JPH03188263A - Metal oxide coated plastics - Google Patents

Abstract

PURPOSE:To improve the adhesive strength between a base material and a metal oxide layer by forming a layer composed essentially of Ni oxide on a plastic substrate and further laminating a metal oxide layer on the above layer. CONSTITUTION:A layer composed essentially of Ni oxide is laminated to about 150Angstrom -1mum thickness on one side of a plastic base material. A different metal oxide is laminated into one or more layers on the above layer. Respective laminations of the above layers are carried out by means of vapor deposition, etc. As the Ni oxide, nickel oxide, etc., are used. As the metal oxide, SiO, SiO2, Al2O3, MgO, ZrO2, TiO2, ZnO, etc., are used as a simple substance or in the form of a mixture, and the thickness of the film is regulated to about 1-30mun. By this method, the metal oxide coated plastics increased in the degree of freedom of film thickness can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to plastics coated with a metal oxide layer.

(Prior art) Lamination of oxides of metals such as zirconium, aluminum, and silicon on plastic substrates by methods such as vapor deposition has been widely studied, but the adhesion between the plastic substrate and metal oxides is poor. This was a practical problem.

In order to improve this adhesion, for example, JP-A-61-25
Publication No. 1801 describes the formation of an organic binder layer between the two layers, and Japanese Patent Publication No. 12601/1986 describes the formation of a silicon monoxide layer between the two layers. There is.

However, the former method requires two steps: applying an organic binder and vapor-depositing a metal oxide, and requires heat treatment to volatilize the solvent in the binder. Therefore, it is not possible to raise the temperature to a high temperature, resulting in poor workability. Furthermore, if the solvent remains in the binder, the solvent will volatilize when the metal oxide is vapor-deposited, and the adhesion between the plastic base material and the metal oxide layer will be hindered.

Also, in the latter method, the silicon monoxide layer has poor moisture resistance;
Particularly under high temperature and high humidity conditions, the plastic base material and the silicon monoxide layer easily separate.

(Problems to be Solved by the Invention) In view of the above drawbacks, an object of the present invention is to provide a metal oxide-coated plastic in which a plastic base material and a metal oxide layer are tightly adhered to each other.

(Means for Solving the Problems) The base material used in the present invention is a plastic, and examples thereof include polycarbonate, diethylene glycol bisallyl carbonate, polymethyl methacrylate, polyethylene terephthalate, polyvinyl chloride, and the like.

In the present invention, a layer containing nickel oxide as a main component is laminated on one surface of a plastic base material.

The minimum thickness of this layer may be at least the thickness at which the nickel oxide film becomes a continuous film, and is preferably at least 150 Å. The maximum film thickness is preferably 18 m or less. 1μm
Above that, it will be easier for Clans to enter.

In producing this layer, nickel oxide may be used as a raw material, or nickel and oxygen gas may be vapor-deposited by reaction. Further, the vapor deposition is preferably carried out under high vacuum, preferably at a pressure of 2 X 10-'Torr or less, more preferably at most 5 X 10"' Torr.

The composition of the formed nickel oxide film is mainly composed of nickel oxide, with the remainder being Mg, Ca, and Ti.

Cr, Mn, Fe, Zn, AI, St, Sr.

Mo, ln, Sn, Ba, Hf, Ta
, W, Pb, or one or more metals or metal oxides. The nickel oxide component is preferably 80 wt% or more.

Further, on the layer containing nickel oxide as a main component, one or more metal oxide layers are further laminated.

The metal oxide forming this layer is not particularly limited, and examples include SiO, SiO□, Al2O3, MgO,
Examples include ZrO, Tto, ZnO, and the like. Also,
The metal oxide may be a single component as described above, or a mixture thereof may be used. The membrane structure and evaporation raw material may be determined as appropriate depending on the application. For example, if wear resistance is required, an AlzOz layer is preferred as the top layer.

The thickness of these metal oxide layers may be determined as appropriate depending on the application, but is generally 1 to 30 μm.

Also, if laminated at a temperature higher than the thermal deformation temperature of the plastic substrate,
Since cracks and peeling are likely to occur, it is preferable that the layers be laminated at a temperature below the thermal deformation temperature of the substrate.

Next, a method for laminating metal oxide layers will be described with reference to the drawings. FIG. 1 is a schematic diagram showing an example of a vacuum evaporation apparatus of the present invention. In the figure, reference numeral 1 denotes a vacuum chamber, which is evacuated to a high vacuum through an exhaust bag W (not shown) directly connected to an exhaust port 8.

A copper hearth 6.61.62 with a cooling device and an electron gun filament 7 are arranged in the vacuum chamber 1, which is supplied with an evaporative substance 5.51.52. Note that the positions of the copper hearths 6, 61 and 62 can be exchanged as desired. A shutter 4 is installed above the copper hearth 6 to block evaporated matter with a desired thickness. Further, above the shutter 4, a board mounting jig 2 for fixing the plastic board 3 is provided. Note that 9 is a film thickness monitor, and 10 is an oxygen gas inlet.

For vapor deposition, the gas pressure in the vacuum chamber 1 is set to 5X10-'To
The pressure is reduced to below rr, nickel oxide is supplied as the evaporation substance 5 to the copper hearth 6, the evaporation substance 5 is heated and melted by the electron gun filament 7, and the nickel oxide is evaporated. Forms a film. Next, the positions of the copper hearth 61 and the copper hearth 6 supplied with, for example, silicon dioxide as the evaporative substance 5I are changed, and the silicon dioxide in the copper hearth 61 is heated and evaporated to form a silicon dioxide film on the nickel oxide layer. . Furthermore, 3
When forming the layers, for example, a copper hearth 62 and a copper hearth 6 to which aluminum oxide is supplied as the evaporation substance 52 are used.
1 and evaporate the aluminum oxide by electron beam heating to form an aluminum oxide layer on the silicon dioxide layer.

If the vacuum is broken, water adsorption and dust adhesion will easily occur on the surface of the deposited film, so the second
It is preferable to form a layer or a third layer.

Although the above manufacturing method is a vacuum evaporation method using an electron beam heating method, physical vapor deposition methods such as sputtering, ion blating, and vacuum evaporation methods can be used as a manufacturing method, but preferably ion blating or This is a vacuum evaporation method.

(Example) Next, the present invention will be explained in detail. In addition, the adhesion is 60°C.
After leaving it in a constant temperature and humidity chamber of 196%R)l for 7 days,
A cross-cut tape test was conducted according to IS D-0202. That is, a razor blade is used to make cuts on the surface of the deposited film at 1-square intervals to form 100 squares of llllIn2. Next, after strongly pressing cellophane adhesive tape on top of it and pulling it off in a 90° direction from the surface,
The number of remaining squares of the deposited film was used as an index of adhesion.

Example 1.2 A polycarbonate (trade name: NILEXAN (trade name: Asahi Glass)) measuring 60 mm x 70 mm x 2 mm was used as a plastic substrate. The metal oxide layer was formed using a vacuum evaporation apparatus shown in FIG. The evaporated substance was heated by an electron beam heating method, and the electron gun was a 2 kW E-type electron gun (model number 7 980-7104) manufactured by Nichiden Anelva.

The manufacturing procedure is as follows: First, the substrate 3 is placed 30 cm above the evaporation material 5.
After mounting at the position shown in Table 1, the vacuum was evacuated to 3 x 10-5 Torr or less, and the evaporated material 5 was heated by electron beam heating to form a nickel oxide film under the conditions shown in Table 1. Furthermore, a SiO□ layer was subsequently formed without breaking the vacuum. As shown in Table 2, the evaporation raw material for the nickel oxide layer was high-purity nickel oxide evaporation pellets, and the evaporation raw material for the Si0g layer was high-purity silicon dioxide. Adhesion was 100.

Example 3 As shown in Table 2, special grade nickel was used as the evaporation raw material for the nickel oxide layer, oxygen was introduced into the vacuum chamber, and 1.
The evaporation source of the inorganic compound layer, the equipment used, the plastic substrate, and the manufacturing procedure were the same as in Example 1, except that the inorganic compound layer was deposited at 5 x 10-'Torr. Adhesion is 100
Met.

Comparative Example 1 The equipment and plastic substrate used were the same as in Example 1. The manufacturing procedure is to set the inside of the vacuum chamber to 3 x 10-5 Torr.
The evaporated material 4 is heated by electron beam heating, and silicon dioxide (
SiO□) was deposited to a thickness of 3 μm.

As shown in Table 2, high-purity silicon dioxide was used as the evaporation source for the SiO□ layer. Adhesion was O.

Comparative Example 2 The same polycarbonate plate as used in Example 1 was immersed in a silicone organic paint (manufactured by Toray Silicone, 5R2410 resin), pulled up at a speed of 1Qcm/min, dried at room temperature for 30 minutes, Dry at °C for 24 hours. The thickness of the silicon-based organic paint layer was 1.5 μm.

Next, it is supplied into a vacuum chamber and 3Xl0-'T is applied.

After evacuation to below rr, high purity silicon dioxide shown in Table 2 was deposited under the conditions shown in Table 1. Adhesion was 0.

Table 2 Table 1 (blank below) 1) YAMANAKA SEMICONDUCTER
LTD, made by Beret 2) YAMANAKA SE stand I
C0NDυ (TERLTD, manufactured by 3) Kishida Kagaku ■ 0 Manufactured by Toray Silicon ■ (Effect of the invention) By providing a layer whose main component is nickel oxide as the first layer on the plastic, it is further provided on top of that. It is possible to obtain a metal oxide-coated plastic with excellent adhesion between the metal oxide layer and the plastic, and with a large degree of freedom in film thickness. Moreover, by selecting the metal oxide film configuration according to the application, it can be used in a wide range of applications.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of a vacuum evaporation apparatus. 1... Vacuum chamber, 2-- Board mounting jig, 3... Board,
5... Evaporated substance, 6- Copper hearth

Claims (1)

[Claims] 1. A metal oxide-coated plastic characterized in that a layer containing nickel oxide as a main component is laminated on one side of a plastic base material, and on top of that a layer or more of metal oxide is laminated.