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WO2024162361A1 - Film protecteur et procédé de production de celui-ci - Google Patents

Film protecteur et procédé de production de celui-ci Download PDF

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Publication number
WO2024162361A1
WO2024162361A1 PCT/JP2024/002949 JP2024002949W WO2024162361A1 WO 2024162361 A1 WO2024162361 A1 WO 2024162361A1 JP 2024002949 W JP2024002949 W JP 2024002949W WO 2024162361 A1 WO2024162361 A1 WO 2024162361A1
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Prior art keywords
oxide film
silicon oxide
protective film
interface
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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PCT/JP2024/002949
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English (en)
Japanese (ja)
Inventor
正規 本川
協 宮木
将俊 秋武
翔太郎 戸波
浩史 西野
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GL Sciences Inc
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GL Sciences Inc
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Publication of WO2024162361A1 publication Critical patent/WO2024162361A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material

Definitions

  • the present invention relates to a protective film and a method for manufacturing the same.
  • the present invention relates to a protective film for inside a pipe and a method for manufacturing the same.
  • Patent Document 1 abrasion-resistant coatings that are applied to substrates by decomposition of dimethylsilane
  • the present invention aims to provide a protective film that is resistant to sulfuric acid and a method for producing the same.
  • the protective film is An oxide film formed on the substrate and containing a metal element derived from the substrate,
  • the protective film used is characterized in that, when the interface between the substrate and the oxide film is defined as a first interface, in a region within the oxide film, the content of metal elements derived from the substrate shows a decreasing tendency starting from the first interface as the distance from the first interface increases, and the oxygen content within the oxide film is greater than the oxygen content at the first interface.
  • the protective film according to Invention 1 is used, characterized in that in the region within the oxide film, the content of all of the metal elements originating from the substrate and amounting to 1% by weight or more shows a decreasing tendency starting from the first interface as the distance from the first interface increases.
  • the protective film according to Invention 1 or 2 is used, characterized in that in the region within the oxide film, the content of all of the metal elements originating from the substrate and amounting to 1% by weight or more shows a decreasing tendency starting from the first interface as the distance from the first interface increases, and decreases to 50% or less of the content of the metal elements at the first interface.
  • ⁇ Invention 8> The protective film according to any one of Inventions 1 to 7 is used, characterized in that the content of metal elements derived from the base material shows a decreasing tendency from the first interface as the distance from the first interface increases, and the region in the oxide film in which the content of oxygen shows an increasing tendency from the first interface as the distance from the first interface increases is 5 nm or more away from the first interface.
  • the protective film according to any one of Inventions 1 to 8 is used, characterized in that a silicon oxide film is formed on the oxide film.
  • the protective film according to the present invention is characterized in that, when the interface between the silicon oxide film and the oxide coating is defined as a second interface, in a region within the oxide coating, the content of non-metallic elements derived from the silicon oxide film shows a decreasing tendency from the second interface as the distance from the second interface increases.
  • ⁇ Invention 12> The protective film according to the tenth or eleventh aspect of the present invention is used, characterized in that the nonmetallic element derived from the silicon oxide film contains silicon.
  • ⁇ Invention 13> The protective film according to any one of Inventions 9 to 12, characterized in that the carbon content in the silicon oxide film is 35 atomic % or more and 45 atomic % or less, is used.
  • ⁇ Invention 14> The protective film according to any one of Inventions 9 to 13 is used on the surface of the silicon oxide film, characterized in that a part of the alkyl group directly covalently bonded to the Si atom derived from the raw material of the silicon oxide film remains.
  • the protective film according to the seventeenth aspect of the present invention is used, characterized in that the functional coating is composed of a film produced by alkylsilylation of silanol groups on the SiO2 surface of the silicon oxide film.
  • the protective film according to any one of Inventions 1 to 18 is used, which is characterized in that the corrosion rate when immersed in a 25% aqueous solution of sulfuric acid is 1.0 g/m 2 /day or less.
  • ⁇ Invention 21> The protective film according to any one of Inventions 9 to 16, characterized in that the static contact angle with hexadecane is 39° or more, is used.
  • ⁇ Invention 22> The protective film according to any one of Inventions 9 to 16 is used, which has a peel strength of 1.83 N/25 mm or less in a 180° tape peel test.
  • ⁇ Invention 23> The protective film according to any one of Inventions 9 to 16 is used, which has a peel strength in a 180° tape peel test that is 0.414 times or less compared to the peel strength in a 180° tape peel test with polytetrafluoroethylene.
  • the method for manufacturing a protective film includes an oxide film forming process in which a metallic substrate is placed in a vacuum chamber and depressurized, the substrate is heated, oxygen and/or ozone is introduced into the vacuum chamber, and an oxide film is formed on the substrate surface, and a silicon oxide film forming process in which the substrate with the oxide film formed thereon is placed in a vacuum chamber and depressurized, the substrate is heated, a raw material gas and oxygen and/or ozone are introduced, and a silicon oxide film is formed on the oxide film.
  • the method for producing a protective film according to the twenty-fourth aspect of the present invention is used, which includes a removing step for removing the silicon oxide film.
  • the protective film of the present invention is resistant to sulfuric acid and can protect the substrate.
  • a protective film on the surface of a metal, particularly stainless steel by chemical vapor deposition (CVD), it is possible to improve corrosion resistance to sulfuric acid and the like.
  • CVD chemical vapor deposition
  • the protective film can be created on any surface of the substrate (for example, the inner surface of a tube) as long as it is within the range of the source gas.
  • the part on the substrate where the protective film is created will be referred to as the "surface" regardless of its three-dimensional positional relationship.
  • FIG. 1A is a cross-sectional view of a protective film according to an embodiment.
  • FIG. 1B is a cross-sectional view of an example in which a protective film according to an embodiment is provided inside a pipe.
  • FIG. 2 is a process flow diagram of an embodiment.
  • FIG. 3 is a cross-sectional view of a protective film of a comparative example.
  • FIG. 4A is a photograph of each of the joint parts of Example 1 and Comparative Example 1 at the time when they started to be immersed in a 25% aqueous sulfuric acid solution at room temperature (25° C.).
  • FIG. 4B is a photograph of each of the joint parts of Example 1 and Comparative Example 1 after immersion in a 25% aqueous sulfuric acid solution at room temperature (25° C.) for 72 hours.
  • FIG. 4C is a graph showing the degree of corrosion of each of the joint parts of Example 1 and Comparative Example 1 after immersion in a 25% aqueous sulfuric acid solution at room temperature (25° C.) for 72 hours.
  • FIG. 5A is a transmission electron microscope photograph of a cross section of a metal plate on which a protective film was formed in Example 2a.
  • FIG. 5B is a transmission electron microscope photograph showing an enlargement of FIG. 5A.
  • FIG. 5C is a transmission electron microscope photograph of a cross section of a metal plate on which a protective film was formed in Comparative Example 2.
  • FIG. 6A is a transmission electron microscope photograph of a cross section of a metal plate on which a protective film was formed in Example 2a.
  • FIG. 6B shows the distribution of each element in the cross section shown in FIG. 6A measured by energy dispersive X-ray spectroscopy.
  • FIG. 6C is a transmission electron microscope photograph of a cross section of a metal plate on which a protective film was formed in Comparative Example 2.
  • FIG. 6D shows the distribution of each element measured by energy dispersive X-ray spectroscopy on the cross section shown in FIG. 6C.
  • 1 shows the results of analyzing the surface of the protective film, i.e., the surface of the silicon oxide film, of the metal plate on which the protective film was formed in Example 2a, using a Fourier transform infrared spectrophotometer (FTIR).
  • FTIR Fourier transform infrared spectrophotometer
  • FIG. 8A is a photograph of an untreated metal plate, a metal plate with a protective film formed in Example 2a, and a metal plate with a protective film formed in Comparative Example 2, all at the time of immersion in a 25% aqueous sulfuric acid solution at room temperature (25° C.) for 72 hours.
  • FIG. 8B is a photograph of an untreated metal plate, a metal plate on which a protective film was formed in Example 2a, and a metal plate on which a protective film was formed in Comparative Example 2, which were immersed in a 25% aqueous sulfuric acid solution at 60° C. for 72 hours, and then each metal plate was taken out of the aqueous sulfuric acid solution.
  • FIG. 8A is a photograph of an untreated metal plate, a metal plate with a protective film formed in Example 2a, and a metal plate with a protective film formed in Comparative Example 2, all at the time of immersion in a 25% aqueous sulfuric acid solution at room temperature (25° C.) for 72 hours.
  • FIG. 9A is a photograph of an untreated metal plate before the salt water combined cycle test and a photograph of a metal plate on which a protective film had been formed in Example 3 (silicon oxide film 11 with a thickness of 40 nm).
  • FIG. 9B is a photograph of an untreated metal plate and a photograph of a metal plate on which a protective film had been formed in Example 3 (silicon oxide film 11 with a thickness of 40 nm) after the salt water combined cycle test.
  • FIG. 10 is a set of photographs showing the static contact angles of an untreated metal plate, a metal plate on which a protective film had been formed in Example 3, and a PTFE plate with ultrapure water and hexadecane, as well as the state of contact for each.
  • FIG. 11 (a) is a photograph of an untreated metal plate coated with a vinyl acetate adhesive and a photograph of the dried vinyl acetate adhesive peeled off.
  • Fig. 11 (b) is a photograph of a metal plate coated with a vinyl acetate adhesive and a photograph of the dried vinyl acetate adhesive peeled off, on which a protective film had been prepared in Example 3.
  • Fig. 11 (c) is a photograph of a metal plate coated with a vinyl acetate adhesive and heated at 400°C for 10 hours on which a protective film had been prepared in Example 3 and coated with a vinyl acetate adhesive and a photograph of the dried vinyl acetate adhesive peeled off.
  • Fig. 11 (c) is a photograph of a metal plate coated with a vinyl acetate adhesive and heated at 400°C for 10 hours on which a protective film had been prepared in Example 3 and coated with a vinyl acetate adhesive and a photograph of the dried vinyl acetate adhesive peeled off.
  • FIG. 12(a) is an overlay of five measured values (N/25 mm) from a 180° tape peel test on a metal plate on which a protective film had been prepared in Example 3.
  • Fig. 12(b) is an overlay of five measured values (N/25 mm) from a 180° tape peel test on a BPTFE plate.
  • Fig. 12(c) is an overlay of five measured values (N/25 mm) from a 180° tape peel test on an untreated metal plate.
  • FIG. 13A is a photograph of the inside of an untreated tube after combined saltwater cycling testing.
  • FIG. 13B is a photograph of the inside of the tube with the protective film formed in Example 4 after the salt water combined cycle test.
  • FIG. 14A is a photograph showing a state in which ultrapure water comes into contact with a metal plate on which an oxide film and a 75 nm silicon oxide film have already been formed.
  • FIG. 14B is a photograph showing the state in which ultrapure water comes into contact with a metal plate on which an oxide film and a 1000 nm silicon oxide film have already been formed.
  • FIG. 15A is a chromatogram collected using a column prepared using the column hardware having an oxide film, a silicon oxide film, and a functional film prepared in Example 6.
  • FIG. 15B is a chromatogram collected using a column prepared using the column hardware having an oxide film and a silicon oxide film prepared in Example 7.
  • FIG. 16 shows the distribution of each element measured by Auger electron spectroscopy on the inner surface of the tube on which the protective film was formed in Example 8.
  • FIG. 1A An embodiment of a protective film 100 is illustrated in FIG. 1A.
  • a protective film 100 is present on the surface of the substrate 13.
  • the protective film 100 is formed on the surface of the substrate 13.
  • the protective film 100 is formed in the following order from the surface of the substrate 13: oxide film 12, silicon oxide film 11, and functional film 10.
  • the silicon oxide film 11 and functional film 10 are not essential and are preferable.
  • the functional film 10 may be a different film depending on the application.
  • the interface between the substrate 13 and the oxide film 12 is referred to as a first interface 14.
  • the interface between the oxide film 12 and the silicon oxide film 11 is referred to as a second interface 15.
  • the substrate 13 is made of metal, particularly various stainless steels including SUS304, SUS316, and SUS316L, or titanium, and is a part or component of various shapes, such as a joint part, metal plate, column hardware, tube, pipe, or piping.
  • a protective film 100 is formed on the surface of the metal plate that is the substrate 13, or on the inner surface of the pipe that is the substrate 13, to protect the substrate 13.
  • Column hardware refers to the components of a separation column used in various types of chromatography other than the packed layer, and is a part that has a flow path through which the mobile phase containing the sample comes into contact with or passes. It refers to the components of a separation column that are composed of some or all of the following: column tube, filter, filter fixing part (end union), distribution plate, filter assembly, and filter insert assembly.
  • the substrate 13 can also be applied to other objects.
  • it can be a mold, a pipe for passing cooling water through the mold, a heat exchanger pipe, a heat exchanger fin, a waste liquid pipe, or metal parts used therein.
  • the substrate 13 is also a concept that includes joints of piping.
  • the protective film 100 may also be provided on the outside of the pipe and the back surface of the substrate 13. It is preferable to provide the protective film 100 on the entire surface of the substrate 13, the entire inner surface of the pipe, and all the joints of the piping.
  • the protective film 100 may be provided only on parts that are susceptible to corrosion, or the protective film 100 may be provided particularly thickly on parts that are susceptible to corrosion.
  • the oxide film 12 is a film that contains, as a metal oxide, a metal element derived from the base material 13. If the base material 13 contains at least one of chromium, iron, and nickel, the oxide film 12 is a film that contains at least one of chromium oxide, iron oxide, and nickel oxide.
  • the content of metal elements derived from the substrate 13 tends to decrease from the first interface 14 as the distance from the interface (first interface 14) between the substrate 13 and the oxide film 12 increases, and it is preferable that the oxygen content in the oxide film 12 is greater than the oxygen content at the first interface 14.
  • a downward trend refers to a state in which the value is decreasing overall.
  • a partial increase is also included in the downward trend. However, if a partial increase in value exceeds 120% of the value at the starting point of the downward trend, it is not included in the downward trend.
  • An increasing trend refers to an overall increase.
  • a partial decrease is also included in the increasing trend. However, if a partial decrease in a value causes it to fall below the starting point of the increasing trend, it is not included in the increasing trend.
  • the content of metal elements derived from the substrate 13 tends to decrease from the first interface 14 as the distance from the interface (first interface 14) between the substrate 13 and the oxide coating 12 increases, and that the content of oxygen tends to increase from the first interface 14 as the distance from the first interface 14 increases.
  • the oxide film 12 is a film that contains metal elements derived from the substrate 13 as metal oxides, and it is preferable that the metal elements derived from the substrate 13 contain at least one of chromium, iron, and nickel.
  • the oxide film 12 contains at least one of the oxides of chromium, iron, and nickel, which are the main components of stainless steel, thereby making it possible to produce a more resistant oxide film 12, and as shown in Example 3, the oxide film 12 becomes more resistant to an aqueous sulfuric acid solution.
  • the oxide film 12 has a thickness of 5 nm or more. This is because, in the production of the oxide film 12, the chemical vapor deposition (CVD) method used in the present embodiment allows the oxide film 12 to be produced with good reproducibility even when the reaction is carried out for a short time of 0.5 minutes. Furthermore, it is preferable that the thickness of the oxide film 12 is 5 nm or more and 100 nm or less. This is because, in the chemical vapor deposition (CVD) method used in the present embodiment, it is difficult to produce an oxide film 12 with a thickness exceeding 100 nm. Note that, if the thickness is 5 nm or more and 30 nm or less, a more stable and homogeneous film can be obtained.
  • the oxide coating 12 preferably has a region in which the content of metal elements derived from the substrate 13 tends to decrease with increasing distance from the interface (first interface 14) between the substrate 13 and the oxide coating 12, and in which the content of oxygen tends to increase with increasing distance from the first interface 14, the region is at a distance of 5 nm or more from the first interface 14.
  • a gradual composition change occurs over a distance of 5 nm or more from an oxide having a higher proportion of metal elements derived from the substrate 13 and a lower proportion of oxygen to an oxide having a lower proportion of metal elements derived from the substrate 13 and a higher proportion of oxygen.
  • the metal element derived from the base material 13 is a metal element that is a main component of the base material 13 and is contained in the base material 13 at 1 wt % or more.
  • the silicon oxide film 11 is a SiO2 -based film formed on the oxide coating 12 using, for example, alkoxysilane as a raw material. It is preferable that the silicon oxide film contains carbon. This will be described in detail below.
  • the silicon oxide film 11 By producing the silicon oxide film 11, it is preferable that in the region within the oxide film 12, as the distance from the interface (second interface 15) between the silicon oxide film 11 and the oxide film 12 increases, the content of non-metallic elements derived from the silicon oxide film 11 tends to decrease from the second interface 15 as the distance increases. As the distance from within the silicon oxide film 11 to within the oxide film 12 increases, the non-metallic elements derived from the silicon oxide film 11 penetrate into the oxide film 12 with a gradual change in their ratio, making the silicon oxide film 11 less likely to peel off from the oxide film 12, and the silicon oxide film 11 and the oxide film 12 are more firmly bonded, thereby increasing the resistance of the silicon oxide film 11.
  • the nonmetallic elements originating from the silicon oxide film 11 are the main components of the silicon oxide film 11 and are nonmetallic elements contained in the silicon oxide film 11 at a concentration of 1% by weight or more. For example, they include silicon (Si), oxygen (O), carbon (C), and hydrogen (H). In the region within the oxide film 12, all of these nonmetallic elements may tend to decrease starting from the second interface 15.
  • the silicon oxide film 11 it is preferable that in the region within the oxide film 12, as the distance from the interface (second interface 15) between the silicon oxide film 11 and the oxide film 12 increases, the content of silicon (Si) originating from the silicon oxide film 11 tends to decrease from the second interface 15 as the starting point. As the distance from within the silicon oxide film 11 to within the oxide film 12 increases, the silicon originating from the silicon oxide film 11 penetrates into the oxide film 12 with a gradual change in its ratio. As a result, the silicon oxide film 11 becomes less likely to peel off from the oxide film 12, the silicon oxide film 11 and the oxide film 12 are more firmly bonded, and the resistance of the silicon oxide film 11 becomes higher as shown in Examples 1, 2, and 3.
  • the carbon content in silicon oxide film 11 is preferably 35 atomic % or more and 45 atomic % or less. As shown in Example 3, the carbon content in silicon oxide film 11 greatly contributes to the water repellency and oil repellency being close to that of polytetrafluoroethylene (PTFE), sufficient releasability being evaluated using a vinyl acetate adhesive, and releasability exceeding that of PTFE being evaluated using tape.
  • PTFE polytetrafluoroethylene
  • the carbon in the silicon oxide film 11 is 35 atomic % or more and 45 atomic % or less
  • the silicon in the silicon oxide film 11 is 21 atomic % or more and 31 atomic % or less
  • the oxygen in the silicon oxide film 11 is 28 atomic % or more and 38 atomic % or less.
  • this is because it is possible to impart performance close to that of polytetrafluoroethylene (PTFE) in terms of water repellency and oil repellency, and it is possible to impart sufficient release properties evaluated using a vinyl acetate adhesive, and it is possible to impart release properties that exceed those of PTFE evaluated using a tape.
  • PTFE polytetrafluoroethylene
  • SiO2 in the silicon oxide film 11 is 17% or more and 27% or less, and SiOxCy+SiOx (x ⁇ 2) in the silicon oxide film 11 is 73% or more and 83% or less.
  • PTFE polytetrafluoroethylene
  • the alkyl groups directly covalently bonded to the Si atoms which originate from the raw material of the silicon oxide film 11, remain on the surface of the silicon oxide film 11.
  • the alkyl group is less likely to be detached from the silicon oxide film 11, and as shown in Example 3, the water repellency and oil repellency can be made to be close to that of polytetrafluoroethylene (PTFE), and sufficient releasability can be obtained as evaluated using a vinyl acetate adhesive, and releasability exceeding that of PTFE as evaluated using a tape can be obtained, and these properties can be maintained for a long time.
  • PTFE polytetrafluoroethylene
  • the amount of silanol groups on the SiO2 surface of the silicon oxide film 11 is reduced, thereby reducing non-specific adsorption of compounds having a base through metal coordination, and it is possible to fabricate column hardware that can maintain a peak shape sufficient for qualitative and quantitative analysis in chromatography of compounds having a base through metal coordination.
  • the thickness of the silicon oxide film 11 is preferably 10 nm or more and 1000 nm or less.
  • a silicon oxide film 11 having a thickness of 10 nm or more can suppress corrosion of a SUS316 substrate caused by a 25% sulfuric acid aqueous solution at 25°C.
  • a silicon oxide film 11 having a thickness of 10 nm or more can impart water repellency to a SUS304 substrate with a static contact angle of 100° with ultrapure water, and a silicon oxide film 11 having high resistance to aqueous solutions can be produced.
  • a silicon oxide film 11 having a thickness of more than 1000 nm is more likely to crack and its quality deteriorates.
  • the thickness of the silicon oxide film 11 is preferably 40 nm or more and 1000 nm or less. As shown in Example 3, a silicon oxide film 11 having a thickness of 40 nm or more can contribute to the resistance of the SUS304 substrate to an aqueous sulfuric acid solution and to salt water, and a silicon oxide film 11 having high resistance to aqueous solutions can be produced. A silicon oxide film 11 having a thickness of more than 1000 nm is prone to cracking and has a reduced quality.
  • the functional coating 10 is a film that performs functions according to the purpose of use. Examples include an anti-soiling film that makes it difficult for dirt and fingerprints to stick, and an infrared filter that transmits and blocks infrared rays that are invisible to the human eye for security purposes.
  • the functional coating 10 is a functional thin film such as a high color rendering filter that illuminates objects with more natural light in LED lighting. If the only purpose is to protect the substrate 13 from chemical solvents and gases, the functional coating 10 may not be necessary.
  • the functional coating 10 can be made of Ni--Cr, TaN, Ta--Si, Ta--Al, TiN as a resistive element, SiO, SiO 2 , Ta 2 O 5 , Al 2 O 3 as a capacitor, Fe, Ni, Co--Cr, Fe--Si--Al, Ni--Fe--Mo, Mn--Zn, Ni--Zn as a magnetic functional film, ITO, SnO 2 , GZO, AZO as a transparent conductive film, Al, Cu, W, Ti, TiN, polycrystalline Si as metal wiring, and PbTiO 3 , PZT, SrTiO 3 , (Ba, Sr)TiO 3 as a ferroelectric. Therefore, the oxide coating 12 and silicon oxide film 11 of the embodiment are also used as protective films for stably forming the functional coating 10 on the substrate 13.
  • the functional coating 10 may also be formed of a film produced by alkylsilylation of silanol groups on the SiO 2 surface of the silicon oxide film 11 .
  • the protective film 100 can be formed uniformly not only on the surface of a planar substrate 13, but also on the surface of a substrate 13 having a three-dimensional complex structure.
  • the protective film 100 can be formed inside a pipe 300.
  • the pipe 300 include pipes for passing various cooling waters, pipes for passing chemical solutions, pipes for passing waste liquids, pipes for use in analytical instruments such as various chromatographs, and column hardware for use in various chromatographs.
  • the protective film 100 without gaps on the surfaces of pipes and column hardware for use in various chromatographs, and on the surfaces of their joints, the peak shape of the analysis target component can be improved, and the qualitative and quantitative analysis of trace amounts of the analysis target component can be performed.
  • Example 3 when the protective film 100 formed on the surface of the substrate 13 made of SUS304 consists only of the oxide film 12, and when the protective film 100 formed on the surface of the substrate 13 consists of the oxide film 12 and the silicon oxide film 11 (film thickness 40 nm), the substrate 13 is hardly corroded even when immersed in a 25% aqueous sulfuric acid solution at 60° C.
  • the protective film 100 formed on the surface of the substrate 13 made of SUS316 consists of the oxide film 12 and the silicon oxide film 11 (film thickness 10 nm)
  • the substrate 13 is hardly corroded even when immersed in a 25% aqueous sulfuric acid solution at 25° C.
  • the corrosion rate when immersed in the 25% aqueous solution is 1.0 g/m 2 /day or less, and preferably 0.11 g/m 2 /day or less.
  • the static contact angle with ultrapure water is 100° or more when the thickness of the silicon oxide film 11 is 10 nm or more, and the static contact angle with ultrapure water increases as the thickness of the silicon oxide film increases.
  • the carbon content in the silicon oxide film 11 being 35 atomic% or more and 45 atomic% or less contributes greatly to the static contact angle with ultrapure water being 100° or more. If the static contact angle of the protective film 100 with ultrapure water is 90° or more, the protective film 100 has water repellency and the substrate 13 has high resistance to aqueous solutions. It is more preferable that the static contact angle of the protective film 100 with ultrapure water is 100° or more.
  • the silicon oxide film 11 has a thickness of 40 nm or more and a static contact angle with hexadecane of 39° or more.
  • the carbon content in the silicon oxide film 11 being 35 atomic% or more and 45 atomic% or less contributes greatly to the static contact angle with hexadecane being 39° or more.
  • the static contact angle of the protective film 100 with hexadecane is 39° or more, and the protective film 100 has oil repellency equivalent to that of PTFE, and the substrate 13 has high resistance to solutions containing organic solvents.
  • the thickness of the silicon oxide film 11 is 40 nm or more, and the peel force in the 180° tape peel test is 1.83 N/25 mm or less.
  • the carbon content in the silicon oxide film 11 being 35 atomic % or more and 45 atomic % or less contributes greatly to the peel force being 1.83 N/25 mm or less in the 180° tape peel test. If the peel force of the protective film 100 in the 180° tape peel test is 1.83 N/25 mm or less, the antifouling properties of the substrate 13 can be improved.
  • the thickness of the silicon oxide film 11 is 40 nm or more, and the peel strength in the 180° tape peel test is 0.414 times or less than the peel strength in the 180° tape peel test with polytetrafluoroethylene.
  • the carbon content in the silicon oxide film 11 being 35 atomic% or more and 45 atomic% or less contributes greatly to the peel strength in the 180° tape peel test being 0.414 times or less than the peel strength in the 180° tape peel test with polytetrafluoroethylene. If the peel strength in the 180° tape peel test of the protective film 100 is 0.414 times or less than the peel strength in the 180° tape peel test with polytetrafluoroethylene, the antifouling properties of the substrate 13 can be improved.
  • ⁇ Production Method> 2 shows a process flow of the method for producing the protective film 100.
  • an oxide film 12 is produced on the surface of the substrate 13.
  • a silicon oxide film 11 is produced on the surface of the oxide film 12.
  • a functional film 10 is produced on the surface of the silicon oxide film 11.
  • the protective film 100 may be composed of only the oxide film 12, or the protective film 100 may be composed of the oxide film 12 and the silicon oxide film 11 by producing the silicon oxide film 11 on the surface of the oxide film 12, or the protective film 100 may be composed of the oxide film 12 and the silicon oxide film 11 by producing the silicon oxide film 11 on the surface of the oxide film 12 and the functional film 10 on the surface of the silicon oxide film 11, and the protective film 10 may be composed of the oxide film 12, the silicon oxide film 11, and the functional film 10.
  • Steps 1-2, 1-3, and 1-4 may be repeated to obtain a desired thickness of the oxide film 12.
  • the surface of the base material 13 may be cleaned to remove any oxide film that has already formed naturally.
  • Silicon Oxide Film 11 2-1
  • the substrate 13 on which the oxide film 12 has been formed is placed in a vacuum chamber, the pressure is reduced, and the substrate 13 is heated to a degree of vacuum of 0.1 kPa abs or less and a temperature of 250° C. or more and 400° C. or less.
  • Gas for producing the silicon oxide film 11 is introduced as a source gas.
  • a gas in which alkoxysilane is diluted with nitrogen gas is introduced.
  • the absolute amount of the source gas and the concentration of the source gas are adjusted according to the desired thickness of the silicon oxide film 11.
  • 2-3 Oxygen and/or ozone are added as the raw material gas.
  • the concentration is 1 g/ m3 or more and 300 g/ m3 or less.
  • Steps 2-2, 2-3, 2-4, and 2-5 may be repeated to obtain a desired thickness of the silicon oxide film 11.
  • step 2-5 the degree of vacuum in the vacuum chamber becomes high, so the degree of vacuum in the vacuum chamber is lowered by step 2-5.
  • step 2-5 it is possible to repeatedly produce and stack silicon oxide films by returning to step 2-2 after step 2-5, such as 2-5 ⁇ 2-2, 2-3, 2-4, 2-5 ⁇ 2-2, 2-3, ....
  • R 1 O-Si-R 2 groups are bonded to silanol groups (Si-OH) on the surface of silicon oxide film 11 to form Si-O-Si-R 2 , thereby reducing the number of silanol groups on the surface of silicon oxide film 11 and making the surface of functional coating 10 R 2. Due to this effect, as shown in Examples 7 and 6, a column produced using liquid chromatography column hardware produced with oxide film 12, silicon oxide film 11, and functional coating 10 can obtain a peak with better symmetry in the analysis of a compound having a base through metal coordination, compared to a column produced using liquid chromatography column hardware produced with oxide film 12 and silicon oxide film 11.
  • the functional coating 10 in this case is a film for reducing silanol groups from the surface of the protective film 100.
  • the functional coating 10 is a functional coating for reducing silanol groups from the surface of the protective film 100 and increasing hydrocarbon groups on the surface of the protective film 100.
  • step 2-1 can be omitted and steps 1-1 to 2-6 can be carried out.
  • steps 2-1 and 3-1 can be omitted and steps 1-1 to 3-5 can be carried out.
  • the oxide film 12, silicon oxide film 11, and functional film 10 are preferably produced by chemical vapor deposition (CVD). This is because chemical vapor deposition (CVD) can produce the oxide film 12, silicon oxide film 11, and functional film 10 not only on the flat surface of the substrate 13, but also on surfaces with complex three-dimensional shapes and on the inner surface of a tube.
  • CVD chemical vapor deposition
  • the oxide film 12, silicon oxide film 11, and functional film 10 can be produced on the inner surface of the tube with a length of 5 m or less if the inner diameter is 0.8 mm or more.
  • the oxide film 12, silicon oxide film 11, and functional film 10 can be produced on the inner surface of the tube with a length of 1 m or less if the inner diameter is 0.1 mm to 0.5 mm.
  • the silicon oxide film 11 and functional film 10 may be produced by other vapor deposition methods or liquid phase reaction methods.
  • the silicon oxide film 11 may be composed of 100 mass % SiO2 , but may also be composed of SiO2 and unavoidable impurities and other components.
  • the silicon oxide film 11 is produced by contacting the raw material for producing SiO2 with the oxide layer 12 and processing it, and therefore may contain components other than SiO2 depending on the reaction conditions, etc. Therefore, the silicon oxide film 11 can be said to be a silicon oxide film 11 containing SiO2 .
  • the silicon oxide film 11 contains components other than SiO2 , it is sufficient as long as it can cover the oxide film 12.
  • the silicon oxide film 11 may be composed of one layer of the first layer composed of one kind of raw material, or may be composed of one layer of the first layer composed of two or more kinds of raw materials. Also, the silicon oxide film 11 may be composed of multiple layers by stacking one or more silicon oxide films 11 composed of one or more raw materials different from the above-mentioned raw materials on the surface of the silicon oxide film 11 composed of one or more raw materials. When the silicon oxide film 11 is constructed by stacking multiple layers in this way, it is preferable that the top layer which becomes the surface of the silicon oxide film 11 is a film made from one or more raw materials selected from alkyltrialkoxysilane and dialkyldialkoxysilane.
  • the top layer which becomes the surface of the silicon oxide film 11 is a film made from dimethyldiethoxysilane as a raw material.
  • Dimethyldiethoxysilane has two ethoxy groups in a molecule, so that a film mainly composed of SiO2 can be easily produced by dealcoholization condensation between a plurality of molecules, and since dimethyldiethoxysilane has two methyl groups directly covalently bonded to the Si atom in the molecule, some of the methyl groups directly covalently bonded to the Si atom derived from the raw material tend to remain on the surface of the silicon oxide film 11. Also, when the alkyl group directly covalently bonded to the Si atom in the raw material molecule is a small methyl group, it is easier to produce a film mainly composed of SiO2 with less steric hindrance.
  • the raw material for producing the silicon oxide film 11 is not particularly limited as long as it can produce a film containing SiO 2 on the oxide film 12 by oxidation and heating, but one or more selected from inorganic polysilazane, tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, trimethylmonoalkoxysilane, ethyltrialkoxysilane, diethyldialkoxysilane, triethylmonoalkoxysilane, propyltrialkoxysilane, dipropyldialkoxysilane, tripropylmonoalkoxysilane, dimethyl-type cyclic siloxane including hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane, diethyl-type cyclic siloxane, dipropyl-type cyclic siloxane, hexamethyldisiloxane, linear poly
  • the inorganic polysilazane is not particularly limited, but perhydropolysilazane can be used.
  • the tetraalkoxysilane is not particularly limited, but tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane can be used.
  • the ethoxy group has a higher reactivity in dealcoholization condensation than the propoxy group, and the methoxy group has a higher reactivity in dealcoholization condensation than the ethoxy group. The higher the reactivity in dealcoholization condensation, the easier it is to prepare the silicon oxide film 11, and the thicker it can be if the preparation conditions are the same.
  • tetraethoxysilane is preferable to tetrapropoxysilane, and tetramethoxysilane is preferable to tetraethoxysilane.
  • tetraethoxysilane which has ethanol as a by-product, is preferable.
  • the methyltrialkoxysilane is not particularly limited, but methyltrimethoxysilane, methyltriethoxysilane, and methyltrippropoxysilane can be used.
  • the ethoxy group has a higher reactivity in dealcoholization condensation than the propoxy group, and the methoxy group has a higher reactivity in dealcoholization condensation than the ethoxy group.
  • the higher the reactivity in dealcoholization condensation the easier it is to fabricate the silicon oxide film 11. Under the same fabrication conditions, the film can be made thicker, so methyltriethoxysilane is preferable to methyltrippropoxysilane, and methyltrimethoxysilane is preferable to methyltriethoxysilane.
  • methyltriethoxysilane which has ethanol as a by-product, is preferred.
  • Dimethyl dialkoxysilane is not particularly limited, but dimethyl dimethoxysilane, dimethyl diethoxysilane, and dimethyl dipropoxysilane can be used. Ethoxy groups have a higher reactivity in dealcoholization condensation than propoxy groups, and methoxy groups have a higher reactivity in dealcoholization condensation than ethoxy groups. The higher the reactivity in dealcoholization condensation, the easier it is to prepare the silicon oxide film 11, and the thicker it can be made under the same preparation conditions. Therefore, dimethyl diethoxysilane is preferable to dimethyl dipropoxysilane, and dimethyl dimethoxysilane is preferable to dimethyl diethoxysilane. On the other hand, considering the toxicity of alcohol, which is a by-product of dealcoholization condensation, dimethyl diethoxysilane, which has ethanol as a by-product, is preferable.
  • the trimethylmonoalkoxysilane is not particularly limited, but trimethylmethoxysilane, trimethylethoxysilane, and trimethylpropoxysilane can be used.
  • the ethoxy group has a higher reactivity in dealcoholization condensation than the propoxy group, and the methoxy group has a higher reactivity in dealcoholization condensation than the ethoxy group.
  • the higher the reactivity in dealcoholization condensation the easier it is to prepare the silicon oxide film 11, and the thicker it can be made under the same preparation conditions. Therefore, trimethylethoxysilane is preferable to trimethylpropoxysilane, and trimethylmethoxysilane is preferable to trimethylethoxysilane.
  • trimethylethoxysilane which has ethanol as a by-product, is preferable.
  • Tetraalkoxysilane, methyltrialkoxysilane, and dimethyldialkoxysilane have multiple alkoxy groups, so that a film mainly composed of SiO 2 can be easily produced by dealcoholization condensation between multiple molecules. From this viewpoint, therefore, it is easier to produce a film mainly composed of SiO 2 in the order of tetraalkoxysilane, methyltrialkoxysilane, and dimethyldialkoxysilane.
  • methyltrialkoxysilane and dimethyldialkoxysilane which have multiple alkoxy groups in the molecule and also have a methyl group in the molecule, are preferred for dealcoholization condensation between multiple molecules.
  • Methyltriethoxysilane and dimethyldiethoxysilane are preferred because they tend to leave some of the methyl groups that are directly covalently bonded to the Si atoms on the surface of the silicon oxide film 11, which is derived from the raw material.
  • the raw material In producing the silicon oxide film 11, in order to bring the raw material into contact with the surface of the oxide film 12 on the substrate 13, the raw material may be diluted with a solvent and applied, or the raw material may be diluted with an inert gas and diffused.
  • the silicon oxide film 11 may be produced by applying or diffusing the raw material in air, in an inert atmosphere, or in a vacuum, contacting the surface of the oxide film 12 on the substrate 13, and then oxidizing and condensing with oxygen in the air by heating only in the air.
  • oxidation and condensation may be performed by supplying oxygen and/or ozone and heating in air, in an inert atmosphere, or in a vacuum.
  • heating in air it is preferable to heat at 250°C or higher in air for 0.5 minutes or more, since this can promote the production of the silicon oxide film 11 by the condensation reaction.
  • the silicon oxide film 11 can be produced by applying or diffusing the raw material in air, an inert atmosphere, or a vacuum to contact the surface of the oxide film 12 on the substrate 13, and then oxidizing and condensing the raw material by supplying oxygen and/or ozone and heating in air, an inert atmosphere, or a vacuum.
  • the silicon oxide film 11 can be produced by applying or diffusing the raw material in air, an inert atmosphere, or a vacuum to contact the surface of the oxide film 12 on the substrate 13, and then oxidizing and condensing the raw material by supplying oxygen and/or ozone and heating in air, an inert atmosphere, or a vacuum.
  • the silicon oxide film 11 can be produced by applying or diffusing the raw material in air, an inert atmosphere, or a vacuum to contact the surface of the oxide film 12 on the substrate 13, and then oxidizing and condensing the raw material by supplying oxygen and/or ozone and heating in air, an inert atmosphere, or a vacuum.
  • the silicon oxide film 11 is preferably produced by diffusing the raw material in a vacuum of 0.1 kPa abs or less, bringing it into contact with the surface of the oxide film 12 on the substrate 13, and repeating the process of oxidation with oxygen and/or ozone and heating to 250°C to 400°C for 0.5 minutes in a vacuum of 0.1 kPa abs or less 10 or more times. This is because the silicon oxide film 11 can be produced under conditions that do not include an absolute vacuum by using this method, and also because the production of the silicon oxide film 11 by the condensation reaction can be promoted by performing oxidation with oxygen and/or ozone and heating to 250°C to 400°C.
  • the raw material when the raw material has a methyl group directly covalently bonded to the silicon atom, such as methyltrialkoxysilane, dimethyldialkoxysilane, or trimethylmonoalkoxysilane, the raw material is diffused in a vacuum of 0.1 kPa abs or less to contact the surface of oxide film 12, and oxidation with oxygen and/or ozone and heating to 250°C to 400°C for 0.5 minutes are repeated 30 times or more to produce silicon oxide film 11.
  • a methyl group directly covalently bonded to the silicon atom such as methyltrialkoxysilane, dimethyldialkoxysilane, or trimethylmonoalkoxysilane
  • a filter with a thickness of 1 mm and a pore size of 0.5 ⁇ m or less can be used. Even with a filter with a very small pore size like this, it is possible to create a silicon oxide film 11 with the desired performance by repeating oxidation and heating for 0.5 minutes 30 times or more.
  • a filter fixing part (end union) with a flow path with the smallest inner diameter that can be internally processed can be used.
  • the flow path in the filter fixing part can be oxidized and heated for 0.5 minutes 30 times or more to create a silicon oxide film 11 to obtain the desired performance.
  • the functional coating 10 is composed of a film produced by alkylsilylation of silanol groups on the SiO 2 surface of the silicon oxide film 11.
  • this functional coating 10 reduces the amount of silanol groups on the SiO 2 surface of the silicon oxide film 11, and reduces non-specific adsorption of compounds having a base in a metal coordination manner. Therefore, it is possible to produce column hardware and piping that can maintain a peak shape sufficient for qualitative and quantitative analysis in chromatography of compounds having a base in a metal coordination manner.
  • the functional coating 10 is produced by alkylsilylating the silanol groups on the SiO 2 surface of the silicon oxide film 11, and therefore, depending on the reaction conditions, etc., some silanol groups may remain.
  • the raw material for producing the functional coating 10 is not particularly limited as long as it can be alkylsilylated by a condensation reaction caused by heating the silanol groups on the SiO2 surface of the silicon oxide film 11 with the raw material.
  • CVD chemical vapor deposition method
  • the by-products of the condensation are not highly dangerous acids or bases such as hydrogen halides, ammonia, and imidazole
  • alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkylmonoalkoxysilane the shorter the alkyl group in the raw material molecule, the less steric hindrance there is in the silanol groups on the SiO2 surface of the silicon oxide film 11, and the higher the coverage of alkylsilylation, so methyltrialkoxysilane, dimethyldialkoxysilane, and trimethylmonoalkoxysilane are most preferred, followed by ethyltrialkoxysilane, diethyldialkoxysilane, and triethylmonoalkoxysilane.
  • the methyltrialkoxysilane is not particularly limited, but methyltrimethoxysilane, methyltriethoxysilane, and methyltrippropoxysilane can be used.
  • the ethoxy group has a higher reactivity in dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the propoxy group, and the methoxy group has a higher reactivity in dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the ethoxy group.
  • the higher the reactivity in dealcoholization condensation the easier it is to prepare the functional coating 10, and the coverage of the silicon oxide film 11 can be increased.
  • methyltrippropoxysilane requires the most energy for the dealcoholization condensation reaction, so methyltriethoxysilane is preferable to methyltrippropoxysilane, and methyltrimethoxysilane is preferable to methyltriethoxysilane.
  • methyltriethoxysilane which has ethanol as a by-product, is preferable.
  • the ethyltrialkoxysilane is not particularly limited, but ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltrippropoxysilane can be used.
  • the ethoxy group has a higher reactivity in dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the propoxy group, and the methoxy group has a higher reactivity in dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the ethoxy group.
  • the higher the reactivity in dealcoholization condensation the easier it is to prepare the functional coating 10, and the coverage of the silicon oxide film 11 can be increased.
  • ethyltrippropoxysilane requires the most energy for reaction, so ethyltriethoxysilane is preferable to ethyltrippropoxysilane, and ethyltrimethoxysilane is preferable to ethyltriethoxysilane.
  • ethyltriethoxysilane which has ethanol as a by-product, is preferable.
  • the dimethyl dialkoxysilane is not particularly limited, but dimethyl dimethoxy silane, dimethyl diethoxy silane, and dimethyl dipropoxy silane can be used.
  • the ethoxy group has a higher reactivity in dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the propoxy group, and the methoxy group has a higher reactivity in dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the ethoxy group.
  • dimethyl diethoxy silane is preferable to dimethyl dipropoxy silane, and dimethyl dimethoxy silane is preferable to dimethyl diethoxy silane.
  • dimethyl diethoxy silane which has ethanol as a by-product, is preferable.
  • the diethyl dialkoxysilane is not particularly limited, but diethyl dimethoxysilane, diethyl diethoxysilane, and diethyl dipropoxysilane can be used.
  • the ethoxy group has a higher reactivity of dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the propoxy group, and the methoxy group has a higher reactivity of dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the ethoxy group.
  • diethyl diethoxysilane is preferable to diethyl dipropoxysilane, and diethyl dimethoxysilane is preferable to diethyl diethoxysilane.
  • diethyl diethoxysilane which has ethanol as a by-product, is preferable.
  • the trimethylmonoalkoxysilane is not particularly limited, but trimethylmethoxysilane, trimethylethoxysilane, and trimethylpropoxysilane can be used.
  • the ethoxy group has a higher reactivity in dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the propoxy group, and the methoxy group has a higher reactivity in dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the ethoxy group.
  • trimethylethoxysilane is preferable to trimethylpropoxysilane, and trimethylmethoxysilane is preferable to trimethylethoxysilane.
  • trimethylethoxysilane which has ethanol as a by-product, is preferable.
  • the triethylmonoalkoxysilane is not particularly limited, but triethylmethoxysilane, triethylethoxysilane, and triethylpropoxysilane can be used.
  • the ethoxy group has a higher reactivity of dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the propoxy group, and the methoxy group has a higher reactivity of dealcoholization condensation with the silanol group on the SiO 2 surface of the silicon oxide film 11 than the ethoxy group.
  • triethylethoxysilane is preferable to triethylpropoxysilane, and triethylmethoxysilane is preferable to triethylethoxysilane.
  • triethylethoxysilane which has ethanol as a by-product, is preferable.
  • Dimethyldiethoxysilane and trimethylethoxysilane are preferred because they can increase the bonding density of the functional coating 10.
  • the functional coating 10 can be produced by applying or diffusing a raw material in air, an inert atmosphere, or a vacuum, bringing it into contact with the surface of the silicon oxide film 11, and then heating it in an inert atmosphere or a vacuum, but it is preferable to diffuse the raw material in a vacuum, bring it into contact with the surface of the silicon oxide film 11, and then heat it in a vacuum. This is because such a method increases the probability that the raw material will come into contact with the surface of the silicon oxide film 11, and can promote the production of the functional coating 10 by a condensation reaction.
  • the functional coating 10 by diffusing the raw material in a vacuum of 0.1 kPa abs or less, bringing it into contact with the surface of the silicon oxide film 11, and heating at 250°C to 400°C for 0.5 minutes or more in a vacuum of 0.1 kPa abs or less.
  • the functional coating 10 can be manufactured under conditions that do not include an absolute vacuum, and the manufacturing of the functional coating 10 by condensation reaction can be promoted by heating at 250°C to 400°C or less.
  • the dehydration condensation of the silanol groups on the surface of the silicon oxide film 11 can be promoted.
  • the protective film 100 of this embodiment will be described below by comparing an example with a comparative example.
  • Example 1a the substrate 13 was a joint part (reducer 1/8" to 1/16") made of SUS316, and an oxide film 12 and a silicon oxide film 11 were formed as a protective film 100 on the joint part made of SUS316.
  • An oxide film 12 was formed on a joint part made of SUS316.
  • the SUS316 joint parts were placed in a vacuum chamber, depressurized to 0.05 kPa abs, and heated to 300° C. 1 L of ozone gas with a concentration of 20 g/m 3 was added as a raw material gas and reacted for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased by the above operation, was depressurized to 0.1 kPa abs.
  • a silicon oxide film 11 was formed. Following the above step 1, the joint part on which the oxide film 12 had been formed was heated to 300°C in a vacuum chamber. As the raw material gas, a gas in which 5.0 g of dimethyldiethoxysilane was diluted with nitrogen gas was added, followed by 1 L of ozone gas with a concentration of 20 g/ m3 , and the reaction was allowed to proceed for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased due to the above operation, was depressurized to 1.5 kPa abs.
  • an oxide film 12 and a silicon oxide film 11 were formed as a protective film 100 on a substrate 13 as Example 1b using a joint part made of SUS316.
  • the thickness of the silicon oxide film 11 formed on the joint part of Example 1a was 12 nm.
  • the thickness of the silicon oxide film 11 formed on the joint part of Example 1b was 10 nm.
  • the conditions for forming the protective film 100 are the same in Example 1a and Example 1b, and the difference in thickness of the silicon oxide film 11 is due to variation.
  • the substrate 23 was a SUS316 joint part (reducer 1/8" to 1/16"), and Company A produced an oxide film 22 and an amorphous silicon film 21 as a protective film 200 on the SUS316 joint part.
  • the detailed structure of the protective film 200 is the same as the protective film 200 in Comparative Example 2. Based on the film quality, shape, etc., the protective films 200 in Comparative Examples 1 and 2 are thought to be protective films produced by chemical vapor deposition, similar to the protective film 100 in the embodiment of the present application.
  • FIG. 4A shows a photograph of each joint part at the time when it started to be immersed in a 25% sulfuric acid aqueous solution at room temperature (25 ° C.).
  • FIG. 4B shows a photograph of each joint part at the time when it was immersed in a 25% sulfuric acid aqueous solution at room temperature (25 ° C.) for 72 hours.
  • FIG. 4C shows a graph of the corrosion rate (values in Table 1) of each joint part after immersion in a 25% aqueous sulfuric acid solution at room temperature (25° C.) for 72 hours.
  • the substrate 13 was a metal plate made of SUS304 (20 mm ⁇ 40 mm, thickness 2 mm), and an oxide film 12 and a silicon oxide film 11 were formed as a protective film 100 on the metal plate made of SUS304.
  • An oxide film 12 was formed on a metal plate made of SUS304.
  • a metal plate made of SUS304 was placed in a vacuum chamber, the pressure was reduced to 0.05 kPa abs, and the plate was heated to 300° C. 1 L of ozone gas with a concentration of 20 g/m 3 was added as a raw material gas, and the reaction was carried out for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased by the above operation, was reduced in pressure to 0.1 kPa abs.
  • a silicon oxide film 11 was formed. Following the above step 1, the metal plate with the oxide film 12 formed thereon was heated to 300°C in a vacuum chamber. As the raw material gas, a gas in which 5.0 g of dimethyldiethoxysilane was diluted with nitrogen gas was added, and 1 L of ozone gas with a concentration of 20 g/ m3 was added and reacted for 0.5 minutes. Thereafter, the vacuum chamber, whose pressure had increased due to the above operation, was depressurized to 1.8 kPa abs.
  • Example 1 the degree of vacuum in the vacuum chamber during the preparation of the silicon oxide film 11 was 1.5 kPa, not 1.8 kPa. Although the material and shape of the substrate 13 were different, the preparation conditions were changed in order to prepare a silicon oxide film 11 having a similar structure. In both Example 1 and Example 2, silicon oxide films 11 having the same structure were prepared.
  • a substrate 13 was a SUS304 metal plate (20 mm x 40 mm, thickness 2 mm) in the same manner as Example 2a, and an oxide film 12 and a silicon oxide film 11 were formed as a protective film 100 on the SUS304 metal plate.
  • protective films 100 were formed on multiple metal plates.
  • the silicon oxide film 11 formed on the metal plate in Example 2a had an average thickness of 170 nm.
  • the silicon oxide film 11 formed on the metal plate in Example 2b had an average thickness of 175 nm.
  • Example 2a The metal plate on which the protective film 100 (oxide film 12, silicon oxide film 11) was formed in Example 2a was cut, and the cross section was observed, photographed, and subjected to elemental measurements using a transmission electron microscope (TEM) equipped with an energy dispersive X-ray spectroscopy (EDS) detector.
  • TEM transmission electron microscope
  • EDS energy dispersive X-ray spectroscopy
  • Figure 5A shows a transmission electron microscope photograph of the cross section of the metal plate on which the protective film 100 was produced in Example 2a.
  • Figure 5B shows a transmission electron microscope photograph of an enlarged view of Figure 5A.
  • Figure 6A shows a transmission electron microscope photograph of the cross section of the metal plate on which the protective film 100 was produced in Example 2a.
  • Figure 6B shows the distribution of each element measured by energy dispersive X-ray spectroscopy for the cross section shown in Figure 6A (substrate 13, oxide film 12, silicon oxide film 11).
  • the thickness of the oxide film 12 in Example 2a was 5 nm to 7 nm.
  • the contents of chromium (Cr), iron (Fe) and nickel (Ni) in the oxide film 12 were all lower than the contents of chromium, iron and nickel in the substrate 13.
  • the contents of chromium and nickel in the oxide film 12 decreased with increasing distance from the interface (first interface 14) between the substrate 13 and the oxide film 12 into the oxide film 12.
  • the content of iron in the oxide film 12 decreased with increasing distance from the interface (first interface 14) between the substrate 13 and the oxide film 12 into the oxide film 12, and in addition, the iron content in the oxide film 12 partially recovered in the oxide film 12 while maintaining a decreasing tendency (recovered within a range of 120% or less of the iron content at the starting point, if the first interface 14 is taken as the starting point), and was also confirmed in the silicon oxide film 11.
  • the chromium, iron and nickel contents in the oxide film 12 decreased with increasing distance from the interface (first interface 14) between the substrate 13 and the oxide film 12 into the oxide film 12, so it is believed that the substrate 13 and the oxide film 12 were firmly bonded.
  • the iron content in the oxide film 12 decreased with increasing distance from the interface (first interface 14) between the substrate 13 and the oxide film 12 into the oxide film 12, and iron was also confirmed in the silicon oxide film 11, so it is believed that the substrate 13, the oxide film 12 and the silicon oxide film 11 were firmly bonded.
  • the silicon (Si) content in the oxide film 12 showed a decreasing tendency with increasing distance from the interface (second interface 15) between the silicon oxide film 11 and the oxide film 12 into the oxide film 12 (when the second interface 15 is taken as the starting point, the silicon content at the starting point showed a decreasing tendency within a range of 120% or less). This also suggests that the oxide film 12 and the silicon oxide film 11 are firmly bonded.
  • Comparative Example 2 a product manufactured by Company A was used in which the substrate 23 was a metal plate made of SUS304 (20 mm x 40 mm, thickness 2 mm) and an oxide film 22 and an amorphous silicon film 21 were manufactured on the metal plate made of SUS304 as a protective film 200. A number of products manufactured by Company A for Comparative Example 2 were obtained. The thicknesses of the amorphous silicon films 21 of the multiple products manufactured by Company A obtained were 200 nm to 228 nm. Although the material and shape of the substrate 23 differ between Comparative Example 1 and Comparative Example 2, the amorphous silicon film 21 formed in both Comparative Examples has a similar structure.
  • the metal plate on which the protective film 200 (oxide film 22, amorphous silicon film 21) of Comparative Example 2 was formed was cut, and the cross section was observed, photographed, and subjected to elemental measurements using a transmission electron microscope (TEM) equipped with an energy dispersive X-ray spectroscopy (EDS) detector.
  • TEM transmission electron microscope
  • EDS energy dispersive X-ray spectroscopy
  • Figure 5C shows a transmission electron microscope photograph of a cross section of a metal plate on which protective film 200 was produced in Comparative Example 2.
  • Figure 6C shows a transmission electron microscope photograph of a cross section of a metal plate on which protective film 200 was produced in Comparative Example 2.
  • Figure 6D shows the distribution of each element measured by energy dispersive X-ray spectroscopy for the cross section shown in Figure 6C (substrate 23, oxide film 22, amorphous silicon film 21).
  • the thickness of the oxide film 22 in Comparative Example 2 was 4.7 nm.
  • the iron (Fe) and nickel (Ni) contents in the oxide film 22 were both lower than the iron and nickel contents in the substrate 23, but the chromium (Cr) content in the oxide film 22 was approximately twice as high as the chromium content in the substrate 23.
  • the iron and nickel contents in the oxide film 22 decreased with increasing distance from the interface (first interface 24) between the substrate 23 and the oxide film 22 into the oxide film 22.
  • the chromium content in the oxide film 22 increased with increasing distance from the interface (first interface 24) between the substrate 23 and the oxide film 22 into the oxide film 22, then decreased within the oxide film 22, and was also confirmed in the amorphous silicon film 21.
  • the chromium content in the oxide film 22 increased across the interface (first interface 24) between the substrate 23 and the oxide film 22.
  • the chromium content in the amorphous silicon film 21 decreased across the interface (second interface 25) between the oxide film 22 and the amorphous silicon film 21.
  • the chromium content in the oxide film 22 changes drastically at the interface between the substrate 23 and the oxide film 22 (first interface 24) and at the interface between the oxide film 22 and the amorphous silicon film 21 (second interface 25), and the chromium content in the oxide film 22 is about twice as much as the chromium content in the substrate 23.
  • the substrate 23 and the oxide film 22 are not firmly bonded, and that the oxide film 22 and the silicon oxide film 21 are not firmly bonded either.
  • the results of analyzing the surface of the protective film 100 of Example 2a, i.e., the surface of the silicon oxide film 11, by a Fourier transform infrared spectrophotometer (FTIR) are shown in Fig. 7 and Tables 2 and 3.
  • the protective film 100 of Example 2a contained SiO2 and Si( CH3 ) x (x is an integer of 1 to 3). It was confirmed that methyl groups directly covalently bonded to Si atoms, derived from dimethyldiethoxysilane, the raw material of the silicon oxide film 11, remained on the surface of the silicon oxide film 11.
  • Example 2a and Example 2b The results of analyzing the elemental composition of the surface of the protective film 100 produced in Example 2a and Example 2b, i.e., the surface of the silicon oxide film 11, using an X-ray photoelectron spectroscopy (XPS) are shown in Tables 4 and 5.
  • XPS X-ray photoelectron spectroscopy
  • the silicon oxide film 11 of Example 2a had 26.3 atomic% silicon (Si), 32.9 atomic% oxygen (O), and 40.8 atomic% carbon (C).
  • the silicon oxide film 11 of Example 2b had 25.9 atomic% silicon (Si), 34.8 atomic% oxygen (O), and 39.3 atomic% carbon (C).
  • SiO2 As shown in Table 5, in the silicon oxide film 11 of Example 2a, SiO2 was 19.6%, and SiOxCy+SiOx (x ⁇ 2) was 80.4%. In the silicon oxide film 11 of Example 2b, SiO2 was 24.2%, and SiOxCy+SiOx (x ⁇ 2) was 75.8%.
  • FIG. 8A shows a photograph of each metal plate immersed in a 25% sulfuric acid aqueous solution at room temperature (25° C.) for 72 hours. From the left, the order is untreated substrate, Example 2a, and Comparative Example 2.
  • FIG. 8B shows a photograph of each metal plate immersed in a 25% sulfuric acid aqueous solution at 60° C. for 72 hours and then taken out of the sulfuric acid aqueous solution. From the left, the order is untreated substrate, Example 2a, and Comparative Example 2.
  • the metal plate made of SUS304 on which the protective film 100 had not been prepared (untreated substrate) and the metal plate on which the protective film 200 had been prepared in Comparative Example 2 were corroded.
  • the metal plate on which the protective film 100 had been prepared in Example 2a was not corroded.
  • the metal plate on which the protective film 100 had been prepared in Example 2a was not corroded when immersed in a 25% sulfuric acid aqueous solution at room temperature (25°C) for 72 hours or when immersed in a 25% sulfuric acid aqueous solution at 60°C for 72 hours.
  • the substrate 13 was a metal plate made of SUS304 (70 mm ⁇ 150 mm, 0.7 mm thick), and an oxide film 12 and a silicon oxide film 11 were formed as the protective film 100 on the metal plate made of SUS304.
  • An oxide film 12 was formed on a metal plate made of SUS304.
  • a metal plate made of SUS304 was placed in a vacuum chamber, the pressure was reduced to 0.05 kPa abs, and the plate was heated to 300° C. 1 L of ozone gas with a concentration of 20 g/m 3 was added as a raw material gas, and the reaction was carried out for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased by the above operation, was reduced in pressure to 0.1 kPa abs.
  • a silicon oxide film 11 was formed. Following the above step 1, the metal plate with the oxide film 12 formed thereon was heated to 300°C in a vacuum chamber. As the raw material gas, a gas in which 2.0 g of dimethyldiethoxysilane was diluted with nitrogen gas was added, and 1 L of ozone gas with a concentration of 20 g/ m3 was added and reacted for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased by the above operation, was depressurized to 1.5 kPa abs.
  • Example 3 a protective film 100 was produced on a plurality of metal plates. The thickness of the silicon oxide film 11 produced on the plurality of metal plates was 40 nm to 45 nm.
  • Comparative Example 3 a SUS304 metal plate (70 mm ⁇ 150 mm, thickness 0.7 mm) was used as the substrate 23, and a product manufactured by Company A was used in which the oxide film 22 and the amorphous silicon film 21 were formed as the protective film 200 on the SUS304 metal plate. A number of Company A products for Comparative Example 3 were obtained. The thicknesses of the amorphous silicon films 21 of the obtained Company A products were 200 nm to 228 nm. In Comparative Examples 1, 2, and 3, protective films 200 having the same structure were fabricated.
  • the corrosion degree is the amount of corrosion (amount of corrosion) per day and 1 m2.
  • the state of each metal plate after the test was confirmed in comparison with the state of each metal plate before the test.
  • the results of Example 3, Comparative Example 3, and untreated substrate are shown in Table 7.
  • Example 3 the metal plate on which the protective film 100 had already been formed (silicon oxide film 11 with a thickness of 40 nm) was immersed in a 25% aqueous sulfuric acid solution at 60°C for 72 hours, and then immersed again in a 25% aqueous sulfuric acid solution at 60°C for 72 hours.
  • the weight of the metal plate remained unchanged at 11.8246 g, the oxide film 12 remained, and the substrate 13 was not corroded.
  • the metal plate on which the protective film 100 had been formed in Example 3 had sufficient resistance to the sulfuric acid aqueous solution even when the protective film 100 consisted of only the oxide film 12.
  • the oxide film 12 is formed by first forming the silicon oxide film 11 on the oxide film 12 and then removing the silicon oxide film 11 (removal step).
  • the removal step uses a 25% aqueous sulfuric acid solution at 60° C., but other methods may be used. Another solution may be used, or the silicon oxide film 11 may be physically removed by polishing or the like.
  • the evaluations using the 25% sulfuric acid aqueous solution at 60° C. and the 25% sulfuric acid aqueous solution at room temperature were accelerated evaluations. In these evaluations, the protective film 100 that exhibits good results is the protective film 100 that exhibits high durability even under normal usage conditions.
  • FIG. 9A shows a photograph (left side of FIG. 9A) of a metal plate (untreated substrate) made of SUS304 on which the protective film 100 had not been prepared before the salt water combined cycle test, and a photograph (right side of FIG. 9A) of a metal plate (silicon oxide film 11 with a thickness of 40 nm) on which the protective film 100 had been prepared in Example 3.
  • FIG. 9B shows a photograph (left side of FIG.
  • Example 9B of a metal plate (untreated substrate) made of SUS304 on which the protective film 100 had not been prepared after the salt water combined cycle test, and a photograph (right side of FIG. 9B) of a metal plate (silicon oxide film 11 with a thickness of 40 nm) on which the protective film 100 had been prepared in Example 3.
  • the metal plate on which the protective film 100 had been formed showed no corrosion or rust even after 10 cycles of saltwater composite testing, but the SUS304 metal plate (untreated substrate) showed corrosion and rust after 10 cycles of saltwater composite testing. From this result, it was confirmed that the metal plate on which the protective film 100 had been formed in Example 3 (silicon oxide film 11 with a thickness of 40 nm) has resistance to saltwater.
  • Example 3 in the case of a metal plate on which a protective film 100 had already been formed (silicon oxide film 11 had a thickness of 40 nm, and the main components of silicon oxide film 11 were SiO 2 and H 3 C-SiO 2 in which methyl groups were directly covalently bonded to Si atoms), the static contact angle of the surface of protective film 100 with ultrapure water was 90° or more, being 105°, which was close to the static contact angle of 109° between a PTFE plate and ultrapure water.
  • protective film 100 consisting of oxide film 12 and silicon oxide film 11 is water-repellent, and that the metal plate on which protective film 100 has already been formed is highly resistant to aqueous solutions.
  • the static contact angle of the surface of the protective film 200 with ultrapure water was less than 90°, being 64°. This indicates that the protective film 200 consisting of the oxide film 22 and the amorphous silicon film 21 is not water repellent, and that the metal plate on which the protective film 200 had already been formed has low resistance to aqueous solutions.
  • Example 3 for a metal plate on which a protective film 100 had already been formed (silicon oxide film 11 having a thickness of 40 nm, the main components of silicon oxide film 11 being SiO 2 and H 3 C-SiO 2 in which methyl groups are directly covalently bonded to Si atoms), the static contact angle of the surface of protective film 100 with hexadecane was 39°, which was close to the static contact angle of 40° between a PTFE plate and hexadecane. Therefore, it is believed that protective film 100 consisting of oxide film 12 and silicon oxide film 11 has oil repellency equivalent to that of PTFE, and that the metal plate on which protective film 100 had already been formed has high resistance to solutions containing organic solvents.
  • FIG. 11A shows a photograph of a vinyl acetate adhesive applied to a metal plate (untreated substrate) made of SUS304 with a mirror-finished surface.
  • the lower part of FIG. 11A shows a photograph of the dried vinyl acetate adhesive peeled off from a metal plate (untreated substrate) made of SUS304 with a mirror-finished surface.
  • the upper part of FIG. 11B shows a photograph of a vinyl acetate adhesive applied to a metal plate on which a protective film 100 has been prepared in Example 3.
  • the lower part of FIG. 11B shows a photograph of the dried vinyl acetate adhesive peeled off from a metal plate on which a protective film 100 has been prepared in Example 3.
  • FIG. 11C shows a photograph of a metal plate on which a protective film 100 has been prepared in Example 3, heated at 400° C. for 10 hours, on which a vinyl acetate adhesive has been applied.
  • the lower part of FIG. 11C shows a photograph of the dried vinyl acetate adhesive peeled off from a metal plate on which a protective film 100 has been prepared in Example 3, heated at 400° C. for 10 hours.
  • the dried vinyl acetate adhesive could not be completely peeled off from a metal plate (untreated substrate) made of SUS304 with a mirror-finished surface, and adhesive traces remained.
  • the dried vinyl acetate adhesive could be peeled off from a metal plate on which a protective film 100 had been prepared in Example 3 and a metal plate on which a protective film 100 had been prepared in Example 3, which was heated at 400°C for 10 hours, and no adhesive traces remained.
  • the protective film 100 consisting of the oxide film 12 and the silicon oxide film 11 can be easily removed even with an adhesive substance such as an adhesive, and that the protective film 100 consisting of the oxide film 12 and the silicon oxide film 11 has antifouling properties.
  • a 25 mm wide, 150 mm long tape was attached to a 25 mm wide, 200 mm long, 2 mm thick metal plate made of SUS304 with a mirror-finished surface, a polytetrafluoroethylene (PTFE) plate, and a metal plate on which the protective film 100 had been prepared in Example 3 (silicon oxide film 11 with a thickness of 40 nm).
  • PTFE polytetrafluoroethylene
  • paper was attached to the exposed adhesive surface with a width of 25 mm and a length of 200 mm, and these were used as the measurement sample.
  • a tester Autograph (registered trademark) AG-100kNXplus, Shimadzu Corporation
  • a 180° tape peel test was performed in accordance with JIS Z0237:2009, and the 180° peel adhesion strength (N/25 mm) was measured.
  • the measurement was performed under the following conditions: test room temperature 23°C ⁇ 2°C, test room humidity 50% ⁇ 5% RH, peel angle 180°, and tensile speed 300 mm/min. The test was performed five times.
  • Figure 12A shows the overlapping of five measured values (N/25 mm) for the metal plate on which the protective film 100 had been prepared in Example 3.
  • Figure 12B shows the overlapping of five measured values (N/25 mm) for the PTFE plate.
  • Figure 12C shows five measurements (N/25 mm) of a mirror-finished SUS304 metal plate (untreated substrate). Table 10 also shows the five measurements and their average values.
  • the average peeling force when the tape was peeled off from a metal plate (untreated substrate) made of SUS304 with a mirror-finished surface was 9.37 N/25 mm
  • the average peeling force when the tape was peeled off from a plate made of PTFE was 4.42 N/25 mm
  • the average peeling force when the tape was peeled off from a metal plate (silicon oxide film 11 with a thickness of 40 nm) on which a protective film 100 had been prepared in Example 3 was 1.83 N/25 mm.
  • the substrate 13 was a tube made of SUS316L (inner diameter 4.35 mm, outer diameter 6.35 mm, length 20 cm), and an oxide film 12 and a silicon oxide film 11 were formed as a protective film 100 on the entire surface of the SUS316L tube.
  • An oxide film 12 was formed on a tube made of SUS316L.
  • the SUS316L tube was placed in a vacuum chamber, depressurized to 0.05 kPa abs, and heated to 300° C.
  • 1 L of ozone gas with a concentration of 30 g/m 3 was added as a raw material gas and reacted for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased by the above operation, was depressurized to 0.1 kPa abs.
  • Example 4 unlike Examples 1, 2, and 3, ozone gas with a concentration of 30 g/ m3 was used instead of 20 g/ m3 . Also, in Example 4, the preparation conditions were changed so that an oxide coating 12 having the same structure as in Examples 1, 2, and 3 was prepared on the surface of the SUS316L tube.
  • step 2 A silicon oxide film 11 was formed. Following step 1, the tube with the oxide film 12 formed thereon was heated to 290°C in a vacuum chamber. As the raw material gas, a gas in which 1.5 g of dimethyldiethoxysilane was diluted with nitrogen gas and 0.17 L of ozone gas with a concentration of 30 g/ m3 were simultaneously introduced and reacted for 1 minute. After that, the vacuum chamber, whose pressure had increased due to the above operation, was depressurized to 0.5 kPa abs.
  • FIG. 13A shows a photograph of the inside of a SUS316 tube (untreated substrate) on which the protective film 100 had not been prepared after the salt water combined cycle test.
  • FIG. 13B shows a photograph of the inside of a SUS316 tube on which the protective film 100 had been prepared in Example 4 after the salt water combined cycle test.
  • the substrate 13 was a metal plate made of SUS304 (20 mm ⁇ 40 mm, thickness 2 mm), and an oxide film 12 and a silicon oxide film 11 were formed as a protective film 100 on the metal plate made of SUS304.
  • An oxide film 12 was formed on a metal plate made of SUS304.
  • a metal plate made of SUS304 was placed in a vacuum chamber, the pressure was reduced to 0.05 kPa abs, and the plate was heated to 300° C. 1 L of ozone gas with a concentration of 20 g/m 3 was added as a raw material gas, and the reaction was carried out for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased by the above operation, was reduced in pressure to 0.1 kPa abs.
  • step 2 A silicon oxide film 11 was formed. Following step 1, the metal plate with the oxide film 12 formed thereon was heated to 300°C in a vacuum chamber. As the raw material gas, a gas in which 5.0 g of dimethyldiethoxysilane was diluted with nitrogen gas was added, and 1 L of ozone gas with a concentration of 20 g/ m3 was added and reacted for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased due to the above operation, was depressurized to 1.5 kPa abs.
  • the static contact angle of these metal plates with ultrapure water was measured by the sessile drop method.
  • the static contact angle of the metal plate with the 10 nm silicon oxide film 11 formed thereon was 100°.
  • the static contact angle of the metal plate with the 75 nm silicon oxide film 11 formed thereon was 106°.
  • the static contact angle of the metal plate with the 600 nm silicon oxide film 11 formed thereon was 110°.
  • the static contact angle of the metal plate with the 1000 nm silicon oxide film 11 formed thereon was 130°.
  • Table 11 shows the relationship between the thickness of the silicon oxide film 11 in Example 5 and the static contact angle with ultrapure water.
  • Figures 14A and 14B show photographs of a metal plate with a 75 nm silicon oxide film 11 already formed thereon and ultrapure water in contact with each other, and a metal plate with a 1000 nm silicon oxide film 11 already formed thereon and ultrapure water in contact with each other, respectively.
  • the silicon oxide film 11 in Example 5 had a thickness of 10 nm or more, a static contact angle with ultrapure water of 100°, and water repellency of 90° or more.
  • the silicon oxide film 11 has water repellency at a thickness of 10 nm or more, and the metal plate on which the protective film 100 consisting of the oxide coating film 12 and the silicon oxide film 11 has already been formed is highly resistant to aqueous solutions.
  • Example 6 the substrate 13 was a liquid chromatography column hardware made of SUS316 (one column tube having an inner diameter of 2.1 mm and a length of 10 cm, two filters, and two filter fixing parts), and an oxide coating 12, a silicon oxide film 11, and a functional coating 10 were formed as a protective film 100 on the SUS316 liquid chromatography column hardware.
  • An oxide film 12 was formed on a liquid chromatography column hardware made of SUS316.
  • a liquid chromatography column hardware made of SUS316 was placed in a vacuum chamber, depressurized to 0.05 kPa abs, and heated to 300° C. 1 L of ozone gas with a concentration of 20 g/m 3 was added as a raw material gas and reacted for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased by the above operation, was depressurized to 0.1 kPa abs.
  • step 2 A silicon oxide film 11 was formed. Following step 1, the liquid chromatography column hardware with the oxide film 12 formed thereon was heated to 300° C. in a vacuum chamber. As the raw material gas, a gas in which 5.0 g of dimethyldiethoxysilane was diluted with nitrogen gas was added, and 1 L of ozone gas with a concentration of 20 g/ m3 was added and reacted for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased due to the above operation, was depressurized to 1.5 kPa abs.
  • a functional coating 10 was prepared. Next, 1.0 g of dimethyldiethoxysilane diluted with nitrogen gas was introduced as a raw material gas into the vacuum chamber, which had been depressurized to 0.1 kPa abs, and the ozone gas was stopped, followed by reaction for 0.5 minutes. Thereafter, the vacuum chamber was depressurized to 1.0 kPa abs.
  • the liquid chromatography column hardware on which the oxide film 12, silicon oxide film 11, and functional film 10 were prepared by steps 1, 2, and 3 above, was filled with octadecylsilylated silica gel (InertSustain (registered trademark) AQ-C18, 3 ⁇ m, GL Sciences, Inc.) to prepare a column with an inner diameter of 2.1 mm and a length of 10 cm.
  • octadecylsilylated silica gel InertSustain (registered trademark) AQ-C18, 3 ⁇ m, GL Sciences, Inc.
  • the substrate 13 was a column hardware for liquid chromatography made of SUS316 (one column tube having an inner diameter of 2.1 mm and a length of 10 cm, two filters, and two filter fixing parts), and an oxide coating 12 and a silicon oxide film 11 were formed as a protective film 100 on the column hardware for liquid chromatography made of SUS316.
  • An oxide film 12 was formed on a liquid chromatography column hardware made of SUS316.
  • a liquid chromatography column hardware made of SUS316 was placed in a vacuum chamber, depressurized to 0.05 kPa abs, and heated to 300° C. 1 L of ozone gas with a concentration of 20 g/m 3 was added as a raw material gas and reacted for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased by the above operation, was depressurized to 0.1 kPa abs.
  • step 2 A silicon oxide film 11 was formed. Following step 1, the liquid chromatography column hardware with the oxide film 12 formed thereon was heated to 300° C. in a vacuum chamber. As the raw material gas, a gas in which 5.0 g of dimethyldiethoxysilane was diluted with nitrogen gas was added, and 1 L of ozone gas with a concentration of 20 g/ m3 was added and reacted for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased due to the above operation, was depressurized to 1.5 kPa abs.
  • the liquid chromatography column hardware on which the oxide film 12 and silicon oxide film 11 were prepared by steps 1 and 2 above, was filled with octadecylsilylated silica gel (InertSustain (registered trademark) AQ-C18, 3 ⁇ m, GL Sciences, Inc.) to prepare a column with an inner diameter of 2.1 mm and a length of 10 cm.
  • octadecylsilylated silica gel InertSustain (registered trademark) AQ-C18, 3 ⁇ m, GL Sciences, Inc.
  • the temperature condition was 35°C.
  • a UV detector was used for detection. The detection wavelength was 254 nm.
  • Sample I an aqueous solution of adenosine diphosphate (ADP, 800 ⁇ g/L) and adenosine monophosphate (AMP, 500 ⁇ g/L) was used as the sample.
  • the sample injection volume was 0.2 ⁇ L.
  • the chromatogram collected using the column of Example 6 is shown in Figure 15A.
  • the chromatogram collected using the column of Example 7 is shown in Figure 15B.
  • Table 12 shows the symmetry coefficients (10%) of the ADP peak and AMP peak in Figure 15A and the ADP peak and AMP peak in Figure 15B.
  • the symmetry coefficient is a coefficient that indicates the degree of symmetry of the peak. The closer to 1, the better the symmetry of the peak. In a chromatogram, peaks with good symmetry are preferable for use in analysis.
  • the substrate 13 was a tube made of SUS316 (inner diameter 2.1 mm, outer diameter 3.18 mm, length 15 cm), and an oxide film 12 and a silicon oxide film 11 were formed as a protective film 100 on the entire surface of the SUS316 tube.
  • An oxide film 12 was formed on a tube made of SUS316.
  • the SUS316 tube was placed in a vacuum chamber, depressurized to 0.05 kPa abs, and heated to 300° C.
  • 1 L of ozone gas with a concentration of 30 g/m 3 was added as a raw material gas and reacted for 0.5 minutes. After that, the vacuum chamber, whose pressure had increased by the above operation, was depressurized to 0.1 kPa abs.
  • step 2 A silicon oxide film 11 was formed. Following step 1, the tube with the oxide film 12 formed thereon was heated to 290°C in a vacuum chamber. As the raw material gas, a gas in which 1.5 g of dimethyldiethoxysilane was diluted with nitrogen gas and 0.17 L of ozone gas with a concentration of 30 g/ m3 were simultaneously introduced and reacted for 1 minute. After that, the vacuum chamber, whose pressure had increased due to the above operation, was depressurized to 0.5 kPa abs.
  • Example 8 The tube on which the protective film 100 (oxide film 12, silicon oxide film 11) was formed in Example 8 was cut, and the inner surface of the tube was subjected to elemental measurement using an Auger electron spectroscopy (AES).
  • AES Auger electron spectroscopy
  • Figure 16 shows the distribution of each element measured by Auger electron spectroscopy on the inner surface of the tube on which the protective film 100 was produced in Example 8.
  • the content of each element was measured by measuring oxygen (O), silicon (Si), carbon (C), iron (Fe), chromium (Cr), and nickel (Ni) in the depth direction from the surface side of the silicon oxide film 11 toward the substrate 13.
  • 0.0 min to 7.5 min on the horizontal axis is the silicon oxide film 11
  • 7.5 min on the horizontal axis is the second interface 15
  • 7.5 min to 10.0 min on the horizontal axis is the oxide film 12
  • 10.0 min on the horizontal axis is the first interface 14
  • 10.0 min to 17.25 min on the horizontal axis is the substrate 13, i.e., SUS316.
  • the content of metal elements (iron, chromium, nickel) derived from the substrate 13 shows a decreasing tendency starting from the first interface 14, and the oxygen content within the oxide coating 12 is greater than the oxygen content at the first interface 14.
  • iron monotonically decreases with increasing distance from the first interface 14, then levels off or slightly increases, and then monotonically decreases again.
  • chromium partially increases within 120% of the value at the first interface 14 with increasing distance from the first interface 14, then monotonically decreases, and then partially increases, decreases, and increases until it reaches the second interface 15.
  • nickel monotonically decreases with increasing distance from the first interface 14, then partially increases slightly, then levels off, and then reaches the second interface 15.
  • the oxygen content shows a tendency to increase with increasing distance from the first interface 14.
  • the oxygen content increases sharply from the first interface 14 and then increases more gradually.
  • the oxygen content changes sharply in the region within the oxide film 12, near one-third of the way towards the first interface 14.
  • the slope of the increase in oxygen concentration becomes large (sudden) from the first interface 14 and then becomes small (gradual).
  • the point of change is around one-quarter to one-third of the way towards the first interface.
  • the content of nonmetallic elements (oxygen, silicon, carbon) derived from the silicon oxide film 11 shows a decreasing tendency with increasing distance from the second interface 15.
  • carbon monotonically decreases with increasing distance from the second interface 15, and then partially increases and decreases before reaching the first interface 14.
  • silicon partially increases or decreases slightly as the distance from the second interface 15 increases, and then reaches the first interface 14.
  • oxygen partially increases within 120% of the value at the second interface 15 as the distance from the second interface 15 increases, and then partially increases or decreases slightly as the distance from the second interface 15 increases, and then reaches the first interface 14.
  • the content of all metal elements originating from the substrate 13 that is 1 wt. % or more tends to decrease from the first interface 14 as the distance from the first interface 14 increases.
  • the content of all metal elements originating from the substrate 13 that is 1% by weight or more tends to decrease from the first interface 14 as a starting point, and tends to decrease to 50% or less of the content of metal elements at the first interface 14.
  • the content of all metal elements originating from substrate 13 that is 1% by weight or more tends to decrease from first interface 14 as the distance from first interface 14 increases, and tends to decrease to 10% or less of the content at first interface 14.
  • the oxide film 12 is not a uniform film, and in the region within the oxide film 12, the oxygen content of the oxides of all metal elements originating from the substrate 13 and present at 1 wt % or more shows a tendency to increase starting from the first interface 14.
  • the content of all non-metallic elements originating from the silicon oxide film that is 1% by weight or more tends to decrease from the second interface 15 as the distance from the second interface 15 increases.
  • at least 1% by weight of metal elements can be measured by an Auger electron spectroscopy (AES).
  • SUS304, SUS316, and SUS316L are used as the substrate 13, but even if the substrate 13 is made of another metal, a protective film of a similar structure can be produced with the same effect.
  • the material of the substrate 13 is an austenitic SUS containing iron, chromium, and nickel
  • a protective film having a similar structure can be produced, and the same effects can be obtained.
  • the material of the substrate 13 is a martensitic SUS containing chromium or a ferritic SUS containing chromium
  • a protective film having a similar structure can be produced, and the same effects can be obtained.
  • Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn are adjacent elements in the fourth period of the periodic table, and when one or more of these elements are contained in the metal substrate 13 in an amount of 1 weight % or more, a protective film of a similar structure can be produced, with the same effect.
  • the conditions for producing the oxide film 12 and the silicon oxide film 11 may differ, but this is simply due to the fact that the conditions for producing the oxide film 12 and the silicon oxide film 11 are changed depending on the material and shape (plate, cylinder, dimensions) of the substrate 13.
  • the oxide film 12 and the silicon oxide film 11 thus produced have the same structure and have the same effect.
  • the protective film of this embodiment can chemically protect various metal substrates.
  • the protective film of this embodiment can protect column hardware of separation columns used in various types of chromatography, pipes for piping various types of chromatographs, molds, pipes for passing cooling water through molds, heat exchanger pipes, heat exchanger fins, waste pipes, or metal parts used therein.

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Abstract

La présente invention aborde le problème de la réalisation d'un film protecteur qui est résistant à l'acide sulfurique. La solution selon l'invention porte sur un film protecteur destiné à protéger un matériau de base qui est formé d'un métal, le film protecteur étant caractérisé en ce que : le film protecteur comprend un film d'oxyde qui est formé sur le matériau de base et contient un élément métallique dérivé du matériau de base ; et si l'interface entre le matériau de base et le film d'oxyde est prise en tant que première interface, dans une région à l'intérieur du film d'oxyde, la teneur de l'élément métallique dérivé du matériau de base indique une tendance à la baisse à partir de la première interface à mesure de l'éloignement de la première interface ; et la teneur en oxygène dans le film d'oxyde est supérieure à la teneur en oxygène au niveau de la première interface.
PCT/JP2024/002949 2023-02-03 2024-01-30 Film protecteur et procédé de production de celui-ci Ceased WO2024162361A1 (fr)

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JP2016046533A (ja) * 2014-08-21 2016-04-04 シルコテック コーポレーション 半導体製造工程
JP2019206740A (ja) * 2018-05-30 2019-12-05 株式会社デンソー 表面被覆部材及びその製造方法

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Publication number Priority date Publication date Assignee Title
JP2010507022A (ja) * 2006-10-20 2010-03-04 スリーエム イノベイティブ プロパティズ カンパニー 易洗浄基材のための方法及びそれによる物品
JP2016046533A (ja) * 2014-08-21 2016-04-04 シルコテック コーポレーション 半導体製造工程
JP2019206740A (ja) * 2018-05-30 2019-12-05 株式会社デンソー 表面被覆部材及びその製造方法

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