JP2001164365A - Translucent organic member coated with diamondlike carbon film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a translucent organic member coated with diamondlike carbon films excellent in translucency and flawing resistance and also excellent in adhesion and particularly suitable for use to automobiles, railway rolling stock, vessels, aircraft, autocycles such as motorcycles and buildings. SOLUTION: In this translucent organic member coated with diamondlike carbon films, a translucent organic member is coated with diamondlike carbon films of two or more layers, the diamondlike carbon film on the side nearest to the translucent organic member has a composition of CHxSiyOzNv where (x), (y), (z) and (v) respectively express molar ratios, and 0.05<=x<=0.7, 0<y<=3.0, 0<=z<=1.0 and 0<=v<=1.0 are satisfied), and the diamondlike carbon film farthest from the translucent organic member has a composition of CHpOqNrFs where (p), (q), (r) and (s) respectively express molar ratios, and 0.05<=p<=0.7, 0<=q<=1.0, 0<=r<=1.0, and 0<=s<=0.2 are satisfied).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a translucent organic member coated with a diamond-like carbon film, and more particularly to a railway vehicle such as an automobile, a train, a boat, an aircraft, a motorcycle, etc. The present invention relates to a diamond-like carbon film used as a light-transmitting organic member in a building or the like and a light-transmitting organic member.

[0002]

2. Description of the Related Art In recent years, various plastics have been used for railway vehicles such as automobiles and trains, ships, aircraft, motorcycles and other bicycles, and buildings. Such plastics are widely used for members requiring light transmission, such as front windows, rear windows, side windows, side mirrors, light covers, fog lamps, and stop lamps of automobiles.

[0003] Such a translucent organic member is installed in a state where it is exposed to the outside air, and is exposed to rain and wind, dust, and the like, thereby causing scratches and transmitting light due to scratches. There is a problem such as a decrease in lightness.

In order to cope with such a problem, it has been proposed to provide a carbon film such as a diamond-like carbon film or a film containing carbon as a main component on a member made of an organic substance such as plastic. For example, Japanese Patent Laid-Open No. 6-882
No. 09 proposes a plastic substrate, such as a plastic lens, whose surface has a melting point of 150 ° C. or less and is covered with a diamond-like carbon film (synonymous with a diamond-like carbon film). The deposition of such a diamond-like carbon film evaporates carbon from the solid carbon source in the chamber while maintaining a pressure low enough to stabilize the electron beam in the vicinity of the electron beam. And the RF voltage is high enough to generate an ionized gas plasma around the substrate.
It is shown that this is done by holding the substrate in a chamber while applying a high frequency RF voltage at a pressure of? This describes that the substrate surface can be hardened and scratch resistance can be imparted while maintaining the temperature of the substrate at or below its melting point.

[0005] Also, Japanese Patent No. 2794074 discloses that
Is _{Si x C 1-x (0} ≦ x ≦ 1) film formation containing hydrogen and fluorine on a substrate having a surface of organic _{material, Si x C 1-x (} 0 containing hydrogen and fluorine with the surface of the organic material ≤
x ≦ 1) There has been proposed an organic composite having a bonding region in which the organic substance and the Si _x C _1-x containing hydrogen and fluorine (0 ≦ x ≦ 1) are mixed at a bonding portion with a coating film. And
Such a bonding region is formed by using a device for supplying a source gas, at least a pair of electrodes, and a reduced-pressure gas-phase reaction device having a power supply for applying DC or AC power to the electrodes. A substrate having an organic material surface is arranged in a reaction space between, and a raw material gas is introduced into the reaction space,
The source gas in the reaction space is turned into plasma by applying power to the electrode, and the Si _x C _1-x containing hydrogen and fluorine is placed on the substrate.
(0 ≦ x ≦ 1) It is shown that when a film is formed, power is strongly applied to the electrode in the initial stage of film formation, and the organic material on the substrate surface is partially melted to form the film. It is described that by providing such a bonding region (partial melt region), an effect of improving the adhesiveness of the coating film having a function as a scratch-resistant film can be obtained.

[0006] Japanese Patent Application Laid-Open No. 10-291895 discloses a diamond-like carbon film to which Si is added,
The carbon in the diamond-like carbon film has sp ³ bonds of sp ²
There is more than bonding, indicating that such a diamond-like carbon film is formed from a carbon-based gas and a silicon-based gas using a plasma CVD method. It is described that by forming a partial melt region on the substrate surface by plasma, the adhesion of the diamond-like carbon film is improved, and an abrasion-resistant film excellent in hardness and light transmittance is obtained.

Further, Japanese Patent Application Laid-Open No. 2-80571 discloses that
A translucent member having an insulating property, wherein 1 ×
A member covered with a carbon film provided with a carbon film having a specific resistance of 10 ^{6 to} 5 × 10 ¹² Ωcm or a film containing carbon as a main component is disclosed. Such a carbon film is provided with a first pair of electrodes for generating high-frequency plasma in a reaction container, an insulating member is provided in the reaction container, and the member is held under reduced pressure, and the member is kept under reduced pressure. It has a second pair of electrodes sandwiching it, applying an AC bias between these electrodes,
It is manufactured by introducing a carbonized gas into the atmosphere under the reduced pressure and applying a high-frequency voltage to the first pair of electrodes to convert the gas into plasma. By this, it is possible to prevent the generation of static electricity due to friction accompanied by dust, thereby preventing the adhesion of dust, devitrification or turbidity due to the generation of minute scratches on the light-transmitting surface due to dust, and improve the wear resistance, and Low-temperature film formation is possible,
It shows that the adhesion is extremely excellent.

Japanese Patent Application Laid-Open No. 2-104665 discloses a light-transmitting member having an insulating property, wherein the member has a hydrophilic surface and a specific resistance of 5 × 10 ¹³ Ωcm or less. A member covered with a carbon film provided with light carbon or a film containing carbon as a main component is disclosed. This indicates that it is possible to form a protective film that prevents dust from accumulating on the light-transmitting surface and prevents irregular reflection of raindrops. It is described that the control of the degree of hydrophilicity, Vickers hardness, and electric conductivity can be performed by adding nitrogen or boron, and that a silicon nitride film may be interposed as an underlayer to improve adhesion. ing.

As described above, various types of carbon films have been proposed, but the diamond-like carbon film disclosed in JP-A-6-88209 does not always have good adhesion. Further, Japanese Patent No. 2794074, Japanese Patent Application Laid-Open
In the diamond-like carbon film disclosed in Japanese Patent No. 291895, a partial melt region is formed in order to improve adhesion or adhesion, so that a substrate as an adherend is easily damaged, and light transmittance due to the damage causes transmittance. Will decrease. In addition, a sufficient transmittance cannot be obtained with the specific resistance of the carbon film disclosed in JP-A-2-80571 and JP-A-2-104665. As for the relationship between the specific resistance and the transmittance, it is known that the transmittance decreases as the specific resistance (resistivity) decreases [M. Nakay
ama, et al.Physical propaties of diamondlike carbo
n films deposited in mixed atmospheres of C ₂ H ₄ -Ar,
C ₂ H ₄ -H ₂ , and C ₂ H ₄ -N ₂ (Journal of Vacuum Science &
Technology A. Volume 14, No.4, P2418〜2426, 199
6.), M.NAKAYAMA, et al. Vacuum ultraviolet, ultravi
olet and visible absorption spectra study of hydro
genated amorphous carbon films prepared by RF plas
ma chemical vapor deposition (Journal of Material S
cience Letters, 12 , pp. 1380-1382, 1993.]].

In particular, when a light-transmitting organic member is coated with a diamond-like carbon film, the adhesion between the light-transmitting organic member and the carbon film becomes a problem, and the light-transmitting effect is obtained by coating the carbon film. It is meaningless to cover the carbon film if the translucency of the conductive organic member is lost. Therefore, it is necessary to ensure the translucency of the coated carbon film itself, and to prevent a decrease in the translucency due to generation of scratches due to aging or use.

Typically, when an automobile is taken as an example, the window and the light cover of the automobile are exposed to rain and wind, dust, and the like, and are used for car washing to remove dust and dirt attached to the automobile. Car washing is performed at home and at a gas station using an automatic car washing machine. The automatic car washer is provided with a nylon brush and the like, and uses the supplied detergent and water as appropriate to rotate the brush to wash the car. For this reason, it is necessary to minimize the occurrence of scratches caused by car washing. In particular, car washing at gas stations is targeted at cars with different dirt conditions, for example, brushes after washing a car with heavy dirt have stains remaining, and the stains on this brush are, for example, sand, etc. In such a case, the next car to be washed will be damaged.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to form a diamond-like carbon film having excellent light transmission and scratch resistance and good adhesion without damaging the adherend. An object of the present invention is to provide a translucent organic member coated with a diamond-like carbon film which does not impair the translucency of the translucent organic member as a body. Especially for automobiles, railway vehicles,
It is suitable for boats, aircraft, motorcycles and other bicycles, and buildings.

[0013]

The above object is achieved by the present invention described below. (1) a light-transmissive organic member coated with two or more layers of diamond-like carbon film, diamond-like carbon film closest to the transparent organic _{member, CH x Si y O z N} v ( here, x, y, z and v each represent a molar ratio;
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. ), And the diamond-like carbon film farthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio,
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A translucent organic member coated with a diamond-like carbon film having the composition of (1). (2) Used as a translucent organic member included in an automobile, the translucent organic member is covered with two or more layers of diamond-like carbon films, and the diamond-like carbon film closest to the translucent organic member is , CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio,
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. ), And the diamond-like carbon film farthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio,
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A translucent organic member coated with a diamond-like carbon film for automobiles having the composition of (1).
(3) The translucent organic member coated with the diamond-like carbon film for an automobile according to the above (2), which is used for washing in an automobile car washer. (4) Used for translucent organic members provided in railway vehicles,
The light-transmitting organic member coated with two or more layers of diamond-like carbon film, diamond-like carbon film closest to the transparent organic _{member, CH x Si y O z N} v ( wherein, x, y, z and v each represent a molar ratio,
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. ), And the diamond-like carbon film farthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio,
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A translucent organic member coated with a diamond-like carbon film for railway vehicles having the composition of (1).

(5) Used as a translucent organic member provided on a ship, the translucent organic member is covered with two or more diamond-like carbon films, and the diamond-like carbon member closest to the translucent organic member is formed. The carbon film is composed of CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio,
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. ), And the diamond-like carbon film farthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio,
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A translucent organic member coated with a marine diamond-like carbon film having the composition of (1). (6) Used for a translucent organic member provided in an aircraft, the translucent organic member is covered with two or more layers of diamond-like carbon films, and the diamond-like carbon film closest to the translucent organic member is , CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio,
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. ), And the diamond-like carbon film farthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio,
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A transparent organic member coated with a diamond-like carbon film for aircraft having the composition of (1). (7) Used as a translucent organic member included in a bicycle, the translucent organic member is covered with two or more diamond-like carbon films, and a diamond-like carbon film closest to the translucent organic member is provided. Wherein CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio,
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. ), And the diamond-like carbon film farthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio,
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A light-transmitting organic member coated with a diamond-like carbon film for a motorbike having the composition of (1). (8) Used as a translucent organic member included in a building, the translucent organic member is covered with two or more diamond-like carbon films, and a diamond-like carbon film closest to the translucent organic member is provided. Wherein CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio,
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. ), And the diamond-like carbon film farthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio,
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A translucent organic member coated with a diamond-like carbon film for buildings having the composition of (1).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The translucent organic member coated with the diamond-like carbon (DLC) film of the present invention is a translucent organic member to be adhered and covered with two or more DLC films. DL like this
The C film coating layer has a composition in which the lowermost DLC film closest to the adherend has Si added thereto (composition I below), and the uppermost DLC film furthest from the adherend does not contain Si. (Composition II below). Composition I CH _x Si _y O _z N _v where x, y, z and v each represent a molar ratio, and
05 ≦ x ≦ 0.7, 0 <y ≦ 3.0 (preferably 0.0
1 ≦ y ≦ 3.0), 0 ≦ z ≦ 1.0, and 0 ≦ v ≦ 1.0. Here composition _{II CH p O q N r F} s, p, q, r and s each represent a molar ratio, 0.
05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.0,
0 ≦ s ≦ 0.2.

Such a DLC film coating layer usually has a two-layer structure. However, in some cases, three or more layers may be used, and when three or more layers are formed, the lowermost layer and the uppermost layer may have the above composition. The other layers are not particularly limited. However, due to the advantages in film formation, the lowermost DL
It is preferable to add Si to the C film, and in some cases, a DLC film to which Si is added and a DLC film to which no Si is added.
A configuration in which films are alternately stacked may be adopted, but it is preferable that such a configuration is not adopted. Further, the uppermost DLC film of the plurality of layers may not include Si.

Thus, the DLC film covering layer is composed of two or more layers, the DLC film of the above composition to which Si is added is provided on the adherend side, and the DLC film of the above composition to which no Si is added as the uppermost DLC film. Is provided, the adhesiveness to the adherend is excellent, and, for example, film peeling does not occur even when the automobile is washed by an automatic car washer. In addition, the film has sufficient hardness, is excellent in light transmittance, is hardly scratched, and does not have a decrease in light transmittance due to scratches. For example, even when an automobile is washed by an automatic car washer, scratches are extremely unlikely to occur. The DLC films of the uppermost layer and the lowermost layer have the above-described compositions I and II in order to obtain sufficient hardness in the uppermost layer and to obtain adhesion to the adherend in the lowermost layer. As described above, in the present invention, sufficient adhesiveness can be obtained in the lowermost layer. Therefore, it is necessary to provide a partial melt region specially on the adherend surface as disclosed in Japanese Patent No. 2794074 and Japanese Patent Application Laid-Open No. 10-291895. There is no.
Therefore, it is possible to avoid damage to the adherend due to the provision of the partial melt region, and it is possible to avoid a decrease in light transmission due to light scattering due to the damage.

On the other hand, when only the DLC film of either the composition I or the composition II is coated, sufficient hardness cannot be obtained with the composition I alone, and adhesion with the adherend is not sufficient with the composition II alone. .

Further, the film composition of the uppermost DLC film is represented by composition II
, The hydrophilicity (for example, increase q), the water repellency (for example, increase s), the electric conductivity (for example, increase r), the hardness (for example, decrease p), etc. Additional functions according to the purpose can be provided.

All of the above-mentioned DLC films can be preferably formed by a CVD method, and can be formed in one batch. Therefore, impurities such as a natural oxide film can be present between the films and in the films. The effect that it does not exist is obtained.

The DLC film to which Si having the composition I is added may be provided as only one layer or two or more layers. When two or more layers are provided, the DLC film may have the same composition. May change the composition. Also, 1
When providing only a layer, even if the film composition is a uniform composition,
A gradient film whose composition continuously changes between the adherend side and the upper DLC film side may be used. In such a case, the Si content or the contents of Si and O are increased on the adherend side. On the side of the upper DLC film, it is preferable to reduce the Si content or the contents of Si and O from the viewpoint of obtaining adhesion. Even when two or more layers are provided, it is preferable that the lower layer and the upper layer maintain this tendency.

It is usually preferable to provide only one DLC film of the composition II to which Si is not added.
More than two layers may be provided. Usually, it is a uniform composition film, but it may be a gradient film.

The thickness of the DLC film to which Si of composition I is added is 10 to 30000 ° (1 to 3
000nm), and even 50-20000Å (5-2000nm), especially 100
It is preferably about 10000 で (10 to 1000 nm). Composition II
The thickness of the DLC film to which no Si is added is preferably 10 to 10,000 ° (1 to 1000 nm) in total when two or more layers are stacked. The total thickness of the DLC film coating layer is 20 to 40,000.
Å (2 to 4000 nm) is preferable.

With such a thickness, the effect of the present invention is improved. On the other hand, when the thickness of the DLC film to which the Si of the composition I is added is small, it is difficult to obtain sufficient adhesion, and when the thickness is large, peeling due to the internal stress of the film is likely to occur. . The composition II
When the film thickness of the DLC film to which no Si is added is small, it is difficult to obtain sufficient hardness. Conversely, when the film thickness is large, peeling due to the internal stress of the film is likely to occur, and visible light transmission The rate drops. Further, if the total thickness is small, the effect of the present invention cannot be obtained, and if the total thickness is large, peeling of the film due to the internal stress of each film and the internal stress difference between the films is likely to occur.

In the present invention, the translucent organic member to be adhered is a translucent organic material for automobiles, railway vehicles such as trains, ships, aircraft, motorcycles and other bicycles, and buildings, specifically, plastics. It is a member formed by. As plastics, polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMM)
A), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), acrylonitrile-styrene (AS) resin, and the like.

Specific examples of such a translucent organic member include a front window, a rear window, a side window, a side mirror, a light cover, a tail lamp cover, a fog lamp cover, and a stop lamp cover.

In particular, the present invention is preferably applied to an automobile or the like which is used for washing in an automatic car washer. The automatic car washer is provided with a brush, and uses a detergent and water to wash an automobile by rotating the brush. The brush is a nylon brush or the like, and the rotation speed of the brush is 30 to 1
Generally, the speed is about 00 rpm. The present invention is particularly effective because such an automatic car washer is easily damaged.

JP-A-6-88209, Patent No. 2794
No. 074, JP-A-10-291895, JP-A-2-8
Nos. 0571 and 2-104665,
Although there are descriptions of scratch resistance, abrasion resistance film, abrasion resistance, and prevention of dust adhesion, there is no mention of prevention of scratches caused by the automatic car washer as described above.

In the present invention, the diamond-like carbon film serving as the coating film, that is, the DLC (Diamond Like Carbon) film has the above-mentioned composition, but a general DLC film will be described.

Diamond-like carbon (DLC: Diamond Li)
The ke Carbon) film is sometimes called a diamond-like carbon film, an i-carbon film, or the like. For the diamond-like carbon film, for example, JP-A-62-145646,
No. 62-145647, New Diamond Forum, No. 4
Vol. 4 (issued on October 25, 1988).

DLC is described in the above document (New Diamond Foru).
as described in m), Raman spectroscopy, broad to 1550cm ^-1 (1520~1560cm
^-1) has a peak of the Raman absorption, and diamond having a sharp peak at 1333 cm ^-1, and graphite having a sharp peak at 1581 cm ^-1, it is a substance having a distinctly different structure.

The DLC film is an amorphous thin film containing carbon and hydrogen as main components, and is formed by randomly existing sp ³ bonds between carbon atoms.
The atomic ratio C: H of DLC is usually 95-60: 5-40.
It is about.

The absorption peak in the Raman spectroscopy of the DLC film was broad (152) at 1550 cm ^-1 as described above.
0-1560 cm ^-1 ), but by containing elements of Si, N, O, and F other than carbon and hydrogen,
It may fluctuate about ± 100 cm ^-1 from this.

It is preferable that all the DLC films are formed by a CVD method, particularly a plasma CVD method.

When the DLC film is formed by the plasma CVD method, the DLC film can be formed by a method described in, for example, JP-A-4-41672. Plasma C
The plasma in the VD method may be either DC or AC, but it is preferable to use AC. The alternating current can be used from a few hertz to a microwave. Also,
ECR plasma described in diamond thin film technology (published by General Technology Center) can also be used. Further, a bias voltage may be applied.

When the DLC film is formed by the plasma CVD method, it is preferable to use one or more of the following compounds as the source gas according to the film composition.

Compounds containing C and H include methane, ethane, propane, butane, pentane, hexane,
And hydrocarbons such as ethylene and propylene.

Compounds containing C, H and Si include:
Methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, diethylsilane, tetraethylsilane, tetrabutylsilane, dimethyldiethylsilane, tetraphenylsilane, methyltriphenylsilane, dimethyldiphenylsilane, trimethylphenylsilane, trimethylsilyl-trimethylsilane, trimethylsilylmethyl -Trimethylsilane and the like. These may be used in combination, or a silane compound and a hydrocarbon may be used.

Compounds containing C + H + O include CH ₃
OH, C ₂ H ₅ OH, HCHO, CH ₃ COCH _{3 and the} like.

Compounds containing C + H + N include ammonium cyanide, hydrogen cyanide, monomethylamine, dimethylamine, allylamine, aniline, diethylamine, acetonitrile, azoisobutane, diallylamine, ethylazide, MMH, DMH, triallylamine, trimethylamine, triethylamine, triphenylamine Amines and the like.

In addition, Si + C + H, Si + C + H + O
Alternatively, a compound or the like containing Si + C + H + N may be combined with an O source or an ON source, an N source, an H source, or the like.

O source, O ₂ , O _3, etc .; C + O source, CO, CO _2, etc .; Si + H source, SiH _4, etc.
As the source, H _2, etc., as H + O source, H ₂ O, and the like, as an N source, as N ₂ N + H source, NH _3, etc., as N + O source, NO, N
Compounds of N and O which can be represented by NO _x such as O ₂ and N ₂ O,
As an N + C source, (CN) ₂ etc. As an N + H + F source,
As an O + F source such as NH ₄ F, OF ₂ , O ₂ F ₂ , O ₃ F ₂ or the like may be used.

The flow rate of the raw material gas may be appropriately determined according to the type of the raw material gas. Operating pressure is typically 0.01
~ 0.5 Torr (1 ~ 100Pa), input power is usually 10
About W to 5 kW is preferable.

The DLC film may be formed by an ionization deposition method other than the CVD method. The ionization vapor deposition method is described in, for example, JP-A-58-174507 and JP-A-59-174.
No. 508, etc. However, the present invention is not limited to the methods and apparatuses disclosed therein, and another type of ion vapor deposition technology may be used as long as the ionized gas for the raw material can be accelerated. As a preferable example of the device in this case, for example, an ion straight type or an ion deflection type described in Japanese Utility Model Laid-Open No. 59-174507 can be used.

In the ionization deposition method, the inside of the vacuum vessel is set to a high vacuum of about 10 ⁻⁶ Torr (1 × 10 ⁻⁴ Pa). A filament that is heated by an AC power supply to generate thermoelectrons is provided in the vacuum vessel. A counter electrode is arranged so as to surround the filament, and a voltage Vd is applied between the filament and the filament. In addition, an electromagnetic coil that surrounds the filament and the counter electrode and generates a magnetic field for trapping ionized gas is arranged. The source gas collides with the thermoelectrons from the filament to generate positive thermal decomposition ions and electrons, and the positive ions are accelerated by the negative potential Va applied to the grid. The composition and film quality can be changed by adjusting Vd, Va and the magnetic field of the coil. Further, a bias voltage may be applied.

When the DLC film is formed by the ionization vapor deposition method, the same material gas as that used in the plasma CVD method may be used. The flow rate of the source gas may be appropriately determined according to the type. The operating pressure is usually 0.01 to
It is preferably about 0.5 Torr (1 to 100 Pa).

The DLC film can be formed by a sputtering method. In this case, a gas such as O ₂ , N ₂ , NH ₃ , CH ₄ , H ₂ or the like is introduced as a reactive gas in addition to a sputtering gas for sputtering such as Ar or Kr, and C, Si,
Targeting SiO ₂ , Si ₃ N ₄ , SiC, etc.
A target may be a mixed composition of C, Si, SiO ₂ , Si ₃ N ₄ , and SiC, and in some cases, C, Si, N, O
May be used. Further, a polymer can be used as a target. A DLC film is formed by applying any one of high-frequency power, AC power, and DC power using such a target, sputtering the target, and sputter depositing the target on a substrate. High frequency sputtering power is usually 50W ~ 2kW
It is about. The operating pressure is typically 10 ^-5 to 10 ^-3 Torr (1
0 ^-3 to 10 ^-1 Pa) is preferred.

[0048]

The present invention will be specifically described below with reference to examples. A comparative example is also shown. Example 1 Polycarbonate (1.5 mm thick) was used as a substrate.
A DLC film (lower layer) and a DLC film (upper layer) were formed in one batch from the substrate side under the following conditions to obtain a coated sample.

Film formation of DLC film (lower layer) Source gas: Si (CH ₃ ) ₄ [Flow rate 50 SCCM (8.5 × 10 ^-2 P
a · m ³ · s ^-1 )] C ₂ H ₄ [Flow rate 50 SCCM (8.5 × 10 ^-2 Pa · m ³ · s ^-1 )] Power supply: RF (13.56 MHz) Operating pressure: 0.5 Torr (66.5 Pa) ) Input power: 500 W Deposition rate: 100 nm / min Film composition: CH _0.23 Si _0.21 Film thickness: 2800Å (280 nm) Film formation of DLC film (upper layer) (Same as upper layer except for raw material gas, film composition and film thickness) Gas: C ₂ H ₄ [Flow rate 50 SCCM (8.5 × 10 ^-2 Pa ・ m ³・ s)
^-1 )] Film composition: CH _0.28 Film thickness: 200 ° (20 nm) The specific resistance ρ of the DLC coating layer was 7 × 10 ¹³ Ω · cm.

Example 2 A coated sample was obtained in the same manner as in Example 1, except that the source gas used for forming the DLC film (lower layer) was as follows.

DLC film (lower layer) Source gas: Si (CH ₃ ) ₄ [Flow rate 40 SCCM (6.8 × 10 ^-2 P
a ・ m ³・ s ^-1 )] C ₂ H ₄ [Flow rate 50 SCCM (8.5 × 10 ^-2 Pa ・ m ³・ s ^-1 )] O ₂ [Flow rate 10 SCCM (1.7 × 10 ^-2 Pa ・ m ³・ s) ^-1 )] Film composition: CH _0.18 Si _0.21 O _0.23 The specific resistance ρ of the DLC coating layer was 9 × 10 ¹³ Ω · cm.

Example 3 A coated sample was obtained in the same manner as in Example 2 except that the source gas used for forming the DLC film (upper layer) was as follows.

DLC film (upper layer) Source gas: C ₂ H ₄ [Flow rate 40 SCCM (6.8 × 10 ^-2 Pa · m ³ · s)
^-1 )] CF ₄ [flow rate 10 SCCM (1.7 × 10 ^-2 Pa · m ³ · s ^-1 )] Film composition: CH _0.12 F _0.10 The specific resistance ρ of the DLC coating layer is 8 × 10 ¹³ Ω · cm. there were.

Comparative Example 1 A coated sample was obtained in the same manner as in Example 1 except that only the DLC film (upper layer) of Example 1 was used. However, the film thickness was 3000 ° (300 nm). In addition,
The specific resistance ρ of the DLC film was 7 × 10 ¹³ Ω · cm.

Comparative Example 2 In Comparative Example 1, the following source gases were used for forming the DLC film.
A coated sample was obtained in the same manner except that the substrate was provided with a partial melt region as disclosed in each publication of 91895.

DLC film Raw material gas: C ₂ H ₄ [Flow rate 16.7 SCCM (2.83 × 10 ^-2 Pa ·
m ³ · s ^-1 )] SiH ₄ [Flow rate 16.7 SCCM (2.83 × 10 ^-2 Pa · m ³ ·
s ^-1 )] H ₂ [flow rate 16.7 SCCM (2.83 × 10 ^-2 Pa · m ³ · s ^-1 )] Film composition: CH _0.20 Si _0.10

The partial melt region is described in JP-A-10-29.
According to the example of the publication No. 1895, the raw material gas for the DLC film is Ar [a flow rate of 50 SCCM (8.5 × 10 ^-2 Pa · m ³ · s ^-1 )].
Was formed at a power density of 6 W / cm ² . Note that DL
The specific resistance ρ of the C film was 8 × 10 ¹³ Ω · cm.

Comparative Example 3 In Comparative Example 1, the source gases used for forming the DLC film were as follows: JP-A-2-80571, JP-A-2-10
As in each publication of No. 4665, the specific resistance ρ is set to 10 ⁷ Ω · c
m, and a coated sample was obtained in the same manner.

DLC film Source gas: C ₂ H ₄ [Flow rate 40 SCCM (6.8 × 10 ^-2 Pa · m ³ · s
^-1 )] N ₂ [Flow rate 10 SCCM (1.7 × 10 ^-2 Pa · m ³ · s ^-1 )] Film composition: CH _0.17 N _0.13

<Comparison of Film Quality> Examples 1 to 3 and Comparative Examples 1 to
The scratch strength and Vickers hardness of the coated samples of No. 3 were measured. However, the Vickers hardness was measured using a sample having an overall thickness of 2.5 μm while maintaining the relationship between the thicknesses of the upper and lower layers when the layers were present. The measured values are standardized by the values of the first embodiment (that is, relative values when the value of the first embodiment is set to 1). Table 1 shows the results.

[0061]

[Table 1]

<Application to Automobile Parts> Coating films under the same conditions as those of the coating samples of Examples 1 to 3 and Comparative Examples 1 to 3 were formed using an automobile light cover (material: polycarbonate) as a base material. The following evaluation was performed. Table 2 shows the results. The light cover without the coating film was evaluated in the same manner and shown as Comparative Example 4.

After running and washing the car and changes in surface condition, a series of operations for washing a car using an automatic car washer were repeated 100 times a day on a paved road at 200 km.

The automatic car washer was equipped with a nylon brush and used for washing a car by rotating the nylon brush, which is usually installed in a gas station or the like. As such an automatic car washer, for example, the number of rotations of a brush is 50 to 100.
rpm, a car wash with water for 2 minutes, a car wash with a detergent solution for 2 minutes, a car wash with water for 2 minutes, and a drying for 2 minutes.

Thereafter, the number of scratches (per 1 cm ² ) existing on the surface was examined by a stereoscopic microscope, and the results are shown in the table based on the following criteria. ○ ... less than 5 / cm ² △ ... 5 / cm ² or more 50 / cm ² or less × ... 50 / cm ² ultra 100 / cm ² or less ×× ... 100 / cm ² or greater

Further, the surface roughness was examined as an index of the surface condition. The surface roughness conforms to Ra defined in JIS B0610, and Ra is measured using a surface roughness meter according to JIS B0610.
It was determined by performing measurement according to No. 0610 (cutoff value 0.08 mm, evaluation length 0.4 mm). Ra is normalized by the value before running and car washing (that is, the relative value when the value before running and car washing is set to 1). In addition, R before running and car washing
a is almost the same value regardless of the presence or absence of the coating film.

[0067]

[Table 2]

From the above results, the effect of the present invention is clear. In addition, the light cover provided with the coating film of the present invention did not show a decrease in light transmittance due to generation of scratches.

[0069]

According to the present invention, a light-transmitting organic member coated with a DLC film having excellent light-transmitting properties and scratch resistance and good adhesion can be obtained.

Claims (8)

[Claims] 1. A translucent organic member is coated with two or more diamond-like carbon films, and the diamond-like carbon film closest to the translucent organic member is CH _x Si _y O _z N _v (here Wherein x, y, z and v each represent a molar ratio,
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. Wherein the diamond-like carbon film furthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio;
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A translucent organic member coated with a diamond-like carbon film having the composition of (1). 2. A light-transmitting organic member provided in an automobile, wherein the light-transmitting organic member is coated with two or more diamond-like carbon films, and a diamond-like carbon member closest to the light-transmitting organic member is provided. The film is composed of CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio;
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. Wherein the diamond-like carbon film furthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio;
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A translucent organic member coated with a diamond-like carbon film for automobiles having the composition of (1). 3. The car washing machine according to claim 2, wherein said car washing machine is used for washing.
A translucent organic member coated with a diamond-like carbon film for automobiles. 4. A light-transmitting organic member used in a railway vehicle, wherein the light-transmitting organic member is covered with two or more diamond-like carbon films, and a diamond-like carbon member closest to the light-transmitting organic member is provided. The carbon film is composed of CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio,
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. Wherein the diamond-like carbon film furthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio;
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A translucent organic member coated with a diamond-like carbon film for railway vehicles having the composition of (1). 5. A light-transmitting organic member provided on a ship, wherein the light-transmitting organic member is covered with two or more diamond-like carbon films, and a diamond-like carbon member closest to the light-transmitting organic member is provided. The film is composed of CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio;
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. Wherein the diamond-like carbon film furthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio;
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A translucent organic member coated with a marine diamond-like carbon film having the composition of (1). 6. A light-transmitting organic member used in an aircraft, wherein the light-transmitting organic member is covered with two or more diamond-like carbon films, and a diamond-like carbon member closest to the light-transmitting organic member is provided. The film is composed of CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio;
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. Wherein the diamond-like carbon film furthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio;
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A transparent organic member coated with a diamond-like carbon film for aircraft having the composition of (1). 7. A light-transmitting organic member provided for an automatic bicycle, wherein the light-transmitting organic member is covered with two or more diamond-like carbon films, and a diamond-like carbon member closest to the light-transmitting organic member is provided. The carbon film is composed of CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio,
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. Wherein the diamond-like carbon film furthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio;
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A light-transmitting organic member coated with a diamond-like carbon film for a motorbike having the composition of (1). 8. A light-transmitting organic member provided in a building, wherein the light-transmitting organic member is covered with two or more diamond-like carbon films, and a diamond-like carbon member closest to the light-transmitting organic member is provided. The carbon film is composed of CH _x Si _y O _z N _v (where x, y, z and v each represent a molar ratio,
0.05 ≦ x ≦ 0.7, 0 <y ≦ 3.0, 0 ≦ z ≦ 1.
0, 0 ≦ v ≦ 1.0. Wherein the diamond-like carbon film farthest from the translucent organic member is CH _p O _q N _r F _s (where p, q, r and s each represent a molar ratio;
0.05 ≦ p ≦ 0.7, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.
0, 0 ≦ s ≦ 0.2. A translucent organic member coated with a diamond-like carbon film for buildings having the composition of (1).