JPH01171856A - Metallized film - Google Patents

Abstract

PURPOSE:To provide a metallized film showing no lowering of the bonding strength of a vapor-deposited metal layer not only under a high temp. and high humidity condition but also in a liquid, by bonding a polymer film and the vapor-deposited metal layer through a plasma polymerization layer formed from an acrylic or methacrylic compound having a glycidyl group. CONSTITUTION:A polyester film is introduced into an internal electrode type plasma polymerization apparatus and, after said apparatus is evacuated to set initial pressure to 1X10<-4>Torr, glycidyl methacrylate is introduced and discharge treatment is performed at power density of 400Wmin/m<2> while pressure is held to 0.2Torr to provide a plasma polymerization layer having a thickness of about 100Angstrom on the surface of the polyester film. Then, a metal vapor- deposited layer is formed on the plasma polymerization layer to obtain 180 deg. wet release strength of 55g/cm exceeding 30g/cm being a practical level in a general use aspect.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a metal vapor-deposited film, which has extremely few vapor deposition holes (pinholes) and has excellent adhesion under high temperature and high humidity conditions and in liquids. It relates to vapor-deposited films.

[Conventional technology] /l, Cu, Pd on the polymer resin film base material.

Films on which metals such as Ti are deposited, so-called metal-deposited films, are used for various purposes.

Examples include capacitors, food packaging materials, transparent conductive films, and magnetic tapes.

However, when a metal is directly deposited on a polymer resin film base material, the adhesion between the metal and the base material is weak, resulting in peeling of the metal deposited film or missing deposition due to pinholes, which poses a practical problem.

For example, in the case of packaging materials in which 80 is deposited on a polyester film, there are problems such as moisture permeability caused by an increase in water vapor permeability or dropouts in magnetic recording tapes.

As a solution to these problems, Japanese Unexamined Patent Publication No. 59-9
No. 6137 proposes a method in which a plasma polymerized film is formed by low-temperature plasma treatment of organosilicon compound gas, and then metallized. However, although the adhesive obtained by this method has excellent adhesive strength under normal humidity conditions, it has the disadvantage that the adhesive strength rapidly decreases under high temperature and high humidity conditions or in liquid. Generally speaking, in terms of manufacturing technology, there is a drawback that polymerization proceeds rapidly during plasma polymerization, and a plasma polymer is deposited in powder form on the surface of the electrode and the treated substrate.

Furthermore, in Japanese Patent Publication No. 13310/1986, after the surface of a polyester film was subjected to corona discharge treatment in a nitrogen gas atmosphere,
A metal vapor-deposited one has been proposed. Although the proposed product is better than the conventional one in terms of preventing deterioration of water vapor barrier properties under high temperature and high humidity, it cannot be used under harsh conditions that have been required in recent years, such as wine containers. When used as a beverage liquid storage container, there is a problem that the vapor deposition layer easily peels off during high temperature sterilization, making it unusable.

When corona discharge treatment is applied to the production of rough plating type flexible printed circuit boards, for example, it is necessary to apply corona discharge treatment to a heat-resistant film, then evaporate CU or the like on it in advance, and then further laminate a thick layer of copper using a plating method. However, in this case, there is a problem in that the deposited film easily peels off from the film when placed in a plating bath.

[Problems to be Solved by the Invention] The present invention was devised in view of the various drawbacks of the prior art, and its purpose is to improve the adhesive strength of the metal-deposited film, especially in liquid, without impairing the mechanical properties of the film. Another object of the present invention is to provide a metal vapor-deposited film that has excellent adhesive strength under high humidity and has few vapor deposition spots.

[Means for Solving the Problems] The object of the present invention is to provide a metal film in which a polymer resin film and a metal vapor deposition layer are bonded via a plasma polymerized layer formed from an acrylic or methacrylic compound having a glycidyl group. Achieved by vapor deposited film.

Examples of the polymer resin film used in the present invention include those commonly used as substrates for vapor deposition, such as polyester films, polypropylene films, polyimide films, and polyphenylene sulfide films. , a polyester film with excellent water resistance, a polypropylene film, and a condensate of pyromellitic dianhydride and 4,4'-diaminodiphenyl ether, or 3,4.3-.

A polyimide film made of a condensate of 4-biphenyltetracarboxylic diaminodiphenyl ether is more preferred, and a polyester film is particularly preferred.

Here, the polyester film is a highly crystalline linear saturated polyester synthesized from an aromatic dibasic acid or its ester-forming derivative and a diol. Terephthalate, polyethylene
Examples include a film obtained by biaxially stretching a blend of 2,6-naphthalate or a copolymer partially substituted with another component, polyalkylene glycol, polycarbonate, etc. by a conventional method.

The thickness of the film is not particularly limited, and may be appropriately selected depending on the purpose.

Generally, for packaging materials, a thickness of around 50 μm is used. Further, the film may be subjected to a pretreatment such as glow discharge, corona discharge, or coating for surface modification.

In the present invention, the plasma polymerized layer refers to an organic compound polymer layer formed by electric discharge in a vapor atmosphere of an acrylic or methacrylic compound having a glycidyl group.

The method of plasma polymerization may be a known method. For example, after setting the film in an internal electrode type device, it is evacuated with a vacuum pump, and then the vapor of an acrylic or methacrylic compound having a glycidyl group is heated to a predetermined pressure (0.01 ~10
For example, after supplying the voltage until the voltage reaches approximately 100 mΩ (TORR), appropriate power is applied to the electrodes.

In the present invention, the acrylic or methacrylic compound having a glycidyl group refers to one represented by the following formula.

CH2=CR 嘱 Coo　(CH2→-CH-CI-121　\1 Here, R represents 1H or 10H3.

n represents an integer of 1 to 3.

Among them, glycidyl methacrylate in which R is 10H3 and n=1 is preferable from the viewpoint of adhesive effect and ease of handling.

The thickness of the plasma polymerized layer is not particularly limited, but from the viewpoint of adhesion effect and curl prevention during vapor deposition, it is 20 to 4μ.
The range of m is preferable, and more preferably 50 to 2000 people.

The metal vapor deposited layer in the present invention is not particularly limited, and a layer formed from a known metal or alloy by a known method such as heating vapor deposition, electron beam vapor deposition, or sputtering can be used. ArL,
A vapor-deposited layer made of metals such as Cu, Zn, Ti, Ni, Go, Fe, alloys thereof, or oxides thereof is preferable because it has strong adhesive strength even at high temperatures or in liquid.

The thickness of the metal vapor deposition layer is not particularly limited, but may be 4
The range is preferably 00 to 50 μm, more preferably 5
00 to 20 μm.

[Example] The present invention will be specifically described below with reference to Examples, and the physical properties in the Examples were measured by the following methods.

[Method for measuring physical properties] (1) Adhesion A between vapor deposited layer and base film, peel strength of cellophane tape A commercially available cellophane adhesive tape manufactured by Chiban Co., Ltd., "'Cello Tape") was applied to the vapor deposition surface of the vapor deposited film. After applying it and pressing it strongly with a finger, it was peeled off at 180 degrees, and the adhesion area after peeling was evaluated using a 5-level index according to the following criteria.

8. Apply an epoxy adhesive (“Araldite Rapid” manufactured by Ciba Geigy Corporation) to an aluminum plate with a sample thickness of 9.5 mm and a wet peel strength of 180 degrees, and attach the vapor deposition surface of the vapor deposition film to the aluminum plate with a sample thickness of 9.5 mm. 'lQmm
A glass rod was rolled and pressed by hand, and cured for 30 minutes in a hot air dryer controlled at 80°C. Rough width'
It was cut into pieces of lQmm, bonded length 75mm, non-bonded length 25mm, and total length 100mm.

(2) Measurement of 180 degree wet peel strength After setting the sample obtained in (1) on a universal tensile tester (Toyo Baldwin, "Tensilon"), drop water with a dropper onto the peel interface (approx. 0.050
After 0)L/, the adhesive strength was measured.

Measurement conditions: tensile speed 200 mm/min Sample dimensions: width '1 mm, length 100 mm.

Adhesion length: 75 mm Example 1 A polyester film (manufactured by Toshiku Co., Ltd.) with a thickness of 38 μm and a width of 15 cm was placed in an internal electrode type plasma polymerization device, and after being evacuated to an initial pressure of 1×10 −4 orr, glycidyl Introducing methacrylate, Q, 21or
After forming a plasma polymerized layer to a thickness of about 100 mm on the surface of the polyester film by maintaining the pressure at a pressure of was formed.

Vapor deposition conditions Equipment: High vacuum evaporation equipment EBB-6 type (manufactured by Japan Vacuum Co., Ltd.) Evaporation metal Nialuminum Vacuum degree: 'l x 'l Q'' 4mmH evaporation thickness 2
When the cellophane tape peel strength of the metallized films obtained by 600 people was measured, it was found to be extremely good with an index of 5. Also 1
The 80 degree wet peel strength was much higher than 55 (J/Cm, which is 30]/Cm, which is considered to be a practical level for general use).

Comparative Example 1 The same polyester film as Example 1 was heated with N2 under the following conditions.
After corona discharge treatment was carried out in the chamber, metal vapor deposition was carried out under the same conditions as in Example 1. The obtained sample had a cellophane tape peel strength of 1 C1/Cm or less, and had no adhesive strength at all.

Corona discharge treatment conditions Equipment: Corona discharge treatment equipment (Kasuga Denki Co., Ltd. HF-401) Lll1 strength: 6,0OOJ/m”N2 flow rate: 2
00D,/min [Effects of the Invention] Since the present invention is configured as described above, the adhesive strength of the vapor-deposited metal layer does not decrease not only under high temperature and high humidity conditions but also in liquid.
It shows excellent performance in a variety of applications including condensers, packaging containers, especially liquid containers subject to high-pressure steam sterilization, electrical equipment, packaging, and decoration.

Claims (1)

[Claims] (1) A metal vapor deposited film in which a polymer resin film and a metal vapor deposited layer are bonded via a plasma polymerized layer formed from an acrylic or methacrylic compound having a glycidyl group.