JPS5954026B2 - Molded product with gold vapor deposited film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a molded product having a gold vapor deposited film that can be applied to interior and exterior parts of automobiles, and decorative parts for consumer electronics, personal items, and the like.

In recent years, the demand for molded products having a gold vapor deposited film has been increasing both domestically and internationally due to their luxury, quality, and conspicuousness.

Since "gold" is expensive and easily damaged and is not practical as a material for this golden vapor deposited film, brass (Cu-Z) is used instead.
u alloy) is used. However, this gold vapor deposited film made from brass is easily discolored and has problems in corrosion resistance, weather resistance, etc., and is particularly unsuitable for use as exterior parts. In view of the above, an object of the present invention is to provide a molded article having a golden vapor deposited film that is resistant to discoloration, has excellent corrosion resistance and weather resistance, and can be used outdoors for a long period of time.

The gist of this invention is that Cu-Zn-Sn mainly composed of Cu
The molded article has a gold-colored vapor-deposited film formed on the surface of the shaped article by sandwiching a metal-deposited film made of an alloy between an undercoat film and a topcoat film.

Hereinafter, this invention will be explained in detail based on FIG. 1.

On the surface of the molded product body 1, an undercoat film 2, a gold vapor deposited film 3, and a top coat film 4 are formed in order from the bottom.

Materials for the molded product body 1 include elastomer materials such as rubber and polyurethane elastomer, plastic materials such as ABS resin, vinyl chloride resin, PP resin, urea resin, and melamine resin, and all kinds of materials such as wood, glass, and ceramics. can be exemplified. Here, when a flexible polymer material such as an elastomer material or a soft plastic material is used, it is not necessary to change the design of the molded product for each shape of the attached member, and a molded product with high versatility can be obtained. be able to. The undercoat film 2 coats the surface of the molded product body 1 with Trique I.
After steam cleaning or spray cleaning with a chlorinated solvent such as lortrifluoroethane, a polyester-based, acrylic-based, or polyurethane-based undercoat is applied by spraying or brushing, and then heated and dried to a film thickness of 8 to 15 μm. get.

The metal vapor deposited film 3 is made of 20 to 45 wt Zn on the undercoat film 2.
A Cu-Zn-Sn alloy with an impurity of 0.5 wt% or less and a balance of Cu of 50 to 70% is processed by sputtering, ion-Frede ink, or vacuum deposition to obtain a film with a thickness of 500 to 1,500 mm.

Here, if Cu is less than 50 wt% and Zn is more than 45 wt%, the color becomes white and cannot be called a normal gold color. On the other hand, if Cu exceeds 70 wt% and Zn is less than 20 wt%, it becomes reddish and also , it can no longer be called a normal golden color.

Furthermore, if the Sn content exceeds 1.5 wt%, the brittleness of the deposited film becomes extremely high, and if the Sn content is less than 2 wt%, the corrosion resistance of the deposited film decreases, both of which are unfavorable. Impurity is 0.5
When Sn exceeds wt%, as in the case where Sn is less than 2wt%,
This causes problems in the corrosion resistance of the deposited film. The main component of impurities is Fe
．． Pb. Sb etc. In addition, in the case of sputtering, a vapor deposited film with the same composition as the alloy is formed, but in the case of ion plating and vacuum vapor deposition, the alloy composition is different due to the difference in evaporation temperature of each elemental metal because the alloy is heated and evaporated. It is difficult to form the same deposited film.

Therefore, it is most desirable that the vapor deposited film of the present invention be formed by sputtering. Normal sputtering conditions are vacuum degree 3 x 1
0-4～1×10-5T0rI′Me argon pressure 1×1
0-3~1x10-4T0rT, voltage 350~600V
, the current density is 1 to 5 A/Dm2.

Here, when the degree of vacuum exceeds 3X10-4T0, the color tone of the sputtered film (deposited film) becomes darker, and on the other hand, when the degree of vacuum exceeds 3X10-4T0
If it is less than T0rr, it will take a long time to reach the vacuum level, which is not practical. Also, the argon pressure is 1×10-3T
If it exceeds 0rr', the metallic luster of the sputtered film will decrease, while if it is less than 1 x 10-TOrr, it will be difficult to maintain the discharge. If the voltage is less than 350V, the discharge becomes unstable, while if it exceeds 600V, the current efficiency decreases, which is not preferable.
Furthermore, regarding the current density, at less than 1A/Dm2,
The formation speed of spatter film is slow and impractical, and on the other hand, 5A
/Dm2, the physical properties of the sputtered film deteriorate. The top coat 4 is made by spraying or brushing a transparent top coat of polyester, acrylic, polyurethane, etc. on the metal vapor deposited film 3 and heating and drying it to a film thickness of 10 to 20 μm.
get something. If corrosion resistance and weather resistance are particularly required, such as in the case of exterior parts, benzotriazole or its derivatives may be added in the top coat as a rust preventive agent in an amount of 0.1 to
Mix 1.0 wt%.

Examples of the rust preventive include 1,2,3-benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, 4,5,6,7-tetrahydrobenzotriazole, and the like.

Among these, especially 1,2,3-benzotriazole. is the most effective. In addition, in the amount of rust preventive added, 0
．． If it is less than 1 Wt%, a sufficient rust prevention effect cannot be obtained;
Even if it exceeds wt%, the rust prevention effect remains the same as if it is less than that.
Moreover, dissolution into paint becomes a problem. Due to the above-described structure, the molded article having a gold vapor deposited film of the present invention can obtain a color appearance that is equal to or better than that of a conventional brass vapor deposited film, and has a color appearance that is equal to or better than that of a conventional brass vapor deposited film, as shown in the examples below. In comparison, it is less likely to change color and has excellent corrosion resistance and weather resistance.

Examples and comparative examples will be shown below in order to confirm the effects of this invention.

The size of the test pieces is (50 mm x 100 mm 1 x
3mmt) ABS resin molded product (Diapet 3001
Mfu (trade name), manufactured by Mitsubishi Rayon Co., Ltd.) was used.

In Examples 1 to 3, 6 to 8, and Comparisons 1 and 2, polyurethane paint was used for the undercoat film, and the dry film thickness was 10 to 1.
It was obtained by spray coating to a thickness of 3 μm. In each of the Examples and Comparative Examples, the top coat film was obtained by spray coating using a transparent acrylic paint so that the 1-dry film thickness was 10 to 13 μm.

However, in Examples 6, 7, and 8 and Comparative Example 2, 0.2w
Example 9
In Example 10, 0.2 wt% of 5-methylbenzotriazole was contained in the paint, and in Example 10, 0.5 wt% of 4-methylbenzotriazole was contained in the paint. The composition of the material (target) in each Example and Comparative Example of the gold vapor deposited film is shown in Table 2, and the sputtering conditions are as follows.

Examples 1 to 36 to 8...Vacuum degree 1 x 10-5T0rr1 Argon pressure 5 x 10-4T0rr1
Voltage 500, current density 3A/Dm2.

Example 459/10...Vacuum degree 3 x 10-5T0rr, argon pressure 3 x 10-4T0rr,
Voltage 500V, current density 2A/Dnl2.

Comparative Examples 1 and 2...Vacuum degree 5 x 105T0rr', argon pressure 4.0 x 10-4T0rT'', voltage 410V, current density 2A/Dm2.

In addition, physical property tests were conducted on the following items, and after each test
Appearance and peeling by ◎ cross cut taping test were observed.

However, for the test (e) below, only the external appearance was observed. Water resistance test: Soaked in 40℃ tap water for 240 hours.

(b) Bead cycle test...1 cycle [80℃×
1h → Room temperature x 30min → -30℃Xlh → Room temperature x 30
min] for 3 cycles. (c) Salt spray test...J
240h by ISZ-2371.

(d) Cast test...1 according to JISD-0201
3 cycles of 16h. (e) Accelerated weather resistance test: Using a weather meter (Standard Sash Yarn Super Long Life Weather Meter (trade name), manufactured by Suga Test Instruments Co., Ltd.) at 50 ± 1°C, 1 cycle 6
0 min (spraying for 18 min) was repeated until an abnormal appearance occurred.

The results of each test were as shown in Table 1. As shown in Table 1, when the top coat does not contain a rust inhibitor (Example 1)
-5 and Comparative Example 1) In the salt spray test, Comparative Example 1 discolored and corroded after about 96 hours, but Examples 1, 2,
No. 4 showed only slight discoloration after 200 hours, and no abnormality was observed in any of the other samples even after 240 hours.

In addition, in the weather resistance test, Comparative Example 1 was cloudy for 104 hours, but Examples 1, 2, and 4 were cloudy for 200 hours, and 3
, 5 became cloudy for the first time after 300 hours. Furthermore, when the top coat contains a rust preventive agent (Examples 6 to 10 and Comparative Example 2)
), in the salt spray test, Comparative Example 2 changed color after 172 hours, but no abnormality was observed in any of the Examples even after 240 hours.Also, in the weather resistance test, Comparative Example 2 became locally cloudy after 300 hours. However, no abnormality was observed in any of the Examples even after 600 hours.

Note that in all Examples, a beautiful golden color was exhibited.

[Brief explanation of drawings]

FIG. 1 is a partial sectional view of a molded product having a metal vapor deposited film. ．． 1...Molded product body, 2...Undercoat film, 3...
Gold paint film, 4...Top coat film.

Claims (1)

[Scope of Claims] 1. A molded article in which a gold vapor deposited film is sandwiched between an undercoat film and a top coat film and formed on the surface of the molded product body, wherein the metal vapor deposited film contains 20 to 45 wt% of Zn and 2 to 45 wt% of Sn. 15wt
%, impurities 0.5wt% or less, balance Cu 50-70wt
% Cu-Zu-Sn alloy as a material. (2) The main body of the molded product is made of a flexible polymeric material, the golden vapor-deposited film is a sputtered film, and the top coat contains benzotriazole or its derivatives in an amount of 0.1 to 1.0%.
A molded article having a gold vapor deposited film according to claim 1, characterized in that the molded article is formed from a paint containing % by weight.