JPH01154744A - Laminate for decoration - Google Patents

Abstract

PURPOSE:To make a mirror surface to be colored and moreover to enable the contour of an object to be projected without deformation by a method in which the film of diamond and/or diamond like carbon is formed on the surface of a reflective substrate, and on said film a transparent protective film is formed. CONSTITUTION:A reflective surface 2 is coated with the film 3 of diamond and/or diamondlike carbon, and further its upper surface is coated with a transparent protective film 4. By this construction, the light h1 having penetrated the transparent protective film 4 and the diamond film 3 reflects at the reflective surface 2. This reflected light h and the reflected light h2 having reflected on the surface of the diamond film 3 after penetrating the traparent protective film 4, interface mutually, whereby the laminate for decoration provides interference color. The reflectance of the reflective surface 2 is preferably 30% or more. As the reflective surface, the nonmetallic mirror surface of the metal such as aluminum and silicon, is used. The thickness of a reflective layer 6 is more thickened sufficient by than the thickness of the diamond film preferably. As the transparent protective film, the film being transparent in visible range and excellent in the adhesion to the diamond film, is used. Number 5 shows a substrate.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention relates to a decorative laminate, and more specifically,
The present invention relates to a decorative laminate that has an interference color due to a film of diamond and/or diamond-like carbon, has excellent durability, and can be suitably used for various accessories such as pendants, earrings, and mirrors.

[Prior art and its problems] Conventionally, decorative laminates have been made of, for example, titanium coated with a titanium oxide film, or a plate, a metal layer, and a diamond and/or diamond-like carbon film. It is known that these are laminated in this order. In particular, a laminate having a film of diamond and/or diamond-like carbon has attracted attention in recent years because various interference colors can be obtained by adjusting the thickness of the film of diamond and/or Guyamond-like carbon.

However, conventional decorative IA layer bodies using diamond and/or diamond-like carbon films as interference films,
Since these interference films are directly exposed on the surface, there is a problem that the interference films are easily peeled off and have poor durability.

Additionally, conventionally, mirrors used for fishing boats are colorless, and in many cases, if a mirror is decorated, it is just a matter of putting some effort into the edges of the mirror or making the outline of the mirror decorative. There were no decorative efforts such as coloring the mirror surface itself. It is not surprising that such decorative devices have not been used in the past, since if decorative devices such as coloring were applied to the mirror surface itself, the mechanism of the mirror would be obstructed and the mirror would no longer be useful.

However, if the mirror surface reflects the shape of the object without distortion and is colored in various colors, the decorative value of such a mirror would further increase.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a decorative laminate having excellent durability of the interference film and being sufficiently usable as accessories such as pendants and earrings.

Another object of the invention is that the mirror surface is colored.

Moreover, it is an object of the present invention to provide a decorative laminate that can reproduce the outline of an object without distortion.

[Means for Solving the Problems] In order to solve the above-mentioned problems, the inventor has made extensive studies and has developed a film of diamond and/or diamond-like carbon with a specific thickness on the surface of a reflective substrate. form,
The inventors have discovered that the object of the invention can be achieved by further forming a transparent protective film on top of the film, and have thus arrived at the invention.

That is, the configuration of the present invention includes a reflective surface, a diamond and/or diamond-like carbon film (hereinafter simply referred to as a diamond film) covering the reflective surface, and a transparent protective film covering the surface of the film. This is a decorative 111-layer body characterized by consisting of:

Here, diamond-like carbon (DLC) refers to hard carbon that is neither diamond crystal nor graphite carbon. This diamond-like carbon generally has the following physical properties.

Density: Approximately 2 g/cm3 Vickers hardness, t, ooo~s, oo.

Specific resistance: 107~1014 Ωcm Refractive index: 1.5~2.8 Optical band gear 2P: 1.0~2.8e V light transmittance: Good Next, regarding the configuration of the present invention, the configuration of the present invention Description will be given with reference to drawings showing one embodiment.

As shown in FIG. 1, the decorative laminate 1 of the present invention is formed by coating one reflective surface 2 with a diamond film 3, and further covering the surface of the film 3 with a transparent protective layer 4.

As shown in FIG. 1, the light h1 transmitted through the transparent protective film 4 and the diamond film 3 is reflected by the reflective surface 2, and the reflected light h1 and the transparent protective film 4 are transmitted through the diamond film. This decorative laminate 1 exhibits an interference color due to the interference of the reflected light h2 reflected on the surface of 3.

Therefore, the reflective surface 2 only needs to have a mirror surface that can exhibit the interference color by reflecting light, and usually has a reflectance of 30% or more.

The reflective surface 2 is not particularly limited in any material and how it is formed as long as it can reflect light in the visible range with high reflectance as described above, but for example, Examples include metallic and non-metallic surfaces that are mirror-like.

The metal may be, for example, aluminum, tungsten, molybdenum, cobalt, chromium, nickel, copper, iron, mercury, or an alloy thereof.

Preferred metals include aluminum and the like.

Examples of the nonmetal include silicon.

By making the surface of such a metal or non-metal a mirror finish, or by depositing a metal or non-metal on the surface of a diamond film formed on the surface of a transparent protective layer, the reflective surface of the present invention can be achieved. can do.

The reflective surface may be supported by a support member.

The supporting member may be made of various materials as long as it can support the reflective surface and withstand heating during formation of the reflective surface, so long as it does not impede the object of the present invention. can be used.

Examples of the material include semimetals such as silicon, oxides, nitrides, and carbides of various metals, or Al203-
Fe system, TiC-Ni system, TiC-(:O system, Tie
-Various cermets such as TiN type and BaC-Fe type,
Furthermore, it is possible to use an appropriate material selected from among various glasses, ceramics, and the like. In some cases, heat-resistant synthetic resins such as phenol resins, polycarbonate resins, polyimide resins, etc. can also be used.

Whether or not the reflective surface is supported by a support member,
When the reflective surface is a metallic or nonmetallic mirror surface, the metallic or nonmetallic material usually has a certain thickness and forms the reflective layer 6, as shown in FIG. is preferably sufficiently thicker than the thickness of the diamond film described later, and is usually 5,000 A or more. By making this thickness sufficiently thicker than the diamond film thickness, it is possible to prevent the diamond film from peeling off from the reflective surface. Furthermore, when a support member is used, it is possible to prevent the reflective layer from peeling off from the support member. The reason for this is presumed to be that the stress generated between the reflective surface and the diamond film or between the reflective layer and the supporting member is alleviated by the atf7/tension. In addition,
From a different perspective, this reflective layer can also be understood as a support member made of the same material as the 5 reflective surfaces.

The diamond film has a thickness of 2,000 to 4.0
0OA is desirable; if the film thickness is 2,000A or less, interference colors may not be seen in the visible region, and even if it exceeds 4,000X, only the same color will appear, so it is necessary to It has no effect.

In this invention, the diamond film may cover the entire surface of the reflective surface, or may partially cover the surface of the reflective surface 2, as shown in FIG. .

Although the reflective surface 2 is shown as an uneven surface in FIG. 2, it goes without saying that a portion of the flat reflective surface may be covered with the diamond film 3.

When the surface of the reflective substrate is partially coated with the diamond film, the shape of the coated surface is not particularly limited;
For example, various shapes or designs such as a circle, an ellipse, a square, a rectangle, a hexagon, etc. can be selected as appropriate.

The transparent protective film is made of a material that is transparent in the visible region, has excellent adhesion to the diamond film, and has excellent wear resistance. In terms of A, the main components are, for example, silica, feldspar, sodium carbonate, sodium nitrate, and borax.

A glass powder obtained by melting a mixture obtained by adding an emulsifying agent such as fluorite, sodium hexafluorosilicate, antimony oxide (■), and titanium dioxide, and then rapidly cooling it, that is, a frit, etc., is preferably used. Can be done.

The thickness of the transparent protective film is usually 5,000 A or more.

The decorative laminate of the present invention can be produced, for example, in a primary manner.

That is, the decorative laminate of the present invention includes (1) a reflective surface formed on the surface of a supporting member that is made of a material different from that of the reflective surface, or a reflective surface of a reflective layer that does not have a supporting member;
A method of forming a diamond film on a reflective surface by contacting a gas obtained by activating a raw material gas containing a carbon source gas, and then forming a transparent protective film on the diamond film,
Alternatively, it can be manufactured by (2) a method in which a diamond film is formed on the transparent protective film in the same manner as described above, and a reflective surface is formed by vapor-depositing metal thereon.

In the manufacturing method of (1) above, a fully refracted or non-metallic reflective surface is formed on the surface of the support member, or (
In the manufacturing method of 2), the surface of the diamond film formed on the entire surface of the transparent protective layer, or the surface of the diamond film formed on the surface of a part of the transparent protective layer and the remaining surface of the transparent protective layer, is completely bent or non-metallic. There is no particular limit to the method for forming the reflective surface, and examples include physical vapor deposition (PVD) such as thermal evaporation, ion blating, and sputtering;
Chemical vapor deposition method (CV) using thermal decomposition reaction, oxidation reaction, etc.
D) or plasma CVD method.

Conventionally known methods such as physicochemical vapor deposition methods such as laser CVD methods can be appropriately selected and used.

The raw material gas used to form the diamond film contains at least a carbon source gas, and may contain hydrogen gas and an inert gas in addition to the carbon source gas.

Examples of the carbon source gas include paraffinic hydrocarbons such as methane, ethane, propane, and butane; ethylene;
Olefinic hydrocarbons such as propylene and butylene; Acetylenic hydrocarbons such as acetylene and arylene; Diolefinic hydrocarbons such as butadiene; Alicyclic hydrocarbons such as dichloropropane, cyclobutane, cyclopentane, and cyclohexane; cyclobutadiene, Aromatic hydrocarbons such as benzene, toluene, xylene, and naphthalene; Ketones such as acetone, diethyl ketone, and benzophenone; Alcohols such as methanol and ethanol Nitrimethylamine;
Amines such as triethylamine; carbon dioxide gas, -carbon oxide; and, although not single substances, dangerous substances of Fire Service Act Class 4 and Class 1 such as gasoline, kerosene, turpentine oil, ginger oil, pine oil, etc. 2 petroleums, tertiary petroleums such as heavy oil, and tertiary petroleums such as gear oil and cylinder oil can also be effectively used. It is also possible to use a mixture of the various carbon compounds mentioned above.

Among these, preferred are paraffinic hydrocarbons such as methane, ethane, and propane, ketones such as acetone and benzophenone, amines such as trimethylamine and triethylamine, carbon dioxide gas, and carbon oxide, and particularly preferred is methane. be.

Hydrogen gas can be used as a diluent gas for the carbon source gas and as a plasma generation gas when plasma decomposing a raw material gas.

When this hydrogen gas is used, the hydrogen gas content in the raw material gas is 99.8 mol% or less, preferably 10 to
It is 99 mol%. If this content exceeds 99.8 mol%, the formation rate of the diamond film may be significantly slowed down, or diamond and/or diamond-like carbon may no longer precipitate.

The inert gas can be used as a carrier gas for the carbon source gas or a mixed gas of the carbon source gas and hydrogen gas.

Examples of this inert gas include nitrogen gas, argon gas, neon gas, and xenon gas. Among these, argon gas is preferred. When this inert gas is used, the content of the inert gas in the raw material gas is 90 mol% or less, preferably 10 to 90 mol%. If this content exceeds 90 mol%, the rate of formation of a diamond film may be significantly slowed, or diamond or diamond-like carbon may not be deposited.

As the means for activating the raw material gas, any method can be used from among the various methods conventionally used in the synthesis of diamond or diamond-like carbon.

Specifically, for example, there are methods for plasma decomposition by applying DC voltage between electrodes, methods for plasma decomposition by applying high frequency waves between electrodes, methods for plasma decomposition by applying microwaves, or methods for plasma decomposition in an ion chamber. Other examples include various plasma decomposition methods such as an ion beam method in which ions are extracted using an ion gun and an electric field, and thermal decomposition methods in which thermal decomposition is performed by heating with a hot filament. Among these, various plasma decomposition methods are preferred.

During the production of the decorative laminate of the present invention, the reaction usually proceeds under the following conditions to form a diamond film on the reflective surface or on the entire surface of the transparent protective layer, or on the surface of the transparent protective layer. A diamond film is completely formed on the surface of the diamond film formed on a portion of the surface and the remaining surface of the transparent protective layer.

That is, the temperature of the surface of the object on which the diamond film is to be deposited varies depending on the means of activating the raw material gas, so it cannot be determined generally, but in the case of plasma decomposition, for example, it is usually between room temperature and t,ooo
It is ℃. If this temperature is lower than room temperature, the rate of diamond film formation may be slow. On the other hand, t,oo
If the temperature exceeds 0° C., the formation rate of the diamond film may become slow.

The reaction pressure is 101 to 103 torr, preferably 10
-5 to 760 torr 0 reaction pressure is 1O-8to
If it is lower than rr, the formation rate of the diamond film may become slow. On the other hand, even if it is made higher than 103 torr, no corresponding effect will be achieved, and in some cases, the formation rate of the diamond film may be reduced.

The reaction time can be appropriately set depending on the desired diamond film formation rate and the diamond film formation rate. For example, the film thickness is 2,000 to 4.5 mm by plasma decomposition method.
When forming a diamond film of 00OA, usually
5~! It is 1 til for 20 minutes.

Furthermore, the plasma output when plasma decomposing the raw material gas is usually 5 W to 2 kW. Even if the plasma output is increased to more than 2 kW, the corresponding effect may not be achieved.

In the manufacturing method (1) above, a transparent protective film is formed on the diamond film formed on the reflective surface under the conditions described above.

The transparent 1 protective film can be formed by, for example, applying a transparent frit for low-temperature firing on the diamond film and firing it.

The annealing temperature at this time varies depending on the materials of the substrate and the metal layer or the characteristics of the frit, so it cannot be determined generally, but for example, aluminum oxide is used for the substrate and the metal layer is formed of aluminum, When forming a transparent protective film using a transparent frit for low-temperature firing, the firing temperature is about 530 to 570°C.

The manufacturing method in (1) above is suitable for coating the entire reflective surface with a diamond film, but the manufacturing method in (2) above is suitable for producing a decorative planted body in which a part of the reflective surface is coated with a diamond film. It can be manufactured by the following method.

That is, as shown in FIG. 3(a), a mask 9 having an opening 8 for forming a diamond film is placed on the surface of a transparent plate 7, such as a glass plate.

There are no particular restrictions on the number, shape, etc. of the openings 8 provided in the mask 9, and a mask having one or more openings with a desired shape or design such as a circle, square, rectangle, or hexagon may be used. can do.

The mask 9 may be made of any material such as metal or alloy that can withstand plasma shock and temperature, and masks made of aluminum, titanium, and stainless steel are particularly preferred.

As shown in FIG. 3(b), a gas obtained by activating a raw material gas containing a carbon source gas is brought into contact with the surface of the plate 7 through the opening 8, and the diamond is injected into the opening 8. Deposit film 3. The conditions for depositing the diamond film 3 are the same as those for forming a diamond film over the entire surface of the reflective substrate.

As shown in FIG. 3(C), after the diamond film 3 is deposited, the mask 9 is removed. the result.

A diamond film 3 formed on a part of the surface of a transparent plate 7 is obtained.

Incidentally, such a diamond film 3 is formed by - masks 9.
The diamond film 3 may be formed at different positions on the transparent plate 7 by using a plurality of masks 9 with different opening positions and depositing the diamond film 3 on each mask 9. A plurality of diamond films 3 may be formed.

Furthermore, by varying the thickness of the diamond film 3 formed at different positions on the surface of the transparent plate 7, in the resulting decorative laminate l, for example, some parts with a diamond film may have a red color, while other parts may have a red color. A purple color and an interference color corresponding to the thickness of the diamond film appear in the area where the diamond film is located, and a highly decorative decorative laminate is obtained.

Even in the same area where a diamond film is formed, if a diamond layer is deposited in multiple stages using multiple masks with different opening areas, diamond v3 with different thicknesses can be formed as shown in Figure 4. can be formed. and,
By depositing diamond films 3 of different thicknesses, it is possible to obtain multiple interference colors.

As described above, by appropriately changing the shape of the opening in the mask, the thickness of the deposited diamond film, etc., it is possible to produce a decorative laminate having a pattern with a complex or mysterious color tone.

After forming the diamond film 3 as described above, the third
As shown in Figure (d), the diamond film 3 of the plate 7
A reflective layer 6 is formed by vapor-depositing metal on the surface where a portion of the reflective layer 6 is deposited. The metal to be deposited is as described in IγI.

The decorative laminate obtained by the manufacturing method described above is useful as a decorative mirror.

The decorative laminate in which a portion of the reflective surface is coated with a diamond film is not limited to the method outlined above in FIG. 3, but can also be produced in the following manner.

That is, a mask with specific openings is placed on the surface (reflective surface) of a reflective layer supported by a support member, and a gas obtained by activating a raw material gas containing a carbon source gas is applied to the plate. A diamond film is deposited within the opening in contact with the surface.

After the diamond film is deposited, the mask is removed, and then, for example, a transparent frit for low-temperature firing is applied onto the diamond film on the exposed mirror surface of the reflective substrate and the surface of the diamond film, and this is fired. By this, a transparent protective layer is formed to obtain a decorative laminate of the present invention.

In this case, the conditions for forming the diamond film, the conditions for forming the transparent protective layer, etc. are as described above.

The decorative carcass of this invention can obtain various interference colors by adjusting the thickness of the diamond film in units of several tens of lambda, and can be used, for example, as pendants, earrings, mirrors colored with interference colors, etc. It can be suitably used as various decorative items.

[Example] Next, Examples of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) Using a substrate made of aluminum 1sjide (Ah(h)), aluminum was deposited on the substrate by a vacuum evaporation method under conditions of a reaction pressure of 5×1 (16 torr).The obtained aluminum layer The layer thickness was 5,338 A.The surface of this vapor-deposited aluminum was a reflective surface.Next, the substrate formed by vapor-depositing this aluminum was placed in a reaction chamber, and the substrate temperature was 200°C and the pressure in the reaction chamber was 0. 1
Under conditions of torr, the plate blade of a high frequency power source (frequency 13.56 MHz) with parallel plate electrodes is soo
At the same time, the raw material gas flow into the reaction chamber was set to 20 sccm of methane gas, and the reaction was carried out for 40 minutes to obtain a deposit with a thickness of 2,381 A on the aluminum layer t of the substrate controlled at the above temperature. Ta.

Raman spectroscopic analysis of the obtained deposit revealed that the Raman scattering spectrum was 1,000 to 1.800.
A broad peak was observed near c-1, confirming that it was diamond-like carbon.

Thereafter, this diamond-like carbon film-L was coated with 9 layers of transparent frit for low-temperature firing suspended in water with a small amount of dextrin added, and fired at a temperature of 530 to 570°C for 5 minutes to increase the film thickness. A decorative laminate was obtained by forming a 1 pm transparent protective layer.

An orange interference color was observed in the obtained decorative laminate, and there was almost no deterioration or peeling of the diamond-like carbon film.

The results are shown in Table 1.

(Example 2) The process was carried out in the same manner as in Example 1 except that the reaction time in forming the diamond-like carbon film was changed from 40 minutes to 50 minutes.
A decorative laminate with a film of seven diamond-like carbons was obtained.

A purple interference color was observed in the obtained decorative laminate, and there was almost no deterioration or peeling of the diamond-like carbon film.

The results are shown in Table 1.

(Example 3) The process was carried out in the same manner as in Example 1 except that the reaction time in forming the diamond-like carbon film was changed from 40 minutes to 60 minutes, and the film thickness was 3.512 mm.
A decorative laminate having a diamond-like carbon film of λ was obtained.

A reddish-purple interference color was observed in the obtained decorative laminate, and there was also deterioration of the diamond-like carbon film and the film! 1 separation almost never happened.

The results are shown in Table 1.

(Gourd, hereinafter referred to as margins) Table 1 Book 1: The film thickness was measured for a diamond film deposited on a glass substrate placed under the same conditions.

(Wooden quince, hereinafter referred to as margin) (Example 4) As shown in Fig. 5, the − side is 50 mm and the thickness is 0.2 mm.
A titanium mask IO was prepared, which was rectangular in size and had a circular opening with a diameter of 15 mm at a distance of 5 mm from one side.

The mask was placed on the surface of a 2 mm thick transparent glass plate having the same planar shape as the mask, with the edges aligned.

Next, the glass plate on which the mask was placed was placed in a reaction chamber, and the substrate temperature was 100°C and the pressure in the reaction chamber was 0.1.
Under the condition of torr, the plate output of a high frequency power supply (frequency 13.56 MHz) with parallel plate electrodes is 600 MHz.
W and the flow rate of the raw material gas into the reaction chamber was set to 20 SCC of methane gas, and the reaction was carried out for 30 minutes to obtain a circular deposit with a thickness of 2.32 OA on the glass plate.

Note that no deposits were formed on the mask.

Thereafter, the mask was again placed on the diamond film coated glass plate 1 so that the first deposit and the opening of the mask did not overlap.

Then, the glass plate with the mask a21 was placed in the reaction chamber, and the reaction was carried out for 45 minutes under the same conditions as above to obtain a circular second deposit with a thickness of 3,659A on the glass plate. Ta.

Raman spectroscopic analysis of the obtained deposit revealed that the Raman scattering spectrum was 1.000 to 1.800.
A broad peak was observed in the vicinity of c and c, confirming that it was diamond-like carbon.

Thereafter, aluminum was vapor-deposited over the entire surface of the glass plate having the first diamond film and the second diamond film on the glass plate under the same operation and conditions as in Example 1 above. The thickness of the obtained aluminum layer was 5
, 338 A.

When observing the obtained decorative laminate from the glass side,
The first diamond film forming area was colored purple, and the second diamond film forming area was colored red. Moreover, the viewer's face could be clearly seen from the glass side.

[9. Effect of light] According to the present invention, (1) A laminate of a diamond film having an interference color formed on a reflective surface having high reflectance and a transparent protective layer formed on the diamond film. Therefore, by adjusting the thickness of the diamond film, various interference colors can be obtained. (2) A transparent protective film is provided on one side of the diamond film, and a reflective layer or Since it forms a supporting member, the diamond film is protected and also prevents the diamond film from peeling off.

(3) Therefore, for example, pendants, earrings,
It is possible to realize a decorative laminate having sufficient durability for practical use as various decorative items such as mirrors.

(4) Furthermore, the decorative laminate of the present invention can be made into an extremely highly decorative decorative article due to the interference color, and (5) the operations required for manufacturing are simple. A decorative laminate having the following can be provided.

[Brief explanation of the drawing]

FIG. 1 is an explanatory cross-sectional view showing one example of the decorative laminate of the present invention, FIG. 2 is a cross-sectional view showing another example, and FIGS. FIG. 4 is a cross-sectional explanatory diagram showing an example of the manufacturing process of the decorative laminate of the present invention, FIG. 4 is a cross-sectional explanatory diagram showing still another example of the decorative laminate of the present invention, and FIG. It is an explanatory view showing an example of a titanium mask that can be used in manufacturing a laminate. l...Decorative laminate, 2...9 reflective surface, 3...diamond film, 4...transparent protective film. Patent applicant: Idemitsu Petrochemical Co., Ltd. Figure 1 Figure 2 Figure 3 (d)

Claims (6)

[Claims] (1) A decorative laminate comprising a reflective surface, a diamond and/or diamond-like carbon film covering the reflective surface, and a transparent protective film covering the surface of the film. (2) The decorative laminate according to claim 1, wherein the reflective surface has a surface reflectance of 30% or more. (3) The decorative laminate according to claim 1, wherein the reflective surface is a mirror surface of the base. (4) The decorative laminate according to claim 1, wherein the reflective surface is a surface of a metal layer provided on the surface of the base. (5) The decorative substrate according to claim 4, wherein the thickness of the metal layer is greater than the thickness of the diamond and/or diamond-like carbon film. (6) The decorative substrate according to any one of claims 1 to 5, wherein the diamond and/or diamond-like carbon film partially covers the reflective surface.