JP2002019023A - Metal foil-laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal foil-laminated film which has good folding resistance and scratch resistance without damaging the characteristics in strength and glossiness of metal foil itself. SOLUTION: In the metal foil-laminated film, a thermoplastic resin film is laminated at least on one side of the metal foil, and the ratio of the thickness of the thermoplastic resin film to that of the metal foil-laminated film is 1-50%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal foil laminated film obtained by laminating a metal foil and a thermoplastic resin film, and more particularly, to maintaining the original mechanical properties and glossiness of the metal foil. In addition, the present invention relates to a metal foil laminated film excellent in breaking resistance and scratch resistance.

[0002]

2. Description of the Related Art Aluminum, stainless steel or gold,
Metal foils such as silver and copper make use of the mechanical, thermal, optical, electrical, and physical properties unique to each metal to make electrical materials, packaging materials, decorative materials, building materials,
It is widely used for all uses such as optical materials.
In particular, utilizing the decorative and design properties unique to metal, interior and exterior wall materials, floor and ceiling materials, interior and exterior materials for houses and structures,
It is used as a surface material for panel materials and door materials, as a component material for furniture and electric appliances, and as a surface material for interior materials and exterior materials for automobiles and aircraft.

However, the conventional metal foil has the following disadvantages. (1) Cracks are partially generated due to bending during molding. (2) The surface is easily scratched by contact or rubbing with another material. (3) The glossiness is reduced due to the above-mentioned effects and the effects of the use environment.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, and provides a metal foil laminate excellent in breaking resistance and abrasion resistance without impairing the original mechanical properties and glossiness of the metal foil. It does not provide films.

[0005]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the metal foil laminated film of the present invention is a laminated film in which a thermoplastic resin film is laminated on at least one surface of the metal foil, and, with respect to the total thickness of the laminated film, the thermoplastic resin film The ratio of the thickness is 1% or more and 50% or less.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been made as a result of intensive studies on the above-mentioned problem, that is, a metal foil laminated film excellent in breaking resistance and scratch resistance without impairing the original mechanical properties and glossiness of the metal foil. A laminated film in which a thermoplastic resin film is laminated on at least one side of the metal foil, and
When the ratio of the thickness of the thermoplastic resin film to the thickness is specified, it has been surprisingly found that such a problem can be solved at once.

That is, in the metal foil laminated film of the present invention, the ratio of the thickness of the thermoplastic resin film to the total thickness of the metal foil laminated film is 1% or more.
It is important to control the ratio of the thickness of the thermoplastic resin film to 0% or less, more preferably 1% to 40%, particularly preferably 1% to 30%. If the proportion of the thickness of the metal foil is less than 1%, it is not preferable because the folding resistance and the scratch resistance are poor. On the other hand, if the proportion of the thickness of the thermoplastic resin film exceeds 50%, the mechanical properties and glossiness inherent in the metal foil are undesirably reduced.

In the present invention, the laminated structure of the thermoplastic film and the metal foil is within a range not impairing the effects of the present invention.
Although it can be arbitrarily designed according to the application and purpose, it is preferably two or more layers, and more preferably two or three layers.

The metal foil referred to in the present invention includes aluminum foil, stainless steel foil, copper foil, nickel foil, titanium foil, tin foil, silver foil,
Various alloy foils such as gold foil or zinc foil can be used.
Another metal or alloy may be laminated on the surface of the metal foil by plating or the like. Further, as long as the object of the present invention is not impaired, the metal foil surface is subjected to a chemical treatment such as phosphoric acid treatment, chromic acid treatment, electrolytic chromic acid treatment,
Electrolytic treatment such as electric tin plating, hot-dip plating such as hot-dip tin plating and hot-dip zinc plating may be performed, and further, various surface treatments such as rust prevention treatment, hardening treatment, polishing and the like may be performed. You may.

The thickness of the metal foil of the present invention is preferably 1 to 50 μm, more preferably 1 to 30 μm, and particularly preferably 1 to 20 μm.

The total thickness of the metal foil laminated film of the present invention is 2
To 100 μm, more preferably 2 to 100 μm.
It is 50 μm, particularly preferably 2 to 30 μm.

As the thermoplastic resin film in the present invention, polyolefin film, polyester film, polyamide film, polyphenylene sulfide film, polycarbonate film, polyimide film, polyetherimide film, cellophane film,
A simple substance such as a polyvinyl chloride film, a fluorine film, a polyacrylonitrile film, a polystyrene film and the like and a laminate thereof can be employed, but a polyester film is particularly preferable in terms of mechanical properties and thermal properties.

As such a polyester, a polyester containing an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid and a diol as main components is more preferably employed. Here, as the aromatic dicarboxylic acid component, for example, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4 ′ -Diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid and the like can be employed, and terephthalic acid, isophthalic acid, 2,6-
Naphthalenedicarboxylic acid and the like are used. As the aliphatic dicarboxylic acid component, for example, adipic acid, suberic acid, sebacic acid, dodecanedioic acid and the like can be employed, among which adipic acid and the like are preferably employed, and as the alicyclic dicarboxylic acid component, , For example, 1,4
-Cyclohexanedicarboxylic acid or the like can be employed. One of these acid components may be used alone, or two or more thereof may be used in combination. Further, an oxyacid such as hydroxybenzoic acid may be partially copolymerized.

As the diol component, for example, ethylene glycol, 1,2-propanediol, 1.3
-Propanediol, neopentyl glycol, 1,3
-Butanediol, 1,4-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 1,2
-Cyclohexanedimethanol, 1.3-cyclohexanedimethanol, 1.4-cyclohexanedimethanol, diethylene glycol, triethylene glycol,
Polyalkylene glycol, 2,2′-bis (4′-β
-Hydroxyethoxyphenyl) propane and the like can be employed. Among them, ethylene glycol is preferably used. These diol components may be used alone or in combination of two or more.

Specific examples of the polyester used for the thermoplastic resin film of the present invention include polyethylene terephthalate, a copolymer of ethylene terephthalate and ethylene isophthalate, a copolymer of ethylene terephthalate and ethylene naphthalate, and a copolymer of polyethylene terephthalate and polyethylene naphthalate. A blend with butylene terephthalate or the like can be employed.

The thermoplastic resin film of the present invention may contain, if necessary, an organic lubricant such as a flame retardant, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a pigment, a dye, a fatty acid ester, or a wax. An antifoaming agent such as siloxane may be blended.

The thermoplastic resin film of the present invention may be unstretched, but is preferably uniaxially or biaxially stretched and oriented.

With respect to the degree of orientation, for example, in the case of a polyester film, the orientation parameter of the surface portion of the film determined by laser Raman spectroscopy is preferably 3 to 10, more preferably 4 to 10, and particularly preferably 5 to 10. 10 to 10.

The orientation parameter of the film as referred to in the present invention is defined as Job Yvon / Rago manufactured by Atago Bussan Co., Ltd.
manor "U-1000 device (light source: NEC Corporation)
GLG3300 Ar ⁺ laser, 514.5 nm,
Microscope: value obtained by laser Raman spectroscopy using an Olympus Optical Co., Ltd. BH-2 type objective lens × 100). The larger the orientation parameter, the higher the degree of molecular orientation.

Next, a method for producing the metal foil laminated film of the present invention will be described. The thermoplastic resin film of the present invention is, for example, after sufficiently drying the thermoplastic resin, melt-extruded using an extruder, and extruded through a T-die die onto a cast drum to obtain an unstretched film. It can be manufactured by stretching a stretched film uniaxially or biaxially.

In the case of biaxial stretching, any of simultaneous biaxial and sequential biaxial methods may be used. In the case of sequential biaxial stretching, the stretching order is the film in the longitudinal direction, width direction,
Alternatively, the reverse may be performed. Further, in the sequential biaxial stretching, stretching in the longitudinal direction or the width direction can be performed twice or more.

The stretching temperature of the film is preferably in the range of not less than the glass transition temperature of the thermoplastic resin used and not more than the crystallization temperature, more preferably not more than (glass transition temperature of the thermoplastic resin + 20 ° C.). Adopted. Further, the preheating before stretching is preferably performed at a lower temperature equal to or lower than the stretching temperature of the film. The stretching ratio in the longitudinal direction and the width direction of the film can be arbitrarily set in the range of 1.5 to 10 times. Either the stretching ratio in the longitudinal direction or the stretching ratio in the width direction may be increased, and may be the same.

Further, heat treatment may be performed after the film is biaxially stretched. This heat treatment can be performed by any method, such as in an oven or on a heated roll. The heat treatment temperature is preferably in the range of 30 ° C. or higher and the melting point of the thermoplastic resin or lower. Although the heat treatment time can be arbitrarily set, it is preferable to perform the heat treatment within a range of 1 to 60 seconds.

The method of laminating the above-mentioned thermoplastic resin film and metal foil is not particularly limited, but it may be attached via an adhesive or may be thermally bonded without using an adhesive.

When an adhesive is used, the adhesive may be coated on the film surface or on the metal foil surface. The coating method is not particularly limited, and methods such as roll coating, bar coating, spray coating, nozzle coating, and dip coating can be employed.

As the adhesive, a solvent type, an emulsion type, a hot melt type and the like can be used.
Polyurethane, acrylic, polyvinyl acetate and epoxy adhesives can be used. The amount of adhesive, as weight after drying per unit area is preferably from 0.01 to 10 g / m ^2, more preferably 0.1-5 g / m ^2.

As a method by thermal bonding, for example, a method in which a metal foil is heated to a temperature equal to or higher than the melting point of the thermoplastic resin film and the metal foil and the film are pressure-bonded with a laminating roll. In this case, it is more preferable that only the adhesive side of the film is heated at the same time, and the film is laminated while the non-adhesive side is in contact with the cooling roll.

As a method of providing a thermoplastic resin film on the surface of a metal foil, it can also be formed by coating a molten or solution-like thermoplastic resin into a film and cooling or removing the solvent by drying. In this case, an aqueous or organic solvent can be used as the solvent to be used.

The metal foil laminated film of the present invention can be subjected to printing on the surface of the thermoplastic resin film, the surface of the metal foil, or both surfaces, depending on the use and purpose. The printing method may be any method such as letterpress, offset, gravure, screen, and flexographic printing. Before printing, an anchor coat treatment may be performed on the surface of the thermoplastic resin film or the surface of the metal foil in order to improve the adhesion with the printing ink. Further, a top coat layer can be formed for protecting the printing surface. As a material of the top coat layer, a polyolefin resin, a silicone resin, a fluorine resin, a polyurethane resin, an epoxy resin, an acrylic resin, a polyester resin, or the like can be used.

The metal foil laminated film of the present invention may be subjected to a molding process before, after, or simultaneously with the printing process. The embossing process is not limited to a simple embossing process, but is preferably performed by embossing a character or a special pattern, because the design and decorative properties are further improved. As a method of the molding process, a method using an embossing roll, a method using a press, and the like can be adopted.

The metal foil laminated film of the present invention may be bonded to another thermoplastic resin material, metal material, stone material, wood, or other composite material. In this case, the shape of the substrate can be a plate, a bar, or any other shape.

<Measurement Method of Properties> (1) Elastic Properties According to the method specified in JIS-Z1702, each sample was measured for tensile modulus using a Tensilon tensile tester (manufactured by Toyo Baldwin Co., Ltd.). Then
The ratio of the tensile modulus of the metal foil laminated film to the tensile modulus of the metal foil alone was determined from the following equation, and the elastic properties were determined as follows.

[0033] The criterion was ◎ for the elastic modulus ratio of 0.9 or more, ○ for the elastic modulus ratio of 0.6 to less than 0.9, and 0.
Those with less than 6 were rated as x. (2) Gloss The gloss at an angle of 60 ° was measured according to JIS K7105, and the gloss was determined from the ratio of the gloss of the metal foil laminated film to the gloss of the metal foil alone as follows.

[0034] Judgment criteria are ◎ when the gloss ratio is 0.9 or more, ○ when the gloss ratio is 0.8 or more and less than 0.9, and 0 when the gloss ratio is 0.
Those with less than 8 were evaluated as x. (3) Folding resistance According to the method specified in JIS P8115-63,
Using an MIT bending tester, the number of times of bending (n) until breaking at a tension of 10 N / mm ² was determined, and determined based on the following criteria.

◎, where n is 10,000 or more, and n is 5
を: less than 10000 times ○, n: 500
Those less than 0 times were evaluated as x. (4) Scratch resistance The surface was rubbed with steel wool # 1000, the degree of scratching was evaluated, and judgment was made based on the following criteria.

も の indicates that scarcely any damage is caused by strong rubbing, ○ indicates that slight scratching occurs when strongly rubbed, and x indicates that scratching is caused by weak friction. (5) Orientation parameter The orientation parameter of the polyester film surface portion was determined by Job Yvon / Atago Bussan Co., Ltd. “Ram”.
Laser Raman spectroscopy using an anor "U-1000 apparatus (light source: GLG3300 Ar ⁺ laser manufactured by NEC Corporation, 514.5 nm, microscope: BH-2 type objective lens × 100 manufactured by Olympus Optical Co., Ltd.) It was determined by the following method.

The micro sample was embedded in PMMA resin and wet polished to form a cross section perpendicular to the width direction of the film. A laser beam is irradiated perpendicularly to the cross section, and the Raman spectrum of the laser beam polarized in the plane direction of the film and the laser beam polarized in the thickness direction of the film is 1
The peak intensities of the 615 cm ^-1 band were calculated as I _YY and I _XX respectively.
And the ratio I _YY / I _XX was used as the orientation parameter.

[0038]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Example 1 As a metal foil, a 5-μm-thick aluminum foil (B) having a roughened surface and a chromate treatment was prepared. Then, toluene / methyl ethyl ketone was used as an adhesive on the surface of the aluminum foil as a diluting solvent, and this was used as an acrylic resin to form “U”
LS-935LH "(manufactured by Yushi Yushi Kogyo KK) was applied at a concentration of 15%.
After drying for an minute, an aluminum foil having an adhesive layer was produced.

On the other hand, a molten polymer is extruded from a polyethylene terephthalate as a raw material into a cast drum by a T-die extrusion method, and then biaxially stretched in the longitudinal and transverse directions.
Heat treatment was performed to produce a biaxially stretched polyester film (A) having a thickness of 1 μm, and the adhesive surface was subjected to EC treatment. The orientation parameter of the film surface was 6.5.

The polyester film is superposed on the aluminum foil having the adhesive layer to form an A / B two-layer structure, and is pressure-bonded with a laminating roll at a temperature of 150 ° C. to produce a metal foil laminated film having a thickness of 6 μm. did.

The properties of the obtained metal foil laminated film are shown in Table 1.
As shown in the above, elastic properties, gloss, breaking resistance,
The scratch resistance was good. Example 2 In Example 1, the thickness of the aluminum foil (B) was set to 2 μm and the thickness of the polyester film (A) was set to 0.5 μm.
A 3 μm-thick metal foil laminated film was produced in the same manner as in Example 1 except that a three-layer structure of / B / A was used. The orientation parameter of the film surface was 6.3.

The properties of the obtained metal foil laminated film are shown in Table 1.
As shown in the above, elastic properties, gloss, breaking resistance,
The scratch resistance was good. Example 3 Stainless steel foil (B) having a thickness of 10 μm instead of aluminum foil
Was prepared. The stainless steel foil and the polyester film (A) having a thickness of 1 μm prepared in Example 1 were supplied to a roll-type laminating apparatus, and the polyester film was rubbed for 200 hours.
℃, the aluminum foil was heated to 280 ℃, respectively. Then
The heated polyester film and the aluminum foil are overlapped and guided to a laminating roll, and pressed at a roll temperature of 180 ° C. and thermally bonded without using an adhesive, thereby forming an A / B two-layered metal foil laminated film having a thickness of 11 μm. Was prepared.
The orientation parameter of the film surface was 5.4.

The properties of the obtained metal foil laminated film are shown in Table 1.
As shown in the above, elastic properties, gloss, breaking resistance,
The scratch resistance was good. Example 4 In Example 1, a biaxially stretched polyphenylene sulfide film (A) having a thickness of 1 μm was prepared using a polyphenylene sulfide raw material instead of the polyethylene terephthalate raw material. Next, an aluminum foil (B) having a thickness of 20 μm was prepared, and an adhesive was applied in the same manner as in Example 1.
/ B A metal foil laminated film having a thickness of 21 μm was formed as a two-layer structure.

The properties of the obtained metal foil laminated film are shown in Table 1.
As shown in the above, elastic properties, gloss, breaking resistance,
The scratch resistance was good. Comparative Example 1 In Example 1, the thickness of the polyester film was set to 10
A thickness of 15 μm was obtained in the same manner as in Example 1 except that the thickness was 15 μm.
A μm metal foil laminated film was produced.

The properties of the obtained metal foil laminated film are shown in Table 1.
As shown in Table 2, the breaking resistance and the scratch resistance were good, but the elastic properties and glossiness were greatly reduced. Comparative Example 2 In Example 1, the thickness of the polyester film was set to 0.
A metal foil laminated film having a thickness of 100.5 μm was produced in the same manner as in Example 1 except that the thickness was 5 μm and the thickness of the aluminum foil was 100 μm.

Table 1 shows the properties of the obtained metal foil laminated film.
And the elastic properties and gloss were good, but the breaking resistance and the scratch resistance were poor. Comparative Example 3 The aluminum foil having a thickness of 5 μm used in Example 1 was prepared. The properties of the aluminum foil were as shown in Table 1. Although the elastic properties and glossiness were good, the aluminum foil was inferior in breaking resistance and scratch resistance.

[0047]

[Table 1]

As is clear from Table 1, in the metal foil laminated films of Examples 1 to 4, the ratio of the thickness of the thermoplastic resin film is 1% to 50% of the total thickness of the laminated film. As a result, the fold resistance and the abrasion resistance were improved without impairing the original elastic properties and glossiness of the metal foil. On the other hand, the elastic properties and glossiness of Comparative Example 1 were impaired, and those of Comparative Examples 2 and 3 were poor in breaking resistance and scratch resistance.

[0049]

According to the present invention, a metal foil laminated film having the following effects can be provided. (1) High strength and elastic modulus. (2) The surface is hardly damaged and has excellent scratch resistance. (3) Excellent moldability with excellent metallic surface gloss. (4) Rust resistant. (5) Excellent moldability. (6) It has excellent conductivity and electromagnetic wave shielding properties. (7) It has excellent light-shielding properties and light-reflecting properties. (8) By printing on the film surface or metal foil surface, it is excellent in design and decoration.

Since the metal foil laminated film of the present invention has the above-mentioned excellent properties, it can be used as a wall material, a ceiling material, a partition material, a floor material, a door material, a bathtub wall, a wall material for a simple storage room, a member of a kitchen facility, and the like. Building materials, desks, chairs, lockers, cabinets, stands, bookshelves, archives, partitions and other furniture materials, refrigerators, TVs, coolers, microwave ovens, washing machines, lighting fixtures, other electrical product parts, decorative parts It can be used in a wide range of fields such as automobile interior materials, toys, leisure goods, agricultural house members, tableware, cans and other containers.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB01A AB10 AB33A AK01B AK25 AK41B AK42 BA02 BA25 CB00 EC18 EH46 EJ17 EJ38 GB08 HB00 HB31 JA20B JB16B JD08 JK01 JK04 JK07 JK09 JK14 JL01 YN00 J21

Claims (7)

[Claims] 1. A laminated film in which a thermoplastic resin film is laminated on at least one surface of a metal foil, and
A metal foil laminated film, wherein the ratio of the thickness of the thermoplastic resin film to the total thickness of the laminated film is 1% or more and 50% or less. 2. The metal foil laminated film according to claim 1, wherein said metal foil has a thickness of 1 to 50 μm. 3. The total thickness of the metal foil laminated film is 2 to 1
The metal foil laminated film according to claim 1 or 2, wherein the thickness is 00 µm. 4. The metal foil laminated film according to claim 1, wherein the thermoplastic resin film is a polyester film. 5. The metal foil laminated film according to claim 4, wherein the polyester film has an orientation parameter of 3 to 10 at the surface portion of the film determined by laser Raman spectroscopy. 6. The thermoplastic resin film and the metal foil,
The metal foil laminated film according to any one of claims 1 to 5, wherein the film is bonded without using an adhesive. 7. The metal foil laminated film according to claim 1, wherein at least one of the surface of the thermoplastic film and the surface of the metal foil is printed.