JP3226194B2 - Corn-type calixarene-based compound derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cone-type calixarene compound derivative comprising a resorcinol cyclic tetramer. Its main use is as a surface modifier.

[0002]

2. Description of the Related Art The surface of a material is extremely important in determining various properties of the material. In recent years, various attempts have been made to control the surface properties of a material by applying various surface modifiers to the surface of the material and modifying the surface, that is, for example, chargeability, electrical conductivity, corrosion protection, hydrophilicity or hydrophobicity. Have been. Also, in the design of composite materials for higher functionality, the importance of surface modification has been pointed out as a technique for controlling the interface between materials generated by the composite.

[0003] In the case of modifying the surface of a material for the purpose of improving the properties and functionalization of the surface, the amount is as small as possible, and
There is a need for surface modifiers that can be treated by simple methods. As such a surface modifier, the modifier molecule has a large number of adsorption points, so that the adsorptivity is large, and since the adsorption is strong, a stable surface modified layer can be formed. In addition, the material surface is strongly required to exhibit high orientation and alignment. Further, there is a strong demand for a surface modifier which can be applied to various kinds of objects to be treated.

Conventionally, surfactants and coupling agents have been widely used as surface modification treatments. The treatment of a material (hereinafter referred to as an object to be treated) with a surfactant includes a method of immersing the material in a solution of a surfactant, and a method of adding and mixing a surfactant with the object to be treated in a compounding process. There is an advantage that processing can be performed by a very simple method.

[0005] In the surface-modified layer made of a surfactant, the hydrophilic part of the surfactant forms a hydrogen bond or a Coulomb bond with the surface of the object to be treated, and the bonding state is reinforced by a hydrophobic bond between long-chain alkyl groups. It is formed by being done.

[0006] The coupling agent is originally intended for bonding between inorganic and organic substances, and silane-based and titanate-based coupling agents are typical. The surface-modified layer formed by the silane coupling agent is formed by a chemical reaction between the 1 to 3 alkoxy groups or chloride groups in the terminal silyl group and the hydroxyl group present on the surface of the object to be treated in the presence of water. Due to the siloxane bond, a strong modified layer is formed. Among the coupling agents, in particular, a titanium coupling agent is capable of treating a wide variety of objects to be processed and has a wide applicability.

[0007]

SUMMARY OF THE INVENTION In addition to having a high adsorptivity, the adsorption is strong, and it shows a high degree of orientation and alignment on the surface of the object to be processed. A possible and widely applicable surface modifier is currently the most demanded, but such a surface modifier has not yet been obtained.

As for the surfactant, the adsorption point of the surfactant molecule on the surface of the object to be treated is adsorbed at a ratio of 1: 1 with a hydrogen bonding point or an electrostatic charge exposed on the surface of the object. Since it largely depends on the number of hydrogen bonding points and the density of electrostatic charges, it is difficult or impossible to artificially control the amount of surfactant adsorbed.

Moreover, in order for a functional group designed and incorporated into a hydrophobic part to exhibit its function, a large amount of treatment is required, and its structure is fragile and easily collapses. For example, there have been many reports of cases in which the compound is liberated in a composite material and adversely affects the properties of the composite (Japanese Patent Application Laid-Open No. Sho 6 (1994)
4-75581 and JP-A-57-92339.

It is also difficult to give order to the orientation and arrangement of the surfactant molecules adsorbed on the surface of the object. The modified layer has a hydrophobic part (generally a long-chain alkyl group)
In the above, there is a restriction on the molecular structure that it is essential that the hydrophobic group is composed of a sufficiently long alkyl group because of utilizing a hydrophobic bond between molecules.

Further, there is a problem in that the surface modification of a surface-treating agent is not always possible for any object to be treated, and the applicable range of the object is restricted.

Among the coupling agents, the silane coupling agent has a drawback that the application range of the object to be treated is restricted similarly to the above-mentioned surfactants. Although it has excellent adsorptivity, it hardly exhibits adsorptivity to materials other than siliceous materials. There is a disadvantage that the conditions of the treatment method are very delicate, and a slight difference is likely to form a modified layer having different properties such as an adsorption form and molecular orientation.

On the other hand, tetraalkyl titanate, which is a kind of titanium coupling agent, has a disadvantage that when it encounters water or humid air, it is rapidly hydrolyzed and is inconvenient to handle.

Therefore, the present invention has a high adsorptivity, a strong adsorption, a high orientation and alignment on the surface of the object to be treated, and furthermore, a variety of objects to be treated can be treated. It is a technical task to obtain a compound that is possible.

[0015]

The above technical object can be achieved by the present invention as described below.

That is, the present invention relates to a compound represented by the following general formula 1 (where R is an alkyl group having 3 to 18 carbon atoms or
A phenyl group is shown, and R 'shows a carboxyalkyl group having 1 to 3 carbon atoms. ) Is a cone-type calixarene-based compound derivative comprising a resorcinol cyclic tetramer represented by the following formula:

[0017]

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Next, various conditions for implementing the present invention will be described.

In the cone-type calixarene-based compound derivative of the present invention, the number of carbon atoms of the alkyl group or the alkenyl group in R in the general formula is preferably from 3 to 18, when using as a surface modifier. It is necessary for sufficiently exhibiting the hydrophobic property of the surface of the object to be treated, and those having 8 to 18 carbon atoms are particularly preferable for further improving such properties. Further, these groups may be bonded to other substituents as long as the expected performance of the present invention as a surface modifier is not significantly reduced.

Further, it is necessary that R ′ is a carboxyalkyl group in order to exhibit more adsorption characteristics to the surface of the object to be treated, and in particular, the alkyl group has 1 to 3 carbon atoms. Are preferred.

Preferred concrete examples of the corn-type calixarene-based compound derivatives of the present invention include the compound derivatives represented by the following formulas (2) to (6).

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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The corn calixarene compound derivative of the present invention generally exists as white to yellow needle-like crystals at room temperature, and can be confirmed by the following means (a) or (b). it can.

(A) Proton By measuring the ¹ H-nuclear magnetic resonance spectrum (NMR), the type and number of protons present in the molecule can be known.

(B) By elemental analysis, each weight ratio of carbon, hydrogen, nitrogen, sulfur, halogen and the like can be determined. In addition, the oxygen weight ratio can be calculated by subtracting the sum of the recognized weight ratios of the elements from 100.

The calixarene-based compound derivative according to the present invention can be synthesized by the following method.

In the present invention, the cone-type calixarene-based compound derivative uses an alcoholic solvent such as methanol, ethanol, isopropyl alcohol, methoxyethyl alcohol, ethoxyethyl alcohol, etc. as a reaction solvent under an inert gas atmosphere such as nitrogen. Then, it can be produced by a method in which resorcinol and an aldehyde represented by the following general formula are refluxed and reacted in the presence of an acid catalyst such as hydrochloric acid, phosphoric acid, and paratoluenesulfonic acid.

R-CHO (where R is an alkyl group having 3 to 18 carbon atoms or
Is an alkenyl group or the above alkyl group or alkenyl
A group capable of introducing a group. )

In this case, the ratio of each raw material is resorcinol 1
The ratio is generally 0.5 to 1.5 moles, preferably equal moles, of the aldehyde with respect to the mole.

The reaction time is preferably at least 2 hours, preferably at least 10 hours, more preferably from 10 to 20 hours, in order to obtain the desired corn-type calixarene-based compound derivative in good yield. .

When R is a group into which an alkyl group or an alkenyl group can be introduced, a predetermined group may be introduced after the reaction by a known means.

As the introduction method, for example, a functional group having a double bond or a halogen at the terminal is introduced in advance, and then the double bond or the halogen or the like is subjected to a known reaction according to the purpose. May be converted with a functional group.

R ′ of the corn type calixarene compound derivative of the present invention can be introduced after the above reaction.

The introduction of R ', ie, a carboxylalkyl group having 1 to 3 carbon atoms, can be carried out by a known method.

To illustrate a typical method, the above reaction product is treated with an ω-halocarboxylic acid ester and N, N dimethylformaldehyde (D) in the presence of a base such as potassium carbonate.
After reacting in a polar solvent such as MF) at 70 to 100 ° C. for 2 to 10 hours, hydrolysis can introduce a carboxyalkyl group.

The calixarene-based compound derivative according to the present invention has a simple production method and a high yield, and is industrially and economically preferable.

Next, a surface modification method using the calixarene-based compound derivative according to the present invention will be described.

As a method for modifying an object to be treated using the surface modifier according to the present invention, a method in which the surface modifier uniformly contacts the surface of the treated object is employed without any particular limitation.

The corn-type calixarene-based compound derivative according to the present invention is obtained in a crystalline state. When used, it may be used as it is in a crystalline state or in a solution state.

Typical examples of the method include a method of immersing a processing object in a processing solution in which a cone-type calixarene-based compound derivative is dissolved, and a method of spraying or coating the processing solution on the processing object. And the like.

In dissolving the cone-type calixarene-based compound derivative, it is effective to dissolve the cone-type calixarene-based compound derivative and to use a low-polarity organic solvent to effectively adsorb the substance to be treated. Preferred for.

Specific examples of such organic solvents include low-polarity organic solvents such as toluene, benzene, chloroform, xylene, methylene chloride, hexane and cyclohexane.

Further, in order to enhance the solubility of the corn-type calixarene-based compound derivative, a polar solvent such as tetrahydrofuran (THF), acetone, alcohols, or the like may be added to the above organic solvent within a range that does not impair the adsorptivity to the substance to be treated. A mixture of solvents may be used.

The concentration of the corn-type calixarene-based compound derivative in the above treatment solution is generally 10 ⁻⁶ to 1
It may be about 0 ^-1 mol / l. Particularly, in order to form a dense modified layer on the surface of the object to be treated, 10 ^-5 to 10 ^-2 mol / l.
It is preferred to employ a concentration of l.

In the present invention, the object to be treated preferably has a polar group on the surface. For example, a metal having a polar group on the surface, a metal oxide and a resin, specifically, iron and an alloy mainly containing iron, copper and an alloy mainly containing copper,
Metals such as titanium and alloys mainly containing titanium, aluminum and alloys mainly containing aluminum, nickel and alloys mainly containing nickel, silicon dioxide such as silica and quartz, and composite metals mainly containing silicon dioxide Oxides,
Metal oxides such as iron oxide, zinc oxide, titania, alumina, and ferrite; powders and molded articles formed of resins such as polyvinyl alcohol, cellulose, polyamide, polyurethane, and polyimide;

Among them, silicon dioxide having a strong surface polarity,
Since iron oxides and the like are very strongly adsorbed by the surface modifier,
A surface modified product having excellent stability can be obtained.

[0051]

First, the most important point of the present invention is that, when used as a surface treatment agent, the calixarene-based compound derivative according to the present invention is easily adsorbed on the surface of the object to be treated, and the adsorption is strong. In addition, it shows a high degree of orientation and alignment on the surface of the object to be processed, and is capable of processing a wide variety of objects to be processed, and has a wide applicability.

Regarding this fact, the present inventor has concluded that the cone-type calixarene-based compound derivative according to the present invention has a characteristic structure that is three-dimensionally rigid and has a plurality of adsorption sites in one direction of the molecule. It is thought to be due to having multiple chemical groups in the opposite direction. That is, one molecule has a plurality of adsorption sites, the influence of the density of the adsorption sites (hydroxyl groups, charges, etc.) on the material surface is reduced, and the adsorptivity increases, and one molecule has a plurality of adsorption equilibrium simultaneously. In the case where a strong adsorption can be achieved and a tight adsorption layer is formed, in addition to the interaction between the plurality of adsorption sites and the material surface, hydrogen can be generated between the adsorbed molecules adsorbed on the surface of the workpiece. It is considered that an interaction due to bonding or the like also occurs to form a strong modified layer having higher orientation and alignment.

[0053]

Next, the present invention will be described in detail with reference to examples. The following examples are not intended to limit the scope of the present invention, but to exemplify the properties of the present invention more clearly.

Next, the present invention will be described with reference to Examples and Comparative Examples.

In the following Examples and Comparative Examples,
The UV spectrum was measured using Hitachi Model UV-320.

The measurement of the contact angle was carried out by using Kyowa Chemical Co., Ltd. CA-P
Using a mold, drop a certain amount of water drops on the processing substrate
Measured after seconds.

The liquid crystal alignment was measured by placing a nematic liquid crystal (NPC-02) manufactured by Roddick Co., Ltd. between two surface-modified quartz plates, and observing this with a conoscope to check the alignment of the liquid crystal.

<Synthesis of Calixarene-Based Compound Derivative Consisting of Cone-Type Resorcinol Cyclic tetramer> Examples 1 to 3;

Example 1 A compound represented by the general formula 1 is used, and R = CH ₃ (C
The compound of H ₂ ) ₁₀ , R ′ = H was prepared by a known method (Jour).
nal of American ChemicalS
ocityty 111 vol.14 1989 539
7-5404).

[0060]

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In a 50 ml three-necked flask equipped with a magnetic stirrer, a water-cooled condenser and a heating device, 1.0 g of the above compound was dissolved in 10 ml of DMF. To this, 2.0 g of potassium carbonate and 1.6 ml of ethyl bromoacetate were added (each corresponding to about 2 equivalents to R 'of the starting compound), and the mixture was stirred for 5 hours while heating to 80 ° C.

The desired product was extracted from the reaction mixture with ether, washed with water, and dried over saturated saline and anhydrous sodium sulfate.

Then, ether was distilled off under reduced pressure to obtain slightly yellow transparent needle-like crystals.

The needle-like crystals have a melting point of 30 to 31 ° C., NM
From the measurement of R, it was found that R ′ was CH ₂ COOC ₂ H ₅ . At this time, the yield was 89%.

In a 50 ml three-necked flask equipped with a magnetic stirrer, a water-cooled condenser and a heating device, 1.0 g of this compound dissolved in 10 ml of ethanol was placed, and 0.5 g of potassium hydroxide (R ′ of the starting compound) was added. About 2
It corresponds to the equivalent. ) Was added. The resulting white precipitate was dissolved by adding an appropriate amount of water. The mixture was stirred for 1 hour while heating to 60 ° C. The pH of the reaction mixture solution was then adjusted to 3.5 with dilute aqueous hydrochloric acid, resulting in the formation of a white precipitate.

This was extracted with ether, washed with water, and dried with saturated saline and anhydrous sodium sulfate.

Then, ether was distilled off under reduced pressure to obtain a white powder. The yield was 98%.

The elemental analysis value of this compound was C: 64.9.
9%, H: 8.31%, and the composition formula C ₈₈ H ₁₂₈ O _24.
Calcd for _{3H 2 O (1624.03) C:} 65.
08% and H: 8.31%.

The ¹ H-nuclear magnetic resonance spectrum (δ;
ppm: tetramethylsilane standard, heavy DMSO solvent), and the results are shown in FIG. The analysis results are as follows.

That is, a triplet corresponding to 12 protons was observed at 0.8 ppm, which can be attributed to four methyl groups (a). At 1.2 ppm, a peak corresponding to 72 protons was observed, which can be attributed to the methylene group (b) in the alkyl chain. A peak corresponding to eight protons was observed at 1.7 ppm, which can be attributed to the methylene group (c) in the alkyl chain. A plurality of peaks corresponding to 20 protons are observed at around 4.0 to 4.7 ppm. This is because two asymmetric points exist in the molecule and two protons of the methylene group in (d) are magnetically generated. Becomes unequal,
Each appears as a doublet and is interpreted as overlapping the peak of the methine group (e) at 4.5 ppm. 6.4p
At pm and 6.6 ppm, two singlets corresponding to eight protons were observed, which can be assigned to the two protons (f) and (g) on the benzene ring. A broad peak corresponding to eight protons was observed at 12.5 ppm, which disappeared when heavy water was added, and can be attributed to the protons (h) and (i) of the carboxylic acid.

From the above results, as shown in Chemical formula 2, the isolated product was R = CH ₃ (CH ₂ ) ₁₀ , R ′ = CH ₂ COO
H was found to be a compound represented by the general formula 1. The melting point of this compound was 174-175 ° C.

[0072]

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Example 2 The starting material was a compound represented by the general formula 1 and R = CH
Synthesis was carried out in the same manner as in Example 1 except that a compound of ₃ (CH ₂ ) ₂ , R ′ = H was used. The yield was 97%.

The elemental analysis value of this compound was C: 57.9.
8% H: and 5.78% formula C ₅₆ H ₆₄ O ₂₄ · 2
Calcd for _{H 2 O (1157.15) C:} 58.1
3%, H: 5.92%.

Further, ¹ H-nuclear magnetic resonance spectrum (δ;
ppm: tetramethylsilane standard, heavy DMSO solvent), and the results are shown in FIG.

That is, a triplet corresponding to 12 protons is observed at 0.8 ppm, which can be attributed to four methyl groups (a). A peak corresponding to eight protons was observed at 1.2 ppm, which can be attributed to the methylene group (b) in the alkyl chain. A peak corresponding to eight protons was observed at 1.7 ppm, which can be attributed to the methylene group (c) in the alkyl chain. A plurality of peaks corresponding to 20 protons are observed at around 4.0 to 4.7 ppm. This is because two asymmetric points exist in the molecule and two protons of the methylene group in (d) are magnetically generated. Becomes unequal,
Each appears as a doublet and is interpreted as overlapping the peak of the methine group (e) at 4.5 ppm. 6.4p
According to pm and 6.6 ppm, two singlet lines corresponding to eight protons are recognized, which can be assigned to two protons (f) and (g) on the benzene ring. A broad peak corresponding to eight protons was observed at 12.5 ppm, which disappeared when heavy water was added, and can be attributed to the protons (h) and (i) of the carboxylic acid.

From the above results, as shown in Chemical formula 3, the isolated product was R = CH ₃ (CH ₂ ) ₂ , R ′ = CH ₂ COO
H was found to be a compound represented by the general formula 1. The melting point of this compound was 209 to 210 ° C.

[0078]

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<Adsorption Test> Use Examples 1 to 3, Comparative Use Examples 1 to 3;

Use Example 1 In the compound represented by the general formula 1 obtained in Example 1, R =
32.5 mg of a compound in which CH ₃ (CH ₂ ) ₁₀ and R ′ = CH ₂ COOH are dissolved in 20 ml of a mixed solvent of toluene and THF (volume ratio 9: 1) (1.0 × 10 ⁻³ mol / l)
Is equivalent to )did. A sufficiently washed quartz plate (1 ×
3 cm) for 15 minutes.

The quartz plate was taken out, washed with toluene and dried.

The same operation was performed for several points while changing the processing density.

The amount of adsorption was measured by UV spectrum measurement (Hitachi U.
V320) and the extinction coefficient ε of the compound = 1.6
The area occupied by one molecule (Å ² / molec) calculated from × 10 ^{4 according} to the Lambert-Beer equation on the assumption of a monolayer.
ule).

The contact angle of the treated quartz plate with respect to a certain amount of water droplets was measured.

Further, as a measure of the orientation of the adsorbed molecules, it was observed with a conoscope whether or not homeotropic alignment of the liquid crystal (NPC-02) was induced between the treated substrates.

The results are shown in Table 1. As can be seen from the graph, the compound represented by the general formula 1 has R = CH ₃ (C
The compound of H ₂ ) ₁₀ , R ′ = CH ₂ COOH is well adsorbed on the quartz plate, and a single molecule occupation area 120 expected from the molecular film type even at a concentration as low as 10 ⁻⁴ / mol / l.
A value close to Å ² / molecule is found. Further, the liquid crystal is oriented even if the amount of adsorption is small.

Use Example 2 The general formula 1 obtained in Example 2 in the same manner as in Use Example 1
R = CH ₃ (CH ₂ ) ₂ , R ′ = CH ₂ CO
The quartz plate was treated with a compound of OH. The results are shown in Table 1. From this, it was found that self-sequence adsorption occurs even without a long alkyl chain.

Comparative Use Example 1 The two hydroxyl groups of 4-dodecylresorcinol were replaced with -OCH ₂
The same procedure as in Use Example 1 was carried out, except that the compound was used in place of COOH. The results are shown in Table 1. The contact angle is low and the orientation of the liquid crystal is slow.

Comparative Example 2 The hydroxyl group of p-dodecylphenol was changed to -OCH ₂ COOH
The same procedure as in Use Example 1 was carried out, except that the compound was used instead of The results are shown in Table 1. The extinction coefficient was as low as about 1600 and the amount of adsorption was small, so that it could not be determined.

Use Example 3 The compound represented by the general formula 1 obtained in Example 1
32.5 mg of a compound in which CH ₃ (CH ₂ ) ₁₀ and R ′ = CH ₂ COOH are dissolved in 20 ml of a mixed solution of toluene and THF (volume ratio 9: 1) (1.0 × 10 ⁻³ mol / l)
Is equivalent to )did. A quartz plate (1 × 3 cm ² ) spin-coated with polyvinyl alcohol was immersed in this for 15 minutes. Thereafter, the coated quartz plate was taken out, washed with toluene, and dried.

The amount of adsorption was determined from the absorbance obtained by measuring the UV spectrum and the extinction coefficient ε = 1.6 × 10 ⁴
The area occupied by one molecule (Å ² / molecule) calculated on the assumption of a monolayer according to the Bert-Beer equation.
In addition, as a measure of the orientation of the adsorbed molecules, a liquid crystal was sandwiched between processing substrates, and it was observed with a conoscope whether or not homeotropic alignment of the liquid crystal (NPC-02) was induced. The results are shown in Table 2. As a result, it was found that good adsorption similar to that of Use Example 1 was obtained.

Comparative Use Example 3 The two hydroxyl groups of 4-dodecylresorcinol were replaced with -OCH
_{The operation} was performed in the same manner as in Use Example 3 using the compound in place of ₂ COOH. The results are shown in Table 2. It was found that the orientation was inferior even when adsorbed.

<Stability of Adsorption Layer> In order to check the stability of the surface-modified layer formed by adsorption, the treated substrates obtained in each of the above-mentioned use examples and comparative use examples were treated with toluene, chloroform, THF, and methanol. And then sequentially wash with a solvent having a high polarity.
It was measured by V spectrum. Table 3 shows the results. Table 3
As shown in the above, it was found that the calixarene-based compound according to the present invention forms a stable adsorption layer as compared with each comparative example.

This effect is presumed to be due to the fact that the corn calixarene compound derivative according to the surface treating agent of the present invention has a large number of adsorption sites in one molecule.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

As described in the above embodiment, the calixarene-based compound derivative according to the present invention has a large adsorptivity, a strong adsorption, and a high orientation property on the surface of the object to be treated. Since it exhibits alignment properties, and can be applied to a wide variety of objects to be treated and has a wide applicability, it is suitable as a surface modifier.

Therefore, by adsorbing the surface treating agent of the present invention on the object having a polar surface, it is possible to easily form an extremely stable modified surface on the object.

[Brief description of the drawings]

FIG. 1 shows R represented by general formula 1 obtained in Example 1.
_{= CH 3 (CH 2) 10} , R '= CH 2 COOH cone type Ca Rex arene-based compound structure and ^one of the derivatives is
It is an H-nuclear magnetic resonance spectrum.

FIG. 2 shows R represented by general formula 1 obtained in Example 2.
_{= CH 3 (CH 2) 2} , R '= CH 2 COOH cone type Ca Rex arene-based compound structure and ^one of the derivatives is
It is an H-nuclear magnetic resonance spectrum.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. The following general formula 1 (wherein R represents an alkyl group or alkenyl group having 3 to 18 carbon atoms,
R 'represents a carboxyalkyl group having 1 to 3 carbon atoms. A) a calixarene-based compound derivative comprising a resorcinol cyclic tetramer represented by the following formula: Embedded image