JPH1030679A - Part for automobile and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide properties excellent in some of a slide property between other article and a member, wear resistance, gas barrier properties, and water repellency. SOLUTION: A vibration control member for an automobile is provided to have a contact surface S1' with other article on which a carbon film F having wear resistance and lubricity is formed. A hose for an automobile is provided to have an outer surface S2' on which a carbon film F having wear resistance, lubricity, and gas barrier properties is formed. A tire for an automobile is provided to have an outer surface S3', except a contact part with a road, on which a carbon film F having wear resistance, lubricity, and gas barrier properties is formed. A diaphragm for an automobile is provided to have an outer surface S4' on which a carbon film F having wear resistance and water repellency is formed. A valve part for an automobile is provided to have a contact surface S5' with other article on which the carbon film F having wear resistance and lubricity is formed. A sealant for an automobile is provided to have a contact surface S6' with other article on which the carbon surface F having wear resistance and lubricity is formed. A windshield is provided to have an outer surface S7' on which the carbon film F having wear resistance and water repellency is formed. A body for an automobile is provided to have an outer surface S8' on which the carbon film F having wear resistance and water repellency is formed. Manufacture thereof is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a component for a vehicle, in particular, a vibration damping member for a vehicle used in a drive portion, a steering portion, an exhaust portion, a body connection portion, a suspension portion, an engine portion, etc. of a vehicle, and a fuel system for a vehicle. Automotive hoses used in air systems, oil systems, refrigerant systems for air conditioning, brake systems, cooling water systems, etc., automotive tires, diaphragm pumps for supplying windshield cleaning liquid, diaphragm pumps used in fuel supply control systems, etc. Automotive diaphragms used, automotive valve parts, seals used for pipe connection parts, piston ring seals, automotive seals such as packings,
The present invention relates to a window glass such as a windshield for an automobile, a body for an automobile (including a part of a finished product), and a method for producing the same.

[0002]

2. Description of the Related Art As a material for a vibration damping member for an automobile, a hose for an automobile, a tire for an automobile, and a sealing material for an automobile, rubber,
Polymer materials such as resins are frequently used. Grease is applied to the surface of automotive anti-vibration members made of a polymer material to improve slidability with other articles, prevent wear due to contact with other articles, and prevent deterioration. Or molding by adding oil to the base material.

[0003] In addition, automotive hoses whose surface is made of a polymer material are provided with grease on the surface in order to improve the slidability with other articles, prevent wear due to contact with other articles, and prevent deterioration. It is applied or molded by adding oil to the substrate. Further, in order to suppress the permeation of oxygen, water vapor and other gases, the outer surface is coated with a resin film having a gas barrier property.

[0004] In addition, in order to prevent abrasion and deterioration due to contact with a wheel, and to prevent deterioration due to external light or exhaust gas, grease or wax is applied to a surface of a vehicle tire, or a base material is used for a vehicle tire. To form oil by adding oil. Further, in order to prevent abrasion and deterioration due to contact with an article sealed by the sealing material, the sealing material for automobiles is formed by applying grease to the surface or molding by adding oil to the base material. .

A diaphragm for an automobile is used for a diaphragm pump for supplying a windshield cleaning liquid, a diaphragm pump for use in a fuel supply control system, a diaphragm valve, and the like. The material of the diaphragm is usually a polymer material such as rubber or resin. Used. In addition, as a material for valve parts for automobiles, polyimide resin having relatively excellent heat resistance,
Resins such as polytetrafluoroethylene resins have been proposed.

[0006] The windshield for automobiles (and the rear glass depending on the type of vehicle) wipes raindrops with a wiper blade. In addition, an automotive body is usually coated with a decorative coating film made of resin.

[0007]

However, in the method of applying grease or wax to the surface of a vibration damping member for an automobile, a hose for an automobile, a tire for an automobile, and a sealing material for an automobile, when these are started to be used, they are incompatible with other articles. Even if desired characteristics such as relatively good sliding properties are obtained, the grease on the surface is dispersed or absorbed or dropped off over time with time, and the surface is worn, deteriorated, The slidability is reduced.

In addition, in a method of adding an oil to a base material to form an anti-vibration member for automobiles, an automobile hose, an automobile tire, and an automobile sealing material, a relatively good sliding property is obtained at the start of use. Even if the desired properties such as the above are obtained, the oil contained in the surface portion decreases over time due to absorption by other articles, and the surface is worn, deteriorated, or slidability is reduced.

Further, the vibration damping member for automobiles is generally used in contact with an article made of metal, and the hose for automobiles is often used by being fixed with a fixture made of metal. Used in contact with
Since automotive sealing materials are usually used in contact with pipes made of metal, etc., in such cases, the method of applying grease to the surface or the method of adding oil to the base material and forming them requires a metal article. It is not possible to sufficiently prevent surface wear and deterioration due to friction.

[0010] In addition, even in the case of an automobile hose coated with a resin film having gas barrier properties, since the surface is made of resin, similarly good sliding properties with other articles cannot be obtained for a long period of time.
In addition, the surface is easily worn and deteriorated due to friction with an article made of a hard material such as metal. In addition, in the case of an automobile tire, water vapor easily permeated from the outside of the tire to the inside, and in the case of having a tube inside, the tube was easily deteriorated by the water vapor. In addition, during rainy weather, water and mud tended to accumulate in the grooves on the outer periphery.

Further, the automotive diaphragm made of a polymer material is liable to be worn and deteriorated by contact with an article made of metal or the like for fixing the diaphragm, and a fluid such as a liquid handled by the diaphragm adheres. There is a problem that it is easy. Further, a valve part made of resin for an automobile is worn, deteriorated, or deteriorated in slidability due to the valve body and the valve seat contacting each other.

Further, in the method of wiping raindrops attached to the window glass for automobiles with a wiper blade, it may not be possible to sufficiently wipe the raindrops, or the raindrops may adhere again immediately after the wiping and may not be sufficiently removed. Further, in the case of an automobile body, the decorative coating is easily peeled off by contact with other articles, and it is difficult to remove dust adhering to the coating film due to poor water repellency.

Accordingly, an object of the present invention is to provide an automobile part which is excellent in several points in terms of slidability with other articles and members, abrasion resistance, water repellency, and gas barrier properties, and a method of manufacturing the same. And In particular, it is an object of the present invention to provide a vibration damping member for an automobile which has good slidability with other articles, is excellent in abrasion resistance, and hardly deteriorates, and a method for manufacturing the same. In particular, it is another object of the present invention to provide an automotive hose having good slidability with other articles, excellent wear resistance, hardly deteriorated, and excellent gas barrier properties, and a method for manufacturing the same.

In particular, it is another object of the present invention to provide an automobile tire which has good slidability with other articles, has excellent wear resistance, is hardly deteriorated, and has excellent gas barrier properties and water repellency, and a method for producing the same. . In particular, it is another object of the present invention to provide an automotive diaphragm excellent in wear resistance, hardly deteriorated, and excellent in water repellency, and a method for manufacturing the same.

In particular, it is another object of the present invention to provide an automotive valve component which has good slidability with other articles, has excellent wear resistance and is hardly deteriorated, and a method of manufacturing the same. In particular, it is another object of the present invention to provide a sealing material for automobiles which has good slidability with other articles, has excellent wear resistance, and is hardly deteriorated, and a method for producing the same. In particular, it is another object of the present invention to provide a window glass for automobiles having excellent wear resistance and water repellency and a method for manufacturing the same.

In particular, it is another object of the present invention to provide an automobile body having excellent wear resistance and water repellency and a method for manufacturing the same.

[0017]

In order to solve the above-mentioned problems, the present invention provides a vehicle protection system in which a carbon film having wear resistance and lubricity is formed on part or all of the surface. A vibration member is provided. Further, the present invention provides a method of manufacturing a vibration damping member for an automobile, comprising a step of forming a carbon film having wear resistance and lubricity on part or all of the surface.

According to another aspect of the present invention, there is provided an automotive hose characterized in that a carbon film having abrasion resistance, lubricity, and gas barrier properties is formed on part or all of the surface. provide. The present invention also provides a method for manufacturing an automobile hose, which comprises a step of forming a carbon film having abrasion resistance, lubricity, and gas barrier properties on a part or all of the surface.

According to another aspect of the present invention, there is provided an automobile wherein a carbon film having abrasion resistance, lubricity, gas barrier properties, and water repellency is formed on part or all of the surface. To provide tires. The present invention also provides a method for manufacturing an automobile tire, which comprises a step of forming a carbon film having abrasion resistance, lubricity, gas barrier properties, and water repellency on part or all of the surface.

Further, in order to solve the above-mentioned problems, the present invention provides a diaphragm for automobiles, wherein a carbon film having abrasion resistance and water repellency is formed on part or all of the surface. The present invention also provides a method for manufacturing an automotive diaphragm, which comprises a step of forming a wear-resistant and water-repellent carbon film on part or all of the surface.

Further, in order to solve the above-mentioned problems, the present invention provides an automotive valve component characterized in that a carbon film having wear resistance and lubricity is formed on a part or the entire surface. . The present invention also provides a method of manufacturing a valve part for an automobile, comprising a step of forming a carbon film having wear resistance and lubricity on part or all of the surface.

According to another aspect of the present invention, there is provided a sealing material for an automobile, wherein a carbon film having wear resistance and lubricity is formed on a part or all of the surface. . Further, the present invention provides a method for producing a sealing material for automobiles, which comprises a step of forming a carbon film having wear resistance and lubricity on a part or the whole of the surface. Further, in order to solve the above-mentioned problems, the present invention provides a window glass for an automobile, wherein a carbon film having abrasion resistance and water repellency is formed on part or all of the surface. The present invention also provides a method for manufacturing a window glass for an automobile, which comprises a step of forming a carbon film having wear resistance and water repellency on a part or the whole of the surface.

In order to solve the above-mentioned problems, the present invention provides an automobile body (a finished product) characterized in that a carbon film having abrasion resistance and water repellency is formed on a part or all of the surface. (Including parts). Further, the present invention provides a method for manufacturing an automobile body (including finished parts), which comprises a step of forming a wear-resistant and water-repellent carbon film on part or all of the surface. .

The anti-vibration member for an automobile according to the present invention has a carbon film having abrasion resistance and lubricity formed on part or all of the surface of the anti-vibration member base for an automobile. And the portion is hardly worn or deteriorated by friction with other articles. Further, since the carbon film is hard to be worn, good lubricity is maintained for a long time.

As a part or the whole of the surface of the vibration isolating member base for an automobile, for example, a contact surface with another article can be considered. Further, in the automotive hose according to the present invention, since a carbon film having abrasion resistance and lubricity is formed on part or all of the surface of the automotive hose base, the part has good slippage with other articles. In addition, the portion is less likely to be worn or deteriorated due to friction with other articles. Further, since the carbon film is hard to be worn, good lubricity is maintained for a long time. Also,
Since the carbon film has a gas barrier property, in the automotive hose according to the present invention, gas hardly permeates from the outside to the inside or from the inside to the outside in the carbon film forming portion of the hose.

A part or all of the surface of the above-mentioned automotive hose base may vary depending on the purpose of forming the carbon film, but may be a contact surface with another article or an outer surface. Also,
The automotive tire according to the present invention, since a carbon film having abrasion resistance and lubricity is formed on part or all of the surface of the automotive tire base, the part has good slip with other articles, and That portion is less likely to wear or deteriorate due to friction with other articles. Further, since the carbon film is hard to be worn, good lubricity is maintained for a long time. In particular, when a carbon film is formed at a contact portion with the wheel, the carbon film is hardly worn or deteriorated even by friction with the wheel. When a carbon film is formed on the outer surface (excluding the contact surface with the road surface), the carbon film is hardly deteriorated even when exposed to external light or exhaust gas. Further, since the carbon film has a gas barrier property,
When a carbon film is formed on the inner surface of the tire, water vapor is difficult to permeate from the outside to the inside of the tire, and in the case of a type having a tube inside the tire, deterioration of the tube due to the water vapor is suppressed. Further, since the carbon film has water repellency, when the carbon film is formed on the inner surface of the groove on the outer periphery of the tire, it is difficult for water, mud and the like to accumulate in the groove even in rainy weather. Incidentally, the automobile tire according to the present invention,
No carbon film is formed on the contact surface with the road surface around the tire.

In the automotive diaphragm according to the present invention, a carbon film having abrasion resistance and water repellency is formed on a part or all of the surface of the automotive diaphragm base. Abrasion and deterioration hardly occur due to friction, and a liquid or the like handled by the diaphragm hardly adheres to that portion. As a part or all of the surface of the automotive diaphragm base, a contact surface of the automotive diaphragm with another article such as a fixture, a contact surface with the liquid or the like can be considered.

In the valve part for an automobile according to the present invention, a carbon film having wear resistance and lubricity is formed on a part or the entire surface of the base for the automobile valve part.
The part has good slip with other articles, and the part is hardly worn or deteriorated by friction with other articles. Further, since the carbon film is hard to be worn, good lubricity is maintained for a long time.

As a part or the whole of the surface of the valve component base for an automobile, a contact surface with another article can be considered.
The contact surface is, for example, a contact surface with the valve seat in the valve body base, and a contact surface with the valve body in the valve seat base. Further, in the automotive sealing material according to the present invention, since a carbon film having abrasion resistance and lubricity is formed on part or all of the surface of the automotive sealing material base, the portion is slippery with other articles. In addition, the portion is less likely to wear or deteriorate due to friction with other articles. Further, since the carbon film is hard to be worn, good lubricity is maintained for a long time.

As a part or all of the surface of the sealing material base for automobile, for example, a contact surface with another article can be considered. Further, in the automotive window glass (for example, a windshield) according to the present invention, since a carbon film having wear resistance and water repellency is formed on a part or the entire surface of the automotive window glass base, that part is not included in other parts. It is hard to be damaged by contact with an article (for example, particles such as sand), and it is hard for raindrops to adhere to that part even in rainy weather.

Further, the vehicle body according to the present invention comprises:
Abrasion resistance on part or all of the surface of the automobile body base,
Because the water-repellent carbon film is formed, it is difficult to damage the decorative coating even when it comes in contact with other articles, and it is difficult for raindrops to adhere to that part even in rainy weather, It is easy to remove the attached dust. In the present invention, the vibration isolating member substrate for an automobile, the hose substrate for an automobile, the diaphragm substrate for an automobile, and the sealing material substrate for an automobile have at least a film-forming surface at least one organic material selected from organic materials such as rubber and resin. It is conceivable that it is made of a material.

Examples of the rubber include natural rubber, butyl rubber, ethylene propylene rubber, chloroprene rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, acrylic rubber, nitrile rubber, urethane rubber, silicone rubber, fluorine rubber and the like. Further, when the anti-vibration member for automobiles of the present invention is one that holds a heavy object, for example, when high strength or hardness is required, a resin having strength or hardness higher than rubber as a material or surface material of the base is used. Can be used.

When the automotive hose of the present invention is a hose for passing a reactive gas such as exhaust gas, a resin which is chemically more stable and harder to deteriorate than rubber is made of a material of the base or a gas contact surface. It can be used as a material. The same applies to the automotive diaphragm and the automotive sealant of the present invention, and when contacting with a highly reactive gas or liquid, a resin that is chemically more stable and harder to deteriorate than rubber is used as the material or gas or liquid. Can be used as a contact surface material. Examples of the resin that can be used as a material or a surface material of the sealing material base for an automobile include a polyamide-based resin and a polytetrafluoroethylene resin.

Further, in the valve component base for an automobile according to the present invention, at least the film forming surface has relatively high heat resistance.
It may be made of a resin such as a polyimide resin or a polytetrafluoroethylene resin or other organic materials. Further, the vehicle body substrate in the present invention,
It is conceivable that at least the film forming surface is made of an organic material such as a resin. Generally, an automobile body has a coating film made of a resin or the like formed on an outer surface of a body body made of a metal or the like. The body body may also be made of resin.

A typical example of the carbon film in the present invention is a DLC (Diamond Like Carbon) film. The DLC film has good lubricity, is hard to be worn due to friction with other articles, and can be adjusted to a thickness so that the base material has flexibility. It is a carbon film having an appropriate hardness that can be reduced to the extent that the properties are not impaired. In addition, it has good gas barrier properties and water repellency, and good electrical insulation properties. In addition, light can be transmitted by adjusting its thickness, and thus it is suitable as a film formed on the surface of an automotive window glass. Further, the film can be easily formed, for example, the film can be formed at a relatively low temperature.

In any case, the thickness of the carbon film can be formed with good adhesion on the substrate, can function sufficiently as a protective film for the substrate, and can be used even when the substrate has flexibility. What is necessary is just to be in the range which does not impair the original flexibility of the base. Also, a method of manufacturing a vibration damping member for a vehicle, a method of manufacturing a hose for a vehicle, a method of manufacturing a tire for a vehicle, a method of manufacturing a diaphragm for a vehicle according to the present invention,
In the method of manufacturing a valve part for an automobile, the method of manufacturing a sealing material for an automobile, the method of manufacturing a window glass for an automobile, and the method of manufacturing a body for an automobile, a film-forming surface of each of the substrates as a pre-treatment before forming the carbon film. May be exposed to a plasma of at least one pretreatment gas selected from a pretreatment gas, for example, a fluorine (F) -containing gas, a hydrogen (H ₂ ) gas and an oxygen (O ₂ ) gas. In this case, in the automotive anti-vibration member, the automotive hose, the automotive tire, the automotive diaphragm, the automotive valve component, the automotive sealing material, the automotive window glass, and the automotive body of the present invention, each of the bases is Such pre-processing is performed.

As the fluorine-containing gas, fluorine (F
₂ ) gas, nitrogen trifluoride (NF ₃ ) gas, sulfur hexafluoride (SF ₆ ) gas, carbon tetrafluoride (CF ₄ ) gas, silicon tetrafluoride (SiF ₄ ) gas, disilicon hexafluoride ( Si ₂
F ₆ ) gas, chlorine trifluoride (ClF ₃ ) gas, hydrogen fluoride (HF) gas and the like. By exposing each of the substrates to the plasma of the pretreatment gas, the substrate surface is cleaned or the substrate surface roughness is further improved. These contribute to improving the adhesion of the carbon film,
A highly adherent carbon film can be obtained.

Further, the film-forming surfaces of the vibration isolating member substrate for automobile, the hose substrate for automobile, the diaphragm substrate for automobile, the valve component substrate for automobile, the sealing material substrate for automobile, and the body substrate for automobile are made of organic materials such as rubber and resin, respectively. When a fluorine-containing gas plasma is employed, the substrate surface is fluorine-terminated, and the hydrogen gas plasma is formed when the fluorine-containing gas plasma is used. When this is adopted, the substrate surface is terminated with hydrogen. Since the fluorine-carbon bond and the hydrogen-carbon bond are stable, by performing the termination treatment as described above, the carbon atoms in the film form a stable bond with the fluorine atoms or the hydrogen atoms on the substrate surface portion. From these facts, it is possible to improve the adhesion between the carbon film formed thereafter and the substrate.

When oxygen gas plasma is employed, dirt such as organic substances adhering to the surface of the substrate can be particularly efficiently removed, and from these facts, the adhesion between the carbon film formed thereafter and the substrate can be improved. Can be. In the method of the present invention, the pretreatment of the substrate with the plasma performed prior to the formation of the carbon film may be performed a plurality of times using the same type of plasma or using different types of plasma. For example, the film-forming surfaces of an automobile vibration-isolating member substrate, an automobile hose substrate, an automobile diaphragm substrate, an automobile valve component substrate, an automobile sealing material substrate, and an automobile body substrate are each made of an organic material such as rubber or resin. In the case of automotive glazings and in the case of automotive tyres, which are usually made of organic materials, the substrate is exposed to an oxygen gas plasma followed by a fluorine-containing gas plasma or a hydrogen gas plasma, and When forming a carbon film, the surface of the substrate is cleaned and then terminated with fluorine or hydrogen, so that the adhesion between the subsequently formed carbon film and the surface of the substrate becomes very good.

The method of forming a carbon film according to the present invention includes a method of forming a film at least in a temperature range that does not cause thermal damage to a substrate using a material having relatively low heat resistance such as rubber or resin as a material of the film forming surface. As a method that can be formed, a plasma CVD method, a sputtering method, an ion plating method, and the like can be given. In particular, when the plasma CVD method is used, the pretreatment of the substrate to be formed with plasma and the formation of the carbon film are the same. It can be done with the device.

When a carbon film is formed by a plasma CVD method, methane (CH ₄ ), ethane (C ₂ H ₆ ), propane (C ₃ H ₈ ), butane A carbon compound gas such as (C ₄ H ₁₀ ), acetylene (C ₂ H ₂ ), benzene (C ₆ H ₆ ), carbon tetrafluoride (CF ₄ ), and carbon difluoride (C ₂ F ₆ ); If necessary, a mixture of these carbon compound gases with a hydrogen gas, an inert gas, or the like as a carrier gas can be used.

[0042]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows the manufacture of a vibration damping member for a vehicle, the manufacture of a hose for a vehicle, the manufacture of a tire for a vehicle, the manufacture of a diaphragm for a vehicle, the manufacture of a valve part for a vehicle, the manufacture of a sealing material for a vehicle, the window of a vehicle according to the present invention. It is a figure which shows the schematic structure of an example of the film-forming apparatus which can be used for manufacture of glass and manufacture of the body for motor vehicles, respectively. FIG. 3A is a cross-sectional view of one example of an automobile anti-vibration member according to the present invention, and FIG. 3B is a cross-sectional view of one example of an automobile hose according to the present invention. FIG. 3C is a cross-sectional view of one example of an automobile tire according to the present invention, FIG. 3D is a cross-sectional view of one example of an automobile diaphragm according to the present invention, and FIG. 1 of automotive valve parts according to
FIG. 3 (F) is a partial side view of an example (valve element), and FIG. 3 (F) is a cross-sectional view of an example of the automotive sealing material according to the present invention.
(G) is a cross-sectional view of one example (a windshield) of a window glass for an automobile according to the present invention, and FIG. 3 (H) is a cross-sectional view of one example of a body for an automobile according to the present invention, particularly, parts thereof.

This apparatus has a vacuum chamber 1 provided with an exhaust device 11, in which an electrode 2 and an electrode 3 are installed at a position facing the electrode 2. The electrode 3 is grounded, and a high frequency power supply 23 is connected to the electrode 2 via a matching box 22. Further, the electrode 2 is provided with a heater 21 for heating the substrate on which the film is to be formed to a film forming temperature. Further, the chamber 1 is provided with a gas supply unit 4 so that a plasma source gas can be introduced therein. The gas supply unit 4 includes mass flow controllers 411, 412,.
422,... Connected to each other through one or more plasma source gases 431, 432,.

In manufacturing the automotive anti-vibration member according to the present invention using this apparatus, the automotive anti-vibration member base S1 is oriented with the contact surface S1 'with another article facing the electrode 3. 2 and the inside of the chamber 1 is set to a predetermined degree of vacuum by the operation of the exhaust device 11. Next, one or more of a fluorine-containing gas, a hydrogen gas, and an oxygen gas are introduced into the chamber 1 from the gas supply unit 4 as a pretreatment gas, and the high frequency power source 23 supplies a matching box 2.
A high-frequency power is supplied to the electrode 2 through the electrode 2 to convert the introduced pretreatment gas into a plasma, and the surface treatment of the substrate S1 is performed under the plasma. Note that this surface treatment (pretreatment) is desirably performed, but is not necessarily required.

Next, if necessary, the inside of the chamber 1 is evacuated again, and then a carbon compound gas is introduced into the chamber 1 from the gas supply unit 4 as a raw material gas for film formation. Is supplied, whereby the introduced carbon compound gas is turned into plasma, and under the plasma, a carbon film is formed on the contact surface S1 ′ of the substrate S1 with another article.

In this way, as shown in FIG. 3A, the contact surface S of the anti-vibration member substrate S1 with another article is provided.
A carbon film-coated automotive anti-vibration member having the carbon film F formed on 1 'is obtained. Also, when manufacturing the automotive hose according to the present invention using this apparatus, the outer surface S2 ′ of the automotive hose base S2 (see FIG. 3) is formed in the same manner as in the manufacture of the automotive anti-vibration member. Perform surface treatment and carbon film formation. During this time, a part of the automotive hose base S2 is brought into contact with the electrode 2, and the base S2 is rotated around its axis by rotating means (not shown), so that the outer surface S2 'of the base S2 is substantially uniformly surface-treated and formed. Let the film take place. The anti-vibration member may be similarly rotated if necessary.

In this way, as shown in FIG. 3 (B), a carbon film-coated automotive hose in which the carbon film F is formed substantially uniformly on the outer surface S2 'of the automotive hose substrate S2 is obtained. Also, when manufacturing the automobile tire according to the present invention using this apparatus, the outer surface of the automobile tire base S3 (excluding the contact portion with the road surface) is manufactured in the same manner as in the production of the automobile anti-vibration member. In S3 '(see FIG. 3), the surface treatment and the formation of the carbon film are performed. During this time, a part of the automobile tire base S3 is brought into contact with the electrode 2, and the base S3 is rotated around its axis by rotating means (not shown).
The surface treatment and film formation are performed substantially uniformly on the outer surface (excluding the contact portion with the road surface) S3 'of the third surface. It should be noted that the film is formed in a state where a portion of the outer surface of the tire base S3 that comes into contact with the road surface is masked with an appropriate film or the like in advance, so that a carbon film is not formed on the portion.

In this manner, as shown in FIG. 3C, the carbon film F having the carbon film F formed almost uniformly on the outer surface (excluding the portion in contact with the road surface) S3 'of the automobile tire base S3. A coated automotive tire is obtained. Also, when manufacturing the automotive diaphragm according to the present invention using this device, the outer surface S4 'of the automotive diaphragm base S4 (see FIG. 3) is formed in the same manner as in the manufacture of the automotive anti-vibration member. Perform surface treatment and carbon film formation.

In this manner, as shown in FIG. 3D, a carbon film-coated automotive diaphragm in which the carbon film F is formed substantially uniformly on the outer surface S4 'of the automotive diaphragm base S4 is obtained. Also, when manufacturing the automotive valve component (valve element used in the intake / exhaust valve of the automobile in the illustrated example) using this apparatus in the same manner as the production of the automobile anti-vibration member. Then, the surface treatment and the carbon film formation are performed on the contact surface (in the illustrated example, the contact surface with the valve seat) S5 '(see FIG. 3) of the automotive valve component base S5 with another article.

In this way, as shown in FIG. 3 (E), a carbon film in which the carbon film F is formed substantially uniformly on the contact surface S5 'of the automobile valve component base S5 with other articles. A coated automotive valve component is obtained. Also, when manufacturing the automotive sealing material according to the present invention using this apparatus, similarly to the manufacturing of the automotive anti-vibration member, other than the automotive sealing material base S6 (here, a ring-shaped one) is used. The surface treatment and the formation of the carbon film are performed on the contact surface S6 ′ (see FIG. 3) with the article.

Thus, as shown in FIG. 3 (F), the contact surface S6 of the sealing material base S6 for the automobile with other articles is formed.
', A carbon film-coated automotive sealing material having a carbon film F formed substantially uniformly is obtained. Also, when manufacturing the automotive windshield according to the present invention using this apparatus, similarly to the manufacturing of the automobile anti-vibration member, the outer surface S7 'of the automotive windshield base S7 (see FIG. 3).
Then, the surface treatment and the formation of the carbon film are performed.

In this way, as shown in FIG. 3 (G), a carbon film-coated automotive windshield in which the carbon film F is formed substantially uniformly on the outer surface S7 'of the automotive windshield base S7 is obtained. . Further, in manufacturing the automobile body (part) according to the present invention using this apparatus, similarly to the production of the automobile anti-vibration member, the outer surface S8 ′ ( (See Fig. 3)
Then, the surface treatment and the formation of the carbon film are performed.

In this manner, as shown in FIG. 3 (H), the carbon film-coated automobile body (part) in which the carbon film F is formed substantially uniformly on the outer surface S8 'of the automobile body (part) substrate S8. ) Is obtained. In carrying out the method of the present invention, a film forming apparatus shown in FIG. 2 can be used instead of the apparatus shown in FIG. 1. In this case, even when the substrate is a three-dimensional structure, the surface of the substrate can be efficiently placed on the substrate. A film can be formed.

FIG. 2 shows an inductively coupled plasma CV
D device, which has a vacuum container 1 ′, and an induction coil electrode 5 is wound around the outer periphery of the container 1 ′, and a matching box 51 and a high-frequency power supply 52 are provided at both ends of the electrode 5.
Is connected. A heater 21 ′ for heating the substrate on which the film is to be formed to a film forming temperature is provided outside the vacuum vessel 1 ′.

Further, an exhaust device 11 'is connected to the vacuum vessel 1' by a pipe, and a gas supply unit 4 'of a film forming material gas is connected by a pipe. A gas for supplying one or more film-forming source gases connected to the gas supply unit 4 'via mass flow controllers 411', 412 ',... And valves 421', 422 ',. Source 431 ', 4
32 ′... Are included.

In manufacturing the automobile anti-vibration member, automobile hose or automobile tire according to the present invention using this apparatus, the automobile anti-vibration member base S1 and the automobile hose base using the apparatus of FIG. In the same manner as the surface treatment and the carbon film formation of S2 and the automobile tire base S3, the source gas is turned into plasma by applying high-frequency power to the induction coil electrode 5. Also in this case, surface treatment (pretreatment) is desirably performed, but is not necessarily required.

Next, the apparatus shown in FIG. 1 is used as a material for a vibration damping member for a vehicle, a hose for a vehicle, a tire for a vehicle, a diaphragm for a vehicle, and a sealing material for a vehicle.
An experimental example in which a DLC film is formed on the surface of a test piece made of a terpolymer rubber (EPDM) of an ethylene-propylene-diene monomer will be described. EXPERIMENTAL EXAMPLE 1 In the manufacture of the anti-vibration member for an automobile using the apparatus of FIG. 1 described above, the DLC film was formed directly on the outer surface of the test piece without performing the pre-treatment of the test piece with the gas plasma for pre-treatment. .

Test piece material EPDM size 20 cm × 20 cm × thickness 1 cm High-frequency electrode 2 size 40 cm × 40 cm Film-forming conditions Film-forming raw material gas Methane (CH ₄ ) 100 sccm High-frequency power Frequency 13.56 MHz, 300 W Film-forming vacuum 0. 1 Torr Film forming speed 500 ° / min Film forming time 20 min Experimental example 2 Prior to film forming, the test piece was subjected to a pretreatment with hydrogen gas plasma under the following conditions before the film formation. The film forming conditions were the same as those in Experimental Example 1.

Pretreatment Conditions Pretreatment Gas Hydrogen (H ₂ ) 100 sccm High Frequency Power Frequency 13.56 MHz, 300 W Processing Vacuum 0.1 Torr Processing Time 5 min Experimental Example 3 In Experimental Example 1, prior to film formation, the same test piece was used. Was subjected to a pretreatment with a fluorine compound gas plasma under the following conditions. The film forming conditions were the same as those in Experimental Example 1.

Pretreatment Conditions Pretreatment Gas Sulfur Hexafluoride (SF ₆ ) 100 sccm High Frequency Power Frequency 13.56 MHz, 300 W Processing Vacuum 0.1 Torr Processing Time 5 min Experimental Example 4 In Experimental Example 1, prior to film formation, The test piece was subjected to a first pretreatment with oxygen gas plasma under the following conditions, and further subjected to a second pretreatment with hydrogen gas plasma. The film forming conditions were the same as those in Experimental Example 1.

First Pretreatment Condition Pretreatment Gas Oxygen (O ₂ ) 100 sccm High Frequency Power Frequency 13.56 MHz, 300 W Processing Vacuum 0.1 Torr Processing Time 5 min Second Pretreatment Condition Pretreatment Gas Hydrogen (H ₂ ) 100 sccm RF power frequency 13.56 MHz, 300 W Processing degree of vacuum 0.1 Torr Processing time 5 min Experimental example 5 Prior to film formation, the test piece was subjected to the first pretreatment with oxygen gas plasma under the following conditions before film formation. Then, a second pretreatment with a fluorine compound gas plasma was performed. The film forming conditions were the same as those in Experimental Example 1.

First pretreatment condition Pretreatment gas Oxygen (O ₂ ) 100 sccm High frequency power Frequency 13.56 MHz, 300 W Processing vacuum degree 0.1 Torr Processing time 5 min Second pretreatment condition Pretreatment gas Sulfur hexafluoride (SF) ₆ ) 100 sccm high frequency power Frequency 13.56 MHz, 300 W Processing vacuum degree 0.1 Torr Processing time 5 min Next, using the apparatus shown in FIG. 1, a test piece made of polyimide which may be used as a material for valve parts for automobiles or the like is prepared. An experimental example in which a DLC film is formed on the surface will be described. Experimental Example 6 In the manufacture of the vibration isolating member for an automobile using the apparatus of FIG. 1 described above, the DLC film was formed directly on the outer surface of the test piece without performing the pretreatment of the test piece with the pretreatment gas plasma. .

Test Piece Material Polyimide Size 20 cm × 20 cm × Thickness 1 cm High Frequency Electrode 2 Size 40 cm × 40 cm Deposition Conditions Deposition Material Gas Methane (CH ₄ ) 100 sccm High Frequency Power Frequency 13.56 MHz, 300 W Deposition degree of vacuum 1 Torr Film forming rate 500 ° / min Film forming time 20 min Experimental Example 7 In Experimental Example 6, prior to film formation, the test piece was subjected to a pretreatment with hydrogen gas plasma under the following conditions. The film forming conditions were the same as those in Experimental Example 6.

Pretreatment Conditions Pretreatment Gas Hydrogen (H ₂ ) 100 sccm High Frequency Power Frequency 13.56 MHz, 300 W Processing Vacuum 0.1 Torr Processing Time 5 min Experimental Example 8 In Experimental Example 6, prior to film formation, the same test piece was used. Was subjected to a pretreatment with a fluorine compound gas plasma under the following conditions. The film forming conditions were the same as those in Experimental Example 6.

Pretreatment Conditions Pretreatment Gas Sulfur Hexafluoride (SF ₆ ) 100 sccm High Frequency Power Frequency 13.56 MHz, 300 W Processing Vacuum 0.1 Torr Processing Time 5 min Experimental Example 9 In Experimental Example 6, prior to film formation, The test piece was subjected to a first pretreatment with oxygen gas plasma under the following conditions, and further subjected to a second pretreatment with hydrogen gas plasma. The film forming conditions were the same as those in Experimental Example 6.

First Pretreatment Condition Pretreatment Gas Oxygen (O ₂ ) 100 sccm High Frequency Power Frequency 13.56 MHz, 300 W Processing Vacuum 0.1 Torr Processing Time 5 min Second Pretreatment Condition Pretreatment Gas Hydrogen (H ₂ ) 100 sccm High frequency power Frequency 13.56 MHz, 300 W Processing vacuum degree 0.1 Torr Processing time 5 min Experimental example 10 Prior to film formation, the test piece was subjected to the first pretreatment with oxygen gas plasma under the following conditions before the film formation. Then, a second pretreatment with a fluorine compound gas plasma was performed. The film forming conditions were the same as those in Experimental Example 6.

First pretreatment condition Pretreatment gas Oxygen (O ₂ ) 100 sccm High frequency power Frequency 13.56 MHz, 300 W Processing vacuum degree 0.1 Torr Processing time 5 min Second pretreatment condition Pretreatment gas Sulfur hexafluoride (SF) ₆ ) 100 sccm high-frequency power Frequency 13.56 MHz, 300 W Processing vacuum degree 0.1 Torr Processing time 5 min Next, the DLC film-coated test pieces obtained in Experimental Examples 1 to 5 and the untreated DLC film-free test pieces were not formed. Of the test pieces (Comparative Experimental Example 1) and the Experimental Examples 6-1
Of the DLC film-coated test piece obtained in accordance with Comparative Example No. 0 and a similar untreated test piece (Comparative Experimental Example 2), the coefficient of friction with the aluminum material, the wear characteristics with the diamond material, and the water repellency Was evaluated. In addition, the adhesion between the DLC film and the test piece was evaluated for each of the DLC film-coated test pieces obtained in Experimental Examples 1 to 10.

The coefficient of friction was determined by contacting the tip of a pin-shaped article made of aluminum against the surface of a test piece, and applying a load of 10 g to the pin-shaped article.
/ Sec was measured at a speed of 20 mm / sec., And the abrasion characteristics were determined by contacting the tip of a pin-shaped article made of diamond on the surface of the test piece and applying a load of 100 g to the test piece at 20 mm / It was moved at a speed of sec and evaluated by measuring the worn depth per hour. For film adhesion, the columnar member is bonded to the film surface using an adhesive,
The columnar member was pulled in a direction perpendicular to the film to peel the film from the test piece main body, and the tensile method for measuring the force required for peeling was evaluated. The water repellency was evaluated by placing a water drop on the test piece and measuring the contact angle.

When the liquid is present on the solid surface in the air, the contact angle is defined as the angle between the cut line drawn through the liquid at the three-phase contact point of solid, liquid, and gas and the solid surface. The larger the included corner, the larger the water repellency. The results are shown in the following table. Coefficient of friction Wear characteristic Film adhesion strength Contact angle (μm / h) (kg / mm ² ) (°) Experimental example 1 0.9 2 100 Experimental example 2 1 0.74 100 Experimental example 3 1 0.74 100 Experimental example 4 1 0.55 100 Experimental example 5 1 0.55 100 Experimental example 6 1 0.7 2 110 Experimental example 7 1 0.64 110 Experimental example 8 1 0.64 110 Experimental example 9 10 5.5 5 110 Experimental Example 10 1 0.5 5 110 Comparative Experimental Example 1 3 2.5 ８０ 80 Comparative Experimental Example 2 3 1.8 ８５ 85 Thus, Experimental Examples 1 to 5 and Experimental Examples in which the DLC film was coated In each of the test pieces of Nos. 6 to 10, the friction coefficient between the test piece and the aluminum material was smaller than that of the test pieces of Comparative Example 1 and Comparative Example 2 not coated with the DLC film, and the lubricity (slidability) was good. You can see that. Further, the wear characteristic value between the diamond material and the diamond material is not compared with the DLC film.
And it was smaller than the test piece of Comparative Experimental Example 2.

The adhesion strength of each of the DLC films of Experimental Examples 1 to 10 to the test piece body was determined by the test of Experimental Examples 2 to 5 in which the surface of the test piece body was subjected to plasma pretreatment prior to the formation of the DLC film. The test pieces were larger in the test pieces than in the test example 1 without the pretreatment, and the test pieces in the test examples 7 to 10 were larger than the test pieces in the test example 6 without the pretreatment.

In each of the test pieces of Experimental Examples 1 to 5 and 6 to 10 coated with a DLC film, the contact angle of water was DLC.
It can be seen that the test pieces of Comparative Experimental Example 1 and Comparative Experimental Example 2, which are not coated with a film, are larger and have better water repellency.
Next, in the same manner as in Experimental Example 1, a DLC film was formed on one surface of a polyvinylidene chloride film (a fatty acid derivative was added as a softener and an epoxidized vegetable oil was added as a stabilizer). The moisture permeability (water vapor transmission rate) and the oxygen transmission rate of the test piece (Experimental Example 11) and the untreated similar film-like test piece having no DLC film formed thereon (Comparative Experimental Example 3) were measured.

Using a gas permeability measuring device manufactured by Mocon, the relative humidity of one space of the film was set to 100% and the relative humidity of the other space of the film was set to almost 0% at a temperature of 25 ° C. Was evaluated by measuring the permeation rate of water vapor. In addition, the oxygen transmission rate is similarly determined by Moco.
Using a gas permeability measurement device manufactured by n company, at a temperature of 25 ° C.,
The oxygen concentration in one space of the film was set to 100%, and the oxygen concentration in the other space of the film was set to 0%.

The results are shown in the following table. Moisture permeability Oxygen permeability (cc / m ² / day) (cc / m ² / day) Experimental example 11 0.9 1.2 Comparative experimental example 3 12.5 14.0 Thus, the DLC film was coated. It can be seen that, in the test piece of Experimental Example 11, the permeation of both water vapor and oxygen was suppressed as compared with the test piece of Comparative Experimental Example 3 not coated with the DLC film.

From the above, it can be seen that the anti-vibration member for an automobile of the present invention in which a carbon film (particularly, a DLC film) is formed on a part or all of the surface is excellent in lubricity and abrasion resistance in that part. The slidability between the carbon film and another article (usually made of metal) in contact with the carbon film is almost the same as the slidability between the carbon film and the aluminum material. Is considered to have excellent slidability with other articles.

Further, from the above, the automotive hose of the present invention in which a carbon film (particularly a DLC film) is formed on a part or all of the surface of the automotive hose base, has lubricity, abrasion resistance and gas barrier properties at that part. It turns out that it is excellent in property. Also,
From the above, the automobile tire of the present invention in which the carbon film (particularly, the DLC film) is formed on a part or the whole of the surface of the automobile tire substrate has lubricity, abrasion resistance, gas barrier properties, and water repellency of the part. It turns out that it is excellent.

In view of the above, a carbon film (particularly a DLC film) is formed on a part or all of the surface of an automotive diaphragm base.
It can be seen that the automotive diaphragm of the present invention in which is formed is excellent in abrasion resistance and water repellency at that portion. From the above, the automotive valve component of the present invention in which a carbon film (particularly a DLC film) is formed on a part or the entire surface of the automotive valve component base has excellent lubricity and wear resistance at that portion. I understand.

Further, from the above, the automotive sealing material of the present invention in which a carbon film (particularly a DLC film) is formed on part or all of the surface of the automotive sealing material substrate, has lubricity and abrasion resistance at that portion. It turns out that it is excellent. Further, from the above, it can be seen that the automobile body of the present invention in which the carbon film (particularly the DLC film) is formed on a part or all of the surface of the automobile body substrate has excellent wear resistance and water repellency at that part. .

Further, it can be seen that the carbon film formed after performing the pretreatment has excellent adhesion. Although not shown here, a carbon film (particularly a DLC film) is partially or entirely provided on the surface.
Similarly, the automotive window glass of the present invention in which was formed was also obtained a result showing good wear resistance and water repellency at that portion.

[0079]

As described above, according to the present invention, it is possible to provide a vibration damping member for an automobile which has good slidability with other articles, has excellent abrasion resistance and is hardly deteriorated, and a method of manufacturing the same. . Further, according to the present invention, it is possible to provide an automotive hose having good slidability with other articles, excellent abrasion resistance, hardly deteriorating, and excellent gas barrier properties, and a method of manufacturing the same.

Further, according to the present invention, there is provided an automobile tire excellent in slidability with other articles, excellent in abrasion resistance, hardly deteriorated, and excellent in gas barrier properties and water repellency, and a method of manufacturing the same. Can be. Further, according to the present invention, it is possible to provide an automotive diaphragm excellent in wear resistance, hardly deteriorated, and excellent in water repellency, and a method for manufacturing the same.

Further, according to the present invention, it is possible to provide an automotive valve component which has good slidability with other articles, has excellent wear resistance and is hardly deteriorated, and a method of manufacturing the same. Also,
ADVANTAGE OF THE INVENTION According to this invention, the slidability with other articles is favorable, it is excellent in abrasion resistance, and the sealing material for motor vehicles which is hard to deteriorate and its manufacturing method can be provided. Further, according to the present invention, it is possible to provide an automotive window glass having excellent wear resistance and water repellency, and a method for producing the same.

Further, according to the present invention, it is possible to provide an automobile body excellent in abrasion resistance and water repellency and a method for producing the same.

[Brief description of the drawings]

FIG. 1 is a diagram showing a schematic configuration of an example of a film forming apparatus that can be used for manufacturing an automobile anti-vibration member and the like according to the present invention.

FIG. 2 is a diagram illustrating a schematic configuration of another example of a film forming apparatus that can be used for manufacturing a vibration isolating member for an automobile and the like according to the present invention.

FIG. 3 (A) is a cross-sectional view of one example of an automobile anti-vibration member according to the present invention, and FIG. 3 (B) is a cross-sectional view of one example of an automobile hose according to the present invention; FIG. 3C is a cross-sectional view of one example of the automobile tire according to the present invention, and FIG.
FIG. 3 is a cross-sectional view of one example of the automotive diaphragm according to the present invention, and FIG. 3E is a side view of a part of one example (valve element) of the automotive valve component according to the present invention. FIG. 3F is a cross-sectional view of one example of the automotive sealing material according to the present invention, and FIG.
(G) is a cross-sectional view of one example (a windshield) of a window glass for an automobile according to the present invention, and FIG. 3 (H) is a cross-sectional view of one example of a body for an automobile according to the present invention, particularly, parts thereof.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1, 1 'Vacuum chamber 11, 11' Exhaust device 2 High frequency electrode 21, 21 'Heater 22, 51 Matching box 23, 52 High frequency power supply 3 Ground electrode 4, 4' Plasma raw material gas supply part 5 Induction coil electrode S1 Film formation Automotive anti-vibration member substrate S1 'Contact surface of substrate S1 with other articles S2 Deposited vehicle hose substrate S2' Outer surface of substrate S2 S3 Deposited automotive tire substrate S3 'Outer surface of substrate S3 S4) Diaphragm substrate for film-forming automobile S4 'Outer surface of substrate S4 S5 Film-forming valve component substrate S5' Contact surface of substrate S5 with other articles S6 Film-forming film sealing material substrate S6 'Surface of substrate S6 in contact with other articles S7 Film-formed automotive windshield substrate S7' Outer surface of substrate S7 S8 Film-formed automotive body substrate S8 ' Outside the body S8 surfaces F carbon film

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C23C 16/26 C23C 16/26 F16J 3/02 F16J 3/02 A F16L 11/04 F16L 11/04 // B05D 5/00 B05D 5/00 B

Claims (60)

[Claims] An anti-vibration member for an automobile, wherein a carbon film having wear resistance and lubricity is formed on part or all of the surface. 2. The vibration damping member according to claim 1, wherein the carbon film is a DLC film. 3. The anti-vibration member for an automobile according to claim 1, wherein the film forming surface of the base of the anti-vibration member for an automobile is made of an organic material. 4. An automotive hose characterized in that a carbon film having abrasion resistance, lubricity and gas barrier properties is formed on part or all of the surface. 5. The automotive hose according to claim 4, wherein said carbon film is a DLC film. 6. The automotive hose according to claim 4, wherein the film-forming surface of the substrate of the automotive hose is made of an organic material. 7. An automobile tire characterized in that a carbon film having abrasion resistance, lubricity, gas barrier properties and water repellency is formed on part or all of the surface. 8. The automobile tire according to claim 7, wherein the carbon film is a DLC film. 9. An automotive diaphragm characterized in that a carbon film having abrasion resistance and water repellency is formed on part or all of the surface. 10. The carbon film is a DLC film.
The automotive diaphragm according to any of the preceding claims. 11. A film forming surface of a base of the automotive diaphragm is made of an organic material.
The automotive diaphragm according to any of the preceding claims. 12. A valve part for automobiles, wherein a carbon film having wear resistance and lubricity is formed on a part or the whole of the surface. 13. The method according to claim 1, wherein the carbon film is a DLC film.
2. The automotive valve component according to 2. 14. The vehicle-formed valve component according to claim 12, wherein the film-forming surface of the base is made of an organic material.
An automotive valve component as described. 15. A sealing material for automobiles, wherein a carbon film having wear resistance and lubricity is formed on part or all of the surface. 16. The method according to claim 1, wherein the carbon film is a DLC film.
5. The sealing material for an automobile according to 5. 17. The automotive sealing material according to claim 15, wherein a film forming surface of the base of the automotive sealing material is made of an organic material. 18. A window glass for automobiles, wherein a carbon film having abrasion resistance and water repellency is formed on part or all of the surface. 19. The method according to claim 1, wherein the carbon film is a DLC film.
8. The window glass for an automobile according to 8. 20. An automobile body characterized in that a carbon film having wear resistance and water repellency is formed on a part or the whole of the surface. 21. The carbon film is a DLC film.
The vehicle body according to 0. 22. The vehicle body according to claim 20, wherein a film forming surface of the base of the vehicle body is made of an organic material. 23. A method of manufacturing a vibration isolating member for an automobile, comprising a step of forming a carbon film having wear resistance and lubricity on a part or the whole of the surface. 24. Prior to the formation of the carbon film, as a pretreatment, a film-forming surface of the base of the vibration damping member for an automobile is formed from a fluorine (F) -containing gas, a hydrogen (H ₂ ) gas and an oxygen (O ₂ ) gas. 24. The method for manufacturing a vibration isolating member for an automobile according to claim 23, wherein the vibration isolating member is exposed to a plasma of at least one selected gas. 25. The method according to claim 23, wherein the carbon film is formed by a plasma CVD method. 26. The carbon film as a DLC film.
26. The method for manufacturing a vibration isolating member for an automobile according to 3, 24 or 25. 27. The method according to claim 23, wherein a film-forming surface of the base of the automotive anti-vibration member is made of an organic material. 28. A method of manufacturing a hose for an automobile, comprising a step of forming a carbon film having abrasion resistance, lubricity and gas barrier properties on a part or all of the surface. 29. Prior to the formation of the carbon film, as a pretreatment, a film-forming surface of the base of the automobile hose is selected from a fluorine (F) -containing gas, a hydrogen (H ₂ ) gas and an oxygen (O ₂ ) gas. 29. The method of manufacturing an automotive hose according to claim 28, wherein the method is exposed to a plasma of at least one gas. 30. The method for manufacturing an automotive hose according to claim 28, wherein the carbon film is formed by a plasma CVD method. 31. The method according to claim 2, wherein the carbon film is a DLC film.
31. The method for producing an automotive hose according to 8, 29 or 30. 32. The method of manufacturing an automotive hose according to claim 28, wherein the film forming surface of the substrate of the automotive hose is made of an organic material. 33. A method for manufacturing an automobile tire, comprising a step of forming a carbon film having abrasion resistance, lubricity, gas barrier properties, and water repellency on part or all of the surface. 34. Prior to the formation of the carbon film, as a pretreatment, a film forming surface of the base of the automobile tire is selected from a fluorine (F) -containing gas, a hydrogen (H ₂ ) gas and an oxygen (O ₂ ) gas. 34. The method of manufacturing an automobile tire according to claim 33, wherein the method is exposed to a plasma of at least one gas. 35. The method for manufacturing an automobile tire according to claim 33, wherein the carbon film is formed by a plasma CVD method. 36. The carbon film as a DLC film.
36. The method for producing an automobile tire according to 3, 34 or 35. 37. A method for manufacturing an automotive diaphragm, comprising a step of forming a wear-resistant and water-repellent carbon film on part or all of the surface. 38. Prior to the formation of the carbon film, as a pretreatment, a film-forming surface of the base of the automotive diaphragm is made of a fluorine (F) -containing gas, a hydrogen (H ₂ ) gas and an oxygen (O ₂ ) gas.
The method for manufacturing a diaphragm for an automobile according to claim 37, wherein the method is exposed to a plasma of at least one gas selected from gases. 39. The method for manufacturing an automotive diaphragm according to claim 37, wherein the carbon film is formed by a plasma CVD method. 40. The carbon film as a DLC film.
40. The method for producing an automotive diaphragm according to 7, 38 or 39. 41. The film forming surface of the base of the automotive diaphragm is made of an organic material.
0. The manufacturing method of the automotive diaphragm according to any one of the above items. 42. A method for manufacturing a valve part for an automobile, comprising a step of forming a carbon film having wear resistance and lubricity on a part or the whole of the surface. 43. Prior to the formation of the carbon film, as a pre-treatment, the film-forming surface of the automobile valve component base is selected from a fluorine (F) -containing gas, a hydrogen (H ₂ ) gas and an oxygen (O ₂ ) gas. 43. The method for manufacturing a valve part for an automobile according to claim 42, wherein the method is exposed to a plasma of at least one gas. 44. The method according to claim 42, wherein the carbon film is formed by a plasma CVD method. 45. The carbon film is a DLC film.
45. The method for producing a valve component for an automobile according to 2, 43 or 44. 46. The film forming surface of the base of the automobile valve component is made of an organic material.
The method for manufacturing a valve part for an automobile according to any one of the above. 47. A method of manufacturing a sealing material for an automobile, comprising a step of forming a carbon film having wear resistance and lubricity on a part or all of the surface. 48. Prior to the formation of the carbon film, as a pretreatment, a film-forming surface of the substrate of the sealing material for an automobile is selected from a fluorine (F) -containing gas, a hydrogen (H ₂ ) gas and an oxygen (O ₂ ) gas. 48. The method for manufacturing a sealing material for an automobile according to claim 47, wherein the method is exposed to plasma of at least one kind of gas obtained. 49. The method according to claim 47, wherein the carbon film is formed by a plasma CVD method. 50. The carbon film as a DLC film.
50. The method for producing a sealing material for an automobile according to 7, 48 or 49. 51. The method of manufacturing a sealing material for an automobile according to claim 47, wherein the film forming surface of the base of the sealing material for an automobile is made of an organic material. 52. A method for manufacturing a window glass for an automobile, comprising a step of forming a wear-resistant and water-repellent carbon film on part or all of the surface. 53. As a pre-treatment, prior to the formation of the carbon film, a film-forming surface of the substrate of the automotive window glass is selected from a fluorine (F) -containing gas, a hydrogen (H ₂ ) gas and an oxygen (O ₂ ) gas. 53. The method for manufacturing a window glass for an automobile according to claim 52, wherein the method is exposed to a plasma of at least one selected gas. 54. The method for manufacturing a window glass for an automobile according to claim 52, wherein the carbon film is formed by a plasma CVD method. 55. The carbon film as a DLC film.
56. The method for producing a window glass for an automobile according to 2, 53 or 54. 56. A method for manufacturing an automobile body, comprising a step of forming a wear-resistant and water-repellent carbon film on part or all of the surface. 57. Prior to the formation of the carbon film, as a pretreatment, a film forming surface of the base of the vehicle body is selected from a fluorine (F) -containing gas, a hydrogen (H ₂ ) gas and an oxygen (O ₂ ) gas. 57. The method for manufacturing an automobile body according to claim 56, wherein the method is exposed to plasma of at least one gas. 58. The method for manufacturing an automobile body according to claim 56, wherein the carbon film is formed by a plasma CVD method. 59. The carbon film as a DLC film.
60. The method for manufacturing an automobile body according to 7, 58 or 59. 60. The method of manufacturing an automobile body according to claim 56, wherein the film forming surface of the substrate of the automobile body is made of an organic material.