JP3226195B2 - Surface modifier and surface modification method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides a calixarene consisting of a resorcinol cyclic tetramer to the surface of an object to be treated, that is, it has a high adsorptivity and a strong adsorption. The present invention relates to a surface modifier having high applicability and alignment on the surface of an object to be processed, capable of processing a wide variety of objects to be processed, and having a wide applicability, and a surface modifying method using the same.

[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. Moreover, it is strongly required that the material surface 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 in a hydrophobic part to exhibit its function, a large amount of processing is required, and the structure of the modified layer is fragile and easily collapses. Met. For example, there have been many reports of cases in which the polymer is liberated in a composite material and adversely affects the properties of the composite (JP-A-64-75581 and JP-A-57-92).
339).

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 an excellent surface modification effect, it hardly exhibits a surface modification effect on 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 object to obtain a possible surface modifier.

[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
It indicates Kenyir group, also, R 'represents a carboxyalkyl group. A) a surface modifying agent comprising a cone-type calixarene-based compound derivative comprising a resorcinol cyclic tetramer represented by the formula:

[0017]

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An object to be treated is represented by the following general formula 1 (however,
R represents an alkyl group or alkenyl having 3 to 18 carbon atoms.
Shows the group, also, R 'represents a carboxyalkyl group. This is a surface modification method comprising contacting a cone-type calixarene-based compound derivative comprising a resorcinol cyclic tetramer represented by the formula (1).

[0019]

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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 carbon number 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 for R ′ to be 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.

Specific examples of suitable surface modifiers of the present invention include compound derivatives represented by the following chemical formulas (2) to (13).

[0024]

[0025]

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[0026]

[0027]

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[0028]

[0029]

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[0030]

[0031]

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[0032]

[0033]

[0034]

[0035]

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

(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 corn calixarene compound derivative according to the present invention can be synthesized by the following method.

That is, an alcoholic solvent such as methanol, ethanol, isopropyl alcohol, methoxyethyl alcohol or ethoxyethyl alcohol is used as a reaction solvent under an atmosphere of an inert gas such as nitrogen, and hydrochloric acid, phosphoric acid, paratoluenesulfonic acid, etc. In the presence of an acid catalyst of the formula (1), and resorcinol is reacted with an aldehyde represented by the following general formula under reflux.

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 2 hours or more, preferably 10 hours or more, and more preferably 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 an 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. What is necessary is just to convert it with a functional group.

In the surface modifier of the present invention, R ′ serving as an adsorption site for an object to be treated can be introduced after the above reaction.

[0047] Such R ', namely, mosquitoes of 1 to 3 carbon atoms
The ruboxylalkyl group can be introduced by a known method.

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

[0049]

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

Next, a surface modifying method using the surface modifying agent 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 object to be treated is employed without any particular limitation.

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

Typical examples of the method include a method of immersing an object to be treated in a treatment solution in which a cone-type calixarene-based compound derivative is dissolved, and a method of spraying or applying the treatment solution to the object to be treated. And the like.

In dissolving the above-mentioned corn-type calixarene-based compound derivative, it is effective to dissolve the corn-type calixarene-based compound derivative and use a low-polarity organic solvent to effectively adsorb to the object 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 organic solvent within a range that does not impair the adsorptivity of the derivative to the object. 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.

[0061]

First, the most important point in the present invention is that, when the object to be treated is treated using the calixarene-based surface modifier according to the present invention, the adsorptivity is high and the adsorption is strong. In addition, it is a fact that it exhibits high orientation and alignment on the surface of the object to be processed, and can be applied to a wide variety of objects to be processed, and has wide applicability.

Regarding this fact, the present inventor has found that the calixarene-based surface modifier according to the present invention has a characteristic structure that is three-dimensionally rigid, and that a plurality of
It is thought to be due to having a carboxyl group adsorption site and having a plurality of chemical groups in the opposite direction. That is, since one molecule has a plurality of adsorption sites, the adsorptivity increases regardless of the density of adsorption sites (hydroxyl groups, charges, etc.) on the material surface, and one molecule can have a plurality of adsorption equilibria at the same time. When strong adsorption can be achieved and a tight adsorption layer is formed, in addition to the interaction between the multiple adsorption sites and the material surface, the mutual interaction between the adsorbed molecules adsorbed on the surface of the object to be treated due to hydrogen bonding, etc. It is considered that a strong modified layer having higher orientation and alignment is formed by the action.

[0063]

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 performed 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 orientation 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 orientation of the liquid crystal.

<Synthesis of Cone-Type Calixarene Compound Derivatives Consisting of Resorcinol Cyclic Tetramer> Synthesis Examples 1-4

SYNTHESIS EXAMPLE 1 A compound represented by the general formula 1 is represented by R ＝ CH ₃ (C
The compound of H ₂ ) ₁₀ , R ′ = H was prepared by a known method (Journ
al of American Chemical S
ocityty 111 vol.14 1989 539
7-5404).

In a 50 ml three-necked flask equipped with a magnetic stirrer, a water-cooled condenser and a heating device, 1.71 g of resorcinol was dissolved in 20 ml of ethanol under a nitrogen gas stream, and 2.85 g of dodecanal was added. After dropping 2.5 ml of 12N-HCl aqueous solution on an ice bath, the mixture was stirred for 10 hours while heating to 70 ° C. When the reaction mixture solution was cooled to room temperature, a yellow precipitate was deposited.

The precipitated yellow precipitate was filtered by suction and the temperature was 80 ° C.
Was washed with 2 liters of warm water, and finally the filtrate was confirmed to be neutral, and the resulting precipitate was dried by heating to 60 ° C. in a vacuum dryer.

The dried product was recrystallized twice with methanol, and then recrystallized once with a mixed solvent of hexane and acetone, and then purified once to obtain white needle crystals. At this time, the yield was 78%.

The elemental analysis value of the compound of the white needle crystal was as follows:
C: 76.83%, H: 10.29%, and the composition formula C
_The calculated values for ₇₂ H ₁₁₂ O ₈ .H ₂ O (1123.69) were in good agreement with the calculated values C: 76.96% and H: 10.23%.

The ¹ H-nuclear magnetic resonance spectrum (δ:
ppm: tetramethylsilane standard, deuterated chloroform solvent, JEOL FT-NMR FX90Q) was measured, and the result is 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). 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. At 2.2 ppm, a peak corresponding to eight protons was observed, which can be assigned to the methylene group (c) in the alkyl chain. A peak corresponding to four protons was observed at 4.3 ppm, which can be assigned to the proton (d) of methine. In addition to 6.1 ppm and 7.2 ppm, two singlets corresponding to eight protons were observed,
It can be assigned to two protons (e) and (f) on the benzene ring. A singlet of eight protons was recognized at 9.3 ppm and 9.6 ppm, and disappeared when heavy water was added. Therefore, the proton (g) of the hydroxyl group of the resorcinol skeleton,
(H).

From the above results, it was clarified that the isolated product was a compound in which R = CH ₃ (CH ₂ ) ₁₀ and R ′ = H, as shown in Chemical formula 2. The melting point of this compound is 2
68-269 ° C.

[0077]

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Synthesis Example 2 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 compound of Synthesis Example 1 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 over 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 (based on tetramethylsilane, heavy DMSO solvent) is 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 3, the isolated product was R = CH ₃ (CH ₂ ) ₁₀ , R ′ = CH ₂ COO
H was found to be a compound. The melting point of this compound was 174-175 ° C.

[0089]

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Synthesis Example 3 In a 50-ml three-necked flask equipped with a magnetic stirrer, a water-cooled condenser and a heating device, 1.71 g of resorcinol was dissolved in 20 ml of ethanol under a stream of nitrogen gas, and 2.61 g of butanal was added. added. 1. on ice bath
After dropwise adding 5 ml of 12N-HCl aqueous solution, the mixture was stirred for 10 hours while heating to 70 ° C. When the reaction mixture solution was poured into 1 liter of water, a yellow precipitate was deposited.

The precipitated yellow precipitate was filtered by suction and the temperature was 80 ° C.
Was washed with 2 liters of warm water, and finally the filtrate was confirmed to be neutral, and the resulting precipitate was dried by heating to 60 ° C. in a vacuum dryer.

The dried product was recrystallized from a mixed solvent of chloroform and ethyl acetate and purified to obtain white granular crystals. At this time, the yield was 72%.

The elemental analysis value of the compound of the white needle crystal was as follows:
C: 60.16%, H: 6.23%, Cl: 15.60
% And a composition formula of C ₄₀ H ₄₉ O ₈ .H ₂ O.1.1 CHC
Calculated value for l ₃ (818.09) C: 60.16
%, H: 6.23%, and Cl: 15.21%.

The ¹ H-nuclear magnetic resonance spectrum (δ:
ppm: tetramethylsilane standard, heavy DMSO solvent) is 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 multiplet line corresponding to 8 protons was observed at 1.2 ppm, which can be attributed to the methylene group (b) in the alkyl chain. A multiplet line corresponding to 8 protons was observed at 2.1 ppm, which can be assigned to the methylene group (c) in the alkyl chain. At 4.2 ppm, a triplet corresponding to four protons was observed, which can be assigned to the proton (d) of methine. At 6.1 ppm and 6.3 ppm, two singlet lines corresponding to eight protons were observed, which can be assigned to the two protons (e) and (f) on the benzene ring. At 8.9 ppm, a singlet corresponding to eight protons was observed, and disappeared when heavy water was added. Thus, it can be assigned to the protons (g) and (h) of the hydroxyl group of the resorcinol skeleton. In addition, a singlet corresponding to about one proton at 8.1 ppm is interpreted as that of chloroform included.

From the above results, it was clarified that the isolated product was a compound in which R = CH ₃ (CH ₂ ) ₂ and R ′ = H as shown in Chemical formula 4. The melting point of this compound is 28
1-282 ° C.

[0097]

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Synthesis Example 4 Synthesis was performed in the same manner as in Synthesis Example 2 except that the starting material was obtained in Synthesis Example 3. 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 5, the isolated product was R = CH ₃ (CH ₂ ) ₂ , R ′ = CH ₂ COO
H was found to be a compound. The melting point of this compound was 209 to 210 ° C.

[0103]

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<Surface Modification Treatment of Workpiece> Examples 1 to 5, Comparative Examples 1 to 7;

REFERENCE EXAMPLE 1 R = CH ₃ (CH ₂ ) ₁₀
Was dissolved in 20 ml of toluene (equivalent to 1.0 × 10 ⁻³ mol / l). A sufficiently washed quartz plate (1 × 3
cm) for 15 minutes.

This 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 determined from the absorbance obtained by measuring the UV spectrum and the extinction coefficient ε = 1.7 × 10 ⁴
The area occupied by one molecule (Å ² / molecule) calculated on the assumption of a monolayer according to the Bert-Beer equation.

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, a liquid crystal was sandwiched between the treated substrates, and it was observed with a conoscope whether or not homeotropic alignment of the liquid crystal (NPC-02) was induced.

Table 1 shows the results. As can be seen from the graph, the compound represented by the general formula 1 has R = CH ₃ (C
H ₂ ) ₁₀ and the compound having an adsorption site R ′ = H
It is well adsorbed on a quartz plate, and even at a concentration as low as 10 ^-4 mol / l, a single molecule occupation area of 120 分子² / molecule expected from a π-A curve in a molecular film type or LB film apparatus.
There are values near the front and back. Further, the liquid crystal is oriented even if the amount of adsorption is small.

Reference Example 2 In the same manner as in Reference Example 1 , R = CH represented by the general formula 1
_The quartz plate was treated with a compound of ₃ (CH ₂ ) ₂ , R ′ = H. The solvent does not dissolve in toluene alone, so THF
Was performed by mixing 10 vol%.

The results are shown in Table 1. From this, it was found that self-sequence adsorption occurs even without a long alkyl chain.

Comparative Example 1 In the same manner as in Reference Example 1 , sodium 1,2-bis (2-
Ethylhexyloxycarbonyl) ethanesulfonate (hereinafter referred to as AOT) was adsorbed on a quartz plate. The adsorption amount could not be measured because AOT had no UV absorption. The results of the contact angle of water and the presence or absence of the induction of liquid crystal alignment are shown in Table 1. Since the contact angle is low and the liquid crystal is not aligned, it is hardly adsorbed.

Comparative Example 2 An adsorption experiment similar to that of Reference Example 1 was performed using 4-dodecylresozinol as the monomer model molecule of Reference Example 1 .
The results are shown in Table 1. The area occupied by one molecule is larger than 20Å ² / molecule expected from the molecular model, and the contact angle is small. In addition, the orientation of the liquid crystal was only partially oriented one hour or more after the liquid crystal was sandwiched between the processing plates.

Comparative Example 3 The same adsorption experiment as in Reference Example 1 was performed using p-dodecylphenol. The results are shown in Table 1. Extinction coefficient 160
It could not be quantified because it was as small as 0 and the amount of adsorption was small.
The contact angle was low and the liquid crystal was not aligned.

Example 1 A compound represented by the general formula 1 is used, and R ＝ CH ₃ (CH ₂ ) ₁₀
And using a compound having an adsorption site of R′'CH ₂ COOH, in the same manner as in Reference Example 1 . Since the solvent was not dissolved only by toluene, THF was mixed at 10 vol%. Table 2 shows the results. The strong adsorption property and the orientation property of Reference Example 1 or more are recognized.

Comparative Example 4 The two hydroxyl groups of 4-dodecylresorcinol were replaced with —OCH
_The procedure was carried out in the same manner as in Example 1 using the compound in place of ₂ COOH. The results are shown in Table 2. Although the results are improved as compared with the results of the hydroxyl group in Comparative Example 2, the contact angle is low and the alignment of the liquid crystal is slow.

Comparative Example 5 The hydroxyl group of p-dodecylphenol was changed to —OCH ₂ COOH
The same procedure as in Example 1 was carried out , except that the compound was used instead of The results are shown in Table 2. The extinction coefficient was as low as about 1600, and the amount of adsorption was small, so that quantification was impossible. The contact angle is low and the liquid crystal is not aligned.

REFERENCE EXAMPLE 3 R = CH ₃ (CH ₂ ) ₁₀
And 22.5 mg of a compound having an adsorption site of R ′ = H
Was dissolved in 20 ml of toluene (1.0 × 10 ⁻³ mol)
/ L. ) Was immersed this polyvinyl alcohol spin-coated quartz plate (1 × 3cm ²⁾ 15 min. 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 = 1.7 × 10 4 of the compound.
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 the processing substrates, and whether or not homeotropic alignment of the liquid crystal (NPC-02) was induced was observed with a polarizing plate. The results are shown in Table 3. As a result, it was found that the same good adsorption as in Reference Example 1 was performed.

Example 2 A compound represented by the general formula 1 is used, and R ＝ CH ₃ (CH ₂ ) ₁₀
And using a compound having an adsorption site of R′'CH ₂ COOH, in the same manner as in Reference Example 1 . The solvent does not dissolve in toluene alone, so 10vol tetrahydrofuran
%. The results are shown in Table 4, and it was found that good adsorption was obtained as in Reference Example 3 .

[0123] using 4-dodecyl resorcinol as a monomer model molecules of Comparative Example 6 Reference Example 1, was carried out in the same manner as adsorption test as in Reference Example 1. The results are shown in Table 3. Since the liquid crystal could not be aligned at all, it was found that the alignment was poor.

Comparative Example 7 The two hydroxyl groups of 4-dodecylresorcinol were replaced with —OCH
_{The same} procedure as in Reference Example 3 was performed using a compound in place of ₂ COOH. The results are shown in Table 3. As in Comparative Example 6 , it was found that the orientation was inferior.

<Stability of Adsorption Layer> In order to check the stability of the surface modified layer formed by adsorption,
The above embodiments, in each of Reference Examples and Comparative Examples, the process concentration washing the processed substrate obtained in 10 ^-3 mol / l toluene, chloroform, THF, at a high sequential polarity in the order of methanol solvent, In each case, which solvent destroyed the adsorption layer was measured by UV spectrum. Table 4 shows the results. As shown in Table 4, it was found that the calixarene-based surface modifier 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.

[0127]

[Table 1]

[0128]

[Table 2]

[0129]

[Table 3]

[0130]

[Table 4]

[0131]

The calixarene-based surface modifier according to the present invention has a high adsorptivity, a strong adsorption, and a high orientation on the surface of the object to be treated, as described in the above embodiment. Since it exhibits properties and arrangement 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.

Accordingly, 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 Synthesis Example 1.
= CH_Three(CH_Two) _Ten, R '= H
Structural formula of xsarene-type compound derivative and¹H-nuclear magnetic
This is a sounding spectrum.

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

FIG. 3 shows R represented by general formula 1 obtained in Synthesis Example 3.
¹ shows the structural formula and ¹ H-nuclear magnetic resonance spectrum of a cone-type curlexarene-type compound derivative in which ＝ CH ₃ (CH ₂ ) ₂ , R ′ = H.

FIG. 4 shows R represented by general formula 1 obtained in Synthesis Example 4.
_{= CH 3 (CH 2) 2} , R '= CH cone mosquito Rex arene type compound structure with ^one of the derivatives is ₂ COOH
It is an H-nuclear magnetic resonance spectrum.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-64379 (JP, A) JP-A-6-175322 (JP, A) JP-A-7-128916 (JP, A) JP-A-7-128 175269 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (5)

(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 . A) a corn-type calixarene-based compound derivative comprising a resorcinol cyclic tetramer represented by the following formula: Embedded image 2. An object to be treated is represented by the following general formula 1 (however,
R represents an alkyl group or alkenyl having 3 to 18 carbon atoms.
Shows the group, also, R 'represents a carboxyalkyl group. A surface modification method characterized by contacting with a cone-type calixarene-based compound derivative comprising a resorcinol cyclic tetramer represented by the formula (1). Embedded image 3. The surface modification method according to claim 2, wherein the object to be treated is one selected from a metal having a polar group on its surface, a metal oxide, and a resin. 4. A surface-modified body in which the surface-modifying agent according to claim 1 is adsorbed on a surface of a treatment object having a polar group. 5. The surface-modified body according to claim 4, wherein the object to be treated is silica or iron oxide.