JPH0280300A - Material covered with carbon film of office supplies - Google Patents

Abstract

PURPOSE:To increase abrasion resistance, prevent dust settlement and also generation of static electricity by providing film consisting of carbon or mainly of carbon, with a specifically inherent resistance to the surface of an organic substance and also light permeability. CONSTITUTION:A thin film is formed which is composed mainly of carbon film or carbon. This carbon film or carbon has a similar C-C bond to diamond with an SP<3> track and a specific resistance (inherent resistance) of 1X10<6> to 5X10<12>OMEGAcm. In addition, it has characteristics which are similar to light- permeable diamond in a visible area with an optical energy band width (called 'Eg') of 1.0eV or more. Polyester resin is used as a material. When the film is formed, halogen element such as fluorine and nitrogen are added to a carbide gas in the presence of plasma CVD and at the same time, these are mixed. A film consisting mainly of carbon with a uniform density gradient in a thickness direction or a multi-layer composite film with the controlled content of an additive can be manufactured.

Description

Detailed Description of the Invention "Field of Application of the Invention" The present invention provides a method for covering the surface of an organic office member with a surface that can rub against paper, the human body, or clothing with a protective coating containing carbon or carbon as a main component. It is something that It also improves abrasion resistance, prevents the adhesion of lumps, and prevents the generation of static electricity.

In the present invention, such a thin film is made of carbon or a coating mainly composed of carbon, which is transparent in the visible region and has sufficient hardness, as a wear-preventing protective film. In particular, this protective film can be closely attached to an organic material, has an electrical resistivity of 1×10' to 5 XIO"ΩcI11, prevents the generation of static electricity, and has a smooth surface. It prevents the adhesion of lumps and cancer.

The present invention aims to form a carbon film or a film containing carbon as a main component on windows such as windshields, side glasses, rear windows, etc. by plasma CVD.

"Prior Art" Generally, in the 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. Furthermore, a method is also known in which a film is formed using a plasma CVD method while also producing a sputtering effect. Regarding the carbon film coating, which is a typical example, the patent application filed by the present inventor is entitled "Composite having a carbon film and its manufacturing method 1" (Japanese Patent Application No. 56-1469).
36 (filed on September 17, 1982) is known.

However, since these are conductive substrates with a substrate placed on one electrode (cathode side) of a parallel plate type using only a pair of electrodes, a carbon film is formed on the top surface of the flat surface using self-generated self-bias. This is a method of forming a film.

"Problems with the Conventional Method" However, in the conventional method of forming a film while producing the sputtering effect, it is not possible to form a film on an office member made of an insulating material. The present invention has been made for this purpose.

``Means to Solve the Problem'' The present invention is directed to the surface of a translucent organic material that is easily scratched or dust-adhered by rubbing against office materials that involve friction, especially paper, the human body, clothing, etc. Carbon or a film containing carbon as a main component is provided as a protective film on a member having carbon. This coating has a specific resistance of 1X10' to 5XIO'' Ωcm, which prevents the generation of static electricity due to friction with chips (generally insulating or mineral), and also prevents dust from adhering to the surface of the light-transmitting surface due to chips. This prevents devitrification or "cloudiness" caused by scratches, and maintains a bright translucent surface at all times.

The present invention provides, as a protective film for such purpose, a carbon or carbon-based film formed by plasma polymerization or CVD, which has a specific resistance of 600 to 6,000 Kg/cm" in terms of Pinkers hardness, and is adhered to the organic substance. Based on the discovery of what can be done.

To form this thin film, a C-0 bond similar to that of diamond with an SP3 orbital is created, and the resistivity (specific resistance) l
×10h~5×101! Ωcam, typically 1×10
Carbon having properties similar to those of diamond, which is transparent in the visible region and has an optical energy band width (referred to as IEg) of 1.0eV or more, preferably 1.5 to 5.5eV. A film or a film containing carbon as the main component (the main subcomponents are hydrogen, fluorine, and nitrogen) was formed.

The translucent organic substance used in the present invention has a specific resistance of 1×1015
It is an insulating member of Ωcm or more, and the material used is polyester resin, alkyd resin, oil-free alkyd resin, unsaturated polyester resin, acrylic resin, or amino resin. In particular, for automobile lines, organic melting type organic materials such as acrylic lacquer, acrylic melamine, and block acrylic urethane were used.

When forming a film using the method of the present invention, a halogen element such as fluorine and nitrogen are mixed simultaneously with carbide gas during plasma CVD to create a film with a uniform concentration gradient in the thickness direction, and the main component is carbon. Multilayer composite membranes may be created with controlled presence or absence of coatings or additives.

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

"Example 1" FIG. 2 shows an outline of a plasma CVD apparatus for carrying out a method of forming a thin film on office materials such as underlays.

In the drawing, a reaction vessel (7) of the plasma CVD apparatus is separated from the outside by a gate valve (9). Gas type (30
), the carrier gas argon is added from (31), the reactive gas hydrocarbon gas such as methane or ethylene is added from (32), and the additive gas fluorocarbon (C
2F4. C3FI) from (33), oxygen, which is the etching gas in the reaction vessel, from (34), and pulp (28).
, the nozzle (2) passes through the flow meter (29) and enters the reaction system (50).
5) Introduce more. When i-tyrene and carbon difluoride are introduced, hydrogen and a diamond-like carbon film (also referred to as DLC, which includes DLC to which additives are added) have many sp' bonds. or a film whose main component is carbon) can be formed.

In order to make a film with the same main components as this, CzFa, CJs
may be formed by introducing from (32) or NHs from (33).

A first pair of electrodes having the same shape are provided above and below this reaction container (7) to form first and second electrodes 1 (3-1).

The zero-reactive gas that makes (3-2) consist of an aluminum metal mesh is discharged downward from the nozzle (25). Further, a third electrode (13-
1), (13-2), ... (13-n) and the other fourth electrode (13°-1), (13'-2)
...(13' -n) (Collect each to form the third
and a fourth electrode) are sandwiched between the members. Member (1-), (1-2)...(1-
n) is an insulating material, and a second alternating voltage was applied thereto to make it substantially conductive in terms of alternating current, and a bias was applied thereto.

A plasma atmosphere or positive cis is created 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 actively generate this negative self-bias, the frequency of the second alternating voltage is set to 10Hz to 100Hz.
KHz and a low frequency such that the ions spread between the third and fourth electrodes during a half cycle. The member (1) has a surface (1゛) on which an organic substance is formed, and the reactive gas that has been turned into plasma by the glow discharge due to the first high-frequency alternating voltage is uniformly dispersed in the reaction space (8). The plasma potential at was made homogeneous.

Furthermore, in order to make the potential distribution in the plasma reaction space more equal, 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 the two power supplies (15-1) form a pair.

(15-2) That is, (15) leads to matching boxes (16-1) and (16-2) made of LCR circuits. The mutual phases in this matching box are adjusted by a phase adjuster (26), so that the signals can be supplied with a difference of 180' or 0° from each other. It has a symmetrical or in-phase output, and the power supply (15-1), (15-2
) are connected to a pair of first and second electrodes (3-1) and (3-2), respectively. Also, each power supply (15
-1), the other end of (15-2) is grounded (5-1).

(5-2) Yes. Second 1O11z=100KH
For example, the alternating voltage of 5011z is the power supply (17), that is, (1
7-1), a pair of third electrodes (1
3-1), ... (13-n) and the fourth electrode (
13'-1) ... (13"-n) and is applied with voltage. The pair of electrodes (13), (
13”), the output from the member sandwiched between this pair of electrodes (
1) is made to have a self-bias.

Plasma (8) is thus generated in the reaction space.

The exhaust system (25) exhausts unnecessary gas through a pressure regulating pulp (21), a turbo molecular pump (22), and a rotary pump (23).

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

In such a space, the frequency of 13.56 MHz is 0.
A first high frequency voltage of -(0.03 to 0.6 W/cm" per unit area), for example, IKW (high energy of 0.6 W/cm" per unit area) is applied to 5 to 5. Further, by applying an AC bias using a second alternating voltage, a negative self-bias voltage of 200 to -600V (for example, the output is IKW) is applied to the surface to be formed, and this negative self-bias voltage accelerates the process. The resulting reactive gas was sputtered onto the member to form a film, and it was possible to form a dense film.

The reactive gas was, for example, a mixed gas of ethylene and carbon fluoride. The ratio is CzFb/CJa = 1/4 to 4/1
It is typically 1/1. By varying this ratio, the transmittance and resistivity can be controlled. The temperature of the member (1) is ~150° C. Typically, the temperature is maintained at room temperature without external heating.

Thus, the resistivity on the surface to be formed is 1Xl0'~5×101
It has a resistance of 2 Ωcm and is formed into a film in close contact with the organic resin. A film containing carbon or carbon as a main component to which fluorine and hydrogen are added, which has an amorphous or crystalline structure that is transparent to visible light, has a thickness of 0.1 to 8 μm, for example, 0.5 μm.
(flat portion) and 1 to 3 μm (convex portion). The deposition rate was 100-1000 people/min.

In this way, a film containing carbon as a main component is formed on the underlay and other members, especially carbon containing 30 atomic percent or less of hydrogen and 0.3 to 10 atoms of chi-fluorine mixed therein. I was able to do that. 100-20 on organic matter
Provide a first carbon with only ethylene to a thickness of 0.00 people,
Furthermore, it was possible to form a multi-layered film containing carbon as a main component to which fluorine and hydrogen were added.

"Example 2" This example is an example in which a film containing carbon as a main component was produced on the main part of a translucent organic material as shown in FIG. 1 using the apparatus used in Example 1.

In FIG. 1 (8), the above-mentioned office supplies (office members) are shown. A longitudinal section thereof is shown in FIG. 1(B).

In FIGS. 1A and 1B, the translucent plastic (1) is lightweight and is made of, for example, acrylic resin. A wear-resistant protective film (45) made of carbon or carbon as a main component on the member (1) having the surface on which it is formed.
was provided with a thickness of 0.1 to 8 μm.

In the present invention, in order to prevent the adhesion of dust due to the generation of static electricity, the coating mainly composed of carbon or fluorine-added carbon has a specific resistance of 1 x 106 to 5 x 10'2.
in the range of Ωcm, particularly preferably from 1 x 107 to lxlOI
The range was set as IQcm.

Figure 1 (C) is a triangular ruler, and the vertical cross-sectional view of A-A'' is (
Shown in D). A coating (45) of carbon or containing carbon as a main component was formed on the upper surface of this ruler to a thickness of 0.5 μm according to Example 1. The present invention is excellent because there is a lot of friction with paper, the human body, clothing, etc., and mineral dust tends to get stuck (as a result, devitrification and turbidity are likely to occur due to wear).

"Effects" The present invention is particularly suitable for coating the upper surface with a carbon-based coating having a Pinkers hardness of 600 to 3,000 Kg/cm and having a fluorine-added coating that has good drainage or a Vickers hardness of 1,000 Kg/cm.
A multilayer film of ~7000 Kg/cm2 of carbon (hydrogen was also added) was closely coated on the organic material. As a result, it was possible to form a thick, wear-resistant film on the convex parts that are easily rubbed by the body, the human body, and clothing.

As shown above, this invention is effective because it realizes the possibility of making plastic windows, which until now were completely unusable due to their softness.

As is clear from the above description, the present invention is particularly effective for materials coated with organic resins or multilayer films thereof. The applications of this composite, as seen in many other examples, are enormous, especially since the carbon can be formed at low temperatures below 150°C, and therefore it is difficult to transform the organic matter of the underlying painted surface. The color tone remains the same, and its hardness and adhesion to substrates or members are extremely excellent.

[Brief explanation of the drawing]

FIG. 1 shows an example in which a carbon film or a protective film mainly composed of carbon is coated on an office member according to the present invention, and its essential parts. FIG. 2 shows an outline of a manufacturing apparatus for a plasma CVD apparatus according to the present invention.

Claims (1)

[Scope of Claims] 1. An organic member having a surface that can rub against paper, the human body, or clothing, the organic material having a surface of 1×10^6 to 5×10^
An office member covered with a carbon film, characterized by being provided with carbon or a film mainly composed of carbon, which has a specific resistance of 1^2 Ωcm and is translucent. 2. An office member covered with a carbon film according to claim 1, characterized in that the office member comprises a ruler, a triangular ruler, an underlay, and the top surface of an office desk.