JPH01176069A - Vapor deposited film - Google Patents

Abstract

PURPOSE:To provide a vapor deposited film having high flexibility and chemical resistance, causing no peeling or cracking and maintaining the barrier property when sterilized by forming a vapor deposited thin layer consisting essentially of an element such as Na or Al and Si or further contg. O on a plastic film. CONSTITUTION:A vapor deposited thin layer consisting essentially of one or more among Na, Mg, Al, K, Ca, Ti, Cr, Mn, Co, Ni, Cu, Zn, Mo, Ag, In, Sn, Sb and Ba (A) and Si (B) or further contg. O (C) is formed on at least one side of a plastic film to obtain a vapor deposited film having high flexibility, superior gas barrier property, chemical and water resistances. When the film is subjected to report or boiling sterilization, peeling and cracking are not caused and the gas and steam barrier property is maintained.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Field of Application) The present invention provides a method for producing a material that has excellent gas barrier properties such as oxygen gas and carbon dioxide gas, water vapor barrier properties, flexibility, water resistance, and chemical resistance. 1. Its performance is stable even under various harsh environments, and it is useful in fields such as packaging materials for food and beverages and pharmaceuticals, electronic materials such as electrically insulating and conductive materials, and medical materials. related to vapor-deposited films.

(Prior Art) Films made by vapor-depositing aluminum on plastic films have been widely used as materials for food packaging and the like. These aluminum deposited fills have poor water resistance, especially boiling water resistance, and transparency.

Retort sterilization, boiling sterilization, or acid.

When it comes into contact with alkali, etc., part of the steamed layer will peel off.

There was a drawback that gas barrier properties and water vapor barrier properties were considerably reduced.

On the other hand, it was proposed in Japanese Unexamined Patent Publication No. 49-41469. 3ixQy (x=1.2
．． )' = 0.1.2.3) Although the vapor-deposited film provided with the vapor-deposited thin film layer of the composition has high chemical resistance, it has low flexibility, and it cannot be sterilized by retort treatment.

For example, when retort sterilization is performed at 125°C for 30 minutes, cracks occur due to the difference in thermal expansion coefficient between the plastic film and the vapor-deposited thin film layer, resulting in a significant drop in gas barrier and water vapor barrier properties. .

(Problems to be Solved by the Invention) The present invention not only has high flexibility and excellent gas barrier properties, water vapor barrier properties, chemical resistance, and water resistance, but also can be sterilized by retort or boiling. The purpose of the present invention is to provide a vapor-deposited film that does not peel or crack, and does not deteriorate its gas barrier properties or water vapor barrier properties.

[Structure of the invention]

(Means for Solving the Problems) The present invention provides at least one side of a plastic film,
(A) Sodium, magnesium, aluminum, potassium, calcium, titanium, chromium, manganese, iron,
At least one element selected from the group consisting of cobalt, nickel, #, lead, molybdenum, silver, indium, tin, antimony, and barium.

This is a vapor-deposited film provided with a vapor-deposited thin film layer containing (B) silicon and, if necessary, (C) oxygen.

In the present invention, the plastic film is not particularly limited, and includes polyesters such as polyethylene terephthalate and polybutylene ethylene phthalate, polyamides, polyvinyl chloride, and polyacrylonitrile.

Polycarbonate, polystyrene, polypropylene.

Films made from saponified ethylene-vinyl acetate copolymer, aromatic polyamide, fluororesin, etc.

Alternatively, there is a laminated film containing one or more of these, whose surface has been subjected to surface treatments such as printing, coating with a silane coupling agent or primer, corona discharge treatment, low-temperature plasma treatment, etc. It may be stretched or double-stretched. Furthermore, in general packaging applications, biaxially oriented polypropylene films, polyester films, etc. are preferably used in terms of gloss 2 strength, and in the field of electronic materials, fluororesin films, polyester films, etc. are used. In addition, when producing by a single winding method, the thickness of the plastic film is preferably 5 to 300 μm from the viewpoint of preventing elongation, wrinkles, cracks, and the like.

These plastic films can contain sodium, magnesium, aluminum, potassium, calcium, titanium, chromium, and manganese on one or both sides.

Iron, cobalt, nickel, copper, zinc, molybdenum.

At least one element selected from the group consisting of i, indium, tin, antimony, and barium, silicon.

And if necessary, a vapor deposited thin film layer containing oxygen as a main component is provided. For food and beverage applications, sodium, magnesium, and aluminum are used for hygiene reasons.

Potassium, calcium, titanium, manganese, iron, silver.

Preferably, the vapor-deposited thin film layer contains at least one element selected from the group consisting of indium, tin, and barium, silicon, and optionally oxygen as the main components.

In the present invention, in order to perform vapor deposition stably.

The amount of element (A) in the deposited thin film layer is preferably o, oos to 50 mol%. Particularly preferably 0.05 to 20 mol%
It is. Further, even if the element (A) is uniformly distributed in the vapor-deposited thin film layer, the concentration of the element (A) may be higher as it approaches the surface of the layer 5, or vice versa. In addition, 1. Elements other than 9 elements (A), silicon and oxygen, 2. For example, carbon,
It may contain nitrogen, sulfur, fluorine, etc.

In the present invention, the vapor deposition raw materials for obtaining these vapor-deposited thin film layers include (2) a simple substance or oxide of element (A);

Elements such as buttride, nitride, carbide, sulfide, etc. (A)
or a mixture thereof, and ■ silicon,
Silicon oxides or mixtures thereof.

and (or) 0 element (A) silicides, silicates,
Alternatively, a mixture of these can be used.

As silicon oxide, Sin, Siz 03.5i3
o4. and Sin, or one or more of them.

The above vapor deposition raw material may contain a binder or a binder, as necessary.
By adding molding aids such as disintegrants and lubricants, and using methods such as wet or dry granulation, compression molding, and extrusion molding, it is shaped into wires, ronds, and doublets.

It is used in the form of pellets, cylinders, cubes, rectangular parallelepipeds, etc. Further, it is preferable to dry or bake the molded product during or after molding in the air, in an inert gas, or in a vacuum to increase the strength of the molded product and to remove contained moisture, built-in gas, and impurities.

There are no particular limitations on the method of vapor deposition heating, and conventionally known heating methods such as high frequency induction heating, direct heating such as resistance heating, radiation heating, and electron beam heating can be used.

In addition, many of these vapor deposition raw materials produce vapor deposition residue during vapor deposition, so if you want to stably obtain a continuous vapor deposition film, the vapor deposition raw material molded product is continuously supplied to the heating section, and It is preferable to use a vapor deposition apparatus equipped with a means for discharging vapor deposition residue.

The vapor-deposited film of the present invention may be further printed or coated, provided with a dry rating layer, or laminated with a plastic film with or without an adhesive or laminating adhesive, if necessary. good.

It can be used as a film or processed into bags, tubes, etc., and used as packaging materials, gas barrier materials, electrically insulating materials, or conductive materials in the fields of food and beverages, pharmaceuticals, medical care, electronic materials, etc. can.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples. In the two examples, the oxygen gas permeability (OP) is the value measured by the isobaric method, and its units are mβ/m', 24 hours, 1 atm, 25°C, 100% RH, and the water vapor transmission rate (WVT). This is a value measured by infrared absorption method, and its unit is ml/rd.
- 24 hours, 40°C, and 90% RH, and all indications of these units have been omitted.

Example 1 Silicon/silicon dioxide/aluminum = 1/110.0
A tablet with a diameter of 4Q mm and a thickness of 35 mm obtained by molding a vapor deposition raw material consisting of 3 (molar ratio) was placed in a cylindrical crucible made of boron nitride, and heated under a vacuum of lXl0-'to r r with high frequency. A polyethylene terephthalate film having a thickness of 12 μm was vapor-deposited by heating to 1250° C. using an induction heating device to obtain a vapor-deposited film having a vapor-deposited thin film layer having a thickness of 1000 μm. In addition, at this time, approximately 40
% by weight of deposition residue.

Polyurethane adhesive for lamination [Atocoat #90
0J (manufactured by Toyo Morton, trade name).

Two bags were made by bonding the obtained vapor-deposited film and an unstretched polypropylene film with a thickness of 70 μm using a conventional method.
It was filled with wt% acetic acid water and subjected to retort sterilization at 125°C for 30 minutes.

OP and WVT were measured at 1 point each before retort sterilization treatment and after retort sterilization treatment, and the average value of the measured values (
A v , ), and the difference between the maximum and minimum measured values (
R) was calculated. The calculated results are shown in Table 1.

Comparative Example 1-1 Table 1 shows the results measured and calculated in the same manner as in Example 1, except that a mixture of silicon/silicon dioxide = 1/1 (molar ratio) was used as the vapor deposition raw material. During vapor deposition, about 30% by weight of vapor deposition residue was produced, and extremely fine cracks were observed in the vapor-deposited thin film layer after retort sterilization.

Comparative Example 1-2 Table 1 shows the results measured and calculated in the same manner as in Example 1 except that aluminum was used as the vapor deposition raw material.

In addition, peeling and dissolution were observed in a part of the vapor-deposited thin film layer after retort sterilization.

(Castle, Life Insurance Table 1) Example 2 The vapor deposition method used in Example 1 was carried out using a vapor deposition apparatus equipped with a means for continuously supplying the vapor deposition raw material molded product to the heating section and continuously discharging the vapor deposition residue from the heating section. The raw material tablet-shaped molded product was continuously fed at a speed of 6 mm/min to a heating section made of boron nitride having a concave cross section, and heated to 1300°C by a resistance heating device under a vacuum of 1XIO-'torr. Thickness 12μ
A continuous film of polyethylene terephthalate having a thickness of 1,000 m thick was subjected to vapor deposition to obtain a continuous vapor-deposited film having a continuous thin film layer of 1000 m thick. The obtained continuous vapor deposited film and an unstretched polypropylene film having a thickness of 70 crm were adhered by a conventional method using Atocoat #900J to make one bag.

Water was sealed and retort sterilization was performed at 125°C for 40 minutes.

OP was measured at 10 points before and after retort sterilization, and the average value (AV, ) of the measured values and the difference (R) between the maximum and minimum measured values were calculated.

The calculated results are shown in Table 2.

Comparative Example 2-1 Table 2 shows the results measured and calculated in the same manner as in Example 2, except that a mixture of silicon/silicon dioxide = 1/1 (molar ratio) was used as the vapor deposition raw material.

In addition, extremely fine cracks were observed in the vapor-deposited thin film layer after retort sterilization.

Comparative Example 2-2 Table 2 shows the results measured and calculated in the same manner as in Example 2 except that aluminum was used as the vapor deposition raw material.

In addition, peeling and dissolution were observed in a part of the vapor-deposited thin film layer after retort sterilization.

Example 3 Using a nickel-chromium alloy consisting of 80% by weight of nickel and 20% by weight of chromium, a mixture of silicon/silicon dioxide/nickel-chromium alloy-1.0/1.010.1 (molar ratio) was used as a vapor deposition raw material. A continuously deposited film was obtained in the same manner as in Example 2, except that the following was used.

The obtained continuously deposited film was exposed to water vapor at 100° C. for 3 hours, and the OP and WVT were measured before and after exposure. The measured results are shown in Table 3.

Comparative Example 3 The continuously deposited film obtained in Comparative Example 2-1 was exposed to water vapor in the same manner as in Example 3, and the OP and WVT before and after exposure were measured. The measured results are shown in Table 3.

Table 3 Example 4 The same procedure as Example 3 was carried out except that a mixture of silicon/silicon dioxide/sodium silicate = 1.5/1.010.5 (mole ratio) was used as the vapor deposition raw material. , water vapor exposure was performed, and OP was measured before and after exposure. The measurement results are shown in Table 4.

Example 5 Silicon/silicon dioxide/silver = 1.5/1 as vapor deposition raw material
．． 010.07 (molar ratio) was used in the same manner as in Example 4 before and after exposure to water vapor.
P was measured. The measured results are shown in Table 4.

Table 4 Examples 6 to 8 Instead of the 12 μm thick polyethylene terephthalate continuous film, a 25 μm thick two-wheel stretched polyamide continuous film (Example 6), a 20 μm thick two-wheel stretched polypropylene continuous film (Example 7), A continuous vapor-deposited film was obtained in the same manner as in Example 2 except that a 25 μm thick fluororesin continuous film (Example 8) was used.

The obtained continuously deposited film was exposed to water vapor at 100° C. for 30 minutes, and the OP and WVT were measured before and after exposure. The measured results are shown in Table 5.

〔Effect of the invention〕

The present invention not only has high flexibility and excellent gas barrier properties, water vapor barrier properties, chemical resistance, and water resistance, but also
It has become possible to obtain a vapor-deposited film that does not peel or crack, and does not deteriorate its gas barrier properties or water vapor barrier properties even when subjected to retort sterilization treatment or boiling sterilization treatment.

(extra meat)

Claims (1)

[Claims] 1. On at least one side of the plastic film, (A)
sodium, magnesium, aluminum, potassium,
Calcium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, silver, indium,
A vapor-deposited film comprising a vapor-deposited thin film layer whose main components are at least one element selected from the group consisting of tin, antimony and barium, (B) silicon, and optionally (C) oxygen.