JPH04341557A - Vapor deposition plated composite material having excellent fanciness and its production - Google Patents

Abstract

PURPOSE:To provide a polychrome fancy material having metallic luster by vapor-depositing an Si plating layer of a specified thickness on the surface of a base material so that the thickness is continuously varied in the transverse direction of the base material. CONSTITUTION:A vapor-deposited Si plating layer of 0.005-0.2mum thickness is formed on the surface of a base material so that the thickness is continuously varied in the transverse direction of the base material. A vapor-deposited amorphous oxide plating layer of 0.05-1.0mum thickness is formed on the surface of a base material. A steel strip 6 as a long-sized base material is travelled in a vacuum deposition chamber, a molten Si bath 10 as starting material for plating is heated by irradiation with electron beams 4 and the base material is plated by vapor deposition. A plated material having excellent fanciness is produced at a low cost.

Description

[Detailed description of the invention]

0001

FIELD OF INDUSTRIAL APPLICATION The present invention relates to a vapor-deposited plating composite material with excellent design properties, and the composite material is useful for various building materials, home appliances, design products, and the like.

0002

BACKGROUND OF THE INVENTION Currently, various color-coated steel sheets are widely used as decorative surface-treated materials in the above-mentioned fields. Color-coated steel sheets are manufactured by applying organic paint to the surface of the steel sheet, but recently pre-painted steel sheets with various properties have been developed to simplify the painting process on the user side. Characteristics that should be possessed as a material,
For example, it is required to have corrosion resistance, scratch resistance, workability, fingerprint resistance, stain resistance, etc., and various play coated steel sheets have been developed and used in accordance with the characteristics required by users.

[0003] However, the color tone and design given to play-coated steel sheets depend on the various dyes and pigments added to the organic paint, and therefore, the luster and bright color tone characteristic of metals are lost by painting. ,
It is impossible to obtain a design product having such characteristics.

[0004] Other decorative materials include colored aluminum,
Materials (hereinafter abbreviated as color materials) that have both metallic luster and bright variegated colors, such as colored stainless steel sheets and colored titanium, are also used. In these color materials, an oxide film is formed on the surface of the substrate by an electrolytic coloring method or a chemical coloring method, and color is generated by light interference in the visible light region. Since the color material has not lost its metallic luster, it has a more luxurious feel than color-coated steel sheets, and is superior in design and aesthetics. In addition, since the treated material itself has excellent corrosion resistance, it is less likely to discolor or lose its metallic luster due to rusting due to corrosion of the treated material under general usage environments.

However, if the surface of these color materials is damaged or if they are used in a relatively harsh corrosive environment where chloride ions are present or in an environment where ultraviolet rays are harshly irradiated, red rust or rust may occur due to corrosion of the treated material. Due to the occurrence of white rust, fading, etc., the design and aesthetics are rapidly impaired. In addition, these materials to be treated are not only expensive, but also have the disadvantage that the electrolytic treatment or chemical treatment for coloring the surface is expensive.

Furthermore, materials have been proposed in which stainless steel plates are coated with various ceramic coating layers such as metal nitrides, metal oxides, metal carbides, etc. using various dry coating methods (vapor phase plating methods). The most common examples include various ion plating methods on stainless steel plates,
There is one in which a TiN film is formed using a CVD method or the like, and the golden color of the TiN film gives a design effect. Since these various ceramic coating layers generally have high hardness, they can be applied to areas that require not only good design but also wear resistance.

However, there is no example of manufacturing these ceramic coated steel sheets on a continuous industrial production scale. The reason for this is that when attempting to provide a desired film thickness with ceramic coating, the film formation speed is extremely slow due to constraints in the manufacturing method, so the traveling speed of the treated zone must be considerably reduced, resulting in low productivity and high manufacturing costs. This is because it becomes extremely expensive. Therefore, the applications are inevitably limited due to the product price.

[0008] Recently, due to changes in user preferences,
In addition to monochromatic materials, polychromatic materials with continuously changing color tones are now required. However, the above-mentioned pre-coated steel sheets, color materials, ceramic coating materials, etc. are difficult to obtain in a plurality of colors in the width direction of the sheet due to the manufacturing method, and are limited to those with a single color tone.

[0009]

[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and has a metallic luster and a color tone that continuously changes in the width direction of the board.
Furthermore, the present invention aims to provide a plating material with low manufacturing cost and excellent design.

0010

[Means for Solving the Problems] The plating material of the present invention, which has achieved the above object, has a film thickness of 0.0 on the surface of the base material.
Vapor deposited Si plating layer of 0.05 to 0.2 μm or film thickness of 0.05 to 0.2 μm.
The gist is that it has a vapor-deposited amorphous oxide plating layer of 0.05 to 1.0 μm, and that the plating thickness of the plating layer changes continuously in the width direction of the base material. In addition, when the above-mentioned plating material is introduced into a vacuum deposition chamber, and the surface of the plating raw material is irradiated with an electron beam while running, and vapor deposition plating is performed by heating the plating raw material, the amount of electron beam irradiated onto the surface of the plating raw material is reduced. It can be manufactured by continuously changing the width direction of the base material.

[0011]

[Function] As a result of various studies conducted by the present inventors, we found that when applying Si plating or amorphous oxide plating on a steel plate by vacuum evaporation method, the thickness of the plating layer is very thin. It has been found that when the film thickness is continuously changed, the surface of the plating material exhibits a continuously different color tone depending on the film thickness. This has a light interference effect in the visible light region within a certain range of thickness of the plating layer,
This is because when the film thickness changes, the wavelength of the interfering light changes accordingly, resulting in a change in color tone. Therefore, by continuously changing the plating film thickness in the board width direction, it was possible to sequentially change the color tone in the board width direction. This will be explained in more detail below.

First, the thickness of the vapor-deposited Si plating layer is 0.005.
It is necessary to set it to ~0.2 μm. Since the design of the present invention has a variety of color tones due to the optical interference effect of the Si plating layer, the plating film thickness is limited to the above-mentioned film thickness range in which this effect can be obtained. FIG. 1 shows the relationship between the Si plating film thickness and the resulting color tone. As shown in Figure 1, the film thickness is 0.
．． If the thickness exceeds 2 μm, a vivid color tone cannot be obtained, and even if the film thickness is increased further, only the color tone of Si itself can be obtained. Moreover, when the film thickness is below the above range, it is technically difficult to continuously obtain a stable color tone.

[0013] The plating film thickness of the vapor-deposited oxide plating layer is 0.0
It is necessary to limit the thickness to a range of 5 to 1.0 μm. Similarly to the above, the design of the present invention is obtained by the optical interference effect of the amorphous oxide plating layer, so the plating film thickness must be limited to a thickness range in which this effect can be obtained. When the present inventors investigated the relationship between the thickness of Al oxide plating film and the color tone obtained as an example of oxide, it was found that Al
It has been found that when the oxide plating film thickness exceeds 1.0 μm, a bright color tone cannot be obtained, and even if the film thickness is further increased, only a colorless or slightly brownish color tone is obtained. Further, in the region where the film thickness is less than 0.05 μm, it is difficult to stably control the film thickness in terms of manufacturing. The plating film thickness range in which various color tones can be obtained by changing the plating film thickness is A.
This was true not only for l oxide but also for other metal oxides.

Further, the oxide plating layer of the present invention needs to have an amorphous structure. As mentioned above, the range in which a variety of color tones of the oxide plating layer can be obtained is only in the region where the plating film thickness is small. It is desirable to minimize plating defects and the like even in areas where the surface area is small. However, defects in the oxide plating layer within the above plating thickness range are far fewer when the plating layer is amorphous than when the plating layer is crystalline. Therefore, it is essential that the vapor-deposited oxide plating layer of the present invention has an amorphous structure.

The type of oxide constituting the amorphous oxide plating layer of the present invention is not particularly limited, but Si oxide or /
and Al oxide. Among various oxide plating layers, the Si oxide plating layer and Al oxide plating layer have an amorphous structure, which makes them extremely stable and does not react with moisture or various corrosive substances in the usage environment. It is less likely to dissolve or change into other compounds, and has particularly excellent weather resistance and corrosion resistance. In addition, both oxides belong to the class of oxides that have the highest evaporation rate when irradiated with electron beams, and are advantageous in terms of productivity in the manufacturing method described below. Note that Si
The amorphous oxide plating layer composed of oxide and Al oxide includes a single oxide plating layer of one type of both oxides, a composite oxide plating of both oxides, two-layer plating, and multi-layer plating. etc. are included.

As a heating/evaporation source for forming the vapor-deposited plating layer of the present invention on the surface of the material to be plated, electron beam (EB) is used.
Use heating. Electron beams are heating sources with high energy and high energy density, and although electron guns (EB guns) for generating electron beams are expensive, they are easy to maintain and can easily generate and stop the electron beams. Can be done. Furthermore, since the electron beam can directly irradiate the surface of the raw material to be evaporated, the heating and evaporation efficiency is high, and as a result, the evaporation rate of the plating raw material can be increased. From the above points, electron beam heating is one of the most effective means when considering industrial production.

The plating layer of the present invention is formed by using the above electron gun as a heating/evaporation source and irradiating the plating raw material evaporation tank placed in the vacuum deposition chamber with an electron beam. It can be manufactured by changing the occupation, that is, the energy amount of the electron beam or the irradiation time in the width direction of the running base material. In other words, if the irradiation energy or irradiation time of the electron beam is continuously changed in the width direction of the plate, the amount of plating raw material vapor generated from the surface of the plating raw material will be continuously and non-uniformly distributed in the width direction of the plate. As a result, the thickness of the deposited plating film changes continuously in the board width direction. By continuously changing the thickness of the vapor-deposited plating film in the width direction of the plate in this manner, it is possible to obtain a plating material that has excellent design and whose color tone changes continuously in the width direction of the plate.

[0018] The vapor deposition means for forming the plating layer is as follows:
It refers to vacuum evaporation method in a broad sense, and includes various ion plating methods, various sputtering methods, and various C
The VD method is also included as a means for obtaining the surface-treated material of the present invention. In particular, if the ion plating method is adopted, the energy contained in the vapor of the deposited metal is higher than in normal vacuum deposition, which improves adhesion to the material to be treated and reduces pinholes in the plating layer, improving weather resistance and corrosion resistance. This is preferable because further improvement is possible.

Although the film thickness of the vapor-deposited plating layer of the present invention is within a very narrow range, defects such as pinholes may occur in such a film thickness range, and the plating base material may corrode through the pinholes. There are cases where This is particularly noticeable when Si plating is applied. Therefore, when using Si-plated materials, if sufficient weather resistance and corrosion resistance are required depending on the usage environment, use various types of stainless steel plates with good corrosion resistance as the material to be treated. becomes. However, since this results in a slight increase in cost, it is also recommended to perform an organic resin coating treatment on the surface of the vapor-deposited Si plating layer as a post-treatment, with or without a chromate treatment layer.

[0020] The organic resin film has a coating amount of 1.0 g/
It is preferable to set it as m2 or more. If it is less than 1.0 g/m2, it is difficult to uniformly apply the organic film layer to the surface of the plating layer, and corrosion tends to occur from thin or defective parts of the organic film layer through pinholes in the underlying plating film. In addition, if the usage environment is severe, it is preferable to apply the coating at 5 to 10 g/m2 or more. There is no particular restriction on the upper limit of the amount of the organic film layer, but from the viewpoint of weather resistance and corrosion resistance, an amount that is more than necessary will only lead to an increase in cost, and depending on the type of organic resin. The characteristic metallic luster of the vapor-deposited Si-plated steel sheet itself may be impaired. Therefore, the amount of organic film layer deposited is 20g/
It is considered that about m2 or less is preferable.

[0021] The type of organic resin constituting the organic film layer is not limited in any way, and any general transparent or translucent organic synthetic resin may be used. For example, if the decorative steel sheet of the present invention has required properties such as fingerprint resistance, scratch resistance, stain resistance, workability, etc. in addition to the above-mentioned designability and weather resistance, polyethylene It is possible to appropriately select and use resins such as epoxy resins, acrylic resins, urethane resins, polyester resins, fluorine resins, mixtures thereof, copolymers, modified resins, and the like. Furthermore, there are no restrictions regarding the resin, including water-soluble resins and organic solvent-based resins, and both baking-type resins and quick-drying resins can be used. Furthermore, small amounts of various pigments, silane coupling agents, and various oxide sols may be added for the purpose of further improving the corrosion resistance, coating adhesion, etc. of the organic film layer. However, since the color tone as a decorative steel sheet may be impaired, it is necessary to adjust the type and amount of the additive as appropriate.

Furthermore, the present invention also includes cases in which various chromate-treated coating layers are provided as an intermediate layer between the lower plating layer and the upper organic coating layer. The main purpose of applying the chromate film layer is to further improve weather resistance and corrosion resistance, and the self-healing action of the chromate film removes microscopic defects in the plating layer and the upper organic coating layer, as well as during handling. It becomes possible to effectively suppress discoloration and corrosion from scratches that occur during processing. Further, it is possible to further improve the coating adhesion of the organic coating layer, which is preferable. However, in order to fully demonstrate this effect of the chromate film layer, the film thickness must be 1.0 mg/m in terms of coating amount.
2 or more are required. If the amount of adhesion is less than 1.0 mg/m2, the effect of applying the chromate film layer will not be exhibited. The upper limit is not particularly limited, but if it is deposited more than necessary, the effects such as corrosion resistance will just be saturated, which is disadvantageous in terms of manufacturing cost. Therefore, it is considered that the appropriate amount of the chromate film layer is 1.0 to 300 mg/m2, more preferably 10 to 100 mg/m2.

The type of the chromate film is not particularly limited, and may include coating type chromate, reactive chromate,
Electrolytic chromates and combinations thereof are considered, but with reactive chromates, the color tone obtained by the Si plating layer may change, and with electrolytic chromates,
Since it is necessary to control the current density, electrolyte, etc., coating type chromate is generally preferred.

In addition, in order to further improve the corrosion resistance, weather resistance, and coating adhesion of the upper organic coating layer of the chromate coating, anticorrosive pigments, oxide sol such as silica, It may also contain a small amount of a silane coupling agent, various surfactants, etc. However, since the color tone as a decorative steel sheet may be impaired, it is necessary to adjust the type and amount of the additive as appropriate.

[0025] In terms of cost, the base material of the present invention is
Although it is preferable to use steel plates such as cold-rolled steel plates and various alloy steel plates, it is also possible to use Al, Cu, Ti, and alloys thereof other than steel plates. Further, the shape is not particularly limited, and a plate-like shape, a rod-like shape, a tubular shape, etc. can also be used.

[0026] The present invention will be explained in more detail with reference to Examples below, but the following Examples do not limit the present invention.
All changes and implementations within the scope of the spirit described below are included within the technical scope of the present invention.

[0027]

【Example】

Examples 1 to 20 Vapor-deposited Si-plated steel sheets were continuously manufactured using the apparatus shown in FIG. 2 under various conditions shown below and in Table 1, using an Al killed steel strip as a substrate to be plated. Furthermore, after applying the vapor-deposited Si plating layer, a coating type chromate treatment was performed (or not), and a desired organic resin was applied using a roll coater to form an organic film layer.

<Vapour-deposited Si plating conditions> Material to be plated: Al-killed steel strip Pretreatment of material to be plated: After alkaline electrolytic degreasing, the steel strip surface is introduced into a vacuum, heated by electron beam irradiation, and Ar ion bombardment. Pre-activation treatment/temperature of plated material before plating: 300℃/evaporation raw material
:Si (purity 99.9% or more) / Evaporation tank : Water-cooled copper evaporation tank / Heating of evaporation raw material Evaporation source: Pierce-type electron gun (maximum output 3
00KW) ・Electron beam irradiation method: As shown in Figure 3 ・Deposition chamber vacuum level: Approximately 1 x 10-2 Pa

<Chromate treatment conditions> ・Type: Sprayed chromate treatment ・Application method: After spraying, dry at 70℃

[
<Organic resin coating conditions> Coating method: After coating with a roll coater, the material was dried at 150° C. The following tests were conducted using the obtained material. Table 1 shows the results.
Shown below.

<Weather resistance evaluation test> -Test-1 After carrying out a constant temperature and constant humidity accelerated test at a temperature of 50°C and a relative humidity of 98% RH for 360 hours, the discoloration and rust occurrence on the surface of the sample material were observed. Weather resistance was evaluated. ○: No or almost no discoloration or rust formation, excellent weather resistance △: Some discoloration or rust formation, slightly poor weather resistance ×: Severe discoloration or rust formation, poor weather resistance

-Test-2 The following test was carried out using a sunshine weather test device. Test conditions: During irradiation, temperature 60℃, relative humidity 50%R
H 30 minutes darkness Temperature 35℃ Relative humidity 95%RH 30
A total of 50 minutes, with a total of 60 minutes during irradiation and darkness as one cycle.
Observe the discoloration and rust occurrence on the surface of the sample material after the cycle test.
Weather resistance was evaluated. ○: No or almost no discoloration or rust formation, excellent weather resistance △: Some discoloration or rust formation, slightly poor weather resistance ×: Severe discoloration or rust formation, poor weather resistance

[0033]

[Table 1]

[0034] The obtained vapor-deposited Si-plated steel sheets were arranged in the order of electron beam irradiation time from blue → purple → in the sheet width direction.
The color tone changed sequentially from pink → yellow → green → blue → purple → pink → yellow, and a decorative steel sheet with a variety of color tones was obtained. Furthermore, as is clear from Table 1, the vapor-deposited Si-plated composite material of the present invention coated with 1 g/m2 or more of organic resin had excellent weather resistance, regardless of the type of organic resin. . On the other hand, those with a small amount of organic resin attached had poor weather resistance regardless of the presence or absence of a chromate film layer.

Examples 21 and 22 Si oxide (Example 21) and Al oxide (
A vapor-deposited plating material was produced in the same manner as in Examples 1 to 20, except that Example 22) was used.

[0036] The obtained vapor-deposited Si oxide plated steel sheet and A
The color tone of oxide-plated steel sheets changes in the order of electron beam irradiation time: green → blue → purple → pink → orange → yellow → green → blue → purple → pink →... A decorative steel sheet with a variety of color tones was obtained.

[0037]

[Effects of the Invention] The present invention is constructed as described above, and it has become possible to provide a design material having metallic luster and a variety of colors at a low cost.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between Si plating film thickness and color tone.

FIG. 2 is a diagram showing the relationship between amorphous Al oxide film thickness and color tone.

FIG. 3 is a diagram showing an example of the method for manufacturing a vapor-deposited plating composite material of the present invention, in which (A) is a perspective view and (B) is a diagram showing an irradiation pattern.

[Explanation of symbols]

1 Payoff reel 2 Entrance side vacuum sealing device 3 Electron gun 4 Electron beam 5 Preheating chamber 6 Continuous steel strip 7 Support roll 8 Magnetron type ion bombardment device 9
Ion bombardment chamber 10 Si molten bath 11 Water-cooled copper vapor deposition tank 12 Vapor deposition chamber 13 Deflector roll 14 Outlet vacuum seal device 15 N2 gas cooling zone 16 Chromate treatment tank 17 Tension reel

Claims (3)

[Claims] Claim 1: A film thickness of 0.005 to 0.2 on the surface of the base material.
A vapor-deposited plating composite material with excellent design, characterized in that it has a vapor-deposited Si plating layer of μm in thickness, and the plating thickness of the plating layer changes continuously in the width direction of a base material. Claim 2: A film thickness of 0.05 to 1.0 μ on the surface of the base material.
Vapor deposition with excellent design, characterized in that it has a vapor-deposited amorphous oxide plating layer of m, and the plating film thickness of the plating layer changes continuously in the width direction of the base material. Plated composite material. 3. While a long base material is traveling in a vacuum deposition chamber, an electron beam is irradiated onto the surface of the plating raw material provided below the travel trajectory, and vapor deposition plating is applied to the base material by electron beam heating. 3. The method for producing a vapor-deposited plating composite material with excellent design according to claim 1 or 2, characterized in that the amount of electron beam irradiated onto the surface of the plating raw material is continuously changed in the width direction of the base material.