JPS62228461A - Metallic vapor deposited film and its production - Google Patents

Abstract

PURPOSE:To reduce the gas permeability and heat conductivity by successively forming an amorphous aluminum oxide layer and a metallic aluminum layer on a traveling plastic film by vacuum deposition so as to increase the adhesive power of the layers to the base film. CONSTITUTION:A plastic film 1 wound around a drawing-out shaft 5 is traveled along a cooling drum 12. Aluminum in a crucible 7 is melted and oxygen is introduced from an oxygen cylinder 10 to form an aluminum oxide layer on the film 1 by vacuum deposition. The film 1 having the formed aluminum oxide layer is wound again around the shaft 5 and a metallic aluminum layer is similarly formed. A film having a lower amorphous aluminum oxide layer and an upper metallic aluminum layer on at least one side is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a metal vapor deposited film that includes a metal aluminum layer with excellent adhesion that does not peel off from a base film and exhibits high gas barrier properties.

(Prior Art) Metal-deposited films have recently been widely used in applications that take advantage of their surface gloss, packaging materials, etc. because they have excellent light reflectivity, light shielding properties, gas barrier properties, and the like.

However, these conventional metallized films are
It has the disadvantage that the layer has poor adhesion to the base film and is easily peeled off from the film surface.

Therefore, various methods have been proposed to solve these drawbacks. For example, the surface of the plus book may be roughened in advance by physical or chemical methods, or electrical corona discharge treatment or glow discharge treatment may be performed. However, these methods do not provide sufficient adhesion strength for practical use, and their uses are limited.

Therefore, in order to solve this problem, attempts have been made to apply a thin layer of adhesive or the like on the surface of the film in advance.

(Problems to be Solved by the Invention) However, the following problems arose in films in which such an adhesive was applied in advance and then metal aluminum was vacuum-deposited.

That is, a. Since it is necessary to apply an adhesive to the film surface in advance before vacuum deposition, the process becomes multi-layered, resulting in high costs.

b. (9) The metallized film still has insufficient adhesive strength and cannot be used for some purposes.

C. Since there is an adhesive layer between the plastic film and the metal deposition layer, when exposed to a high temperature atmosphere, the adhesive layer loses its heat resistance and moves, causing the aluminum deposition source to lose its luster. There is a big problem that it loses its color and turns white.

d. Especially when using a metallized film as a packaging material, the thickness of the aluminum-deposited layer has a correlation with the gas barrier properties and its stability, and in this sense (the thicker the metallized layer is, the better However, for example, metal aluminum "
The thermal conductivity of cum is approximately 2. OQKcal, /m # h
・QC is about 1000 times that of general plastic film. When used for packaging materials, heat will escape from the heat sealing part of the laminate film if the heat conductivity is high, so the metal vapor deposition layer is used. There is a conflicting problem in that it is desirable that the thickness of the material be as thin as possible.

An object of the present invention is to provide a metallized film that does not have the above-mentioned drawbacks, that is, does not lose its metallic luster and has excellent gas barrier properties even when used at high temperatures, and a method for producing the same.

(Means for Solving the Problems) In other words, the present invention provides a metal film characterized in that it has an aluminum oxide layer on at least one side of a plastic film, and a metal aluminum layer laminated on the aluminum oxide 1 cum layer. Deposited film. The method for producing a metal-deposited film according to claim 1, characterized in that the aluminum oxide layer and the metal aluminum layer are continuously formed by vacuum deposition while the film is running in the same vacuum container.

- Provide Oru Shinode.

The plastic film used in the present invention includes polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate-1, polyamides such as nylon 6 and nylon 12, aromatic polyamides, polyimides, and the like. Furthermore, the plastic film used in the present invention may be made of the above-mentioned polymers or copolymers with other vehicle chassis bodies. In general, these multi-width composites may be melt-extruded, -axially stretched or biaxially stretched, depending on the use, and are not particularly limited.

Further, antistatic agents, ultraviolet absorbers, colorants, heat stabilizers, internal lubricants, etc. may be added to these i'i +a polymers by known methods.

The plastic film according to the present invention may have mechanical strength, thermal dimensional stability, and other suitability as a plastic vapor-deposited film material.

These plastic films may be subjected to surface treatment such as corona discharge treatment or plasma treatment, or surface roughening treatment by physical or chemical methods without causing any problems, prior to the formation of the aluminum oxide layer.

Further, in order to improve adhesion, adhesive may be applied in advance by a known method, but it is necessary to have an aptitude that does not cause the above-mentioned whitening phenomenon of high-temperature bodies. .

The thickness of the plastic film of the present invention is not particularly limited, but is preferably from 2 to 250 μm in terms of flexibility, thermal properties, and mechanical properties, and more preferably from 9 to 125 μm.

The aluminum oxide used in the present invention is Aσ01AQ2
These are aluminum oxides such as 02 and AQ203. In addition, other impurities may be contained in the aluminum oxide layer (=j) within a range that does not impair the strength.

In addition, in the present invention, aluminum oxide (amorphous) is preferable in order to exhibit flexibility and formability. If crystalline aluminum oxide is contained, the film may be made thicker or may be bent. If this happens, cracks may occur in the film, which is not desirable.

In addition, crystalline or amorphous! The F11 constant can be easily measured using an ordinary X-ray diffraction device.

That is, the amorphous aluminum oxide in J5 of the present invention means one in which no specific diffraction is observed by X-ray diffraction.

The thickness of the aluminum oxide layer is preferably measured depending on the base film and the intended use, and is generally 20 to 1000 mm thick for the adhesion of the metal aluminum vapor deposited layer.
Good range of people. More preferably, 50 to 300 people are required. If the thickness of the aluminum oxide layer is less than 20 Å, the adhesion of the subsequently laminated aluminum vapor-deposited layer will not be sufficient, and if it is more than 1,000 Å, iris coloration will occur due to light interference, which is undesirable.

The aluminum oxide layer can be formed by vacuum evaporation, sputtering, or vacuum evaporation of 1 µm of aluminum oxide powder in an ion-blating tank, or by introducing aluminum cum metal and oxygen scum to form the above-mentioned It is possible to adopt a method of forming by vacuum evaporation method. Alternatively, aluminum may be deposited thinly in advance by a known method and then oxidized.

In step d3 of the present invention, the metal aluminum layer is formed by a conventional method. The thickness of the aluminum layer is not particularly limited, but it is preferably within a range that provides sufficient surface gloss, electrical conductivity, light shielding properties, and scum shielding properties depending on the purpose.

In addition, the present inventors have invented the following method as a method for efficiently and cost-effectively forming such an aluminum oxide layer and a metal aluminum layer.

However, in the elegant apparatus shown in FIG. 2, when the plastic film 1 is vacuum-deposited along the cooling drum 12, a gas flow controller 9 is used to inject an oxygen cylinder 10 at the beginning of the deposition section. Oxygen gas is introduced through the waste outlet 8 (5), and an aluminum oxide layer is formed by reactive vapor deposition, and the latter part (this is a method in which a regular aluminum layer is formed without introducing oxygen). By using this method, you can easily deposit two layers of aluminum oxide and metal aluminum by controlling the position of the waste outlet 8 and the flow rate of oxygen gas, just like the conventional method of vacuum-depositing only aluminum. can be formed continuously with high thickness accuracy.

(Function) The metal-deposited film according to the present invention has a strong labor-saving effect on the metal aluminum cum layer and does not cause whitening due to heat. It can be used for decoration, electrical parts, etc. In particular, when used as a packaging material, the required gas barrier properties (91) are required, but since only a metal vapor-deposited layer is needed which is larger than conventional ones, the heat transfer rate is low (91), and sealing can be easily performed. There are advantages.

J: The metal-based film according to the present invention can be used for the following purposes (laminating with other materials, lamination, printing of letters, designs, etc., surface protection coating, etc.) as appropriate. can become.

(Examples) The present invention will be explained below using examples. Na(13,1
The following method was used to measure and evaluate sex.

B. Cu Kα using a crystalline X-ray diffraction device (Rigaku Denki Co., Ltd.) of aluminum oxide layer
Ray (using a Ni filter) S: The diffraction intensity was measured using a scintillation counter (manufactured by Rigakuden) while rotating the sample and X-ray source using a goniometer.

B. Composition analysis of aluminum oxide diagram The deposited layer was analyzed with an ESC△ spectrometer (12', ESCA750 manufactured by Tsu Seisakusho Co., Ltd.), and the aluminum oxide composition was confirmed from the binding energy of the AQ2P spectrum.

C. Aluminum oxide IC15 and the thickness of the metal aluminum layer The thickness of the aluminum oxide layer is determined by applying polyester adhesive tape (manufactured by Nitto Electric Co., Ltd.) NO31B to the substrate film in advance.
IC was pasted and vapor-deposited on it.

Peel off this adhesive tape to create a step between the vapor-deposited area and the blue area. This step was measured using a high-precision step measuring device (Koita Research Institute).
Measurements were made using the ET-10>. Further, metal aluminum 1 was also measured in the same manner.

C. Adhesion of metal aluminum layer: An aluminum oxide layer was deposited on top of the plastic film, and then an adhesive was applied on top of the metal aluminum layer.

Thereafter, the two plastic films were peeled off, and the peeling force at that time was measured as the adhesion strength. Specifically, it is as described below.

An aluminum oxide layer and a metal aluminum layer were sequentially formed on the plastic film, and then the following grooved adhesive was applied to a thickness of 2 μm, dried at 80°C for 11 minutes, and then heated at 50°C.
It is pressed together with a μm Gitosting Polyzo I” pyrene film.

Adhesive (1) Reikahonto Sei-270 (manufactured by Dainichiseika Co., Ltd., urethane paint) 100 parts (2) Goikahonto C-26 (in Japan: Koka ° () vermilion), isocyanate 1 ~ curing agent) 20 parts (3) Ethyl oxide
40' of crimped 120 parts
After Zincing for 2 hours, cut to a width of 15 mm, and test using a Tensile Compression Tester (Minebea Equipment, TCM).
-50), and was peeled off at a speed of 20 cm/min in a 90 degree direction, and the peeling force at that time was measured as the "I" striking strength.

2. Sequentially forming an aluminum oxide layer and a metal aluminum layer on the whitened plastic film C3-t! , the change in gloss of the film surface was measured when heat treated.

Specifically, it is as described below.

A serous aluminum layer and a metal aluminum layer were sequentially formed on a plastic film and heat-treated at 150° C. for 15 minutes, and then the gloss was measured with a digital variable angle photometer (UGV-4D, manufactured by Ska Test Co., Ltd.).

In the example, a 111111 stretched polyethylene terephthalate film (12, aN7) was prepared with a width of 1000 mm and a length of 6000 nm.
1] The unwinding shaft 5 of the vapor deposition apparatus shown in FIG.
I watched A. 800 ml of 99.9% pure aluminum
Fill the small crucible 7 with 0 car and vacuum container 4 5.0×]
It was evacuated to -4 Torr.

Next, the aluminum in the carbon crucible 7 is melted using a high frequency induction heating method, and the film 1 is spread over a distance of 200 m.
, runs in 7 minutes! However, the surface resistance was adjusted to 1.5Ω'.

;By the waste flow control device 1 9, the oxygen scum from the oxygen cylinder 10 was passed through the nozzle blower 8/8-, and l? ,I+
In the Kf state, 1 tree (blue) (moxibustion 1 and 80.7 minutes were introduced, 1 to 1 regenerated aluminum 1 to 1 (Fig. After that, the vapor-deposited film was taken out and the rimple was analyzed by X-ray diffraction and an ESCA Spec 1 herometer, and it was confirmed that it was amorphous aluminum oxide (80203).3 Next, aluminum oxide was vapor-deposited. The obtained film was mounted on the unwinding shaft 5 of the vapor deposition apparatus shown in FIG.

Fill an 800Cl carbon crucible 7 with aluminum with a purity of 99.9%, evacuate the vacuum container to 5 x 10' Torr, melt the aluminum in the carbon crucible 7 using a high frequency induction heating method, and heat the film to 250 Cl carbon crucible 7.
The metal aluminum layer 3 was adjusted so that the surface resistance value was 1.5 Ω/mouth by running at a speed of m/min. After continuing for about 10 minutes while controlling the amount of aluminum deposited, the deposited film was taken out. The deposited films were evaluated. The results were as shown in Table 2.

Example 2.3 The aluminum oxide layer 2 and the metal aluminum layer 3 were formed in 111 parts by the same method as in Example 1, and the formation steps for the aluminum oxide layer 2 are shown in Table 1. The conditions for forming the metal aluminum layer 3 were the same as in Example 1.

Table 1 Note) Base film Yes 1F Polyethylene terephthalate 1 (12μ thick) Example 4 Biaxially stretched polyethylene terephthalate film (12μ thick)
Metallic aluminum was vapor-deposited on the substrate (mJl) using the vapor deposition apparatus shown in FIG. At that time, the surface resistance (direction) of aluminum is
, 007, and then the gas flow rate controller 9 introduced the oxygen gas into the gas outlet 8 at a rate of 2 M/min (converted to the volume of 1 quasi-state) for evaporation. continued.

As a result of evaluating the deposited film, it was found that the thickness of the aluminum oxide layer 2 between the base film 1 and the metal aluminum layer 3 was uneven between 70 and 120 people, but the thickness of the metal aluminum layer 3 (1430 people was uniform). When the adhesion strength was measured, it showed a high value of 250 Q/15mm.

From this, the aluminum oxide layer 2 has a non-uniform thickness rather than the case where the aluminum oxide layer 2 has a uniform thickness as in Example 1.2.3 in which the aluminum oxide layer 2 and the metal aluminum layer 3 are formed sequentially. It can be seen that the adhesive strength is higher.

According to a cross-sectional observation using an electron microscope, Example 1 was formed in which the aluminum oxide layer 2 and the metal aluminum layer 3 were sequentially formed.
As shown in Figure 1, in 2.3, the aluminum oxide thin film layer was uniformly formed, whereas the sample of this example had a large surface area as shown in Figure 3, V. .

Comparative Example 1 Film to polyethylene terephthalate 1 (12 μm thickness)
An aluminum layer having a surface resistance of 1.5 Ω/hole was coated on top of the aluminum layer at a running speed of 250 m/min in a vacuum of 5.0×IQ-4 Torr without introducing a cleaning gas.

Example 5.6.7 Aluminum oxide layer 2 was deposited on a cast polypropylene film (125 μm) by a method similar to Example 1.
and the metal aluminum layer 3 are sequentially formed.
The conditions for forming the regenerated aluminum layer 2 were changed.

Example 8 An aluminum oxide layer 2 and a metal aluminum layer 3 were simultaneously formed on a cast polypropylene film (25 μm) by the same method as in Example 4. As a result, observation using an electron microscope revealed that the surface area was too large as shown in FIG.

Comparative Example 2 Oxygen gas was introduced onto a polypropylene film (25 μm thick) at 4.3 x 1Q-4 TOrr (1) in a vacuum at a running speed of 240 x 1
surface resistance value 1./min. /1Ω/Aluminum layer at the mouth/!
- Deposited.

Table 2 shows the measurement results of Example 1911 and Comparative Example.

(Rino Song of the Invention) The metal vapor deposited film according to the present invention has a feature that the adhesion of the vapor deposited layer to the base film is strong, and there is no change in surface gloss in a high temperature atmosphere.

Furthermore, the metallized film according to the present invention has a scum barrier 1
Since it is rich in heat conductivity and can keep heat conductivity low, it has the advantage that it can be easily sealed when used as a packaging film.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing an embodiment of the present invention, FIG. be. 1 Nibrush stick film 2: Aluminum oxide layer 3: Metal) 'Aluminum layer 4: Vacuum container 5: Advance shaft 6: Apricot shaft 7: Crucible 8: Gas outlet 9: Dregs flow rate controller 10: Oxygen cylinder 11: Mask 12: Cooling drum

Claims (3)

[Claims] (1) A metal-deposited film comprising an aluminum oxide layer on at least one side of the plastic film, and a metal aluminum layer laminated on the aluminum oxide layer. (2) The metal vapor deposited film according to claim 1, wherein the aluminum oxide layer is amorphous. (3) A method for producing a metal-deposited film, which comprises continuously forming an aluminum oxide layer and a metal aluminum layer by vacuum deposition while the plastic film is running in the same vacuum container.