JPH02229032A - Laminated film - Google Patents

Abstract

PURPOSE:To manufacture an inexpensive film superior in gas permeability resistance, by laminating a fluorine resin film and high-molecular resin film having a metallic oxide layer on one side or both sides of the same. CONSTITUTION:A fluorine resin film A and high-molecular weight film B having a metallic oxide layer C on one side or both sides of the same are laminated. A number of carbons of alpha-fluoroolefin is preferably 2-6, especially preferably 2-4, in the fluorine resin film A. Among those films the film comprised of a copolymer such as a tetrafluoroethylene-hexafluoropropylene copolymer or a chlorotrifluoroethylene polymer is suitable and the same whose thickness is normally about 5-300mum is used from a view point of its flexibility Polyolefin or polyester are mentioned as the high-molecular resin film B. The metallic oxide layer C is formed on one side or both sides of the high-molecular resin film B prior to lamination of fluorine resin film A and high-molecular resin film B. Preferable metallic oxide is selected out of a group comprised of Ti, Al, Fe, Cr, Ni, Si, In, Sn, Zn and Zr.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is applicable to foods, pharmaceuticals, pharmaceutical raw materials, electroluminescent lamps (EL clamps, solar cells, etc.) whose quality performance is significantly deteriorated due to the permeation of gases such as water vapor and oxygen. electronic devices such as

It relates to a laminated film that is applied to sealing materials or packaging materials for aerospace industry parts, etc., and is intended to maintain quality performance and improve durability of steam product parts.

[Prior Art] Different materials are used for gas permeability (gas barrier) films depending on the type of gas to be used.

Various materials have been proposed for oxygen gas, etc., but for water vapor, there is currently no good material other than fluororesin film. However, since fluororesin films are extremely expensive, their range of application is limited, and furthermore, products using fluororesin films as sealing materials or packaging have to be expensive.

Further, fluororesin films have a problem in that although water vapor permeation is extremely small, oxygen permeation is relatively large.

[Object of the Invention] The present invention was made in view of the current situation, and it is an object of the present invention to provide an inexpensive film with excellent gas permeation resistance.

[Structure and operation of the invention] As a result of intensive studies to provide an inexpensive film with excellent gas permeability resistance, the present inventor has developed a polymer comprising a fluororesin film and a metal oxide layer formed on one or both sides. The present invention was achieved by discovering that by laminating a resin film, it is possible to reduce the thickness of an expensive fluororesin film and still have sufficient water vapor permeability for practical purposes, and also improve oxygen gas permeability. did.

However, the present invention is a laminated film of a fluororesin film (A) and a polymer resin film (B) having a metal oxide layer (C) on one or both sides.

A detailed description of the present invention is provided below.

The fluororesin film (A) used in the present invention is a fluorinated olefin polymer, that is, an α-fluoroolefin, particularly a perfluorinated polymer or a polymer of a compound containing hydrogen together with fluorine, a halogen-containing α-fluoroolefin, or a perfluorinated α-fluoroolefin. All known fluororesin films such as fluoroalkoxyethylene polymers and copolymers using at least two of the above α-fluoroolefins, halogen-containing α-olefins, or perfluoroalkoxyethylenes can be used. The α-fluoroolefin preferably has 2 to 6 carbon atoms, particularly preferably 2 to 6 carbon atoms.
It is 4. Among them, te 1 - fluoroethylene-hexafluoropropylene copolymer (FEP), chlorotrifluoroethylene polymer (CTFE), ru 1 - copolymer of lifluoroethyl 1-non and vinylidene fluoride, chlortrifluoride A film made of a copolymer of fluoroethylene and ethylene is suitable, and a film having a thickness of usually 5 to 300 μm is used because of its flexibility. Particularly preferably from the viewpoint of cost, the thickness is 5 to 200 μm.

Polymer resin film (B) is obtained by melting or melt-extruding the following representative organic polymers and stretching them in the longitudinal direction and/or width direction as necessary, or by coordinating two or more types of organic polymers. It is extruded.

Typical organic polymers include polyolefins such as polyethylene and polypropylene, and polyethylene terephthalate 1.
~． Polyesters such as poly(lower dylene-26-naphthalate), polyamides such as nylon 6 and nylon 12, vinyl chloride, vinylidene chloride, polyvinyl alcohol, and aromatic polyamides.

polyamideimide, polyimide, polyetherimide,
Polysulfone, polyethersulfone.

Polyetheretherketone, polyarylate.

Polyphenylene sulfide, polyphenylene oxide, polycarbonate, cellulose 1 ~ lyacete 1 ~
．． Examples include polyacryloni 1-lyl.

These organic polymers may be copolymers with other organic polymers or may contain other organic polymers. Another method is to laminate one organic polymer film with another organic polymer layer.

It may be laminated by a coating method or the like.

Known additives such as antistatic agents, ultraviolet absorbers, plasticizers, lubricants, colorants, etc. may be added to these organic polymers.

The thickness of the polymer resin film of the present invention is not particularly limited, but is preferably in the range of 5 to 200 μm in terms of mechanical properties and flexibility.

A metal oxide layer (C) is formed on one or both sides of the polymer resin film (B). Prior to forming the metal oxide layer (C), corona discharge treatment, plasma treatment, glow discharge treatment, and sputter etching treatment.

Surface treatment such as roughening treatment or known anchor coating treatment may be performed, or printing may be performed.

Known methods such as vacuum evaporation, sputtering, and ion blasting can be applied to form the metal oxide layer (C).

In addition, metal oxide @ (C) is a fluororesin film (A)
Before laminating the polymer resin film (B) and the polymer resin film (B), it is formed on one or both sides of the polymer resin film (B), but in the case of only one side, the fluororesin film (8) and the polymer resin film (B) are formed on one side or both sides of the polymer resin film (B). After laminating the polymer resin film (B
) A metal oxide layer (C) may be formed on top of the metal oxide layer (C).

Preferred metal oxides include Ti, ΔL Fe, C
r.

N1. At least one metal oxide selected from the group consisting of Sr, In, Sn, Zn, and Zr,
It may be a mixture of two or more metal oxides or a composite oxide.

These metal oxides are not necessarily stoichiometric oxides, and may contain a small amount of unoxidized metal atoms.

The metal oxide layer also contains elements other than those mentioned above, such as B.
A small amount of i, Sb, C, No, W, Cu, etc. may be included.

The thickness of the metal oxide layer is preferably in the range of 10 to 2,000 thick in terms of gas barrier properties and flexibility. If it is used by less than 10 people, the gas barrier properties will be insufficient, and if it is used by more than 2,000 people, cracking or peeling will easily occur due to bending or the like.

Preferably 20 to 500 people, particularly preferably 2
0 to 400 people.

The metal oxide layer (C) is formed as a metal oxide layer from the beginning on the polymer resin film (B), or is converted into a metal oxide layer in an oxidizing atmosphere after being formed as a metal layer.

The method of laminating the fluororesin film (A) and the polymer resin film (B) formed with a metal oxide layer (C) on one or both sides is not particularly limited. An example of a method is to provide a human-sealable adhesive layer on at least one of the surfaces on which the molecular resin film (B) is to be laminated, and to laminate the layers by heat-pressing. In order to improve the adhesion between the fluororesin film (A) and the adhesive layer, on the surface of the fluororesin film,
Surface treatment such as corona discharge treatment, plasma treatment, glow discharge treatment, sputter etching treatment, surface roughening treatment, chemical treatment, etc. may be performed in advance.

When applying a laminated film formed by laminating a fluororesin film (A) and a polymer resin film (B) formed with a metal oxide layer (C) on one or both sides as a sealing material or a packaging material, further , it is preferable to laminate a heat-sealable adhesive layer (D).

The heat-sealable adhesive layer (D) refers to a plastic layer that can be bonded by heat-pressing. Typical examples include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers, polyesters,
Polyamide, ionomer, ethylene/vinyl acetate copolymer, acrylic resin such as acrylic ester, methacrylic ester, polyvinyl acetal, phenol.

Modified epoxy resin, ethylene/ethyl acrylate copolymer, ethylene/ethyl acrylate/maleic anhydride 3
Original copolymers, ethylene/glycidyl methacrylate/vinyl acetate ternary copolymers, and copolymers and mixtures thereof are included. Further, the heat-sealable adhesive layer (D) does not need to have a single layer structure, and may have a laminated structure.

Among these, polyolefin, ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, ethylene/ethyl acrylate/maleic anhydride ternary copolymer, ethylene/glycidyl methacrylate/vinyl acetate 3
Preferably, the original copolymer and a mixture or laminate thereof are used.

The thickness of the heat-sealable adhesive layer ([)) is selected depending on the application, but from the viewpoint of adhesive strength and gas barrier properties, it should be 1 to 2.
The range is preferably 00 μm, more preferably 10 to 15
0 μm, particularly preferably 10 to ioo μm.

The heat-sealable adhesive layer (D) can be used depending on the purpose of use.
It can be provided on one or both sides of the laminated film.

Heat-sealable adhesive @(
When providing D), the fluororesin film is subjected to surface treatment, for example, corona discharge treatment.

Plasma treatment, glow discharge treatment, sputter etching treatment, surface roughening treatment, chemical treatment, etc. may be performed.

Methods for laminating the heat-sealable adhesive layer (D) include a method of coating a solution of the adhesive layer components, a method of melting the adhesive layer components and extrusion lamination, or a method of preparing the adhesive layer sheet in advance, A known method such as dry laminating or other adhesive lamination can be applied.

[Effects of the Invention] The laminated film of the present invention is inexpensive and has gas barrier properties sufficient for practical use, and is widely used as a sealing material or packaging material for foods, medicines, parallax materials, electronic elements, electronic parts, mechanical parts, etc. It is available.

Examples of the present invention are shown below.

Examples 1-3. Comparative Examples 1-2 Polyethylene terephthalate (PE) with a thickness of 25 μm
The film was placed in a DC Magne 1 to Ron sputtering device, and sputtering was performed using an In target in an 8r10z (0220%) atmosphere to form an In203 film on both sides of the P sun-dried film to a film thickness of 200%. was formed. Hereinafter, it will be referred to as film 1.

In addition, InSn was added to one side of a 25 μm thick PET film.
Using target (Sn5%), 8r102 (0220
%) Sputtering was performed in an atmosphere to form an ITO film to a thickness of 100 nm, then a T1 target was used on the opposite side to form a T1 film to a thickness of 50 nm in an Ar atmosphere. 3. After drying, it was treated in a hot air dryer maintained at 150°C for 1 hour. Hereinafter, it will be referred to as film 2.

On the other hand, one side of a 20-μm-thick copolymer film of chlorotrifluoroethylene and vinylisodine fluoride was roughened by 1-nondo blasting, and then subjected to corona discharge treatment. An adhesive layer was formed. Hereinafter, it will be referred to as film 3.

Film] or 2 and film 3 were laminated by heat-pressing via the adhesive layer. Thereafter, a 20 μm thick adhesive layer made of ethylene/vinyl acetate copolymer was formed on the metal oxide surface of the laminated film to obtain Example 1,
A laminated film of No. 2 was created.

As Comparative Example 1, polyvinylidene chloride was coated on a PE film having a thickness of 25 μm so that the film thickness after drying was 20 μm.

Examples 1 and 2. As Comparative Example 1 and Comparative Example 2, the oxygen permeability and water vapor permeability of Film 3 were measured. The results are not shown in Table 1.

The laminated film of the present invention exhibits practically sufficient permeation resistance to oxygen and water vapor.

Table 1 Measurement conditions 1) 20'C, Q%R1-12) 40°
C, 90%RH

Claims (1)

[Claims] 1. A laminated film of a fluororesin film (A) and a polymer resin film (B) having a metal oxide layer (C) on one or both sides.