JP3171986B2 - Novel fluorine derivative of imidazole, method for producing the same, and surface treating agent using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treating agent for lubricating, rust-proofing, water-repelling, oil-repelling, etc. the surface of a metal or polymer material, and particularly to a copper-clad laminate for a printed circuit. The present invention relates to a novel imidazole fluorine derivative suitable as a surface treatment agent for a copper foil used, a heat transfer tube of a heat exchanger, and a magnetic disk or the like, a method for producing the same, and uses thereof.

[0002]

2. Description of the Related Art A copper-clad laminate for a printed circuit is formed by laminating a copper foil with a paper-phenol resin-impregnated base material or a glass-epoxy resin-impregnated base material by heating and pressing, and etching this. By forming a circuit network and mounting elements such as a semiconductor device on the circuit network, a board for electronic equipment is manufactured.
In these processes, adhesion to the substrate, heating, immersion in an acid or alkaline solution, application of resist ink, soldering, etc. are performed, so the adhesiveness, heat resistance, moisture resistance, and chemical resistance of the copper foil Performance is required. Further, it is required that the copper foil does not undergo oxidative discoloration during storage.

In order to satisfy these requirements, a brass layer forming treatment is applied to a copper foil (JP-B-51-35711, JP-A-54-35711).
6701), chromate treatment, coating treatment of zinc or a mixture of zinc and chromium groups composed of zinc oxide and chromium oxide (Japanese Patent Publication No. 58-7077), and a silane coupling agent is applied thereto. A method for improving the adhesiveness between a copper foil and a resin substrate has also been proposed (Japanese Patent Publication No. 2-19994, Japanese Patent Application Laid-Open No. 63-183178, Japanese Patent Application Laid-Open No. 2-26097).

[0004]

However, as printed circuits have become more and more compact recently, the characteristics required of the copper foil for printed circuits used have become increasingly severe. Further, in condensers, capillaries, evaporators, and the like of refrigeration systems such as refrigerators, sludge-like substances are generated due to deterioration of refrigerants and lubricating oils or elution of organic material components in the systems, and this causes clogging particularly in capillaries. I have. Further, the evaporator has a problem that the lubricating oil film remains on the inner surface of the evaporator when the refrigerant evaporates, so that the heat transfer efficiency is poor and the cooling efficiency is reduced.

Further, magnetic desks are required to have low friction, water repellency and oil repellency. Conventionally, fluorine-based polymers have been used. However, further improvement in performance is required for high-density recording. ing.

In view of this situation, the present invention forms a film with excellent adhesion and peel resistance on the surface of various metals such as copper and polymer materials, and has remarkable water repellency and oil repellency on the surface. It is an object of the present invention to provide a novel compound useful as an excellent surface treatment agent capable of imparting lubricity and rust prevention, and to provide a surface treatment agent using the same.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by a specific group of imidazole derivatives containing fluorine, and have reached the present invention.

[0008] That is, the present invention provides a novel imidazole fluorine derivative represented by the following general formula (1).

[0009]

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Wherein R ¹ represents hydrogen, a vinyl group or a polyethylene group, R ² represents a group represented by the following general formula (2), and R ³ represents hydrogen or a group represented by the following general formula (3) R ⁴ in the following general formula (2) represents a fluorine or trifluoromethyl group, and n is an integer of 1 to 15.)

[0011]

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[0012] The method for producing an imidazole fluorine derivative as described above, wherein imidazole or 4-vinylimidazole is reacted with a 1,2-epokinepropane compound represented by the following general formula (4).

[0013]

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(Wherein, R ² represents a group represented by the following general formula (2); R ⁴ in the general formula (2) represents a fluorine or trifluoromethyl group; and n is an integer of 1 to 15) It is.

[0015]

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A metal surface treating agent comprising as an active ingredient at least one of the above-mentioned imidazole fluorine derivatives represented by the general formula (1). As the novel imidazole fluorine derivative represented by the general formula (1) of the present invention, particularly preferred are the following.

[0017]

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[0018]

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[0019]

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The fluorine derivative of imidazole represented by the general formula (1) of the present invention is obtained by reacting imidazole or 4-vinylimidazole with a 1,2-epoxypropane compound represented by the following general formula (4) at 100 to 150 ° C. By doing so, it can be easily manufactured.

[0021]

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(Wherein R ¹ , R ² and R ³ are the same as described above) As the 1,2-epoxypropane compound represented by the general formula (4), 3-perfluorooctyl-1,2-
Epoxypropane, 3-perfluorodecyl-1,2-
Epoxypropane, 3- (perfluoro-9-methyldecyl) -1,2-epoxypropane and the like are preferred.

The reaction between the above imidazole or 4-vinylimidazole and a 1,2-epoxypropane compound is performed by
The reaction may be carried out while dropping 0.5 to 2 mol of the 1,2-epoxypropane compound into imidazole or vinylimidazole heated to a temperature of 00 to 150 ° C., and the reaction time is about 10 minutes to 6 hours. This reaction does not require a solvent, but dimethylformamide, dimethylacetamide or the like may be used as a reaction solvent. In addition, since this reaction dislikes water, it is preferable to carry out the reaction in an atmosphere of a dry inert gas such as nitrogen or argon so that water is not mixed.

When 4-vinylimidazole is used, an addition polymerization reaction of a vinyl group occurs together with the above-mentioned reaction. If it is desired to suppress this, a well-known polymerization inhibitor such as hydroquinone is used. I do. On the contrary, when a compound in which an imidazole fluorine derivative is pendant to polyethylene by addition polymerization of a vinyl group is desired, the reaction is preferably carried out without using a polymerization inhibitor and without using a solvent.

The fluorine derivative of the present invention is suitable as a metal surface treating agent. The film of the imidazole fluorine derivative of the present invention formed on the metal surface exhibits remarkable water repellency of Teflon grade and oil repellency as described below, and can significantly improve the rust prevention of the metal surface. .

In addition, the imidazole fluorine derivative of the present invention is applied not only to a metal surface but also to various base materials such as a polymer material and an inorganic material, and the water repellency, oil repellency and lubricity are similarly applied to the base material. Can be provided. Further, by adding to a synthetic resin such as an epoxy resin, the resin can be similarly provided with water repellency, oil repellency, and lubricity.

The case where the imidazole fluorine derivative of the present invention is used as a metal surface treating agent is further described as follows.
The target metal is not particularly limited. For example, it is useful as a surface treatment agent for copper, aluminum, iron, and alloys thereof. However, it is preferable to use it as a surface treatment agent for copper and copper alloys, and particularly when using it as a surface treatment agent for copper foil used in copper-clad laminates for printed circuits, etc., the effect of the present invention is sufficiently exhibited. be able to. Examples of the copper foil include those obtained by roughening the surface of a copper foil, those obtained by forming a brass layer on a copper foil, those subjected to a chromate treatment, and those subjected to a zinc-chromium group mixture coating treatment.

Further, it can be used as a surface treatment agent for the inner wall surfaces of condensers, capillaries and evaporators of refrigeration systems such as refrigerators. Can prevent adhesion of sludge-like substances and blockage due to the adhesion. Furthermore, on the inner wall of the evaporator, when the refrigerant mixed with the lubricating oil evaporates, the lubricating oil becomes droplets due to the strong oil-repellent performance of the surface treatment agent, and does not form an oil film. The cooling efficiency of the system can be increased.

Further, the surface treating agent of the present invention is suitable as a surface coating agent for a magnetic desk because it has a lubricating property that imparts low friction in addition to strong water and oil repellency. It is convenient to dilute at least one of the above-mentioned imidazole fluorine derivatives with a solvent such as an alcohol such as methanol or ethanol so as to have a concentration of 0.001 to 20% by weight, and to apply a metal by immersion in the liquid. preferable. In addition, this imidazole fluorine derivative may be used alone, but may be used by mixing a plurality of imidazole silane compounds, or may be used by mixing with another rust preventive or a coupling agent. .

[0030]

EXAMPLES Example 1 Synthesis of Imidazole Fluorine Derivative 1 Imidazole and 3-perfluorooctyl-1,2-
Synthesis of Compound Represented by the Following Formula (1-1) from Reaction with Epoxypropane

[0031]

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1.36 g of imidazole (0.02 mol
1) was melted at 130 ° C., and 9.52 g (0.02 mol) of 3-perfluorooctyl-1,2-epoxypropane was added dropwise over 30 minutes while stirring under an argon stream. After the completion of the dropwise addition, the reaction was further performed at a temperature of 130 ° C. for 15 minutes.

The reaction product was black, but was washed with ethanol to remove unreacted monomers, and was obtained as 3.45 g (yield 31.7%) of white powder. The melting point of this compound was 210 ° C. as a result of DSC measurement.
Met. ¹ H-NMR, FT-IR and ¹⁹ F-NMR
The results are shown in FIGS. Table 1 shows the results of elemental analysis.

[0034]

[Table 1]

Example 2 Synthesis of Fluorine Derivative of Imidazole 2 From the reaction of 4-vinylimidazole with 3-perfluorooctyl-1,2-epoxypropane, the following formula (1-
Synthesis of compound represented by 2)）

[0036]

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1.88 g of 4-vinylimidazole (0.
02 mol) and hydroquinone 0.0 as a polymerization inhibitor
188 g was stirred at 130 ° C. under an argon stream, and 9.52 g (0.02 mol) of 3-perfluorooctyl-1,2-epoxypropane was added dropwise thereto over 30 minutes. After completion of the dropwise addition, the reaction was further performed at 130 ° C. for 1 hour.

The obtained compound was prepared as benzene 9 as a mobile phase.
Purified and isolated by column chromatography using 5%, 5% methanol, and silica gel as a filler. The isolated compound was a white powdery compound of 1.12 g (9.8% yield), and the melting point was 149 ° C as a result of DSC measurement. The results of the elemental analysis are shown in Table 2, ¹ H-NMR, FT-
The results of IR are shown in FIGS.

[0039]

[Table 2]

Example 3 Synthesis of Fluorine Derivative of Imidazole 3 From the reaction of ｛4-vinylimidazole with 3-perfluorooctyl-1,2-epoxypropane, the following formula (1-
Synthesis of compound represented by 3)）

[0041]

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1.88 g of 4-vinylimidazole (0.
02 mol) at 130 ° C. under a stream of argon.
Thereto, 9.52 g (0.02 mol) of 3-perfluorooctyl-1,2-epoxypropane was dropped over 30 minutes. After completion of the dropwise addition, the reaction was further performed at 130 ° C. for 1 hour.

The obtained compound has a black color and is thoroughly washed with ethanol in order to remove unreacted monomers.
A brown powdery compound was obtained. Table 3 shows the results of the elemental analysis.
The results of ¹ H-NMR and FT-IR are shown in FIGS.

[0044]

[Table 3]

The intrinsic viscosity of the obtained polymer was determined using hexafluoropropanol as a solvent.
It was 3.

Example 4 Synthesis of fluorine derivative of imidazole 4 {Synthesis of compound represented by the following formula (1-4) from reaction of 4-vinylimidazole with 3-perfluoro-9-methyldecyl-1,2-epoxypropane}

[0047]

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1.88 g of 4-vinylimidazole (0.
02 mol) and hydroquinone 0.0 as a polymerization inhibitor
188 g were dissolved in 50 ml of dimethylformamide.
11. This solution was treated with 3-perfluoro-9-methyldecyl-1,2-epoxypropane at 130 ° C. under a stream of argon.
53 g (0.02 mol) of dimethylformamide 10
A solution dissolved in 0 ml was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was continued for another 5 hours. After completion of the reaction, the precipitate was removed by filtration, the filtrate was concentrated, and the obtained solid was further separated into a component soluble in methanol and a component insoluble in methanol. The methanol-soluble component is benzene 95 as the mobile phase.
%, Methanol 5%, and column chromatography using silica gel as a filler. The isolated compound was 0.17 g (yield 1.2%) of a white powdery compound. As a result of DSC measurement, the melting point was 150 ° C. Table 4 shows the results of the elemental analysis, and ¹ H-NMR and FT
The results of -IR and ¹⁹ F-NMR are shown in FIGS.

[0049]

[Table 4]

EXAMPLE 5 Synthesis of Fluorine Derivative of Imidazole 5 Imidazole and 3-perfluoro-9-methyldecyl-
From the reaction with 1,2-epoxypropane, the following formula (1-
Synthesis of compounds represented by 5) and (1-6)}

[0051]

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1.36 g of imidazole (0.02 mol)
l) was dissolved in 25 ml of dimethylacetamide. This solution was added with 3-perfluoro-
9-methyldecyl-1,2-epoxypropane 12.53
g (0.02 mol) in 35 ml of dimethylacetamide
Was added dropwise over 30 minutes. After the completion of the dropwise addition, the reaction was continued for another 6 hours. After the completion of the reaction, the precipitate was removed by filtration and washed with dimethylacetamide on a glass filter. The obtained powdery compound was further separated into a component soluble in methanol and a component insoluble in methanol. The component insoluble in methanol was dried under reduced pressure. The components soluble in methanol were treated with activated carbon and purified by distilling off methanol. All of the isolated compounds were white powdery compounds, the former of which was 2.06 g (yield 14.8).
%), And the latter is 0.67 g (4.8% yield), DS
As a result of the C measurement, the melting point was 125 ° C. (methanol soluble component) and 196 ° C. (methanol insoluble component). The results of elemental analysis are shown in Table 5, and ¹ H-NMR, FT-IR,
FIGS. 11, 12, 13, 14, 1 show the results of ¹⁹ F-NMR.
5 and 16.

[0053]

[Table 5]

Example 6 Synthesis of Fluorine Derivatives of Imidazole 6 From the reaction of imidazole with 3-perfluorodecyl-1,2-epoxypropane, the following formulas (1-7) and (1
Synthesis of compound represented by -8)

[0055]

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1.36 g of imidazole (0.02 mol)
l) was dissolved in 25 ml of dimethylacetamide. A solution prepared by dissolving 11.52 g of 3-perfluoro-decyl-1,2-epoxypropane in 35 ml of dimethylacetamide was added dropwise to this solution over 30 minutes at 120 ° C. under an argon stream. After the completion of the dropwise addition, the reaction was continued for another 6 hours.

After completion of the reaction, the precipitate was removed by filtration.
Washed with dimethylacetamide on a glass filter. The obtained powdery compound was further separated into a component soluble in methanol and a component insoluble in methanol. The component insoluble in methanol was dried under reduced pressure. The components soluble in methanol were treated with activated carbon and purified by distilling off methanol. Each of the isolated compounds was a white powdery compound. The former was 0.45 g (yield 3.5%), and the latter was 0.8
As a result of DSC measurement, the melting point was 139 ° C (methanol-soluble component) and 117 ° C (methanol-insoluble component). Table 6 shows the results of elemental analysis.
The results of ¹ H-NMR, FT-IR, and ¹⁹ F-NMR are shown in FIGS. 17, 18, ¹⁹ , ²⁰ , ²¹ , and ²² .

[0058]

[Table 6]

Example 7 Synthesis of a Fluorine Derivative of Imidazole 7 Imidazole and 3-perfluorooctyl-1,2-
Synthesis of Compound Represented by the Following Formula (1-9) from Reaction with Epoxypropane

[0060]

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1.36 g of imidazole (0.02 mol
l) was dissolved in 25 ml of dimethylformamide. 9.52 g (0.02 g) of 3-perfluorooctyl-1,2-epoxypropane was added to this solution at 120 ° C. under a stream of argon.
2 mol) in 25 ml of dimethylformamide was added dropwise over 30 minutes. After the completion of the dropwise addition, the reaction was continued for another 6 hours. After the completion of the reaction, the precipitate was removed by filtration and washed with dimethylacetamide on a glass filter. The obtained powdery compound was further separated into a component soluble in methanol and a component insoluble in methanol. The component soluble in methanol was recrystallized twice from a mixed solvent of chloroform / methanol, treated with activated carbon, and purified by distilling off the solvent. 0.89 g of the isolated compound
(Yield 8.2%) as a white powdery compound, DSC
As a result of the measurement, the melting point was 124 ° C. Table 7 shows the results of the elemental analysis. In addition, ¹ H-NMR, FT-IR, ¹⁹ F-
The results of NMR are shown in FIGS.

[0062]

[Table 7]

Example 8 An electrolytic copper foil (4.5 × 4.5 cm, thickness 70 μm) was ultrasonically washed with acetone for 5 minutes, then washed with water, and immersed and pickled with a 3% aqueous sulfuric acid solution for 1 minute. Then, it wash | cleaned in order of water and acetone, and dried with the dryer. The glossy surface of this electrolytic copper foil was spin-coated at 500 RPM using a 0.2% hexafluoro-2-propanol solution of the imidazole fluorine derivative represented by the formula (1-1). afterwards,
After drying at 100 ° C. for 30 minutes, the surface wettability was evaluated using a CA-D type contact angle measuring device manufactured by Kyowa Interface Science. Table 8 shows the evaluation results.

[0064]

[Table 8]

* Literature values L. Jarvis and W.S. A. Zisma
n; Encyclopedia of Chemica
l Technology Vol. 9,707L.
S. Penn and E. R. Bowler; Sur
face andInterface Analysis
s, vol. 3, No. 4 161 (1981) Example 9 An electrolytic copper foil (4.5 × 4.5 cm, thickness 70 μm) was ultrasonically washed with acetone for 5 minutes, then washed with water, and 3% sulfuric acid aqueous solution. For 1 minute. Then, it wash | cleaned in order of water and acetone, and dried with the dryer. The glossy surface of the electrolytic copper foil was spin-coated at 500 RPM using a 0.2% methanol solution of the imidazole fluorine derivative represented by the above formula (1-2). Thereafter, the resultant was dried at 100 ° C. for 30 minutes, and its surface wettability was evaluated using a CA-D contact angle measuring device manufactured by Kyowa Interface Science. Table 9 shows the evaluation results.

[0066]

[Table 9]

* The above literature values Example 10 Electrodeposited copper foil (4.5 × 4.5 cm, thickness 70 μm) was ultrasonically washed with acetone for 5 minutes, then washed with water, and immersed and pickled with a 3% sulfuric acid aqueous solution for 1 minute. did. Then, it wash | cleaned in order of water and acetone, and dried with the dryer. The glossy surface of the electrolytic copper foil was spin-coated at 500 RPM using a 0.2% hexafluoro-2-propanol solution of the imidazole fluorine derivative represented by the above formula (1-3). afterwards,
After drying at 100 ° C. for 30 minutes, the surface wettability was evaluated using a CA-D type contact angle measuring device manufactured by Kyowa Interface Science. Table 10 shows the evaluation results.

[0068]

[Table 10]

* The above literature values Examples 11 and 12 Aluminum plate (Example 11) and stainless steel plate (Example 1)
2) was ultrasonically washed with acetone for 5 minutes, and then washed with water. On these substrates, 0.2% hexafluoro-2-% of the imidazole fluorine derivative represented by the above formula (1-1) was added.
Spin coating was performed at 500 RPM using a propanol solution. Thereafter, the resultant was dried at 100 ° C. for 30 minutes, and its surface wettability was evaluated using a CA-D contact angle measuring device manufactured by Kyowa Interface Science. Table 11 shows the evaluation results.

[0070]

[Table 11]

* The above-mentioned literature values Comparative Examples 1 and 2 The same method as in the Examples was used by using the electrolytic copper foil (Comparative Example 1 after degreasing and pickling) and the Teflon plate (Comparative Example 2) used in the Examples. The surface wettability was evaluated. Table 12 shows the results.

[0072]

[Table 12]

* The above literature values Comparing the above Examples 8 to 12 with the above Comparative Examples shows that the imidazole fluorine derivative of the present invention exhibits remarkable water repellency and oil repellency. These performances are superior to a typical water-repellent material, a fluorine material (Teflon).

Example 13 Various substrates were treated with an imidazole fluorine derivative {the formula (1-
2) The surface treatment was carried out in the same manner as in Example 9 and the adsorptivity thereof was examined by washing with methanol, which is a good solvent for the derivative, for 1 minute. The adsorption amount was determined by measuring the absorbance using a high sensitivity reflection method of FT-IR. Table 13 shows the results.

[0075]

[Table 13]

Note 1 ED Copper; electrolytic copper foil, 1B; Cu 70% Z
n 30%, 2B; Cu 65%, Zn 35%, 1C; Cu
100% (rolled copper foil), 2N; Cu 64%, Zn 18%
Ni 18%, 5P; Cu 95%, Sn 5%, 1T
C; Cu 97% Ti 3% Note 2 Calculated assuming the amount of adsorption before washing as 100% The above results show that the imidazole fluorine derivative of the present invention
It shows that it has specific adhesiveness to copper and copper alloy.

Example 14 An electrolytic copper foil (4.5 × 4.5 cm, thickness 70 μm) was ultrasonically washed with acetone for 5 minutes, then washed with water, and immersed and pickled with a 3% aqueous sulfuric acid solution for 1 minute. Then, it wash | cleaned in order of water and acetone, and dried with the dryer. The glossy surface of the electrolytic copper foil was spin-coated at 500 RPM using a 0.2% hexafluoro-2-propanol solution of the imidazole fluorine derivative represented by the above formula (1-1),
Dry at 00 ° C. for 30 minutes. A copper foil surface-treated for the purpose of evaluating the rust-proofing effect of the imidazole fluorine derivative on copper was immersed in boiling water for 5 minutes, and the discoloration of the surface after immersion was observed. The evaluation results are shown in Table 14 together with the results when the imidazole fluorine derivatives represented by the above formulas (1-2) and (1-3) were used and the results for the untreated copper foil.

[0078]

[Table 14]

Example 15 In the same manner as in Example 14, the moisture resistance of a copper foil surface-treated with the above-mentioned imidazole fluorine derivative shown in Table 15 was evaluated. The evaluation was performed by exposing the surface-treated copper foil in a constant temperature bath at a relative humidity of 95% and a temperature of 80 ° C. for 24 hours. Discoloration of the copper foil surface after exposure was observed.

The heat resistance was evaluated in the same manner. The heat resistance was evaluated by placing a copper foil surface-treated on a 260 ° C. solder bath with the treated surface facing up, taking it out after 10 seconds, and observing discoloration of the copper foil surface.

Further, the solder wettability was similarly evaluated. Evaluation of the solder wettability was performed by treating the surface-treated copper foil with Autoflux JS-64 (manufactured by Yamaei Chemical Co., Ltd.) and immersing it in a 255 ° C. solder bath (JIS H64A) for 1 second. The condition was observed. These results are shown in Table 15 together with the results of the untreated copper foil.

[0082]

[Table 15]

Example 16 A copper flat plate (11 × 4.5 cm, thickness 0.35 mm, surface roughness R _max 0.1 μm) was degreased by soxhlet extraction with trichloroethane for 5 days, and an etching solution (50 ml of hydrogen peroxide, (Immersion in sulfuric acid 10 ml, ion exchanged water 1 liter) for 60 seconds, immersion in 5% sulfuric acid aqueous solution for 1 minute, then immersion in ion exchanged water twice for 1 minute, washing with water, and drying with a dryer. Eight kinds of imidazole fluorine derivatives (indicated by the formula numbers) were spin-coated on the copper plate under the conditions shown in Table 16 so that the film thickness became 0.02 μm, and then dried at 100 ° C. for 30 minutes. . Rolling bearing steel balls (diameter 3.96 mm, two types of bearing steel) using a Bowden-Leben type reciprocating friction tester to evaluate the lubricating properties of the imidazole fluorine derivative and the shear durability of the film.
, And tested under the conditions shown in Table 17. Table 16 shows the average coefficient of friction of the coating during the test and the number of times of friction when the coating was broken. The coefficient of friction of the copper plate not spin-coated with the imidazole fluorine derivative was 0.35, and the coefficient of friction of the surface of the copper plate surface-treated with the imidazole fluorine derivative of the present invention was significantly reduced, showing a very good lubricity. It can be seen that this has Furthermore, it can be seen that this surface film is not broken even under friction under severe conditions and has excellent durability.

[0084]

[Table 16]

MeOH: methanol, HFP: hexafluoro-2-propanol

[0086]

[Table 17]

Example 17 In the same manner as in Example 14, the surface of the copper foil was treated using the imidazole fluorine derivative of the above formula (1-2). To see if it can be used in refrigeration systems such as refrigerators,
The durability to the refrigerant was evaluated. The evaluation was performed by placing the surface-treated copper foil in a glass ampule and adding the refrigerant R-134a
And after degassing with a vacuum pump, seal the
C. and 100.degree. C. were placed in a thermostat for 67 hours, and the change in the contact angle of water on the copper foil surface was measured. As a result, the contact angle of the treated copper foil before the test was 114 degrees, 111 degrees after the test at 50 ° C., and 114 degrees after the test at 100 ° C., almost no change was observed, and it had durability to the refrigerant. It can be used in refrigeration systems such as refrigerators.

[0088]

As described above, the novel imidazole fluorine derivative of the present invention has remarkable water and oil repellency on its surface.
Rust prevention and lubricity can be imparted.

[Brief description of the drawings]

FIG. 1 shows a fluorine derivative of an imidazole of the present invention {formula (1-
1) ¹ H-NMR spectrum of｝

FIG. 2 shows a fluorine derivative of an imidazole of the present invention {formula (1-
1) IR spectrum of｝

FIG. 3 is a diagram illustrating an imidazole fluorine derivative of the present invention {formula (1-
1) ¹⁹ F-NMR spectrum of｝

FIG. 4 shows a fluorine derivative of an imidazole of the present invention {formula (1-
2) ¹ H-NMR spectrum of｝

FIG. 5 is an imidazole fluorine derivative of the present invention {formula (1-
2) IR spectrum of｝

FIG. 6 shows the imidazole fluorine derivative of the present invention {formula (1-
3) ¹ H-NMR spectrum of｝

FIG. 7 shows a fluorine derivative of an imidazole of the present invention {formula (1-
3) IR spectrum of｝

FIG. 8 is a diagram illustrating an imidazole fluorine derivative of the present invention {formula (1-
4) ¹ H-NMR spectrum of｝

FIG. 9 shows a fluorine derivative of an imidazole of the present invention {formula (1-
4) IR spectrum of｝

FIG. 10 shows a fluorine derivative of an imidazole of the present invention {formula (1)
-4) ¹⁹ F-NMR spectrum of｝

FIG. 11 shows the imidazole fluorine derivative of the present invention {formula (1)
-5) ¹ H-NMR spectrum of｝

FIG. 12 shows a fluorine derivative of an imidazole of the present invention {formula (1)
-5) IR spectrum of｝

FIG. 13 shows a fluorine derivative of an imidazole of the present invention {formula (1)
-5) ¹⁹ F-NMR spectrum of｝

FIG. 14 shows a fluorine derivative of an imidazole of the present invention {formula (1)
-6) ¹ H-NMR spectrum of｝

FIG. 15 shows a fluorine derivative of an imidazole of the present invention {formula (1)
-6) IR spectrum of｝

FIG. 16 shows a fluorine derivative of an imidazole of the present invention {formula (1)
-6) ¹⁹ F-NMR spectrum of｝

FIG. 17 shows a fluorine derivative of an imidazole of the present invention {formula (1)
-7) ¹ H-NMR spectrum of｝

FIG. 18 shows a fluorine derivative of an imidazole of the present invention {formula (1)
-7) IR spectrum of｝

FIG. 19 shows a fluorine derivative of an imidazole of the present invention {formula (1)
-7) ¹⁶ F-NMR spectrum of｝

FIG. 20 shows a fluorine derivative of an imidazole of the present invention {formula (1)
-8) ¹ H-NMR spectrum of｝

FIG. 21 shows the imidazole fluorine derivative of the present invention {formula (1)
-8) IR spectrum of｝

FIG. 22 shows the imidazole fluorine derivative of the present invention {formula (1)
-8) ¹⁶ F-NMR spectrum of｝

FIG. 23 shows the imidazole fluorine derivative of the present invention {formula (1)
-9) ¹ H-NMR spectrum of｝

FIG. 24 shows the imidazole fluorine derivative of the present invention {formula (1)
-9) IR spectrum of｝

FIG. 25 shows the imidazole fluorine derivative of the present invention {formula (1)
-9) ¹⁶ F-NMR spectrum of｝

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09K 13/06 C09K 13/06 C23G 5/036 C23G 5/036 // C07D 303/08 C07D 303/08 C08J 7/04 C08J 7 / 04 A C10M 133/46 C10M 133/46 C10N 30:12 40:00 40:18 50:02 (72) Inventor Yukio Ogino Nihon Mining Co., Ltd. 56) References JP-A-63-199724 (JP, A) US Pat. No. 4,404,247 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 233/60 C08F 8/30 CA (STN ) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A novel imidazole fluorine derivative represented by the following general formula (1). Embedded image (Wherein, R ¹ represents hydrogen, a vinyl group or a polyethylene group, R ² represents a group represented by the following general formula (2), and R ³ represents hydrogen or a group represented by the following general formula (3), respectively. R ⁴ in the following general formula (2) represents a fluorine or trifluoromethyl group, and n is an integer of 1 to 15.) 2. The method according to claim 1, wherein imidazole or 4-vinylimidazole is reacted with a 1,2-epokinepropane compound represented by the following general formula (4).
3. The method for producing an imidazole fluorine derivative according to item 1. Embedded image (In the formula, R ² represents a group represented by the following general formula (2), R ⁴ in the general formula (2) represents a fluorine or trifluoromethyl group, and n is an integer of 1 to 15. ) 3. A surface treatment agent comprising, as an active ingredient, at least one of the imidazole fluorine derivatives represented by the general formula (1) according to claim 1.