JPS61238961A - Reforming method of base material surface - Google Patents

Abstract

PURPOSE:To securely and uniformly form a thin film of a compd. havin a fluorine-carbon bond on a base body by bringing the carbon-contg. film formed on the base material surface and the fluorine contg. gaseous plasma generated when carbon fluoride or sulfur fluoride compd. is electrically discharged. CONSTITUTION:The C-contg. film is formed on the surface of the base material consisting of a metal, metallic oxide, ceramics, plastics, etc.,by at least one of an electric plasma method, physical vapor deposition method and chemical vapor deposition method. The C-contg. film is thereafter brought into contact with the F-contg. gaseous plasma generated when the carbon fluoride compd. and/or sulfur fluoride compd. is electrically discharged. The gaseous plasma generated when the gaseous mixture contg. the hydrocarbon compd. and the carbon fluoride compd. and/or sulfur fluoride compd. is electrically discharged is brought into contact with the base material. The thin film of the compd. having the F-C bond is thus safely, quickly, uniformly and securely formed on the base material, by which the base material surface is reformed.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to a substrate made of metal, metal oxide, ceramics, plastics, etc. when a thin film of a compound containing a fluorine-carbon bond is formed on the substrate surface. This invention relates to a method for modifying.

There is a known method of forming a thin film of a fluorine-containing compound on the surface of a substrate made of metal, metal oxide, ceramics, plastics, etc. to impart chemical resistance, hydrophobicity, abrasion resistance, lubricity, etc. . Generally, a method of wet coating of tetrafluoroethylene is widely used as such a method, but tetrafluoroethylene is expensive, and it is difficult to coat materials such as metals and ceramics with tetrafluoroethylene.

Since ethylene itself has a low surface energy, it is difficult to form a film with excellent adhesion, and there is a problem that it peels off and flows out during use, reducing its functionality.

In addition, chemical treatment methods in fluorine gas and methods for forming fluorocarbons on metal surfaces are also being researched.
In addition to the fact that fluorine gas is dangerous, the processing conditions are complicated and it is not suitable for practical use.

In addition, when metals, ceramics, etc. are directly treated with fluorine plasma gas, the metals and ceramics are
Since it contains only a trace amount of carbon, it is not possible to form a fluorocarbon compound. Especially when a metal is directly treated with a fluorine plasma gas, the surface of the metal becomes hydrophilic and brittle as a metal fluoride. However, it cannot play the role of protecting the metal.

Means for Solving the Problems The present inventor formed a strong thin film of a compound having a fluorine-carbon bond on the surface of metals, ceramics, plastics, etc. to improve hydrophobicity, lubricity, wear resistance, As a result of intensive research aimed at imparting chemical resistance, etc., metal,
By forming a carbon-containing film on a base material such as ceramics or plastics, and then bringing the carbon-containing film into contact with a fluorine-containing plasma gas generated by discharging a fluorocarbon compound and/or a sulfur fluoride compound, It has been found that it is possible to uniformly and firmly form a thin film of a compound having a fluorine-carbon bond on a substrate. In addition, fluorine can be uniformly and firmly applied to a substrate by contacting the substrate with plasma gas generated by discharging a mixed gas containing a hydrocarbon compound and a fluorocarbon compound and/or a sulfur fluoride compound. - It has been found that it is possible to form a thin film of a compound having carbon bonds. The present invention is based on such knowledge.

That is, the present invention provides the following method.

■ Generated by forming a carbon-containing film on a substrate by at least one of discharge plasma method, physical vapor deposition method, and chemical vapor deposition method, and then discharging a fluorocarbon compound and/or a sulfur fluoride compound. A method for modifying the surface of a substrate, the method comprising bringing a fluorine-containing plasma gas into contact with a carbon-containing film.

(2) A substrate surface characterized by bringing plasma gas generated by discharging a mixed gas containing i) a hydrocarbon compound, and K i) a fluorocarbon compound and/or a fluorinated sulfur compound into contact with the substrate. modification method.

In the present invention, the base material is not particularly limited, but for example, metals, metal oxides, ceramics, plastics, etc. can be used. The types of these base materials are not particularly limited, but examples of metals include copper, iron,
Nickel, aluminum, rim, tungsten, tin,
Examples include all metals including zinc, silicon, manganese, titanium, indium, etc., and alloys thereof.

Examples of the metal oxide include oxides of the above metals.

Ceramics include glasses such as silicate glass, quartz glass, borate glass, and phosphate glass;
Examples include cements such as alumina cement, Portland cement, and magnesia cement, magnesia, zircon, aluminum trisium, titanium oxide, silicon carbide, and silicon titanide.

There are no particular restrictions on the plastics, and a wide variety of materials can be used, such as polyethylene resin, polypropylene resin, boria t-tar resin, acrylic resin, nylon resin, cellulose resin, polycarbonate resin, phenolic resin, Polyester resin, polyurethane resin, diallyl phthalate resin, phenol formaldehyde resin, urea resin, melamine/aldehyde resin, Evo+Si resin, furan resin, +Silene resin, silicone resin, Boristyrene: J resin, Jinyl resin, Algydo resin , chlorinated polyether resin, and the like.

The shape of the base material is not particularly limited, and may be any shape such as a round rod shape, a prismatic shape, or a plate shape.

In the present invention, first, a carbon-containing film is formed on a base material.

The method for forming the carbon-containing film must be a method that can form a carbon-containing film on the base material with good adhesion, and at least one of discharge plasma method, physical vapor deposition method, and chemical vapor deposition method is used. conduct. These methods may be performed alone or two or more methods may be used in combination. As the discharge plasma method, C〃C2H C2H6,
C3H,, CaH engineering. etc. as a carbon source by a known discharge plasma method, and if necessary, N2s lr%
An inert gas such as Ht may be mixed to adjust the discharge voltage, or hydrogen or sometimes oxygen may be mixed to improve the performance of the formed film and the bonding property xl with the base material. Processing conditions may be determined as appropriate depending on the type of substrate and the properties of the carbon-containing film, including gas pressure, gas flow rate, electric power, power frequency,
Turn on the substrate temperature and discharge.

A desired carbon-containing film can be obtained by adjusting the repetition of OFF and the like.

The physical vapor deposition method and the chemical vapor deposition method may be a method of forming a carbon-containing film according to a conventional method using a carbon source such as activated carbon, graphite, or amorphous carbon powder.

According to discharge plasma method, physical vapor deposition method or chemical vapor deposition method,
A thin carbon-containing film with good adhesion can be formed. Therefore, compared to a carbon-containing film formed by coating, the carbon-containing film is less likely to peel off due to a difference in expansion coefficient from the base material.

In addition, the coating method has the disadvantage that the formation of compounds having fluorine-carbon bonds is hindered by the residues of dispersants and solvents contained in the coating agent, but the method of the present invention eliminates the contamination of impurities. , the formation of fluorine-carbon bonds is not hindered.

After forming the carbon-containing film on the base material, a fluorocarbon compound and/or a sulfur fluoride compound is discharged, and the fluorine-containing plasma gas generated by the discharge is brought into contact with the carbon-containing film formed on the base material. By this, a thin film of a compound having a fluorine-carbon bond is formed on the substrate.

The fluorine compounds used in the present invention include:

Any fluorinated carbon compound and/or fluorinated sulfur compound that is a gas at room temperature or gasified at the temperature during discharge treatment can be used, such as CF, C2F6, C, F,, C.
HF3, sp6, etc. may be used. These may be used alone or in combination, and inert gases such as N2, Ar, Hz, etc., and sometimes oxygen may be mixed for the purpose of adjusting the discharge voltage. The method of the present invention is advantageous in terms of safety because it does not use fluorine molecular gas, which is dangerous to handle and is used as a fluorine raw material in the production of fluorinated graphite by the conventional discharge plasma method.

The plasma generation methods used in the present invention include: ■ DC current discharge or low-frequency discharge using an internal electrode method, ■ High-frequency discharge using an internal cross-pole method, external gutter method or coil type method, and ■ Wave-guided discharge. Examples include, but are not limited to, microwave discharge using a tube type system, ■electron cyclotron resonance discharge (ECR discharge), and ■induction coil type high frequency discharge that does not use electrodes. Any method may be used as long as it causes a reaction with the containing film.

The discharge treatment may be carried out according to a conventional method, and the discharge conditions may be appropriately determined depending on the properties required for the surface of the substrate under conditions where fluorine-containing plasma is generated.

In the present invention, fluorine-carbon can also be formed on a substrate by bringing plasma gas generated by discharging a mixed gas containing a hydrocarbon compound and a fluorocarbon compound and/or a fluorinated sulfur compound into contact with the substrate. A thin film of a compound having a bond can be formed. If necessary, gases such as N2 and Ift may be added to this gas mixture to adjust the discharge voltage and the like, and the performance of the film to be formed and the base material may be mixed. Hydrocarbon compounds used in the mixed gas include, for example, CH, C2H6, C3
'15, C4M□. Examples of fluorocarbon compounds and sulfur fluoride compounds include cp, C2F6, C,F
8, CHF3, SF6, etc. The mixing ratio and processing conditions may be appropriately determined depending on the required properties of the thin film.

In the present invention, the position of the base material placed in the discharge device may be within the electric field that generates plasma, or it may be outside the electric field as long as it is within the range that the gas passing through the plasma of the fluorine-containing compound reaches in an active state. There may be. Particularly when using plastic as a base material, for example, if the base material is subjected to microwave discharge in an electric field, the plastic may melt. It is necessary to place the base material outside the electric field and within the reach of the active gas that has passed through the plasma gold.

Furthermore, when a base material is placed in an electric field and discharged, a thin film of a compound having a fluorine-carbon bond may be formed while the surface of the base material or a carbon-containing film is etched.
It is necessary to determine the processing conditions depending on the required surface properties of the base material.

According to the method of the present invention, the type of sample gas, the pressure, the discharge method such as alternating current, direct current, high frequency, etc., the discharge time,
By adjusting various conditions such as the distance between electrodes, substrate temperature, and repeated ON/OFF discharge, the degree of fluorination of the carbon-containing film can be controlled, and the hydrophobic performance of the substrate surface can be adjusted. is possible. The degree of fluorination can be quantitatively measured by the ratio of F, /C, calculated by XMA photoelectron spectrum (ESCA spectrum) analysis. Furthermore, a wide variety of carbon-containing films can be formed by adjusting discharge conditions and deposition conditions.
By adjusting the properties of the carbon-containing film and the degree of fluorination, thin films with a wide variety of fluorine-carbon bonds can be formed.

According to the method of the present invention, a uniform and strong thin film of a compound having a fluorine-carbon bond with excellent adhesiveness can be formed on the surface of a substrate, regardless of the type of the substrate. Also,
The method of the present invention is a method with excellent safety because it does not use fluorine molecular gas as a fluorine raw material. First, the method of the present invention has the great advantage that the target product can be obtained in an extremely short time compared to chemical treatment methods.

Furthermore, the method of the present invention can form a thin film of a compound having excellent hydrophobicity and nine fluorine-carbon bonds than polytetrafluoroethylene, and the substrate treated by the method of the present invention has chemical resistance. , has excellent hydrophobicity, wear resistance, lubricity, etc.

Substrates treated by the method of the present invention are useful for, for example, magnetic tapes, moisture-proof films for precision instruments, artificial blood vessels, blood bags, etc. in the case of plastics, and artificial bones, in the case of t-lanics. Can be effectively used as roof tiles, etc.
Metals have a wide range of uses, such as being used as materials for machines used in liquids, sliding materials, etc.

Hereinafter, the present invention will be described in detail with reference to Examples.

Note that the gas flow rate in the examples is a value measured under atmospheric pressure.

Example 1 A plasma discharge device using high frequency discharge shown in FIG. 1 was used as a plasma discharge device. The plasma discharge device shown in Fig. 1 consists of a raw material, + Yariakasu supply path l, and a high frequency power source 2.
, a plasma reaction system 3, a discharge electrode 4, and an exhaust path 5.

An aluminum plate with a thickness of 0.5 fl is placed in the discharge device 11.
After placing the discharge device on top and thoroughly evacuating and depressurizing the inside of the discharge device,
Maintaining a pressure of 1 torr, CHl gas was added at 25 d/
100F while flowing at a flow rate of min.

Plasma was generated by applying high frequency power (radio waves) of 13.5 MHz to the electrode, and treatment was performed for about 30 minutes to form a carbon-containing film on the aluminum surface.

Next, place this aluminum plate on the discharge electrode,
After sufficiently exhausting and reducing the pressure inside the discharge device, high frequency power (radio waves) of 503F and 13.5MHI was applied to the electrodes while maintaining a pressure of 5 Torr and flowing CF and gas at a flow rate of I Od / WIi s. to generate plasma, 5
Discharge was performed for a minute. Through this treatment, the carbon-containing film on the aluminum surface was significantly hydrophobicized, and the contact angle of water was about 100 degrees, which was much larger than the contact angle of water on the carbon-containing film itself. FIG. 2 shows a graph of the relationship between the discharge time in CFK gas and the contact angle of waste water on the sample surface.

Example 2 The same plasma discharge device as in Example 1 was used, and the thickness was 0.5
Cod aluminum plate outside the discharge electrode and cow? Graphite powder was placed on the electrode in the downstream direction with respect to the rear gas, and after sufficient evacuation, 100F, 1
A high frequency power (radio wave) of 3.5 MHI was applied to the electrode to generate plasma, and the treatment was performed for about 40 minutes to form a carbon film on the aluminum surface.

Next, this aluminum plate was placed on the discharge electrode of the plasma generator, and after sufficiently exhausting and reducing the pressure inside the discharge device, the CF and gas were heated to 10 tcd while maintaining the pressure of 5 torr.
Introduced at a flow rate of /min, 50W.

High frequency power (radio waves) of 13.5 MHz was applied to the electrodes to generate plasma and discharge was performed for 5 minutes. Through this treatment, the carbon film on the aluminum surface was significantly hydrophobicized, and the contact angle of water was 130 degrees, which was much higher than the contact angle of water of graphite itself, which was 50 to 60 degrees. Further, FIG. 3 shows the results of measuring the ESCA spectrum JLI (X-ray photoelectron spectrum) for the reactant layer on the aluminum surface.

In Figure 3, CI! In addition to J-K, there is a peak of FIf9, and Flj before treatment with fluorine-containing laser.
Since there was no heat leak, it was clear that a carbon-fluorine bond was formed. Furthermore, spectra of CF, CF2, CF, and bonds were present on the higher wavelength side of CI and Nojiri, and this also confirmed the formation of a fluorine-containing compound film.

[Brief explanation of the drawing]

Figure 1 is an example! Figure 2 is a graph showing the relationship between plasma treatment time and water contact angle, Figure 3 is a diagram showing the ES of the substrate surface after discharge.
This is a club that exhibits the CA spectrum. In the figure, (1) indicates the raw material, the cattle P rear gas supply path, and (2
) is a high frequency power source, (3) is a plasma reaction system, (4) is a discharge electrode, and (5) is an exhaust path. (The above) Agent Patent attorney Eiji Saegusa ′−・)−−
11' Closing Procedures Amendment Portion (Frog) July 7, 1985 Patent Application No. 78981 of 1985 2 Name of the invention Method for modifying the surface of a substrate 3 Relationship with the case of the person making the amendment Patent applicant Tokyo 2-20-11 Takaido Higashi, Suginami-ku Sachiko Okazaki (and 1 other person) 4 Agent 2-10 Hirano-cho, Higashi-ku, Osaka City Sawanotsuru Building Sponsor 6 The section “Claims” in the specification to be amended and the amendment Content 1゜ The statement in the claims section of the specification is corrected as shown in the attached sheet. 2o The statement "Confirmed" on page 17, line 12 of the specification is corrected as follows. "Confirmed." After sufficiently exhausting and reducing the pressure inside the discharge device, the Ar-CH4 mixed gas was heated to 0.2 torr (ArO, 1 torr, CHa 0.1
20 cm3 (N, T, P,
)/min, 50W, 13.5MH
Plasma is generated by applying high frequency power (radio waves) of
．． A carbon-containing film of 2 μm was formed. Next, after sufficiently exhausting and reducing the pressure inside the discharge device, 10 cm3 of SFs gas (N, T,
50W, 13.5 while flowing at a flow rate of P, )/min.
Plasma was generated by applying MHz high frequency power (radio waves) to the electrodes, and discharge was performed for 5 minutes. By this treatment, the carbon-containing film on the surface of the sample was significantly hydrophobicized, and the contact angle of water was 90 to 110 degrees, with an average of about 100 degrees. , Example 4 5IJ pretreated in Ar gas in the same manner as Example 3
A S304 thin plate was used as a sample, and the sample was placed on the discharge electrode of the same plasma generator as in Example 1, and 5Fs-CH4 mixed gas (SFs 0.134 Torr,
CH40,066 Torr) at a flow rate of 100 m3 (N. T, P,)/min, 50 W, 13
．． Plasma was generated by applying 5 MHz high frequency power (radio waves) to the electrode, and the treatment was performed for 3 minutes. As a result, a film with a thickness of 1.0 μm was formed on the sample surface, and the contact angle of water droplets was 99 to 101 degrees, with an average of about 100 degrees. (Above) Claims ■ After forming a carbon-containing film on a base material by at least one of discharge plasma method, physical vapor deposition method, and chemical vapor deposition method, fluorocarbon compound and/or fluoride A method for modifying the surface of a substrate, which comprises bringing a carbon-containing film into contact with a fluorine-containing plasma gas generated by discharging a sulfur compound. (2) A substrate surface characterized by contacting the substrate with a plasma gas generated by discharging a gas mixture containing i) a hydrocarbon compound, and ii) a fluorocarbon compound and/or a fluorosulfide. modification method.

Claims (2)

[Claims] (1) Generated by forming a carbon-containing film on a base material by at least one of a discharge plasma method, a physical vapor deposition method, and a chemical vapor deposition method, and then discharging a fluorocarbon compound and/or a sulfur fluoride compound. A method for modifying the surface of a substrate, the method comprising bringing a fluorine-containing plasma gas into contact with a carbon-containing film. (2) The surface of a substrate is characterized by contacting the substrate with a plasma gas generated by discharging a gas mixture containing i) a hydrocarbon compound and ii) a fluorocarbon compound and/or a fluorosulfide. How to improve.