JP2627939B2 - Office materials covered with carbon film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Application of the Invention" The present invention covers the surface of an organic office member having a surface that can be rubbed with paper, a human body, or clothing with a protective coating mainly composed of carbon or carbon. It is a thing. Further, the abrasion resistance is improved, the adhesion of dust is prevented, and the generation of static electricity is prevented.

According to the present invention, as such a thin film, carbon or a film containing carbon as a main component having sufficient hardness while having a light-transmitting property in a visible region is used as a protective film for preventing wear. In particular, this protective film can be brought into close contact with an organic material, and has an electric resistivity of 1 × 10 ^{6 to} 5 × 10 ¹² Ωcm, thereby preventing the generation of static electricity and having a smooth surface. The adhesion of dust is cancer prevention.

In the present invention, a carbon film or a film containing carbon as a main component is formed on a window such as a windshield, a side glass, and a rear window by a plasma CVD method.

"Prior Art" Generally, in a plasma CVD method, a method of forming a film in a planar shape on a conductive substrate having a flat surface is considered to be industrially effective. Further, a method of forming a film with a sputtering effect while being a plasma CVD method is also known. Regarding the coating of a carbon film, which is a typical example, see the patent application “Composite with a carbon film and a method for producing the same” (Japanese Patent Application No. 56-146936, Showa 56) filed by the present inventor.
(Filed on September 17, 2008). However, since these are conductor substrates, the substrate is disposed on one electrode (cathode side) of a parallel plate type using only a pair of electrodes, and a carbon film is formed on the upper surface of a flat surface using self-bias generated by itself. This is a method for forming a film.

"Conventional Problems" However, in the conventional example in which a film is formed with such a sputtering effect, a film cannot be formed on an office member made of an insulating material. The present invention has been made for such a purpose.

"Means for Solving the Problem" The present invention relates to a surface of an organic material having a light-transmitting property that is easily scratched or easily adhered to dust by rubbing with an office member having friction, particularly paper, a human body, clothes, or the like. Is provided on the member having the above, as a protective film, a film containing carbon or carbon as a main component. This film has a specific resistance of 1 × 10 ^{6 to} 5 × 10 ¹² Ωcm to prevent the generation of static electricity due to friction caused by dust (generally insulating or mineral), and thus to adhere to dust and to transmit light due to dust. It prevents the devitrification or "smearing" due to the generation of micro scratches, and always preserves a vivid light-transmitting surface.

According to the present invention, as a protective film for this purpose, a film having carbon or carbon as a main component by plasma polymerization or a CVD method having a specific resistance of Vickers hardness of 600 to 6000 kg / cm ² can be adhered to an organic material. Based on the discovery of

As the formation of this thin film, a similar CC bond of diamond having SP ³ orbitals is formed, and a specific resistance (specific resistance) 1
× 10 ^{6 to} 5 × 10 ¹² Ωcm, typically 1 × 10 ^{7 to} 5 × 10 ¹¹ Ωcm
cm, and a carbon film or carbon having properties similar to diamond that is transparent in the visible region having an optical energy bandwidth (Eg) of 1.0 eV or more, preferably 1.5 to 5.5 eV. The main components were hydrogen, fluorine and nitrogen).

The translucent organic substance using the present invention has a specific resistance of 1 × 10 ¹⁵ Ω.
It is an insulating member of cm or more, and the material is polyester resin, alkyd resin, oil-free alkyd resin, unsaturated polyester resin, acrylic resin, amino resin. In particular, for an automobile line, an organic melting type organic material of acrylic lacquer, acrylic melamine, and block acrylic urethane was used.

When forming a film by the method of the present invention, a halogen element such as fluorine and nitrogen are simultaneously added to a carbide gas during plasma CVD and mixed together, and the main component is carbon having a uniform concentration gradient in a thickness direction. A multilayer composite film with or without a coating or with or without additives may be made.

 The manufacturing method of the present invention will be described below with reference to the drawings.

Example 1 FIG. 2 shows an outline of a plasma CVD apparatus for performing a thin film forming method on an office member such as an underlay.

In the drawing, a reaction vessel (7) of a plasma CVD apparatus is separated from the outside by a gate valve (9). Gas system (30)
In the above, argon as a carrier gas was changed from (31) to
Reactive hydrocarbon gases, such as methane and ethylene, were added from (32) to fluorocarbon (C ₂ F ₆ , C ₆ F
₈ ) From (33), oxygen as the etching gas for the reaction vessel is introduced from (34) through the valve (28) and the flow meter (29) through the nozzle (25) into the reaction system (50). . When ethylene and carbon difluoride were introduced, hydrogen and fluorine were added.
A diamond-like carbon film having a large number of SP ³ bonds (also referred to as DLC, including DLC to which an additive is added, in the present invention is referred to as carbon or a film containing carbon as a main component) can be formed.

In order to form a coating of the same main component, C ₂ F ₆ and C ₆ F ₈ (3
Alternatively, NH ₃ may be introduced from (33).

A first pair of electrodes are formed above and below the reaction vessel (7) to have the same shape, and the first and second electrodes (3-1),
(3-2) is constituted by an aluminum metal mesh. The reactive gas is discharged downward from the nozzle (25). Further, a third electrode (13-
(1), (13-2),... (13-n) and other fourth electrodes (13′-1), (13′-2). The third and fourth electrodes are sandwiched between the members. Members (1-), (1-
2)... (1-n) is an insulating material.
, And a bias was applied in a substantially AC-conducting manner. A plasma atmosphere or a positive sheath is formed on the surface (1 ') on which the organic substance is formed on the member (1), and a negative self-bias is applied. In order to positively generate this negative self-bias, the frequency of the second alternating voltage is set to 10 Hz to 100 KHz and a low frequency such that ions spread between the third and fourth electrodes for a half cycle (half cycle). And The member (1) has a surface (1 ') on which an organic substance is to be formed, and the reactive gas converted into a plasma of the glow discharge by the first high-frequency alternating voltage is uniformly dispersed in the reaction space (8). The plasma potential at was made homogeneous.

Further, in order to make the potential distribution in the plasma reaction space more uniform, alternating voltages of two independent frequencies can be applied to the power supply system (40). The first alternating voltage is a high frequency of 1 to 100 MHz, for example, 13,56 MHz, and is supplied from a pair of two power supplies (15-1) and (15-2), that is, (15).
Matching boxes (16-1), (16
-2). The phase of each of the matching boxes is adjusted by a phase adjuster (26) so that they are 180 ° and 0 ° from each other.
供給 Supply can be made out of alignment. The power supplies (15-1) and (15-2) each have one end (4-1) and (4-2) of a symmetric or in-phase output. 3-1) and (3-2). In addition, each power supply (15-1), (15-
The other end of 2) is grounded (5-1) and (5-2).
A second 10 Hz to 100 KHz, for example, an alternating voltage of 50 Hz is a power supply (17)
That is, from (17-1) and (17-2), a pair of third electrodes (13
-1),... (13-n) and the fourth electrode (13'-
1)... (13′-n) are connected and applied. The output from the pair of electrodes (13) and (13 ') is configured to apply a self-bias to the member (1) sandwiched between the pair of electrodes.

Thus, plasma (8) is generated in the reaction space. The exhaust system (25) exhausts unnecessary gas through a pressure adjusting valve (21), a turbo molecular pump (22), and a rotary pump (23).

These reactive gases are present in the reaction space (60) at 0.001 to 1.0
torr For example, 0.05 torr.

In such a space, 0.5 to 5 KW of 13.56 MHz frequency
(Per unit area 0.03~3W / cm ²⁾ for example adding the first high frequency voltage of 1 KW (high energy per unit area 0.6W / cm ^2). Further, by applying an AC bias by the second alternating voltage, a negative self-bias voltage of -200 to -600 V (for example, the output is 1 KW) is applied on the surface to be formed,
The reactive gas accelerated by the negative self-bias voltage was formed on the member while being sputtered, thereby forming a dense film.

The reactive gas was, for example, a mixed gas of ethylene and carbon fluoride. The ratio is C ₂ F ₆ / C ₂ H ₄ = 1/4 to 4/1, typically 1/1. By changing this ratio, the transmittance and the specific resistance can be controlled. The temperature of the member (1) is maintained at 150150 ° C., typically at room temperature without external heating.

Thus, the specific resistance is 1 × 10 ^{6 to} 5 × 10 ¹² Ωc on the surface to be formed.
m, and is formed in close contact with an organic resin to form a film. For variable light, a carbon or carbon-based coating containing fluorine and hydrogen having a light-transmitting amorphous structure or a crystalline structure added with 0.1 to 8 μm, for example, 0.5 μm (flat portion), 1
３3 μm (projections). Deposition rate is 100-1000
Å / min.

Thus, the underlay as a member and other members could form a coating containing carbon as a main component, particularly carbon containing not more than 30 atomic% of hydrogen in carbon and containing 0.3 to 10 atomic% of fluorine. The first carbon consisting of only ethylene was provided on the organic material to a thickness of 100 to 2000 mm, and a multilayer film mainly composed of carbon to which fluorine and hydrogen were added could be formed thereon.

Example 2 In this example, as shown in FIG. 1, a film containing carbon as a main component was formed on a main part of a translucent organic material using the apparatus used in Example 1.

In FIG. 1 (A), the above-mentioned office supplies (office members) are shown. The longitudinal section is shown in FIG. 1 (B).

In FIGS. 1A and 1B, the light-transmitting plastics (1) is lightweight, and is made of, for example, an acrylic resin. On the member (1) having the surface to be formed, carbon or a wear-resistant protective film (45) containing carbon as a main component is used.
The thickness was set to 1 to 8 μm.

In the present invention, in particular, the coating mainly composed of carbon or carbon to which fluorine is added has a specific resistance of 1 × 10 ^{6 to} 5 × 10 ¹² Ωcm in order to prevent adhesion of dust due to generation of static electricity.
, Particularly preferably 1 × 10 ^{7 to} 5 × 10 ¹¹ Ωcm.

FIG. 1 (C) is a triangular ruler, and FIG. 1 (D) is a longitudinal sectional view taken along line AA '. On the upper surface of this ruler, a coating (45) containing carbon or carbon as a main component was formed to a thickness of 0.5 μm according to Example 1. The present invention is excellent because it has high friction with paper, human body, clothes, etc., and is liable to rub off dust of mineral substances, and as a result, devitrification and turbidity are easily generated by abrasion.

"Effects" The present invention is particularly applicable to a coating mainly composed of carbon having a Vickers hardness of 600 to 3000 kg / cm ^{2 and} a carbon (hydrogen having a Vickers hardness of 1000 to 7000 kg / cm ²⁾ to which fluorine having good drainage is added. Was also applied onto the organic material. As a result, it was possible to form a thick and wear-resistant film by the convex portions that easily rub against paper, the human body, and clothing.

As described above, it is effective to realize the possibility of making a plastic window that has been unusable because of its softness.

As is clear from the above description, the present invention is particularly effective for those provided with an organic resin or a multilayered film formed by coating. This composite, as seen in many other embodiments, is of immeasurable application, especially when the carbon can be formed at low temperatures below 150 ° C. The feature is that the color tone does not change, and the hardness and the adhesion to a substrate or a member are extremely excellent.

[Brief description of the drawings]

FIG. 1 shows an example in which a carbon film or a protective film containing carbon as a main component is coated on an office member of the present invention, and an essential part thereof. FIG. 2 shows an outline of a plasma CVD apparatus manufacturing apparatus according to the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Mari Sasaki 398 Hase, Hase, Atsugi-shi, Kanagawa Prefecture (72) Inventor Sannori Sanya 398 Hase, Atsugi-shi, Kanagawa, Japan Semiconductor Energy Research Institute (72 ) Inventor Atsushi Kawano 398 Hase, Atsugi-shi, Kanagawa Pref. Examiner at Semiconductor Energy Laboratory Co., Ltd. Yoshiko Arai (56) References JP-A-55-146799 (JP, A) Sho-55-115892 (JP, U) Sho-sho 58-143291 (JP, U)

Claims (2)

(57) [Claims] An organic member having a surface that can be rubbed with paper, a human body, and clothes, wherein the organic material has a surface of 1 × 10 ^{6 to} 5 × 10
An office member covered with a carbon film, provided with carbon or a film having carbon as a main component, which has a specific resistance of ¹² Ωcm and a translucency. 2. An office member covered with a carbon film according to claim 1, wherein the office member comprises a ruler, a triangle ruler, an underlay, and a top surface of an office desk.