JPH06157471A - New imidazole fluorine derivative, its production and surface treating agent using the same - Google Patents

Abstract

PURPOSE:To obtain a new compound, capable of forming a film having excellent adhesion and peeling resistance on the surface of a metal, a polymeric material, etc., and imparting water and oil repellency, lubricity and rust preventing properties to the surface and useful as a surface treating agent. CONSTITUTION:The compound of formula I {R<1> is H, vinyl or polyethylene; R<2> is formula II [R<4> is F or trifluoromethyl; (n) is 1-15]; R<3> is H or formula III}, e.g. a compound of formula IV. This compound of formula I is obtained by reacting imidazole or 4-vinylimidazole with a 1,2-epoxypropane compound of formula V at 100-150 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for lubrication, rust prevention, water repellency, oil repellency, etc. of a surface of a metal or a polymer material, especially a copper clad laminate for printed circuits. The present invention relates to a novel imidazole fluorine derivative suitable for use as a copper foil used, a heat transfer tube for a heat exchanger, and a surface treatment agent for magnetic disks, a method for producing the same, and uses thereof.

[0002]

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

In order to meet these demands, a brass layer forming treatment is applied to a copper foil (Japanese Patent Publication No. 51-35711, 54-54).
6701), chromate treatment, zinc-chromium group mixture coating treatment comprising zinc or zinc oxide and chromium oxide (Japanese Patent Publication No. 58-7077), and a silane coupling agent is applied to these. There has also been proposed a method for improving the adhesiveness between a copper foil and a resin substrate (Japanese Patent Publication No. 2-19994, Japanese Patent Laid-Open No. 63-183178, Japanese Patent Laid-Open No. 2-26097).

[0004]

However, since the printed circuit has been densified recently, the characteristics required for the copper foil for the printed circuit used have become more and more severe. Further, in condensers, capillaries, evaporators, etc. of refrigeration systems such as refrigerators, sludge-like substances are generated due to deterioration of refrigerant and lubricating oil or elution of organic material components in the system, which causes clogging especially in capillaries. There is. Further, in the evaporator, the lubricating oil film remains adhered on the inner surface of the evaporator during the evaporation of the refrigerant, so that the heat transfer efficiency is poor and the cooling efficiency is lowered.

Further, the magnetic desk is required to have low friction, water repellency, and oil repellency, and a fluorine-based polymer has been conventionally used, but further improvement in performance is required for high density recording. ing.

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

[0007]

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 completed the present invention.

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

[0009]

[Chemical 5]

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

[0011]

[Chemical 6]

The method for producing an imidazole fluorine derivative as described above, which comprises reacting imidazole or 4-vinylimidazole with a 1,2-epokinpropane compound represented by the following general formula (4).

[0013]

[Chemical 7]

(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. It is.}

[0015]

[Chemical 8]

A metal surface treating agent comprising at least one kind of the imidazole fluorine derivative represented by the above general formula (1) as an active ingredient. Particularly preferable examples of the novel imidazole fluorine derivative represented by the general formula (1) of the present invention are shown below.

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

The imidazole fluorine derivative 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]

[Chemical 12]

(Wherein R ¹ , R ² and R ³ are the same as above), the 1,2-epoxypropane compound represented by the above general formula (4) is 3-perfluorooctyl-1,2-
Epoxy propane, 3-perfluorodecyl-1,2-
Epoxy propane, 3- (perfluoro-9-methyldecyl) -1,2-epoxy propane and the like are preferable.

The reaction between the imidazole or 4-vinylimidazole and the 1,2-epoxypropane compound is 1
It may be carried out while dropping 0.5 to 2 mol of a 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. Since this reaction does not like water, it is preferable to carry out the reaction in an atmosphere of dry inert gas such as nitrogen or argon so as not to mix water.

When 4-vinylimidazole is used, addition polymerization reaction of vinyl group occurs together with the above reaction. Therefore, when it is desired to suppress this, a known polymerization inhibitor such as hydroquinone is used. To do. On the other hand, when a compound in which a imidazole fluorine derivative is pendant to polyethylene is desired by addition-polymerizing a vinyl group, it is preferable to carry out the reaction without a solvent without using a polymerization inhibitor.

The imidazole 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 a metal surface exhibits remarkable Teflon-grade water repellency and oil repellency as described below, and can significantly improve the rust preventive property of the metal surface. .

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

The case of using the imidazole fluorine derivative of the present invention as a metal surface treating agent will be further described below.
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 suitable to be used as a surface treatment agent for copper and copper alloys, and particularly when used as a surface treatment agent for a copper foil used for a copper clad laminate for a printed circuit or the like, the effect of the present invention is sufficiently exhibited. be able to. The copper foil includes a copper foil whose surface has been roughened, a copper foil which has been subjected to a brass layer formation treatment, a chromate treatment, a zinc-chromium group mixture coating treatment, and the like.

Further, it can be used as a surface treatment agent for inner wall surfaces of condensers, capillaries and evaporators of refrigeration systems such as refrigerators, and the strong water and oil repellency of this surface treatment agent makes it possible, in particular, on the inner wall of the capillaries. Can prevent the adhesion of sludge-like substances and the blockage due to this 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 repellency of the surface treatment agent and does not form an oil film, improving heat transfer efficiency and refrigeration. The cooling efficiency of the system can be increased.

Further, the surface treatment agent of the present invention has strong water repellency and oil repellency as well as lubricity that imparts low friction, and is therefore suitable as a surface coating agent for magnetic desks. It is easy to apply at least one of the imidazole fluorine derivatives by diluting at least one of them with a solvent such as alcohols such as methanol and ethanol to a concentration of 0.001 to 20% by weight, and dipping a metal in this solution. preferable. The imidazole fluorine derivative may be used alone, or a plurality of imidazole silane compounds may be mixed and used, or may be mixed with another rust preventive agent, a coupling agent or the like. .

[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) by reaction with epoxypropane}

[0031]

[Chemical 13]

1.36 g of imidazole (0.02 mo
l) 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 dropping was completed, the reaction was further performed at a temperature of 130 ° C. for 15 minutes.

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

[0034]

[Table 1]

Example 2 Synthesis of imidazole fluorine derivative 2 From the reaction of {4-vinylimidazole and 3-perfluorooctyl-1,2-epoxypropane, the following formula (1-
Synthesis of compound represented by 2)}

[0036]

[Chemical 14]

1.88 g of 4-vinylimidazole (0.
02 mol) and hydroquinone as a polymerization inhibitor 0.0
188 g was allowed to stir 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 the dropping was completed, the reaction was further performed at 130 ° C. for 1 hour.

The obtained compound is benzene 9 as a mobile phase.
Purified and isolated by column chromatography using 5%, methanol 5%, and silica gel as a packing material. The isolated compound was 1.12 g (yield 9.8%) of a white powdery compound, and the melting point was 149 ° C. as a result of DSC measurement. The results of 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 imidazole fluorine derivative 3 From the reaction of {4-vinylimidazole and 3-perfluorooctyl-1,2-epoxypropane, the following formula (1-
Synthesis of compound represented by 3)}

[0041]

[Chemical 15]

4-Vinylimidazole 1.88 g (0.
02 mol) at 130 ° C. under an argon stream,
9.52 g (0.02 mol) of 3-perfluorooctyl-1,2-epoxypropane was added dropwise thereto over 30 minutes. After the dropping was completed, the reaction was further performed at 130 ° C. for 1 hour.

The obtained compound has a black color and is thoroughly washed with ethanol for the purpose of removing unreacted monomers.
A brown powdery compound was obtained. The results of elemental analysis are shown in Table 3,
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 by using hexafluoropropanol as a solvent.
It was 3.

Example 4 Synthesis of imidazole fluorine derivative 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]

[Chemical 16]

4-Vinylimidazole 1.88 g (0.
02 mol) and hydroquinone as a polymerization inhibitor 0.0
188 g was dissolved in 50 ml of dimethylformamide.
This solution was added with 3-perfluoro-9-methyldecyl-1,2-epoxypropane 12.
53 g (0.02 mol) of dimethylformamide 10
The solution dissolved in 0 ml was added dropwise over 30 minutes. After the dropping was completed, the reaction was continued for 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 methanol-soluble component and an insoluble component. Methanol-soluble component is benzene 95 as mobile phase.
%, Methanol 5%, and purified and isolated by column chromatography using silica gel as a packing material. The isolated compound was 0.17 g (yield 1.2%) of a white powdery compound, and the melting point was 150 ° C. as a result of DSC measurement. The results of elemental analysis are shown in Table 4, ¹ H-NMR and FT.
The results of -IR and ¹⁹ F-NMR are shown in FIGS.

[0049]

[Table 4]

Example 5 Synthesis of imidazole fluorine derivative 5 {Imidazole and 3-perfluoro-9-methyldecyl-
From the reaction with 1,2-epoxypropane, the following formula (1-
5) and synthesis of compounds represented by (1-6)}

[0051]

[Chemical 17]

1.36 g of imidazole (0.02 mo
1) was dissolved in 25 ml of dimethylacetamide. 3-perfluoro-
9 Methyldecyl-1,2-epoxypropane 12.53
35 g of dimethylacetamide (g (0.02 mol))
The solution dissolved in was added dropwise over 30 minutes. After the dropping was completed, the reaction was continued for another 6 hours. After the reaction was completed, the precipitate was removed by filtration and washed with dimethylacetamide on a glass filter. The obtained powdery compound was further separated into a methanol-soluble component and an insoluble component. The components insoluble in methanol were dried under reduced pressure. The component soluble in methanol was treated with activated carbon and purified by distilling off methanol. Each of the isolated compounds was a white powdery compound, the former being 2.06 g (yield 14.8).
%), The latter is 0.67 g (yield 4.8%), DS
As a result of 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, ¹ H-NMR, FT-IR,
The results of ¹⁹ F-NMR are shown in FIGS. 11, 12, 13, 14, and 1.
5,16.

[0053]

[Table 5]

Example 6 Synthesis of imidazole fluorine derivative 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]

[Chemical 18]

1.36 g of imidazole (0.02 mo
1) 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 at 120 ° C. over 30 minutes under an argon stream. After the dropping was completed, the reaction was continued for another 6 hours.

After the reaction was completed, the precipitate was removed by filtration,
It was washed with dimethylacetamide on a glass filter. The obtained powdery compound was further separated into a methanol-soluble component and an insoluble component. The components insoluble in methanol were dried under reduced pressure. The component soluble in methanol was treated with activated carbon and purified by distilling off methanol. The isolated compounds are white powdery compounds, the former 0.45 g (yield 3.5%), the latter 0.8.
It was 6 g (yield 6.7%), and as a result of DSC measurement, the melting point was 139 ° C. (methanol-soluble component) and 117 ° C. (methanol-insoluble component). The results of elemental analysis are shown in Table 6.
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 imidazole fluorine derivative 7 {Imidazole and 3-perfluorooctyl-1,2-
Synthesis of a compound represented by the following formula (1-9) from a reaction with epoxypropane}

[0060]

[Chemical 19]

1.36 g of imidazole (0.02 mo
l) was dissolved in 25 ml of dimethylformamide. 9.52 g of 3-perfluorooctyl-1,2-epoxypropane (0.0
A solution prepared by dissolving 2 mol) in 25 ml of dimethylformamide was added dropwise over 30 minutes. After the dropping was completed, the reaction was continued for another 6 hours. After the reaction was completed, the precipitate was removed by filtration and washed with dimethylacetamide on a glass filter. The obtained powdery compound was further separated into a methanol-soluble component and an insoluble component. The component soluble in methanol was purified by repeating recrystallization twice from a chloroform / methanol mixed solvent, treating with activated carbon and distilling off the solvent. 0.89 g of isolated compound
(Yield 8.2%), white powdery compound, DSC
As a result of the measurement, the melting point was 124 ° C. The results of elemental analysis are shown in Table 7. 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 cleaned with acetone for 5 minutes, then washed with water, and immersed in a 3% sulfuric acid aqueous solution for 1 minute for pickling. Then, it was washed with water and acetone in that order and dried with a dryer. A 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 by a Kyowa Interface Science CA-D type contact angle measuring device. The evaluation results are shown in Table 8.

[0064]

[Table 8]

* Reference value N. L. Jarvis and W.D. A. Zisma
n; Encyclopedia of Chemica
l Technology Vol. 9,707L.
S. Penn and E. R. Bowler; Sur
face and Interface Analysis
s, vol. 3, No. 4 161 (1981) Example 9 An electrolytic copper foil (4.5 × 4.5 cm, thickness 70 μm) was ultrasonically cleaned with acetone for 5 minutes, and then washed with water, and a 3% sulfuric acid aqueous solution was used. It was soaked and pickled for 1 minute. Then, it was washed with water and acetone in that order and dried with a dryer. The glossy surface of this 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). Then, it was dried at 100 ° C. for 30 minutes and its surface wettability was evaluated by a Kyowa Interface Science CA-D type contact angle measuring device. The evaluation results are shown in Table 9.

[0066]

[Table 9]

* The above literature values Example 10 An electrolytic copper foil (4.5 × 4.5 cm, thickness 70 μm) was ultrasonically cleaned with acetone for 5 minutes, then washed with water, and immersed in a 3% sulfuric acid aqueous solution for 1 minute for pickling. did. Then, it was washed with water and acetone in that order and dried with a dryer. A 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 above formula (1-3). afterwards,
After drying at 100 ° C. for 30 minutes, the surface wettability was evaluated by a Kyowa Interface Science CA-D type contact angle measuring device. The evaluation results are shown in Table 10.

[0068]

[Table 10]

* The above literature values Examples 11 and 12 Aluminum plate (Example 11) and stainless 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 used.
It was spin-coated at 500 RPM using a propanol solution. Then, it was dried at 100 ° C. for 30 minutes and its surface wettability was evaluated by a Kyowa Interface Science CA-D type contact angle measuring device. The evaluation results are shown in Table 11.

[0070]

[Table 11]

* Reference values above Comparative Examples 1 and 2 In the same manner as in Examples, the electrolytic copper foil (after degreasing and pickling, Comparative Example 1) and the Teflon plate (Comparative Example 2) used in Examples were used. The wettability of the surface was evaluated. The results are shown in Table 12.

[0072]

[Table 12]

* The above literature values By comparing Examples 8 to 12 with the above Comparative Example, it can be seen that the imidazole fluorine derivative of the present invention exhibits remarkable water repellency and oil repellency. These performances are superior to the fluorine material (Teflon) which is a typical water repellent material.

Example 13 Various substrates were prepared by using an imidazole fluorine derivative {the above formula (1-
2)} was surface-treated in the same manner as in Example 9, and their adsorptivity 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 the high sensitivity reflection method of FT-IR. The results are shown in Table 13.

[0075]

[Table 13]

Note 1 ED Copper; electrolytic copper foil, 1B; Cu 70% Z
n30%, 2B; Cu65%, Zn35%, 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 adsorption amount before washing as 100%. The above results show that the imidazole fluorine derivative of the present invention is
It shows that it has specific adhesion to copper and copper alloys.

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 in a 3% sulfuric acid aqueous solution for 1 minute to be pickled. Then, it was washed with water and acetone in that order and dried with a 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), and then 1
It was dried at 00 ° C. for 30 minutes. The surface-treated copper foil was immersed in boiling water for 5 minutes for the purpose of evaluating the anticorrosive effect of the imidazole fluorine derivative on copper, and the discoloration of the surface after the immersion was observed. The evaluation results are shown in Table 14 together with the results of using the imidazole fluorine derivative represented by the formulas (1-2) and (1-3) and the results of the untreated copper foil.

[0078]

[Table 14]

Example 15 In the same manner as in Example 14, the moisture resistance of the copper foil surface-treated with the above formula imidazole fluorine derivative shown in Table 15 was evaluated. For the evaluation, the surface-treated copper foil was exposed for 24 hours in a thermostat at a relative humidity of 95% and a temperature of 80 ° C. The discoloration of the copper foil surface after the exposure was observed.

The heat resistance was evaluated in the same manner. To evaluate the heat resistance, the surface-treated copper foil was placed on a solder bath at 260 ° C. with the treated surface facing upward, and after 10 seconds, the copper foil was taken out and the discoloration of the copper foil surface was observed.

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

[0082]

[Table 15]

Example 16 A copper plate (11 × 4.5 cm, thickness 0.35 mm, surface roughness R _max 0.1 μm) was degreased by Soxhlet extraction for 5 days with trichloroethane, and the etching solution (hydrogen peroxide 50 ml, It was dipped in 10 ml of sulfuric acid and 1 liter of ion-exchanged water) for 60 seconds, then dipped in a 5% sulfuric acid aqueous solution for 1 minute, then dipped in ion-exchanged water twice for 1 minute, washed with water, and dried with a dryer. Eight imidazole fluorine derivatives (shown by the above formula number) were spin-coated on this copper plate under the conditions shown in Table 16 to a film thickness of 0.02 μ, and then dried at 100 ° C. for 30 minutes. . Steel balls for rolling bearings (diameter 3.96 mm, bearing steel 2 types) with a Bowden-Leben reciprocating friction tester to evaluate the lubricity of the imidazole fluorine derivative and the shear durability of the film.
Was tested under the conditions shown in Table 17. Table 16 shows the average friction coefficient of the coating during the test and the number of frictions when the coating broke. 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 greatly reduced, showing very good lubricity. It turns out that it has. Further, it can be seen that this surface film is not broken even if it is rubbed 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 with the imidazole fluorine derivative of the above formula (1-2). For the purpose of checking whether it can be used in a refrigeration system such as a refrigerator,
The durability against the refrigerant was evaluated. For evaluation, the surface-treated copper foil was put in a glass ampoule, and the refrigerant R-134a was placed in this.
Was injected, degassed with a vacuum pump, sealed, and
It was carried out by placing it in a constant temperature bath of 100 ° C. and 67 ° C. for 67 hours and measuring the change in the contact angle of water on the surface of the copper foil. As a result, the contact angle of the treated copper foil before the test was 114 degrees, after the test at 50 ° C. was 111 degrees, and after the test at 100 ° C. was 114 degrees, showing almost no change and having durability against the refrigerant. It was found that 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 the surface.
Rust prevention and lubricity can be imparted.

[Brief description of drawings]

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

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

FIG. 3 shows an imidazole fluorine derivative of the present invention (formula (1-
1)} ¹⁹ F-NMR spectrum

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09K 3/18 103 8318-4H 13/06 C23G 5/036 9271-4K // C07D 303/08 C08J 7/04 A C10M 133/46 9159-4H C10N 30:12 40:00 Z 8217-4H 40:18 50:02 (72) Inventor Kazuo Yoshida 3-17-35, Shinsōnan, Toda City, Saitama Prefecture Kyoseki products Inside the Technical Research Institute (72) Inventor Yukio Ogino 3-17-35, Shinsōnan, Toda City, Saitama Prefecture Japan Mining Co., Ltd.

Claims (3)

[Claims] 1. A novel imidazole fluorine derivative represented by the following general formula (1). [Chemical 1] (In the formula, 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.) 2. The imidazole or 4-vinylimidazole is reacted with a 1,2-epokinpropane compound represented by the following general formula (4).
The method for producing the imidazole fluorine derivative as described in 1. [Chemical 3] (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. ) [Chemical 4] 3. A surface treatment agent comprising at least one kind of the imidazole fluorine derivative represented by the general formula (1) according to claim 1 as an active ingredient.