JPH04341560A - Production of transparent vapor-deposited film - Google Patents

Abstract

PURPOSE:To produce a transparent vapor-deposited film having excellent light transmissivity by heating a mixture of silicon dioxide with a metal such as Al in a hermetically sealed vacuum system and sticking the resulting vapor to a base material. CONSTITUTION:A mixture of silicon dioxide with a metal selected among Al, Ti and Zr is heated by an electric resistance method in a hermetically sealed vacuum system and the resulting vapor is stuck to a base material (film) 1 to be subjected to vapor deposition. The mixing ratio between the silicon dioxide and metal is regulated to (80:20) to (40:60). A device is evacuated, the film 1 is travelled at a prescribed speed and a vapor depositing source 4 is heated to vaporize the material 2 for vapor deposition. A transparent vapor-deposited film can be produced by a vacuum deposition method using resistance heating.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing transparent vapor-deposited films. More specifically, the present invention relates to a method for manufacturing a transparent vapor-deposited film by attaching a colorless and transparent vapor-deposited film to a substrate to be vapor-deposited by a vacuum vapor deposition method using a resistance heating method.

0002

[Prior Art] A transparent vapor-deposited film made by vacuum-depositing a vapor-deposited film of a metal oxide on a base film made of a polymer is well known, and is popular for food products because of its transparency and excellent gas barrier properties. (Japanese Patent Publication No. 51-48511, Japanese Patent Publication No. 63-28017, Japanese Patent Publication No. 2-15382, etc.).

Silicon oxide is mainly used as such metal oxide.

[0004] Silicon oxide includes silicon monoxide and silicon dioxide, but commercially available silicon monoxide is more oxidized and S
It usually has an oxidation degree of about iO1.5,
Silicon dioxide is represented by SiO2.

Among these, silicon monoxide can be vacuum deposited by resistance heating, but the deposited film is 350 nm thick.
There is absorption in the low wavelength region of about 1000 yen, and it appears as a pale yellow color. For this reason, when a film coated with silicon monoxide is used as a packaging material for foods, etc., the packaging may be mistaken for the contents to be discolored.

On the other hand, silicon dioxide generally forms a colorless and transparent vapor deposited film, but the heating temperature required to obtain the vapor pressure required for practical vapor deposition is high, making vacuum vapor deposition by resistance heating difficult. If vacuum evaporation using resistance heating was attempted, the boat containing these evaporation materials would evaporate due to the high temperature.

[0007] Therefore, as a method for vacuum-depositing these materials, electron beam heating, which is less likely to cause heating of the boat, has been attempted, but this method requires a larger apparatus than the resistance heating method, and also The film is charged by the secondary electrons, and since the vapor deposition material itself is electrically insulating, the charge remains and obstructs the adhesion of the next charged vapor deposition material, resulting in transparent vapor deposition with a stable and uniform film thickness and composition. It was not possible to produce a film.

[0008]

[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and provides a method for producing a transparent vapor-deposited film by vacuum-depositing a colorless and transparent oxide vapor-deposited film using a resistance heating method. The purpose is to provide

[0009]

[Means for Solving the Problems] In order to achieve this object, the present invention heats a mixture of silicon dioxide and a metal consisting of aluminum, titanium, or zirconium in a vacuum-sealed system by an electrical resistance method. The present invention provides a method for producing a transparent vapor-deposited film, which is characterized in that the transparent vapor-deposited film is adhered to a substrate to be vapor-deposited.

The vapor deposition material according to the present invention is silicon dioxide, aluminum, titanium, or zirconium.

[0011] The heating temperature for evaporating such a vapor deposition material depends on the degree of vacuum, but is, for example, 10-3 Pascal (Pa).
It is sufficient to heat it to about 1500° C. with a certain degree of vacuum. The boat may be a normal boat used for vacuum deposition. For example, molybdenum boats.

The substrate to be deposited may be any material, but a transparent polymer film is preferred in order to take advantage of the transparency and oxygen barrier properties of the deposited film. For example, polyolefins (polyethylene, polypropylene, polybutene, etc.), polystyrene, polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, etc.), polyamides (nylon-6, nylon-1, etc.)
1, fully aromatic polyamide, etc.), polycarbonate, polyvinyl chloride, polyvinylidene chloride, fluororesin (polyfluoroethylene, etc.), polyimide, or copolymers of monomers of these polymers.

[0013] Furthermore, the substrate to be vapor-deposited may contain known additives in addition to these polymers. For example, antistatic agents, UV inhibitors, plasticizers, lubricants, colorants, etc.

The substrate to be deposited is preferably a stretched film from the viewpoints of strength, dimensional stability and heat resistance, but a non-stretched film can also be used.

[0015] From the viewpoint of production efficiency and cost, it is preferable to use a strip-shaped film as the substrate to be deposited. The strip-shaped film is continuously run within the vacuum-sealed system of the vapor deposition machine, and is continuously vacuum-deposited.

There is no limit to the thickness of the substrate to be deposited, but from the viewpoint of strength, a film having a thickness of 3 to 400 μm is generally suitable. Preferably it is in the range of 6 to 200 μm.

The transparent vapor-deposited film according to the present invention can be produced specifically using the apparatus shown in FIG. FIG. 1 is an explanatory diagram of an apparatus used in the manufacturing method of the present invention.

That is, in FIG. 1, the entire interior of the apparatus is evacuated and maintained at a pressure of 10-3 to 10-6 Pa. Exhaust can be achieved by a pump (not shown) connected to the exhaust port.

The base film 1 is in the form of a band, and is unwound from the unwinding roll 11, passes through a guide roll 31, etc., runs while being held by a cooling roll 32, passes through the guide roll 31, etc., and is unwound. It is wound up on a take-up roll 12.

A vapor deposition source 4 consisting of a boat containing vapor deposition material 2 is arranged below the cooling roll 32 and can be heated by an electric resistance connected to a power source.

In order to produce a transparent vapor-deposited film using this apparatus, first, the inside of the apparatus is evacuated to create a vacuum state, and then the vapor-deposition source 4 is heated while the base film 1 is run at a predetermined speed. The vapor deposition material 2 may be vaporized.

[0022]

【Example】

<Example 1> (A) Apparatus: The apparatus shown in Figure 1. (B) Pressure due to exhaust - 2 x 10-3 or less.

(C) Substrate to be deposited. (a) Material Biaxially stretched polyethylene terephthalate film. (b) Thickness: 12 μm. (c) Traveling speed: 50 m/min.

(D) Vapor deposition source. (a) Composition Silicon dioxide/aluminum metal (mixing ratio is listed in the table) (b) Boat Boat made of molybdenum. (c) Heating temperature: 1550°C.

Under the above conditions, the substrate to be deposited was moved and vacuum deposited. The oxygen permeability (MO
MOCON OX-TRAN-10/50 manufactured by CON
A, 25°C, 75% R. H. ), 3
Table 1 shows the light transmittance at 50 nm (measured with a spectrometer).

[0026]

[Table 1]

[0027] In the table, the unit of oxygen permeability is ml/m.
2 ・atm・day, the unit of light transmittance is %.

<Example 2> A transparent vapor-deposited film was prepared in the same manner as in Example 1 except that metal titanium was used instead of metal aluminum. Table 2 shows the oxygen transmittance and light transmittance.
Shown below.

[0029]

[Table 2]

<Example 3> A transparent vapor-deposited film was prepared in the same manner as in Example 1 except that metal zirconium was used instead of metal aluminum. The oxygen transmittance and light transmittance are shown in Table 3.

[0031]

[Table 3]

<Reference Example> Silicon monoxide (S
iO1.5) by vacuum evaporation using resistance heating method,
Furthermore, Table 4 shows the oxygen transmittance and light transmittance of films deposited using silicon dioxide (SiO2) to a thickness of 1500 Å and 1200 Å, respectively, by vacuum deposition using an electron beam heating method.

[0033]

[Table 4]

[0034]

Effects of the Invention As described above, according to the present invention, 150
A transparent vapor-deposited film having an oxygen barrier property equivalent to or better than that of a silicon monoxide vapor-deposited film with a thickness of 0 Å and an outstandingly excellent light transmittance can be produced by a vacuum vapor deposition method using a resistance heating method.

[0035]

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of a manufacturing apparatus according to the present invention.

[Explanation of symbols]

1 Base film 2 Vapor deposition material 31 Guide roll 32 Cooling roll 4 Vapor deposition source

Claims (2)

[Claims] [Claim 1] A transparent method characterized in that a mixture of silicon dioxide and a metal consisting of aluminum, titanium, or zirconium is heated by an electrical resistance method in a vacuum-sealed system to adhere it to a substrate to be deposited. Method for producing vapor deposited film. 2. The transparent material according to claim 1, wherein the mixing ratio of silicon dioxide and a metal consisting of aluminum, titanium, or zirconium is 80:20 to 40:60 in terms of molar ratio. Method for producing vapor deposited film.