JPH04247865A - Vapor deposited si plated composite material having excellent designability and weatherability - Google Patents

Abstract

PURPOSE:To inexpensively provide the material which is a designable material having metallic gloss and a variety of colors and has excellent corrosion resistance. CONSTITUTION:This vapor deposited Si plated composite material has vapor deposited Si plating layers having 0.005 to 0.2mum film thickness on the surface of a base material and has a transparent or translucent resin coated layer having >=1.0g/m<2> deposition thereon. The material having a chromate coated layer of >=1.0g/m<2> total Cr deposition between the above-mentioned Si plating layer and the resin coated layer has the additionally higher weatherability.

Description

[Detailed description of the invention]

0001

FIELD OF INDUSTRIAL APPLICATION The present invention relates to a vapor-deposited Si-plated composite material with excellent design and weather resistance, and the composite material is useful for various building materials, household electrical appliances, and the like.

0002

BACKGROUND OF THE INVENTION Various color-coated steel plates are widely used as decorative surface-treated materials in the above-mentioned fields. Various color-coated steel sheets are manufactured by applying organic paints, but recently pre-painted steel sheets with various properties have been developed to simplify the painting process on the user side, and the demand for them is increasing year by year. . Characteristics other than design include corrosion resistance, scratch resistance, workability, fingerprint resistance, stain resistance, etc., and various play-coated steel sheets have been developed and used according to the characteristics required by users.

[0003] However, the color tone and design properties given to play-coated steel sheets are obtained by various dyes and pigments added to organic paints, and the design properties of play-coated steel sheets have the luster and vivid color tone characteristic of metals. It is impossible to obtain.

[0004] As other decorative materials, materials (color materials) having both metallic luster and bright variegated colors, such as colored aluminum, colored stainless steel sheets, and colored titanium, are also used. These color materials can be produced by coating or electrodepositing a colored organic resin paint in the same way as the above-mentioned color-coated steel sheets (including play-coated steel sheets), or by applying an oxide film to the surface of the base material using an electrolytic coloring method or a chemical coloring method. By forming and changing the thickness of the oxide film,
It imparts a variety of color tones through light interference. Since the color material has the luster of a metal treated material as described above, it has a more luxurious feel than a color-coated steel plate, and is superior in design and aesthetics. Moreover, since the treated material itself has excellent corrosion resistance, the color tone is less likely to fade or the metallic luster to be lost due to rusting due to corrosion of the treated material under general usage environments.

However, if the surface is damaged or used in a relatively harsh corrosive environment, the design and aesthetics will rapidly deteriorate due to corrosion of the treated material, the formation of red rust, white rust, fading, etc. It will be damaged. Moreover, not only are the prices of these treated materials themselves high, but the cost of electrolytic treatment or chemical treatment for coloring the surface is also high. In addition, when trying to continuously manufacture the above-mentioned material to be treated,
Not only is new equipment required for the electrolytic coloring process, but unless the electrolytic conditions are strictly controlled, color unevenness tends to occur in the running direction and width direction of the plate, resulting in a decrease in product yield. . Therefore, it is quite expensive, and its uses are often limited due to price.

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 is used to give a design feature. 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.

[0007] However, there have been no examples of producing these ceramic coated steel sheets on a continuous industrial production scale. This is because, taking into account the very small size, the traveling speed of the treated zone must be considerably reduced, resulting in low productivity and very high manufacturing costs. Therefore, the use of the product is inevitably limited due to the product price.

[0008]

[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a surface-treated material that is excellent in design and weather resistance and is low in manufacturing cost. .

[0009]

[Means for Solving the Problems] The material of the present invention that has achieved the above object has a film thickness of 0.005 mm on the surface of the base material.
Vapor-deposited Si plating having a vapor-deposited Si plating layer of ~0.2 μm and having a transparent to translucent organic resin film layer with a coating amount of 1.0 g/m2 or more on the vapor-deposited Si plating layer. It is a composite material. Further, those having a chromate film layer having a total Cr deposition amount of 1.0 mg/m2 or more between the vapor-deposited plating layer and the transparent or semi-transparent organic resin film layer have even better corrosion resistance.

0010

[Operation] As a result of various studies, the present inventors found that when a Si plating layer is applied on a steel plate by vacuum evaporation,
It has been found that in a region where the thickness of the plating layer is very thin, if the thickness of the plating layer is continuously changed, the surface of the Si-plated steel sheet exhibits a different color tone depending on the thickness. This has a light interference effect in the visible light range within a certain range of Si film thickness, and as the film thickness changes, the wavelength of the interfered light changes accordingly, resulting in a change in color tone. This is due to this. Therefore, this change in tone is also repeated in a fixed pattern.

Next, the suitability of the Si-plated steel sheet having various color tones as a design material was investigated. As a result, it was found that in a severely corrosive environment, red rust due to corrosion of the base steel plate occurs early, which significantly impairs the appearance. This is because, as mentioned above, a variety of colors can only be obtained in areas where the thickness of the Si plating layer is very thin, so it is difficult to avoid the presence of pinholes in the plating layer, and through these pinholes, the base steel sheet due to corrosion. Furthermore, since the Si plating layer has a slightly more noble potential than the steel plate, it does not exhibit sacrificial corrosion protection and is much more susceptible to corrosion when scratched than a Zn-based plated steel plate or the like.

[0012] Therefore, the present inventors thought that it was necessary to improve the corrosion resistance, weather resistance, etc. of vapor-deposited Si-plated steel sheets, and first investigated improving the corrosion resistance of the material to be plated. Specifically, a Cr-containing low-alloy steel plate, a weathering steel plate, and a low-grade stainless steel plate were used as materials to be plated, and their corrosion resistance and weather resistance were investigated. This has certainly improved the above performance compared to those using ordinary cold-rolled steel sheets, but in harsh environments, corrosion from the pinholes in the plating layer itself is unavoidable, which may impair the aesthetics. I found out something. Furthermore, when a high-grade stainless steel plate is used as the plated material, although the above-mentioned performance is further improved, the cost increases considerably, and the cost advantage is reduced compared to the color stainless steel plate, which is one of the currently used materials.

Next, we considered protecting the Si plating layer. As a result, it was discovered that a decorative vapor-deposited plated composite steel sheet with excellent corrosion resistance could be obtained by coating the surface of the plating layer with a transparent or semi-transparent organic resin, and the present invention was completed. That is, the material of the present invention has a vapor-deposited Si plating layer on the surface of the base material, and further has a transparent to semitransparent organic resin film layer thereon. Further, depending on the case, by forming a chromate film layer between the plating layer and the organic resin film layer, the corrosion resistance can be further improved. This will be explained in detail below.

First, the vapor-deposited Si plating layer will be explained. The thickness of the plating layer must be 0.005 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 the figure, if the film thickness exceeds 0.2 μm, vivid color tones cannot be obtained, and even if the film thickness is increased further, S
Only the color tone of i itself was obtained. Furthermore, if the film thickness is below the above range, it is technically difficult to continuously obtain a stable color tone.

The heating/evaporation source for forming the vapor-deposited Si plating layer of the present invention on the surface of the material to be plated is not particularly limited, and electron beam (EB) heating, laser beam heating, etc. may be used as appropriate. be able to. Among these, the electron beam is a heating source with high energy and high energy density, and although the electron gun (EB gun) for generating the electron beam is expensive, it is easy to maintain and can be used to easily generate and stop the electron beam. This is an advantageous heating means because it can be easily carried out. Further, 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 Si can be increased. From the above points, electron beam heating is considered to be one of the most effective means when considering industrial production.

Further, the vapor deposition method for forming the Si plating layer means a vacuum vapor deposition method in a broad sense, and in addition to the usual vapor deposition method, various ion plating methods, various sputtering methods, and various CVD methods are also applicable to the surface treatment of the present invention. Included as a means to obtain materials. In particular, if the ion plating method is adopted, the energy of the evaporated metal vapor will be higher than in normal vacuum evaporation. This is preferable because weather resistance and corrosion resistance can be further improved by reducing pinholes.

Next, the transparent or semi-transparent organic resin film of the upper layer will be explained. The coating must have an adhesion amount of 1.0 g/m2 or less. If the amount is too low, remove the organic film layer.
It is not easy to apply it uniformly to the surface of the i-plated layer, and therefore corrosion tends to occur from thin parts and defective parts of the organic film layer through pinholes in the underlying Si plating film. Furthermore, if the usage environment is severe, it is preferable to apply the coating at 5 to 10 g/m2 or more. Note that 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. may impair the characteristic metallic luster of the vapor-deposited Si-plated steel sheet itself. Therefore, it is considered that the amount of the organic film layer deposited is preferably about 20 g/m2 or less.

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 characteristics other than design and weather resistance, such as fingerprint resistance, scratch resistance, stain resistance, workability, etc., polyethylene resin,
Epoxy resins, acrylic resins, urethane resins, polyester resins, fluorine resins and mixtures thereof,
It is possible to appropriately select and use copolymers, modified resins, etc. 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, for the purpose of further improving the performance of the organic coating layer, such as corrosion resistance and coating adhesion,
Small amounts of various pigments, silane coupling agents, and various oxide sols may be added. 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 film layers are provided as intermediate layers between the lower Si plating layer and the upper organic film 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 allows Si
Microscopic defects in the plating layer and the upper organic coating layer,
It is also possible to effectively suppress discoloration and corrosion from scratches that occur during handling and processing. Moreover, it is also possible to further improve the coating film adhesion of the upper organic film layer, which is preferable. However, in order to fully exhibit this effect of the chromate film layer, the film thickness needs to be 1.0 mg/m2 or more in terms of the amount of adhesion. The adhesion amount is 1
．． If it is less than 0 mg/m2, the effect of providing the chromate film layer will not be exhibited. Although the upper limit is not particularly limited, excessive adhesion will not only saturate effects such as corrosion resistance, but will also be disadvantageous in terms of manufacturing costs. Therefore, the amount of adhesion of the chromate film layer is 1.0
~300mg/m2, more preferably 10-100mg
/m2 is considered appropriate.

[0020] The type of the chromate film is not particularly limited, and may include coated chromate, reactive chromate, electrolytic chromate, and combinations thereof. Since the color tone may change and electrolytic chromate requires control of 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.

[0022] In terms of cost, the base material of the present invention is as follows:
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.

[0023] 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.

[0024]

[Examples] Examples 1 to 15, Comparative Examples 1 to 9 Using an Al killed steel strip as a substrate to be plated, Si-plated steel plates were deposited using the apparatus shown in FIG. 2 under various conditions shown below and in Table 2. was produced continuously. 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) ・Deposition chamber vacuum level: Approximately 1 x 10-2Pa

<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.

<Weather resistance evaluation test> Test-1 After carrying out a constant temperature and constant humidity acceleration 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 Sunshine weather test device The following test was conducted using 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

[0029]

[Table 1]

As is clear from Table 1, the vapor-deposited Si of the present invention
The plated composite material had excellent weather resistance regardless of the type of organic resin. On the other hand, Comparative Examples 1 to 9, in which the amount of organic resin attached was outside the value specified by the present invention, had poor weather resistance regardless of the presence or absence of the chromate film layer. Moreover, Comparative Example 9, in which the thickness of the deposited Si film exceeded the upper limit specified in the present invention, had no design property even though it had excellent weather resistance.

[0031]

[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, and also having excellent weather resistance at a low cost. Ta.

[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 illustrating an example of the method for manufacturing the vapor-deposited Si-plated composite material of the present invention.

[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 16 Chromate treatment tank 17 Tension reel

Claims (2)

[Claims] Claim 1: A film thickness of 0.005 to 0.2 on the surface of the base material.
Excellent in design and corrosion resistance, characterized by having a vapor-deposited Si plating layer of 1.0 g/m2 or more and a transparent or translucent organic resin film layer with a coating amount of 1.0 g/m2 or more on the vapor-deposited Si plating layer. Vapor-deposited Si plating composite material. 2. A total amount of Cr deposited between the vapor deposited plating layer according to claim 1 and the transparent to semitransparent organic resin film layer is 1.0.
A vapor-deposited Si-plated composite material with excellent design and weather resistance, characterized by having a chromate film layer of mg/m2 or more.