JP2018181784A - Ionic liquid-modified substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem of a method for fixing an exotic compound by ionic liquids as disclosed in the prior application already cited, thereby providing an ionic liquid-modified substrate which enables the fixing of various exotic molecules without causing a leak out of a substrate surface, and stabilization and activation of each exotic molecule by ionic liquid.SOLUTION: An ionic liquid-modified substrate is provided by strictly specifying the size and property of each ionic liquid for modification on a substrate, in which a space constructed on the substrate is made a reaction field that enables stabilization of an exotic molecule and the increase in the reactivity thereof. The ionic liquid-modified substrate comprises a substrate modified with ionic liquids given by the following chemical formula: [Z-R-X][A], where [Z-R-X]is represented by the general formulas (1) to (10). In the ionic liquid-modified substrate, the space that enables the fixing the exotic molecules can be provided on the substrate. An optimum reaction field can be provided according to the size and property of the exotic molecule. The exotic molecule thus fixed exhibits the stabilization and the increase in reactivity.SELECTED DRAWING: Figure 2

Description

The present invention relates to an ionic liquid modified substrate in which foreign molecules are immobilized on the substrate using an ionic liquid.

Various techniques have been proposed for modifying the surface of a substrate such as an electrode or a sensor with a compound for the purpose. In particular, a great deal of research has been conducted on the method of modifying a compound on the substrate surface using a self-assembled monolayer, due to its simplicity and the like. However, in this method, it is necessary to introduce a functional group having binding properties to the compound itself, and the compound substrate is obtained by bonding directly to the substrate surface or a compound separately modified on the substrate surface through these functional groups. Realization of immobilization on the surface is realized. Therefore, it is necessary to introduce a functional group to the molecule to be modified on the substrate surface, and it is often reported that redesign of the compound structure or the introduction of the functional group significantly changes the properties.

In order to overcome the problems as described above, the research group of the inventors has developed a technique for immobilizing on the surface of the substrate without modifying the molecules to be introduced (Patent Document 1, Non-patent Document 1). . The present invention shows a method of synthesizing a quaternary ammonium or quaternary phosphonium type ionic liquid which can be modified to the substrate surface, and a method of producing a substrate modified with such an ionic liquid. The ionic liquid modified on the substrate is sparsely modified on the substrate from its steric hindrance, creating a space between the ionic liquids. It is a technology that can trap functional molecules there.

However, in this prior application, there is a problem that the target compound can not always be immobilized, and molecules trapped in the ionic liquid gap formed on the substrate leak out. Also, depending on the nature of the molecule to be introduced, some could not be immobilized in the space generated on the substrate. Also, in recent years, it has been reported that the ionic liquid itself stabilizes the unstable compound or accelerates the catalytic reaction, but the conventional technology is limited to trapping the functional molecule, and if it is immobilized as it is Stabilization and activation could not be performed (Non-patent Document 2).

Japanese Patent Application No. 2012-167045

Chem. Commun. 49, 10184-10186 (2013) Bull. Korean. Chem. Soc. , 25, 1531-1537 (2004).

The object of the present invention is to solve the problem of the method for immobilizing foreign compounds using the ionic liquid of the prior application as described above, to immobilize various foreign molecules on the substrate surface without leakage, and to make foreign matter by ionic liquid. It is to provide an ionic liquid modified substrate capable of stabilizing and activating a molecule.

The present inventors arrived at the present invention as a result of extensively studying the structures and properties of conventional ionic liquid modified electrodes and ionic liquids which have been reported so far.

That is, the first feature of the present invention occurs when the ionic liquid is modified on the substrate surface by strictly controlling the size of the ionic liquid, not the bulky ionic liquid as in the prior application. It is possible to define the size of the space between the ionic liquids. As a result, the size of the space between the ionic liquids can be strictly controlled in accordance with the size of the functional molecules to be trapped on the substrate surface, and the trapped molecular leakage can be prevented.

The second feature is that the properties (polarity, viscosity, hydrophobicity, hydrophilicity, etc.) of the ionic liquid to be modified on the substrate surface can be reflected in the nature of the space between the ionic liquids formed on the substrate surface . This makes it possible to impart various properties to the space created between the ionic liquids, and to affect the stability and reactivity of the functional molecule to be immobilized. Further, according to the above first feature, by optimizing the distance between the modified ionic liquid and the functional molecule, it becomes possible to control the stability and reactivity of the molecule trapped in the space.

The conceptual diagram which shows the structure of an ionic liquid. The conceptual diagram which shows the relationship of the space and foreign factor which are formed with an ionic liquid and a board | substrate. The conceptual diagram which shows the kind of foreign factor. (A) mononuclear metal complex, (b) polynuclear metal complex, (c) organic molecule, (d) protein, (e) nano particle The figure which showed the conceptual diagram of the cobalt complex fixed to the ionic liquid modification board | substrate, and the result of the cyclic voltammetry measurement in the water. The figure which showed the measurement result of the oxygen activation ability by the conceptual diagram of the iron binuclear complex fixed to the ionic liquid modification board | substrate, and its rotation disc electrode.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the following embodiments, and changes, modifications, and improvements can be made without departing from the scope of the invention.

First Embodiment
The ionic liquid used in the present invention has a structure as shown in FIG. 1, and the chemical formula [Z-R ⁿ -X] ⁺ [A] ^- (wherein [Z-R ⁿ -X] ⁺ is a cation, [A] ^- is represented by the anion) (where n is an integer of up to 1-12).

A plurality of substituents R ⁿ controlling the distance between the ionic liquid modified on the substrate controls the distance between bulky ionic liquid molecules modified on the substrate. The length of the substituent R ⁿ determines the intermolecular distance when bulky ionic liquid molecules are modified on the substrate surface. That is, the distance between the ionic liquids is a range in which the bulky ionic liquids modified on the substrate do not collide with each other (approximately twice the length of the substituent R ⁿ ), and the horizontal size of the space formed on the substrate It will be

At least one end of the substituent R ⁿ is a substituent X which immobilizes the bulky ionic liquid to the substrate and controls the distance between the central portion of the bulky ionic liquid and the modified substrate. As the substituent X, one of thiol group, disulfide group, thioether group, carboxyl group, aldehyde group, -amino group, silanol group, phosphoric acid group, alkenyl group, alkynyl group, or azide group is selected and bonded. There is. In the formula, Z represents various atoms or relatively small organic compounds. However, in Z in the general formulas (9) and (10), P atom and N atom are excluded, and further, a hydrogen atom in the substituent R ⁿ and / or an aldehyde group in the substituent X are included. The distance between the central part of the ionic liquid and the substituent X defines the vertical dimension of the space formed on the substrate. Further, the length of the remaining substituent R ^{n where} the substituent X is not present defines the horizontal size of the space formed on the substrate.

Anion [A] ^- as is the anion with a monovalent or number more valent, can be a known anion. Various halogen ions, BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ SO ₃ ⁻ (abbr. TfO ⁻ ), (CF ₃ SO ₂ ) ₂ N ⁻ (abbr. Tf ₂ N ⁻ ), and the like are suitably used.

^{[Z-R n -X] +} is Formula (1) represented by the following general formula (1) ~ ^(10), R 1 to R ⁶ are independently a hydrogen atom, 1 to carbon atoms 30 alkyl group, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 30 carbon atoms, alkoxyalkyl group having 1 to 30 carbon atoms, aminoalkyl group having 1 to 30 carbon atoms, and 1 to 30 carbon atoms - fluoroalkyl group, ants having 6 to 30 carbon atoms - group, an alkyl group, an alkenyl group, ants having an aralkyl group or a carbonyl group, having 7 to 30 carbon atoms - represents Le group or aralkyl group, or a R ⁿ R ^{n + 1} (n is an integer of 1 to 5) may be bonded to have a cyclic structure.

In Formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 4) may be bonded to have a cyclic structure.

In Formula (3), R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 5) may be bonded to have a cyclic structure.

In the general formula (4), R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 9) may be bonded to have a cyclic structure.

In the general formula (5), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 3) may be bonded to have a cyclic structure.

In the general formula (6), R ^{1 to} R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 11) may be bonded to have a cyclic structure.

In Formula (7), R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 5) may be bonded to have a cyclic structure.

In the general formula (8), R ^{1 to} R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 2) may have a cyclic structure

In Formula (9), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 3) may be bonded to have a cyclic structure. However, at least one of R ^{1 to} R ⁴ is a hydrogen atom. Also, if there is no hydrogen atom in R ¹ to R ^4, the substituents X is limited to an aldehyde group.

In the general formula (10), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 3) may be bonded to have a cyclic structure. However, at least one of R ^{1 to} R ⁴ is a hydrogen atom. Also, if there is no hydrogen atom in R ¹ to R ^4, the substituents X is limited to an aldehyde group.

Second Embodiment
At least one end of the substituent R ⁿ of the ionic liquid is a substituent X which immobilizes the bulky ionic liquid to the substrate and controls the distance between the central portion of the bulky ionic liquid and the modified substrate. The substituent X is strongly bound to the substrate for modifying the ionic liquid, and has the role of fixing the ionic liquid to the substrate. As the substituent X, a thiol group, a disulfide group, a thioether group, a carboxyl group, an aldehyde group, an -amino group, a silanol group, a phosphoric acid group, an alkenyl group, an alkynyl group, an azidic group, or a phenyl group, a naphthyl group, One of the substituents having aromaticity such as pyrenyl group is selected and bonded. However, in the general formulas (9) and (10), at least one of the substituents R ⁿ is a hydrogen atom. Further, in the general formulas (9) and (10), when a hydrogen atom is not contained in the substituent R ⁿ , the substituent X is limited to an aldehyde group.
The length of the substituent R ^{n in} which the substituent X is present and the central portion of the ionic liquid define the vertical size of the space constructed on the substrate. Specifically, the actual length of the R ⁿ substituent connecting between the cation site of each ionic liquid and the substituent X is the size in the vertical direction of the space generated by the substrate-modified ionic liquid. When the R ⁿ substituent does not bend and assumes a fully stretched orientation, the vertical dimension of the space produced is greatest.
The remaining substituents R ⁿ where the substituent X is not present and the length of the central portion of the ionic liquid define the horizontal size of the space constructed on the substrate. Specifically, in the case where the substituent R ⁿ of each ionic liquid is in a completely stretched state without bending each other and in a state of being oriented on the surface without being in contact with each other, the ionic liquid modified on the substrate The distance between the central portions between them is the horizontal dimension of the space that occurs.
The hydrophobic, hydrophilic, viscous, and other properties of each R ⁿ substituent define the nature of the space to be built up on the substrate. For example, if the R ⁿ substituent is a highly hydrophobic alkyl group, the nature of the space in which the ionic liquid is built on the modified substrate will be hydrophobic. In addition, foreign components confined in a space in which a highly viscous ionic liquid is built on a modified substrate are affected by the viscosity of the ionic liquid that builds up the space, and molecular motion in the space is delayed.

A schematic diagram of an ionic liquid modified substrate according to the present invention is shown in FIG.
In the case of modifying an ionic liquid on a substrate, it is necessary to select the ionic liquid to be used according to the type of substrate, the size and nature of the foreign molecule to be introduced, and the like.
As the substrate to be modified, various metals, various metal oxides, glass, silicon, inorganic carbon materials and the like are suitably used. It is necessary to select the substituent X of the ionic liquid in accordance with the type of substrate to be modified. For example, metal substrates such as gold and copper, which are substituents having a sulfur atom as a substituent X, are thiol groups such as thiol groups, disulfide groups, thioether groups, and titanium oxides such as carboxyl groups, glass, and silicon. Aromatic substituents such as phenyl, naphthyl and pyrenyl are preferably used as silanol and carbon materials.
The nature of the substrate to be modified influences the nature of the space built up on the substrate by modification of the ionic liquid. Since the space constructed on the substrate by modification of the ionic liquid is a space surrounded by the substrate surface and the modified ionic liquid molecules on the surface, the physical properties of the substrate surface are constructed directly and indirectly on the substrate It affects the properties of the space, such as hydrophobicity, hydrophilicity, reactivity, stability, conductivity, etc.

A conceptual view of the foreign molecule to be immobilized on the ionic liquid modified substrate in the present invention is shown in FIG.
The foreign component fixed in the space built on the substrate by the modification of the ionic liquid can fix any molecule as long as it can be fixed in the space. Specifically, various metal complexes, various organic compounds, biomolecules such as proteins, and metal fine particles are suitably used. However, the space built on the substrate needs to have a sufficient size to fix the foreign molecule, but when fixing, it can completely contain the foreign molecule. It does not have to be space. When the space is extremely small, the exogenous molecule can not be immobilized in the space, but immobilization of the exogenous molecule is possible even to some extent, for example, about half the space of the exogenous molecule. In that case, for example, the reactivity or reaction rate of the foreign molecule such as electron transfer reaction or catalytic reaction can be controlled depending on how much the foreign molecule is exposed from the ionic liquid molecule modified on the substrate. .

There are various methods for immobilizing foreign molecules in the space where the ionic liquid is built on the modified substrate. The most convenient method is to immerse the substrate modified with the ionic liquid in a solution containing foreign components. It is possible to immobilize the molecules by moving the molecules in the solution to the space between the ionic liquids by equilibrium. In addition, when modifying an ionic liquid on a substrate, a method is also possible in which an exogenous molecule is made to coexist and the exogenous molecule is immobilized while modifying the ionic liquid on a substrate. It can also be produced by dissolving a foreign molecule in the ionic liquid to be modified itself and immersing or dropping the substrate on the substrate. In addition, by immersing the substrate modified with the ionic liquid in a solution containing foreign molecules and applying an electric potential or a magnetic field from the outside, the foreign molecules can be forcibly moved to the vicinity of the substrate and immobilized on the substrate. It is.

Third Embodiment
The foreign molecules immobilized in the space on the ionic liquid modified substrate according to the present invention are changed in various properties and reactivity due to the interaction from the ionic liquid and the substrate or the effect of the isolation of the molecule in the space. Happens.
For example, in the case of a water-insoluble foreign molecule, by immobilizing it on an ionic liquid-modified substrate according to the present invention, it is possible to utilize its reactivity even in water (FIG. 4). FIG. 4 (1) is a schematic view of a cobalt complex immobilized on an ionic liquid modified substrate according to the present invention. Fig. 4 (2) a shows the result of electrochemical measurement of the cobalt complex in water, and Fig. 4 (2) b shows the result of electrochemical measurement of the cobalt complex immobilized by the ionic liquid modified substrate in water. Although this complex was insoluble in water, its properties in water could not be confirmed, but the properties and reactivity in water were clarified by the present invention.
Also, in the case of an extremely unstable foreign molecule in water, a large stabilization effect is obtained by immobilizing it using an ionic liquid modified substrate matched to the structure of the molecule. As a result, it is possible to observe its electrochemical behavior even in water (Fig. 5). FIG. 5 (1) is a schematic view of an iron dinuclear complex immobilized on an ionic liquid modified substrate according to the present invention. The complex is usually difficult to measure in water because it is easily decomposed by water, but the immobilization on an ionic liquid modified substrate according to the present invention enables electrochemical measurement in water.
Also, in terms of changes in reactivity, in particular, by controlling the size of the space on the ionic liquid-modified substrate, the reactivity of foreign molecules immobilized in the space with other molecules is suppressed. It is possible to define its stability and electron transfer reaction rate. Control of the reactivity of such foreign molecules can cause, for example, a significant reduction in overpotential in electrochemical catalysis. It is also possible to cause an improvement in reactivity. FIG. 5 (2) is a measuring device of a rotating disk electrode using an iron dinuclear complex immobilized on an ionic liquid modified substrate according to the present invention. The complex is fixed to the ionic liquid modified substrate from the slope of the straight line obtained from each plot, so that the oxygen reduction reaction, which is usually a two-electron reduction process, proceeds in the four-electron process, that is, the ionic liquid This shows that the modified substrate has improved the reactivity.

The technology described in the present application makes it possible to immobilize various molecular catalyst materials on the substrate surface, and it is possible to improve the efficiency of the catalytic reaction and the durability of the catalyst itself. Specific applications include application to various electrode catalyst materials such as fuel cells and secondary batteries, electrode materials such as an electrolytic hydrogen production apparatus and an ammonia production apparatus, and the like. Moreover, utilization as a support | carrier of the substance conversion catalyst in carbon dioxide reduction or C1 chemistry is also possible.

1 ionic liquid 2 substrate 3 foreign molecule 4 space on ionic liquid modified substrate

Claims (6)

Formula ^{[Z-R n -X] +} [A] - ([Z-R n -X] + cation, [A] ^- anion, Z is atom or an organic compound, X is bonded substituent) In the ionic liquid represented by the above, [ZR ⁿ -X] ⁺ is represented by the general formulas (1) to (10). An ionic liquid modified substrate capable of closely controlling the distance between ionic liquids modified on a substrate by a plurality of substituents R ⁿ of the ionic liquid represented by the general formulas (1) to (10). Of the plurality of substituents R ⁿ of the ionic liquid represented by the general formulas (1) to (10), the distance from Z to the substrate is strictly determined by R ⁿ having a binding substituent X at at least one end. Ionic liquid modified substrate that can be controlled. An ionic liquid modified substrate capable of immobilizing foreign molecules between ionic liquids by modifying the ionic liquids represented by the general formulas (1) to (10). An ionic liquid modified substrate capable of improving the stabilization of foreign molecules immobilized between ionic liquids. An ionic liquid modified substrate capable of improving the stabilization and reactivity of foreign molecules immobilized between ionic liquids.

In the general formula (1), R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 5) may be bonded to have a cyclic structure.

In Formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 4) may be bonded to have a cyclic structure.

In Formula (3), R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 5) may be bonded to have a cyclic structure.

In the general formula (4), R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 9) may be bonded to have a cyclic structure.

In the general formula (5), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 3) may be bonded to have a cyclic structure.

In the general formula (6), R ^{1 to} R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 11) may be bonded to have a cyclic structure.

In Formula (7), R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 5) may be bonded to have a cyclic structure.

In the general formula (8), R ^{1 to} R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 2) may have a cyclic structure

In Formula (9), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 3) may be bonded to have a cyclic structure. However, at least one of R ^{1 to} R ⁴ is a hydrogen atom. Also, if there is no hydrogen atom in R ¹ to R ^4, the substituents X is limited to an aldehyde group.

In the general formula (10), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, 1 to 30 alkoxyalkyl group, C1 to C30 aminoalkyl group, C1 to C30 perfluoroalkyl group, C6 to C30 aryl group, C7 to C30 aralkyl group, Or an alkyl group having a carbonyl group, an alkenyl group, an aryl group or an aralkyl group, or R ⁿ and R ^{n + 1} (n is an integer of 1 to 3) may be bonded to have a cyclic structure. However, at least one of R ^{1 to} R ⁴ is a hydrogen atom. Also, if there is no hydrogen atom in R ¹ to R ^4, the substituents X is limited to an aldehyde group.