅ] of one PFPE was obtained by dividing the book and 99 of HD-10 by a total of 105.

  The above operation was performed for Examples 3 to 15 in Table 1. FIG. 10C is a diagram in which the average cross-sectional area of one HD-10 PFPE chain is plotted against the ratio of PFPE chains derived from HD-10 among all PFPE chains. FIG. 10 (c) shows that the average cross-sectional area of one PFPE chain decreases as the ratio of HD-10-derived PFPE chains increases.

<Comparison with van der Waals radius>
Regarding the van der Waals radius, the molecular volume was determined under the condition that the radius of the adjacent group that recognizes the side chain was minimized, and further divided by the obtained molecular length to determine the average cross-sectional area of each. As a result, the diameter of the PFPE chain was 4.36 mm, and the molecular cross section was 14.93 sq mm. However, in the present invention, it has been found that the experimental value of the limit occupation cross-sectional area of one HD-10 PFPE chain is 0.5 sqÅ or less, and a value smaller by one digit or more is obtained.

  From the above, when an LB film of a PFPE chain alone is formed, the limit occupation cross-sectional area is obtained, and the PFPE chain has a limit occupation cross-section of 1/10 or less of the cross-sectional area assumed from the van der Waals radius. Got a certain result.

Furthermore, FIG. 10 (c) shows that the molecular occupation area of HD-10 is clearly smaller than the molecular occupation area of one PFPE chain in HD-1. That is, it is clear that a high densification phenomenon that could not be considered by the concept of van der Waals radius can occur in the compound having this PFPE chain. In addition, the fact that the occupying area of the LB film in which most of the PFPE chain is HD-10 was obtained as a value of 0.75 sqÅ in the same order as the cross-sectional area of 0.485 sqÅ of PFPE obtained by ab Initio calculation is PFPE chain It can be said that the high densification phenomenon of a series of compounds with the above shows not only the embedding of the irregularities of the ring structure but also the truth that the PFPE chain itself can be extremely densified and the accuracy of this experiment.

(Examples 18 to 20)
In Examples 18 to 20, a plurality of PFPEs similar to HD-1 to HD-3 with respect to ring structures having different ring diameters and ring structures other than triphenylmelamine rings having unclear and unclear ring shapes. The disc-like compounds HD-4 to HD-6 in which the chains extend radially from the central ring were examined in the same manner as in Example 1. Here, the apparatus of Example 1 was used, and decompression and compression were performed under the following conditions.
Fluorine solution of HD-4 [concentration: 376.074 μmol / L Vertrel 75 μL at 25.0 ° C.]
Fluorine-based solution of HD-5 [concentration: 397.282 μmol / L Vertrel 75 μL at 25.0 ° C.]
Fluorine-based solution of HD-6 [concentration: 284.834 μmol / L Vertrel 100 μL at 25.0 ° C.]

FIG. 11 is a π-A curve in forming an LB monolayer film of HD-4 to HD-6. HD-4 to HD-6 all showed clear inflection points. The order of the molecular occupation area at the inflection point corresponds to the order of the molecular occupation area of the disk-shaped nucleus obtained from the molecular orbital calculation, but the inflection point is much larger than the disk-shaped nucleus itself. The point which has welcomed is greatly different from HD-1. The FT-IR RAS spectrum shows that any side chain of HD-4 to HD-6 stands perpendicular to the interface from the low concentration before the inflection point. It may be influenced by the connecting group part to be connected.
Regarding plateau following the inflection point, HD-6 is a smooth monotonous increase and is different from HD-4 and 5, but not because the irregularities are not clear or because the skeleton is relatively soft and deformed. It can be considered. In the HD-4 to HD-6 LB monolayer films, the occupied cross-sectional area of the molecular chain was 10 sqÅ or less.

(Analysis of membrane structure)
<Collecting Langmuir film and analyzing molecular orientation>
Next, the orientation state of HD-1 molecules of LB monolayer films collected on a gold substrate and having different compressibility was analyzed. For the analysis, an FT-IR RAS method as shown in FIG. A normal FT-IR spectrum has a thickness of about 0.1 μm which is almost the limit of measurement. However, when the FT-IR RAS method is used, a monomolecular film of an organic compound, that is, an IR spectrum of a sample having a thickness of about 1 nm is obtained. It is done. That is, the FT-IR RAS method is a measurement method having a sensitivity close to 100 times that of a general FT-IR method. As shown in FIG. 12A, when IR light is applied at a low incident angle so as to be totally reflected on a light-reflective metal surface, vibrations in the direction perpendicular to the incident surface (in the substrate surface) are mutually On the other hand, since the reflected IR light in which the vibration in the plane of incidence, that is, the direction perpendicular to the metal surface is intensified is obtained, only the vibration in the direction perpendicular to the substrate is captured with high sensitivity. Furthermore, since IR light enters at a low incident angle, the optical path length passing through the sample can be increased several times compared to the vertical reflection or transmission method, so that information on molecular orientation in the ultrathin film can be obtained with high sensitivity. it can. Therefore, it is possible to extract information on the molecular orientation of the monomolecular film by comparing with the IR spectrum in the non-oriented state. In the present invention, FT-IR 6300 (manufactured by JASCO Corporation) was used as the FT-IR spectrometer. Here, the entire optical path from the IR laser to the optical interferometer, sample chamber, and MCP detector can be degassed to a vacuum system, and extremely sensitive RAS measurement with almost no CO ₂ and H ₂ O absorption bands is possible. ing.

As shown in the left diagram of FIG. 12B, when the PFPE chain is oriented perpendicular to the substrate, the difluoromethylene group is oriented parallel to the substrate, so that only vibrations perpendicular to the substrate are detected. The In the FT-IR RAS method, the peak of symmetric stretching vibration (˜1290 cm ⁻¹ ) of the difluoromethylene group CF ₂ , which is overwhelmingly large as the number of functional groups, is not visible, and conversely, the terminal C having an overwhelmingly small number of functional groups. Only the peak of C—C stretching of the —CF ₃ group (1255-1265 cm ⁻¹ ) will be detected. On the other hand, when the PFPE chain is oriented horizontally on the substrate, Fomblin Z-Tetraol (manufactured by Solvay Solexis), which is a lubricant for HDD, which is a representative compound, is a protective film for magnetic recording materials. are well known in that they are horizontally aligned over the diamond-like carbon film, the so difluoromethylene groups in this case are oriented perpendicularly to the substrate of the antisymmetric stretching vibration of difluoromethylene groups CF ₂ peak (~ 1290 cm ⁻¹ ) will be detected.
FIG. 12B shows an FT-IR RAS spectrum of a molecular film of HD-1 collected on an Au substrate. Here, it is clearly shown that HD-1 horizontally aligns the disk-shaped nuclei on the Au substrate surface, and the PFPE chains are sharply aligned vertically. That is, it was found that the side chain groups were considered to be oriented perpendicular to the water surface.

Further, as shown in FIG. 13, due to the compression of the Langmuir film, the peak wave number of the PFPE chain terminal C-CF ₃ stretching vibration is changed from the lowest compression (1251.6 cm ⁻¹ ) to the highest compression (1265.1 cm ^{−). The} wave number is shifted by about 13.5 cm ⁻¹ up to ¹ ). This is because the PFPE chain undergoes a continuous change in which the side chain that is most affected by compression gradually increases the bond energy by increasing the side chain length in terms of interaction with adjacent groups, that is, a high wavenumber shift. It is thought that there is.

<Analysis of irregularities and film thickness on Langmuir film surface by non-contact optical system>
Next, it was verified whether the molecular film obtained in the example was not a multilayer film but a homogeneous monolayer film. The optical interference film thickness measurement was used for this verification. Here, in order to demonstrate that a film having a homogeneity equal to or less than the thickness of the side chain PFPE to be used was formed, the following film thickness measurement was performed on the HD-1 molecular film collected on the Au substrate. . For the evaluation, an ultra-high resolution non-contact three-dimensional surface shape measurement system BW-A50X (manufactured by Nikon) was used.

The following four types of samples were used for measurement.
Reference Example 20: Infrared RAS mirror substrate without a molecular film as a reference [Au 15 mm × 25 mm × 45 nm thickness on 26 mm × 77 mm × 1 mm thickness glass manufactured by JASCO Engineering Co., Ltd.]
Example 21: HD-1 molecular film 200% compressed product Example 22: HD-1 molecular film 400% compressed product Example 23: HD-1 molecular film 400% compressed product (Spotted surface has scattered parts) Sample)

The Au substrate of Reference Example 20 was measured. The measurement result of the cross-section (displacement in the depth direction) is 6 mm even in the entire fluctuation range, and the statistical two-dimensional roughness is 2.7 mm in the depth direction. It was found that there was no place where the step was generated (FIG. 14A).
The measurement was performed on a two-month-old product of “HD-1 molecular film 200% compressed product” in Example 21. Usually, the step of the organic film is made by rubbing with the tip of a bamboo spat. However, since the Au substrate is very easily damaged, the step was measured at a point where a fine crack was generated in the film within two months. The crack depth was 1.5 nm or less, and the statistical two-dimensional roughness was 5.8 mm in the depth direction. Since this Example 21 is a 200% compression product, if multiple layers are formed, the film thickness should be at least 2 nm, and the crack should have occurred, but such a deep crack is seen in it. (FIG. 14 (b)).
The measurement was performed on the two-month product of “HD-1 molecular film 400% compressed product” in Example 22. In the same manner as in Example 21, the level difference was measured at a location where a fine crack was generated in the film. However, as a result of the measurement, it was found that the film was formed with a very uniform film thickness. Although the crack depth was 2 nm at maximum, it was understood that the crack was uniform over a very wide field of view, and the crack part was selected on top of that. . Because it is a 400% compressed product, if it is made of multiple layers, it should have a thickness and crack of at least about 4 nm in each place, but such a place was not seen (FIG. 14 (c)). .
The measurement was performed on a two-month-old product of Example 23, “HD-1 molecular film 400% compressed product (sample in which the surface is scattered in a striped pattern)”. The striped pattern was found to be a protruding band having a height of ˜15 mm and a width of 60 mm. Since this is composed of HD-1, it is presumed that it is made of lumps of about 1 layer 3 rows. This is the most worrisome phenomenon, but it can be clearly detected when it happens, so conversely, such a phenomenon has hardly occurred so far and such partial multilayering has occurred in homogeneous samples. On the contrary, the results strongly suggest the homogeneity of the molecular film so far (FIG. 14 (d)). FIG. 14E shows a three-dimensional representation of the surface having the protrusion band. Through analysis of Examples 21 to 23, it was found that the molecular film of HD-1 was a homogeneous thin film having a thickness of about 10 mm corresponding to the PFPE side chain length. Further, the other examples were also found to be homogeneous thin films like the HD-1 molecular film.

<Analysis of PFPE chain characteristics by molecular orbital calculation>
The characteristics of each side chain from the viewpoint of molecular orbital calculation were analyzed. In order to verify why high densification is possible using a PFPE chain, a long-chain alkoxy group, a polyethyleneoxy group, a perfluoroalkyloxy group, and a side chain of a triarylmelamine that is the central skeleton of HD-1 Regarding the perfluoroethyleneoxy group, the difference and similarity between the latter and the former were compared. For each side chain, the number of constituent chain length elements was combined in a model manner, and the calculation was performed using WINMOS TAR. The result of the analysis is shown in FIG.

  As shown in FIG. 15, the alkyl group has a small carbon chain and the carbon surface is clearly visible. On the other hand, it can be seen that when the hydrogen atom of the alkyl group is replaced by fluorine, the covering efficiency of the carbon surface is remarkably increased. Note that in the case where the hydrogen atom of the alkyl group is replaced with bromine, the atomic radius of bromine is too large compared to carbon, so that a gap is formed. From this, it was found that the PFPE chain was covered with fluorine, and the electron density of the carbon chain was low. In other words, the alkyl chain has an electronic structure that is easily polarized by both carbon and hydrogen, and is susceptible to the polarization of adjacent groups, while the PFPE chain has an electron definite component, It was found that the element is the lowest polarizability among the elements, hardly affected by the surrounding electronic environment, and is efficiently coated with an element that is difficult to give.

  Moreover, it was found that the PFPE chain is highly flexible. FIG. 16 shows the result of calculating the rotational barrier energy of the C—C—C bond or C—CO—C bond of each side chain. As can be seen from FIG. 16, the greatest feature of the PFPE chain is that the rotation barrier energy is small at any angle, so that it can be flexibly adapted to the surrounding structure.

<Measurement of film thickness and film density by X-ray reflectivity measurement>
A Langmuir film was formed on a silicon wafer, and X-ray reflectivity measurement was performed. In the X-ray reflectivity measurement method, the density and film thickness can be directly measured simultaneously. Since the refractive index of a substance with respect to X-rays is slightly smaller than 1, when X-rays are incident on a surface of a substance having a flat surface, total reflection occurs. By measuring the incident angle dependency of the total reflection X-ray intensity (reflectance) on the thin film surface with respect to the incident X-ray intensity, an incident angle dependency profile of the X-ray reflectance as shown in FIG. 17 can be obtained. The structural parameters (density, film thickness, roughness) of the thin film can be evaluated nondestructively. For this measurement, a substrate that is as smooth as possible is necessary, and a silicon wafer is most suitable for the purpose. Therefore, the following three kinds of molecular film samples were formed on the silicon wafer on the silicon wafer.
Example 24; It was prepared by changing the degree of compression of HD-1 + HD-10 (1: 1) in three ways (Examples 24-1 to 24-3). In these examples, since the adsorption force of the silicon wafer was small, the molecular film in a highly compressed state could not be maintained at that density, and all of them had a medium density film of the same level. There was found.
Example 25; HD-1 + HD-16 (1:99)
HD-16 should be nearly twice as thick as HD-10, and HD-16 is equivalent to 6 mol of HD-16 and almost equivalent to 1 mol of HD-1, so the overwhelming ratio of occupied area is about 1: 16.5. In particular, a molecular film was prepared with the expectation that an LB film having a large amount of HD-16, that is, about twice as thick, could be obtained.
Example 26; HD-7
HD-7 is a compound having a PFA group at the end of the side chain and giving a general π-A curve having no inflection point like HD-1, but its side chain is rigid, A molecular film was prepared with the expectation that the intermolecular force is smaller than that of the alkyl group and densification by compression is possible to some extent.

The apparatus used for the X-ray reflectivity measurement is Rigaku ATX-G. A Cu target was used as the X-ray source, and X-rays were generated at 50 kV-300 mA. Detailed conditions are shown below.
Reflectance measurement S1 slit width 1.0 mm, height 10 mm
Incident side optical element None S2 slit Width 1.0 mm, Height 10 mm
Receiving slit width 1.0 mm, height 10 mm
Light receiving side optical element None Gurd slit Width 0.5 mm, Height 10 mm
Scan axis: 2θ / (, scan range 0-20 (, sampling width 0.01 (,
Scan rate: 0.1 (/ min (2θ / ω = 0 ° to 2 °), 0.05 (/ min (2θ / ω = 0.5 ° to 20 °))
Measurement of 2θ / ω = 0 ° to 2 °; A separate article (manufactured attenuator) on which eight Al foils were stacked was installed (for the purpose of detector protection).

From the data of 0.5 ° to 2 ° of the measurement of 2θ / ω = 0 ° to 2 ° and the data of 0.5 ° to 2 ° of the measurement of 2θ / ω = 0.5 ° to 20 ° X-ray attenuation was corrected. After connecting both data by the sigmoid function, X-rays scattering (Thomson scattering, Compton scattering) by the 2θ / ω = 15 ° ~20 ° of data substrate Si calculate the fraction ¹⁾ were corrected data. A simulation was performed on the obtained reflectance data.

In the X-ray reflectivity method, the absolute value evaluation accuracy of the expected thin film of about 1 nm is unconfirmed, so the magnitude relationship with respect to the Si wafer as the substrate (the ratio of the P wave and S wave of the interface reflected wave is reversed). Therefore, the relative magnitude relationship between the samples was investigated. Since the error was not evaluated for the film thickness, it was analyzed by relative comparison.
Table 2 shows the density and film thickness results of the monolayer samples for each simulation. Since the film thickness is small, the reliability of the absolute value of the numerical value is low, so the relative relationship was considered.

The film thicknesses of the three types of Examples 24-1 to 24-3 and Example 26 are almost the same, and only Example 25 is thick, and is predicted from the structure of the compound (the length of the molecular chain having a perfluoro group). Consistent with the trend.
The simulated density values for all samples were at least higher than the theoretical density of Si, 2.33 g / cm ³ . When the samples were compared, no clear difference could be detected between the highest density example 24-1 and the second highest density example 24-2, but the lowest density example 24-3 was qualitative. Therefore, the density order estimated from the π-A curve was consistent with the density order evaluated by X-ray reflectivity.
In Example 25, the density higher than that of Si was the same as in Example 24, and was 7 g / cm ³ or more. Moreover, Example 26 which has a molecular chain which has a perfluoro group which is a more rigid side chain was also 7 g / cm < ³ > or more.
The chain lengths of the compounds used in Example 24 and Example 26 were almost the same, and the measured film thicknesses were all about 0.7 nm. On the other hand, the chain length of the compound used in Example 25 has a chain length almost twice that of the compounds used in Example 24 and Example 26, but the measured film thickness is about twice that of 1.66 nm. It was found that the chain length and the film thickness corresponded.
All samples were denser than the Si wafer substrate (document density 2.33 g / cm ³ ). The density expected from the π-A curve and the relative density order evaluated from the X-ray reflectivity coincided. Moreover, the order of the film thickness expected from the structure and the order of the relative film thickness evaluated from the X-ray reflectance coincided.
When the depth at which the X-ray intensity decreases to 1 / e is defined as the X-ray penetration depth, the penetration depth exceeds 18 μm at 2θ / ω> 15 °. The contribution of scattering derived from a sample with a surface number of nm is negligible, and Thomson scattering and Compton scattering are considered to be mostly derived from the substrate Si.

  The Au substrate is not as smooth as Si wafer, but if the same X-ray reflectivity measurement as described above can be performed, it is considered that a higher density can be demonstrated, and the above-described sample substrate density and film thickness were evaluated. As a result, it was found that a monomolecular layer having the same thickness as that of the Si wafer substrate was formed.

<Evaluation of refractive index of Langmuir film>
About the Langmuir film created in the Example, the refractive index was evaluated using the surface plasmon resonance method. In general, light does not couple with an electron wave (plasmon), but an electron wave mode that causes coupling with light occurs on a metal surface due to its particularity. This is a surface plasmon. An evanescent wave is generated on the total reflection surface, and only the evanescent wave is coupled with the surface plasmon. If this phenomenon is used, only a sample (dielectric thin film) of about 1 nm is adsorbed on the metal surface, and the resonance angle of the reflected light of the light changes according to the dielectric constant. The dielectric constant, that is, the refractive index can be measured with higher sensitivity. This method has already been established (Surface Plasmon Spectroscopy of Organic monolayer Assemblies I. Pockland, JD Swalen, JG Gordon II and m. R. Philpott,
Surface Science 74, 237-244 (1977)), and is useful as a high-sensitivity sensor for enzymes in biological systems, and its application development is progressing widely.

  In this example, a Kretschmann type optical device as shown in FIG. 18A was assembled, and the angle at which the near-infrared light was totally reflected was precisely evaluated. As shown in FIG. 18 (b), the relationship between the reflectance and the incident angle shows that the plasmon resonance is strongest at the light reflection angle (45 °) indicated by the dotted line in the state of only a normal Au substrate without a dielectric film. Resulting in the lowest reflectivity. However, when a dielectric thin film is attached to the Au film, the plasmon resonance state changes, and the angle at which the reflectivity decreases most changes as shown by the solid line. Since the amount of change in the angle, the dielectric constant of the dielectric thin film, and the film thickness are in a relationship that can be theoretically calculated, the relationship is obtained in advance by simulation, and from the correspondence between the measured value and the experimental value, The refractive index of the molecular film can be obtained.

  As a result, it was found that the Langmuir films (Examples 27 to 32) prepared under the conditions shown in Table 3 below exhibited a large refractive index of 3 to 4, which is not conceivable with organic compounds. Since the refractive index of the fluorine compound HD-1 + HD-7 + HD-10 constituting this film is 1.33, the Langmuir film thereby becomes highly dense and this data except that the electron density per unit volume is increased. This high refractive index data strongly suggests that the amphiphilic Langmuir film having the fluorine compound of the present invention has a super close packed structure.

(Relationship between compressibility and molecular film)
Moreover, in this invention, the compression rate was changed and the monomolecular film was created. The molecular diameter corresponding to the occupied cross-sectional area of one molecule of HD-1 at each compression rate and the film thickness were determined from the molecular orbital calculation of the PFPE chain. FIG. 19 shows a graph in which the C—C stretching peak (1255-1265 cm ⁻¹ ) strength of the PFPE chain terminal C—CF ₃ group is plotted with respect to the compression ratio (horizontal axis) of the area. This is because the FTPE-IR RAS spectrum measured for each LB monolayer taken at each compression end point in the eight π-A curves of HD-1 shows the C of the PFPE chain end C-CF ₃ group. -C stretching peak (1255-1265 cm ^-1 ) strength is plotted with respect to the compression ratio (horizontal axis) of the area.

In FIG. 19, the vertical axis of the graph is C-CF ₃ peak intensity, and the horizontal axis is 100% when the molecular occupation area is 210 sqÅ (the inflection point of the π-A curve), 200% for 105 sqÅ, and 300 for 70 sqÅ. % Is expressed as a compression rate. As shown in FIG. 19, the peak intensity and the compression ratio show a clean proportional relationship, and the normal compression phenomenon occurs until the compression process exceeds at least four times compression (400%).
However, where the π-A curve shows the inflection point, the occupied cross-sectional area of one PFPE chain reaches a value (27.5 sqÅ) that is more compressed than the occupied cross-sectional area of perfluoroalkyl groups already known in the literature. From that, it is impossible to further compress at least four times at normal temperature and normal pressure based on past knowledge.

In addition, FIG. 19 shows the molecular density corresponding to the occupied cross-sectional area of one HD-1 molecule at each compressibility, the film density calculated as the side chain length of 13 mm obtained from the molecular orbital calculation of the molecular chain, and The occupied sectional area per PFPE side chain is displayed.
As a result of this, if the "mutual embedding hypothesis by recognizing irregularities between adjacent molecules" occurs in the LB film formation process of the HD-1 molecule, the IR absorption intensity of the side chain group is reduced by a special interaction in the compression process. This is a natural result as long as the transducer strength does not change.

(Evaluation of gradual compression)
Furthermore, in the present invention, compression was repeated to create a monomolecular film. The same apparatus as Example 1 and the process of forming a monolayer film, and then holding the barrier of the LB film production apparatus in the most compressed state for 2 hours, then completely opening it and repeating compression and opening again Was repeated 17 times.
FIG. 20 shows the transition of the π-A curve when compression-relaxation is repeated a total of 17 times in the HD-2 LB film formation process. As shown in FIG. 20, it was found that the initial occupation area decreased with each repetition and the degree of decrease gradually decreased. In addition, the surface pressure after the fifth repetition has converged to a constant value, and the decreasing range after the ninth repetition is remarkably reduced and tends to converge to a certain (limit) value. Furthermore, since the 15th and 16th repetitions coincide, this is considered to be the limit convergence value.
Looking at the transition of such a π-A curve, it is predicted that the compression process of the compression process recognizes the molecular shape of the adjacent molecule and densifies by inserting a convex part into the concave part.

  According to the present invention, a highly dense single layer molecular film can be obtained. Since the molecular film of the present invention is an ultra-high densified film, the occupied cross-sectional area per amphiphilic molecule is very small and the film density is very high. Moreover, it has the characteristic that a refractive index is high. Therefore, the present invention provides a lubricant, antifouling property, chemical resistance, surface protective film for preventing oxidation, optical thin film, release film, various sensors, functional elements for precisely controlling reflection, transmittance, etc. Various applications such as semiconductor elements, display elements, recording media, coating materials, liquid crystal alignment films, nonlinear optical elements, ultrafine pattern resists, selective transmission films, gas shielding films, switching elements, thermoelectric conversion films or insulating films The industrial applicability is very high.

1 Amphiphilic molecule 2 Hydrophobic group 4 Hydrophilic group 5 Molecular film (monomolecular film)
6 Cumulative film 10 Barrier 20 Substrate S Development solution W Water phase

Claims (22)

A molecular film containing an amphiphilic molecule represented by the following general formula (1):
The amphiphilic molecules are oriented perpendicular to the plane direction in the molecular film,
A molecular film characterized in that the occupied cross-sectional area of one amphiphilic molecule is 10 sqÅ or less.
(In General Formula (1), X represents an alkylene group having 1 to 10 carbon atoms, and one carbon atom or two or more carbon atoms not adjacent to each other may be substituted with oxygen or sulfur atoms. Y represents a polar group or an atomic group having a polar group, p1 represents an integer of 1 to 20, p2 and p3 each represents an integer of 0 to 8, and p4 represents an integer of 0 or 1. Q represents an integer of 0 to 30, n represents an integer of 1 to 10, and s represents an integer of 1 to 30, provided that-[(CF ₂ ) _p1 ( CF (CF ₃ )) _{p 2} (C (CF ₃ ) ₂ ) _{p 3} (O) _{p 4} } _—p1 (CF ₂ ), p2 (CF (CF ₃ )) and p3 (C ( CF _{3) 2} bond order) is not limited Incidentally, when q is 2 or more, a plurality of _{-. [(CF 2) p1} (CF (CF 3)) p2 (C (C _{3) 2) p3 (O)} p4} -. , Respectively may be the same or different from each other hand, when s is 2 or more, the plurality of n and q, each be the same or different from each other May be.)   2. The molecular film according to claim 1, wherein an occupied cross-sectional area of one of the amphiphilic molecules is 5 sqÅ or less.   2. The molecular film according to claim 1, wherein an occupied cross-sectional area of one of the amphiphilic molecules is 1 sqÅ or less. The molecular film according to claim 1, wherein a film density of the molecular film is 3.5 g / cm ² or more.   The molecular film according to claim 1, wherein a refractive index of the molecular film is 3.0 or more.   The molecular film according to claim 1, wherein a surface pressure of the molecular film is 5 mN / m or more.   The molecular film according to claim 1, wherein an average film thickness of the molecular film is 0.5 to 20 nm.   8. The molecular film according to claim 1, wherein an occupied cross-sectional area of one of the amphiphilic molecules is 1/3 or less of an occupied cross-sectional area calculated from a van der Waals radius. .   In the said General formula (1), p2 and p3 are integers of 0, respectively, The molecular film of any one of Claims 1-8 characterized by the above-mentioned.   In the said General formula (1), when Y represents the atomic group which has a polar group, Y has the cyclic group which may be substituted, The any one of Claims 1-9 characterized by the above-mentioned. Molecular film.   In the said General formula (1), when Y represents a polar group, Y is a hydroxyl group, The molecular film of any one of Claims 1-10 characterized by the above-mentioned.   It contains an amphiphilic molecule (a) in which Y is an atomic group having a polar group in the general formula (1) and an amphiphilic molecule (b) in which Y is a polar group in the general formula (1). The molecular film according to claim 1, wherein:   13. The molecular film according to claim 12, wherein in the amphiphilic molecule (a), Y is a cyclic structure-containing atomic group having a polar group.   The molecular film according to claim 12 or 13, wherein a molar ratio of the amphiphilic molecule (a) to the amphiphilic molecule (b) is 1: 6 to 400: 1.   The molecular film according to claim 1, wherein the amphiphilic molecule has a molecular weight of 200 to 5,000.   The molecular film according to claim 1, wherein the molecular film is a single layer film.   The molecular film according to claim 1, wherein the amphiphilic molecule is fixed in the molecular film.   A laminated molecular film comprising the molecular film according to any one of claims 1 to 17 and a substrate.   The laminated molecular film according to claim 18, wherein the substrate is a gold substrate.   The laminated molecular film according to claim 18, wherein the substrate is a resin substrate.   A cumulative film, wherein the molecular film according to any one of claims 1 to 17 is formed by laminating two or more layers.   A stacked cumulative film comprising the cumulative film according to claim 21 and a substrate.