JPH0288233A - Metal covered synthetic resin material excellent in deterioration-preventing property - Google Patents

Abstract

PURPOSE:To obtain the metal covered synthetic resin material excellent in deterioration preventing property by a method in which the silver or copper film as a first layer is provided on transparent synthetic resin material, and at least one metallic film layer having larger chemical affinity than that of the metal in the first layer is provided on the first layer. CONSTITUTION:As the film structure provided on a transparent synthetic resin, it is necessary to provide the silver or copper film as a first-layer and at least one metallic having larger chemical affinity than that of the metal in the first layer arranged on said first layer, As the second layer composed of the metallic film having larger chemical affinity than that of the metal in the first layer, aluminum is preferably arranged. As the film thickness of these films, the thickness of the first layer is 500Angstrom -1500Angstrom , and it is preferably 500-1000Angstrom . The thickness of the second layer is 100Angstrom -2000Angstrom , and it is preferably 100Angstrom -1500Angstrom . By such method, while the metallic film of hte second layer separates the silver or copper in the first layer from the moisture or oxygen in the atmosphere, the effect of elector chemical corrosion- prevention, i.e., the effect preventing the silver or copper in the first layer form being corroded by causing the metal in the second layer to be a sacrificial electrode, is expected, whereby it is excellent in deterioration-preventing property.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a metal-coated synthetic resin material with excellent deterioration resistance, particularly as a synthetic resin reflector and synthetic resin ornament with excellent deterioration prevention property. This invention relates to useful metal-coated synthetic resin materials.

(Prior Art and Problems to be Solved by the Invention) Conventionally, silver has been used as a reflective film, and has a texture that is difficult to replace with other reflective films, such as the high reflectance that gives people a sense of luxury. For glass mirrors, vapor deposition on the glass surface,
It has already been put into practical use by forming a silver film using a dry process such as sputtering or a wet process using a silver mirror reaction, and then lining it with moisture-proof paint.

However, in transparent synthetic resin materials, the resin itself is permeable to moisture and oxygen and is subject to deterioration from the resin side as well, so silver reflective films have problems with deterioration and have been difficult to put into practical use. For this reason, aluminum reflective films have only been put into practical use for synthetic resin mirrors and synthetic resin decorative materials.

Copper is also desired to be applied to synthetic resin materials, such as decorative materials that take advantage of copper's unique reflective color.
Practical implementation was slow due to the problem of deterioration of the silver-like reflective film.

Therefore, in order to solve the above-mentioned problems, the present invention uses a synthetic resin material as a base material to provide a metal coating with excellent deterioration prevention properties, which has a reflective film that has a high reflectance and maintains a luxurious texture. The purpose is to obtain synthetic resin materials.

(Means for Solving the Problems) As a result of intensive studies on oxygen and moisture blocking and electrochemical crotch action, the present inventors provided a metal thin film with high reflectance as the first layer, and The present invention has been completed by discovering that the object of the present invention can be achieved by providing at least one thin layer of a metal having a chemical affinity greater than that of the first layer of metal.

In other words, the gist of the present invention is to provide a thin film of silver or copper as a first layer on a transparent synthetic resin material, and to deposit a metal having greater chemical affinity than the metal of the first layer on top of the thin film of silver or copper as a first layer. This is a metal-coated synthetic resin material with at least one thin film layer and excellent deterioration prevention properties.

(Function) The synthetic resin used in the present invention refers to a transparent organic polymer, and from the viewpoint of transparency, acrylic resin, polycarbonate resin,
Polyethylene terephthalate resin is preferred, and acrylic resin is most preferably used. These resins may contain coloring agents such as dyes and pigments, heat stabilizers, lubricants, ultraviolet absorbers, etc., as long as the transparency required as a reflective material is not impaired.

The synthetic resin material of the present invention is formed by molding the above synthetic resin into films, sheets, and molded products of various shapes, and the surface of these materials is coated with acrylic or silicone coating, which is necessary as a reflective material. There is no problem even if the surface is treated to the extent that the transparency is not impaired.

The film structure provided on the transparent synthetic resin material t1 of the present invention includes a thin film of silver or copper as the first layer, and at least one thin film of a metal having a higher chemical affinity than the metal of the first layer thereon. A first layer consisting of a thin film of silver or copper, a second layer consisting of a thin film of a metal having greater chemical affinity than the metal of the first layer, and further a layer of metal having a higher chemical affinity than the metal of the second layer. It is preferable to provide at least one layer of metals having the highest chemical affinity in order of decreasing chemical affinity.The outermost layer is preferably aluminum that forms a passive film.The thickness of these films is as follows: The first layer is 500
1500 people, preferably 500A to 1000 people, most preferably 700A to 1000 people, and the second layer is 1
00 to 2000 people, preferably 100 to 1500 people, most preferably 200 to 1300 people, and the third layer or higher layer is 100 to 2000 people, preferably 200 people.
The range is from 300 to 1300 people, most preferably from 300 to 1300 people.

Note that the present invention also includes a film structure in which a thin film other than metal is placed in the third layer and any position above the third layer! Included in r5.

Chemical affinity as used in the present invention refers to the tendency of one element to bond with another element or element, and if the chemical affinity is ranked in terms of greater and smaller, Cs, Rb, Na, Li, Ba, Sr
, Ca, Mg, Be, Y, S(: , AJ, Zr
, Th, Ce, La, Cr, Mn, Zn, C
d, TI, Fe, Co, Ni, Sn, Pb, H, Ge
, In, Ga, sb, Bi, u, As, cu, Hg, A
g, pd, Ru, Pt, Ir, Os, Au, S+, TN
b, Ta, Te, C, B, W, Mo, V, P, 0, Se
, N, I, Br, CJ, F.

As an example of a WA material with the above structure, the structure is written in order from the synthetic resin base material side: 1, 11 /Aβ, Ag7cr, A(
1/Zn, AC+/Fe, AC+/CIJ
, Cu/Aj! , Cu/Cr, Cu/Zn
, Cu/Fe, Ag/Fe/Al, A(]/C
u /A j:, Ag /Cu /Cr, Cu/Fe/
A1, A (J /CIJ /A I1203, A!1
1/Cu /Al120s /A(,A!II /Cu
/si o/A4, etc., Ag /AJ2
, Ag 2 /Fe, Ag 2 /Cu 2 /Afl, are preferred, and A(17Cu 2 /Aβ is the most preferred embodiment).

As described above, the metal-coated synthetic resin material of the present invention has a thin film of silver or copper as a first layer on a transparent synthetic resin material, and a metal having a higher chemical affinity than the metal of the first layer. At least one thin film layer is provided, so the second or higher metal thin film blocks the first layer of silver or copper from moisture and oxygen in the outside air, and also has an electrochemical corrosion protection effect, that is, the second layer of metal thin film. Since the metal acts as a sacrificial electrode and can be expected to have the effect of preventing corrosion of the first layer of IN or copper, it is excellent in preventing deterioration.

As a method for metal coating the synthetic resin material of the present invention, any method such as a wet process or a dry process can be used as long as it is possible to form the above-mentioned film structure with the film thickness on the synthetic resin material. However, preferably, a dry process for forming a dry thin film, such as vacuum evaporation, sputtering, ion blating, ion assisted deposition, CVD, etc., is used, and in particular, vacuum evaporation or sputtering is used to form the above film structure. It is preferable.

The metal-coated synthetic resin material of the present invention forms a reflective film by the method described above, but these films are easily scratched when rubbed with tissue paper or cloth. It is desirable to coat with a synthetic resin paint (hereinafter referred to as back coat paint) for protection.

As the back coat paint, synthetic resin paints such as cellulose-based, alkyd-based, melamine-based, acrylic-based, and polybutadiene-based paints are used. As a coating method for the above-mentioned paint, methods such as spray coating, casting coating, brush coating, dip coating, and spin coating may be used.

(Example) Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 After injection molding acrylic resin for injection molding (Parabet HR-N manufactured by Kyowa Gas Chemical Industry Co., Ltd.) into a prism mirror shape,
Acrylic curing liquid (Fujihard EXP-19 manufactured by Fujikura Kasei)
60H) and gently pulled out. After that, put it in a hot air drying oven and pre-cure at 80℃ for 30 minutes, then UV light amount 80
A transparent cured film was formed at W/an, UV irradiation distance M=100 mm, and conveyance rate of 0.25 m/l1 inch. Silver (purity 99.99%) was deposited on one side of this synthetic resin material by vacuum evaporation, and then aluminum was deposited to form a silver film with a thickness of 1000 and an aluminum film with a thickness of 500. . The vacuum evaporation conditions were as follows: Vacuum evaporation equipment 2 Japan Vacuum Technology ■ 5RC-10D film formation Medium pressure Crab silver... 5 x 10-5 Torr, Aluminum 11 x 10 z 0 `` Substrate quality 2 20 to 30 ℃ Heating method: Two-resistance heating method, Silver: Tantalum boat, Aluminum: Tungsten filament Deposition rate: Silver: 5-10 people/sec, Aluminum: 35-40
person/sec.

Next, a polybutadiene backcoat f4 (Revolver MD manufactured by Origin Electric Co., Ltd.) was spray-painted on the aluminum film and cured for 260 minutes at 70'C in a hot air dryer. The thickness was approximately 30 μm.

A metal-coated synthetic resin material was created as described above.

A moisture resistance test was carried out in which this metal-coated synthetic resin material was left in an atmosphere of 50° C. and 95% RH for 96 hours, but almost no deterioration of the silver reflective film occurred. The results are shown in Table 1.

Bisame Example 1 An acrylic cured film was formed on an acrylic resin molded product having a prism mirror shape by the same method as in Example 1 except that only a silver film was formed, and on one side of this synthetic resin material, After silver was deposited using a vacuum deposition method, a back coat treatment was performed to obtain a metal-coated synthetic resin material.

When the same moisture resistance test as in Example 1 was conducted, white spot-like deterioration occurred over the entire surface of the silver reflective film.

The results are shown in Table 1.

Example 2 A cured acrylic film was formed on an acrylic resin molded article having a prism mirror shape according to the method of Example 1. On one side of the synthetic resin material, silver was first deposited using a vacuum evaporation method, and then copper was deposited on one side of the synthetic resin material. Then, aluminum was further vapor-deposited thereon. The vacuum evaporation conditions were as follows: Vacuum evaporation equipment 5RC-10D film made by Nippon Shinkujujutsu Medium pressure crab silver...5 X 10-5 Torr, Copper...6
X 10-510", Aluminum...3.8x
10-5 Torr substrate temperature = 30 to 40°C Heating method: resistance heating method, silver, copper... tantalum boat,
Aluminum...Tungsten filament deposition rate: Silver...5 to 6 people/sec, Copper...7 to 9 people/Se
C, Aluminum - 60-70 people/sec Film thickness: Silver...750 people, Copper...300 people, Aluminum...
・There were 530 people. Next, a back coat treatment was performed in the same manner as in Example 1 to obtain a metal-coated synthetic resin material.

A moisture resistance test similar to that in Example 1 was conducted, but no deterioration occurred at all, and the film had a good reflective surface.

Example 3 The reflection described in Example 2 was achieved using two thick plate products: an acrylic cast plate (Paraglass manufactured by Kyowa Gamata Chemical Industry Co., Ltd.) and an acrylic extruded plate (Comoglas manufactured by Kyowa Gas Chemical Industry Co., Ltd.) as synthetic resin materials. Film composition: 750 people in the first layer, 30 people in the second layer
A third layer aluminum film was formed by vacuum evaporation.

Next, a rough coat treatment was performed in the same manner as in Example 1 to obtain a metal-coated synthetic resin material. A moisture resistance test similar to that in Example 1 was conducted, but no deterioration occurred at all.

Example 4, Comparative Example 2 A test was conducted using a stretched acrylic film with a thickness of 90 μm as the synthetic 1!1 resin material.

A reflective film having a three-layer structure of silver only or silver/@/aluminum was formed on an acrylic film under the vapor deposition conditions described in Examples 1 and 2, respectively.

When this metal-coated synthetic resin material was subjected to a moisture resistance test, white spot-like deterioration occurred on the entire reflective surface with silver alone, but no deterioration was observed with the three-layer film of silver/@/aluminum.

Example 5 A polyethylene terephthalate (hereinafter abbreviated as PET) film with a thickness of 125 μm was used as a synthetic resin material.

On this film, a reflective film having the same structure as described in Example 2, that is, a first layer of 750 copper layers, a second layer of 300 layers, and a third layer of aluminum 530 layers, was formed by vacuum deposition. When this metal-coated synthetic resin material was subjected to a moisture resistance test in the same manner as in Example 1, no abnormalities such as deterioration occurred.

Example 6 As a synthetic resin material, a polycarbonate (hereinafter abbreviated as PC) board with a thickness of 20% was used. On this sheet, the reflective film structure described in Example 2, that is, the first layer has 750 copper layers and the second layer has 3 copper layers.
A third layer of aluminum 530 was formed by vacuum evaporation. When this metal-coated synthetic resin material was subjected to a moisture resistance test in the same manner as in the examples, no abnormality such as deterioration of quality occurred.

Examples 7 to 12, Comparative Examples 3 to 5 Using the acrylic resin molded product having the prism shape of Example 1 as a synthetic resin material, an acrylic cured film was formed,
After forming various films thereon by vacuum deposition, the degree of deterioration was examined by the same moisture resistance test as in Example 1. The results are also shown in Table 1.

Margin below.

(Effects of the Invention) As described above, the present invention provides a thin film of silver or copper as a first layer on a transparent synthetic resin material, and a metal having a higher chemical affinity than the metal of the first layer. Because it is a metal-coated synthetic resin material with at least one thin film layer, it has a high reflectance and maintains a luxurious feel.
Furthermore, since a metal thin film, which has poor deterioration prevention properties, can be provided on a synthetic resin material that is excellent in mass production, it is useful as a synthetic resin mirror decorative material, a reflective material, an optical material, etc.

Claims (6)

[Claims] (1) A thin film of silver or copper is provided as a first layer on a transparent synthetic resin material, and at least one thin film of a metal having a higher chemical affinity than the metal of the first layer is provided thereon. A metal-coated synthetic resin material with excellent deterioration prevention properties. (2) A thin film of silver or copper is provided as a first layer on a transparent synthetic resin material, a thin film of a metal having greater chemical affinity than the metal of the first layer is provided thereon as a second layer, and A metal-coated synthetic resin material with excellent deterioration prevention properties, characterized in that at least one layer of metals having greater chemical affinity than the two layers of metals is provided in order of decreasing chemical affinity. (3) The metal-coated synthetic resin material according to claim 1 or 2, wherein the outermost layer is a thin film of aluminum. (4) Claim 1, in which the metal thin film is a dry thin film.
The metal-coated synthetic resin material according to items 3 to 3. (5) The metal-coated synthetic resin material according to claims 1 to 4, wherein the synthetic resin is one resin selected from the group consisting of acrylic resin, polycarbonate resin, and polyester resin. (6) The metal-coated synthetic resin material according to any one of claims 1 to 4, wherein the synthetic resin is an acrylic resin.