JP4352125B2 - Method for producing fluorinated solid material and product thereof - Google Patents

Description

The present invention relates to a method for producing a fluorinated solid material, more particularly, super-stable by surface treatment with perfluoroalkyl radicals, it relates to how to produce the fluorinated solid material whose surface is coated with fluorine It is.
In the technical field of surface functionalization for producing a highly functional material by surface-treating the surface of a solid material, in recent years, in addition to mechanical properties such as toughness, water repellency and wear resistance With the wide variety of new applications that require high functionality such as performance, chemical resistance, low friction properties, and non-adhesiveness, ultra-stable perfluoro radicals are used as fluorine coating agents. no environmental impact, in the process of low emissions, conveniently, and reproducibly, prepared how novel fluorinated solid material which allows the surface to produce a fluorinated solid material that is coated with fluorine It is useful as a thing to provide.

  The enhancement of the function of the material is efficiently achieved by enhancing the function of the material surface. In the field of surface functionalization of material development, for example, industrial appreciation is given to materials having wear resistance, oxidation resistance, and the like and having high strength. In addition, further enhancement of functionality by modifying the material surface is being studied with the aim of expanding its application range. Among them, further enhancement of functionality by fluorination treatment of materials is particularly important because its application extends to the nanotechnology field such as magnetic recording media.

  In the prior art documents, for example, when a DLC film is formed on a ferromagnetic metal thin film of a magnetic recording medium, a method of fluorination using a discharge gas containing a fluorocarbon compound in addition to hydrocarbon is proposed. (See Patent Documents 1 and 2). In addition, a method of forming a fluorinated DLC film on various magnetic recording media using a similar method has been proposed (see Patent Documents 3 and 4).

  In addition to patent literature, many literatures have proposed methods for producing fluorinated materials using fluorinated hydrocarbons as a fluorine source (see Non-Patent Literatures 1 to 4). However, with these methods, the uniformity of the properties of the resulting film and the control of the properties of the resulting film depending on the shape and size, as well as the reproduction, due to the complexity of the apparatus for film formation and the difficulty of setting the experimental conditions There are major obstacles in terms of sex.

  Surface treatment with fluorine gas not only has the disadvantage of using a highly reactive and dangerous substance called fluorine, but it may form not only a water-repellent surface but also a hydrophilic surface by fluorination. It is difficult to perform control with good reproducibility. Therefore, development of a new fluorination treatment technique capable of fluorinating a solid surface in a safe and simple manner with good reproducibility has been strongly desired in this technical field.

JP-A 63-275035 Japanese Patent Laid-Open No. 03-183010 Japanese Patent Application Laid-Open No. 08-129747 Japanese Patent Application Laid-Open No. 08-212545 K.-L. Choy J. Zhao, ScriptaMaterialia, 39 (7), 839-845 (1998) R. Hatada, K. Baba, Nuclear Instruments and Methods in Physics Research B 148, 655-658 (1999) M. Hakovirta, S. M. He, M. Nastasi, J. Appl. Phys. 88 (3), 1456-1459 (2000) M. Hakovirta, D. H. Lee, X. M. He, M. Natasi, Materials Research Society Symposium Proceedings 593 (Amorphous and NanostructuredCarbon), 285-290 (2000)

Under such circumstances, in view of the above-described conventional technology, the present inventors formed a solid surface by a low-emission process that is safe and simple, has good reproducibility, and has no environmental impact. As a result of intensive research aimed at developing a new method for producing fluorinated solid materials that can be fluorinated, the surface of a solid material substrate is made of a group of perfluoro-based radicals called extremely stable perfluoroalkyl radicals. It has been found that the intended purpose can be achieved by treating with a compound, and further studies have been made to complete the present invention.
In the present invention, the fluorination treatment for imparting high-functional properties such as water repellency / oil repellency and non-adhesiveness to the surface of the solid material can be easily performed under mild conditions without violating the substrate at all. Moreover safely, reproducibly, it is an object to provide a manufacturing how novel fluorinated solid material which makes it possible to perform in an environmentally friendly manner.

The present invention for solving the above-described problems comprises the following technical means.
(1) Extremely stable perfluoroalkyl radicals that are well-dissolved in perfluoro compounds in the vapor phase and / or liquid phase on the surface of a solid material substrate and are extremely chemically and physically stable. provide Reinforced the fluorination treatment can be confirmed that the proceeding of the fluorination changing the contact angle of water on the substrate surface by ESCA spectra were reacted to impart water repellency and oil repellency to the substrate surface solid a method of manufacturing a solid material you produce materials,
1) A reaction in which a very stable perfluoroalkyl radical is dispersed or dissolved in a perfluoro compound, which is an inert medium, by applying heat from outside in a state where the solid material is suspended or submerged, is caused to react.
2) Put a very stable perfluoroalkyl radical and a solid material in a sealed container and react by applying heat, or
3) The heated solid material is reacted with the extremely stable perfluoroalkyl radical as it is or by spraying a solution in which this is dispersed or dissolved in a perfluoro compound,
A method for producing a solid material.
(2) The extremely stable perfluoroalkyl radical is perfluoro-2,4-dimethyl-3-isopropyl-3-pentyl, perfluoro-2,4-dimethyl-3-ethyl-3-pentyl, or perfluoro-3. -The manufacturing method of the solid material which provided the water repellency and oil repellency as described in said (1) which is ethyl-3,4-dimethyl- 4-hexyl.
( 3 ) The solid material is a metal, a metal alloy composed of two or more components, an inorganic compound, or a material coated with these materials, an organic polymer, or an organic-inorganic composite thereof, or a combination thereof. is either coated material with a material, a manufacturing method of the solid material according to (1) or (2).

Next, the present invention will be described in more detail.
The present invention is characterized in that the surface of a solid material, that is, a solid material or a solid material base material, is surface-treated with an extremely stable perfluoroalkyl radical to produce a solid material whose surface is fluorine-coated. is there. As the solid material used in the present invention, for example, a metal such as iron, aluminum, gold, silver, or platinum, an alloy of a metal composed of two or more components, an inorganic compound such as silicon carbide, Carbide-based inorganic materials such as titanium carbide and boron carbide, nitride-based inorganic materials such as silicon nitride, carbon homologues such as carbon nanotube fullerene, metal oxides and surfaces coated with them, organic polymers or inorganics Examples thereof include organic composites or surfaces coated with them, but are not limited to these, and any of those having the same effect or similar to these can be used. Further, in the present invention, the solid material base means a member obtained by processing these materials into an arbitrary shape and structure. In the present specification, these are described as a solid material. The extremely stable perfluoroalkyl radical used in the present invention is a perfluoro-based substance, and the solvent used as a reaction solvent is also a perfluoro-based solvent. These perfluoro-based substances are chemically Inactive, and does not interact with any solid material, so there are no restrictions on the solid material substrate.

  In the present invention, the extremely stable perfluoroalkyl radical is basically a perfluoroalkyl radical that is chemically and physically stable at room temperature, and is mild (room temperature-150 ° C.), preferably (room temperature- Those that gradually generate perfluoroalkyl radicals at 120 ° C. are used. The perfluoroalkyl radical having such properties is preferably, for example, perfluoro-2,4-dimethyl-3-isopropyl-3-pentyl, perfluoro-2,4-dimethyl-3-ethyl-3- Examples include pentyl and perfluoro-3-ethyl-3,4-dimethyl-4-hexyl. Among these, since perfluoro-2,4-dimethyl-3-isopropyl-3-pentyl and perfluoro-2,4-dimethyl-3-ethyl-3-pentyl can be synthesized at low cost and in high yield, Perfluoro-2,4-dimethyl-3-ethyl-3-pentyl is particularly preferable because it can be recycled.

  Examples of the reaction method of the extremely stable perfluoroalkyl radical include (1) a method of reacting in a gas phase system without diluting with a solvent as it is, (2) a method of reacting in a liquid phase system with dilution with a solvent, and (3) A method of reacting in a system in which both phases of a gas phase and a liquid phase are present, and the reaction method to be used is appropriately selected depending on the properties of the solid material substrate. For example, if the base material is a metal, the whole base material is heated, and a very stable perfluoroalkyl radical is directly diluted or diluted with a perfluoro solvent on the heated base surface. The method of spraying is used. For surface treatment of the substrate in the gas phase, the substrate is put in a sealed container, degassed, and the container is heated to an appropriate temperature under vacuum, and then an extremely stable perfluoroalkyl radical is introduced into the container. Alternatively, a method of applying heat to the container after introducing a very stable perfluoro radical is used. At this time, the surface treatment is preferably performed, for example, under vacuum or in the presence of an inert gas such as nitrogen, helium, argon, or xenon.

  The surface treatment in the liquid phase is performed by dissolving or dispersing a very stable perfluoroalkyl radical in a perfluoro solvent. That is, the base material is put in a sealed container, and a perfluoro solvent in which a very stable perfluoroalkyl radical is dissolved or dispersed is added so that the base material is completely submerged on the liquid surface or comes out above the liquid surface. The container is sealed with the inside of the sealed container completely deaerated, and the surface treatment reaction is performed by heating from the outside. As a simpler method, a perfluoro solvent having a high boiling point, for example, commercially available EF-L102 (boiling point 102 ° C.), FC-3283 (boiling point 128 ° C.), EF-155 (boiling point 155 ° C.) By using EF-L174 (boiling point 174 ° C.), EF-L215 (boiling point 215 ° C.) or the like, the surface treatment reaction can be performed in a closed system or under reflux conditions.

  All perfluoro solvents are commercially available or industrially utilized general compounds. For example, FC-72 (based on perfluorohexane), FC43 (perfluoro-tri-n-butylamine) and the like used in Examples described later are industrially produced.

For the very stable perfluoroalkyl radical perfluoro-2,4-dimethyl-3-ethyl-3-pentyl, the hexafluoropropene trimer perfluoro-2,4-dimethyl-3-ethyl-3-pentene and It can be synthesized by direct fluorination of a mixture of perfluoro-2,4-dimethyl-3-ethyl-2-pentene (KV Scherer, T. Ono, K. Yamanouchi, R. Fernandez, P. Henderson, J.
Am. Chem. Soc., 107, 718-719 (1985)). Perfluoro-2,4-dimethyl-3-isopropyl-3-pentyl can be synthesized by directly fluorinating perfluoro-2,4-dimethyl-3-isopropyl-3-pentene ( Ono et al., Japanese Patent Application 2001-352474). Further, perfluoro-3-ethyl-3,4-dimethyl-4-hexyl can be synthesized by directly fluorinating a tetrafluoroethylene pentamer (U.
Gross et al. J. Fluorine Chem. 76, 139-144 (1996)).

  A mixture of the hexafluoropropene trimer perfluoro-2,4-dimethyl-3-ethyl-3-pentene and perfluoro-2,4-dimethyl-3-ethyl-2-pentene is described in the literature (W. Dmowski , WT Flowers, RN Haszeldine, J. Fluorine Chem., 9, 94-96 (1977)).

Perfluoro-2,4-dimethyl-3-ethyl-3-pentyl, which is a very stable perfluoroalkyl radical, is described, for example, by Scherer et al. In 1985 in hexafluoropropene trimer (perfluoro-2,4 (A mixture of dimethyl-3-ethyl-3-pentene and perfluoro-2,4-dimethyl-3-ethyl-2-pentene) is reported to be obtained in high yield by direct fluorination ( KV Scherer, T. Ono, K. Yamanouchi, R. Fernandez, P. Henderson, H.
Goldwhite, J. Am. Chem. Soc., 107, 718-719 (1985)).

  This radical has the property of generating a trifluoromethyl radical by β-cleavage under mild conditions. Because of this property, this radical has been reported to be usable as a radical initiator in polymer synthesis (eg, KV Scherer, T. Ono, K. Yamanouchi, US Pat. No. 4,626,608). . In addition, a method has been developed that can synthesize perfluoro-2,4-dimethyl-3-isopropyl-3-pentyl, a very stable perfluoroalkyl radical that does not react even with fluorine in a quantitative yield (Ono et al. Application No. 2001-352474). This perfluoro-2,4-dimethyl-3-isopropyl-3-pentyl is also known to have a property of generating a trifluoromethyl radical by β-cleavage under mild conditions. A patent application regarding use as an initiator has been filed (Ono et al., Japanese Patent Application No. 2001-352475).

These extremely stable radicals are not only physically very stable, but also chemically very stable, so that conventionally known peroxide systems (WH Gumprecht, RH Dettre,
J. Fluorine Chem., 5, 245-263 (1975)), or nitroso (T. Umemoto,
A. Ando, Bull. Chem. Soc. Jpn., 59, 447 (1986)) is considered to be an ideal trifluoromethyl radical generating reagent without the danger of explosion as the trifluoromethyl radical generating reagent. It is done.

  In general, it is known that high functionality such as non-adhesiveness and water repellency can be imparted by fluorinating the substrate surface. Conventionally, for such a fluorinated surface treatment of the substrate surface, a method using a fluorine gas or a method using a plasma apparatus has been known, but there are problems in terms of danger and reproducibility, and a complicated apparatus Need. In order to manufacture highly functionalized fluorinated solid materials, it is necessary to develop a fluorination treatment method by a low emission process that is simpler, more reproducible, cheaper, safe to handle, and has no environmental impact. desired.

  Since the fluorine-containing alkyl radical is a highly reactive reactive species, there is a possibility that a reagent that generates such an active species binds to, for example, sp2 carbon that forms a DLC film. Against this background, the present inventors have studied various methods for fluorinating solid materials using extremely stable perfluoroalkyl radicals on the basis of an index (surface contact angle of water) relating to surface wetting. However, it has been found that this method can be used as an ideal fluorination treatment method capable of clearing all the above-mentioned problems.

  Perfluoroacyl peroxide, N-perfluoroalkyl-N-nitrososulfonamide-based compounds, and the like are conceivable as reagents for generating fluorine-containing alkyl radicals, which may be applicable to fluorination of the substrate surface. However, these compounds have problems in chemical stability and are dangerous for industrial use. The above-mentioned extremely stable perfluoroalkyl radical can be a chemically extremely stable and easy-to-handle perfluoroalkyl radical generating reagent. Further, since it is a perfluoro compound, it is dissolved in a perfluoro solvent.

Here, it is important in the method of the present invention that the extremely stable perfluoroalkyl radical is well dissolved in the perfluoro compound. This property allows processing in the liquid phase of the substrate. That is, it is known that perfluoro compounds are extremely stable both chemically and physically (AV Grosse and GH Cady, Ind. Eng. Chem.,
1947, 39, 367-374; DD Dixon and D.
G. Holland, Fed. Proc. 1975, 34, 1444-1448; KC Lowe, Sci.
Prog. 1997, 80, 169-193; JG Riess,
Chem. Rev. 2001, 101, 2797-2019,), this chemical inertness not only dissolves all materials other than perfluoro, but also dissolves and swells resins such as plastics. Absent. Therefore, even when the base material contains a resin, the base material surface can be modified in the liquid phase using a perfluoro solvent without any problem. The inertness of perfluoro-based solvents does not give the possibility of radical deactivation due to hydrogen abstraction reaction with trifluoromethyl radicals generated from mildly stable perfluoroalkyl radicals under mild conditions. Therefore, except for the deactivation process due to radical-radical recombination, it is possible to provide a reaction field that is extremely effectively used as a fluorine source for surface modification.

Perfluoro solvents are also used as artificial blood (oxygen-carrying infusion) (L. Clark and F. Gollan, Science, 1966, 152, 1755-1756; Kazumasa Yokoyama, Yoshio Tsuda, oxygen-carrying infusion “Fluozole” in Hiroshi Mizushima DDS
Progress, 1995-96, Tokyo: Nakayama Shoten, 1995, 228-231; Junichi Yamauchi, Development Status and Prospects of Perfluorochemical Oxygen Carrier, in Artificial Organs 1994-96. Tokyo: Nakayama Shoten, 1994,
22, 955-963; Kunihiko Nakai, Ichiro Sakuma, Shoji Fukushima, Yukazu Takeuchi, Hiroshi Sato, Akira Kitakuma, Artificial Blood, 2000, 8, 43-51) and microbial media (KC)
Lowe, J. Fluorine Chem., 2002, 118, 19-26), liquid breathing (Kenichi Matsuda, Hiroyuki Hirasawa, Pharmaceutical Gate, 2000, 10,
287-294; Kenichi Matsuda, Hiroyuki Hirasawa, Yo Hirayama, Emergency Medicine, 2002,
26, 1557-1562) or organ preservation (E. Klar, Th
Kraus, P. Reuter, A. Mehrabi, LP Fernandes, M. Angelescu, MM Gebhard and Ch Herfarth,
Transplantation Proc., 1998, 30, 3707-3710) are known to be not toxic enough to be used, but these points are also important when constructing actual industrial surface treatment processes. It becomes.

Perfluoro compounds are known to have low intermolecular forces (M. Howe-Grant,
Ed., Kirk-Othmer, Fluorine Chemistry: A Comprehensive
Treatment, Encyclopedia Reprint Series, John Wiley & Sons, 1995, 260). For this reason, it is easy to disperse the solid substance and to facilitate stirring. Furthermore, it has the convenience that it can be recovered with high energy efficiency by distillation or vaporization. In relation to the small intermolecular force, the small surface energy is particularly important in the surface treatment of a substrate having a complicated shape. That is, since these compounds easily penetrate into narrow gaps and fine structures with complicated shapes, a uniform film surface treatment on the substrate surface becomes possible.

  Furthermore, unlike ordinary hydrocarbon organic solvents, perfluoro compounds have a large specific gravity and can easily float powdered solids, which facilitates dispersion of powdered solid particles by stirring. To. The present invention has been completed by obtaining the knowledge described above, and according to the present invention, almost all the surfaces of the base material can be easily, reproducibly and efficiently fluorinated. It becomes possible to do.

  According to the present invention, (1) it is possible to impart high functionality to a substrate by fluorinating the surface of various solid material substrates, regardless of their shapes, extremely easily and with good reproducibility. (2) The surface can be uniformly fluorinated regardless of the shape and complexity of the substrate to be treated. (3) The process itself is safe, highly reproducible, and fluorine-coated perfluoro compounds. Because it can be recycled, it has low emissions and has no environmental impact. (4) New surface treatment technology and advanced technology can be provided by fluorination of the base material. (5) Complex equipment and difficult experimental conditions (6) When the industry using conventional organic solvents is reconsidered from the viewpoint of green chemistry, it is easy to recover and can avoid risk factors such as toxicity and explosiveness. Practical industrial process of the present invention using a perfluorinated compound as a solvent is expected, the significant effect that is achieved is.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by these Examples.

(1) Production of fluorinated solid material base material SUS sample piece (DLC film thickness 500 nm, SUS plate thickness 1 mm, SUS plate size 8 × 8 mm) having a DLC film formed on its surface, perfluoro solvent (FC-72, 10 ml), perstable radical perfluoro-2,4-dimethyl-3-ethyl-3-pentyl (0.6 mmole) is put into an ampule (20 mmφ × 100 mm) made of Pyrex (registered trademark). It was. The inside of the ampoule was subjected to freeze-and-thaw three times and replaced with argon, and then sealed under vacuum. The ampoule was immersed in an oil bath heated to 100 ° C., heated for 10 minutes, and the surface of the solid material was surface-treated with an extremely stable perfluoroalkyl radical to produce a fluorinated sample.

(2) Test method and result The ampoule returned to room temperature was opened, the SUS sample piece was taken out, and the contact angle of the surface was measured. The contact angle of the substrate surface was measured at 4 points by placing 2 μl of distilled water on the substrate surface. The results were as follows. Contact angle of substrate surface: 65.5, 65.5, 62.0, 66.0 °; average value 64.8 °.

  The same experiment as in Example 1 was performed with a heating time of 30 minutes. The results were as follows. Contact angle of substrate surface: 76.0, 76.0, 76.5, 76.0 °; average value 76.1 °.

  The same experiment as in Example 1 was performed with a heating time of 1 hour. The results were as follows. Contact angle on substrate surface: 77.0, 78.0, 75.0, 77.0 °; average value 76.8 °.

  The same experiment as in Example 1 was performed with a heating time of 2 hours. The results were as follows. Contact angle on substrate surface: 85.0, 84.0, 86.0, 84.0 °; average value 84.8 °.

  The same experiment as in Example 1 was performed with a heating time of 3 hours. The results were as follows. Contact angle on substrate surface: 91.0, 87.5, 92.0, 88.0 °; average value 89.6 °.

(1) Production of fluorinated solid material SUS sample piece (DLC film thickness 500 nm, SUS plate thickness 1 mm, SUS plate size 8 × 8 mm) with a DLC film formed on its surface, perfluoro solvent (FC -72, 10 ml), an extremely stable radical perfluoro-2,4-dimethyl-3-ethyl-3-pentyl (0.12 mmole) was placed in an ampule (20 mmφ × 100 mm) made by Pyrex (registered trademark). The inside of the ampoule was subjected to freeze-and-thaw three times and replaced with argon, and then sealed under vacuum. The ampoule was immersed in an oil bath heated to 110 ° C., heated for 3 hours, and the surface of the solid material was surface-treated with a very stable perfluoroalkyl radical to produce a fluorinated sample.

(2) Test method and result The ampoule returned to room temperature was opened, the SUS sample piece was taken out, and the contact angle of the surface was measured. The contact angle of the substrate surface was measured at 4 points by placing 2 μl of distilled water on the substrate surface. The results were as follows. Contact angle of substrate surface: 79.0, 79.0, 80.5, 79.0 °; average value 79.4 °.

  An experiment similar to Example 6 was performed using the extremely stable radical perfluoro-2,4-dimethyl-3-ethyl-3-pentyl (0.24 mmole). The results were as follows. Contact angle on substrate surface: 85.0, 84.5, 84.5, 84.5 °; average value 84.6 °.

  An experiment similar to Example 6 was performed using the extremely stable radical perfluoro-2,4-dimethyl-3-ethyl-3-pentyl (0.48 mmole). The results were as follows. Contact angle on substrate surface: 87.0, 86.5, 87.0, 86.5 °; average value 86.8 °.

  An experiment similar to Example 6 was performed using the extremely stable radical perfluoro-2,4-dimethyl-3-ethyl-3-pentyl (0.96 mmole). The results were as follows. Contact angle of substrate surface: 89.3, 88.0, 90.5, 89.5 °; average value 89.3 °.

Control Experiment for Example 6-9 A control experiment was conducted in the experiment of Example 6 that did not include the perstable radical perfluoro-2,4-dimethyl-3-ethyl-3-pentyl. The results were as follows. Contact angle on substrate surface: 73.0, 70.0, 72.0, 72.0 °; average value 71.8 °.

ESCA measurement of the surface of the substrate fluorinated in Example 6 FIG. 1 shows the ESCA spectrum of the surface of the SUS sample piece obtained in the experiment of Example 6. Peaks derived from F1s, O1s, and C1s were observed at 688.5, 532.7, and 285.0 eV. The ratio calculated from each area is 3.56, 14.95, 81.49%, and it can be seen that under these conditions, the progress of fluorination is small. In addition, fluorination progressed by increasing the usage-amount of a very stable radical.

ESCA measurement of the surface of the substrate fluorinated in Example 8 FIG. 2 shows the ESCA spectrum of the surface of the SUS sample piece obtained in the experiment of Example 8. Peaks derived from F1s, O1s, and C1s were observed at 688.5, 532.7, and 285.0 eV. The ratio calculated from each area was 20.60, 10.40, 69.99%, and it was confirmed that fluorination was proceeding considerably. This indicates a result consistent with the fact that the contact angle of water on the surface of the base material of the sample has increased to a value almost equal to that of Teflon (registered trademark).

As described above in detail, the present invention according to the manufacturing how fluorinated solid material, the present invention, a variety of solid surfaces, regardless of its shape, very easily, and reproducibly, Can be fluorinated. Conventionally, the modification of solid surfaces has ranged from the leading edge of nanotechnology such as magnetic recording media, which plays a key role in the information industry, to biomaterials such as artificial bones, whose surface characteristics are important, and finally to the surface treatment of pachinko balls. However, in recent years, in addition to mechanical properties such as toughness, high functionality such as water repellency, wear resistance, chemical resistance, low friction properties, and non-adhesiveness is also required in recent years. In this wide range of applications, the method of the present invention is applied to the surface of a solid material substrate with a stable and easy-to-handle extremely stable perfluoroalkyl radical in the gas phase or liquid phase. By processing, regardless of the shape and complexity of the substrate to be processed, the surface can be homogeneously fluorinated, the process itself is safe, highly reproducible, and the perfluoro-based compound of the processing agent can be recycled. , With low emissions, there is no load on the environment. As described above, since the present invention is an environmentally friendly technology, various industrial applications are expected. In particular, the present invention is useful for enabling the creation of new industries in the field of nanotech industries where future development is expected. .

The ESCA spectrum of the surface-treated SUS sample piece surface is shown. The ESCA spectrum of the surface-treated SUS sample piece surface is shown.

Claims (3)

On the surface of a solid material substrate, a very stable perfluoroalkyl radical that reacts well with a perfluoro compound in a gas phase and / or a liquid phase and is extremely stable chemically and physically is reacted. producing advanced by that changing the contact angle of water facilities to the substrate surface fluorination process can be confirmed that the solid material imparted with water repellency and oil repellency to the substrate surface of the fluorinated by ESCA spectrum Te a method of manufacturing a solid material you,
1) A reaction in which a very stable perfluoroalkyl radical is dispersed or dissolved in a perfluoro compound, which is an inert medium, by applying heat from outside in a state where the solid material is suspended or submerged, is caused to react.
2) Put a very stable perfluoroalkyl radical and a solid material in a sealed container and react by applying heat, or
3) The heated solid material is reacted with the extremely stable perfluoroalkyl radical as it is or by spraying a solution in which this is dispersed or dissolved in a perfluoro compound,
A method for producing a solid material.   The extremely stable perfluoroalkyl radical is perfluoro-2,4-dimethyl-3-isopropyl-3-pentyl, perfluoro-2,4-dimethyl-3-ethyl-3-pentyl, or perfluoro-3-ethyl- The method for producing a solid material imparted with water repellency and oil repellency according to claim 1, which is 3,4-dimethyl-4-hexyl. A solid material is coated with a metal, a metal alloy composed of two or more components, an inorganic compound, or a material coated with these materials, an organic polymer, or an organic-inorganic composite thereof, or a material thereof. is either material, manufacturing method of the solid material according to claim 1 or 2.

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